HAIR COLOURING DYE, HAIR COLOURING COMPOSITION CONTAINING THE DYE, AND PROCESS FOR PRODUCING THE DYE

Abstract

[Problem] The present invention aims to provide a hair coloring dye that exhibits a long shelf life and excellent heat resistance, as well as a method for producing the hair coloring dye. [Solution] The present invention therefore relates to a hair coloring dye represented by the following general formula (1), the hair coloring dye having a proportion of a polyatomic anion (An) or impurities derived from An of 1% by mass or less: wherein in formula (1), D represents a cationic fraction of the hair coloring dye; An represents a polyatomic anion; and a and b each independently represent a value from 0 to 1. Figure to be published with the abstract: None

Description

Title of the invention: Hair coloring dye, hair coloring composition containing the dye, and dye production process. 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. Context of the invention

[0002] In recent years, an increasing number of individuals across a wide age range have been enjoying hair coloring and dyeing their hair, whether black or white. A large number of hair coloring agents, such as coloring materials and hair dyes, and a large number of hair colorants, such as hair coloring treatments and conditioning treatments, are marketed. In the hair coloring process, an oxidative hair coloring agent (permanent hair coloring agent), which uses an oxidative dye with high hair coloring power and good color retention, has been predominantly used, but it can damage the hair and cause skin irritation, including allergies.In these circumstances, rather than oxidation dyeing, hair dyes that use a basic dye with a high degree of safety have been proposed (see, for example, PTL 1 to 6).

[0003] An HC dye used in combination with a basic dye has been used as a semi-permanent hair color, and for example, HC Blue 15 is used as a blue HC dye. However, a hair color using HC Blue 15 exhibits a heat resistance problem after dyeing, and presents a problem of discoloration and color alteration during heating during production, as well as discoloration and color alteration during long-term storage and when used with hot water (approximately 40°C). There is a demand for hair coloring dyes including the blue dye that do not present a discoloration problem and that can maintain a clear color. List of quotations - Patent literature

[0004] PTL 1: JP-A-2002-37718 PTL 2: JP-A-2004-285048 PTL3: WO 2018 / 180515 PTL4: WO 2009 / 041514 PTL 5: WO 2013 / 190774 PTL 6: WO 2014 / 203771 Summary of the invention Technical problem

[0005] The present invention aims to provide a hair coloring dye that has a long life and excellent heat resistance, as well as a method for producing the hair coloring dye. Technical solution

[0006] The present invention is the result of the most serious investigations aimed at solving the problem, and consists of the following contents.

[0007] 1. A hair coloring dye represented by the general formula (1) the following, hair coloring dye having a proportion of a polyatomic anion (An) or impurities derived from An of 1% by mass or less:

[0008] [Chem.l] (D)(An) (1)

[0009] wherein in formula (1), D represents a cationic fraction of the hair coloring dye; An represents a polyatomic anion; and a and p each independently represent a value from 0 to 1.

[0010] 2. The hair coloring dye, in which the general formula (1), D represents a cationic fraction of a triarylmethane tincture, a xanthene tincture, a phenothiazine tincture, a phenazine tincture, a phenoxazine tincture, an azo tincture, an azomethine tincture, or an HC tincture.

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

[0012] [Chem.2]

[0013] wherein in formula (2), R1 to R13 each independently represent -H, a halogen atom, -NO2, -NO, -CN, -OH, 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, provided that the adjacent groups of each combinations of R and R, R and R, and R to R can be linked together to form a cycle.

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

[0015] [Chem.3]

[0016] wherein in formula (3), R14 to R21 each independently represent -H, a halogen atom, -NO2, -NO, -CN, -OH, an amino group having from 0 to 20 carbon atoms, which may have a substituent, a linear or branched alkenyl group having from 2 to 20 carbon atoms, which may have a substituent, a linear or branched alkyl group having from 1 to 20 carbon atoms, which may have a substituent, a linear or branched alkoxy group having from 1 to 20 carbon atoms, which may have a substituent, an acyl group having from 1 to 20 carbon atoms, which may have a substituent, an aromatic hydrocarbon group having from 6 to 30 carbon atoms, which may have a substituent, or a heterocyclic group having from 2 to 30 carbon atoms, which may have a substituent, provided that groups adjacent from R14 to R21 can be linked to each other to form a cycle;and Q represents -CH=, -N=, -O-, -S-, an amino group having from 0 to 30 carbon atoms, which may have a substituent, or a methylene group, which may have a substituent. ;

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

[0018] [Chem.4] [ R^N^N—R 23 | e t 4 )

[0019] in which in formula (4), R22 and R23 each represent an amino group having from 0 to 20 carbon atoms, which may have a substituent, a linear or branched alkenyl group having from 2 to 20 carbon atoms, which may have a substituent, an aromatic hydrocarbon group having from 6 to 30 carbon atoms, which may have a substituent, or a heterocyclic group having from 2 to 30 carbon atoms, which may have a substituent.

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

[0021] [Chem.5] p 26

[0022] in which in formula (5), R24 to R26 each independently represent an amino group having from 0 to 20 carbon atoms, which may have a substituent, a linear or branched alkenyl group having from 2 to 20 carbon atoms, which may have a substituent, a linear or branched alkyl group having from 1 to 20 carbon atoms, which may have a substituent, a linear or branched alkoxy group having from 1 to 20 carbon atoms, which may have a substituent, an acyl group having from 1 to 20 carbon atoms, which may have a substituent, an aromatic hydrocarbon group having from 6 to 30 carbon atoms, which may have a substituent, or a heterocyclic group having from 2 to 30 carbon atoms, which may have a substituent, provided that R25 and R26 can be linked to each other to form a ring.

[0023] 7. Hair coloring dye, in which the general formula (2), R1, R2, R5, and R6 each represent -H or a methyl group; R3, R4, R7, and R8 each represent -H, a methyl group, or an ethyl group; and R9 to R13 each represent -H, -Cl, an amino group having from 0 to 10 carbon atoms, which may have a substituent, an alkenyl group having from 2 to 10 carbon atoms, which may have a substituent, an alkyl group having from 1 to 10 carbon atoms, which may have a substituent, or an acyl group having from 1 to 10 carbon atoms, which may have a substituent.

[0024] 8. The hair coloring dye, in which the general formula (1), An represents an anion containing hydrogen.

[0025] 9. The hair coloring dye, in which the coloring dye capillary has a lifespan of 6 months or more at room temperature (20 to 25°C) or 7 days or more at 40 to 60°C.

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

[0027] 11. A method for producing a hair coloring dye shown by the following general formula (6), the process including the execution of a step 1 and a step 2:

[0028] [Chem.6] (D)(AnHCI®k (6)

[0029] wherein in formula (6), D represents a cationic fraction of the hair coloring dye; An represents a polyatomic anion; and a and b each independently represent a value from 0 to 1,

[0030] Step 1: Purification of a hair coloring dye containing a polyatomic anion (An) with water and activated charcoal; and Step 2: Dissolving the hair coloring dye obtained in step 1 with water and salt, then subjecting to a salt exchange.

[0031] In accordance with steps 1 and 2 carried out, the hair coloring dye represented by the general formula (6) has a proportion of the polyatomic ion (An) or impurities derived from An contained in the hair coloring dye of 1% by mass or less. [Advantageous effect 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 can effectively suppress the discoloration of dyed hair can be provided using the hair coloring dye. A hair coloring dye that has a long shelf life and excellent heat resistance can be provided by the production process of the present invention. Description of the implementation methods

[0033] Embodiments of the present invention will be described in detail below. The present invention is not limited to the following embodiments and can be carried out with various modifications while remaining within its scope.

[0034] The "hair coloring dye" represented by the general formula (1) has a water-soluble dye formed from a compound which is used as a basic dye (or cationic dye) for dyeing mainly human hair, and which has a group exhibiting basicity (cationicity) in the molecular structure. In the general formula (1), D represents a cationic fraction of the hair dye. The cation represented by D forms the hair dye by bonding with an anion. D preferably represents a monovalent cation. In the general formula (1), An represents a polyatomic anion, and the hair dye of the present invention may contain a polyatomic anion (An) or "An-derived impurities" derived from the polyatomic anion (An), and is represented by the following general formula (1), wherein the proportion (concentration ratio) of the "polyatomic anion (An) or An-derived impurities" in the total hair dye is 1% by mass or less. The hair dye represented by the general formula (1) contains a chloride ion (Cl⁻).

[0035] [Chem.l] (fDÏÏAn) (Cl 88 f 11

[0036] In the general formula (1), assuming that the molar ratio of D in the hair coloring dye is 1, "a" represents the molar ratio of An, and "b" represents the molar ratio of Cl. a and b each independently represent a value from 0 to 1, a preferably represents a value that is less than b, and a preferably represents a value of 0 close to 0. b preferably represents 1 or a value close to 1. For example, in the case where D represents a monovalent cation, and An represents a monovalent anion, a + b can be 1. D preferably represents a monovalent cation, and in this case, a + b is preferably 1.

[0037] The hair coloring dye product represented by the general formula (1) may contain impurities depending on its production process and the storage conditions after production. Examples of impurities include material that did not react during synthesis, impurities attached to the raw materials, solvent molecules, an organic compound or an inorganic compound other than the target coloring component, an impurity derived from the cation or ion (e.g., a decomposed product thereof, a substance in which the ion has bonded to another substance, or equivalents), a compound containing a hydrogen atom containing a proton (hydrogen ion) or equivalents (e.g., a A reactive impurity containing an anion and a cation), an insoluble impurity, and a mixed substance within it before, after, or during production. In the present invention, the polyatomic cation (An) or a reaction product (product material) derived from the presence of An is designated as an impurity, which is unfavorable to the target function of the hair coloring in the present invention (in other words, heat resistance and long-term stability). Accordingly, the proportion (concentration ratio) of the polyatomic anion (An) or impurities derived from An in the total hair coloring dye is 0.1% by mass or less, and preferably 0.05% by mass or less. Examples of "An-derived impurities" include a decomposition product of An, a substance in which An is bound to another substance, for example the cationic fraction (D) of hair coloring dye, and a reaction product thereof.

[0038] In the general formula (1), the "polyatomic anion (An)" is specifically an anion having 2 or more atoms, and examples of this include an inorganic anion, an organic anion, and a complex ion (complex anion). More specific examples of this include a dihydrogen phosphate ion (H2PO4), a monohydrogen phosphate ion (HPO42), a phosphate ion (PO43), P2O74, a cyanide ion (CN), a nitrate ion (NO3), a nitrite ion (NO2), a hypochlorite ion (ClO2), a chlorite ion (C1O2), a chlorate ion (C1O3), a permanganate ion (MnO4), a carbonate ion (CO32), a bicarbonate ion (HCO3), a hydrogen sulfate ion (HSO4), a sulfate ion (SO42), a sulfite ion (SO32), a thiosulfate ion (S2O32), a methyl sulfate ion (CH3SO4), a hydrogen sulfide ion (HS), a thiocyanate ion (SCN), an ion tetrahydroxide aluminate ([Al(OH)4], [Al(OH)4(H2O)2]), a tetrahydroxide chromate(III) ion ([Cr(OH)4]), a chromate ion (CrO42),a dichromate ion (Cr2O72), a zincate(II) tetrahydroxide ion ([Zn(OH)4]2), a zincate(II) tetracyanide ion ([Zn(CN)4]2), ((l / 2)[ZnCl2]Cl), a zincate(II) tetrachloride ion ([ZnCl4]2), a cuprate(II) tetrachloride ion ([CuCl4]2), an iron(III) hexacyanide ion ([Fe(CN)6]3), an iron(II) hexacyanide ion ([Fe(CN)6]4), a stannate(IV) hexahydroxide ion ([Sn(OH)6]2), a plumbate(II) tetrahydroxide ion [Pb(OH)4]2), an acetate ion (CH3COO), a hydrogen oxalate ion (H(COO)2 ), an oxalate ion ((COO)22), a benzoate ion (C6H5COO), a citrate ion (C6H5O73), ions of various amino acids, and ions of other organic acids having a carboxy group.

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

[0040] In the hair coloring dye represented by the general formula (1), while D and An can each be a single component or a mixture of several components, D is preferably a single component and in general An is preferably a single component.

[0041] In the hair coloring dye represented by the general formula (1), D may be a cationic fraction of a basic dye (cationic dye). In the general formula (1), D is specifically preferred to be a cationic fraction 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 coloring dye of the present invention represented by the general formula (1) include an arylmethane dye, preferably a triarylmethane dye, for example CI Basic Blue 77 (in which CIrepresents the color index (Color Index); which can simply be referred to as Basic Blue 77 in the present invention, and the names of the following dyes are presented in this manner), Basic Blue 1, 5, 7, 11, 15, or 26, Basic Green 1 or 4, and Basic Violet 2, 3, 11:1, 4, or 14; a xanthene dye, for example Basic Violet 10 or 11, Basic Red 1 or 1:1, etrhodamine 110; a phenothiazine dye, for example Basic Blue 9 or 17; a phenazine dye, for example Basic Red 2; a phenoxazine dye, for example Basic Blue 3 or 124; an acridine dye; an azo dye, for example Basic Brown 16, Basic Red 22, 51, or 76, Basic Orange 31, and Basic Yellow 57; an azomethine tincture, for example Basic Yellow 11, 13, 29, 36, or 40, and Basic Violet 16; and an HC tincture, for example 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 formulas (2) to (5).

[0044] In general formulas (2), (3), and (5), examples of the "halogen atom" represented by R to R and R to R include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0045] In general formulas (2) to (5), examples of the "amino group having 0 to 20 carbon atoms, which may have a substituent" represented by R1 to R26 include -NH2, a monosubstituted amino group, for example an ethylamino group, an acetylamino group, and a phenylamino group, and a disubstituted amino group, for example a diethylamino group, a diphenylamino group, and an acetylphenylamino group. A quaternary ammonium group, which may have a substituent, formed by the amino group having in addition a substituent bonded to it, such as a trialkylamino (or trialkylammonio) group, for example, a trimethylamino (or trimethylammonio) group and a triethylamino (or triethylammonio) group, and a triphenylamino (or triphenylammonio) group, is also included in the "amino group having 0 to 20 carbon atoms, which may have a substituent", and these substituents may be identical or different from each other.

[0046] In general formulas (2) to (5), specific examples of the "linear or branched alkenyl group having from 2 to 20 carbon atoms" in the "linear or branched alkenyl group having from 2 to 20 carbon atoms, which may have a substituent" represented by R1 to R26 include a vinyl group, an allyl group, an isopropenyl group, a 2-butenyl group, a 1-hexenyl group, and a linear or branched group containing a plurality of these alkenyl groups bonded to one another.

[0047] In general formulas (2), (3), and (5), specific examples of the "linear or branched alkyl group having from 1 to 20 carbon atoms" in the "linear or branched alkyl group having from 1 to 20 carbon atoms, which may have a substituent" represented by R to R and R to R include a linear alkyl group, for example a methyl group, an ethyl group, an n-propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group; and a branched alkyl group, such as an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an isooctyl group, and a tert-octyl group.The "linear or branched alkyl group having from 1 to 20 carbon atoms" can form a ring to contain a cycloalkyl group having from 3 to 20 carbon atoms, for example a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, and a cyclododecyl group.

[0048] In general formulas (2), (3), and (5), specific examples of the "linear or branched alkoxy group having from 1 to 20 carbon atoms" in the "linear or branched alkoxy group having from 1 to 20 carbon atoms, which may have a substituent" represented by R to R and R to R include a linear alkoxy group, for example a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group, an n-pentyloxy group, an n-hexyloxy group, a heptyloxy group, an octyloxy group, a nonyloxy group, and a decyloxy group; and a branched alkoxy group, for example an isopropoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, an isooctyloxy group, and a tert-octyloxy group. The "linear or branched alkoxy group having from 1 to 20 carbon atoms" can form a ring to contain a cycloalkoxy group having from 3 to 20 carbon atoms, for example a group cyclopropoxy, a cyclobutoxy group, a cyclopentyloxy group, and a cyclohexyloxy group.

[0049] In general formulas (2), (3), and (5), specific examples of the "acyl group having from 1 to 20 carbon atoms" in the "acyl group having from 1 to 20 carbon atoms, which may have a substituent" represented by R1 to R21 and R24 to R26 include a formyl group, a carbonyl group, an acetyl group, a propionyl group, an acrylyl group, and a benzoyl group.

[0050] In general formulas (2) to (5), specific examples of the "aromatic hydrocarbon group having from 6 to 30 carbon atoms" in the "aromatic hydrocarbon group having from 6 to 30 carbon atoms, which may have a substituent" represented by R1 to R26 include a phenyl group, a biphenylyl group, a terphenylyl group, a tetrakisphenyl group, a styryl group, a naphthyl group, an anthryl group, an acenaphtenyl group, a phenanthryl group, a fluorenyl group, an indenyl group, a pyrenyl group, and a triphenylenyl group. The "aromatic hydrocarbon group" in the present invention comprises an aromatic hydrocarbon group and a condensed polycyclic aromatic group.

[0051] In general formulas (2) to (5), specific examples of the "heterocyclic group having from 2 to 30 carbon atoms" in the "heterocyclic group having from 2 to 30 carbon atoms, which may have a substituent" represented by R1 to R26 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 carbolynyl 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, a naphthyridinyl group, a phenanthrolinyl group, an acrydinyl group, and a hydantoin group.

[0052] In general formulas (2) to (5), specific examples of the "substituent" in the "amino group having 0 to 20 carbon atoms having a substituent", the "linear or branched alkenyl group having 2 to 20 carbon atoms having a substituent", the "linear or branched alkyl group having 1 to 20 carbon atoms having a substituent", the "linear or branched alkoxy group having 1 to 20 carbon atoms having a substituent", the "acyl group having 1 to 20 carbon atoms having a substituent", the "aromatic hydrocarbon group having 6 to 30 carbon atoms having a substituent", and the "heterocyclic group having 2 to 30 carbon atoms having a substituent” represented by R1 to R26 and the “amino group having from 0 to 30 carbon atoms the methylene group having a substituent” represented by Q include a nitro group (-NO2), a nitroso group (-NO), a cyano group (-CN), a hydroxy group (-OH), a halogen atom, for example a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; and an unsubstituted amino group; a monosubstituted or disubstituted amino group having a linear or branched alkyl group having from 1 to 20 carbon atoms or an aromatic hydrocarbon group having from 6 to 30 carbon atoms, for example a methylamino group, a dimethylamino group, a diethylamino group, an ethylmethylamino group, a methylpropylamino group, a di-tert-butylamino group, and a diphenylamino group; a sulfonamide group (-S(=O)2-NRR') (in which "-NRR'" in the group represents an unsubstituted amino group;a monosubstituted or disubstituted amino group having a linear or branched alkyl group having from 1 to 20 carbon atoms or an aromatic hydrocarbon group having from 6 to 30 carbon atoms, for example a methylamino group, a dimethylamino group, a diethylamino group, an ethylmethylamino group, a methylpropylamino group, a di-tert-butylamino group, and a diphenylamino group); a linear or branched alkyl group having from 1 to 20 carbon atoms, for example a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an n-hexyl group, an isohexyl group, a heptyl group, an n-octyl group, a tert-octyl group, an isooctyl group, a nonyl group, and a decyl group;a cycloalkyl group having from 3 to 20 carbon atoms, for example a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, and a cyclododecyl group; a linear or branched alkoxy group having from 1 to 20 carbon atoms, for example a methoxy group, an ethoxy group, a propoxy group, a tert-butoxy group, an n-pentyloxy group, and an n-hexyloxy group; a cycloalkoxy group having from 3 to 20 carbon atoms, for example a cyclopropoxy group, a cyclobutoxy group, a cyclopentyloxy group, and a cyclohexyloxy group;a linear or branched alkenyl group having from 2 to 20 carbon atoms, for example 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, an isobutenyl group, and a group containing a plurality of these alkenyl groups bonded to each other; an acyl group having from 1 to 20 carbon atoms, for example a formyl group, an acetyl group, a propionyl group, an acrylyl group, and a benzoyl group; an aromatic hydrocarbon group having from 6 to 30 carbon atoms; for example a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, a triphenylenyl group, an indenyl group, a fluorenyl group, and a styryl group; a heterocyclic group having from 2 to 30 carbon atoms, for example a pyridyl group, a pyrimidinyl group, a triazinyl group, a pyrrolyl group, an imidazolyl group, a pyrazolyl group, a triazolyl group, a pyrazinyl group, a pyridazinyl group, a piperidinyl group, a piperadinyl group, a quinolyl group, an isoquinolyl group, a naphthyridinyl group, an indolyl group, a benzimidazolyl group, a carbazonyl group, a carbolynyl group, a pyridoindolyl group, an acridinyl group, a phenanthrolinyl group, a phenanthridinyl group, a hydantoin group, a furyl group, a benzofuryl group, a dibenzofuryl group, a pyranyl group, a coumarinyl group, an isobenzofuryl group, a xanthenyl group, a group oxanthrenyl,a pyranonyl group, a thienyl group, a thiopyranyl group, a benzothienyl group, a dibenzothienyl group, a thioxanthenyl group, an oxazolyl group, a benzoxazolyl group, a morpholinyl group, a thiazolyl group, and a benzothiazolyl group; and a cyclic olefin group having from 3 to 30 carbon atoms, for example a cyclopropenyl 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. For these "substituents," only one of them may be contained, and a plurality of them may be contained, and in the case where a plurality of them are contained, the substituents may be identical or different from one another. Each of these "substituents" can also have the substituent. In the case where the "substituent" contains a carbon atom, the carbon atom is counted in the "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 general formulas (2) to (5). These substituents can be linked to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom, or a sulfur atom, so as to form a ring.

[0053] In the general formula (2), R1 to R13 each preferably represent -H, a halogen atom, an amino group having from 0 to 20 carbon atoms, which may have a substituent, an alkenyl group having from 2 to 20 carbon atoms, which may have a substituent, or a linear or branched alkyl group having from 1 to 10 carbon atoms, which may have a substituent.

[0054] In the general formula (2), adjacent groups from R1 to R13 can be linked to each other to form a cycle, and in the case where a cycle is formed, we prefer / 1 “7 Q Û that R and R, R and R, and R to R are each linked to form a cycle, and it is preferred that the cycle be a 5-link cycle or a 6-link cycle.

[0055] In the general formula (3), R14 to R21 each preferably represent -H, an amino group having from 0 to 20 carbon atoms, which may have a substituent, or an aromatic hydrocarbon group having from 6 to 30 carbon atoms, which may have a substituent.

[0056] In the general formula (3), adjacent groups from R14 to R21 can be linked together to form a cycle, and in the case where a cycle is formed, it is preferred that R14 to R17 or R18 to R21 be linked to form a cycle, and it is more preferred that the cycle be a 5-link cycle or a 6-link cycle.

[0057] In the general formula (4), R22 and R23 each preferably represent an aromatic hydrocarbon group having from 6 to 30 carbon atoms, which may have a substituent, or a heterocyclic group having from 2 to 30 carbon atoms, which may have a substituent.

[0058] In the general formula (5), R24 to R26 each preferably represent a linear or branched alkyl group having from 1 to 20 carbon atoms, which may have a substituent, an aromatic hydrocarbon group having from 6 to 30 carbon atoms, which may have a substituent, or a heterocyclic group having from 2 to 30 carbon atoms, which may have a substituent.

[0059] In the general formula (5), R25 and R26 can be linked together to form a cycle, and in the case where a cycle is formed, it is preferred that the cycle be a 5-link cycle or a 6-link cycle.

[0060] Specific examples of the compound preferred as a hair coloring dye of the present invention, represented in the general formula (1), are given below. The structural formulas given as examples are for the case where a is 0 and b is 1 in the general formula (1). The present invention is not limited to these compounds. In the following structural formulas, hydrogen atoms are partially omitted from the description, and even where stereoisomers are present, only the planar structural formula is given.

[0061] [Chem.7]

[0062]

[0063]

[0064] [Chem. 8]

[0065]

[0066] [Chem. 11]

[0067] [Chem. 13] tB- 2)

[0068] [Chem. 14]

[0070]

[0071]

[0072]

[0069] [Fabric. 16] (D-3) [Chem.17] HO ' Xssss (F-1) (E-1) [Fabric. 18] (D— 2) (D-4) (F-2) HOUSE ® / HO hn-H >=\ J X (F-3)

[0073] [Fabric. 19] / Cl e « / I >-n=n-4 >-n (F − 4) (F-5) (F-6)

[0074] [Chem.20]

[0077] [Chem.23]

[0078] Specific examples of the hair coloring dye of the present invention are given above, and when these dyes are actually used in a hair coloring dye composition, preference is given to select the dye that has no toxicity or allergenic potency whenever possible, and to use the dye that has a high safety profile.

[0079] The hair coloring dye represented by general formula (1) can be produced (synthesized) using a commercially available dye (or colorant, for example, a pigment) as a raw material. The compound represented by general formula (1) can also be produced using a newly synthesized coloring compound as a raw material. An example of a process for producing the hair coloring dye of the present invention will be described below. There is no particular limitation on the dye used as a raw material, and this is preferably a basic dye having a cationic chromogenic portion and an anionic non-chromogenic portion. Examples of the raw material include a dye having a structure obtained by The anionic fraction of the aforementioned specific example of hair dye may be replaced by an anion other than a chloride ion. However, a dye containing a chloride ion in a certain proportion of the raw material may be used.

[0080] The process for producing a hair dye of the present invention is a process for producing a hair dye represented by the following general formula (6). A dye represented by a similar general formula (6) can also be used as a raw material in the process for producing a hair dye of the present invention.

[0081] [Chem.6] (D)(AnHCI®k (6) 8 U

[0082] In the general formula (6), for example, D represents the cationic fraction of the target hair coloring dye of the present invention; An represents a polyatomic anion, which may contain Cl; and a and b each independently represent a value from 0 to 1, provided that there is no limit to the magnitude relationship between a and b.

[0083] In the production process 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 may be a dye having D corresponding to the cationic fraction represented by general formulas (2) to (5). A triarylmethane dye represented by general formula (2) will be described below as a specific example.

[0084] In the case where the hair coloring dye of the present invention is a triarylmethane dye, it is preferred that in the general formula (2), R1, R2, R5, and R6 each represent -H or a methyl group, R3, R4, R7, and R8 each represent -H, a methyl group, or an ethyl group, and R9 to R13 each represent -H, -Cl, an amino group having from 0 to 10 carbon atoms, which may have a substituent, an alkenyl group having from 2 to 10 carbon atoms, which may have a substituent, an alkyl group having from 1 to 10 carbon atoms, which may have a substituent, or an acyl group having from 1 to 10 carbon atoms, which may have a substituent.

[0085] In the case where, in the general formula (6), D represents a cationic fraction represented by the general formula (2), in which R1, R2, R5, and R6 each represent a methyl group, R3, R4, R7, R8, and R10 to R12 each represent -H, and R9 and R13 each represent -Cl, a is 1, b is 0, and An represents H2PO4, the general formula (6) presents a dye for hair coloring represented by the following formula (2-IX) (dye HC, HC Blue 15, molecular mass: 495.34).

[0086] [Chem.24] ss © (2-1X) U

[0087] The process for producing a hair dye of the present invention includes carrying out steps 1 and 2 shown below. An example will be given in which the basic dye represented by formula (2-IX) containing a polyatomic anion as the principal anion other than a chloride ion in the dye is used as a raw material in the process for producing a hair dye of the present invention.

[0088] Step 1: Purification of a hair coloring dye containing a polyatomic anion (An) with water and activated charcoal

[0089] Step 2: Dissolving the hair coloring dye obtained in step 1 with water and salt, then subjecting to a salt exchange

[0090] In step 1, the "purification with water and activated carbon" step may specifically include the following steps. The dye provided as raw material is dissolved in water under suitable conditions, including concentration, temperature, and stirring. The solution is then mixed with suitable activated carbon and purified with it under suitable conditions, including temperature and stirring. After this, a purified specimen can be obtained by washing, filtration, and the equivalent.

[0091] Next, in step 2, the step of "dissolving the hair dye obtained in step 1 with water and a salt, and then performing a salt exchange" may specifically include the following steps. The specimen obtained by purification in step 1 is mixed with water and a salt (NaCl) and then processed under suitable conditions, including salt concentration, temperature, and agitation, to provide a target hair dye by salting out. According to the procedure, the hair dye represented by the general formula (6) may be obtained, wherein a portion, most, or all of the polyatomic anion contained in the dye prior to steps 1 and 2 is replaced by a chloride ion (salt exchange). Filtration, washing, drying, and the like may, appropriately, be carried out during, before, or after step 2. By carrying out steps 1 and 2 as described above, the hair coloring dye represented by the general formula (6) which has a proportion of the polyatomic ion (An) or An-derived impurities contained of 1% by mass or less can be obtained.

[0092] Step 1 and step 2 of the production process will be described in detail below. There is no particular limit to the "water" used, and ordinary water may be used, examples of which include tap water, deionized water, distilled water, and industrial water. The concentration of components other than the cation and anion contained in the target dye is, preferably and as far as possible, low, as long as the advantageous effects of the present invention are not impaired. The water in the present invention may be public water, for example, tap water.

[0093] In step 1, there is no particular limit to the mixing ratio when the hair dye and water are mixed, provided that the dye can be sufficiently dissolved at that concentration. Specifically, the mass of water used can be 5 to 1000 times, and more preferably 10 to 100 times, the mass of the dye.

[0094] There are no particular limitations on the container used in steps 1 and 2, provided that the container is intended for ordinary synthesis, purification, mixing, and stirring. The material of the container may be selected from suitable materials, for example, a glass container such as a flask, a metal container, a resin container, or an enameled container. A container made of a material resistant to the use of water and salt (NaCl) is preferably used. The stirring device used may be a commercially available product, and there are no limitations on the shape of the stirring blade or the type of stirrer.

[0095] The temperature during the stirring of the tincture and water in step 1 is preferably from room temperature (approximately 20 to 25 °C) to 100 °C, and more preferably from 40 to 80 °C. There is no particular limit to the stirring time required for dissolution, as long as the tincture is sufficiently dissolved, and is preferably from 30 minutes to 12 hours, and more preferably from 30 minutes to 3 hours. The appropriate temperature and stirring time depend on the type and mass of tincture to be dissolved, and thus the tincture is preferably dissolved at a temperature and with a stirring time appropriate for it.

[0096] The purification in the production process of the present invention can be carried out, for example, by a known process, for example by purification by column chromatography; by purification by adsorption with silica gel, activated carbon, activated clay, or equivalents; and by recrystallization or crystallization with a solvent, and activated carbon is preferably used as in step 1. The processes The aforementioned purification processes can be carried out before and after the use of activated carbon, and it is possible to use only activated carbon. In the purification described in the present invention, it is preferable to use only activated carbon.

[0097] In step 1, the activated carbon used can be various commercially available products used for water clarification, decolorization, and the purification of chemical compounds, and there are no particular limitations. Examples of activated carbon particle shapes include powder, granular, rod, and fibrous forms, with powdered activated carbon being preferred. The pore diameter on the surface of the activated carbon can be, for example, 2 to 3 nm. The properties of the activated carbon can be appropriately selected based on the types of cations and anions contained in the raw materials.

[0098] In step 1, it is preferred that the activated carbon be added to the solution in which the dye is sufficiently dissolved, before being mixed and stirred. The quantity of activated carbon used is preferably not excessive relative to the mass of the dye as a raw material, and is preferably from 1 to 100% by mass, more preferably from 5 to 30% by mass, based on the mass of the dye. With respect to the mixing conditions of the activated carbon in the solution, the stirring conditions, such as the temperature and duration of stirring, can be similar to those during the initial dissolution of the dye.

[0099] In step 1, after the activated carbon treatment, the activated carbon is filtered and washed with water. During filtration and washing, the resulting aqueous dye solution may be at room temperature or heated, and the aqueous solution is preferably heated to a temperature within a certain range. The aqueous dye solution thus purified in step 1 is transferred to step 2.

[0100] The aqueous solution of the hair dye obtained in step 1 is supplied in step 2. Salt (NaCl) is added to the aqueous solution of the hair dye and dissolved therein under stirring at a temperature of 20 to 80 °C before stirring. The temperature during stirring can be within a suitable range of 20 to 80 °C, and is preferably 30 to 70 °C, and more preferably 40 to 65 °C. There is no particular limit to the amount of salt added, and it preferably has a lower quantity of impurities; it is possible to use a food-grade or industrial product. There is no particular limit to the form of the particles, and any form of powder, pulverized form, or granules can be used.Its water content can be any grade generally applied to commercial, industrial, or food use. The salt concentration can be from 1.5 to . 25% by mass, and preferably 5 to 20% by mass, based on the solvent (water). The salt can be added to the solution as an aqueous solution using water.

[0101] In step 2, the liquid obtained by dissolving the salt in the aqueous solution containing the hair dye is heated to a suitable temperature for a certain period. The heating time can be approximately selected from 1 to 24 hours. After heating, the liquid can be cooled to room temperature at a suitable cooling rate. During cooling to room temperature, the liquid is preferably stirred for a sufficiently long period of time, for example, approximately 5 to 24 hours.During the process of adding salt and cooling under stirring, the reaction (salt exchange) of exchanging some or all of the anion in the dye before step 1 for a chloride ion (Cl) occurs, and the hair coloring dye represented by the general formula (1) can be obtained as an undissolved component in the aqueous solution, in other words, a precipitated solid.

[0102] The hair coloring dye of the present invention, obtained by dissolving water and salt and by salt exchange as in step 2—in other words, the solid matter precipitated by salt exchange—can be filtered and washed with an aqueous solution containing salt (saline). The salt concentration in the water is preferably from 1.5 to 20% by mass. The temperature during filtration can be appropriately selected from ambient temperature to 40 °C. After filtration, the resulting composition containing the hair coloring dye of the present invention and water (which can be, for example, in the form of a solid, a powder, or a cake) has a certain water content. The composition can be dehydrated with a suction filter or equivalent.

[0103] For the composition containing the hair coloring dye of the present invention and the water obtained in step 2, the water (or water content) in the composition containing the hair coloring dye can be regulated or removed with a suitable dryer. The composition can be dried to provide the hair coloring composition of the present invention by transferring it to a container having a wide base area, such as a plate or tray. The composition can be dried with a hot air dryer or a vacuum dryer. The drying time can be a suitable period to provide the target water content and can be selected from 1 hour to 3 days. The water content in the composition containing the hair coloring dye is preferably 10% by mass or less, and more preferably 8% by mass or less.The composition can be dried substantially completely to 1% by mass or less, or water can remain up to a certain extent. degree. The temperature during drying is preferably in a range of 20 to 100 °C, more preferably from 30 to 80 °C.

[0104] The hair coloring dye of the present invention is obtained by the process including step 1 and step 2 described above, and modified known steps may be added before or after the steps.

[0105] The hair coloring dye of the present invention, represented by the general formula (1), can be subjected to UV-visible (UV-Vis) spectral analysis or absorbance analysis, thermogravimetric and differential thermal analysis (TG-DTA), high-performance liquid chromatography (HPLC), gas chromatography (HPLC), nuclear magnetic resonance (NMR), and equivalents, for the identification and evaluation of the compound's properties. In absorbance analysis and HPLC measurement, a comparison based on molecular structure and color can be performed, and thus the purity of the target hair coloring dye in the specimen and the concentration of impurities in the specimen can be evaluated.For example, the purity or concentration ratio of the main component can be measured in such a way that the HPLC measurement is carried out at particular measurement wavelengths to provide peak areas of the peaks measured at retention times, from which the ratios (surface ratios) of the main components and impurities are determined.

[0106] The hair dye of the present invention, represented by the general formula (1), is obtained by the aforementioned steps. Due to the purification process, the concentration of the component that is not soluble in water, in other words, the insoluble component, in the hair dye can be reduced to 1% by mass or less, preferably 0.5% by mass or less, and more preferably 0.1% by mass or less. As one of the characteristic features of the process for producing a hair dye of the present invention, the concentration of the anion present before the purification and salt exchange steps can be reduced, and thus the alteration and deterioration of quality caused by the anion present in the hair dye before these steps can be prevented.

[0107] The mechanism for preventing alteration and deterioration of the quality of the hair coloring dye of the present invention, represented by the general formula (1), specifically includes the advantage that the main component of the anion after the steps is the chloride ion, and thus the anion does not decompose by itself. In other words, the possibility of alteration occurring due to the decomposition of the polyatomic ion contained in the dye before the steps, alteration due to a reaction of the polyatomic ion and the The dye (chromogenic component) and the alteration due to a reaction with water molecules or the component in the hair coloring composition can be reduced. In the case where the polyatomic anion is a hydrogen-containing anion, in particular, a hydrogen ion released from the ion is considered to influence the decomposition of the dye molecule and other components. The aforementioned alteration and decomposition reaction of the component is considered to occur not only around room temperature, but also when the temperature is above room temperature, and in particular, the decomposition and alteration reaction accelerates at the temperature at which the hair coloring composition is used, especially at 35°C or higher.

[0108] The shelf life of the hair dye of the present invention and the degree of alteration of the hair dye can be measured by HPLC measurement, absorbance analysis, or equivalent methods. Specifically, the purity of the hair dye at the beginning of the evaluation, as a reference, is preferably 99% or higher. The purity is preferably maintained at 99% or higher for a period of several days or more until a time-dependent change occurs. The temperature for measuring the time-dependent change can be room temperature, ambient temperature, or higher, preferably 40°C or higher, and preferably 40°C to 60°C. The period during which the purity is maintained is preferably 6 months or more at room temperature. The shelf life is preferably 6 months or more at room temperature (20 to 25°C) or 7 days or more at room temperature (40 to 60°C).

[0109] The chromatic characteristics (such as color valence and shade) of the hair coloring dye of the present invention can be evaluated by measuring the absorbance, the visible light absorption spectrum or the reflection spectrum, for example, in a range of 400 to 700 nm, the chromaticity coordinates (x, y) in the xy chromaticity diagram of the CIE 1931 colorimetric system using a spectrocolorimeter or a color difference measuring device, the density (K / Sd), the chromatic tone (L*, a*, b*) of the CIE 1976 colorimetric system, the color difference (AE*) and equivalents, in the state of a powder (solid), a solution, a dispersion, or a thin film.There are cases where solutions, powders, or thin films of compounds with the same molecular structure have different visual colors, and to objectively quantify the color difference, measurement with a spectrocolorimeter or a color difference measuring device can be performed. Visual evaluation with standard color samples, a color chart, or equivalents can also be carried out. The chromatic tone obtained by actually dyeing fibers, for example, a specimen of white hair, can be evaluated.

[0110] The hair coloring dye of the present invention retains the structure of the dye molecule derived from the chromogenic portion, since purification and salt exchange are carried out before and after the steps, and the chromatic characteristics thereof are not altered. The absorbance before purification is preferably 0.5 or greater.

[0111] According to the process for producing a hair coloring dye and the process for evaluating a hair coloring dye, the hair coloring dye of the present invention having a long life and excellent heat resistance can be obtained.

[0112] The hair coloring dye according to the present invention, the compound represented by the general formula (1), and the hair coloring composition containing the hair coloring dye are preferably used in the form of hair dyes. The hair coloring dye represented by the general formula (1) can be used after mixing with a component such as another dye, an additive, and an auxiliary agent. An embodiment that is suitable for the hair coloring dye of the present invention is a hair coloring composition, which may contain a hair coloring dye containing the compound represented by the general formula (1), at least one type of auxiliary agent selected from the group consisting of a wetting agent, a swelling agent, a penetrating agent, a solvent, a pH modifier, a surfactant, a fragrance, and a thickener, and water.

[0113] Examples of the wetting agent include glycerin, propylene glycol, a sorbitol compound, 1,3-butylene glycol, and a polyethylene glycol compound. If the wetting agent is used, its content is preferably from 0.1 to 20% by mass, and more preferably from 0.5 to 10% by mass, based on the total amount of the hair coloring composition.

[0114] Examples of the blowing agent include an alkaline aqueous solution containing ammonia (ammonium hydroxide) or monoethanolamine (MEA). If the blowing agent is used, its concentration is preferably from 0.1 to 20% by mass, and more preferably from 0.5 to 10% by mass, based on the total amount of the hair coloring composition.

[0115] Examples of the penetrating agent and solvent include a monohydric alcohol having an alkyl group having from 1 to 6 carbon atoms, such as ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, and butoxyethanol; a polyhydric alcohol having from 3 to 8 carbon atoms or an ether thereof, such as propanediol, butanediol, pentanediol, hexanediol, hexanetriol, heptanediol, heptanetriol, octanediol, octanetriol, isoprene glycol, propylene glycol, glycerin, and diethylene glycol monoethyl ether; a N-alkylpyrrolidone which is in a liquid state at room temperature (about 25 °C), for example N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, N-butyl-2-pyrrolidone, and N-cyclohexyl-2-pyrrolidone; an alkylene carbonate (lower alkylene carbonate), such as ethylene carbonate and propylene carbonate; and an aromatic alcohol, such as benzyloxyethoxyethanol, benzyl alcohol, benzyloxyethanol, cinnamyl alcohol, p-anisyl alcohol, p-methylbenzyl alcohol, phenoxyethanol, phenoxyisopropanol, 2-benzylethanol, and [3-phenylethyl alcohol. Among these, an aromatic alcohol and an N-alkylpyrrolidone are preferred, and benzyl alcohol, benzyloxyethoxyethanol, and benzyloxyethanol are preferred more.In the case where the penetrating agent or solvent is used, its content is preferably from 2 to 40% by mass, and more preferably from 5 to 20% by mass, based on the total quantity of the hair coloring composition.

[0116] Examples of pH modifiers include an acid, such as phosphoric acid, lactic acid-sodium lactate, and citric acid-sodium citrate, and a base, such as aqueous ammonia, sodium hydroxide, potassium hydroxide, and sodium carbonate. When a pH modifier is used, its concentration is preferably from 0.1 to 10% by mass, and more preferably from 0.5 to 5% by mass, based on the total amount of the hair coloring composition.

[0117] As a surfactant, a cationic or nonionic surfactant is primarily used. Specific examples of these include, but are not limited to, a silicone compound, such as polysiloxane, a polyoxyethylene alkyl ether, a polyoxyethylene fatty acid ester, a polyglycerin fatty acid ester, an aliphatic amine or a quaternary ammonium salt thereof (such as trimethylstearylammonium chloride), a polyol ether compound, such as a sorbitol alkyl ether, and a polyoxyethylenated sorbitan fatty acid ester. Of these, a polyoxyethylenated sorbitan fatty acid ester is preferred. The use of a polyoxyethylenated sorbitan fatty acid ester further enhances the skin contamination reduction effect (skin contamination prevention capacity).

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

[0119] In the case where the surfactant is used, its content is preferably from 0.1 to 20% by mass, and more preferably from 0.5 to 10% by mass, based on of the total quantity of the hair coloring composition from the point of view of reducing skin contamination.

[0120] Examples of the fragrance include vanillin, cinnamic acid, heliotropin, coumarin, 2-methyl-3-(3,4-methylenedioxyphenyl)propanal, 4-(4-hydroxyphenyl)-2-butanone, benzaldehyde, anisyl alcohol, 3,4-dimethoxybenzaldehyde, heliotropyl acetate, phenylacetaldehyde dimethyl acetal, phenoxyethyl alcohol, phenylacetaldehyde glyceryl acetal, furaneol, sugar lactone, maltol, ethyl maltol, ethyl diglycollate, benzyl acetate, linalool, camphor, terpineol, citronellol, geraniol, 2,6-nonadienal, methyloctyl carbonate, the 3,7-Dimethyl-2,6-octadienal, and nonanal. If perfume is used, its content is preferably 0.00001 to 2% by mass based on the total quantity of the hair coloring composition.

[0121] Examples of thickeners include thickeners derived from guar gum and a derivative thereof, hydroxyethyl cellulose, xanthan gum, collagen, gelatin, a sodium salt of carboxymethyl cellulose, Carbopol (trade name), sodium alginate, gum arabic, a cellulose derivative, and poly(ethylene oxide). The thickener increases the viscosity of the hair coloring composition to form a gel-like consistency, which is easy to handle. When used, its concentration is preferably from 0.1 to 20% by mass, and more preferably from 0.5 to 10% by mass, based on the total quantity of the hair coloring composition.

[0122] There is no particular limit to the water used in the composition of hair coloring, and ion-exchanged water, purified water, clean water, tap water, and equivalents may be used.

[0123] The hair coloring dye represented by the general formula (1) of the present invention itself exhibits excellent hair coloring power and excellent resistance as a hair coloring dye, and can dye hair uniformly. Its color can be regulated to different colors (for example, purple, green, brown, and black) by combining a hair coloring dye containing the compound represented by the general formula (1) and a hair coloring compound of another color.

[0124] Examples of the basic compound to be combined include a direct dye having an amino acid group or an amino group substituted in the molecule, and specific examples of these include 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 the HC dye to be combined include a direct dye having a nitro group in the molecule, and specific examples of these include CI HC Blue 2 or 15; CI HC Red 1, 3, 7, 11, or 13; CI HC Yellow 2, 4, 5, 9, 11, or 13, CI HC Orange 1 or 2; CI HC Violet 1 or 2; and 4-hydroxypropylamino-3-nitrophenol.

[0126] The hair coloring composition according to the present invention in one embodiment preferably contains the hair coloring dye represented by the general formula (1) in an amount of 0.001 to 5% by mass based on the total amount of the hair coloring composition, with the remainder containing at least one type of auxiliary agent selected from the group consisting of a wetting agent, a swelling agent, a penetrating agent, a solvent, a pH modifier, a surfactant, a perfume, and a thickener, and water. If the hair coloring dye content is less than 0.001% by mass, the color retention and uniform coloring effect may be difficult to achieve, and if more than 5% by mass is added, the improvement in the coloring effect and equivalents may be minimal.The content of the hair colouring dye is preferably from 0.01 to 5% by mass, and preferably from 0.05 to 2% by mass, based on the total quantity of the hair colouring composition.

[0127] The pH value of the hair coloring composition of the present invention is preferably from 4 to 9, more preferably from 5 to 7. The pH value of the hair coloring composition can be regulated by a known method and is preferably regulated using a pH modifier, such as citric acid monohydrate or trisodium citrate dihydrate. Specifically, if a hair coloring composition with a pH of 6 is to be produced, citric acid monohydrate and trisodium citrate dihydrate are dissolved in water to prepare an aqueous solution with a pH of 6 in advance. Then, the hair coloring dye containing the compound represented by the general formula (1) and, if necessary, other additives (such as the auxiliary agent) are added to the aqueous solution to provide the hair coloring composition with a pH of 6.

[0128] The hair coloring composition according to the present invention may further contain a known cosmetic component within a range such that it does not alter the effects of the present invention. Examples of the cosmetic component that may be added include a higher alcohol, Vaseline, a polyhydric alcohol, an ester compound, an antiseptic, a bactericide, a silicone derivative, and a water-soluble polymer.

[0129] The hair dyeing process using the hair coloring composition of the present invention can specifically be a process in which an object to be dyed, for example human hair or cattle hair, is brought into contact with the hair coloring composition of the present invention. The hair dyeing temperature is preferably from 5 to 60 °C, and considering that the operation is carried out close to the scalp, is more preferably from 15 to 45 °C. The hair dyeing time is preferably from 5 to 60 minutes, and more preferably from 10 to 30 minutes.

[0130] After hair dyeing, a post-treatment, such as washing and rinsing, is generally carried out. Washing can be done until the hair dye color no longer eludes at all, and can be achieved, for example, by rinsing with running water at 5 to 40 degrees Celsius and 5 to 15 liters per minute for 0.5 to 2 minutes. Drying after washing can be natural drying (generally at 5 to 40 °C for 10 minutes to 10 hours), and a hot air dryer (generally at 40 to 60 °C for 10 minutes to 10 hours) can be used as needed.

[0131] After washing with water, soaping can be carried out. Soaping can be carried out, for example, by washing generally at a temperature of 15 to 50 °C for 1 to 10 minutes with an appropriate quantity of soaping liquid (which may be a mixture of shampoo and hot water), then by washing with water until the liquid is completely removed.

[0132] The resulting test specimen can be evaluated with a spectrocolorimeter. The hair dye density (K / Sd) can be evaluated in the following procedure. Specifically, it is possible to measure the reflectance (R0) of the test specimens before hair dyeing (white hair) and after hair dyeing (dyed hair) at a wavelength (X) with a spectrocolorimeter, and to calculate the optical density (K / S) using the following Kubelka-Munk expression. The hair dye density (K / Sd) can be obtained by subtracting the optical density (K / S) of white hair from the optical density (K / S) of dyed hair. Kubelka-Munk expression: K / S = I - Rj^R, R: reflectance at wavelength (X), X: 400 to 700 nm (interval: 10 nm)

[0133] The chromatic tone of the test specimen resulting after hair staining can be evaluated by measuring the chromatic tone (L*, a*, b*) with the CIE L*a*b* chromaticity system. L* is lightness, and a higher value of this indicates a lower intensity of staining; a* and b* are the chromaticity exhibiting the Hue and saturation: a* corresponds to the red / green axis, where a positive value is directed towards red and a negative value towards green; b* corresponds to the yellow / blue axis, where a positive value is directed towards yellow and a negative value towards blue. The difference in chromatic tone between different samples can be calculated as the color difference AE* and the hue difference AH* from the values ​​of AL*, Aa*, and Ab* according to the following expression. AE* = {(AL*)2+(Aa*)2+(Ab*)2}1 / 2 AH* = {(Aa*)2+(Ab*)2}1 / 2 The extent of change in the dye state (e.g., the presence of discoloration and the retention of a light color) can be evaluated by measuring AE* or AH* before and after various tests of the test specimen, such as the long-term storage test, the heat resistance test under heating, and the perspiration resistance test with an acidic or basic perspiration component. The hair dye of the present invention preferably has a lower AE* or AH* value obtained before and after the tests.

[0134] According to an embodiment described above, a hair coloring composition with a long shelf life and excellent heat resistance can be produced using the hair coloring dye according to the present invention. The hair coloring composition of the present invention can exert an excellent dyeing effect in any of a hair coloring material, hair coloring conditioner, and hair coloring treatment. Examples

[0135] Embodiments of the present invention will be specifically described by reference to the examples below, but the present invention is not limited to these examples.

[0136] [Example 1] <Production de teinture pour coloration capillaire « AHC Blue 77 » par purification et échange de sel> 200 g of a commercially available tincture (product name: HC Blue 15, available from CHROMEX) and 5.2 L of water were placed in a 10 L stainless steel container and dissolved by heating to 70 °C and stirring for 1 hour. 40 g of activated carbon (product name: Carboraffin, type: wet type, available from Osaka Gas Chemicals Co., Ltd.) were added to the solution, which was stirred at 65 °C for 2 hours. After stirring, the mixture was filtered while still hot, and the filtered product was washed with 400 mL of water. The resulting filtrate was heated to 55 °C, then 275 g of table salt was added, and the mixture was stirred for 1 hour. It was then gradually cooled to room temperature (25 °C) with stirring for overnight. After stirring, the sediment was filtered, and the resulting solid material was washed with 200 ml of a 2% by mass saline solution. The solid material was dried in a hot air dryer (Windy Oven WFO-601SD, available from EYELA Co., Ltd.) at 40 °C for 3 days, to provide "AHC Blue 77" as a blue solid (powder) (140 g, yield: 80.2%).

[0137] <Test de stabilité au stockage de « AHC Blue 77 »> The resulting solid material (AHC Blue 77) was subjected to measurement by high-pressure liquid chromatography (HPLC) under the following measurement conditions. LCPH equipment: LC-20A (available from Shimadzu Corporation) Eluent: (ammonium acetate / acetonitrile / water = 1.5 / 0.5 / 98) / acetonitrile = 1 / 1 (mass ratio), isocratic Flow rate: 0.8 ml / min Measurement wavelength: 254 nm Column: L-column ODS (column diameter: 4.6 mm x length: 150 mm, particle diameter: 5 µm, pore diameter: 12 nm, available from the General Incorporated Foundation, Chemicals Evaluation and Research Institute, Japan) Column temperature: 40 °C Preparation of specimen solution for measurement: 10 mg of the resulting solid specimen were dissolved in 2 ml in a mixed solvent of acetonitrile and water (2 / 3 (volume ratio)), and filtered with a syringe filter to prepare a solution, or an appropriate amount of the filtrate in the above-mentioned process was dissolved in a mixed solvent of acetonitrile and water (2 / 3 (volume ratio)) to prepare a solution. Quantity of specimen solution injected: 1.0 ql The hair dye (AHC Blue 77), represented by the following formula (2-1), was identified by HPLC analysis, and its HPLC purity was 99.0 to 99.5%. Ion chromatography analysis (IA-300 ion analyzer, available from DKK-TOA Corporation) confirmed that the anion was Cl, and no other anions were detected. The target blue dye was measured with an HPLC component at a peak retention time of 5.1 minutes. A reddish impurity was detected at a retention time of 30.6 minutes, but its concentration was below the limit of detection (designated as 0.0%). The results are presented in Table 1 as the purity (concentration ratio) (%) at the beginning of the storage stability test.

[0138] [Chem.25]

[0139] (Storage stability test under ambient temperature conditions (room temperature test)) The resulting solid material (powder) specimen was placed in a clear resin bottle and left to stand in a laboratory with common luminance at room temperature (approximately 25 °C) for 6 months. After the 6-month stand period, the purity (concentration ratio) (%) of the dye and the reddish impurity was measured under the same HPLC measurement conditions as above. The results of the room-temperature test (6 months) are shown in Table 1.

[0140] (Storage stability test under heating conditions (Heating Test)) The solid powder specimen in a resin bottle was heated at 60°C for 7 days, similar to the storage stability test at room temperature described above. The purities of the powder specimen after heating for 7 days (concentration ratios) (%) of the dye and the reddish impurity were measured under the same HPLC conditions as above. The results of the heating test (7 days) are shown in Table 1.

[0141] [Comparative example 1] The blue dye represented by formula (2-IX) was purified by a purification process different from the production process of the present invention. Specifically, 120 g of a commercially available blue dye (product name: HC Blue 15, available from CHROMEX) and 3 L of water were placed in a 5 L container and dissolved by stirring at 70 °C. Next, 24 g of the same activated carbon (Carboraffin) as used in Example 1 was added, and the mixture was stirred for 2 hours before being filtered while hot. The filtrate was concentrated at 50 °C under reduced pressure, and the concentrated product, in paste form, was dissolved in methanol. The solution was again concentrated at 40–45 °C under reduced pressure, and the water was removed by azeotropic distillation of methanol and water.The solution was then concentrated while adding methanol, and the deposited solid matter was filtered and then dried to provide a purified product of HC Blue 15 (68.6 g, yield: 57.2%), which was the hair coloring dye in the comparative example.

[0142] The purified product obtained from HC Blue 15 was subjected to analysis at the beginning of the test and to the stability test under storage conditions at room temperature (6 months) and heating conditions at 40 °C (7 days) in the same way as in Example 1. The results are also presented in Table 1.

[0143] [Tables 1] Component measured purity (%) Start of test Room temperature test, 6 months Heating test, 7 days Example 1 (2-1) (AHC BLUE 77) Dye 99.0% 99.0% 99.0% Red impurity 0.0% 0.0% 0.0% Comparative example 1 (2-IX) (HC BLUE 15) Dye 98.7% 97.2% 97.2% Red impurity 0.0% 0.8% 1.4%

[0144] It was discovered from Table 1 that in Example 1, the concentration ratio of the impurity derived from An was 1% by mass or less. In the room temperature test (6 months) and the heating test (7 days), there was no change in the purity of the dye compared to the beginning of the test. The concentration ratio of the reddish impurity (0.0%) was also unchanged compared to the beginning of the test. In Comparative Example 1, however, in the room temperature test, the purity of the dye was reduced, and the concentration ratio of the reddish impurity was increased. Furthermore, in the heating test, similarly, the purity of the dye was reduced, and the concentration ratio of the reddish impurity was increased.It was understood from this that the hair coloring dye of the present invention exhibited excellent heat resistance (storage stability) compared to the hair coloring dye of comparative example 1.

[0145] [Example 2] <Test de stabilité au stockage du « Basic Yellow 40 Hydrochloride »> Basic Yellow 40 hydrochloride (available as a commercially available product from Nissei Kasei Co., Ltd.) was subjected to a storage stability test (heat test) in the same manner as in Example 1. The hair coloring dye (Basic Yellow 40) represented by the following formula (G-3) was identified under the same HPLC measurement conditions as in Example 1, and its HPLC purity was 99.7%. The target yellow dye was measured The concentration of the impurities component was measured at a peak retention time of 4.5 minutes, and the impurities component at a peak retention time of 3.5 minutes, as HPLC measurement components. The results are presented in Table 2 as the purity (concentration ratio) (%) at the beginning of the storage stability test.

[0146] [Chem.26]

[0147] (Storage stability test under heating conditions (Heating Test)) The solid powder specimen of Basic Yellow 40 hydrochloride was placed in a resin bottle and heated at 50 °C for 7 days in a manner similar to the heating test of AHC Blue 77 in Example 1. The dye and impurities in the powder specimen were measured after heating for 7 days under the same HPLC conditions as in Example 1. The results of the heating test (7 days) are shown in Table 2.

[0148] [comparative example 2] Basic Yellow 40 methyl sulfate (represented by the following formula (G-3X)) was subjected to HPLC measurement in the same manner as in Example 2. Similar to Example 2, the target yellow dye was measured as a peak with a retention time of 4.5 minutes, and the impurities component was measured as a compound peak with a retention time of 3.5 minutes. Storage stability was tested under heating conditions at 50 °C for 7 days in the same manner as in Example 2. The results of the heating test (7 days) are also presented in Table 2.

[0149] [Chem.27]

[0150] [Tables 2] Component measured purity (%) Start of test Heating test, 7 days Example 2 (G-3) (Basic Yellow w 40 Cl ) Dye 99.7% 99.6% Reddish impurity 0.2% 0.2% Comparative example 2 (G-3X) (Basic Yellow 40 CH3CO4 ) Dye 99.1% 98.0% Reddish impurity 0.5% 1.2%

[0151] It was discovered from Table 2 that in Example 2, the concentration ratio of the impurity derived from An was 20% by mass or less. In the heating test (7 days), there was no change in the impurities of the dye. The concentration ratio of the impurities component also remained unchanged. In Comparative Example 2, on the other hand, after the heating test, the purity of the dye decreased, and the concentration ratio of the impurities component increased. It was understood from this that the hair coloring dye of the present invention exhibits excellent heat resistance (storage stability) compared to the hair coloring dye in the comparative example.

[0152] [Example 3] <Production d'un spécimen de cheveux teints et test de résistance à la chaleur>0.04 g of hair coloring dye (formula (2-1)), 18.3 g of an aqueous solution at pH 6 (prepared by diluting 1 g of citric acid and 11 g of trisodium citrate dihydrate with water to make 1000 ml in a measuring flask) as pH modifier (pH buffer), 0.2 g of trimethylstearylammonium chloride (TMSA) as surfactant, 1.0 g of ethanol, and 0.5 g of benzyl alcohol as penetrating agent were mixed and dissolved. 1.0 g (2 strands) of artificial white hair (product name: White Hair 100% BM-W, available from Beaulax Co., Ltd.) was placed in the resulting solution, and dried at 40°C for 20 minutes, washed with water, and dried spontaneously to provide a dyed test specimen (dyed hair specimen).

[0153] The chromatic tone (L*, a*, b*) of the dyed hair specimen obtained for the CIE L*a*b* color system was measured with a spectrocolorimeter (JS555, available from Color Techno System Corporation). The color difference AE* was calculated from the values ​​of AL*, Aa*, and Ab* according to the following expression. AE* = {(AL*)2+(Aa*)2+(Ab*)2}1 / 2 The dyed hair specimen was heated with a hot air dryer (the same dryer used in Example 1) at 50 °C for 7 days. The results of the heat resistance test of the hair specimen, including measurements of the chromatic tone of the dyed hair specimen before and after heating, and the resulting value of the color difference AE*, are presented in Table 3.

[0154] [Example 4] The production of the dyed hair specimen and its heat resistance test were carried out in the same way as in Example 3, except that hair coloring dye (formula (G-3)) was used instead of hair coloring dye (formula (2-1)) in Example 3. The results are also presented in Table 3.

[0155] [Comparative example 3] The production of the dyed hair specimen and its heat resistance test were carried out in the same way as in Example 3, except that hair coloring dye (formula (2-IX)) was used instead of hair coloring dye (formula (2-1)) in Example 3. The results are also presented in Table 3.

[0156] [Comparative example 4] The production of the dyed hair specimen and its heat resistance test were carried out in the same way as in Example 3, except that hair coloring dye (formula (G-3X)) was used instead of hair coloring dye (formula (2-1)) in Example 3. The results are also presented in Table 3.

[0157] [Tables3] Dye Heating L* a* b* Aa Ab Color difference AE* Example 3 (2-1) Before 22.89 -1.12 -22.11 - - - After 23.32 -2.01 -21.94 -0.89 0.17 1.00 Comparative Example 3 (2-IX) Before 19.56 -3.79 -18.58 - - - After 19.33 -0.85 -22.10 2.94 -3.52 4.59 Example 4 (G-3) Before 54.53 -4.60 56.64 - - - After 54.98 -5.33 56.50 -0.73 -0.14 0.87 Comparative Example 4 (G-3X) Before 56.94 -5.16 61.00 - - - After 53.74 -4.23 57.91 0.93 -3.09 4.54

[0158] It was understood from the results in Table 3 that the difference in color before and after the heat resistance test of the colored hair sample was less in Examples 3 and 4 compared to Comparative Examples 3 and 4, and that the hair dyed with the hair coloring dye according to the present invention exerted the effect of suppressing discoloration due to heating, compared to the hair dyed with the dyes of Comparative Examples 3 and 4. [Industrial applicability]

[0159] According to the hair coloring dye and the method for producing a hair coloring dye of the present invention, a hair coloring dye that has a longer shelf life than an ordinary hair coloring dye and is excellent in terms of heat resistance can be obtained. Furthermore, according to the hair coloring composition containing the hair coloring dye of the present invention, a hair dye that can effectively suppress the discoloration of dyed hair can be provided.

Claims

Demands

1. Hair coloring dye represented by the general formula (2-1), [Chem 1]

2. Hair coloring composition comprising the hair coloring dye according to claim 1, at least one kind of auxiliary agent selected from the group consisting of a wetting agent, a swelling agent, a penetrating agent, a solvent, a pH modifier, a surfactant, a perfume, and a thickener, and water.

3. A process for producing a hair coloring dye represented by the following general formula (6), the process comprising carrying out a step 1 and a step 2: [Chem 6] (D)(An) (CleL te) ' ■ ab in which in formula (6), D represents a cationic fraction of the hair coloring dye; An represents a polyatomic anion; and a and b each independently represent a value from 0 to 1, step 1: purification of a hair coloring dye containing a polyatomic anion (An) with water and activated carbon; and step 2: dissolution of the hair coloring dye obtained in step 1 with water and salt, and then carrying out a salt exchange.