Hair dye, hair dye composition containing the dye, and method for producing the dye

Abstract

To provide a dye for hair coloration that has a long shelf life and is excellent in heat resistance, and a method for producing the dye for hair coloration.SOLUTION: A dye for hair coloration is represented by the following general formula (1), the dye for hair coloration having a proportion of a polyatomic anion (An) or impurities derived from An of 1 mass% or less, where in the formula (1), D represents a cationic moiety of the dye for hair coloration; An represents a polyatomic anion; and a and b each independently represent a value of 0 to 1.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a hair-coloring dye, a hair-coloring composition containing the dye, and a method for producing the dye. [Background technology]

[0002] In recent years, an increasing number of people of all ages are enjoying various hair colors by dyeing their black or gray hair, and a wide variety of hair dyes, including hair colorants, hair dyes, hair manicures, and hair color treatments, are commercially available. Oxidative hair dyes (permanent hair dyes) using oxidative dyes, which have high dyeing power and long-lasting color, have been primarily used for hair dyeing. However, these dyes have the problem of easily causing hair damage and skin irritation, such as allergies. Therefore, hair dyes using safer basic dyes have been proposed as an alternative to oxidative dyes (see, for example, Patent Documents 1 to 6).

[0003] HC dyes are used in combination with basic dyes as semi-permanent hair dyes, and for example, HC BLUE 15 is used as a blue HC dye. However, hair dyes using HC BLUE 15 have issues with heat resistance after dyeing, and suffer from color fading and discoloration due to the heating process during formulation, as well as problems with color fading and discoloration due to long-term storage and use in hot water (around 40°C). There is a demand for hair dyes that do not fade and maintain vivid colors, including blue hair dyes. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2002-37718 [Patent Document 2] Japanese Patent Application Laid-Open No. 2004-285048 [Patent Document 3] International Publication No. 2018 / 180515 [Patent Document 4] International Publication No. 2009 / 041514 [Patent Document 5] International Publication No. 2013 / 190774 [Patent Document 6] International Publication No. 2014 / 203771 Summary of the Invention [Problem to be solved by the invention]

[0005] The problem to be solved by the present invention is to provide a hair-dyeing dye having a long shelf life and excellent heat resistance, and to provide a method for producing the hair-dyeing dye. [Means for solving the problem]

[0006] The present invention was achieved as a result of extensive research aimed at solving the above problems, and comprises the following:

[0007] 1. A hair dye represented by the following general formula (1): The hair-dyeing dye has a ratio of polyatomic anions (An) or impurities derived from An of 1% by mass or less.

[0008] [ka]

[0009] [In formula (1), D represents a cation moiety of a hair-coloring dye, An represents a polyatomic anion, and a and b each independently represent a value of 0 to 1.]

[0010] 2. A hair dye represented by the general formula (1), wherein D is a cationic moiety of a triarylmethane dye, a xanthene dye, a phenothiazine dye, a phenazine dye, a phenoxazine dye, an azo dye, an azomethine dye, or an HC dye.

[0011] 3. A hair dye in which D in the general formula (1) is represented by the following general formula (2):

[0012] [ka]

[0013] [In formula (2), R 1 ~R 13 each independently represents —H, a halogen atom, —NO2, —NO, —CN, —OH, an amino group of 0 to 20 carbon atoms which may have a substituent, a linear or branched alkenyl group of 2 to 20 carbon atoms which may have a substituent, a linear or branched alkyl group of 1 to 20 carbon atoms which may have a substituent, a linear or branched alkoxy group of 1 to 20 carbon atoms which may have a substituent, an acyl group of 1 to 20 carbon atoms which may have a substituent, an aromatic hydrocarbon group of 6 to 30 carbon atoms which may have a substituent, or a heterocyclic group of 2 to 30 carbon atoms which may have a substituent; R 3 and R 4 , R 7 and R 8 , R 9 ~R 13 Adjacent groups may be bonded to each other to form a ring.

[0014] 4. A hair dye in which D in the general formula (1) is represented by the following general formula (3):

[0015] [ka]

[0016] [In formula (3), R 14 ~R 21 each independently represents —H, a halogen atom, —NO2, —NO, —CN, —OH, an amino group of 0 to 20 carbon atoms which may have a substituent, a linear or branched alkenyl group of 2 to 20 carbon atoms which may have a substituent, a linear or branched alkyl group of 1 to 20 carbon atoms which may have a substituent, a linear or branched alkoxy group of 1 to 20 carbon atoms which may have a substituent, an acyl group of 1 to 20 carbon atoms which may have a substituent, an aromatic hydrocarbon group of 6 to 30 carbon atoms which may have a substituent, or a heterocyclic group of 2 to 30 carbon atoms which may have a substituent; R14 ~R 21 Adjacent groups may be bonded to each other to form a ring. Q represents —CH═, —N═, —O—, —S—, an amino group having 0 to 30 carbon atoms which may have a substituent, or a methylene group.]

[0017] 5. A hair dye in which, in the general formula (1), D is represented by the following general formula (4):

[0018] [ka]

[0019] [In formula (4), R 22 and R 23 represents an amino group having 0 to 20 carbon atoms which may have a substituent, a linear or branched alkenyl group having 2 to 20 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent, or a heterocyclic group having 2 to 30 carbon atoms which may have a substituent.

[0020] 6. A hair dye in which, in the general formula (1), D is represented by the following general formula (5):

[0021] [ka]

[0022] [In formula (5), R 24 ~R 26 each independently represents an amino group having 0 to 20 carbon atoms which may have a substituent, a linear or branched alkenyl group having 2 to 20 carbon atoms which may have a substituent, a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent, a linear or branched alkoxy group having 1 to 20 carbon atoms which may have a substituent, an acyl group having 1 to 20 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent, or a heterocyclic group having 2 to 30 carbon atoms which may have a substituent; R 25and R 26 may be bonded to each other to form a ring.

[0023] 7. In the general formula (2), R 1 , R 2 , R 5 , R 6 is —H or a methyl group, and R 3 , R 4 , R 7 , R 8 is —H, a methyl group, or an ethyl group, and R 9 ~R 13 is —H, —Cl, an amino group having 0 to 10 carbon atoms which may have a substituent, an alkenyl group having 2 to 10 carbon atoms which may have a substituent, an alkyl group having 1 to 10 carbon atoms which may have a substituent, or an acyl group having 1 to 10 carbon atoms which may have a substituent.

[0024] 8. A hair-dyeing dye, wherein An in the general formula (1) is a hydrogen-containing anion.

[0025] 9. A hair dye having a shelf life of 6 months or more at room temperature (20-25°C) or 7 days or more at 40-60°C.

[0026] 10. A hair dye composition containing the hair dye, at least one auxiliary selected from the group consisting of a wetting agent, a swelling agent, a penetrating agent, a solvent, a pH adjuster, a surfactant, a fragrance, and a thickener, and water.

[0027] 11. A method for producing a hair dye represented by the following general formula (6): A manufacturing method characterized by carrying out steps 1 and 2.

[0028] [ka]

[0029] [In formula (6), D represents a cation moiety of a hair-coloring dye, An represents a polyatomic anion, and a and b each independently represent a value of 0 to 1.]

[0030] Step 1: Purifying a hair dye containing polyatomic anions (An) using water and activated carbon. Step 2: Dissolving the hair dye obtained in step 1 in water and salt, and then performing salt exchange.

[0031] By undergoing steps 1 and 2, the hair-coloring dye represented by the general formula (6) has a ratio (concentration ratio) of polyatomic anions (An) or impurities derived from An contained in the hair-coloring dye of 1 mass % or less. [Effects of the Invention]

[0032] The hair-coloring dye of the present invention has a long shelf life and excellent heat resistance, and a hair-coloring composition that effectively suppresses fading of dyed hair using the hair-coloring dye can be provided. Furthermore, the production method of the present invention can provide a hair-coloring dye that has a long shelf life and excellent heat resistance. DETAILED DESCRIPTION OF THE INVENTION

[0033] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in detail below with reference to the preferred embodiments. However, the present invention is not limited to the following embodiments and can be practiced in various modified forms within the scope of the present invention.

[0034] The "hair dye" represented by general formula (1) is a compound that is used primarily as a basic dye (or cationic dye) for dyeing human hair, and represents a water-soluble dye consisting of a compound having a basic (cationic) group in its molecular structure. In general formula (1), (D) represents a cation moiety in the hair-coloring dye. The cation represented by D bonds with an anion to form the hair-coloring dye. D is preferably a monovalent cation. In general formula (1), (An) represents a polyatomic anion, and the hair dye of the present invention may contain polyatomic anions (An) or "An-derived impurities" resulting from the polyatomic anions (An), and is represented by the following general formula (1), and the ratio (concentration ratio) of "polyatomic anions (An) or An-derived impurities" in the entire hair dye is 1 mass % or less. Furthermore, the hair dye represented by general formula (1) may contain chlorine ions (Cl - ) is included.

[0035] [ka]

[0036] In the general formula (1), when the molar ratio of (D) in the hair dye is 1, "a" represents the molar ratio of (An), and "b" represents the molar ratio of (Cl - ) represents the molar ratio. a and b each independently represent a value of 0 to 1, and a is preferably a small value relative to b, and a is preferably 0 or a value close to 0. b is preferably 1 or a value close to 1. For example, when D is a monovalent cation and An is a monovalent anion, a+b may be 1. Here, D is preferably a monovalent cation, and in that case, a+b is preferably 1.

[0037] Hair dyes represented by general formula (1) may contain impurities during their production process and storage conditions after production. These impurities include unreacted materials from the synthesis, impurities contained in the raw materials, solvent molecules, organic or inorganic compounds other than the intended color-producing component, impurities derived from cations or anions (decomposition products, substances bound to other substances, etc.), hydrogen-containing compounds containing protons (hydrogen ions) (reactive impurities including anions and cations), insoluble impurities, and other substances introduced before, during, or after production. In the present invention, polyatomic anions (An) or reaction products derived from the presence of An are considered impurities and are considered to be undesirable for the intended hair dyeing function (heat resistance, long-term storage stability) of the present invention. Therefore, the ratio (concentration ratio) of "impurities derived from polyatomic anions (An) or An" in the entire hair dye is 0.1% by mass or less, and preferably 0.05% by mass. Here, "impurities derived from An" include decomposition products of An or other substances, such as substances bonded to the cation moiety (D) of the hair dye, or reaction products.

[0038] In the general formula (1), the "polyatomic anion (An)" specifically refers to an anion having two or more atoms, such as an inorganic anion (inorganic anion), an organic anion (organic anion), or a complex ion (complex salt anion). More specifically, a dihydrogen phosphate ion (H2PO4 - ), monohydrogen phosphate ion (HPO4 2- ), phosphate ions (PO4 3- ), P2O7 4- , cyanide ion (CN - ), nitrate ions (NO3 - ), nitrite ion (NO2 - ), hypochlorite ion (ClO - ), chlorite ion (ClO2 - ), chlorate ion (ClO3 - ), permanganate ions (MnO4 - ), carbonate ions (CO3 2- ), bicarbonate ion (HCO3 -), hydrogen sulfate ion (HSO4 - ), sulfate ions (SO4 2- ), sulfite ions (SO3 2- ), thiosulfate ion (S2O3 2- ), methyl sulfate ion (CH3SO4 - ), hydrogen sulfide ion (HS - ), thiocyanate ion (SCN - ), tetrahydroxide aluminate ion ([Al(OH)4] - , [Al(OH)4(H2O)2] - ), tetrahydroxide chromate(III) ion ([Cr(OH)4 - ]), chromate ion (CrO4 2- ), dichromate ion (Cr2O7 2- ), tetrahydroxide zincate(II) ion ([Zn(OH)4] 2- ), tetracyanide zincate(II) ion ([Zn(CN)4] 2- ), ((1 / 2)[ZnCl2]·Cl - ), tetrachloridozinc(II) ion ([ZnCl4] 2- ), tetrachlorocuprate(II) ion ([CuCl4] 2- ), hexacyanidoferrate(III) ion ([Fe(CN)6] 3- ), hexacyanidoferrate(II) ion ([Fe(CN)6] 4- ), hexahydroxystannate(IV) ion ([Sn(OH)6] 2- ), tetrahydroplumbate(II) ion ([Pb(OH)4] 2- ), acetate ion (CH3COO - ), hydrogen oxalate ion (H(COO)2 - ), oxalate ion ((COO)2 2- ), benzoate ion (C6H5COO - ), citrate ion (C6H5O7 3- ), various amino acid ions, and other organic acid ions having a carboxy group.

[0039] In the general formula (1), the polyatomic anion (An) is preferably a hydrogen-containing anion, specifically, H2PO4 - , HCO3 - , HSO4 - , CH3COO - , or CH3SO4 - is preferred.

[0040] In the hair dye represented by general formula (1), D and An may each be one type or a mixture of multiple types, but it is preferable that D is one type, and usually it is preferable that An is one type.

[0041] In the hair-coloring dye represented by general formula (1), D may be the cationic moiety of a basic dye (cationic dye). Specifically, in general formula (1), D is preferably the cationic moiety of an arylmethane dye, a triarylmethane dye, a xanthene dye, a phenothiazine dye, a phenazine dye, a phenoxazine dye, an azo dye, an azomethine dye, or an HC dye.

[0042] Specific examples of the hair dye represented by general formula (1) of the present invention include arylmethane dyes, preferably triarylmethane dyes, such as CI Basic Blue 77 (CI stands for Color Index. In the present invention, it is abbreviated to Basic Blue 77, or Basic Blue 77, or Basic Blue 77. The following dyes will be represented by either of these notations.), Basic Blue 1, 5, 7, 11, 15, or 26, Basic Green 1 or 4, and Basic Violet 2, 3, 11:1, 4, or 14; xanthene dyes, such as Basic Violet 10 or 11, Basic Red 1 or 1:1, and Rhodamine 110; phenothiazine dyes, such as Basic Blue 9 or 17; phenazine dyes, such as Basic Red 2; phenoxazine dyes, such as Basic Blue 3 or 124; acridine dyes; azo dyes, such as Basic Brown 16, Basic Red 22, 51, or 76, Basic Orange 31, and Basic Yellow 57; azomethine dyes such as HC Yellow 11, 13, 29, 36, or 40, and Basic Violet 16; and HC dyes such as HC Blue 8, HC Red 13, and HC Yellow 9.

[0043] In the general formula (1), D is preferably represented by any one of the general formulae (2) to (5).

[0044] In the general formulas (2), (3) and (5), R 1 ~R 21 , R 24 ~R 26 Examples of the "halogen atom" represented by the formula (I) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0045] In the general formulas (2) to (5), R 1 ~R 26Examples of the "amino group having 0 to 20 carbon atoms which may have a substituent" represented by the formula (I) include monosubstituted amino groups such as -NH2, ethylamino, acetylamino, and phenylamino, and disubstituted amino groups such as diethylamino, diphenylamino, and acetylphenylamino. Furthermore, these amino groups are further bonded with a substituent, such as trialkylamino (trialkylammonio) groups such as trimethylamino (or trimethylammonio), triethylamino (or triethylammonio), and triphenylamino (or trimethylammonio), which may have a substituent, and these quaternary ammonium groups are also included in the "amino group having 0 to 20 carbon atoms which may have a substituent," and these substituents may be the same or different from each other.

[0046] In the general formulas (2) to (5), R 1 ~R 26 Specific examples of the "straight-chain or branched alkenyl group having 2 to 20 carbon atoms" in the "straight-chain or branched alkenyl group having 2 to 20 carbon atoms which may have a substituent" represented by the formula (1) include a vinyl group, an allyl group, an isopropenyl group, a 2-butenyl group, a 1-hexenyl group, and a straight-chain or branched group in which a plurality of these alkenyl groups are bonded.

[0047] In the general formulas (2), (3) and (5), R 1 ~R 21 , R 24 ~R 26Specific examples of the "straight-chain or branched alkyl group having 1 to 20 carbon atoms" in the "straight-chain or branched alkyl group having 1 to 20 carbon atoms, which may have a substituent," represented by the formula (1), include straight-chain alkyl groups such as methyl, ethyl, n-propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl; and branched alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-butyl, isooctyl, and tert-octyl. These "straight-chain or branched alkyl groups having 1 to 20 carbon atoms" may form a ring and contain a cycloalkyl group having 3 to 20 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, or cyclododecyl.

[0048] In the general formulas (2), (3) and (5), R 1 ~R 21 , R 24 ~R 26 Specific examples of the "straight-chain or branched alkoxy group having 1 to 20 carbon atoms" in the "straight-chain or branched alkoxy group having 1 to 20 carbon atoms, which may have a substituent," represented by the formula (1), include straight-chain alkoxy groups such as methoxy, ethoxy, propoxy, n-butoxy, n-pentyloxy, n-hexyloxy, heptyloxy, octyloxy, nonyloxy, and decyloxy; and branched alkoxy groups such as isopropoxy, isobutoxy, sec-butoxy, tert-butoxy, isooctyloxy, and tert-octyloxy. These "straight-chain or branched alkoxy groups having 1 to 20 carbon atoms" may form a ring and contain a cycloalkoxy group having 3 to 20 carbon atoms, such as a cyclopropoxy group, cyclobutoxy group, cyclopentyloxy group, or cyclohexyloxy group.

[0049] In the general formulas (2), (3) and (5), R 1 ~R 21 , R 24 ~R 26Specific examples of the "acyl group having 1 to 20 carbon atoms" in the "acyl group having 1 to 20 carbon atoms which may have a substituent" represented by the formula (1) include a formyl group, a carbonyl group, an acetyl group, a propionyl group, an acrylyl group, and a benzoyl group.

[0050] In the general formulas (2) to (5), R 1 ~R 26 Specific examples of the "aromatic hydrocarbon group having 6 to 30 carbon atoms" in the "aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent" represented by the formula (1) include a phenyl group, a biphenylyl group, a terphenylyl group, a tetrakisphenyl group, a styryl group, a naphthyl group, an anthracenyl group, an acenaphthenyl group, a phenanthryl group, a fluorenyl group, an indenyl group, a pyrenyl group, a triphenylenyl group, etc. Here, the "aromatic hydrocarbon group" of the present invention represents an aromatic hydrocarbon group and a condensed polycyclic aromatic group.

[0051] In the general formulas (2) to (5), R 1 ~R 26 Specific examples of the "heterocyclic group having 2 to 30 carbon atoms" in the "heterocyclic group having 2 to 30 carbon atoms which may have a substituent" represented by the formula (I) include a triazinyl group, a pyridyl group, a pyrimidinyl group, an imidazolyl group, a furyl group, a pyrrolyl group, a thienyl group, a quinolyl group, an isoquinolyl group, a benzofuryl group, a benzothienyl group, an indolyl group, a carbazolyl group, a carbolinyl group, a pyridoindolyl group, an oxazolyl group, a benzoxazolyl group, a thiazolyl group, a benzothiazolyl group, a quinoxalyl group, a benzimidazolyl group, a pyrazolyl group, a dibenzofuryl group, a dibenzothienyl group, a naphthyridinyl group, a phenanthrolinyl group, an acridinyl group, and a hydantoin group.

[0052] In general formulas (2) to (5), R 1 ~R 26"A substituted amino group having 0 to 20 carbon atoms," "A substituted linear or branched alkenyl group having 2 to 20 carbon atoms," "A substituted linear or branched alkyl group having 1 to 20 carbon atoms," "A substituted linear or branched alkoxy group having 1 to 20 carbon atoms," "A substituted acyl group having 1 to 20 carbon atoms," "A substituted aromatic hydrocarbon group having 6 to 30 carbon atoms," "A substituted heterocyclic group having 2 to 30 carbon atoms," or "A substituted Specific examples of the "substituent" in the "amino group or methylene group having 0 to 30 carbon atoms" include a nitro group (-NO2), a nitroso group (-NO), a cyano group (-CN), a hydroxyl group (-OH); a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom; an unsubstituted amino group; a linear or branched alkyl group having 1 to 20 carbon atoms, such as a methylamino group, a dimethylamino group, a diethylamino group, an ethylmethylamino group, a methylpropylamino group, a di-tert-butylamino group, or a diphenylamino group; is a mono- or di-substituted amino group having an aromatic hydrocarbon group having 6 to 30 carbon atoms; a sulfonamide group (—S(═O)2—NRR′) (wherein “—NRR′” is an unsubstituted amino group; a linear or branched alkyl group having 1 to 20 carbon atoms, such as a methylamino group, a dimethylamino group, a diethylamino group, an ethylmethylamino group, a methylpropylamino group, a di-tert-butylamino group, or a diphenylamino group, or a mono- or di-substituted amino group having an aromatic hydrocarbon group having 6 to 30 carbon atoms); a methyl group, linear or branched alkyl groups having 1 to 20 carbon atoms, such as ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, n-hexyl, isohexyl, heptyl, n-octyl, tert-octyl, isooctyl, nonyl, and decyl; cycloalkyl groups having 3 to 20 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, and cyclododecyl;A linear or branched alkoxy group having 1 to 20 carbon atoms, such as a methoxy group, an ethoxy group, a propoxy group, a tert-butoxy group, an n-pentyloxy group, or an n-hexyloxy group; a cycloalkoxy group having 3 to 20 carbon atoms, such as a cyclopropoxy group, a cyclobutoxy group, a cyclopentyloxy group, or a cyclohexyloxy group; a vinyl group, a 1-propenyl group, an allyl group, a 1-butenyl group, a 2-butenyl group, a 1-pentenyl group, a 1-hexenyl group, an isopropenyl group, or an isobutenyl group; is a linear or branched alkenyl group having 2 to 20 carbon atoms in which multiple alkenyl groups are bonded; an acyl group having 1 to 20 carbon atoms, such as a formyl group, an acetyl group, a propionyl group, an acrylyl group, or a benzoyl group; an aromatic hydrocarbon group having 6 to 30 carbon atoms, such as a phenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a triphenylenyl group, an indenyl group, a fluorenyl group, or a styryl group; a pyridyl group, a pyrimidinyl group, a triazinyl group, a pyrrolyl group, or an imidazolyl group. group, pyrazolyl group, triazolyl group, pyrazinyl group, pyridazinyl group, piperidinyl group, piperazinyl group, quinolyl group, isoquinolyl group, naphthyridinyl group, indolyl group, benzimidazolyl group, carbazonyl group, carbolinyl group, pyridoindolyl group, acridinyl group, phenanthrolinyl group, phenanthridinyl group, hydantoin group, furyl group, benzofuryl group, dibenzofuryl group, pyranyl group, coumarinyl group, isobenzofuryl group, xanthenyl group, oxanthrenyl group, pyrano heterocyclic groups having 2 to 30 carbon atoms, such as a cyclopentenyl group, a cyclobutenyl group, a cyclopentenyl group, a cyclohexenyl group, a cycloheptenyl group, a (1,3- or 1,4-)cyclohexadienyl group, and a 1,5-cyclooctadienyl group;and the like. Only one or more of these "substituents" may be contained, and when more than one is contained, they may be the same or different. Furthermore, these "substituents" may have the substituents exemplified above. Note that when these "substituents" contain carbon atoms, the carbon atoms are counted as "0 to 20 carbon atoms," "2 to 20 carbon atoms," "1 to 20 carbon atoms," "6 to 30 carbon atoms," and "2 to 30 carbon atoms" in the general formulae (2) to (5). Furthermore, these substituents may be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom, or a sulfur atom to form a ring.

[0053] In general formula (2), R 1 ~R 13 As the alkyl group, —H, a halogen atom, an amino group having 0 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, or a linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent is preferred.

[0054] In general formula (2), R 1 ~R 13 Adjacent groups may be bonded to each other to form a ring, and when a ring is formed, R 3 and R 4 , R 7 and R 8 , R 9 ~R 13 are preferably bonded to each other to form a ring, and the ring is preferably a 5-membered or 6-membered ring.

[0055] In general formula (3), R 14 ~R 21 As the group, —H, an amino group having 0 to 20 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent is preferred.

[0056] In general formula (3), R 14 ~R 21 Adjacent groups may be bonded to each other to form a ring, and when a ring is formed, R14 ~R 17 , or R 18 ~R 21 are preferably bonded to each other to form a ring, and the ring is preferably a 5-membered or 6-membered ring.

[0057] In general formula (4), R 22 or R 23 As the group, an aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent, or a heterocyclic group having 2 to 30 carbon atoms which may have a substituent is preferred.

[0058] In general formula (5), R 24 ~R 26 As the group, a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent, or a heterocyclic group having 2 to 30 carbon atoms which may have a substituent is preferred.

[0059] In general formula (5), R 25 and R 26 may be bonded to each other to form a ring, and when they form a ring, it is preferably a 5-membered or 6-membered ring.

[0060] Specific examples of compounds represented by general formula (1) that are preferred as hair dyes of the present invention are shown below. In general formula (1), the structural formula when a is 0 and b is 1 is shown as an example. The present invention is not limited to these compounds. In the structural formulas below, some hydrogen atoms are omitted, and even if stereoisomers exist, the planar structural formulas are shown.

[0061] [ka]

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[0075] [ka]

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[0078] Although the specific compounds are shown above as examples of hair-dyeing dyes of the present invention, when these dyes are actually used as hair-dyeing dye compositions, it is preferable to select dyes that are non-toxic and non-allergenic as much as possible and use dyes that are highly safe.

[0079] The hair dye represented by general formula (1) can be produced (synthesized) using commercially available dyes (or coloring matters such as pigments) as starting materials. Alternatively, the compound represented by general formula (1) may be produced using a newly synthesized coloring matter compound as starting material. An example of a method for producing the hair dye of the present invention is described below. The dye used as the starting material is not particularly limited, but is preferably a basic dye in which the color-forming portion is cationic and the non-color-forming portion is anionic. Examples of starting materials include dyes represented by a structure in which the anionic portion of the specific examples of hair dyes listed above is replaced with an anion other than chloride ion. However, the dye may contain chloride ions at a certain ratio in the raw material.

[0080] The method for producing a hair-dyeing dye of the present invention is a method for producing a hair-dyeing dye represented by the following general formula (6): Alternatively, a dye represented by the same formula (6) may be used as a starting material in the method for producing a hair-dyeing dye of the present invention.

[0081] [ka]

[0082] For example, in the general formula (6), D represents the cationic moiety of the target hair-dyeing dye of the present invention, An represents a polyatomic anion, and Cl - a and b can each independently be represented by a value in the range of 0 to 1. There are no limitations on the magnitude of a and b.

[0083] In the production method of the present invention, the basic dye (cationic dye) represented by general formula (6) may be, for example, an arylmethane dye, a triarylmethane dye, a xanthene dye, a phenothiazine dye, a phenazine dye, a phenoxazine dye, an azo dye, an azomethine dye, or an HC dye, and D corresponding to the cation moiety may be a dye represented by any of the general formulae (2) to (5). Here, the triarylmethane dye represented by general formula (2) will be described as a specific example.

[0084] When the hair-coloring dye of the present invention is a triarylmethane dye, R 1 , R 2 , R 5 , R 6 is —H or a methyl group, and R 3 , R 4 , R 7 , R 8 is —H, a methyl group, or an ethyl group, and R 9 ~R 13 is preferably —H, —Cl, an amino group of 0 to 10 carbon atoms which may have a substituent, an alkenyl group of 2 to 10 carbon atoms which may have a substituent, an alkyl group of 1 to 10 carbon atoms which may have a substituent, or an acyl group of 1 to 10 carbon atoms which may have a substituent.

[0085] In the general formula (6), D is R 1 , R 2 , R 5 , R6 is a methyl group, and R 3 , R 4 , R 7 , R 8 , R 10 ~R 12 is -H and R 9 and R 13 is a cation moiety represented by the general formula (2) in which a is —Cl, a is 1, b is 0, and An is H2PO4 - In this case, general formula (6) becomes a hair-dyeing dye (HC dye, HC BLUE 15) represented by the following formula (2-1X) (molecular weight: 495.34).

[0086] [ka]

[0087] The method for producing a hair-dyeing dye of the present invention is a production method characterized by carrying out the following steps 1 and 2. An example will be described in which a basic dye represented by the formula (2-1X) above, which contains a polyatomic anion as the main anion other than chloride ions in the dye, is used as a starting material in the method for producing a hair-dyeing dye of the present invention.

[0088] Step 1: Purifying a hair dye containing polyatomic anions (An) using water and activated carbon.

[0089] Step 2: Dissolving the hair dye obtained in step 1 in water and salt, and then performing salt exchange.

[0090] In step 1, "purifying using water and activated carbon" specifically includes the following steps: First, the prepared starting dye is dissolved in water at an appropriate concentration, temperature, and stirring conditions. Next, the solution is mixed with appropriate activated carbon, and purification is carried out at an appropriate temperature and stirring conditions. After that, the purified sample can be obtained through washing, filtration, etc.

[0091] Next, in step 2, the step of "dissolving the hair-dyeing dye obtained in step 1 in water and salt, followed by salt exchange" specifically includes the following steps: First, the sample purified in step 1 is mixed with water and salt (NaCl), and treated at an appropriate salt concentration, at an appropriate temperature, under appropriate stirring conditions, etc., to obtain the desired hair-dyeing dye by salting out. This operation allows the hair-dyeing dye represented by general formula (6) to be obtained, in which some, most, or all of the polyatomic anions contained in the dye have been exchanged with chloride ions (salt exchange) before steps 1 and 2. Filtration, washing, drying, etc. can be performed as appropriate during, before, or after step 2. By carrying out steps 1 and 2 as described above, it is possible to obtain a hair-dyeing dye represented by the general formula (6) in which the ratio of polyatomic anions (An) or impurities derived from An is 1 mass % or less.

[0092] Step 1 or step 2 of the production method is described in detail below. The "water" used is not particularly limited and may be ordinary water, such as tap water, deionized water, distilled water, or industrial water. It is preferable that the concentration of components other than cations and anions contained in the target dye be as low as possible, provided that this does not interfere with the advantageous effects of the present invention. The water used in the present invention may be what is known as public city water, such as tap water.

[0093] In the step 1, the mixing ratio of the hair dye and water is not particularly limited as long as the concentration is such that the dye can be sufficiently dissolved. Specifically, the mass of water used may be 5 to 1000 times, and more preferably 10 to 100 times, the mass of the dye.

[0094] The vessels used in steps 1 and 2 are not particularly limited as long as they are used for ordinary synthesis, purification, mixing, and stirring. The vessel material can be selected appropriately, for example, a glass vessel such as a Kolben, a metal vessel, a resin vessel, or a glass-lined vessel. Containers made of a material that is durable enough to withstand the use of water and salt (NaCl) are preferred. Commercially available stirring equipment can be used, and the shape of the stirring blades and the type of stirrer are not particularly limited.

[0095] In the stirring of the dye and water in step 1, the temperature is preferably room temperature (around 20 to 25°C) to 100°C, more preferably 40 to 80°C. The stirring time required for dissolution is not limited as long as sufficient dissolution is achieved, but is preferably 30 minutes to 12 hours, more preferably 30 minutes to 3 hours. Note that the temperature and stirring time suitable for stirring depend on the type of dye and the mass of the dye to be dissolved, so it is preferable to dissolve at an appropriately appropriate temperature and stirring time.

[0096] In the production method of the present invention, purification can be performed by known methods such as purification by column chromatography; adsorption purification using silica gel, activated carbon, activated clay, etc.; and recrystallization or crystallization using a solvent, but it is preferable to use activated carbon, as shown in the above-mentioned step 1. Furthermore, the above-mentioned purification method may be performed before or after the use of activated carbon, or activated carbon alone may be used. It is preferable to use activated carbon alone in the purification in the present invention.

[0097] The activated carbon used in step 1 is not particularly limited and may be any of various commercially available products used for water purification, decolorization, and purification of pharmaceutical compounds. The activated carbon particles may be in the form of powder, granules, rods, fibers, etc., with powder being preferred. The pore diameter on the surface of the activated carbon may be 2 to 3 nm. The properties of the activated carbon can be appropriately selected depending on the types of cations and anions contained in the raw material.

[0098] In step 1, activated carbon is preferably added to a solution in which the dye has been sufficiently dissolved, and then mixed and stirred. The amount of activated carbon used is preferably not excessively large relative to the mass of the raw dye, and is more preferably 1 to 100 mass% of the mass of the dye, and even more preferably 5 to 30 mass%. Conditions for mixing with activated carbon in the solution, such as temperature and stirring time, may be similar to those used when the dye was initially dissolved.

[0099] In step 1, after treatment with activated carbon, filtration and washing of the activated carbon are carried out using water. During filtration and washing, the obtained aqueous solution of the dye may be at room temperature or heated, but it is preferable to heat it within a certain temperature range. The aqueous solution of the dye purified in step 1 is then transferred to step 2.

[0100] In the step 2, the aqueous solution of the hair-dyeing dye obtained in the step 1 is provided. While stirring the aqueous solution containing the hair dye at a temperature between 20 and 80°C, salt (NaCl) is added to the solution and stirred. The temperature during stirring may be any suitable temperature between 20 and 80°C, preferably between 30 and 70°C, and more preferably between 40 and 65°C. The salt to be added is not particularly limited, but salt with few impurities is preferred, and it may be either edible or industrial grade. The form of the granules is not limited, and may be powder, pulverized, or granulated. The water content may be of any quality typically used for commercial, industrial, or edible purposes. The salt concentration may be 1.5 to 25% by mass, preferably 5 to 20% by mass, relative to the solvent (water). Alternatively, water may be added to the solution.

[0101] In step 2, the liquid obtained by dissolving salt in an aqueous solution containing a hair dye is heated at an appropriate temperature for a certain period of time. This heating time can be selected appropriately between 1 hour and 24 hours. After heating, the liquid can be cooled to room temperature at an appropriate temperature drop rate. During this cooling to room temperature, stirring is preferably carried out for a sufficiently long period of time, about 5 to 24 hours. During the process of adding salt and cooling after stirring, some or all of the anions in the dye in the state before step 1 are converted to chloride ions (Cl - ) occurs (salt exchange), and the hair dye represented by the general formula (1) can be obtained as a precipitated solid as a component that is not dissolved in the aqueous solution.

[0102] The hair dye of the present invention obtained by dissolving the dye in water and salt and then salt exchange as in step 2 above can be filtered and washed with an aqueous salt-containing solution (brine) to form a solid precipitated by salt exchange. The salt concentration in the brine is preferably 1.5 to 20% by mass. The temperature during filtration can be appropriately selected between room temperature and 40°C. After filtration, a composition (solid, powder, cake, etc.) containing the hair dye of the present invention and water is obtained with a certain moisture content. This composition may be dehydrated using a suction filter or the like.

[0103] The composition containing the hair dye of the present invention and water obtained in step 2 can be dried using an appropriate dryer to adjust or remove the moisture (or moisture content) in the composition containing the hair dye. Drying to obtain the hair dye composition of the present invention may be carried out by transferring the composition to a container with a large base area, such as a dish or a tray, and drying. Alternatively, drying may be carried out using a hot air dryer or vacuum dryer. The drying time may be an appropriate time to obtain the desired moisture content, and may be selected from one hour to three days. The moisture content of the composition containing the hair dye is preferably 10% by mass, more preferably 8% by mass or less. It may be dried almost completely to 1% by mass or less, or a certain amount of moisture may be left. The drying temperature is preferably in the range of 20°C to 100°C, more preferably 30°C to 80°C.

[0104] The hair dye of the present invention is obtained by a method including the above-mentioned steps 1 and 2, and a known improved step may be added before or after each step.

[0105] The hair dye of the present invention represented by general formula (1) can be analyzed by ultraviolet-visible absorption spectroscopy (UV-Vis) or absorbance analysis, thermogravimetry-differential thermal analysis (TG-DTA), high-performance liquid chromatography (HPLC), gas chromatography (GC), nuclear magnetic resonance (NMR), and other techniques for compound identification and property evaluation. Absorbance analysis and HPLC measurements allow comparison based on differences in molecular structure and color, making it possible to determine the purity of the target hair dye in a sample and the concentration of impurities in the sample. For example, the purity of the main component or the concentration ratio of impurities can be determined by calculating the ratio (area ratio) of the main component to the impurities from the peak areas of the peaks measured at each retention time obtained by HPLC measurement at a specific measurement wavelength.

[0106] The hair dye of the present invention obtained by general formula (1) is obtained through the above-described process. Because it is purified, the concentration of water-insoluble components in the hair dye, i.e., the insoluble matter, can be kept at 1% by mass or less, more preferably 0.5% by mass or less, and even more preferably 0.1% by mass or less. A feature of the method for producing a hair dye of the present invention is that the concentration of anions contained therein can be reduced before the purification and salt exchange steps, thereby preventing alteration or deterioration of the quality of the hair dye due to the anions contained therein before the steps.

[0107] The hair dye obtained by formula (1) of the present invention is prevented from deteriorating or degrading in quality because the main component of the anion after the process is chloride ion, which prevents the anion itself from decomposing. This means that the possibility of decomposition due to decomposition of polyatomic ions contained in the dye before the process, decomposition due to reaction between the polyatomic ions and the dye (color-forming moiety), and decomposition due to reaction with water molecules or components in the hair dye composition can be reduced. In particular, when the polyatomic ions are hydrogen-containing anions, hydrogen ions separated from the ions may affect the decomposition of the dye molecules and other components. The above-mentioned decomposition and component decomposition reactions not only proceed at around room temperature, but are also thought to be accelerated at temperatures higher than room temperature, particularly at temperatures above 35°C, which is the temperature at which the hair dye composition is used.

[0108] The storage period of the hair-dyeing dye of the present invention or the degree of deterioration of the hair-dyeing dye can be measured by HPLC measurement, absorbance analysis, or the like. Specifically, the purity of the hair-dyeing dye at the start of the evaluation, which serves as a reference, is preferably 99% or more. Furthermore, it is preferable that the purity be maintained at 99% or more for a certain period of time or longer due to changes over time. The temperature for measuring the changes over time is room temperature or above room temperature, preferably 40°C or above, and more preferably 40 to 60°C. The period for maintaining purity at room temperature is preferably 6 months or longer. The storage period is preferably 6 months or longer at room temperature (20 to 25°C) or 7 days or longer at 40 to 60°C.

[0109] The color properties of the hair dye of the present invention (color value, hue, etc.) can be evaluated in the form of powder (solid), solution, dispersion, or thin film by measuring the absorbance, for example, the visible light absorption spectrum or reflectance spectrum at 400 to 700 nm, the chromaticity coordinates (x, y) according to the xy chromaticity diagram of the CIE 1931 color system using a spectrophotometer or a color difference meter, the density (K / Sd), and the color (L) according to the CIE 1976 color system. * , a * , b * ), color difference (ΔE *) can be measured and evaluated. Even solutions, powders, and thin films of compounds with the same molecular structure may have clearly different colors when visually inspected, and such color differences can be objectively quantified using a spectrophotometer or color difference meter. Standard color samples or color swatches may also be used for visual inspection. Furthermore, fibers such as gray hair samples may actually be dyed and their color evaluated.

[0110] The hair dye of the present invention undergoes purification and salt exchange before and after the above-mentioned steps, and therefore the dye molecule structure resulting from the color-forming portion is not lost, and the color characteristics are not impaired. The absorbance before purification is preferably 0.5 or more.

[0111] By using the above-described method for producing a hair-dyeing dye and the method for evaluating the hair-dyeing dye, it is possible to obtain a hair-dyeing dye according to the present invention, which has a long shelf life and excellent heat resistance.

[0112] The hair-coloring dye of the present invention, the compound represented by general formula (1), or a hair-coloring composition containing the hair-coloring dye is preferably used in the form of a so-called hair colorant. The hair-coloring dye represented by general formula (1) can be used by mixing it with other dyes, additives, auxiliaries, and other components. An embodiment suitable for the hair-coloring dye of the present invention is a hair-coloring composition, which contains a hair-coloring dye containing a compound represented by general formula (1), at least one auxiliary selected from the group consisting of a humectant, a swelling agent, a penetrating agent, a solvent, a pH adjuster, a surfactant, a fragrance, and a thickener, and water.

[0113] Examples of humectants include glycerin, propylene glycol, sorbitols, 1,3-butylene glycol, polyethylene glycols, etc. When a humectant is used, the content thereof is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, based on the total amount of the hair dye composition.

[0114] The swelling agent may be an aqueous alkaline solution containing ammonia (ammonium hydroxide) or monoethanolamine (MEA). When a swelling agent is used, its content is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, based on the total amount of the hair dye composition.

[0115] Examples of penetrants and solvents include monohydric alcohols having an alkyl group with 1 to 6 carbon atoms, such as ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, and butoxyethanol; polyhydric alcohols having 3 to 8 carbon atoms, such as propanediol, butanediol, pentanediol, hexanediol, hexanetriol, heptanediol, heptanetriol, octanediol, octanetriol, isoprene glycol, propylene glycol, glycerin, and diethylene glycol monoethyl ether, or ethers thereof; and N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone. Examples of suitable penetrating agents include N-alkylpyrrolidones that are liquid at room temperature (around 25°C), such as N-propyl-2-pyrrolidone, N-butyl-2-pyrrolidone, and N-cyclohexyl-2-pyrrolidone; alkylene carbonates (lower alkylene carbonates) such as ethylene carbonate and propylene carbonate; and aromatic alcohols such as benzyloxyethoxyethanol, benzyl alcohol, benzyloxyethanol, cinnamyl alcohol, p-anisyl alcohol, p-methylbenzyl alcohol, phenoxyethanol, phenoxyisopropanol, 2-benzylethanol, and β-phenylethyl alcohol. Among these, aromatic alcohols or N-alkylpyrrolidones are preferred, with benzyl alcohol, benzyloxyethoxyethanol, and benzyloxyethanol being more preferred. When a penetrating agent or solvent is used, its content is preferably 2 to 40% by mass, more preferably 5 to 20% by mass, based on the total amount of the hair dye composition.

[0116] Examples of pH adjusters include acids such as phosphoric acid, lactic acid-sodium lactate, and citric acid-sodium citrate, and bases such as aqueous ammonia, sodium hydroxide, potassium hydroxide, and sodium carbonate. When a pH adjuster is used, its content is preferably 0.1 to 10% by mass, and more preferably 0.5 to 5% by mass, based on the total amount of the hair dye composition.

[0117] As the surfactant, cationic surfactants or nonionic surfactants are mainly used. Specific examples include, but are not limited to, silicone compounds such as polysiloxane, polyoxyethylene alkyl ethers, polyoxyethylene fatty acid esters, polyglycerin fatty acid esters, aliphatic amines and their quaternary ammonium salts (e.g., trimethylstearyl ammonium chloride), sugar alcohol ethers such as sorbitol alkyl ethers, and polyoxyethylene sorbitan fatty acid esters. Among these, polyoxyethylene sorbitan fatty acid esters are preferred. The use of polyoxyethylene sorbitan fatty acid esters further improves the effect of reducing skin contamination (skin contamination prevention performance).

[0118] The polyoxyethylene sorbitan fatty acid ester is preferably at least one selected from the group consisting of polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, and polyoxyethylene sorbitan monooleate.

[0119] When a surfactant is used, its content is preferably from 0.1 to 20% by mass, more preferably from 0.5 to 10% by mass, based on the total amount of the hair dye composition, from the viewpoint of reducing contamination of the skin.

[0120] Examples of fragrances include vanillin, cinnamic alcohol, heliotropin, coumarin, 2-methyl-3-(3,4-methylenedioxyphenyl)propanal, 4-(4-hydroxyphenyl)-2-butanone, benzaldehyde, anise alcohol, 3,4-dimethoxybenzaldehyde, heliotropyl acetate, phenylacetaldehyde dimethyl acetal, phenoxyethyl alcohol, phenylacetaldehyde glyceryl acetal, furaneol, sugar lactone, maltol, ethyl maltol, ethyl diglycol, benzyl acetate, linalool, camphor, terpineol, citronellol, geraniol, 2,6-nonadienal, methyl octyl carbonate, 3,7-dimethyl-2,6-octadienal, nonanal, etc. When a fragrance is used, its content is preferably 0.00001 to 2% by mass based on the total amount of the hair dye composition.

[0121] Examples of thickeners include guar gum and its derivatives, hydroxyethyl cellulose, xanthan gum, collagen, gelatin, carboxymethylcellulose sodium salt, Carbopol (registered trademark), sodium alginate, gum arabic, cellulose derivatives, and thickeners derived from poly(ethylene oxide). These thickeners have the effect of increasing the viscosity of the hair dye composition and turning it into a gel-like form that is easy to handle. When a thickener is used, its content is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, based on the total amount of the hair dye composition.

[0122] The water used in the hair dye composition of the present invention is not particularly limited, but ion-exchanged water, purified water, clean water, tap water, etc. can be used.

[0123] The hair-coloring dye of the present invention represented by general formula (1) is excellent in dyeing power and fastness as a hair-coloring dye by itself, and can dye hair uniformly. Furthermore, by combining a hair-coloring dye containing the compound represented by general formula (1) with a hair dye of other colors, it is possible to obtain various colors (purple, green, brown, black).

[0124] Examples of basic dyes to be combined include direct dyes having an amino group or a substituted amino group in the molecule, such as Red No. 213 (CI Basic Violet 10, Rhodamine B), Red No. 214 (CI Basic Violet, Rhodamine B acetate); Basic Blue (CI Basic Blue) 7, 9, 26, 75, or 99; Basic Red (CI Basic Red) 2, 22, 51, or 76; Basic Yellow (CI Basic Yellow) 57 or 87; Basic Orange (CI Basic Orange) 31; Basic Brown (CI Basic Brown) 16 or 17; and Basic Violet (CI Basic Violet) 2, 3, 4, or 14.

[0125] Examples of HC dyes to be combined include direct dyes having a nitro group in the molecule, such as CIHC Blue 2 or 15; CIHC Red 1, 3, 7, 11, or 13; CIHC Yellow 2, 4, 5, 9, 11, or 13, CIHC Orange 1 or 2; CIHC Violet 1 or 2; and 4-hydroxypropylamino-3-nitrophenol.

[0126] In an embodiment of the hair dye composition of the present invention, the hair dye represented by general formula (1) is preferably present in an amount of 0.001 to 5% by mass based on the total amount of the hair dye composition, with the remainder containing at least one auxiliary selected from the group consisting of a humectant, a swelling agent, a penetrating agent, a solvent, a pH adjuster, a surfactant, a fragrance, and a thickener, and water. If the content of the hair dye is less than 0.001% by mass, it is difficult to achieve the effects of color tone maintenance and dye leveling, and even if the content exceeds 5% by mass, the improvement in effects such as dyeing is small. The content of the hair dye is preferably 0.01 to 5% by mass, and more preferably 0.05 to 2% by mass, based on the total amount of the hair dye composition.

[0127] The pH value of the hair dye composition of the present invention is preferably 4 to 9, more preferably 5 to 7. The pH value of the hair dye composition can be adjusted by known methods, but is preferably adjusted using a pH adjuster such as citric acid monohydrate or trisodium citrate dihydrate. That is, for example, when preparing a hair dye composition with a pH of 6, citric acid monohydrate and trisodium citrate dihydrate are dissolved in water to prepare an aqueous solution with a pH of 6 in advance, and then a hair dye containing a compound represented by general formula (1) and, if necessary, other additives (auxiliaries, etc.) are added to the aqueous solution to obtain a hair dye composition with a pH of 6.

[0128] The hair dye composition of the present invention may contain known cosmetic ingredients, such as higher alcohols, petrolatum, polyhydric alcohols, esters, preservatives, disinfectants, silicone derivatives, and water-soluble polymers, as long as the effects of the present invention are not impaired.

[0129] Specifically, the hair dyeing method using the hair dye composition of the present invention involves bringing the hair dye composition into contact with the object to be dyed, such as human hair or livestock hair. The dyeing temperature is preferably 5 to 60°C, and more preferably 15 to 45°C, considering that the dyeing is performed near the scalp. The dyeing time is preferably 5 to 60 minutes, more preferably 10 to 30 minutes.

[0130] After dyeing, post-treatments such as rinsing and drying are usually performed. Rinsing should be continued until the color of the hair dye is completely dissolved, for example, by rinsing for 0.5 to 2 minutes with running water at 5 to 40°C and 5 to 15 L / min. Drying after rinsing can be done naturally (usually at 5 to 40°C for 10 minutes to 10 hours), or, if necessary, using a hot air dryer (usually at 40 to 60°C for 10 minutes to 10 hours).

[0131] After rinsing with water, soaping may be performed by, for example, washing with an appropriate amount of soaping liquid (a mixture of shampoo and lukewarm water) at a temperature of 15 to 50°C for 1 to 10 minutes, followed by rinsing with water until the soaping liquid is completely removed.

[0132] The test sample obtained may be evaluated using a spectrophotometer. d ) may be evaluated by the following procedure. Specifically, the reflectance (R ) at each wavelength (λ) of the test specimen before dyeing (white hair) and after dyeing (dyed hair) is λ ) may be measured with a spectrophotometer and the optical density (K / S) may be calculated using the Kubelka-Munk equation below. d ) is calculated by subtracting the optical density of gray hair (K / S) from the optical density of dyed hair (K / S). Kubelka-Munk formula: K / S=Σ(1-R λ ) 2 / 2R λ R λ : Reflectance at wavelength (λ) λ: 400~700nm (10nm interval)

[0133] In addition, the color of the test sample obtained after dyeing was measured using the CIE L * a * b * Using the color system, color (L * , a * , b * ) can be measured and evaluated. * is the brightness, and the larger it is, the less intense the coloring is. * and b * is the chromaticity that indicates the hue and saturation. * corresponds to the red / green axis, with positive being red and negative being green. * corresponds to the axis of the yellow / blue pair, with positive being yellow and negative being blue. The difference in color between different samples is the difference ΔL * , Δa * and Δb * From the value of , the color difference ΔE is calculated using the following formula: * and hue difference ΔH * can be calculated. ΔE * ={(ΔL * ) 2 +(Δa * ) 2 +(Δb* ) 2} 1 / 2 ΔH * ={(Δa * ) 2 +(Δb * ) 2} 1 / 2 The ΔE value was measured before and after various tests on the test specimen, specifically, long-term storage tests, heat resistance tests by heating, sweat resistance tests by acidic or basic sweat components, etc. * or ΔH * By measuring ΔE , it is possible to evaluate the degree of change in the dyeing state (presence or absence of fading, maintenance of vivid color, etc.). For the hair dye of the present invention, the ΔE * or ΔH * A smaller value is preferable.

[0134] In the above-described manner, a hair dye composition having a long shelf life and excellent heat resistance can be prepared using the hair dye of the present invention. Furthermore, the hair dye composition of the present invention can exhibit excellent dyeing effects for hair color, hair manicure, and hair color treatment. [Example]

[0135] Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to the following examples.

[0136] [Example 1] <Preparation of hair dye "AHC BLUE 77" through purification and salt exchange> A 10-liter stainless steel vessel was charged with 200 g of a commercially available blue dye (manufactured by CHROMEX, product name: HC BLUE 15) and 5.2 L of water, heated to 70°C, and stirred for 1 hour to dissolve. Next, 40 g of activated carbon (manufactured by Osaka Gas Chemicals Co., Ltd., product name: Carboraffin, model: wet type) was added to this solution, and the mixture was stirred at 65°C for 2 hours. After stirring, the mixture was filtered while hot, and the filter cake was washed with 400 mL of water. The resulting filtrate was heated to 55°C, 275 g of salt was added, stirred for 1 hour, and slowly cooled to room temperature (25°C) while stirring overnight. After stirring, the precipitate was filtered, and the resulting solid was washed with 200 mL of 2% by weight brine. The solid was dried for 3 days in a hot air dryer at 40°C (Tokyo Rikakikai Co., Ltd., constant temperature blower dryer (windy oven) WFO-601SD) to obtain a blue solid (powder) of "AHC BLUE 77" (140 g, yield 80.2%).

[0137] <Storage stability test of "AHC BLUE 77"> The obtained solid (AHC BLUE 77) was subjected to high performance liquid chromatography (HPLC) measurement under the following measurement conditions. HPLC equipment: LC-20A (Shimadzu Corporation) Eluent: (ammonium acetate / acetonitrile / water = 1.5 / 0.5 / 98) / acetonitrile = 1 / 1 (mass ratio), isocratic Flow rate: 0.8mL / min Measurement wavelength: 254nm Column: L-column ODS (manufactured by Chemicals Evaluation and Research Institute, Japan, column diameter 4.6 mm x length 150 mm, particle diameter 5 μm, pore size 12 nm) Column temperature: 40℃ Preparation of sample solution for measurement: 10 mg of the obtained solid sample was dissolved in 2 mL of a mixed solvent of acetonitrile / water (2 / 3 (volume ratio)) and filtered with a syringe filter. Alternatively, an appropriate amount of the filtrate from the above process was prepared in the same manner using the above mixed solvent of acetonitrile / water (2 / 3 (volume ratio)). Sample injection volume: 1.0 μL The hair dye (AHC BLUE 77) represented by the following formula (2-1) was identified by HPLC measurement, and the HPLC purity was 99.0 to 99.5%. In addition, ion chromatography (ion analyzer, manufactured by DKK-TOA Corporation, IA-300) measurement revealed that the anion was Cl. - It was confirmed that the dye was soluble in water, and no other anions were detected. The target blue dye was measured as a peak with a retention time of 5.1 minutes by HPLC. A reddish impurity with a retention time of 30.6 minutes was also detected as an impurity, but its content was below the limit of quantitation (assumed to be 0.0%). The results are shown in Table 1 as purity (concentration ratio) (%) at the start of the storage stability test.

[0138] [ka]

[0139] (Storage stability test at room temperature (room temperature test)) The resulting solid (powder) sample was placed in a transparent plastic bottle and left at room temperature (approximately 25°C) in a normally lit laboratory for six months. After six months, the purity (concentration ratio) (%) of each component of the dye and reddish impurity was measured for the powder sample using the same HPLC measurement conditions as above. The results of the room temperature test (six months) are summarized in Table 1.

[0140] (Storage stability test under heating conditions (heating test)) As in the storage stability test at room temperature described above, a solid powder sample placed in a plastic bottle was heated at 60°C for 7 days. After 7 days, the purity (concentration ratio) (%) of each component of the dye and reddish impurity was measured for the powder sample using the same HPLC measurement conditions as described above. The results of the heating test (7 days) are summarized in Table 1.

[0141] [Comparative Example 1] The blue dye represented by formula (2-1X) was purified using a purification method different from the production method of the present invention. Specifically, 120 g of a commercially available blue dye (manufactured by CHROMEX, product name: HC BLUE 15) and 3 L of water were placed in a 5 L container and stirred at 70°C for dissolution. Next, 24 g of the same activated carbon (carboraffin) used in Example 1 was added, stirred for 2 hours, and then hot filtered. The filtrate was concentrated under reduced pressure at 50°C, and the paste-like concentrate was dissolved in methanol. The mixture was again concentrated under reduced pressure at 40-45°C, and water was distilled off by azeotropic distillation with methanol / water. Further concentration was performed while adding methanol, and the precipitated solid was filtered and dried to obtain a purified product of HC BLUE 15 (68.6 g, yield 57.2%), a hair dye for comparison.

[0142] The obtained purified product of HC BLUE 15 was subjected to a storage stability test at room temperature (for 6 months) and at 40°C (for 7 days) at the start of the test in the same manner as in Example 1. The results are summarized in Table 1.

[0143] [Table 1]

[0144] As shown in Table 1, in Example 1, the concentration ratio of impurities derived from An was 1% by mass or less. Furthermore, in the room temperature test (6 months) and the heating test (7 days), there was no change in the purity of the dye from the start of the test. Furthermore, the concentration ratio of reddish impurities (0.0%) also remained unchanged from the start of the test. On the other hand, in Comparative Example 1, the purity of the dye decreased in the room temperature test, and the concentration ratio of reddish impurities increased. Furthermore, in the heating test, the purity of the dye also decreased, and the concentration ratio of reddish impurities increased. This demonstrates that the hair dye of the present invention has superior heat resistance (storage stability) to the hair dye of Comparative Example 1.

[0145] [Example 2] <Storage stability test for "Basic Yellow 40 Hydrochloride"> A storage stability test (heating test) was performed on Basic Yellow 40 hydrochloride (a commercially available product from Nissei Chemical Co., Ltd.) using the same method as in Example 1. The hair dye (Basic Yellow 40) represented by the following formula (G-3) was identified using the same HPLC measurement conditions as in Example 1, and the HPLC purity was 99.7%. The target yellow dye was measured as a peak at a retention time of 4.5 minutes in the HPLC analysis. Impurity components were measured as a peak at a retention time of 3.5 minutes. The results are shown in Table 2 as purity (concentration ratio) (%) at the start of the storage stability test.

[0146] [ka]

[0147] (Storage stability test under heating conditions (heating test)) Similar to the heating test of AHC BLUE 77 in Example 1, a solid powder sample of Basic Yellow 40 hydrochloride placed in a plastic bottle was heated at 50°C for 7 days. After 7 days, the powder sample was analyzed for dye and impurity components under the same HPLC measurement conditions as in Example 1. The results of the heating test (7 days) are shown in Table 2.

[0148] Comparative Example 2 HPLC measurement of Basic Yellow 40 methyl sulfate (formula (G-3X) below, manufactured by Nissei Chemical Co., Ltd.) was carried out in the same manner as in Example 2. As in Example 2, the target yellow dye was measured as a peak at a retention time of 4.5 minutes, and impurity components were measured as a peak at a retention time of 3.5 minutes. As in Example 2, a storage stability test was carried out under heating conditions at 50°C for 7 days. The results of the heating test (7 days) are also shown in Table 2.

[0149] [ka]

[0150] [Table 2]

[0151] As can be seen from Table 2, in Example 2, the concentration ratio of impurities derived from An was 1% by mass or less. Furthermore, there was no change in the purity of the dye during the heating test (7 days). There was also no change in the concentration ratio of the impurity components. On the other hand, in Comparative Example 2, the purity decreased and the concentration ratio of the impurity components increased after the heating test. This demonstrates that the hair dye of the present invention has superior heat resistance (storage stability) to the hair dye of the comparative example.

[0152] [Example 3] <Preparation of hair dye test specimens and heat resistance test> 0.04 g of hair dye (formula (2-1)), 18.3 g of a pH 6 aqueous solution (prepared by diluting 1 g of citric acid·H2O and 11 g of citric acid·trisodium·2H2O in a volumetric flask to 1000 mL with water) as a pH adjuster (pH buffer), 0.2 g of trimethylstearylammonium chloride (TMSA) as a surfactant, 1.0 g of ethanol, and 0.5 g of benzyl alcohol as a penetrant were mixed and dissolved. Two strands of 1.0 g of human gray hair (Beaulux Co., Ltd., product name: Gray Hair 100% BM-W) were placed in this solution and dyed at 40°C for 20 minutes, rinsed, and air-dried to obtain the dyed test specimen (hair dye test specimen).

[0153] The color of the obtained hair dye test sample was measured using the CIE L * a * b * Using the color system, a spectrophotometer (Color Techno System Co., Ltd., JS555) was used to measure the color (L * , a * , b * ) was measured. The difference between them, ΔL * , Δa * and Δb * From the value of , the color difference ΔE is calculated using the following formula: * was calculated. ΔE * ={(ΔL * ) 2 +(Δa * ) 2 +(Δb * )2} 1 / 2 Furthermore, the hair dye test specimen was heated for 7 days in a hot air dryer at 50°C (the same dryer as used in Example 1). As a result of the heat resistance test of the hair dye test specimen, the measurement results of the color of the hair dye test specimen before and after heating and the obtained color difference ΔE * The values ​​are shown in Table 3.

[0154] [Example 4] The preparation of hair dye test specimens and the heat resistance test were carried out in the same manner as in Example 3, except that the hair dye (formula (G-3)) was used instead of the hair dye (formula (2-1)) in Example 3. The results are summarized in Table 3.

[0155] Comparative Example 3 A hair dye test sample was prepared and a heat resistance test was carried out in the same manner as in Example 3, except that a hair dye (formula (2-1X)) was used instead of the hair dye (formula (2-1)) in Example 3. The results are summarized in Table 3.

[0156] Comparative Example 4 The preparation of hair dye test specimens and the heat resistance test were carried out in the same manner as in Example 3, except that the hair dye (formula (G-3X)) was used instead of the hair dye (formula (2-1)) in Example 3. The results are summarized in Table 3.

[0157] [Table 3]

[0158] The results in Table 3 show that the color difference before and after the heat resistance test of the hair dye test specimens in Examples 3 and 4 was smaller than that in Comparative Examples 3 and 4, and that hair dyed with the hair dye of the present invention is more effective in suppressing color fading due to heat than hair dyed with the dyes of Comparative Examples 3 and 4. [Industrial Applicability]

[0159] The hair-coloring dye and the method for producing the hair-coloring dye according to the present invention can provide a hair-coloring dye that has a longer shelf life and excellent heat resistance than conventional hair-coloring dyes. Furthermore, a hair-coloring composition containing the hair-coloring dye according to the present invention can provide a hair dye that effectively prevents fading of dyed hair.

Claims

[Claim 1] A method for producing a hair dye represented by the following formula (2-1): A manufacturing method characterized by carrying out the following steps 1 and 2: 【Chemistry 1】 In formula (6), D represents a cation moiety of a hair-coloring dye, An represents a polyatomic anion, a and b each independently represent a value of 0 to 1.] 【Chemistry 2】 Step 1: A starting dye in which the cation moiety in the formula (6) is the cation moiety in the formula (2-1), a=1, and b=0 is dissolved in water and purified by stirring with activated carbon; Step 2: Further dissolve in water and salt (NaCl) for salt exchange.

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