Triarylmethane dye, colored composition containing that dye, coloring agent for color filter, and color filter

Abstract

To provide: a triarylmethane dye excellent in heat resistance; and a coloring agent for a color filter having favorable color characteristics by means of a colored composition using the dye.SOLUTION: The invention provides: a triarylmethane dye represented by the general formula (1) in the figure; a colored composition containing the dye; a coloring agent for a color filter; and a color filter. (In the formula (1), R1 to R4 each represent H, an alkyl group, or an aromatic hydrocarbon group; R5 and R6 each represent H, a halogen atom, OH, CF3, NO2, CN, an alkyl group, an alkoxy group, or an aryloxy group; AH represents a heterocyclic group; An represents an anion; and m represents a natural number.)SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a triarylmethane colorant, a coloring composition containing the colorant, a colorant for color filters containing the colorant or the coloring composition, and a color filter using the colorant. [Background technology]

[0002] Liquid crystal display devices, organic electroluminescent (OLED) display devices, and solid-state imaging devices such as CCD and CMOS sensors use color filters, which have red (R), green (G), and blue (B) pixels. Color filters are typically made with pigments or dyes, but because they are exposed to high temperatures of over 200°C and UV radiation during production, pigments have generally been used, as they offer better heat and light resistance than dyes. For example, the blue pigment used to form the blue pixel area is typically an ε-type copper phthalocyanine pigment (CI Pigment Blue 15:6), with a small amount of purple dioxazine violet pigment (CI Pigment Violet 23) added for color adjustment, if necessary.

[0003] In recent years, there has been a trend toward power saving in image display devices, and there is an increasing demand for higher brightness color filters to improve backlight utilization efficiency. In particular, the blue pixel section has a relatively lower backlight utilization efficiency than the red and green pixel sections, and improvement is desired.

[0004] Pigments are generally insoluble in solvents, so they exist in the form of fine particles in color filters containing resins, etc. Therefore, color filters using pigments are known to have a decrease in brightness and an effect on color purity due to the reflection and scattering of transmitted light on the surface of the pigment particles, and also to have a decrease in the contrast ratio of color display devices due to the depolarization effect caused by reflection.

[0005] In order to solve the problem of reduced brightness and contrast ratio, the use of dyes alone as colorants, rather than just pigments, has been studied (for example, Patent Document 1). Because dyes are soluble in solvents, color filters using dyes have a reduced depolarizing effect compared to when pigments alone are used as colorants, and are excellent in spectral characteristics, which are expected to improve brightness, contrast, etc. For this reason, the use of dyes, which generally have better solubility than pigments, has attracted attention, particularly for color filters in the blue pixel portion.

[0006] In particular, triarylmethane dyes have good spectral properties, and for example, attempts to use triarylmethane dyes as colorants for color filters are described in Patent Documents 2 to 5. Furthermore, Patent Documents 3, 4, and 6 and Non-Patent Document 1 describe triarylmethane dyes having a heterocyclic skeleton, which have attracted attention because they exhibit excellent spectral properties and high stability. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Application Publication No. 6-75375 [Patent Document 2] Japanese Patent Application Laid-Open No. 2008-304766 [Patent Document 3] International Publication No. 2012 / 128318 [Patent Document 4] Japanese Patent Application Laid-Open No. 2015-28121 [Patent Document 5] Japanese Patent Application Laid-Open No. 2012-83652 [Patent Document 6] Japanese Patent Application Laid-Open No. 2003-165918 [Non-patent literature]

[0008] [Non-Patent Document 1] Helvetica, (US), February 13, 1985, Vol. 68, Issue 1, p. 64-71 [Non-patent document 2] Hiroshi Horiguchi, "Advanced synthetic dyes", Sankyo Publishing Co., Ltd., July 15, 1969, p.79-109 Summary of the Invention [Problem to be solved by the invention]

[0009] However, when color filters are produced using triarylmethane dyes of conventional structures as described in Patent Documents 1 to 3, there is a problem that the hue is easily changed due to the thermal history during the production process. High heat resistance is an important property required of colorants for color filters. Patent Documents 4 and 5 each describe triarylmethane dyes having specific structures as colorants for color filters with excellent heat resistance, but the heat resistance of both dyes is insufficient, and further improvement in heat resistance is desired. Patent Documents 3 and 6 and Non-Patent Document 1 explicitly describe triarylmethane dyes with excellent solvent resistance and light resistance, but make no mention of heat resistance. An object of the present invention is to provide a dye having superior heat resistance compared to conventional triarylmethane dyes, and to provide a colorant for color filters having good color properties (color gamut, brightness, contrast ratio, etc.) by using a coloring composition that uses the dye. [Means for solving the problem]

[0010] The present invention was achieved as a result of extensive research aimed at solving the above problems, and is summarized as follows.

[0011] 1. A triarylmethane dye represented by the following general formula (1):

[0012] [ka]

[0013] [In formula (1), R 1 ~R 4each independently represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent; R 5 , R 6 each independently represents a hydrogen atom, a halogen atom, —OH, —CF3, —NO2, —CN, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms which may have a substituent, or an aryloxy group having 6 to 20 carbon atoms which may have a substituent, A H represents a heterocyclic group represented by the following general formula (2): An represents an anion, and m represents a natural number.

[0014] [ka]

[0015] [In formula (2), X 1 is a nitrogen atom, CR 9 or NR 10 represents X 2 is CR 9 or NR 10 represents X 1 and X 2 At least one of the following is NR 10 represents R 7 ~R 9 are each independently a hydrogen atom, a halogen atom, -OH, -CF3, -NO2, -CN, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent; a linear, branched or cyclic alkenyl group having 2 to 20 carbon atoms which may have a substituent; a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms which may have a substituent; an aryloxy group having 6 to 20 carbon atoms which may have a substituent; an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent; an optionally substituted heterocyclic group having 5 to 20 ring atoms; -NR 11 R 12 , an acyl group having 1 to 20 carbon atoms which may have a substituent; a linear, branched or cyclic alkoxycarbonyl group having 2 to 20 carbon atoms which may have a substituent, or represents an aryloxycarbonyl group having 7 to 20 carbon atoms which may have a substituent, R 10 represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, a linear, branched or cyclic alkenyl group having 2 to 20 carbon atoms which may have a substituent; an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or represents an optionally substituted heterocyclic group having 5 to 20 ring atoms, R 11 and R 12 each independently represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or represents an optionally substituted heterocyclic group having 5 to 20 ring atoms, R 7 ~R 12 adjacent groups may be bonded to each other via a single bond, a double bond, a substituted or unsubstituted methylene group, an oxygen atom, or a sulfur atom to form a ring, The dashed line represents the bond to general formula (1).

[0016] 2. In the general formula (1), A H is a heterocyclic group represented by any one of the following general formulae (2-1) to (2-4):

[0017] [ka]

[0018] [In formula (2-1), R 7 ~R 10 is R in general formula (2) 7 ~R 10 and the adjacent R 7 and R 9 and R 8 and R 9 may each independently bond to each other via a single bond, a double bond, a substituted or unsubstituted methylene group, an oxygen atom, or a sulfur atom to form a ring, The dashed line represents the bond to general formula (1).

[0019] [ka]

[0020] [In formula (2-2), R 7 ~R 10 is R in general formula (2) 7 ~R 10 and the adjacent R 7 and R 9 may be bonded to each other via a single bond, a double bond, a substituted or unsubstituted methylene group, an oxygen atom, or a sulfur atom to form a ring, The dashed line represents the bond to general formula (1).

[0021] [ka]

[0022] [In formula (2-3), R 7 , R 8 and R 10 is R in general formula (2) 7 , R 8 and R 10The dashed line represents the bond to general formula (1).

[0023] [ka]

[0024] [In formula (2-4), R 13 and R 15 ~R 18 is R in general formula (2) 7 ~R 9 represents a group similar to 14 represents a hydrogen atom, and the dashed line represents the bond to general formula (1).

[0025] 3. In the general formula (1), A H is a heterocyclic group represented by the general formula (2-1), and R 7 , R 8 and R 10 are each independently an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, and R 9 is a hydrogen atom.

[0026] 4. In the general formula (1), A H is a heterocyclic group represented by the general formula (2-1), and R 7 is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may have a substituent, and R 8 and R 10 are each independently an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, and R 9 is an acyl group having 1 to 10 carbon atoms which may have a substituent, a linear, branched or cyclic alkoxycarbonyl group having 2 to 10 carbon atoms which may have a substituent, or an aryloxycarbonyl group having 7 to 10 carbon atoms which may have a substituent.

[0027] 5. In the general formula (1), A H is a heterocyclic group represented by the general formula (2-1), and R 7 is an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, and R 8 is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may have a substituent, and R 9 is a hydrogen atom, and R 10 is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.

[0028] 6. In the general formula (1), A H is a heterocyclic group represented by the general formula (2-2), and R 7 and R 9 are each independently a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may have a substituent, and R 8 and R 10 are each independently a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.

[0029] 7. In the general formula (1), A H is a heterocyclic group represented by the general formula (2-3), and R 7 But-NR 11 R 12 and R 8 and R 10 are each independently a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, and R 11 and R 12are each independently a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.

[0030] 8. In the general formula (1), A H is a heterocyclic group represented by the general formula (2-4), and R 13 is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.

[0031] 9. In the general formula (1), R 1 and R 2 are each independently a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may have a substituent, and R 3 and R 4 and each independently represent an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.

[0032] 10. The triarylmethane dye according to 1 above, wherein in the general formula (1), An is a perfluoroalkylsulfonate anion, a perfluoroalkylsulfonimide anion, a tris(trifluoromethanesulfonyl)methide anion, or a heteropolyacid anion.

[0033] 11. The triarylmethane dye according to 1 above, wherein the maximum absorption wavelength in the absorption band in the ultraviolet-visible absorption spectrum (wavelength range of 350 to 800 nm) measured at 23 to 27°C using a propylene glycol monomethyl ether (PGME) solution of the triarylmethane dye is in the wavelength range of 570 nm to 640 nm.

[0034] 12. A coloring composition containing the triarylmethane colorant described in any one of 1. to 11.

[0035] 13. A colorant for color filters containing the coloring composition according to 12 above.

[0036] 14. A color filter using the colorant for color filters described in 13 above. [Effects of the Invention]

[0037] The triarylmethane dye of the present invention is excellent in spectral properties and heat resistance, and a colored composition containing the dye is useful as a colorant for color filters. DETAILED DESCRIPTION OF THE INVENTION

[0038] Hereinafter, embodiments of the present invention will be described in detail. Note that the present invention is not limited to the following embodiments and can be practiced with various modifications within the scope of the gist. First, the triarylmethane dye represented by the general formula (1) will be described.

[0039] In general formula (1) and general formula (2), R 1 ~R 12Specific examples of the "straight-chain, branched or cyclic alkyl group having 1 to 20 carbon atoms" in the "straight-chain, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent" include straight-chain alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group and dodecyl group; isopropyl group, isobutyl group, s-butyl group, t-butyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylpropyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, 1-methylpentyl group, 2-methylpentyl ... Examples include branched alkyl groups such as pentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethyl-1-methylpropyl, isooctyl, and 2-ethylhexyl; cyclic alkyl groups (cycloalkyl groups) such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, 2-ethylcyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl; norbornyl, 1-adamantyl, 2-adamantyl, and bicyclo[4.3.0]nonyl. It will be understood by those skilled in the art that the lower limit of the carbon number of a "branched or cyclic alkyl group" is the number of carbon atoms that allows the group to have a branched or cyclic structure (i.e., 3 carbon atoms).

[0040] In general formula (1) and general formula (2), R 1 ~R 4 and R 7 ~R 12Specific examples of the "aromatic hydrocarbon group having 6 to 20 carbon atoms" in the "aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent" represented by the formula (1) include aromatic hydrocarbon groups such as a phenyl group, a biphenylyl group, a terphenylyl group, a naphthyl group, an azulenyl group, an anthryl group, a phenanthryl group, a fluorenyl group, an indenyl group, a pyrenyl group, a perylenyl group, a fluoranthenyl group, and a triphenylenyl group. In the present invention, the "aromatic hydrocarbon group" also includes an aryl group or a condensed polycyclic aromatic group.

[0041] In general formula (1) and general formula (2), R 5 ~R 10 Examples of the "halogen atom" represented by the formula (I) include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. The "halogen atom" is preferably a fluorine atom or a chlorine atom.

[0042] In general formula (1) and general formula (2), R 5 ~R 9 Specific examples of the "straight-chain, branched, or cyclic alkoxy group having 1 to 20 carbon atoms" in the "straight-chain, branched, or cyclic 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, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, and decyloxy; branched alkoxy groups such as isopropoxy, isobutoxy, s-butoxy, t-butoxy, and isooctyloxy; cyclic alkoxy groups (cycloalkoxy groups) such as cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, cyclooctyloxy, cyclononyloxy, and cyclodecyloxy; and 1-adamantyloxy and 2-adamantyloxy groups.

[0043] In general formula (1) and general formula (2), R 5 ~R 9Specific examples of the "aryloxy group having 6 to 20 carbon atoms" in the "aryloxy group having 6 to 20 carbon atoms which may have a substituent" represented by the formula (1) include a phenyloxy group, a tolyloxy group, a biphenylyloxy group, a naphthyloxy group, an anthryloxy group, and a phenanthryloxy group.

[0044] In general formula (2), R 7 ~R 10 Specific examples of the "straight-chain, branched or cyclic alkenyl group having 2 to 20 carbon atoms" in the "straight-chain, branched or cyclic alkenyl group having 2 to 20 carbon atoms which may have a substituent" represented by the formula (1) include alkenyl groups such as a vinyl group, an allyl group, a 1-propenyl group, a 1-butenyl group, a 2-butenyl group, a 1-pentenyl group, a 1-hexenyl group, an isopropenyl group and an isobutenyl group.

[0045] In general formula (2), R 7 ~R 12Specific examples of the "heterocyclic group having 5 to 20 ring atoms" in the "heterocyclic group having 5 to 20 ring atoms which may have a substituent" represented by the formula (I) include a pyridyl group, a pyrimidinyl group, a quinolyl group, an isoquinolyl group, a pyrazinyl group, a triazinyl group, an acridinyl group, a phenanthrolinyl group, a carbolinyl group, a purinyl group, a naphthyridinyl group, a phthalazinyl group, a quinoxalinyl group, a quinazolyl group, a cinnolinyl group, a pteridinyl group, a phenanthridinyl group, a perimidinyl group, an anthyridinyl group, a pyrrolyl group, a pyrazolyl group, an imidazolyl group, a triazolyl group, a tetrazolyl group, a dihydropyrrolopyrrolyl group, an indolyl group, an isoindolyl group, an indolizinyl group, an indazolyl group, a benzimidazolyl group, a benzotriazolyl group, a carbazolyl group, an azaindolyl ... Examples of heterocyclic groups (or heteroaromatic hydrocarbon groups) include a dazolyl group, a pyrazolopyrimidinyl group, an adenyl group, a guanidinyl group, a phenazinyl group, a furyl group, a thienyl group, a benzofuranyl group, an isobenzofuranyl group, a benzothienyl group, an isobenzothiophenyl group, a dibenzofuranyl group, a dibenzothienyl group, an oxazolyl group, an isoxazolyl group, a thiazolyl group, an isothiazolyl group, an oxadiazolyl group, a thiadiazolyl group, a furopyrrolyl group, a thienopyrrolyl group, a benzoxazolyl group, a benzisoxazolyl group, a benzothiazolyl group, a benzisothiazolyl group, a benzothiadiazolyl group, a phenoxathiinyl group, an imidazopyridyl group, an oxazolopyridyl group, an oxazolopyrazyl group, a benzo[1,2-b:4,5-b']dithiophenyl group, and a bipyridinyl group. In the present invention, the term "heterocyclic group" includes a heteroaryl group and a condensed polycyclic aromatic heterocyclic group.

[0046] In general formula (2), R 7 ~R 9 Represented by "-NR 11 R 12 " means "R 11 and R 12 "R" represents an amino group having 11 and R 12 The term "amino group having the formula" refers to "an unsubstituted amino group, or a mono- or di-substituted amino group having 1 to 20 carbon atoms which may have a substituent." In the "mono-substituted amino group or di-substituted amino group having 1 to 20 carbon atoms which may have a substituent," the "mono-substituted amino group" refers to "—NR 11 R 12 "In "R 11 and R 12 " represents an amino group in which one of the groups is a hydrogen atom and the other is a group other than a hydrogen atom, and a "disubstituted amino group" is "—NR 11 R 12 "In "R 11 and R 12 " each independently represents an amino group other than a hydrogen atom. In the "mono- or di-substituted amino group having 1 to 20 carbon atoms which may have a substituent," the term "optionally substituted" means "-NR 11 R 12 "In "R 11 and R 12 " indicates that the group may have a substituent, and "R 11 and R 12 "The "substituent" in " is R 7 ~R 9 The same applies to the "substituents" in each group represented by the following formula: Specific examples of the monosubstituted amino group include an ethylamino group, a butylamino group, an acetylamino group, a phenylamino group, etc. Specific examples of the disubstituted amino group include a dialkylamino group having 2 to 20 carbon atoms, such as a dimethylamino group, a diethylamino group, a dipropylamino group, a dibutylamino group, a dihexylamino group, and a bis(2-methoxyethyl)amino group; a dialkenylamino group having 4 to 20 carbon atoms, such as a diallylamino group; a diphenylamino group, an N-acetyl-N-phenylamino group, and an (n-butyl)-N-phenylamino group.

[0047] In general formula (2), R 7 ~R 9 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 (I) is "-(C=O)-R 19 " means a group represented by the formula "R 19 is R 11and R 12 Specific examples of the "acyl group having 1 to 20 carbon atoms" include acyl groups such as formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, isovaleryl, pivaloyl, hexanoyl, octanoyl, chloroacetyl, trifluoroacetyl, cyclopentanecarbonyl, cyclohexanecarbonyl, benzoyl, methoxybenzoyl, chlorobenzoyl, nicotinoyl, furancarbonyl, and thiophenecarbonyl.

[0048] In general formula (1), R 7 ~R 9 In the "linear, branched or cyclic alkoxycarbonyl group having 2 to 20 carbon atoms which may have a substituent" or "aryloxycarbonyl group having 7 to 20 carbon atoms which may have a substituent" represented by the formula (I), the "linear, branched or cyclic alkoxycarbonyl group having 2 to 20 carbon atoms" or "aryloxycarbonyl group having 7 to 20 carbon atoms" is "-(C=O)-O-R 19 " means a group represented by the formula "R 19is as defined above. Specific examples of the "aryloxycarbonyl group having 7 to 20 carbon atoms" include a carboxy group, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, a pentyloxycarbonyl group, a hexyloxycarbonyl group, a heptyloxycarbonyl group, an octyloxycarbonyl group, a nonyloxycarbonyl group, a decyloxycarbonyl group, an isopropoxycarbonyl group, an isobutoxycarbonyl group, an s-butoxycarbonyl group, a t-butoxycarbonyl group, an isooctyloxycarbonyl group, a cyclopropyloxycarbonyl group, a methyl ... Examples of oxycarbonyl groups (ester groups) include a cyclobutoxycarbonyl group, a cyclopentyloxycarbonyl group, a cyclohexyloxycarbonyl group, a cycloheptyloxycarbonyl group, a cyclooctyloxycarbonyl group, a cyclononyloxycarbonyl group, a cyclodecyloxycarbonyl group, a 1-adamantyloxycarbonyl group, a 2-adamantyloxycarbonyl group, a phenyloxycarbonyl group, a naphthyloxycarbonyl group, a pyridyloxycarbonyl group, and a benzyloxycarbonyl group.

[0049] In general formula (1) and general formula (2), R 1 ~R 12 It is represented by either "a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent"; "a linear, branched or cyclic alkenyl group having 2 to 20 carbon atoms which may have a substituent", "an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent"; "an optionally substituted heterocyclic group having 2 to 20 carbon atoms"; "a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms which may have a substituent"; "an aryloxy group having 6 to 20 carbon atoms which may have a substituent", "a mono- or di-substituted amino 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", "a linear, branched or cyclic alkoxycarbonyl group having 2 to 20 carbon atoms which may have a substituent", or The "substituent" in the "aryloxycarbonyl group having 7 to 20 carbon atoms which may have a substituent" is specifically Deuterium atom, hydroxy group (―OH), thiol group (―SH), cyano group (―CN), nitro group (―NO2), trifluoromethyl group (―CF3), carbonyl group (―(C=O)―); Halogen atoms such as fluorine, chlorine, bromine, and iodine atoms; A linear or branched alkyl group having 1 to 20 carbon atoms; a cycloalkyl group having 3 to 20 carbon atoms; a linear or branched alkenyl group having 2 to 20 carbon atoms; a linear or branched alkynyl group having 2 to 20 carbon atoms; a linear or branched alkoxy group having 1 to 20 carbon atoms; a cycloalkoxy group having 3 to 20 carbon atoms, a 1-adamantyloxy group, or a 2-adamantyloxy group; an aromatic hydrocarbon group or a condensed polycyclic aromatic group having 6 to 20 carbon atoms; heterocyclic groups having 2 to 20 carbon atoms; an aryloxy group having 6 to 20 carbon atoms; Unsubstituted amino groups; mono- or di-substituted amino groups having 1 to 20 carbon atoms; —COOH, —COOM, an acyl group having 1 to 20 carbon atoms which may have a substituent; an alkoxycarbonyl group having 2 to 20 carbon atoms; an aryloxycarbonyl group having 7 to 20 carbon atoms; an amide group having 1 to 20 carbon atoms (carbamoyl group); Examples include —SO3H, —SO3M, and a sulfonyl group or sulfonamide group (sulfamoyl group) having 0 to 20 carbon atoms which may have a substituent (wherein M represents an inorganic cation or an organic cation). These "substituents" may be present in only one group or in multiple groups, and when multiple "substituents" are present, they may be the same or different. Furthermore, in groups having these "substituents," when there are multiple possible positions at which the "substituents" are bonded, such as any of the four carbon atoms in an n-butyl group or the para, meta, or ortho positions in a phenyl group, the "substituents" may be substituted at any of these positions. When there are multiple possible positions at which the "substituents" can become bonds, such as in a pyridyl group or naphthyl group, the "substituents" may be bonded at any of these positions. Furthermore, these "substituents" may further have the substituents exemplified above. Therefore, these "substituents" may be expressed, for example, as "a linear or branched, unsubstituted or substituted alkyl group having 1 to 20 carbon atoms," "an unsubstituted or substituted cycloalkyl group having 3 to 20 carbon atoms," "a linear or branched, unsubstituted or substituted alkenyl group having 2 to 20 carbon atoms," "a linear or branched, alkynyl group having 2 to 20 carbon atoms," "an unsubstituted or substituted cycloalkoxy group having 3 to 20 carbon atoms," "an unsubstituted or substituted aryloxy group having 6 to 20 carbon atoms," "an unsubstituted or substituted amino group having 0 to 20 carbon atoms," "an unsubstituted or substituted amido group having 1 to 20 carbon atoms," "an unsubstituted or substituted ammonium group having 0 to 20 carbon atoms," "an unsubstituted or substituted phenyl group having 6 to 20 carbon atoms," "an unsubstituted or substituted phenoxy group having 6 to 20 carbon atoms," "a phenyl group having 6 to 20 carbon atoms substituted with a linear or branched alkyl group having 1 to 20 carbon atoms substituted with a halogen atom," etc. When the "substituent" contains a carbon atom, the carbon atom is counted in the above "1 to 20 carbon atoms," "2 to 20 carbon atoms," "6 to 20 carbon atoms," and "7 to 20 carbon atoms." Furthermore, these substituents may be bonded to each other via a single bond, a double bond, a substituted or unsubstituted methylene group, an oxygen atom, or a sulfur atom to form a ring.

[0050] In general formula (1) and general formula (2), R 1 ~R 12 In the above-mentioned various "groups" having "substituents" represented by the following formula, "A linear or branched alkyl group having 1 to 20 carbon atoms" "Cycloalkyl group having 3 to 20 carbon atoms" "A linear or branched alkenyl group having 2 to 20 carbon atoms", "a linear or branched alkynyl group having 2 to 20 carbon atoms"; "A linear or branched alkoxy group having 1 to 20 carbon atoms," "a cycloalkoxy group having 3 to 20 carbon atoms", "Aromatic hydrocarbon group or condensed polycyclic aromatic group having 6 to 20 carbon atoms", "a heterocyclic group having 2 to 20 carbon atoms", "An aryloxy group having 6 to 20 carbon atoms," "a mono- or di-substituted amino group having 1 to 20 carbon atoms", "An acyl group having 1 to 20 carbon atoms," "Alkoxycarbonyl group having 2 to 20 carbon atoms", "An aryloxycarbonyl group having 7 to 20 carbon atoms," "Amido group having 1 to 20 carbon atoms", or Specific examples of the "sulfonamide group having 0 to 20 carbon atoms" include: linear or branched alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, n-hexyl, 2-ethylhexyl, heptyl, octyl, isooctyl, nonyl, and decyl; cycloalkyl groups such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a cyclononyl group, and a cyclodecyl group; alkenyl groups such as vinyl, 1-propenyl, allyl, 1-butenyl, 2-butenyl, 1-pentenyl, 1-hexenyl, isopropenyl, and isobutenyl groups, or linear or branched alkenyl groups in which multiple alkenyl groups are bonded; Alkynyl groups such as ethynyl, propargyl, and butynyl groups, or straight-chain or branched alkynyl groups formed by bonding multiple alkynyl groups; mixed groups of alkenyl and alkynyl groups such as pent-3-en-1-ynyl and hex-2-en-4-ynyl groups; linear or branched alkoxy groups such as methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, isopropoxy, isobutoxy, s-butoxy, t-butoxy, and isooctyloxy; cycloalkoxy groups having 3 to 20 carbon atoms, such as a cyclopropoxy group, a cyclobutoxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cyclononyloxy group, and a cyclodecyloxy group; aromatic hydrocarbon groups or condensed polycyclic aromatic groups such as a phenyl group, a biphenylyl group, a terphenylyl group, a naphthyl group, an anthracenyl group (anthryl group), a tetracenyl group, a phenanthryl group, a fluorenyl group, an indenyl group, a pyrenyl group, a perylenyl group, a fluoranthenyl group, or a triphenylenyl group; heterocyclic groups such as thienyl, furyl (furanyl), pyrrolyl, thiazolyl, oxazolyl, imidazolyl, pyrazolyl, triazolyl, benzothienyl, benzofuranyl, indolyl, isoindolyl, benzothiazolyl, benzoxazolyl, benzimidazolyl, benzotriazolyl, purinyl, carbazolyl, dibenzothienyl, dibenzofuranyl, pyridyl, pyrimidinyl, triazinyl, quinolyl, isoquinolyl, naphthyridinyl, acridinyl, phenanthrolinyl, naphthyridinyl, and carbolinyl groups; aryloxy groups such as a phenyloxy group, a tolyloxy group, a biphenylyloxy group, a naphthyloxy group, an anthracenyloxy group, or a phenanthrenyloxy group; mono- or di-substituted amino groups having a linear or branched alkyl group, a cycloalkyl group, or an aromatic hydrocarbon group, such as a methylamino group, a dimethylamino group, a diethylamino group, an ethylmethylamino group, a dipropylamino group, a dibutylamino group, a di(2-ethylhexyl)amino group, a di-t-butylamino group, or a diphenylamino group; acyl groups such as formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, isovaleryl, pivaloyl, hexanoyl, octanoyl, chloroacetyl, trifluoroacetyl, cyclopentanecarbonyl, cyclohexanecarbonyl, benzoyl, methoxybenzoyl, chlorobenzoyl, nicotinoyl, furancarbonyl, and thiophenecarbonyl groups; Carboxy group, methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, pentyloxycarbonyl group, hexyloxycarbonyl group, heptyloxycarbonyl group, octyloxycarbonyl group, nonyloxycarbonyl group, decyloxycarbonyl group, isopropoxycarbonyl group, isobutoxycarbonyl group, s-butoxycarbonyl group, t-butoxycarbonyl group, isooctyloxycarbonyl group, cyclopropoxycarbonyl group, cyclobutoxycarbonyl group, cyclobutoxycarbonyl group, Oxycarbonyl groups (alkoxycarbonyl groups or aryloxycarbonyl groups) such as a cyclopentyloxycarbonyl group, a cyclohexyloxycarbonyl group, a cycloheptyloxycarbonyl group, a cyclooctyloxycarbonyl group, a cyclononyloxycarbonyl group, a cyclodecyloxycarbonyl group, a 1-adamantyloxycarbonyl group, a 2-adamantyloxycarbonyl group, a phenyloxycarbonyl group, a naphthyloxycarbonyl group, a pyridyloxycarbonyl group, or a benzyloxycarbonyl group; Amide groups such as unsubstituted amido groups, N-methyl amido groups, N-ethyl amido groups, Nn-propyl amido groups, N-isopropyl amido groups, N-hexyl amido groups, N-phenyl amido groups, N-naphthyl amido groups, N,N-dimethyl amido groups, N,N-diethyl amido groups, N-methyl-N-(2-hydroxyethyl) amido groups, N-methyl-N-phenyl amido groups, N-ethyl-N-phenyl amido groups, N-propyl-N-naphthyl amido groups, N-methyl-N-(4-methylphenyl) amido groups, and diphenyl amido groups; Examples of sulfonamide groups (sulfamoyl groups) include unsubstituted sulfonamide groups, N-methylsulfonamide groups, N-ethylsulfonamide groups, Nn-propylsulfonamide groups, N-isopropylsulfonamide groups, N-hexylsulfonamide groups, N-phenylsulfonamide groups, N-naphthylsulfonamide groups, N,N-dimethylsulfonamide groups, N,N-diethylsulfonamide groups, N,N-bis(2-hydroxyethyl)sulfonamide groups, N-methyl-N-phenylsulfonamide groups, N-ethyl-N-phenylsulfonamide groups, N-propyl-N-naphthylsulfonamide groups, N-methyl-N-(4-methylphenyl)sulfonamide groups, and diphenylsulfonamide groups.

[0051] In the general formula (1), when an "inorganic cation" or "organic cation" represented by "M" is present, the "organic cation" is specifically R 20 R 21 R 22 R 23 N + The ammonium ion is represented by the formula R 20 ~R 23 are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, and may be bonded to each other to form a ring. 20 ~R 23 For details of "substituents," "linear or branched alkyl groups having 1 to 20 carbon atoms," and "aromatic hydrocarbon groups having 6 to 20 carbon atoms," see R1 ~R 12 The same applies to M. Furthermore, examples of the "inorganic cation" include alkali metal ions such as lithium ion and sodium ion, and alkaline earth metal ions such as magnesium ion, calcium ion and barium ion. M is preferably an alkali metal ion.

[0052] In the general formula (1), when an "amide group having 1 to 20 carbon atoms which may have a substituent" is present, "-(C=O)-NR 11 R 12 " where R 11 and R 12 is as defined above.

[0053] In the general formula (1), when a "sulfonyl group or sulfonamide group having 0 to 20 carbon atoms which may have a substituent" is present, "-SO2-R 19 ” (or “―S(=O)2―R 19 ") or "—S(=O)2—NR 11 R 12 " means a group represented by "—SO2—R 19 ” (or “―S(=O)2―R 19 ") in R 19 , "-S(=O)2-NR 11 R 12 "R" 11 and R 12 is as defined above.

[0054] In the general formula (1), An is not particularly limited, and examples thereof include a halide ion or an organic anion. Cl - , Br - , I - ;(CF3SO2)2N - (or Tf2N - ), (CF3SO2)3C - (or Tf3C - ), (C2F5SO2)2N- , (C4F9SO2)2N - , (C6F5SO2)2N - , (C2F5)3F3P - , (CN)2N - , (CN)3C - , NC-S - , ; (C6H4SO3 - )O(C6H3(C 12 H 25 )(SO3 - ))、 C6H4(C 12 H 25 )(SO3 - );PF6 - , BF4 - ; (P.W. 12 O 40 ) 3- , (P2W 18 O 62 ) 6- , (SiW 12 O 40 ) 4- , (PMo 12 O 40 ) 3- , (SiMo 12 O 40 ) 3- , (P.W. 12-x Mo x O 40 ) 3- , (SiW 12-x Mo x O 40 ) 4- , (P2W 18-y Mo y O 40 ) 6- (wherein x represents an integer of 1 to 11, and y represents an integer of 1 to 17), and the like heteropoly acid anions; Alternatively, anions represented by the structural formulae (Z-1) to (Z-16) below may be used.

[0055] [ka]

[0056] [ka]

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[0059] In general formula (1), An may be a single anion or a combination of two or more different anions. An is preferably a single anion or any combination of two or three anions selected from the anions exemplified above, and more preferably a single anion or any combination of two or three anions selected from perfluoroalkylsulfonate anions (more preferably perfluoroalkylsulfonate anions having 1 to 24 carbon atoms), perfluoroalkylsulfonimide anions (more preferably perfluoroalkylsulfonimide anions having 1 to 24 carbon atoms), tris(trifluoromethanesulfonyl)methide anions, or heteropolyacid anions. Therefore, "m" in general formula (1) is selected from any natural number depending on the valence of the entire [An] in formula (1) and the valence of the cation in the triarylmethane skeleton structure within [ ] so that formula (1) is electrically neutral as a whole molecule. From the viewpoint of molecular design, An is preferably a single anion, and is preferably a perfluoroalkylsulfonimide anion or a heteropolyacid anion, and more preferably a trifluoromethanesulfonimide anion or a phosphotungstate anion (PW 12 O 40 3- ) is more preferable.

[0060] In the general formulas (2-1) to (2-4), R 7 ~R 9 , R 13and R 15 ~R 18 is R in general formula (2) 7 ~R 9 and R in the above general formula (2) represents the same group as 7 ~R 9 You can refer to the explanation and examples for

[0061] In the general formulas (2-1) to (2-3), R 10 is R in general formula (2) 10 and R in the above general formula (2) represents the same group as 10 You can refer to the explanation and examples for

[0062] In the general formulas (2-1) to (2-4), R 11 and R 12 is R in general formula (2) 11 and R 12 and R in the above general formula (2) represents the same group as 11 and R 12 You can refer to the explanation and examples for

[0063] Specific examples of compounds that are preferred as the triarylmethane dye of the present invention represented by general formula (1) are shown below, but the present invention is not limited to these compounds. The following formulas (B-1) to (B-87) represent the triarylmethane dye portion of general formula (1), and the anion portion represented by [An] is omitted. In the following structural formulas, some hydrogen atoms are omitted, and all possible stereoisomers and tautomers are included, and planar structural formulas are depicted.

[0064] [ka]

[0065] [ka]

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[0093] In general formula (1), R 1 ~R 4 R is preferably a "hydrogen atom," "a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may have a substituent," or "an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent." 1 and R 3 Preferably, one of R is a "linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms which may have a substituent," and more preferably the other is a "linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms which may have a substituent" or an "aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent." 2 and R 4It is preferable that one of R is a "linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may have a substituent," and the other is a "linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may have a substituent" or an "aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent." 1 and R 3 At least one of R is preferably a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may have a substituent, and R 2 and R 4 At least one of R is preferably a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may have a substituent. 1 ~R 4 Examples of the aryl group include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an i-butyl group, a 2-ethylhexyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group, a methylphenyl group, a methoxyphenyl group, a difluorophenyl group, a dichlorophenyl group, a dimethylphenyl group, a mesitylene group (a 2,4,6-trimethylphenyl group), a 1-naphthyl group, and a 2-naphthyl group.

[0094] In general formula (1), R 5 and R 6 As R, "hydrogen atom", "halogen atom", or "straight-chain, branched or cyclic alkyl group having 1 to 10 carbon atoms which may have a substituent" is preferred, and "hydrogen atom", "fluorine atom", "chlorine atom", or "straight-chain, branched or cyclic alkyl group having 1 to 4 carbon atoms which may have a substituent" is more preferred. 5 and R 6 Examples of R include hydrogen atoms, fluorine atoms, chlorine atoms, methyl groups, ethyl groups, n-propyl groups, and i-propyl groups. From the viewpoint of molecular design, R 5 and R 6 are preferably the same group.

[0095] In general formula (2), R 7 and R8 Examples of the alkyl group include "a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may have a substituent," "a linear, branched or cyclic alkenyl group having 2 to 20 carbon atoms which may have a substituent," "an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent," and "—NR 11 R 12 " is preferred, and "a branched alkyl group having 1 to 10 carbon atoms which may have a substituent", "an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent", or "—NR 11 R 12 " is more preferred. Preferred R 7 and R 8 Examples of the aryl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a t-butyl group, a vinyl group, a propenyl group, a phenyl group, a fluorophenyl group, a chlorophenyl group, a methylphenyl group, a methoxyphenyl group, a dichlorophenyl group, a dimethylphenyl group, a mesitylene group, a naphthyl group, a methylamino group, an ethylamino group, a phenylamino group, a dimethylamino group, a diethylamino group, a dipropylamino group, an N-ethyl-phenylamino group, an N-ethyl-(4-fluorophenyl)amino group, and an N-ethyl-(2-methylphenyl)amino group.

[0096] In general formula (2), R 9 As R, "hydrogen atom", "straight-chain, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent", or "straight-chain, branched or cyclic alkoxycarbonyl group having 2 to 20 carbon atoms which may have a substituent" are preferred. 9 Examples of the alkyl group include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a t-butyl group, a methoxycarbonyl group, an ethoxycarbonyl group, and a benzyloxycarbonyl group.

[0097] In general formula (2), R 10As R, "a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may have a substituent" or "an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent" is preferred. 10 Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an i-butyl group, a phenyl group, a fluorophenyl group, a chlorophenyl group, a methylphenyl group, a methoxyphenyl group, a difluorophenyl group, a dichlorophenyl group, a dimethylphenyl group, and a mesityl group.

[0098] In general formula (2), R 11 and R 12 As R, "hydrogen atom", "linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may have a substituent", or "aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent" is preferred. 11 and R 12 Examples of the alkyl group include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an i-butyl group, a phenyl group, a fluorophenyl group, a chlorophenyl group, a methylphenyl group, a methoxyphenyl group, a difluorophenyl group, a dichlorophenyl group, a dimethylphenyl group, and a mesityl group.

[0099] In general formula (1), A H In the general formulae (2-1) to (2-3), preferred R are heterocyclic groups represented by the following general formulae (2-1) to (2-4). 7 ~R 12 Examples of R in general formula (2) include 7 ~R 12 In the general formula (2-4), preferred R 13 ~R 18 Examples of R in general formula (2) include 7 ~R 12 You can refer to the explanation and examples for

[0100] In general formula (1), A H is a heterocyclic group represented by general formula (2-1), R7 and R 8 means "a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent", "an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent", or "—NR 11 R 12 " is preferably "a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may have a substituent" or "an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent" is more preferred, and R 7 and R 8 It is particularly preferred that at least one of R is an "aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent." 9 is preferably a "hydrogen atom", "a linear, branched or cyclic alkoxycarbonyl group having 2 to 20 carbon atoms which may have a substituent", or "an aryloxycarbonyl group having 7 to 20 carbon atoms which may have a substituent", more preferably a "hydrogen atom" or "a linear, branched or cyclic alkoxycarbonyl group having 2 to 10 carbon atoms which may have a substituent", and from the viewpoint of heat resistance, "a linear, branched or cyclic alkoxycarbonyl group having 2 to 10 carbon atoms which may have a substituent" is preferred. 10 is preferably a "linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent" or an "aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent", and more preferably an "aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent". 7 ~R 12 Preferred examples of R in general formula (2) include 7 ~R 12 You can refer to the explanation and examples for

[0101] In general formula (1), A H is a heterocyclic group represented by general formula (2-2), R 7 ~R 10is preferably a "hydrogen atom," "a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent," or "an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent." 7 ~R 10 Preferred examples of R in general formula (2) include 7 ~R 10 You can refer to the explanation and examples for

[0102] In general formula (1), A H is a heterocyclic group represented by general formula (2-3), R 7 "-NR 11 R 12 " is preferable. R 8 and R 10 ~R 12 is preferably a "linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent" or an "aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent", and more preferably a "linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent" or an "aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent". 11 and R 12 At least one of R is preferably an "aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent", and from the viewpoint of molecular design, R 11 and R 12 and at least one of R 10 It is preferable that R 8 and R 10 ~R 12The "substituent" in the "straight-chain, branched, or cyclic alkyl group of 1 to 20 carbon atoms which may have a substituent" or the "aromatic hydrocarbon group of 6 to 20 carbon atoms which may have a substituent" represented by any one of the above is preferably a deuterium atom, a hydroxy group (—OH), a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, a straight-chain or branched alkyl group of 1 to 10 carbon atoms, a cycloalkyl group of 3 to 10 carbon atoms, an aromatic hydrocarbon group or condensed polycyclic aromatic group of 6 to 10 carbon atoms, or a heterocyclic group of 2 to 10 carbon atoms, and more preferably a fluorine atom, a chlorine atom, a straight-chain or branched alkyl group of 1 to 10 carbon atoms, or an aromatic hydrocarbon group of 6 to 10 carbon atoms. 7 ~R 12 Preferred examples of R in general formula (2) include 7 ~R 12 You can refer to the explanation and examples for

[0103] In general formula (1), A H is a heterocyclic group represented by general formula (2-4), R 13 is preferably a "linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent" or an "aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent." 14 is preferably a hydrogen atom. 15 ~R 18 is preferably a "hydrogen atom," a "halogen atom," "-OH," "-CF3," "-NO2," "-CN," "a linear, branched or cyclic alkyl group of 1 to 20 carbon atoms which may have a substituent," "an aromatic hydrocarbon group of 6 to 20 carbon atoms which may have a substituent," or "a heterocyclic group of 5 to 20 ring atoms which may have a substituent," and more preferably a "hydrogen atom," "a halogen atom," "a linear or branched alkyl group of 1 to 20 carbon atoms which may have a substituent," or "an aromatic hydrocarbon group of 6 to 20 carbon atoms which may have a substituent." R 13 and R 15 ~R 18Preferred examples of R in general formula (2) include 7 ~R 12 You can refer to the explanation and examples for

[0104] The method for producing the triarylmethane dye compound represented by general formula (1) is not particularly limited, and can be produced by applying known methods (e.g., Non-Patent Document 2) using reagents having various groups corresponding to general formula (1) and general formula (2) or other appropriate reagents. One embodiment of the method for producing the compound of the present invention is described below. However, the present invention is not limited thereto.

[0105] The triarylmethane dye represented by general formula (1) can be obtained by a condensation reaction between a benzophenone derivative having a corresponding substituent and a heterocyclic compound having a corresponding substituent. Furthermore, if necessary, salt exchange with a salt having a corresponding structure can be performed to produce the triarylmethane dye represented by general formula (1). The chemical reaction in this production can be carried out in the presence of an aqueous solvent or an organic solvent, or can be carried out without a solvent.

[0106] The isolation and purification of each product in the production method of the present invention can be carried out by appropriately combining known methods used in conventional organic synthesis, such as purification by column chromatography; adsorption purification using silica gel, activated carbon, activated clay, etc.; and recrystallization or crystallization using a solvent. Furthermore, nuclear magnetic resonance analysis (NMR), absorbance measurement using a spectrophotometer, ultraviolet-visible absorption spectroscopy (UV-Vis), thermogravimetry-differential thermal analysis (TG-DTA), etc. can be used to identify, analyze, and evaluate the optical, thermal, and other physical properties of these compounds. These analytical methods can also be used to evaluate the solubility, color, and heat resistance of the resulting compounds.

[0107] The triarylmethane dye of the present invention may be used alone or in combination (e.g., mixed) with two or more types having different molecular structures. When two or more types are used, the mass concentration ratio of the one triarylmethane dye that is the smallest in the mass concentration ratio of the entire triarylmethane dye is 0.1 to 50 mass%. It is preferable that the type of triarylmethane dye is one or two types.

[0108] The triarylmethane dye of the present invention, the coloring composition containing the dye, and the colorant for color filters containing the dye or the coloring composition must be well dissolved or dispersed in an organic solvent containing a resin or the like during the production process of the colorant and the color filter. Therefore, it is preferable that the dye has high solubility and dispersibility in the organic solvent. The organic solvent is not particularly limited, but specific examples include aromatic hydrocarbons such as benzene, toluene, and xylene; ethers such as propylene glycol monomethyl ether acetate (PGMEA), methyl cellosolve acetate, ethyl cellosolve acetate, and propylene glycol monomethyl ether (PGME); ketones such as methyl ethyl ketone, acetone, cyclohexanone, 2-heptanone, and 3-heptanone; alcohols such as methanol, ethanol, 2-propanol, and propylene glycol; and 3-ethoxyethanol. Examples of suitable solvents include esters such as methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, ethyl acetate, butyl acetate, and methyl 3-methoxypropionate; diacetone alcohol (DAA); amides such as N,N-dimethylformamide (DMF) and N-methylpyrrolidone (NMP); and dimethyl sulfoxide (DMSO). PGME, PGMEA, cyclohexanone, and DAA are preferred, and PGME or PGMEA is particularly preferred from the viewpoint of achieving both resin solubility and triarylmethane dye solubility. These solvents may be used alone or in combination.

[0109] The triarylmethane dye of the present invention has excellent solubility in organic solvents, particularly in PGMEA, and its solubility in PGMEA is preferably 1% by mass or more, more preferably 3% by mass or more, and particularly preferably 5% by mass or more. In consideration of application to color filters with a high contrast ratio, the higher the solubility, the better.

[0110] The triarylmethane dye of the present invention has a maximum absorption wavelength, which indicates the greatest absorbance in the visible light region (e.g., a wavelength range of 350 to 800 nm) of the ultraviolet-visible absorption spectrum when measured at around room temperature (e.g., 23 to 27°C) using a solution prepared by dissolving the dye in an organic solvent. In the present invention, the maximum absorption wavelength in the PGME solution is preferably in the wavelength range of 550 to 650 nm, more preferably in the wavelength range of 570 to 640 nm. The dye concentration is preferably 0.005 to 0.02 mmol / L. The solvent is not limited as long as it can dissolve the dye, but it is preferably one in which the absorption wavelength in the ultraviolet-visible absorption spectrum does not shift significantly depending on the dissolution conditions, and PGME is preferred.

[0111] The triarylmethane dye of the present invention can be mixed with various resin solutions and coated on a glass substrate to prepare a coating film. The resulting coating film can be measured using a spectrophotometer to obtain the color value of the coating film, allowing color evaluation. The color value is measured using the CIE L * a * b * A color system such as the color value L of the film sample is generally used. * , a * , b * The color difference (ΔE * ab When applied to color filters, the color difference at temperatures around 230°C can be used as an index of heat resistance. ΔE * abThe smaller the value, the less discoloration due to thermal decomposition occurs and the higher the heat resistance, and it is preferably 10 or less, more preferably 8 or less, and even more preferably 6 or less. In addition, the heat resistance of dyes may be compared by evaluation using thermogravimetry. For example, the 5% mass loss temperature is measured by thermogravimetry under an inert gas atmosphere such as nitrogen, and a higher decomposition temperature is preferred.

[0112] The colorant for color filters of the present invention comprises a triarylmethane dye represented by general formula (1) or a coloring composition containing at least one such triarylmethane dye, and components commonly used in the manufacture of color filters. Typical color filters are obtained, for example, using a photolithography process. A liquid prepared by mixing a dye, pigment, or other dye with a resin component (including a monomer or oligomer) and a solvent is applied to a substrate such as glass or resin, photopolymerized using a photomask, and a colored pattern of a solvent-soluble / insoluble dye-resin composite film is formed. The resulting film is then washed and heated. Electrodeposition and printing processes also produce colored patterns using a mixture of a dye and a resin or other components. Therefore, specific components of the colorant for color filters of the present invention include at least one triarylmethane dye represented by general formula (1), other dyes or pigments, resin components, an organic solvent, and other additives such as a photopolymerization initiator. These components may be selected or omitted, and other components may be added as needed.

[0113] When the triarylmethane colorant of the present invention or a coloring composition containing the triarylmethane colorant is used as a colorant for a color filter, it may be used in a color filter of any color, but is preferably used as a colorant for a blue or green color filter.

[0114] In the colorant for color filters of the present invention, one or more triarylmethane colorants may be used alone, or in order to adjust the color tone, i.e., the spectral characteristics, known colorants such as other dyes or pigments as described below may be further mixed therewith.

[0115] When used as a colorant for a blue color filter, examples thereof include, but are not limited to, basic dyes such as CI Basic Blue 3, 7, 9, 54, 65, 75, 77, 99, 129, and CI Basic Violet 10; acid dyes such as CI Acid Blue 9 and 74 and CI Acid Red 52 and 289; disperse dyes such as Disperse Blue 3, 7, and 377; spiron dyes; cyanine-based, indigo-based, phthalocyanine-based, anthraquinone-based, methine-based, triarylmethane-based, indanthrene-based, oxazine-based, dioxazine-based, azo-based, and xanthene-based dyes not belonging to the present invention; and other blue lake pigments. When used as a colorant for a green color filter, examples thereof include, but are not limited to, green pigments such as CI Pigment Green 7, 10, 36, 47, 58, 59, 62, and 63; yellow pigments such as CI Pigment Yellow 83, 138, 139, 150, 180, and 185; spiron dyes; cyanine-based, indigo-based, phthalocyanine-based, anthraquinone-based, methine-based, triarylmethane-based, indanthrene-based, oxazine-based, dioxazine-based, azo-based, xanthene-based, isoindoline-based, and quinophthalone-based dyes not belonging to the present invention; and other lake pigments.

[0116] In the present invention, when used as a colorant for a blue color filter, the dye to be mixed to adjust the color tone is preferably a triarylmethane dye not belonging to the present invention, such as CI Basic Blue 7, or a xanthene dye, such as CI Basic Violet 10 or CI Acid Red 52 or 289. When used as a colorant for a green color filter, a quinophthalone dye, such as CI Pigment Yellow 138, an isoindoline dye, such as CI Pigment Yellow 139, or an azo dye. By using these dyes with a triarylmethane dye belonging to the present invention, it is possible to obtain a blue or green color filter having excellent brightness and contrast ratio.

[0117] The pigment may be subjected, as necessary, to a rosin treatment, a surface treatment using a pigment derivative into which an acidic group or a basic group has been introduced, a graft treatment onto the pigment surface using a polymer compound or the like, a microparticulation treatment using a sulfuric acid microparticle method or the like, a washing treatment using an organic solvent or water to remove impurities, a treatment to remove ionic impurities using an ion exchange method or the like, etc. It is preferable that the particle size of each pigment is uniform.

[0118] The mixing ratio of the other colorants in the colorant for color filters of the present invention is preferably 5 to 2000 mass % and more preferably 10 to 1000 mass % relative to the triarylmethane colorant (total of the triarylmethane colorants when two or more types are used). The mixing ratio of the colorant component such as a dye in the liquid colorant for color filters is preferably 0.5 to 70 mass % and more preferably 1 to 50 mass % relative to the total colorant.

[0119] As the resin component of the colorant for color filters of the present invention, any known resin can be used as long as it has the properties required for the manufacturing method and use of the color filter resin film formed using it. Specific examples include acrylic resins, olefin resins, styrene resins, polyimide resins, urethane resins, polyester resins, epoxy resins, vinyl ether resins, phenol (novolac) resins, other transparent resins, photocurable resins, and thermosetting resins. These monomers or oligomer components can be used in appropriate combination. Copolymers of these resins can also be used in combination. The resin content in these colorant for color filters, when used as a liquid colorant, is preferably 5 to 95% by mass, more preferably 10 to 50% by mass.

[0120] To enhance the performance of the coloring composition of the present invention as a colorant for color filters, other components of the compound may be added, such as surfactants, dispersants, antifoaming agents, leveling agents, antioxidants, UV absorbers, and other additives mixed during the production of color filter colorants. However, the content of these additives in the coloring composition is preferably an appropriate amount, and is preferably within a range that does not reduce the solubility of the coloring composition of the present invention in the solvent or increase it more than necessary, or that does not affect the effects of other additives of the same type used during the production of color filters. These additives can be added at any time during the preparation of the coloring composition.

[0121] Other additives in the colorant for color filters of the present invention include components necessary for polymerizing and curing resins, such as photopolymerization initiators and crosslinking agents, as well as surfactants and dispersants necessary for stabilizing the properties of components in the liquid colorant for color filters. Any of these additives may be known for use in color filter production, and are not particularly limited. The total mixing ratio of these additives to the total solid content of the colorant for color filters is preferably 5 to 60% by mass, more preferably 10 to 40% by mass. [Example]

[0122] Hereinafter, the embodiments of the present invention will be specifically explained by way of examples, but the present invention is not limited to the following examples. The reagents used in the synthesis examples were manufactured by Tokyo Chemical Industry Co., Ltd., Sigma-Aldrich, Alfa Aesar, Duksan, Daejung, etc. All reactions in the synthesis examples were carried out in a reaction vessel equipped with a condenser, a stirrer, and a thermometer, under a nitrogen stream unless otherwise specified. The identification of compounds in the synthesis examples below was carried out by 1 H-NMR analysis (Bruker nuclear magnetic resonance spectrometer, model: Ascend TM This was performed using a frequency of 400 MHz.

[0123] [Synthesis Example 1] Synthesis of Compound (C-1) The following reaction was carried out under airflow. A reaction vessel was charged with 35.7 g (333 mmol) of p-toluidine, 40.0 g (333 mmol) of acetophenone, 27.6 g (166 mmol) of potassium iodide, 21.1 g (83.2 mmol) of iodine, and 650 mL of chlorobenzene, and the mixture was stirred at 120°C for 5 days. The reaction mixture was cooled to room temperature, filtered under reduced pressure, and the solvent from the filtrate was evaporated under reduced pressure. 600 mL of 5% aqueous sodium thiosulfate solution and 600 mL of ethyl acetate were added to the resulting residue, and the mixture was stirred at room temperature (23-28°C), after which the organic layer was extracted. The mixture was dried over anhydrous magnesium sulfate, filtered under reduced pressure, and the solvent from the filtrate was evaporated under reduced pressure. The residue was purified by column chromatography (carrier: silica gel, solvent: n-heptane), and the solvent was evaporated under reduced pressure. The residue was dried under reduced pressure to obtain the following (Intermediate 100) (15.8 g, yield: 32%).

[0124] [ka]

[0125] The following reaction was then carried out under a nitrogen stream. A reaction vessel was charged with 35.0 g (139 mmol) of 4,4'-dichlorobenzophenone, 33.8 g (279 mmol) of 2,6-dimethylaniline, 37.5 g (390 mmol) of sodium t-butoxide, and 280 mL of xylene. While stirring at room temperature, 1.56 g (6.97 mmol) of palladium acetate and 6.64 g (13.9 mmol) of 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (XPhos) were added and stirred at 110 °C for 3 hours. After cooling the reaction mixture to room temperature, 200 mL of water and 50 mL of isopropanol were added, followed by stirring. The solid was then filtered off. The resulting solid was suspended and washed in 200 mL of water, and the solid was then filtered off. The obtained solid was dried under reduced pressure at 80°C to obtain the following (Intermediate 101) (55.0 g, yield 94%).

[0126] [ka]

[0127] Next, 150 g (357 mmol) of the (Intermediate 105) and 530 mL of dimethylformamide were added to a reaction vessel and cooled to 5°C while stirring. 120 g (1.07 mol) of potassium t-butoxide was slowly added to this solution, and then 167 g (1.07 mol) of iodoethane was added dropwise while maintaining the temperature at 5°C. After the dropwise addition, the temperature was raised to 35°C and stirred for 3 hours. This reaction solution was added dropwise to 3.0 L of a 10% aqueous sodium chloride solution, and the precipitated solid was collected by filtration. The obtained solid was suspended and washed in 1.5 L of water, and then the solid was collected by filtration. The obtained solid was suspended and washed in a mixed solvent of 500 mL of water and 1.0 L of methanol, and then the solid was collected by filtration. The obtained solid was dried under reduced pressure at 80°C to obtain the following (Intermediate 102) (152 g, yield 90%).

[0128] [ka]

[0129] Next, 23.1 g (48.5 mmol) of the (Intermediate 102) and 100 mL of toluene were placed in a reaction vessel and stirred at room temperature (23 to 28°C). 11.9 g (77.6 mmol) of phosphorus oxychloride was added dropwise thereto, and the mixture was stirred at room temperature (23 to 28°C) for 1 hour. 15.0 g (48.5 mmol) of the (Intermediate 100) was then added to this solution, and the mixture was stirred at 100°C for 5 hours. After the reaction solution was cooled to room temperature, 300 mL of dichloromethane and 100 mL of water were added, and the organic layer was extracted. Anhydrous magnesium sulfate was added, and the organic layer was dried, filtered, and the filtrate was concentrated under reduced pressure. The resulting residue was purified by column chromatography (carrier: silica gel, solvent: dichloromethane / methanol = 100 / 1 to 10 / 1 (volume ratio)), and the solvent was distilled off under reduced pressure. The residue was added to 90 mL of methanol and stirred to dissolve the solid, after which 17.4 g (60.6 mmol) of lithium bis(trifluoromethanesulfonyl)imide (LiN(SOCF)) was added. After stirring at 45°C for 1 hour, the mixture was cooled and the precipitated solid was collected by filtration. The resulting solid was dried under reduced pressure at 80°C to obtain the target compound (C-1) as a brown solid (48.5 g, 95% yield).

[0130] The obtained brown solid was subjected to NMR measurement, and the following 54 hydrogen signals were detected, identifying the structure as the compound represented by the following formula (C-1).

[0131] 1 H-NMR (400MHz, DMSO-d6): δ(ppm)=7.58(1H), 7.35-6.70(26H), 5.72(2H), 3.70(4H), 2.14(3H), 2.08-1.75(12H), 1.13(6H).

[0132] [ka]

[0133] [Synthesis Example 2] Synthesis of Compound (C-2) A reaction vessel was charged with 18.0 g (17.2 mmol) of the compound (C-1) and 680 mL of methanol. After dissolving the solid, a solution of 25.1 g of phosphotungstic acid hydrate in 230 mL of methanol was added dropwise. The solution was stirred at room temperature (23-28°C) for 1 hour, and the reaction solution was filtered. The resulting solid was suspended and washed in 200 mL of methanol, filtered, and then dried under reduced pressure at 80°C to obtain the target compound (C-2) as a blue solid (26.6 g, 90% yield).

[0134] The obtained blue solid was subjected to NMR measurement, and the following 162 hydrogen signals were detected, identifying the structure as the compound represented by the following formula (C-2).

[0135] 1 H-NMR (400MHz, DMSO-d6): δ(ppm)=7.58(3H), 7.35-6.70(78H), 5.72(6H), 3.70(12H), 2.14(9H), 2.08-1.75(36H), 1.13(18H).

[0136] [ka]

[0137] [Synthesis Example 3] Synthesis of Compound (C-3) The following (Intermediate 103) was obtained (3.99 g, yield 46%) in the same manner as in Synthesis Example 1 (Intermediate 100), except that acetophenone was changed to 4'-fluoroacetophenone.

[0138] [ka]

[0139] Subsequently, the same procedure as in Synthesis Example 1 for the synthesis of compound (C-1) was repeated, except that (Intermediate 100) was replaced with the above (Intermediate 103), to obtain the target compound (C-3) as a brown solid (4.26 g, yield 68%).

[0140] The obtained brown solid was subjected to NMR measurement, and the following 52 hydrogen signals were detected, identifying the structure as the compound represented by the following formula (C-3).

[0141] 1 H-NMR (400MHz, DMSO-d6): δ(ppm)=7.55(1H), 7.35-6.70(24H), 5.72(2H), 3.70(4H), 2.14(3H), 2.08-1.75(12H), 1.14(6H).

[0142] [ka]

[0143] [Synthesis Example 4] Synthesis of Compound (C-4) The following reaction was carried out under airflow. A reaction vessel was charged with 1.89 g (17.6 mmol) of p-toluidine, 4.00 g (23.5 mmol) of 1'-acetonaphthone, 0.98 g (5.88 mmol) of potassium iodide, 0.60 g (2.35 mmol) of iodine, and 40 mL of 1,1,2,2-tetrachloroethane, and the mixture was stirred at 120 °C for 18 hours. After cooling the reaction mixture to room temperature, 30 mL of 5% aqueous sodium thiosulfate solution was added. After stirring at room temperature (23-28 °C), 50 mL of dichloromethane was added, and the organic layer was extracted. After drying over anhydrous magnesium sulfate, the mixture was filtered under reduced pressure, and the solvent in the filtrate was evaporated under reduced pressure. The residue was purified by column chromatography (carrier: silica gel, solvent: n-heptane / ethyl acetate = 100 / 1 (volume ratio)), and the solvent was evaporated under reduced pressure. The residue was dried under reduced pressure to obtain the following (Intermediate 104) (2.00 g, yield 42%).

[0144] [ka]

[0145] Subsequently, the same procedure as in Synthesis Example 1 for the synthesis of compound (C-1) was repeated, except that (Intermediate 100) was replaced with the above (Intermediate 104), to obtain the target compound (C-4) as a brown solid (4.80 g, yield 86%).

[0146] The brown solid obtained was subjected to NMR measurement, and the following 58 hydrogen signals were detected, identifying the structure as the compound represented by the following formula (C-4).

[0147] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 8.50-6.10 (31H), 5.54 (2H), 3.63 (4H), 2.20-1.40 (15H), 1.06 (6H).

[0148] [ka]

[0149] [Synthesis Example 5] Synthesis of Compound (C-5) The following (Intermediate 105) was obtained (2.23 g, yield 59%) in the same manner as in Synthesis Example 4 (Intermediate 104), except that 1'-acetonaphthone was changed to 2'-methylacetophenone.

[0150] [ka]

[0151] Subsequently, the target compound (C-5) was obtained as a brown solid (5.58 g, yield 79%) in the same manner as in Synthesis Example 1, except that (Intermediate 100) was replaced with the above (Intermediate 105).

[0152] The obtained brown solid was subjected to NMR measurement, and the following 58 hydrogen signals were detected, identifying the structure as the compound represented by the following formula (C-5).

[0153] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.60 (1H), 7.40-6.70 (24H), 5.80-5.60 (2H), 3.70 (4H), 2.35-1.80 (21H), 1.16 (6H).

[0154] [ka]

[0155] [Synthesis Example 6] Synthesis of Compound (C-6) The following (Intermediate 106) was obtained (1.90 g, yield 39%) in the same manner as in Synthesis Example 4 (Intermediate 104), except that 1'-acetonaphthone was changed to 2'-chloroacetophenone.

[0156] [ka]

[0157] Subsequently, the target compound (C-6) was obtained as a brown solid (4.01 g, yield 71%) in the same manner as in Synthesis Example 1, except that (Intermediate 100) was replaced with the above (Intermediate 106).

[0158] The obtained brown solid was subjected to NMR measurement, and the following 52 hydrogen signals were detected, identifying the structure as the compound represented by the following formula (C-6).

[0159] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.63-6.65 (25H), 5.83-5.65 (2H), 3.71 (4H), 2.06 (3H), 2.01-1.85 (12H), 1.15 (6H).

[0160] [ka]

[0161] [Synthesis Example 7] Synthesis of Compound (C-7) The following (Intermediate 107) was obtained (3.00 g, yield 51%) in the same manner as in Synthesis Example 4 (Intermediate 104), except that 1'-acetonaphthone was changed to 2',4'-dichloroacetophenone.

[0162] [ka]

[0163] Subsequently, the target compound (C-7) was obtained as a brown solid (6.35 g, yield 85%) in the same manner as in Synthesis Example 1, except that (Intermediate 100) was replaced with the above (Intermediate 107).

[0164] The obtained brown solid was subjected to NMR measurement, and the following 50 hydrogen signals were detected, identifying the structure as the compound represented by the following formula (C-7).

[0165] 1H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.73-6.72 (23H), 5.83-5.65 (2H), 3.74 (4H), 2.07 (3H), 2.01-1.85 (12H), 1.16 (6H).

[0166] [ka]

[0167] [Synthesis Example 8] Synthesis of Compound (C-8) 30 mL of tetrahydrofuran was added to a reaction vessel and stirred at 0°C. 4.17 g (0.104 mol) of sodium hydride (60%, dispersed in liquid paraffin) was added to the reaction solution, and a solution of 3.00 g (26.1 mmol) of 3,3'-dimethylbutan-2-one oxime in 7 mL of tetrahydrofuran was added dropwise. 4.97 g (26.1 mmol) of p-toluenesulfonic acid chloride in 7 mL of tetrahydrofuran was added dropwise, and the mixture was stirred at room temperature (23-28°C) for 1 hour. 3.91 g (26.1 mmol) of 4'-methoxyacetophenone was added, and the mixture was stirred at room temperature (23-28°C) for 1 hour, then heated to 50°C and stirred for 44 hours. 30 mL of dichloromethane was added to the reaction solution, and the solution was washed with 200 mL of water. The organic layer was extracted, dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure, and the residue was purified by column chromatography (carrier: silica gel, solvent: toluene). The solvent was distilled off under reduced pressure to obtain the following (Intermediate 108) (2.46 g, yield 41%).

[0168] [ka]

[0169] Next, 2.00 g (8.72 mmol) of the above (Intermediate 108), 0.35 g (8.72 mmol) of sodium hydride (60%, dispersed in liquid paraffin), and 6 mL of dimethylformamide were placed in a reaction vessel and stirred at room temperature (23-28°C) for 30 minutes. 1.06 g (8.72 mmol) of 4-trifluorobenzonitrile was then added and stirred at room temperature (23-28°C) for 30 minutes. The mixture was then heated to 70°C and stirred for 1 hour. After cooling the reaction mixture to room temperature, 50 mL of ethyl acetate was added, and this solution was washed with 20 mL of water. The organic layer was extracted, dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure, and the residue was purified by column chromatography (carrier: silica gel, solvent: ethyl acetate / n-heptane = 100 / 1 to 10 / 1 (volume ratio)). The solvent was removed under reduced pressure. The resulting residue was dispersed and washed with 10 mL of methanol. This solution was filtered, and the resulting solid was dried under reduced pressure to obtain the following (Intermediate 109) (2.07 g, yield 72%).

[0170] [ka]

[0171] Subsequently, the target compound (C-8) was obtained as a blue solid (2.44 g, yield 38%) in the same manner as in Synthesis Example 1, except that (Intermediate 100) was replaced with the above (Intermediate 109).

[0172] The resulting blue solid was subjected to NMR measurement, and the following 57 hydrogen signals were detected, identifying the structure as the compound represented by the following formula (C-8).

[0173] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.58-6.75 (21H), 6.00-5.83 (2H), 3.93-3.65 (7H), 2.13-1.85 (12H), 1.25-0.90 (15H).

[0174] [ka]

[0175] [Synthesis Example 9] Synthesis of Compound (C-9) A reaction vessel was charged with 5.00 g (47.1 mmol) of benzaldehyde, 4.39 g (47.1 mmol) of aniline, 6.13 g (47.1 mmol) of ethyl acetoacetate, 2.23 g (9.42 mmol) of 1-butyl-3-methylimidazolidium hydrogen sulfate, and 47 mL of nitromethane, and the mixture was stirred at 90°C for 3 hours. After cooling to room temperature, 300 mL of ethyl acetate was added to the reaction mixture, and the resulting solution was washed with 300 mL of water. The organic layer was extracted, dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure, and the residue was purified by column chromatography (carrier: silica gel, solvent: toluene). The solvent was removed under reduced pressure to obtain the following (Intermediate 110) (5.51 g, 38% yield).

[0176] [ka]

[0177] Subsequently, the target compound (C-9) was obtained as a blue solid (0.60 g, yield 18%) in the same manner as in Synthesis Example 1, except that (Intermediate 100) was replaced with the above (Intermediate 110).

[0178] The resulting blue solid was subjected to NMR measurement, and the following 54 hydrogen signals were detected, identifying the structure as the compound represented by the following formula (C-9).

[0179] 1 H-NMR (400MHz, DMSO-d6): δ(ppm)=7.60(1H), 7.45-6.65(21H), 5.84-5.55( 2H), 4.05(2H), 3.75(4H), 3.42(3H), 2.13-1.85(12H), 1.16(6H), 1.02(3H).

[0180] [ka]

[0181] [Synthesis Example 10] Synthesis of Compound (C-10) 3.82 g (38.9 mmol) of cyclohexanone, 3.20 g (38.9 mmol) of pyrrolidine, and 76 mL of toluene were placed in a reaction vessel and stirred for 15 hours at 100° C. The solvent was distilled off under reduced pressure to obtain the following (Intermediate 111) (2.80 g, yield 48%).

[0182] [ka]

[0183] Next, 0.70 g (3.24 mmol) of the intermediate 111, 0.81 g (5.37 mmol) of sodium iodide, and 25 mL of N-methyl-2-pyrrolidone were placed in a reaction vessel and stirred at room temperature (23-28°C) for 30 minutes. Furthermore, 5.12 g (25.7 mmol) of phenacyl bromide was dissolved in 43 mL of N-methyl-2-pyrrolidone, and the solution was added dropwise to the reaction vessel over 60 minutes. The reaction solution was stirred at room temperature (23-28°C) for 10 hours, after which 112 mL of water was added and the mixture was stirred for an additional 11 hours. This solution was extracted twice with ethyl acetate and water, and the organic layer was washed three times with water. After extraction, the organic layer was dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure, and the residue was purified by column chromatography (support: silica gel, solvent: ethyl acetate / n-heptane = 20 / 1 (volume ratio)). The solvent was evaporated under reduced pressure to obtain the following (Intermediate 112) (0.70 g, yield 18%).

[0184] [ka]

[0185] Next, 0.70 g (3.24 mmol) of the (Intermediate 112), 0.30 g (3.24 mmol) of aniline, and 7 mL of glacial acetic acid were placed in a reaction vessel and stirred at 110°C for 3 hours. After the reaction solution was cooled to room temperature, 12 mL of water was added, and the suspension was stirred at room temperature (23-28°C) for 18 hours. 50 mL of ethyl acetate was added, and the solution was washed with 20 mL of water. The organic layer was extracted, dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure, and the residue was purified by column chromatography (carrier: silica gel, solvent: ethyl acetate / n-heptane = 20 / 1 (volume ratio)). The solvent was removed under reduced pressure to obtain the following (Intermediate 113) (0.50 g, yield 57%).

[0186] [ka]

[0187] Subsequently, the target compound (C-10) was obtained as a blue solid (0.60 g, yield 32%) in the same manner as in Synthesis Example 1, except that (Intermediate 100) was replaced with the above (Intermediate 113).

[0188] The obtained blue solid was subjected to NMR measurement, and the following 54 hydrogen signals were detected, identifying the structure as the compound represented by the following formula (C-10).

[0189] 1 H-NMR (400MHz, DMSO-d6): δ(ppm)=8.00-6.75(22H), 5.86(2H), 3.75(4H), 2.38(2H), 2.02(14H), 1.75(2H), 1.61(2H), 1.15(6H).

[0190] [ka]

[0191] [Synthesis Example 11] Synthesis of Compound (C-11) A reaction vessel was charged with 19.9 g (100 mmol) of phenacyl bromide, 9.31 g (100 mmol) of 2-methylpyridine, and 500 mL of acetone, and the mixture was stirred at 60°C for 5 hours. The reaction solution was filtered, and the residue was dissolved in 200 mL of water and then stirred at 60°C for 10 minutes. 13.8 g of potassium carbonate was added to this solution, and the mixture was stirred at 60°C for 1 hour. The reaction solution was filtered, and the residue was washed with 50 mL of methanol. The resulting solid was dried under reduced pressure to obtain the following (Intermediate 114) (10.2 g, 53% yield).

[0192] [ka]

[0193] Subsequently, the target compound (C-11) was obtained as a blue solid (8.95 g, yield 93%) in the same manner as in Synthesis Example 1, except that (Intermediate 100) was replaced with (Intermediate 114).

[0194] The resulting blue solid was subjected to NMR measurement, and the following 46 hydrogen signals were detected, identifying the structure as the compound represented by the following formula (C-11).

[0195] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.83 (2H), 7.50-6.70 (20H), 5.84 (2H), 3.74 (4H), 2.19-1.83 (12H), 1.15 (6H).

[0196] [ka]

[0197] [Synthesis Example 12] Synthesis of Compound (C-12) The target compound (C-12) was obtained as a purple solid (3.5 g, yield 65%) in the same manner as in Synthesis Example 1 for the synthesis of compound (C-1), except that (Intermediate 102) was changed to 4,4'-bis(diethylamino)benzophenone.

[0198] The obtained purple solid was subjected to NMR measurement, and the following 46 hydrogen signals were detected, identifying the structure as the compound represented by the following formula (C-12).

[0199] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.50-6.95 (15H), 6.95-6.55 (8H), 3.53 (8H), 2.12 (3H), 1.13 (12H).

[0200] [ka]

[0201] [Synthesis Example 13] Synthesis of Compound (C-13) A reaction vessel was charged with 2.50 g (10.9 mmol) of the above (Intermediate 108), 0.48 g (12.0 mol) of sodium hydride (60%, dispersed in liquid paraffin), and 27 mL of dimethylformamide, and the mixture was stirred at 5°C for 20 minutes. 1.96 g (12.5 mmol) of iodoethane was then added, and the mixture was stirred at room temperature (23-28°C) for 1.5 hours. 100 mL of ethyl acetate was added to the reaction mixture, and the resulting solution was washed with 20 mL of water. The organic layer was extracted, dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure, and the residue was purified by column chromatography (carrier: silica gel, solvent: ethyl acetate / n-heptane = 1 / 10 (volume ratio)). The solvent was distilled off under reduced pressure. The resulting residue was dried under reduced pressure to obtain the following (Intermediate 115) (1.94 g, yield 69%).

[0202] [ka]

[0203] Subsequently, the target compound (C-13) was obtained as a blue solid (3.70 g, yield 63%) in the same manner as in Synthesis Example 1, except that (Intermediate 100) was replaced with the above (Intermediate 115).

[0204] The resulting blue solid was subjected to NMR measurement, and the following 58 hydrogen signals were detected, identifying the structure as the compound represented by the following formula (C-13).

[0205] 1 H-NMR (400MHz, DMSO-d6): δ(ppm)=7.85-6.95(16H), 6.70-6.53(1H), 6.20-6.05(2H) , 4.00-3.70(7H), 3.45(2H), 2.19-1.83(12H), 1.21(6H), 1.08-0.83(9H), 0.65(3H).

[0206] [ka]

[0207] [Synthesis Example 14] Synthesis of Compound (C-14) A reaction vessel was charged with 23.1 g (166 mmol) of choline chloride and 19.9 g (331 mmol) of urea, and the mixture was stirred at 80°C for 30 minutes. Furthermore, 6.50 g (30.8 mmol) of 1,3-diphenylguanidine, 3.66 g (23.7 mmol) of 2-chloroacetophenone, and 3.30 mL (23.7 mmol) of triethylamine were added, and the mixture was stirred at 80°C for 2 hours. 50 mL of water was added to the reaction solution, and the reaction solution was filtered. The residue was washed with 50 mL of ethyl acetate / n-heptane = 1 / 5 (volume ratio). The resulting solid was dried under reduced pressure to obtain the following (Intermediate 116) (4.00 g, 54% yield).

[0208] [ka]

[0209] Next, 4.00 g (12.9 mmol) of the above (Intermediate 116), 0.57 g (14.1 mol) of sodium hydride (60%, dispersed in liquid paraffin), and 32 mL of dimethylformamide were placed in a reaction vessel and stirred at 5°C for 20 minutes. 2.80 g (14.8 mmol) of iodoethane was then added and stirred at room temperature (23-28°C) for 1 hour. 200 mL of ethyl acetate was added to the reaction solution, and this solution was washed with 50 mL of water. The organic layer was extracted, dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure, and the residue was purified by column chromatography (carrier: silica gel, solvent: ethyl acetate / n-heptane = 1 / 10 (volume ratio)). The solvent was distilled off under reduced pressure. The resulting residue was dried under reduced pressure to obtain the following (Intermediate 117) (3.10 g, yield 71%).

[0210] [ka]

[0211] Subsequently, the target compound (C-14) was obtained as a blue solid (9.28 g, yield 97%) in the same manner as in Synthesis Example 1, except that (Intermediate 100) was replaced with the above (Intermediate 117).

[0212] The resulting blue solid was subjected to NMR measurement, and the following 56 hydrogen signals were detected, identifying the structure as the compound represented by the following formula (C-14).

[0213] 1 H-NMR (400MHz, DMSO-d6): δ(ppm)=7.77-6.55(27H), 5.70(2H), 3.97(2H), 3.68(4H), 2.14-1.73(12H), 1.17(3H), 1.10(6H).

[0214] [ka]

[0215] [Synthesis Example 15] Synthesis of Compound (C-15) A reaction vessel was charged with 61.3 g (439 mmol) of choline chloride and 80.8 g (877 mmol) of glycerol and stirred at 70 °C for 10 minutes. Furthermore, 15.0 g (62.7 mmol) of 1,3-di-ortho-tolylguanidine, 9.69 g (62.7 mmol) of 2-chloroacetophenone, and 8.74 mL (62.7 mmol) of triethylamine were added and stirred at 80 °C for 2 hours. 300 mL of ethyl acetate was added to the reaction solution, and this solution was washed with 100 mL of water. The organic layer was extracted, dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure, and the residue was washed with 100 mL of diethyl ether / n-heptane = 1 / 4 (volume ratio). The resulting solid was dried under reduced pressure to obtain the following (Intermediate 118) (14.0 g, 66% yield).

[0216] [ka]

[0217] Next, 15.0 g (44.2 mmol) of the (Intermediate 118), 1.94 g (48.6 mol) of sodium hydride (60%, dispersed in liquid paraffin), and 100 mL of dimethylformamide were placed in a reaction vessel and stirred at 5°C for 20 minutes. 7.93 g (50.8 mmol) of iodoethane was then added and stirred at room temperature (23-28°C) for 1 hour. 300 mL of ethyl acetate was added to the reaction solution, and this solution was washed with 100 mL of water. The organic layer was extracted, dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure, and the residue was washed with 50 mL of methanol. The resulting solid was dried under reduced pressure to obtain the following (Intermediate 119) (14.7 g, 91% yield).

[0218] [ka]

[0219] Subsequently, the target compound (C-15) was obtained as a blue solid (26.6 g, yield 81%) in the same manner as in Synthesis Example 1, except that (Intermediate 100) was replaced with the above (Intermediate 119).

[0220] The resulting blue solid was subjected to NMR measurement, and the following 60 hydrogen signals were detected, identifying the structure as the compound represented by the following formula (C-15).

[0221] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.77-5.42 (27H), 4.18-3.50 (6H), 2.15-1.60 (18H), 1.29 (3H), 1.20-0.99 (6H).

[0222] [ka]

[0223] [Synthesis Example 16] Synthesis of Compound (C-16) A reaction vessel was charged with 6.50 g (30.8 mmol) of 1,3-diphenylguanidine, 5.29 g (23.7 mmol) of 2,2',4'-trichloroacetophenone, 3.3 mL (23.7 mmol) of triethylamine, and 40 mL of tetrahydrofuran, and the mixture was stirred at 65°C for 15 hours. 200 mL of ethyl acetate was added to the reaction mixture, and the resulting solution was washed with 50 mL of water. The organic layer was extracted, dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure, and the residue was purified by column chromatography (carrier: silica gel, solvent: ethyl acetate / n-heptane = 1 / 6 (volume ratio)). The solvent was distilled off under reduced pressure. The residue was washed with 50 mL of diethyl ether / n-heptane = 1 / 50 (volume ratio). The resulting solid was dried under reduced pressure to obtain the following (Intermediate 120) (5.34 g, 59% yield).

[0224] [ka]

[0225] Next, 3.00 g (8.84 mmol) of the (Intermediate 120), 0.39 g (9.72 mol) of sodium hydride (60%, dispersed in liquid paraffin), and 22 mL of dimethylformamide were placed in a reaction vessel and stirred at 5°C for 30 minutes. 1.59 g (10.2 mmol) of iodoethane was then added and stirred at room temperature (23-28°C) for 30 minutes. 50 mL of ethyl acetate was added to the reaction solution, and this solution was washed with 20 mL of water. The organic layer was extracted, dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure, and the residue was washed with 50 mL of methanol / water = 4 / 1 (volume ratio). The resulting solid was dried under reduced pressure to obtain the following (Intermediate 121) (3.17 g, yield 98%).

[0226] [ka]

[0227] Subsequently, the target compound (C-16) was obtained as a purple solid (4.41 g, yield 73%) in the same manner as in Synthesis Example 1, except that (Intermediate 100) was replaced with the above (Intermediate 121).

[0228] The obtained purple solid was subjected to NMR measurement, and the following 54 hydrogen signals were detected, identifying the structure as the compound represented by the following formula (C-16).

[0229] 1 H-NMR (400MHz, DMSO-d6): δ(ppm)=7.76(1H), 7.54-6.63(24H), 5.80-5.57(2H), 4.40-3.82(6H), 2.14-1.73(12H), 1.28-1.00(9H).

[0230] [ka]

[0231] [Synthesis Example 17] Synthesis of Compound (C-17) The target compound (C-17) was obtained as a blue solid (20.4 g, yield 99%) in the same manner as in Synthesis Example 2 for compound (C-2), except that compound (C-1) was replaced with compound (C-15).

[0232] The obtained blue solid was subjected to NMR measurement, and the following 180 hydrogen signals were detected, identifying the structure as the compound represented by the following formula (C-17).

[0233] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.77-5.42 (81H), 4.18-3.50 (18H), 2.15-1.60 (54H), 1.29 (9H), 1.20-0.99 (18H).

[0234] [ka]

[0235] [Synthesis Example 18] Synthesis of Compound (C-18) The target compound (C-18) was obtained as a purple solid (11.3 g, yield 87%) in the same manner as in Synthesis Example 1 for the synthesis of compound (C-1), except that (Intermediate 100) was changed to (Intermediate 119) and (Intermediate 102) was changed to 4,4'-bis(diethylamino)benzophenone.

[0236] The obtained purple solid was subjected to NMR measurement, and the following 52 hydrogen signals were detected, identifying the structure as the compound represented by the following formula (C-18).

[0237] 1 H-NMR (400MHz, DMSO-d6): δ(ppm)=7.62-6.03(21H), 3.95-3.65(2H), 3.60-3.25(8H), 1.92(3H), 1.84(3H), 1.32(3H), 1.21-0.90(12H).

[0238] [ka]

[0239] [Synthesis Example 19] Synthesis of Compound (C-19) The target compound (C-19) was obtained as a purple solid (4.53 g, yield 62%) in the same manner as in Synthesis Example 1 for the synthesis of compound (C-1), except that (Intermediate 100) was changed to (Intermediate 121) and (Intermediate 102) to 4,4'-bis(diethylamino)benzophenone.

[0240] The obtained purple solid was subjected to NMR measurement, and the following 46 hydrogen signals were detected, identifying the structure as the compound represented by the following formula (C-19).

[0241] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.62-6.50 (21H), 3.89 (2H), 3.51 (8H), 1.19-1.00 (15H).

[0242] [ka]

[0243] [Synthesis Example 20] Synthesis of Compound (C-20) A reaction vessel was charged with 8.09 g (57.9 mmol) of choline chloride and 10.67 g (116.9 mmol) of glycerol, and the mixture was stirred at 70 °C for 10 minutes. Furthermore, 7.63 g (31.9 mmol) of 1,3-di-ortho-tolylguanidine, 5.00 g (29.0 mmol) of 4'-fluoroacetophenone, and 4.0 mL (29.0 mmol) of triethylamine were added, and the mixture was stirred at 80 °C for 1 hour. 10 mL of water was added to the reaction solution, and the precipitated solid was filtered and washed with 50 mL of water. The filter cake was further suspended and washed in 10 mL of methanol, and the solid was collected by filtration and then dried under reduced pressure at 80 °C to obtain the following (Intermediate 122) (7.50 g, yield 72%).

[0244] [ka]

[0245] Next, 7.00 g (19.6 mmol) of the (Intermediate 122), 2.64 g (23.5 mol) of potassium t-butoxide, and 16 mL of dimethylformamide were placed in a reaction vessel and stirred at 5°C for 10 minutes. 3.67 g (23.5 mol) of iodoethane was then added and stirred at room temperature (23-28°C) for 30 minutes. 10 mL of water was added to the reaction solution, and the precipitated solid was filtered. The residue was then suspended and washed in 20 mL of methanol, and the solid was collected by filtration and dried under reduced pressure at 80°C to obtain the following (Intermediate 123) (6.76 g, yield 90%).

[0246] [ka]

[0247] Subsequently, the target compound (C-20) was obtained as a purple solid (8.49 g, yield 97%) in the same manner as in Synthesis Example 1, except that (Intermediate 100) was replaced with (Intermediate 123).

[0248] The obtained purple solid was subjected to NMR measurement, and the following 59 hydrogen signals were detected, identifying the structure as the compound represented by the following formula (C-20).

[0249] 1 H-NMR (400MHz, DMSO-d6): δ(ppm)=7.85-6.94(24H), 5.77(1H), 5.56(1H), 4.08-3.65(6H), 2.20-1.62(18H), 1.42-0.95(9H).

[0250] [ka]

[0251] [Synthesis Example 21] Synthesis of Compound (C-21) The target compound (C-21) was obtained as a purple solid (6.34 g, yield 84%) in the same manner as in Synthesis Example 1 for the synthesis of compound (C-1), except that (Intermediate 100) was changed to (Intermediate 123) and (Intermediate 102) was changed to 4,4'-bis(diethylamino)benzophenone.

[0252] The obtained purple solid was subjected to NMR measurement, and the following 51 hydrogen signals were detected, identifying the structure as the compound represented by the following formula (C-21).

[0253] 1 H-NMR (400MHz, DMSO-d6): δ(ppm)=7.62-6.36(18H), 6.33(1H), 6.20(1H), 3.95 -3.80(2H), 3.58-3.34(8H), 1.92(3H), 1.84(3H), 1.32(3H), 1.18-0.95(12H).

[0254] [ka]

[0255] [Synthesis Example 22] Synthesis of Compound (C-22) The target compound (C-22) was obtained as a purple solid (1.67 g, yield 20%) in the same manner as in Synthesis Example 1 for the synthesis of compound (C-1), except that (Intermediate 100) was changed to (Intermediate 118) and (Intermediate 102) was changed to 4,4'-bis(diethylamino)benzophenone.

[0256] The obtained purple solid was subjected to NMR measurement, and the following 48 hydrogen signals were detected, identifying the structure as the compound represented by the following formula (C-22).

[0257] 1 H-NMR (400MHz, DMSO-d6): δ(ppm)=8.47(1H), 7.62-6.23(21H), 3.58-3.34(8H), 2.22(3H), 2.15(3H), 1.18-0.95(12H).

[0258] [ka]

[0259] [Synthesis Example 23] Synthesis of Compound (C-23) The target compound (C-23) was obtained as a purple solid (11.5 g, yield 84%) in the same manner as in Synthesis Example 1 for the synthesis of compound (C-1), except that (Intermediate 100) was changed to (Intermediate 117) and (Intermediate 102) was changed to 4,4'-bis(diethylamino)benzophenone.

[0260] The obtained purple solid was subjected to NMR measurement, and the following 48 hydrogen signals were detected, identifying the structure as the compound represented by the following formula (C-23).

[0261] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.70-6.55 (23H), 3.87 (2H), 3.61-3.28 (8H), 1.22-0.98 (15H).

[0262] [ka]

[0263] [Synthesis Example 24] Synthesis of Compound (C-24) A reaction vessel was charged with 3.00 g (8.84 mmol) of the above (Intermediate 118), 1.19 g (10.6 mol) of potassium t-butoxide, and 9 mL of dimethylformamide, and the mixture was stirred at 5°C for 10 minutes. 1.81 g (10.6 mol) of benzyl bromide was then added, and the mixture was stirred at room temperature (23-28°C) for 2 hours. 50 mL of ethyl acetate was added to the reaction solution, and the solution was washed with 50 mL of water. The organic layer was extracted, dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure, and the residue was purified by column chromatography (carrier: silica gel, solvent: ethyl acetate / n-heptane = 1 / 10 (volume ratio)). The solvent was distilled off under reduced pressure. The resulting residue was dried under reduced pressure to obtain the following (Intermediate 124) (3.50 g, yield 92%).

[0264] [ka]

[0265] Subsequently, the target compound (C-24) was obtained as a purple solid (8.58 g, yield 90%) in the same manner as in Synthesis Example 1, except that (Intermediate 100) was replaced with (Intermediate 124).

[0266] The obtained purple solid was subjected to NMR measurement, and the following 62 hydrogen signals were detected, identifying the structure as the compound represented by the following formula (C-24).

[0267] 1 H-NMR (400MHz, DMSO-d6): δ(ppm)=7.75-5.95(30H), 5.77(1H), 5.55(1H), 5.25-4.91(2H), 3.67(4H), 2.28-1.55(18H), 1.29-0.90(6H).

[0268] [ka]

[0269] [Synthesis Example 25] Synthesis of Compound (C-25) The target compound (C-25) was obtained as a blue solid (20.0 g, yield 100%) in the same manner as in Synthesis Example 2 for compound (C-2), except that compound (C-1) was replaced with compound (C-23).

[0270] The resulting blue solid was subjected to NMR measurement, and the following 144 hydrogen signals were detected, identifying the structure as the compound represented by the following formula (C-25).

[0271] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.70-6.55 (69H), 3.87 (6H), 3.61-3.28 (24H), 1.22-0.98 (45H).

[0272] [ka]

[0273] [Synthesis Example 26] Synthesis of Compound (C-26) The target compound (C-26) was obtained as a blue solid (19.3 g, yield 100%) in the same manner as in Synthesis Example 2 for compound (C-2), except that compound (C-1) was replaced with compound (C-23).

[0274] The resulting blue solid was subjected to NMR measurement, and the following 168 hydrogen signals were detected, identifying the structure as the compound represented by the following formula (C-26).

[0275] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.77-6.55 (81H), 5.70 (6H), 3.97 (6H), 3.68 (12H), 2.14-1.73 (36H), 1.85-1.89 (27H).

[0276] [ka]

[0277] [Synthesis Example 27] Synthesis of Compound (C-27) A reaction vessel was charged with 2.50 g (8.03 mmol) of the above (Intermediate 116), 1.08 g (9.63 mol) of potassium t-butoxide, and 8 mL of dimethylformamide, and the mixture was stirred at 5°C for 30 minutes. 1.65 g (9.63 mol) of benzyl bromide was then added, and the mixture was stirred at room temperature (23-28°C) for 1 hour. 20 mL of water was added to the reaction solution, and the precipitated solid was filtered. The residue was further suspended and washed in 20 mL of methanol, and the solid was collected by filtration and then dried under reduced pressure at 80°C to obtain the following (Intermediate 125) (2.90 g, yield 90%).

[0278] [ka]

[0279] Subsequently, the target compound (C-27) was obtained as a purple solid (4.00 g, yield 81%) in the same manner as in Synthesis Example 1, except that (Intermediate 100) was changed to (Intermediate 125) and (Intermediate 102) to 4,4'-bis(diethylamino)benzophenone.

[0280] The obtained purple solid was subjected to NMR measurement, and the following 50 hydrogen signals were detected, identifying the structure as the compound represented by the following formula (C-27).

[0281] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.70-6.55 (28H), 5.05 (2H), 3.54 (8H), 1.15 (12H).

[0282] [ka]

[0283] [Synthesis Example 28] Synthesis of Compound (C-28) A reaction vessel was charged with 2.50 g (8.03 mmol) of the above (Intermediate 116), 1.08 g (13.6 mmol) of potassium t-butoxide, and 8 mL of dimethylformamide, and the mixture was stirred at 5°C for 30 minutes. 1.65 g (13.2 mol) of 2-iodopropane was then added, and the mixture was stirred at room temperature (23-28°C) for 1 hour. 20 mL of water was added to the reaction solution, and the precipitated solid was filtered. The residue was further suspended and washed in 20 mL of methanol, and the solid was collected by filtration and dried under reduced pressure at 80°C to obtain the following (Intermediate 126) (2.32 g, yield 82%).

[0284] [ka]

[0285] Subsequently, the target compound (C-28) was obtained as a purple solid (4.60 g, yield 86%) in the same manner as in Synthesis Example 1, except that (Intermediate 100) was changed to (Intermediate 126) and (Intermediate 102) to 4,4'-bis(diethylamino)benzophenone.

[0286] The obtained purple solid was subjected to NMR measurement, and the following 50 hydrogen signals were detected, identifying the structure as the compound represented by the following formula (C-28).

[0287] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.70-6.62 (21H), 5.32 (2H), 4.62 (1H), 2.51 (8H), 1.24 (6H), 1.11 (12H).

[0288] [ka]

[0289] [Synthesis Example 29] Synthesis of Compound (C-29) A reaction vessel was charged with 5.00 g (14.7 mmol) of the above (Intermediate 118), 1.98 g (17.7 mmol) of potassium t-butoxide, and 15 mL of dimethylformamide, and the mixture was stirred at 5°C for 20 minutes. 3.27 g (17.7 mol) of 2-methylbenzyl bromide was then added, and the mixture was stirred at room temperature (23-28°C) for 1 hour. 40 mL of ethyl acetate was added to the reaction mixture, and the resulting solution was washed with 100 mL of water. The organic layer was extracted, dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure, and the residue was purified by column chromatography (carrier: silica gel, solvent: ethyl acetate / n-heptane = 1 / 10 (volume ratio)). The solvent was distilled off under reduced pressure. The resulting residue was dried under reduced pressure to obtain the following (Intermediate 127) (5.01 g, yield 77%).

[0290] [ka]

[0291] Subsequently, the target compound (C-29) was obtained as a purple solid (4.66 g, yield 85%) in the same manner as in Synthesis Example 1, except that (Intermediate 100) was changed to (Intermediate 127).

[0292] The obtained purple solid was subjected to NMR measurement, and the following 64 hydrogen signals were detected, identifying the structure as the compound represented by the following formula (C-29).

[0293] 1 H-NMR (400MHz, DMSO-d6): δ(ppm)=7.76-6.00(29H), 5.80(1H), 5.55(1H), 5.33(1H), 4.97(1H), 3.65(4H), 2.21-1.52(21H), 1.26-0.92(6H).

[0294] [ka]

[0295] [Synthesis Example 30] Synthesis of Compound (C-30) A reaction vessel was charged with 5.00 g (14.7 mmol) of the above (Intermediate 118), 1.98 g (17.7 mmol) of potassium t-butoxide, and 15 mL of dimethylformamide, and the mixture was stirred at 5°C for 20 minutes. Furthermore, 3.23 g (17.7 mol) of (bromomethyl)cyclohexane was added, and the mixture was stirred at room temperature (23-28°C) for 1 hour. 40 mL of ethyl acetate was added to the reaction solution, and this solution was washed with 100 mL of water. The organic layer was extracted, dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure, and the precipitated solid was collected by filtration and dried under reduced pressure at 80°C to obtain the following (Intermediate 128) (4.61 g, 72% yield).

[0296] [ka]

[0297] Subsequently, the target compound (C-30) was obtained as a purple solid (4.53 g, yield 84%) in the same manner as in Synthesis Example 1, except that (Intermediate 100) was changed to (Intermediate 128).

[0298] The obtained purple solid was subjected to NMR measurement, and the following 68 hydrogen signals were detected, identifying the structure as the compound represented by the following formula (C-30).

[0299] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.85-5.37 (27H), 4.00 (2H), 3.62 (4H), 2.25-1.45 (24H), 1.28-0.90 (11H).

[0300] [ka]

[0301] [Synthesis Example 31] Synthesis of Compound (C-31) The target compound (C-31) was obtained as a purple solid (3.67 g, yield 78%) in the same manner as in Synthesis Example 1 for the synthesis of compound (C-1), except that (Intermediate 100) was changed to (Intermediate 128) and (Intermediate 102) was changed to 4,4'-bis(diethylamino)benzophenone.

[0302] The obtained purple solid was subjected to NMR measurement, and the following 60 hydrogen signals were detected, identifying the structure as the compound represented by the following formula (C-31).

[0303] 1 H-NMR (400MHz, DMSO-d6): δ(ppm)=7.55-6.36(19H), 6.30(1H), 6.01(1H), 3.97(2H), 3.58-3.34(8H), 2.02(3H), 1.89-1.54(9H), 1.31-0.95(17H).

[0304] [ka]

[0305] [Synthesis Example 32] Synthesis of Compound (C-32) A reaction vessel was charged with 5.00 g (14.7 mmol) of the above (Intermediate 118), 1.98 g (17.7 mmol) of potassium t-butoxide, and 15 mL of dimethylformamide, and the mixture was stirred at 5°C for 20 minutes. Furthermore, 4.27 g (17.7 mol) of (1-bromoethyl)benzene was added, and the mixture was stirred at room temperature (23-28°C) for 1 hour. 40 mL of ethyl acetate was added to the reaction solution, and this solution was washed with 200 mL of water. The organic layer was extracted, dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure, and the residue was purified by column chromatography (carrier: silica gel, solvent: ethyl acetate / n-hexane = 1 / 10 (volume ratio)). The solvent was distilled off under reduced pressure. The resulting residue was washed with 20 mL of n-hexane, and the precipitated solid was collected by filtration and dried under reduced pressure at 80°C to obtain the following (Intermediate 129) (3.57 g, yield 55%).

[0306] [ka]

[0307] Subsequently, the target compound (C-32) was obtained as a purple solid (3.08 g, yield 68%) in the same manner as in Synthesis Example 1, except that (Intermediate 100) was changed to (Intermediate 129).

[0308] The obtained purple solid was subjected to NMR measurement, and the following 64 hydrogen signals were detected, identifying the structure as the compound represented by the following formula (C-32).

[0309] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.85-5.38 (32H), 3.63 (4H), 3.48 (1H), 2.29-1.22 (21H), 1.22-0.92 (6H).

[0310] [ka]

[0311] [Synthesis Example 33] Synthesis of Compound (C-33) A reaction vessel was charged with 5.00 g (14.7 mmol) of the above (Intermediate 118), 1.98 g (17.7 mmol) of potassium t-butoxide, and 15 mL of dimethylformamide, and the mixture was stirred at 5°C for 20 minutes. Furthermore, 4.24 g (17.7 mol) of 2,6-dichlorobenzyl bromide was added, and the mixture was stirred at room temperature (23-28°C) for 1 hour. 40 mL of ethyl acetate was added to the reaction solution, and this solution was washed with 200 mL of water. The organic layer was extracted, dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure, and the resulting residue was washed with 20 mL of n-hexane. The precipitated solid was collected by filtration and dried under reduced pressure at 80°C to obtain the following (Intermediate 130) (5.35 g, 73% yield).

[0312] [ka]

[0313] Subsequently, the target compound (C-33) was obtained as a purple solid (3.41 g, yield 69%) in the same manner as in Synthesis Example 1, except that (Intermediate 100) was changed to (Intermediate 130).

[0314] The obtained purple solid was subjected to NMR measurement, and the following 60 hydrogen signals were detected, identifying the structure as the compound represented by the following formula (C-33).

[0315] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.75-4.75 (30H), 3.63 (4H), 3.47 (2H), 2.42-1.20 (18H), 1.20-0.92 (6H).

[0316] [ka]

[0317] [Synthesis Example 34] Synthesis of Compound (C-34) The target compound (C-34) was obtained as a purple solid (2.00 g, yield 46%) in the same manner as in Synthesis Example 1 for the synthesis of compound (C-1), except that (Intermediate 100) was changed to (Intermediate 130) and (Intermediate 102) was changed to 4,4'-bis(diethylamino)benzophenone.

[0318] The obtained purple solid was subjected to NMR measurement, and the following 52 hydrogen signals were detected, identifying the structure as the compound represented by the following formula (C-34).

[0319] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.65-5.45 (24H), 5.00 (2H), 3.43 (8H), 2.29-1.53 ​​(6H), 1.13-0.97 (12H).

[0320] [ka]

[0321] [Synthesis Example 35] Synthesis of Compound (C-35) The target compound (C-35) was obtained as a blue solid (15.0 g, yield 81%) in the same manner as in Synthesis Example 2 for compound (C-2), except that compound (C-1) was replaced with compound (C-33).

[0322] The resulting blue solid was subjected to NMR measurement, and the following 180 hydrogen signals were detected, identifying the structure as the compound represented by the following formula (C-35).

[0323] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.75-4.75 (90H), 3.63 (12H), 3.47 (6H), 2.42-1.20 (54H), 1.20-0.92 (18H).

[0324] [ka]

[0325] [Synthesis Example 36] Synthesis of Compound (C-36) A reaction vessel was charged with 25.0 g (458.3 mmol) of N-methylaniline, 51.4 g (458.3 mmol) of potassium t-butoxide, and 255 mL of dimethylformamide, and the mixture was stirred at 5°C for 20 minutes. A solution of 25.0 g (114.6 mol) of 4,4-difluorobenzophenone in 25 mL of DMF was then added dropwise, and the mixture was stirred at room temperature (23-28°C) for 2 hours. 150 mL of ethyl acetate and 300 mL of water were added to the reaction mixture, and the mixture was stirred at room temperature (23-28°C) for 2 hours. The precipitated solid was collected by filtration and dried under reduced pressure at 80°C to obtain the following (Intermediate 131) (39.2 g, 87% yield).

[0326] [ka]

[0327] Subsequently, the target compound (C-36) was obtained as a purple solid (27.6 g, yield 99%) in the same manner as in Synthesis Example 1, except that (Intermediate 100) was changed to (Intermediate 119) and (Intermediate 102) to (Intermediate 131).

[0328] The obtained purple solid was subjected to NMR measurement, and the following 48 hydrogen signals were detected, identifying the structure as the compound represented by the following formula (C-36).

[0329] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.70-6.10 (31H), 3.88 (2H), 3.32 (6H), 1.94 (3H), 1.77 (3H), 1.26 (3H).

[0330] [ka]

[0331] [Synthesis Example 37] Synthesis of Compound (C-37) The target compound (C-35) was obtained as a blue solid (15.0 g, yield 81%) in the same manner as in Synthesis Example 2 for compound (C-2), except that compound (C-1) was replaced with compound (C-33).

[0332] The resulting blue solid was subjected to NMR measurement, and the following 144 hydrogen signals were detected, identifying the structure as the compound represented by the following formula (C-37).

[0333] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.55-6.22 (93H), 3.82 (6H), 3.31 (18H), 1.94 (9H), 1.77 (9H), 1.26 (9H).

[0334] [ka]

[0335] [Synthesis Example 38] Synthesis of Compound (C-38) A reaction vessel was charged with 17.1 g (100.8 mmol) of diphenylamine, 13.4 g (119.2 mmol) of potassium t-butoxide, and 220 mL of dimethylformamide, and the mixture was stirred at 60°C for 20 minutes. 10.0 g (45.8 mol) of 4,4-difluorobenzophenone was then added, and the mixture was stirred at 110°C for 7 hours. 1500 mL of water and 300 mL of saturated brine were added to the reaction solution, and the precipitated solid was collected by filtration. The resulting solid was dissolved in 500 mL of chloroform, concentrated, and then recrystallized by adding 200 mL of methanol. The precipitated solid was collected by filtration and dried under reduced pressure at 80°C, yielding the following (Intermediate 132) (11.8 g, 50% yield).

[0336] [ka]

[0337] Subsequently, the target compound (C-38) was obtained as a purple solid (4.33 g, yield 69%) in the same manner as in Synthesis Example 1, except that (Intermediate 100) was changed to (Intermediate 119) and (Intermediate 102) to (Intermediate 132).

[0338] The obtained purple solid was subjected to NMR measurement, and the following 52 hydrogen signals were detected, identifying the structure as the compound represented by the following formula (C-38).

[0339] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.70-6.20 (41H), 3.90 (2H), 2.02 (3H), 1.80 (3H), 1.26 (3H).

[0340] [ka]

[0341] [Synthesis Example 39] Synthesis of Compound (C-39) The target compound (C-39) was obtained as a purple solid (6.16 g, yield 38%) in the same manner as in Synthesis Example 1 for the synthesis of compound (C-1), except that (Intermediate 100) was changed to (Intermediate 118).

[0342] The obtained purple solid was subjected to NMR measurement, and the following 56 hydrogen signals were detected, identifying the structure as the compound represented by the following formula (C-39).

[0343] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 8.77 (1H), 7.95-6.35 (25H), 5.60 (2H), 3.56 (4H), 2.45-1.50 (18H), 1.18-0.95 (6H).

[0344] [ka]

[0345] [Synthesis Example 40] Synthesis of Compound (C-40) 5.00 g (14.7 mmol) of the above (Intermediate 118), 1.98 g (17.7 mmol) of potassium t-butoxide, and 20 mL of dimethylformamide were placed in a reaction vessel and stirred at 5°C for 20 minutes. 3.29 g (17.7 mol) of methyl p-toluenesulfonate was then added, and the mixture was stirred at room temperature (23-28°C) for 1 hour. 20 mL of water was added to the reaction solution, and the precipitated solid was filtered. The residue was further suspended and washed in 20 mL of methanol, and the solid was collected by filtration and dried under reduced pressure at 80°C to obtain the following (Intermediate 133) (4.30 g, yield 83%).

[0346] [ka]

[0347] Subsequently, the target compound (C-40) was obtained as a purple solid (5.13 g, yield 80%) in the same manner as in Synthesis Example 1, except that (Intermediate 100) was changed to (Intermediate 133).

[0348] The obtained purple solid was subjected to NMR measurement, and the following 58 hydrogen signals were detected, identifying the structure as the compound represented by the following formula (C-40).

[0349] 1 H-NMR (400MHz, DMSO-d6): δ(ppm)=7.75-6.04(25H), 5.95-5.35(2H), 3.78-3.50(4H), 3.38(3H), 2.18-1.52(18H), 1.23-0.89(6H).

[0350] [ka]

[0351] [Synthesis Example 41] Synthesis of Compound (C-41) The target compound (C-41) was obtained as a purple solid (4.02 g, yield 48%) in the same manner as in Synthesis Example 1 for the synthesis of compound (C-1), except that (Intermediate 100) was changed to (Intermediate 133) and (Intermediate 102) was changed to 4,4'-bis(diethylamino)benzophenone.

[0352] The obtained purple solid was subjected to NMR measurement, and the following 50 hydrogen signals were detected, identifying the structure as the compound represented by the following formula (C-41).

[0353] 1 H-NMR (400MHz, DMSO-d6): δ(ppm)=7.55-6.05(21H), 3.56-3.30(8H), 3.35(3H), 1.90(3H), 1.79(3H), 1.07(6H), 1.01(6H).

[0354] [ka]

[0355] [Synthesis Example 42] Synthesis of Compound (C-42) The target compound (C-42) was obtained as a blue solid (14.7 g, yield 91%) in the same manner as in Synthesis Example 2 for compound (C-2), except that compound (C-1) was replaced with compound (C-40).

[0356] The resulting blue solid was subjected to NMR measurement, and the following 174 hydrogen signals were detected, identifying the structure as the compound represented by the following formula (C-42).

[0357] 1 H-NMR (400MHz, DMSO-d6): δ(ppm)=7.75-6.04(75H), 5.95-5.35(6H), 3.78-3.50(12H), 3.38(9H), 2.18-1.52(54H), 1.23-0.89(18H).

[0358] [ka]

[0359] [Synthesis Example 43] Synthesis of Compound (C-43) The target compound (C-43) was obtained as a blue solid (8.29 g, yield 97%) in the same manner as in Synthesis Example 2 for compound (C-2), except that compound (C-1) was replaced with compound (C-41).

[0360] The resulting blue solid was subjected to NMR measurement, and the following 150 hydrogen signals were detected, identifying the structure as the compound represented by the following formula (C-43).

[0361] 1 H-NMR (400MHz, DMSO-d6): δ(ppm)=7.55-6.05(63H), 3.56-3.30(24H), 3.35(9H), 1.90(9H), 1.79(9H), 1.07(18H), 1.01(18H).

[0362] [ka]

[0363] [Synthesis Example 44] Synthesis of Compound (C-44) The target compound (C-44) was obtained as a blue solid (6.38 g, yield 75%) in the same manner as in Synthesis Example 2 for compound (C-2), except that compound (C-1) was replaced with compound (C-18).

[0364] The resulting blue solid was subjected to NMR measurement, and the following 156 hydrogen signals were detected, identifying the structure as the compound represented by the following formula (C-44).

[0365] 1 H-NMR (400MHz, DMSO-d6): δ(ppm)=7.50-6.03(63H), 3.66-3.20(30H), 1.87(9H), 1.80(9H), 1.27(9H), 1.14-0.95(36H).

[0366] [ka]

[0367] [Synthesis Example 45] Synthesis of Compound (C-45) A reaction vessel was charged with 3.90 g (3.52 mmol) of the compound (C-15) and 165 mL of methanol. After dissolving the solid, a solution of 2.63 g of tungstosilicic acid hydrate in 35 mL of methanol was added dropwise. The solution was stirred at room temperature (23-28°C) for 2 hours, and the reaction mixture was filtered. The resulting solid was suspended and washed twice in 75 mL of methanol, filtered, and then dried at 80°C under reduced pressure to obtain the target compound (C-45) as a blue solid (3.60 g, 74% yield).

[0368] The resulting blue solid was subjected to NMR measurement, and the following 240 hydrogen signals were detected, identifying the structure as the compound represented by the following formula (C-45).

[0369] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.77-5.42 (108H), 4.00-3.55 (24H), 2.15-1.58 (72H), 1.25 (12H), 1.24-0.93 (24H).

[0370] [ka]

[0371] [Synthesis Example 46] Synthesis of Compound (C-46) A reaction vessel was charged with 5.00 g (4.52 mmol) of the compound (C-15) and 215 mL of methanol. After dissolving the solid, a solution of 3.03 g of silicomolybdic acid hydrate in 100 mL of methanol was added dropwise. The solution was stirred at room temperature (23-28°C) for 1.5 hours, and the reaction mixture was filtered. The resulting solid was suspended and washed twice in 400 mL of methanol. The solid was then filtered and dried under reduced pressure at 80°C to obtain the target compound (C-46) as a blue solid (3.88 g, 67% yield).

[0372] The obtained blue solid was subjected to NMR measurement, and the following 240 hydrogen signals were detected, identifying the structure as the compound represented by the following formula (C-46).

[0373] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.77-5.42 (108H), 4.00-3.73 (8H), 3.72-3.54 (16H), 2.10-1.58 (72H), 1.24 (12H), 1.23-0.93 (24H).

[0374] [ka]

[0375] [Synthesis Example 47] Synthesis of Compound (C-47) By the method described in paragraph

[0121] of Patent Document 6 (WO 2019-044096), an inorganic compound (E-1) represented by the following formula was obtained as a yellow solid.

[0376] [ka]

[0377] Next, 7.00 g (6.32 mmol) of the (C-15) compound and 490 mL of methanol were placed in a reaction vessel. After dissolving the solid, a solution of 4.88 g of the inorganic compound (E-1) dissolved in 100 mL of purified water was added dropwise. This solution was stirred at 70 °C for 1 hour, and the reaction solution was filtered. The resulting solid was suspended and washed in 500 mL of methanol, filtered, and then dried under reduced pressure at 80 °C to obtain the target compound (C-47) as a blue solid (26.6 g, yield 90%).

[0378] The resulting blue solid was subjected to NMR measurement, and the following 360 hydrogen signals were detected, identifying the structure as the compound represented by the following formula (C-47).

[0379] 1H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.77-5.42 (162H), 4.18-3.50 (36H), 2.15-1.60 (108H), 1.29 (18H), 1.20-0.99 (36H).

[0380] [ka]

[0381] [Synthesis of Comparative Example Compound (D-1)] Comparative Example Compound (D-1) represented by the following formula was obtained as a brown solid by the method described in Synthetic Example 1, paragraph

[0058] of Patent Document 5 (JP-A No. 2012-83652).

[0382] The obtained brown solid was subjected to NMR measurement, and the following 40 hydrogen signals were detected, identifying the structure as the compound represented by the following formula (D-1).

[0383] 1 H-NMR (400MHz, CDCl3): δ(ppm)=8.01(1H), 7.54-7.18(8H), 6.90-6.62(5H), 6.18(1H), 3.62-3.51(10H), 1.47(3H), 1.30(12H).

[0384] [ka]

[0385] [Synthesis of Comparative Example Compound (D-2)] According to the method described in paragraphs

[0320] to

[0322] of Patent Document 3, a comparative compound (D-2) represented by the following formula was obtained as a brown solid.

[0386] The obtained brown solid was subjected to NMR measurement, and the following 40 hydrogen signals were detected, identifying the structure as the compound represented by the following formula (D-2).

[0387] 1H-NMR (400MHz, CDCl3): δ(ppm)=7.80(1H), 7.48-7.17(11H), 6.93(1H), 6.90-6.66(4H), 3.85(3H), 3.55(8H), 1.15(12H).

[0388] [ka]

[0389] [Synthesis of Comparative Example Compound (D-3)] According to the method described in Example 1 of paragraphs

[0208] to

[0211] of Patent Document 4, a comparative compound (D-3) represented by the following formula was obtained as a blue-purple solid.

[0390] The obtained blue-purple solid was subjected to NMR measurement, and the following 45 hydrogen signals were detected, identifying the structure as the compound represented by the following formula (D-3).

[0391] 1 H-NMR (400MHz, CDCl3): δ(ppm)=7.56-7.41(4H), 7.40-7.23(6H), 7.21-7.11(3H), 6.84-6.72(4H), 4.31(1H), 3.91(1H), 3.50(8H), 2.31(3H), 1.29(3H), 1.11(12H).

[0392] [ka]

[0393] [Synthesis of Comparative Example Compound (D-4)] In the synthesis of compound (C-1) in Synthesis Example 1, the same method was used except that (Intermediate 100) was replaced with (Intermediate 108), and comparative compound (D-4) represented by the following formula was obtained as a blue-purple solid (7.65 g, yield 91%).

[0394] The obtained blue-purple solid was subjected to NMR measurement, and the following 54 hydrogen signals were detected, identifying the structure as the compound represented by the following formula (D-4).

[0395] 1 H-NMR (400MHz, DMSO-d6): δ(ppm)=11.83(1H), 7.87(2H), 7.60-6.95(15H), 6.07(2H), 3.82(7H), 2.06(12H), 1.21(6H), 1.01(9H).

[0396] [ka]

[0397] [Synthesis of Comparative Example Compound (D-5)] 1.0 g (1.03 mmol) of the comparative compound (D-4) and 20 mL of methanol were placed in a reaction vessel and stirred at room temperature (23-28°C) for 30 minutes. 2 mL of 40% by mass aqueous sodium hydroxide solution was added to this solution, and the mixture was stirred at room temperature for 30 minutes. 100 mL of water was then added, and the mixture was stirred at room temperature for 30 minutes. The reaction solution was filtered under reduced pressure, and the residue was washed with 50 mL of water. The resulting solid was dried under reduced pressure to obtain comparative compound (D-5) represented by the following formula as a brown solid (0.65 g, yield 92%).

[0398] The obtained brown solid was subjected to NMR measurement, and the following 53 hydrogen signals were detected, identifying the structure as the compound represented by the following formula (D-5).

[0399] 1 H-NMR (400MHz, DMSO-d6): δ(ppm)=7.81(2H), 7.25-6.81(17H), 3.79(3H), 3.64(4H), 2.12-2.01(12H), 1.20-1.12(6H), 0.95(9H).

[0400] [ka]

[0401] [Synthesis of Comparative Example Compound (D-6)] The following (Intermediate 134) was obtained (1.40 g, yield 18%) in the same manner as in Synthesis Example 11 (Intermediate 114), except that 2-methylpyridine was changed to 2-ethylpyridine.

[0402] [ka]

[0403] Subsequently, in the synthesis of compound (C-1) in Synthesis Example 1, a comparative compound (D-6) represented by the following formula was obtained as a purple solid (5.12 g, yield 80%) in the same manner as above, except that (Intermediate 100) was changed to (Intermediate 134).

[0404] The obtained purple solid was subjected to NMR measurement, and the following 48 hydrogen signals were detected, identifying the structure as the compound represented by the following formula (D-6).

[0405] 1 H-NMR (400MHz, DMSO-d6): δ(ppm)=8.66(1H), 7.59-6.35(20H), 6.15-5.45(2H), 3.93-3.40(4H), 2.51(3H), 2.19-1.83(12H), 1.15(6H).

[0406] [ka]

[0407] [Example 1] (Measurement of maximum absorption wavelength) The compound (C-1) obtained in Synthesis Example 1 was dissolved in propylene glycol monomethyl ether (PGME) to prepare a solution with a concentration of 0.01 mmol / L. The spectroscopic characteristics of the solution were measured using a UV-visible spectrophotometer (manufactured by JASCO Corporation, model: V-650) to measure the UV-visible absorption spectrum (wavelength range of 350 to 800 nm) at room temperature (25°C), and the maximum absorption wavelength in the measured wavelength range was measured. The measurement results are shown in Table 1.

[0408] (Measurement of 5% mass loss temperature) The compound (C-1) obtained in Synthesis Example 1 was subjected to TG-DTA measurement (sample mass: 5.0 to 6.0 mg, heating rate: 10°C / min) under a nitrogen gas flow using a thermogravimetry-differential thermal analyzer (TG-DTA 2000S, manufactured by Mac Science Co., Ltd.) to measure the 5% mass loss temperature. The measurement results are shown in Table 1.

[0409] (Evaluation of heat resistance) 20 mg of compound (C-1) obtained in Synthesis Example 1 and 5 g of a 25% by mass DMF-PGMEA mixed solution of a copolymer of methacrylic acid, acrylic acid ester, and styrene were placed in a sample bottle and mixed by stirring for 30 minutes. The resulting colored resin solution was filtered through a syringe filter, and 1 g of the filtrate was applied to a glass substrate (spin coating method, 1000 rpm, 6 seconds), and heated and dried at 100°C for 2 minutes to produce a thin film. The color value of the resulting film was measured using a spectrophotometer (CM-5, manufactured by Konica Minolta, Inc.). It was then heated at 230°C for 20 minutes, and the color value was measured in the same manner. The color difference (ΔE * ab ) was used as an index of heat resistance, and the results are shown in Table 1.

[0410] [Examples 2 to 47] Except for using compounds (C-2) to (C-47) obtained in Synthesis Examples 2 to 47 instead of compound (C-1) in Example 1, the maximum absorption wavelength, 5% mass loss temperature, and heat resistance were measured in the same manner as in Example 1. The results are summarized in Table 1.

[0411] [Comparative Examples 1 to 6] For comparison, the comparative compounds (D-1) to (D-6), which are triarylmethane dyes not belonging to the present invention, were used instead of the compound (C-1) of the example, and the maximum absorption wavelength, 5% mass loss temperature, and heat resistance were measured in the same manner as in Example 1. The results are summarized in Table 1.

[0412] [Table 1]

[0413] As shown in Table 1, the triarylmethane dyes which are compounds of the examples of the present invention are superior to the triarylmethane dyes of the comparative examples in that they have a high 5% mass loss temperature and high heat resistance during film formation. [Industrial Applicability]

[0414] The coloring composition containing the triarylmethane colorant according to the present invention has high heat resistance and can be used as a coloring material for various applications such as a colorant for color filters.

Claims

1. A triarylmethane dye represented by the following general formula (1): 【Chemical 1】 [In formula (1), R １ ~R ４ are each independently a hydrogen atom, represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, R ５ , R ６ are each independently a hydrogen atom, a halogen atom, ―OH、―CF ３ 、―NO ２ 、―CN、 a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent; a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms which may have a substituent, or represents an aryloxy group having 6 to 20 carbon atoms which may have a substituent, A Ｈ represents a heterocyclic group represented by the following general formula (2): An represents an anion, and m represents a natural number. 【Chemistry 2】 [In formula (2), X １ is a nitrogen atom, CR ９ or NR １０ represents X ２ is CR ９ or NR １０ represents X １ and X ２ At least one of the following is NR １０ represents R ７ ~R ９ are each independently a hydrogen atom, a halogen atom, ―OH、―CF ３ 、―NO ２ 、―CN、 a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent; a linear, branched or cyclic alkenyl group having 2 to 20 carbon atoms which may have a substituent; a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms which may have a substituent; an aryloxy group having 6 to 20 carbon atoms which may have a substituent; an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent; an optionally substituted heterocyclic group having 5 to 20 ring atoms, ―NR １１ R １２ 、 an acyl group having 1 to 20 carbon atoms which may have a substituent; a linear, branched or cyclic alkoxycarbonyl group having 2 to 20 carbon atoms which may have a substituent, or represents an aryloxycarbonyl group having 7 to 20 carbon atoms which may have a substituent, R １０ represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, a linear, branched or cyclic alkenyl group having 2 to 20 carbon atoms which may have a substituent; an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or represents an optionally substituted heterocyclic group having 5 to 20 ring atoms, R １１ and R １２ each independently represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or represents an optionally substituted heterocyclic group having 5 to 20 ring atoms, R ７ ~R １２ adjacent groups may be bonded to each other via a single bond, a double bond, a substituted or unsubstituted methylene group, an oxygen atom, or a sulfur atom to form a ring, The dashed line represents the bond to general formula (1).

2. In the general formula (1), A Ｈ is a heterocyclic group represented by any one of the following general formulas (2-1) to (2-4): 【Chemistry 3】 [In formula (2-1), R ７ ~R １０ is R in general formula (2). ７ ~R １０ and the adjacent R ７ and R ９ and R ８ and R ９ may each independently bond to each other via a single bond, a double bond, a substituted or unsubstituted methylene group, an oxygen atom, or a sulfur atom to form a ring, The dashed line represents the bond to general formula (1). 【Chemistry 4】 [In formula (2-2), R ７ ~R １０ is R in general formula (2). ７ ~R １０ and the adjacent R ７ and R ９ may be bonded to each other via a single bond, a double bond, a substituted or unsubstituted methylene group, an oxygen atom, or a sulfur atom to form a ring, The dashed line represents the bond to general formula (1). 【Chemistry 5】 [In formula (2-3), R ７ , R ８ and R １０ is R in general formula (2). ７ , R ８ and R １０ The dashed line represents the bond to general formula (1). 【Chemistry 6】 [In formula (2-4), R １３ and R １５ ~R １８ is R in general formula (2). ７ ~R ９ represents a group similar to １４ represents a hydrogen atom, and the dashed line represents the bond to general formula (1).

3. In the general formula (1), A Ｈ is a heterocyclic group represented by the general formula (2-1), and R ７ , R ８ and R １０ are each independently an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, and R ９ The triarylmethane dye according to claim 2 , wherein is a hydrogen atom.

4. In the general formula (1), A Ｈ is a heterocyclic group represented by the general formula (2-1), and R ７ is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may have a substituent, and R ８ and R １０ are each independently an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, and R ９ is an optionally substituted acyl group having 1 to 10 carbon atoms, a optionally substituted linear, branched, or cyclic alkoxycarbonyl group having 2 to 10 carbon atoms, or an optionally substituted aryloxycarbonyl group having 7 to 10 carbon atoms.

5. In the general formula (1), A Ｈ is a heterocyclic group represented by the general formula (2-1), and R ７ is an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, and R ８ is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may have a substituent, and R ９ is a hydrogen atom, and R １０ is a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.

6. In the general formula (1), A Ｈ is a heterocyclic group represented by the general formula (2-2), and R ７ and R ９ are each independently a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may have a substituent, and R ８ and R １０ and each independently represent a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.

7. In the general formula (1), A Ｈ is a heterocyclic group represented by the general formula (2-3), and R ７ But-NR １１ R １２ and R ８ and R １０ are each independently a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, and R １１ and R １２ each independently represents a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.

8. In the general formula (1), A Ｈ is a heterocyclic group represented by the general formula (2-4), and R １３ is a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.

9. In the general formula (1), R １ and R ２ are each independently a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may have a substituent, and R ３ and R ４ and each independently represent an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.

10. 2. The triarylmethane dye according to claim 1, wherein in the general formula (1), An is a perfluoroalkylsulfonate anion, a perfluoroalkylsulfonimide anion, a tris(trifluoromethanesulfonyl)methide anion, or a heteropolyacid anion.

11. The triarylmethane dye according to claim 1, wherein the ultraviolet-visible absorption spectrum (wavelength range of 350 to 800 nm) measured at 23 to 27°C using a propylene glycol monomethyl ether (PGME) solution of the triarylmethane dye has an absorption band with a maximum absorption wavelength in the wavelength range of 570 nm to 640 nm.

12. A coloring composition containing the triarylmethane colorant according to any one of claims 1 to 11.

13. A colorant for color filters, comprising the coloring composition according to claim 12.

14. A color filter using the colorant for color filters according to claim 13.

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