Triarylmethane dye, coloring composition containing the dye, coloring agent for color filters, and color filters

Abstract

To provide a dye which has a maximum absorption wavelength on a longer wavelength side as compared with the conventional triarylmethane dye.SOLUTION: A triarylmethane dye is represented by the following general formula (1) [where R1-R4 each independently represent H, an alkyl group, an aromatic hydrocarbon group or a heterocyclic group; R1 and R2, and R3 and R4 may be bonded to each other to form a ring; R5 and R6 each independently represent H, -NO2, a halogen atom, an alkyl group, an alkoxy group, an aromatic hydrocarbon group, a heterocyclic group, an amino group, a sulfonyl group or the like; R7 and R8 each independently represent H, -CN, -NO2, a halogen atom, an alkyl group, an alkoxy group, an aromatic hydrocarbon group, a heterocyclic group, an amino group, a carbonyl group, a sulfonyl group or the like; Ar represents a heterocyclic group; An represents an anion; a represents an integer of 1-3; and b represents an integer of 0-6].SELECTED DRAWING: None

Description

[Technical Field]

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

[0002] Color filters are used in liquid crystal displays, electroluminescent (EL) displays, and image sensors such as CCDs and CMOS sensors. Color filters are manufactured by laminating colored layers, such as thin dye films or dye-resin composite films, onto a translucent substrate such as glass or transparent resin using dyeing, pigment dispersion, printing, or electrodeposition methods. Triarylmethane dyes (or dyes) represented by the following formulas (B-1) and (B-2) are compounds used as colorants for color filters due to their spectral characteristics (Patent Documents 1 and 2, etc.). For example, by using a triarylmethane dye such as CI Basic Blue 7 (formula (B-1)) (CI is an abbreviation for color index), an excellent blue hue can be obtained (Patent Document 1).

[0003] [ka]

[0004] On the other hand, conventional triarylmethane dyes have a maximum absorption wavelength around 590-600 nm, resulting in insufficient absorption of visible light at wavelengths longer than 640 nm. Since visible light at wavelengths longer than 640 nm exhibits red light, it needs to be absorbed when used as a blue or green color filter. Therefore, there is a need for dyes that efficiently absorb visible light in this wavelength range, specifically dyes whose maximum absorption wavelength in a propylene glycol monomethyl ether (PGME) solution is in the wavelength range of 638 nm to 680 nm. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2008-304766 [Patent Document 2] Japanese Patent Publication No. 2011-068866 [Patent Document 3] Japanese Patent Publication No. 2017-149805 [Patent Document 4] Japanese Patent Publication No. 2015-028121 [Patent Document 5] Japanese Patent Publication No. 2018-154661 [Patent Document 6] Japanese Patent Publication No. 2003-003081 [Patent Document 7] Japanese Patent Publication No. 2017-083852 [Non-patent literature]

[0006] [Non-Patent Document 1] "Tetrahedron," 2002, (Netherlands), Vol. 58, pp. 2137-2146. [Non-Patent Document 2] "Organic Syntheses," 1997, (USA), Vol. 74, p. 257 [Non-Patent Document 3] "Organic Syntheses," 1984, (USA), Vol. 62, p. 158.

[0007] Attempts have been made to improve the fastness of dyes by making part of the triarylmethane dye an aromatic heterocycle. For example, Patent Document 3 discloses a triarylmethane dye having two thiophene rings. However, regarding the spectral characteristics, while it is stated that the optical density (OD value) in cyan is high, the differences from conventional triarylmethane dyes are not clearly stated.

[0008] Furthermore, Patent Documents 4 to 6 disclose triarylmethane dyes having one or two thiazole rings, and Patent Document 6 in particular describes that long-wavelength color-developing dyes can be obtained. However, according to the inventors' research, while triarylmethane dyes having one thiazole ring showed a shift in the maximum absorption wavelength to a longer wavelength compared to conventional triarylmethane dyes, it was insufficient. In addition, it was found that triarylmethane dyes having two thiazole rings have a maximum absorption wavelength at a shorter wavelength than conventional triarylmethane dyes. [Overview of the Initiative] [Problems that the invention aims to solve]

[0009] The object of this invention is to provide a dye having a maximum absorption wavelength at a longer wavelength than conventional triarylmethane dyes. [Means for solving the problem]

[0010] As a result of diligent research to solve the above-mentioned problems, the present inventors have found that a triarylmethane dye having a specific structure has a maximum absorption wavelength on the longer wavelength side compared to conventional triarylmethane dyes. In other words, the gist of the present invention is as follows.

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

[0012] [ka]

[0013] [In formula (1), R 1 ~R 4 Each of them independently consists of a hydrogen atom, Linear or branched alkyl groups having 1 to 30 carbon atoms, which may have substituents. Aromatic hydrocarbon groups having 6 to 30 carbon atoms, which may have substituents, This represents a heterocyclic group having 1 to 30 carbon atoms, which may have substituents. R1 and R 2 , R 3 and R 4 may be bonded to each other to form a ring. R 5 and R 6 are each independently a hydrogen atom, —NO2, a halogen atom, a linear or branched alkyl group having 1 to 30 carbon atoms which may have a substituent, a linear or branched alkoxy group having 1 to 30 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent, a heterocyclic group having 1 to 30 carbon atoms which may have a substituent, an aryloxy group having 1 to 30 carbon atoms which may have a substituent, an amino group having 0 to 30 carbon atoms which may have a substituent, —SO3 - , —SO3H, —SO3M, or a sulfonyl group or sulfonamide group having 0 to 30 carbon atoms which may have a substituent. R 7 and R 8 are each independently a hydrogen atom, —CN, —NO2, a halogen atom, a linear or branched alkyl group having 1 to 30 carbon atoms which may have a substituent, a linear or branched alkoxy group having 1 to 30 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent, a heterocyclic group having 1 to 30 carbon atoms which may have a substituent, an aryloxy group having 1 to 30 carbon atoms which may have a substituent, an amino group having 0 to 30 carbon atoms which may have a substituent, —COO - , —COOH, —COOM, a carbonyl group, ester group or amide group having 1 to 30 carbon atoms which may have a substituent, —SO3 -, -SO3H, -SO3M, or a sulfonyl or sulfonamide group having 0 to 30 carbon atoms, which may have substituents. M represents an inorganic cation or an organic cation. Ar represents a heterocyclic group having 1 to 30 carbon atoms, which may have substituents. An represents an anion, a represents an integer from 1 to 3, and b represents an integer from 0 to 6.

[0014] 2. In the above general formula (1), R 5 and R 6 However, a triarylmethane dye is a phenyl group having 6 to 30 carbon atoms, which may have substituents.

[0015] 3. In the above general formula (1), R 1 ~R 4 However, the triarylmethane dye is a linear or branched alkyl group having 1 to 12 carbon atoms, which may have substituents, or an aromatic hydrocarbon group having 6 to 12 carbon atoms, which may have substituents.

[0016] 4. A triarylmethane dye in the general formula (1) above, wherein Ar is a pyrrolyl group, indolyl group, thienyl group, thiazolyl group, furanyl group, or oxazolyl group having 3 to 30 carbon atoms, which may have substituents.

[0017] 5. In the general formula (1) above, An is a halide ion, (CF3SO2)2N - A triarylmethane dye which is a sulfonylimide anion or a sulfonate anion.

[0018] 6. A colored composition containing a triarylmethane dye whose maximum absorption wavelength in the absorption band of 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 638 nm to 680 nm.

[0019] 7. A colorant for color filters containing the triarylmethane dye or the coloring composition.

[0020] 8. A color filter using the coloring agent for color filters. [Effects of the Invention]

[0021] The triarylmethane dye of the present invention has a maximum absorption wavelength on the long wavelength side of 638 nm or higher, and a coloring composition containing this dye is useful as a coloring agent for color filters. [Modes for carrying out the invention]

[0022] Embodiments of the present invention will be described in detail below. However, the present invention is not limited to the embodiments described below and can be implemented in various ways within the scope of its gist.

[0023] The triarylmethane dye of the present invention is represented by the following general formula (1).

[0024] [ka]

[0025] In general formula (1), R 1 ~R 8 In the expression "linear or branched alkyl group having 1 to 30 carbon atoms which may have substituents," the "linear or branched alkyl group having 1 to 30 carbon atoms" specifically refers to: Linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups; Examples of branched alkyl groups include isopropyl, isobutyl, s-butyl, t-butyl, isooctyl, and 2-ethylhexyl groups.

[0026] In general formula (1), R 1 ~R 8In the "aromatic hydrocarbon group having 6 to 30 carbon atoms which may have substituents" represented by , the "aromatic hydrocarbon group" includes aryl groups and condensed polycyclic aromatic groups. Specifically, examples of "aromatic hydrocarbon groups having 6 to 30 carbon atoms" include aromatic hydrocarbon groups such as phenyl group, biphenyl group, terphenyl group, naphthyl group, anthryl group, phenanthryl group, fluorenyl group, indenyl group, pyrenyl group, perilenyl group, fluoranthenyl group, and triphenylenyl group.

[0027] In general formula (1), R 1 ~R 8 Furthermore, the "heterocyclic group" in "a heterocyclic group having 1 to 30 carbon atoms which may have substituents," represented by Ar, includes fused polycyclic aromatic heterocyclic groups, and specifically, as "a heterocyclic group having 1 to 30 carbon atoms," Pyridyl group, pyrimidinyl group, quinolyl group, isoquinolyl group, pyrazinyl group, triazinyl group, naphthilidinyl group, acridinyl group, phenanthrolinyl group, carbolinyl group, prinyl group, indolidinyl group, naphthilidinyl group, phthalazinyl group, quinoxalinyl group, quinazolinyl group, synnolinyl group, pteridinyl group, phenanthridinyl group, perimidinyl group, antilydinyl group, Pyrrolyl group, pyrazolyl group, imidazolyl group, triazolyl group, tetrazolyl group, dihydropyrrolopyrrolyl group, indolyl group, isoindolyl group, indollidinyl group, indazolyl group, benzimidazolyl group, benzotriazolyl group, carbazolyl group, azaindolyl group, azaindazolyl group, pyrazolopyrimidinyl group, prinyl group, adenyl group, guanidinyl group, acridinyl group, phenadinyl group, Furanyl group, thiophenyl group, benzofuranyl group, isobenzofuranyl group, benzothienyl group, isobenzothiophenyl group, dibenzofuranyl group, dibenzothienyl group, Oxazolyl group, isoxazolyl group, thiazolyl group, isothiazolyl group, oxadiazolyl group, thiadiazolyl group, phlopyrrolyl group, thienopyrrolyl group, benzoxazolyl group, benzoisoxazolyl group, benzothiazolyl group, benzoisothiazolyl group, benzothiadiazolyl group, phenoxathiinyl group, Examples include aromatic heterocyclic groups such as the benzo[1,2-b:4,5-b']dithiophenyl group and the bipyridinyl group.

[0028] In general formula (1), R 1 ~R 8 In the "linear or branched alkyl group having 1 to 30 carbon atoms that may have substituents," "aromatic hydrocarbon group having 6 to 30 carbon atoms that may have substituents," or "heterocyclic group having 1 to 30 carbon atoms that may have substituents," represented by either Ar, the "substituents" are, specifically, Deuterium atom, -OH, -CN, -CF3, -NO2, =O; Halogen atoms such as fluorine, chlorine, bromine, and iodine; A linear or branched alkyl group having 1 to 20 carbon atoms; Cycloalkyl groups with 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; Cycloalkoxy groups or 1-adamantyloxy groups, 2-adamantyloxy groups, having 3 to 20 carbon atoms; Acyl groups with 1 to 20 carbon atoms; Aromatic hydrocarbon groups or condensed polycyclic aromatic groups having 6 to 20 carbon atoms; Heterocyclic groups with 2 to 20 carbon atoms; Aryloxy groups with 6 to 20 carbon atoms; Unsubstituted amino group; monosubstituted or disubstituted amino group with 1 to 20 carbon atoms. ; ―COO - , -COOH, -COOM, a carbonyl group having 1 to 20 carbon atoms which may have substituents, an ester group or an amide group, ―SO3 -, -SO3H, -SO3M, or a sulfonyl or sulfonamide group having 0 to 20 carbon atoms, which may have substituents (where M represents an inorganic or organic cation). These are some examples. Each of these "substituents" may contain only one or more, and if there are multiple substituents, they may be the same or different from each other. Furthermore, each of these "substituents" may have the substituents exemplified above. Therefore, these "substituents" may be expressed as, for example, "linear or branched unsubstituted or substituted alkyl groups having 1 to 20 carbon atoms," "unsubstituted or substituted cycloalkyl groups having 3 to 20 carbon atoms," "linear or branched unsubstituted or substituted alkenyl groups having 2 to 20 carbon atoms," "linear or branched alkynyl groups having 2 to 20 carbon atoms," "unsubstituted or substituted cycloalkoxy groups having 3 to 20 carbon atoms," "unsubstituted or substituted aryloxy groups having 6 to 20 carbon atoms," "unsubstituted or substituted amino groups having 0 to 20 carbon atoms," "unsubstituted or substituted amide groups having 1 to 20 carbon atoms," "unsubstituted or substituted ammonium groups having 0 to 20 carbon atoms," "unsubstituted or substituted phenyl groups having 6 to 20 carbon atoms," "unsubstituted or substituted phenoxy groups having 6 to 20 carbon atoms," or "phenyl groups having 6 to 20 carbon atoms substituted with linear or branched alkyl groups having 1 to 20 carbon atoms substituted with halogen atoms." Furthermore, if a "substituent" includes a carbon atom, that carbon atom is included in the above-mentioned "1 to 30 carbon atoms" and "6 to 30 carbon atoms." In addition, these substituents may be bonded to each other via single bonds, double bonds, substituted or unsubstituted methylene groups, oxygen atoms, or sulfur atoms to form a ring.

[0029] In general formula (1), if there is an "inorganic cation" or "organic cation" represented by "M", then the "organic cation" is specifically R 9 R 10 R 11 R 12 N + The ammonium ion represented by the formula R is an example, 9 ~R 12Each of these independently represents -H, a linear or branched alkyl group having 1 to 20 carbon atoms which may have substituents, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have substituents, and they may be bonded to each other to form a ring. In the above formula, R 9 ~R 12 Details of the "substituents," "linear or branched alkyl groups having 1 to 30 carbon atoms," and "aromatic hydrocarbon groups having 6 to 30 carbon atoms" in the above general formula (1) are as follows: 1 ~R 8 Similar principles apply. Furthermore, "inorganic cations" include alkali metal ions such as lithium ions and sodium ions, or alkaline earth metal ions such as magnesium ions, calcium ions, and barium ions. Alkali metal ions are preferred for M.

[0030] Note that in general formula (1), R 1 ~R 8 In the above various "groups" having a "substituent" represented by, the "substituent" listed is "Linear or branched alkyl groups with 1 to 20 carbon atoms," "Cycloalkyl groups with 3 to 20 carbon atoms" "Linear or branched alkenyl groups with 2 to 20 carbon atoms," "Linear or branched alkynyl groups with 2 to 20 carbon atoms," "Linear or branched alkoxy groups with 1 to 20 carbon atoms," "Cycloalkoxy groups with 3 to 20 carbon atoms" "Acyl groups with 1 to 20 carbon atoms", "Aromatic hydrocarbon groups or condensed polycyclic aromatic groups with 6 to 20 carbon atoms," "Heterocyclic groups with 2 to 20 carbon atoms" "Aryloxy groups with 6 to 20 carbon atoms," or Specifically, "monosubstituted or disubstituted amino groups with 1 to 20 carbon atoms" include: Linear or branched alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, n-pentyl group, isopentyl group, n-hexyl group, 2-ethylhexyl group, heptyl group, octyl group, isooctyl group, nonyl group, and decyl group; Cycloalkyl groups such as cyclopropyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclononyl, and cyclodecyl groups; Alkenyl groups such as vinyl groups, 1-propenyl groups, allyl groups, 1-butenyl groups, 2-butenyl groups, 1-pentenyl groups, 1-hexenyl groups, isopropenyl groups, and isobutenyl groups, or linear or branched alkenyl groups formed by the bonding of multiple such groups; Alkynyl groups such as ethynyl, propargyl, and butynyl groups, or linear or branched alkynyl groups formed by the bonding of multiple such groups; mixed groups of alkenyl and alkynyl groups such as penta-3-en-1-inyl and hexa-2-en-4-inyl 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 groups; Cycloalkoxy groups with 3 to 20 carbon atoms, such as cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy, cyclononyloxy, and cyclodecyloxy groups; Acyl groups such as formyl, acetyl, propionyl, acryl, and benzoyl groups; Aromatic hydrocarbon groups or condensed polycyclic aromatic groups such as phenyl group, biphenylyl group, terphenylyl group, naphthyl group, anthracenyl group (anthryl group), tetracerenyl group, phenanthryl group, fluorenyl group, indenyl group, pyrenyl group, perilenyl group, fluoranthenyl group, triphenylenyl group; Heterocyclic groups such as thienyl group, furyl group (furanyl group), pyrrolyl group, thiazolyl group, oxazolyl group, imidazolyl group, pyrazolyl group, triazolyl group, benzothienyl group, benzofuranyl group, indolyl group, isoindolyl group, benzothiazolyl group, benzooxazolyl group, benzimidazolyl group, benzotriazolyl group, prinyl group, carbazolyl group, dibenzothienyl group, dibenzofuranyl group, pyridyl group, pyrimidylinyl group, triazinyl group, quinolyl group, isoquinolyl group, naphthilidinyl group, acridinyl group, phenanthrolinyl group, naphthilidinyl group, and carbonyl group; Aryloxy groups such as phenyloxy group, tolyloxy group, biphenylyloxy group, naphthyloxy group, anthracenyloxy group, and phenantrenyloxy group; Examples include linear or branched alkyl groups such as methylamino group, dimethylamino group, diethylamino group, ethylmethylamino group, dipropylamino group, dibutylamino group, di(2-ethylhexyl) group, di-t-butylamino group, and diphenylamino group, or monosubstituted or disubstituted amino groups having an aromatic hydrocarbon group.

[0031] In general formula (1), R 1 ~R 4 From the viewpoint of extending the maximum absorption wavelength to a longer wavelength, "aromatic hydrocarbon groups having 6 to 30 carbon atoms that may have substituents" or "heterocyclic groups having 1 to 30 carbon atoms that may have substituents" are preferred, and "aromatic hydrocarbon groups having 6 to 12 carbon atoms that may have substituents" are more preferred. From the viewpoint of suppressing absorption at wavelengths shorter than the maximum absorption wavelength, "linear or branched alkyl groups having 1 to 30 carbon atoms that may have substituents" are preferred, and "linear or branched alkyl groups having 1 to 12 carbon atoms that may have substituents" are more preferred. Also, R 1 and R 2 , R 3 and R 4 They may be joined to each other to form a ring.

[0032] In general formula (1), R 1~R 4 From the viewpoint of heat resistance, "linear or branched alkyl groups having 1 to 30 carbon atoms, which may have substituents" are preferred, and "linear or branched alkyl groups having 1 to 12 carbon atoms, which may have substituents" are more preferred. Also, R 1 and R 2 , R 3 and R 4 They may be bonded to each other to form a ring, but from the viewpoint of heat resistance, R 1 and R 2 , R 3 and R 4 It is more preferable that they do not form rings.

[0033] In general formula (1), R 5 ~R 8 Examples of "halogen atoms" represented by this formula include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. Fluorine atoms or chlorine atoms are preferred as the "halogen atoms".

[0034] In general formula (1), R 5 ~R 8 The "linear or branched alkoxy group having 1 to 30 carbon atoms, which may have substituents" as expressed in the formula includes, specifically, linear alkoxy groups such as methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, and decyloxy groups; and branched alkoxy groups such as isopropoxy, isobutoxy, s-butoxy, t-butoxy, and isooctyloxy groups.

[0035] In general formula (1), R 5 ~R 8In the expression "linear or branched aryloxy group having 1 to 30 carbon atoms which may have substituents," examples of "linear or branched aryloxy group having 1 to 30 carbon atoms" include aryloxy groups such as phenyloxy group, tolyloxy group, biphenylyloxy group, naphthyloxy group, anthracenyloxy group, and phenantrenyloxy group.

[0036] In general formula (1), R 5 ~R 8 The "amino group having 0 to 30 carbon atoms which may have substituents" represented by may or may not have substituents, and if it does have substituents, it is represented as "-NR 13 R 14 "The substituent R is expressed as " 13 and R 14 The amino group includes an amino group having a substituent, and examples include an unsubstituted amino group (-NH2), a monosubstituted amino group, a disubstituted amino group, etc. The number of carbon atoms in the monosubstituted or disubstituted amino group is, for example, 1 to 30, may be 1 to 20, or may be 2 to 10. The amino group having 0 to 30 carbon atoms which may have substituents may be a group to which the following are bonded via -NH-, -N< or -N=CH-: a linear or branched alkyl group having 1 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, an acyl group having 1 to 20 carbon atoms, or a heterocyclic group having 1 to 30 carbon atoms. Examples of monosubstituted amino groups include ethylamino group, butylamino group, acetylamino group, and phenylamino group. Examples of disubstituted amino groups include dialkylamino groups with 2 to 30 carbon atoms, such as dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, and dihexylamino group; dialkenylamino groups with 4 to 30 carbon atoms, such as diallylamino group; and diphenylamino group, N-acetyl-N-phenylamino group, and (n-butyl)-N-phenylamino group.

[0037] In general formula (1), R 1 ~R 8The "carbonyl group, ester group or amide group having 1 to 20 or 30 carbon atoms which may have a substituent" contained in 15 is a group represented by "―(C=O)―R 15 ", "―(C=O)―O―R 13 ", or "―(C=O)―NR 14 R 15 ". R 13 and "―NR 14 R 1 ~R 4 in 5 ~R 8 are the same as the "substituent" in R 13 ~R 14 and the "―NR

[0038] In the general formula (1), the "substituent" in the "linear or branched alkoxy group having 1 to 30 carbon atoms which may have a substituent", "aryloxy group having 1 to 30 carbon atoms which may have a substituent", or "amino group having 0 to 30 carbon atoms which may have a substituent" represented by R 1 ~R 8 is the same as the "substituent" in R 15 ~R 15 and the "―NR 13 R 14 " represented by R 15 and "―NR 13 R 14 " are the same as the "substituent" in R 1 ~R 4 and the "―NR 5 ~R 8 13 14 R 14 " represented by R

[0039] In the general formula (1), the "substituent" in the "linear or branched alkoxy group having 1 to 30 carbon atoms which may have a substituent", "aryloxy group having 1 to 30 carbon atoms which may have a substituent", or "amino group having 0 to 30 carbon atoms which may have a substituent" represented by R 5 ~R 8 is the same as the "substituent" in R 1 ~R 4The same principle applies to the "substituents" in each group represented by [the formula].

[0040] In general formula (1), R 5 and R 6 The atoms are preferably a hydrogen atom, an alkyl group having 1 to 30 carbon atoms which may have substituents, or an aromatic hydrocarbon group having 6 to 30 carbon atoms which may have substituents, and more preferably a phenyl group having 6 to 30 carbon atoms which may have substituents.

[0041] In general formula (1), Ar is preferably a pyrrolyl group, indolyl group, thienyl group, thiazolyl group, furanyl group, or oxazolyl group having 3 to 30 carbon atoms, which may have substituents. Thiazolyl groups are more preferred from the viewpoint of suppressing absorption at wavelengths shorter than the maximum absorption wavelength, and indolyl or thiazolyl groups are more preferred from the viewpoint of heat resistance.

[0042] In general formula (1), "a" represents the number of triarylmethane dye portions (general formula (2) below) in general formula (1). "An" represents an anion, and "b" represents the number of An. In general formula (1), if the triarylmethane dye portion is a cation with a total charge of 1 or more in the entire molecule, that is, if b is an integer from 1 to 3, it can form a salt or complex with any anion represented by 1 or 2 or more "An" as a counterion. However, in the compound represented by general formula (1), a and b are selected so that the compound as a whole is electrically neutral. a represents an integer from 1 to 3, with 1 or 2 being preferred. b represents an integer from 0 to 6, with 1 to 4 being preferred.

[0043] [ka]

[0044] In general formula (1), "An" is not particularly limited and can be an inorganic anion such as a halide ion, or an organic anion. Specifically, Cl - , Br- , I - ;(CF3SO2)2N - (or Tf2N) - ), (CF3SO2)3C - (or Tf3C) - ), (C2F5SO2)2N - (C4F9SO2)2N - , (C6F5SO2)2N - , (CN)2N - (CN)3C - NC-S-, (C2F5)3F3P - , (C6H4SO3 - )O(C6H3(C 12 H 25 )(SO3 - )), C6H4(C 12 H 25 )(SO3 - ), PF6 - BF4 - , (PW 12 O 40 )3 - , Alternatively, anions represented by the structural formulas (Z-1) to (Z-16) below are examples.

[0045] [ka]

[0046] [ka]

[0047] [ka]

[0048] [ka]

[0049] In general formula (1), An may be a single anion or a combination of two or more different anions, preferably a single anion or any combination of two or three anions selected from the examples given above, such as a halide ion or (CF3SO2)2N - It is more preferable that the anion be a single or any combination of two or three selected from either a sulfonylimid anion or a sulfonate anion.

[0050] The method for producing the triarylmethane dye represented by general formula (1) is not particularly limited and can be produced by applying known methods (e.g., Patent Document 5, Non-Patent Documents 1 and 2, etc.) and using reagents having various corresponding groups of general formula (1) or other suitable reagents. One embodiment of the method for producing the compound of the present invention is described below. However, the present invention is not limited to these.

[0051] A triarylmethane dye represented by general formula (1) can be obtained by condensing a ketone having a corresponding substituent, such as bis(5-morpholino-4-phenylthiophen-2-yl)methanone, with an arylamine having a corresponding substituent, such as 1-methyl-2-phenylindole, in a solution such as toluene under appropriate heating conditions to obtain a product containing the compound represented by general formula (1). Alternatively, a ketone having a corresponding substituent and an aryl halide having a corresponding substituent, such as 3-bromo-1-methyl-2-phenylindole, can be obtained by condensing them in a suitable solvent such as tetrahydrofuran (THF) using n-butyllithium under appropriate cooling conditions to obtain a product containing the compound represented by general formula (1).

[0052] Specific examples of preferred compounds as the triarylmethane dye of the present invention, represented by general formula (1), are shown in formulas (D-1) to (D-28) below, but the present invention is not limited to these compounds. Note that in general formula (1), only the triarylmethane dye portion is shown, and the anionic 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 shown.

[0053] [ka]

[0054] [ka]

[0055] [ka]

[0056] [ka]

[0057] [ka]

[0058] [ka]

[0059] [ka]

[0060] [ka]

[0061] [ka]

[0062] [ka]

[0063] The triarylmethane dyes of the present invention may be used individually or in combination (e.g., mixed) of two or more types with different molecular structures. When using two or more types, the mass concentration ratio of the least abundant triarylmethane dye in the total mass concentration ratio of the triarylmethane dyes is 0.1 to 50% by mass. It is preferable that there be one or two types of triarylmethane dyes.

[0064] During the synthesis of the triarylmethane dye of the present invention, known methods for purifying the product include purification by column chromatography; adsorption purification using silica gel, activated carbon, activated clay, etc.; and recrystallization or crystallization using solvents. Furthermore, if necessary, nuclear magnetic resonance analysis (NMR), absorbance measurement or ultraviolet-visible absorption spectroscopy (UV-Vis) measurement using a spectrophotometer, and thermogravimetric analysis-differential thermal analysis (TG-DTA) can be used for identification and analysis of these compounds. These methods can also be used to evaluate the solubility, heat resistance, and color of the obtained compounds.

[0065] The triarylmethane dye of the present invention, the coloring composition containing the dye, and the coloring agent for color filters containing the dye or the coloring composition need to be well dissolved or dispersed in an organic solvent containing resin or the like during the manufacturing process of the coloring agent and the color filter. Therefore, it is preferable that they have high solubility and dispersibility in organic solvents. The organic solvent is not particularly limited, but specifically includes esters such as ethyl acetate and n-butyl acetate; ethers such as diethyl ether, propylene glycol monomethyl ether (PGME), and ethylene glycol monoethyl ether (ethyl cellosolve); ether esters such as propylene glycol monomethyl ether acetate (PGMEA); ketones such as acetone and cyclohexanone; alcohols such as methanol, ethanol, and 2-propanol; diacetone alcohol (DAA), etc.; aromatic hydrocarbons such as benzene, toluene, and xylene; amides such as N,N-dimethylformamide (DMF) and N-methylpyrrolidone (NMP); dimethyl sulfoxide (DMSO); chloroform (trichloromethane), etc., with PGME, PGMEA, cyclohexanone, or DAA being preferred, and PGME or cyclohexanone being particularly preferred from the viewpoint of balancing the solubility of the resin and the solubility of the xanthene dye. These solvents may be used individually or in mixtures of two or more types.

[0066] The solubility of the triarylmethane dye of the present invention in organic solvents can be measured, for example, as follows: The triarylmethane dye and the organic solvent are mixed in an appropriate ratio, subjected to sonication, and then the solubility can be evaluated by visually checking for the presence or absence of insoluble matter at room temperature (25°C). The organic solvent used for measuring solubility is not particularly limited, and any of the above organic solvents can be used, but PGME, PGMEA, cyclohexanone, or DAA are preferred, and PGME or PGMEA are more preferred.

[0067] The triarylmethane dye of the present invention exhibits excellent solubility in organic solvents, particularly in PGME. The solubility in PGME is preferably 1% by mass or more, more preferably 3% by mass or more, and particularly preferably 5% by mass or more. When considering applications in high-contrast color filters, higher solubility is preferable.

[0068] The triarylmethane dye of the present invention exhibits a maximum absorption wavelength in the visible light region (e.g., wavelength range of 350 to 800 nm) of the ultraviolet-visible absorption spectrum 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 638 nm or higher, more preferably 645 nm or higher, even more preferably 650 nm or higher, preferably 680 nm or lower, more preferably 675 nm or lower, and even more preferably 670 nm or lower. For example, it is preferably in the wavelength range of 638 to 680 nm, and more preferably in the range of 645 to 670 nm. The dye concentration is preferably 0.005 to 0.02 mmol / L, and the absorbance at the maximum absorption wavelength is preferably 1 or higher and 2 or lower.

[0069] The triarylmethane dye of the present invention can be mixed with various resin solutions and applied to a glass substrate to produce a coating film. The resulting coating film can be color-evaluated by measuring its color using a spectrophotometer to obtain its color value. The color value is CIE L * a * b * Color systems are commonly used. Specifically, the color value L of a film sample is used. * a * , b * Measure the color difference (ΔE) of the color values ​​before and after heating at an appropriate temperature. * ab ) allows us to determine heat resistance. When applied to color filters, the color difference at temperatures around 230°C can be used as an indicator of heat resistance. ΔE * abThe smaller the value, the less discoloration due to thermal decomposition; a value of 10 or less is preferable, and 3 or less is more preferable.

[0070] The coloring agent for color filters of the present invention comprises a triarylmethane dye represented by general formula (1), or a coloring composition containing at least one of the triarylmethane dyes, and components commonly used in the manufacture of color filters. A typical color filter is obtained, for example, by using a photolithography process, by mixing a dye such as a dye or pigment with a resin component (including monomers and oligomers) and a solvent to prepare a liquid, which is then applied to a substrate such as glass or resin, photopolymerized using a photomask, to create a colored pattern of a dye-resin composite film that is soluble / insoluble in the solvent, and then heated after washing. In electrodeposition and printing methods, a colored pattern is also created using a mixture of dyes with resin and other components. Therefore, specific components of the coloring agent for color filters of the present invention include at least one triarylmethane dye represented by general formula (1), other dyes such as dyes and pigments, resin components, organic solvents, and other additives such as photopolymerization initiators. Furthermore, these components may be selected or omitted, and other components may be added as needed.

[0071] When using the triarylmethane dye of the present invention or a coloring composition containing the triarylmethane dye as a coloring agent for color filters, it may be used for color filters of each color, but it is preferable to use it as a coloring agent for blue or green color filters.

[0072] The colorants for color filters of the present invention may use one or more triarylmethane dyes alone, or other known dyes such as other dyes or pigments may be mixed in to adjust the color tone. When used as a coloring agent for blue color filters, examples of blue or red dyes or pigments include, but are not particularly limited, 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, 74 and CI Acid Red 52, 289; disperse dyes such as Disperse Blue 3, 7, 377; spiron dyes; cyanine, indigo, phthalocyanine, anthraquinone, methine, triarylmethane, indanthrene, oxazine, dioxazine, azo, and xanthene dyes not belonging to the present invention; and other blue lake pigments. When used as a coloring agent for green color filters, examples of blue, yellow, or green dyes or pigments include, but are not particularly limited, green pigments such as CI Pigment Green 7, 10, 36, 47, 58, 59, 62, 63; yellow pigments such as CI Pigment Yellow 83, 138, 139, 150, 180, 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.

[0073] In the present invention, when used as a colorant for blue color filters, preferred dyes are triarylmethane dyes not belonging to the present invention, such as CI Basic Blue 7, or xanthene dyes such as CI Basic Violet 10, CI Acid Red 52, and 289. When used as a colorant for green color filters, preferred dyes are quinophthalone dyes such as CI Pigment Yellow 138, isoindoline dyes such as CI Pigment Yellow 139, or azo dyes. By using these dyes and triarylmethane dyes belonging to the present invention, blue or green color filters with excellent brightness and contrast ratio can be obtained.

[0074] The mixing ratio of other pigments in the coloring agent for color filters of the present invention is preferably 5 to 2000% by mass, and more preferably 10 to 1000% by mass, relative to the triarylmethane pigment (the total amount if there are two or more types). The mixing ratio of pigment components such as dyes in the liquid coloring agent for color filters is preferably 0.5 to 70% by mass, and more preferably 1 to 50% by mass, relative to the total coloring agent.

[0075] As the resin component in the colorant for color filters of the present invention, any known resin can be used as long as it has the properties necessary for the manufacturing method and use of the color filter resin film formed using it (for example, the "binder resin (B1)" described in Patent Document 7, paragraph

[0229] , Synthesis Example 23). Examples include acrylic resin, olefin resin, styrene resin, polyimide resin, urethane resin, polyester resin, epoxy resin, vinyl ether resin, phenol (novolac) resin, other transparent resins, photocurable resins, or thermosetting resins, and these can be used in appropriate combinations with monomer or oligomer components. Copolymers of these resins can also be used in combination. The resin content in these colorant for color filters is preferably 5 to 95% by mass, and more preferably 10 to 50% by mass, in the case of a liquid colorant.

[0076] To enhance the performance of the coloring composition of the present invention as a coloring agent for color filters, other components of the compound may include organic compounds such as surfactants, dispersants, defoamers, leveling agents, and other additives mixed during the manufacture of coloring agents for color filters. However, the content of these additives in the coloring composition is preferably appropriate, and is preferably within a range that does not decrease or excessively increase the solubility of the coloring composition in the solvent, nor does it affect the effect of other similar additives used during the manufacture of color filters. These additives can be added at any time during the preparation of the coloring composition.

[0077] Other additives in the colorant for color filters of the present invention include components necessary for the polymerization and curing of resins, such as photopolymerization initiators and crosslinking agents, as well as surfactants and dispersants necessary for stabilizing the properties of the components in the liquid colorant for color filters. Known additives for color filter manufacturing can be used for any of these, and are not particularly limited. The mixing ratio of the total amount of these additives in the total solid content of the colorant for color filters is preferably 5 to 60% by mass, and more preferably 10 to 40% by mass. [Examples]

[0078] The embodiments of the present invention will be described in detail below with reference to 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., Merck KGaA (Sigma-Aldrich), Thermo Fisher Scientific (Alfa Aesar), Duksan, Daejung, etc. Furthermore, all reactions in the synthesis examples were carried out under a nitrogen atmosphere using a reaction vessel equipped with a condenser, a stirrer, and a thermometer. The identification of the compounds obtained in the synthesis examples was as follows: 1 The analysis was performed using 1H-NMR (Bruker nuclear magnetic resonance spectrometer, model: Magnet System 300MHz / 54mm UltraShield), and the measurement results and identified structures are shown in the synthesis examples below.

[0079] [Synthesis Example 1] Synthesis of Compound (L-1) In a 100 mL four-necked flask, 2.0 g (3.9 mmol) of bis(5-morpholino-4-phenylthiophen-2-yl)methanone (see below (intermediate 101)), 0.9 g (4.3 mmol) of 1-methyl-2-phenylindole, 1.8 g (12 mmol) of phosphorus oxychloride, and 40 mL of toluene were added, and the mixture was heated under reflux (98°C) and stirred for 3 hours. The reaction mixture was allowed to cool to room temperature, 100 mL of water was added to the reaction mixture, and it was extracted twice with 100 mL of dichloromethane. The organic layer was washed with 100 mL of water and 100 mL of saturated brine, dried over anhydrous magnesium sulfate, filtered under reduced pressure, and the solvent of the filtrate was removed under reduced pressure. The residue was purified by column chromatography (support: silica gel, solvent: dichloromethane / methanol = 100 / 1 to 10 / 1 (volume ratio)), and the solvent was removed under reduced pressure. The residue was dried under reduced pressure at room temperature for 12 hours to obtain an intermediate pigment (see below (Intermediate D-1)) (2.9 g, yield 100%) as a black solid.

[0080] [ka]

[0081] [ka]

[0082] Next, 2.9 g (3.9 mmol) of the aforementioned (intermediate D-1), 1.5 g (5.3 mmol) of lithium bis(trifluoromethanesulfonyl)imide (LiN(SO2CF3)2 or LiNTf2), and 20 mL of methanol were placed in a 100 mL four-necked flask, and the mixture was stirred at room temperature for 1 hour. After removing the solvent from the reaction mixture under reduced pressure, the residue was washed twice with 100 mL of water. The residue was dried under reduced pressure at 60°C for 6 hours to obtain the target compound (L-1) (3.5 g, yield 97%) as a purple solid.

[0083] NMR measurements were performed on the obtained dark red solid, and the following 40 hydrogen signals were detected, identifying the structure of the compound represented by the following formula (L-1).

[0084] 1 H-NMR (300MHz, CDCl3): δ (ppm) = 7.54-7.18 (21H), 3.82 (3H), 3.80-3.66 (8H), 3.50-3.28 (8H).

[0085] [ka]

[0086] [Synthesis Example 2] Synthesis of Compound (L-2) In Synthesis Example 1, an intermediate dye (Intermediate D-2) (2.5 g, yield 77%) was obtained as a black solid by the same method as in the previous example, except that 1.3 g (4.3 mmol) of a thiazole derivative (Intermediate 104 below) prepared by a known method (Patent Document 4, paragraph

[0222] ) was used instead of 0.9 g (4.3 mmol) of 1-methyl-2-phenylindole.

[0087] [ka]

[0088] [ka]

[0089] Next, in Synthesis Example 1, the target compound (L-2) (2.1 g, yield 83%) was obtained as a dark purple solid by the same method as above, except that 2.0 g (2.4 mmol) of (intermediate D-2) was used instead of (intermediate D-1) and 0.9 g (3 mmol) of lithium bis(trifluoromethanesulfonyl)imide was used.

[0090] NMR measurements were performed on the obtained dark red solid, and the following 44 hydrogen signals were detected, identifying the structure of the compound represented by the following formula (L-2).

[0091] 1H-NMR (300MHz, CDCl3): δ(ppm)=7.63-7.56(2H), 7.46-7.33(12H), 7.33-7.22(4H), 7.16(1 H), 6.95(1H), 4.25(1H), 3.87(1H), 3.78-3.68(8H), 3.42-3.29(8H), 2.34(3H), 1.28(3H).

[0092] [ka]

[0093] [Synthesis Example 3] Synthesis of Compound (L-3) In a 100 mL four-necked flask, 2.0 g of ketone (intermediate 107 below) prepared by a known method (non-patent literature 1-3), 0.9 g (4.3 mmol) of 1-methyl-2-phenylindole, and 1.9 g (12 mmol) of phosphorus oxychloride were added. 40 mL of toluene was then added, and the intermediate dye (intermediate D-3 below) (1.8 g, yield 62%) was obtained as a blue-black solid by the same method as in Synthesis Example 1.

[0094] [ka]

[0095] [ka]

[0096] Next, in Synthesis Example 1, the target compound (L-3) (2.1 g, yield 86%) was obtained as a black solid by the same method as above, except that 1.8 g (2.6 mmol) of (intermediate D-3) was used instead of (intermediate D-1) and 0.9 g (3 mmol) of lithium bis(trifluoromethanesulfonyl)imide was used.

[0097] NMR measurements were performed on the obtained dark red solid, and the following 44 hydrogen signals were detected, identifying the structure of the compound represented by the following formula (L-3).

[0098] 1 H-NMR (300MHz, CDCl3): δ(ppm)=7.97-7.88(1H), 7.71-7.63(1H), 7.55-7.18(13H), 7.12-6.72(3H), 3.56-3.36(10H), 1.44(3H), 1.26-1.13(12H).

[0099] [ka]

[0100] [Synthesis Example 4] Synthesis of Compound (L-4) In a 100 mL four-necked flask, 3.0 g (10 mmol) of 3-bromo-1-methyl-2-phenyl-1H-indole and 30 mL of dry tetrahydrofuran (THF) were placed. The mixture was cooled to -50°C using dry ice / methanol as a refrigerant, then 6.4 mL (10 mmol) of n-butyllithium (n-BuLi) (1.6 M n-hexane solution) was added, and the mixture was stirred at -50°C for 20 minutes. 2.0 g (3.4 mmol) of a ketone (see below (intermediate 112)) prepared by a known method (Non-Patent Literature 1-3) was added to the reaction mixture, and the mixture was stirred for 3 hours while gradually increasing the temperature to 10°C without adding dry ice as a refrigerant. The reaction mixture was cooled to -10°C, 10 mL of water was added to stop the reaction, then 10 mL of concentrated hydrochloric acid was added, and the mixture was stirred at room temperature for 30 minutes. The mixture was diluted with 100 mL of water and then extracted twice with 100 mL of dichloromethane. The organic layer was washed with 100 mL of water and 100 mL of saturated brine, dried over anhydrous magnesium sulfate, filtered under reduced pressure, and the solvent of the filtrate was removed by distillation under reduced pressure. The residue was purified by column chromatography (support: silica gel, solvent: dichloromethane / methanol = 100 / 1 to 10 / 1 (volume ratio)), and then dried under reduced pressure at room temperature for 12 hours to obtain the intermediate pigment (see below (Intermediate D-4)) (2.8 g, yield 100%) as a black solid.

[0101] [ka]

[0102] [ka]

[0103] Next, in Synthesis Example 1, the target compound (L-4) (3.4 g, yield 92%) was obtained as a dark purple solid by the same method, except that 2.9 g (3.6 mmol) of (intermediate D-4) was used instead of (intermediate D-1) and 1.3 g (4.5 mmol) of lithium bis(trifluoromethanesulfonyl)imide was used.

[0104] NMR measurements were performed on the obtained dark red solid, and the following 44 hydrogen signals were detected, identifying the structure of the compound represented by the following formula (L-4).

[0105] 1 H-NMR (300MHz, CDCl3): δ(ppm)=7.56-7.37(8H), 7.36-7.25(3H), 7.16-7.03(10 H), 7.03-6.98(2H), 6.98-6.89(8H), 3.95-3.86(4H), 3.83(3H), 1.28-1.21(6H).

[0106] [ka]

[0107] [Synthesis Examples 5-8] Synthesis of Compounds (L-5)-(L-7) In Synthesis Example 4, the corresponding intermediate dye was obtained by the same method, except that 2.0 g of a ketone having the corresponding substituent, prepared by a known method (Non-Patent Documents 1-3), was used instead of (intermediate 112), and three times the molar amount of the ketone was used for the aryl halide having the corresponding heterocyclic group and n-butyllithium (1.6 M n-hexane solution). Next, compounds (L-5) to (L-7) were obtained by the same method as in Synthesis Example 1, except that the corresponding intermediate dye was used instead of (intermediate D-1), and lithium bis(trifluoromethanesulfonyl)imide was used in an amount equal to 1.2 times the amount of the intermediate dye. The yield, yield yield, color, and shape of each compound are shown below.

[0108] The obtained solids were subjected to NMR measurements, and the signals of the corresponding number of hydrogen atoms were detected, identifying the structure of the compound represented by the following formulas (L-5) to (L-7). The yields shown below are based on 2.0 g of the corresponding substituent ketone.

[0109] Compound (L-5) 0.4g, yield 10%, blackish-blue solid, 42 hydrogen signals.

[0110] 1 H-NMR (300MHz, CDCl3): δ(ppm)=8.32-8.19(4H), 7.59-7.19(15H), 3.82(3H), 3.38(8H), 1.15(12H).

[0111] [ka]

[0112] Compound (L-6) 2.9g, yield 82%, black solid, 42 hydrogen signals.

[0113] 1 H-NMR (300MHz, CDCl3): δ(ppm)=7.69-7.61(4H), 7.51-7.31(10H), 7.30-7.19(5H), 3.81(3H), 3.37(8H), 1.14(12H).

[0114] [ka]

[0115] Compound (L-7) 2.9g, yield 83%, black solid, 62 hydrogen signals.

[0116] 1H-NMR (300MHz, CDCl3): δ(ppm)=7.50-7.13(11H), 7.05-6.92(4H), 6.68-6.58(4H), 3.79(3H), 3.46-3.30(16H), 1.21-1.10(24H).

[0117] [ka]

[0118] [Synthesis Comparison Example 1] Synthesis of Comparative Compound (H-1) In Synthesis Example 1, 10 g (19 mmol) of CI Basic Blue 7 represented by the above formula (B-1) was used as an intermediate instead of (intermediate D-1), and 5.6 g (19 mmol) of lithium bis(trifluoromethanesulfonyl)imide was used. The target comparative example compound (H-1) (13.4 g, yield 91%) was obtained as a brown solid by the same method.

[0119] NMR measurements were performed on the obtained brown solid, and signals from the following 39 hydrogen atoms were detected, identifying the structure of the compound represented by the following formula (H-1).

[0120] 1 H-NMR (300MHz, CDCl3): δ(ppm)=8.01(1H), 7.54-7.18(7H), 6.90-6.62(5H), 6.18(1H), 3.62-3.51(10H), 1.47(3H), 1.30(12H).

[0121] [ka]

[0122] [Synthesis Comparison Example 2] Synthesis of Comparative Compound (H-2) In Synthesis Example 1, 5.0 g (15.4 mmol) of 4,4'-bis(diethylamino)benzophenone (see below (Intermediate 201)) was used instead of (Intermediate 101), and 3.2 g (15.4 mmol) of 1-methyl-2-phenylindole and 3.1 g (20.0 mmol) of phosphorus oxychloride were used instead of N-ethyl-1-naphthylamine hydrobromide. The intermediate dye (see below (Intermediate 202)) (8.2 g, yield 97%) was obtained as a deep blue solid by the same method.

[0123] [ka]

[0124] In Synthesis Example 1, the target comparative example compound (H-2) (2.5 g, yield 81%) was obtained as a brown solid by the same method as in Example 1, except that 2.0 g (3.9 mmol) of (intermediate 202) was used instead of (intermediate D-1) and 1.1 g (3.9 mmol) of lithium bis(trifluoromethanesulfonyl)imide was used.

[0125] NMR measurements were performed on the obtained brown solid, and the following 40 hydrogen signals were detected, identifying the structure of the compound represented by the following formula (H-2).

[0126] 1 H-NMR (300MHz, DMSO-d6): 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).

[0127] [ka]

[0128] [Synthesis Comparative Example 3] Synthesis of Comparative Compound (H-3) Compound (H-3) was obtained as a blue-violet solid by a known method (Patent Document 4, paragraph

[0211] ).

[0129] NMR measurements were performed on the obtained blue-violet solid, and the following 45 hydrogen signals were detected, identifying the structure of the compound represented by the following formula (H-3).

[0130] 1 H-NMR (300MHz, DMSO-d6): 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).

[0131] [ka]

[0132] [Synthesis Comparative Examples 4 and 5] Synthesis of Comparative Compounds (H-4) and (H-5) In Synthesis Example 1, instead of (intermediate D-1), an intermediate dye (see Patent Document 5, paragraph

[0139] or paragraph

[0137] below) prepared by an intermediate dye (see (intermediate 203) or (intermediate 204)) was used, and lithium bis(trifluoromethanesulfonyl)imide was used in an amount equal to 1.2 times the molar amount of the intermediate dye, respectively. Otherwise, compounds (H-4) and (H-5) were obtained as follows by the same method.

[0133] [ka]

[0134] The obtained solids were subjected to NMR measurements, and the signals of the corresponding number of hydrogen atoms were detected, identifying the structures of the compounds represented by the following formulas (H-4) and (H-5).

[0135] Comparative compound (H-4), 0.1 g, dark blue solid, 33 hydrogen signals.

[0136] 1H-NMR (300MHz, CDCl3): δ(ppm)=8.00-7.71(2H), 7.88(1H), 7.59-7.20(4H), 6.63(1H), 3.90-3.58(10H), 1.60-1.10(15H).

[0137] Comparative example compound (H-5) 0.1g, black solid, 38 hydrogen signals.

[0138] 1 H-NMR (300MHz, CDCl3): δ(ppm)=8.00-7.92(2H), 7.65(1H), 7.45-7.14(7H), 4.33(1H), 3.86(1H), 3.83-3.32(8H), 2.35(3H), 1.42-1.10(15H).

[0139] [ka]

[0140] [Example 1] (Measurement of maximum absorption wavelength) The compound (L-1) obtained in Synthesis Example 1 was dissolved in propylene glycol monomethyl ether (PGME) to prepare a 0.02 mmol / L solution. The ultraviolet-visible absorption spectrum (wavelength range of 350-800 nm) was measured at room temperature (25°C) using a UV-Vis spectrophotometer (JASCO Corporation, model: V-650) to determine the spectral characteristics, and the maximum absorption wavelength in the measured wavelength range was determined. The measurement results are shown in Table 1.

[0141] [Examples 2-7] In Example 1, the spectral characteristics (ultraviolet-visible absorption spectrum (maximum absorption wavelength in the wavelength range of 350-800 nm)) of the PGME solution were measured in the same manner as in Example 1, except that the compound shown in Table 1 was used instead of compound (L-1). The results are summarized in Table 1.

[0142] [Comparative Example 1 to Comparative Example 5] For comparison, the spectral characteristics of the PGME solution were measured in the same manner as in Example 1, except that the aforementioned triarylmethane dye compounds (H-1) to (H-5), which are not part of the present invention, were used instead of the compound (L-1) of the example. The results are summarized in Table 1.

[0143] [Table 1]

[0144] As shown in Table 1, the triarylmethane dye, which is an example compound of the present invention, is superior to the conventional triarylmethane dye of the comparative example in that it has a maximum absorption wavelength on the longer wavelength side. [Industrial applicability]

[0145] The coloring composition containing the triarylmethane dye according to the present invention has a maximum absorption wavelength in the visible light region at a long wavelength of 638 nm or higher, and can be used as a dye material for various applications such as colorants for color filters. Furthermore, by using this coloring composition as a colorant for color filters, it is possible to produce color filters with excellent color characteristics (color gamut, brightness, contrast ratio, etc.).

Claims

1. A triarylmethane dye represented by the following general formula (1), wherein the maximum absorption wavelength of 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 represented by the following general formula (1) is in the wavelength range of 638 nm to 680 nm. 【Chemistry 1】 [In formula (1), R １ And R3 are, independently, hydrogen atoms, Linear or branched alkyl groups having 1 to 30 carbon atoms, which may have substituents. A substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, or This represents a heterocyclic group having 1 to 30 carbon atoms, which may have substituents. R2 and R4 each independently represent a linear or branched alkyl group having 1 to 30 carbon atoms, which may have substituents. R １ and R ２ , R ３ and R ４ They may be joined to each other to form a ring. R ５ and R ６ Each of them operates independently. This represents a phenyl group having 6 to 30 carbon atoms, which may have substituents. R ７ and R ８ each independently represents a hydrogen atom, -CN, -NO ２ , a halogen atom Linear or branched alkyl groups having 1 to 30 carbon atoms, which may have substituents. A linear or branched alkoxy group having 1 to 30 carbon atoms, which may have substituents. Aromatic hydrocarbon groups having 6 to 30 carbon atoms, which may have substituents. A heterocyclic group having 1 to 30 carbon atoms, which may have substituents. An aryloxy group having 1 to 30 carbon atoms, which may have substituents. An amino group having 0 to 30 carbon atoms, which may have substituents. ―COO － , -COOH, -COOM, a carbonyl group having 1 to 30 carbon atoms which may have substituents, an ester group or an amide group, ―SO ３ － , -SO ３ H, -SO ３ M represents a sulfonyl group or sulfonamide group having 0 to 30 carbon atoms, which may have substituents. M represents an inorganic cation or an organic cation. Ar represents a heterocyclic group having 1 to 30 carbon atoms, which may have substituents. An represents an anion, a represents an integer from 1 to 3, and b represents an integer from 0 to 6.

2. In the above general formula (1), R １ The triarylmethane dye according to claim 1, wherein R 3 is a linear or branched alkyl group having 1 to 12 carbon atoms, which may have substituents, or an aromatic hydrocarbon group having 6 to 12 carbon atoms, which may have substituents.

3. In the above general formula (1), Ar may have substituents, having 3 to 30 carbon atoms. Pyrrolyl group, indolyl group, thienyl group, thiazolyl group, furanyl group, or oxazolyl group A triarylmethane dye according to claim 1 or claim 2, which is a base.

4. In the above general formula (1), An is a halide ion, (CF ３ SO ２ ) ２ N － The triarylmethane dye according to any one of claims 1 to 3, wherein the triarylmethane dye is a sulfonylimide anion or a sulfonate anion.

5. A colored composition containing the triarylmethane dye according to any one of Claims 1 to 4.

6. A triarylmethane dye according to any one of claims 1 to 4, A coloring agent for color filters containing the coloring composition described in claim 5.

7. A color filter using the coloring agent for color filters described in claim 6.

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