Triarylmethane dye, coloring composition containing dye, colorant for color filter, and color filter

Abstract

To provide a triarylmethane dye with excellent heat resistance, and also to provide a colorant for color filters with excellent color characteristics by utilizing a coloring composition containing the dye.SOLUTION: Provided is a triarylmethane dye represented by the general formula (1). [In the formula, R1 to R5 represent H, an alkyl group, an aromatic hydrocarbon group, or the like; R6 to R10 represent H, a halogen atom, OH, CF3, NO2, CN, or the like; R11 to R14 represent H, an alkyl group, or the like; at least one of R8 and R12 to R14 is an alkyl group or an aromatic hydrocarbon group].SELECTED DRAWING: None

Description

Technical Field

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

Background Art

[0002] Color filters are used in liquid crystal display devices, organic electroluminescence (organic EL) display devices, and solid-state imaging devices such as CCDs and CMOS sensors, and have red pixels (R), green pixels (G), and blue pixels (B). As colorants used in color filters, there are pigments and dyes, etc. However, during the manufacture of color filters, since they are exposed to conditions such as high temperatures of 200°C or higher and ultraviolet irradiation, pigments that are superior in heat resistance and light resistance to dyes have generally been used. For example, as a blue pigment for forming a blue pixel portion, generally, an ε-type copper phthalocyanine pigment (C.I. Pigment Blue 15:6) is used, and if necessary, for color adjustment, a small amount of a purple dioxazine violet pigment (C.I. Pigment Violet 23) is used in combination.

[0003] In recent trends, power saving of image display devices has been demanded, and the demand for higher brightness of color filters has increased in order to improve the utilization efficiency of backlights. In particular, the blue pixel portion has a relatively low utilization efficiency of the backlight compared to the red and green pixel portions, and improvement is desired.

[0004] Since pigments are generally insoluble in solvents, they exist in the form of fine particles in color filters containing resins, etc. Therefore, a color filter using a pigment is known to cause a decrease in brightness and color purity due to reflection and scattering of transmitted light on the surface of the pigment particles, and also a decrease in the contrast ratio of a color display device due to the depolarizing action of reflection.

[0005] In order to improve the problem of reduction in luminance and contrast ratio, not only conventional pigments but also dyes are being considered as colorants (for example, Patent Document 1). Since dyes are soluble in solvents, color filters using dyes have a suppressed depolarization effect compared to the case where only pigments are used as colorants, have excellent spectral characteristics, and are expected to improve luminance, contrast, etc. For this reason, in particular, the use of dyes, which are generally more soluble than pigments, has attracted attention for color filters in the blue pixel portion.

[0006] In particular, since triarylmethane dyes have good spectral characteristics, examples of their use as colorants for color filters have been proposed (for example, Patent Documents 2 and 3). However, when conventionally known triarylmethane dyes are used in the preparation of color filters, there has been a problem that the hue is likely to change due to the heat history in the manufacturing process. Further, although Patent Document 4 clearly states that triarylmethane dyes having a specific structure exhibit high stability against alkaline conditions, there is no description regarding heat resistance.

Prior Art Documents

Patent Documents

[0007]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Non-Patent Documents

[0008]

Non-Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0009] Having heat resistance is an important property required in the manufacturing process of color filters. An object of the present invention is to provide a triarylmethane dye having excellent heat resistance, and an object of the present invention is to provide a colorant for color filters having good color characteristics (color gamut, luminance, contrast ratio, etc.) using the dye.

Means for Solving the Problems

[0010] As a result of intensive studies to solve the above problems, the present inventors have found a triarylmethane dye having excellent heat resistance compared to conventional triarylmethane dyes. That is, the present invention has the following gist.

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

[0012]

Chemical formula

[0013] [In formula (1), R 1 ~R 5 are each independently, -H, a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or a heterocyclic group having 2 to 20 carbon atoms which may have a substituent, R 1 and R 2 , R 3 and R 4 may be bonded to each other to form a ring. R 6 ~R 10 are each independently, -H, a halogen atom, -OH, -CF 3 , -NO 2 , -CN, A linear, branched or cyclic alkyl group having 1 to 12 carbon atoms which may have a substituent, or, represents a linear, branched or cyclic alkoxy group having 1 to 12 carbon atoms which may have a substituent, R 11 ~R 14 each independently represents ―H, a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, R 8 and R 12 ~R 14 at least one of which represents a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent. An represents an anion and m represents a natural number.]

[0014] 2. In the general formula (1), the triarylmethane dye according to 1., wherein R 1 and R 3 are each independently an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.

[0015] 3. In the general formula (1), the triarylmethane dye according to 2., wherein R 1 and R 3 are the same.

[0016] 4. In the general formula (1), the triarylmethane dye according to 1., wherein R 5 is a linear alkyl group having 1 to 3 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.

[0017] 5. In the general formula (1), the triarylmethane dye according to 1., wherein R 11 is ―H, and R 8 、R 12 ~R 14The triarylmethane dye according to 1., wherein the substituent is a linear alkyl group having 1 to 3 carbon atoms which may have a substituent.

[0018] 6. In the general formula (1), An is The triarylmethane dye according to 1., which is a perfluoroalkylsulfonic acid anion, a perfluoroalkylsulfonimide anion, a tris(trifluoromethanesulfonyl)methide anion, or a heteropolyacid anion.

[0019] 7. The triarylmethane dye of the 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, is 570 nm or more and 640 nm or less. The triarylmethane dye according to 1.

[0020] 8. The triarylmethane dye of the general formula (1), wherein the 5% mass loss temperature in the TG-DTA measurement (sample mass: 5.0 to 6.0 mg, heating rate: 10 °C / min) performed under a nitrogen stream (nitrogen flow rate: 50 mL / min) using a thermogravimetric-differential thermal analyzer is 270 °C or higher. The triarylmethane dye according to 1.

[0021] 9. A coloring composition containing the triarylmethane dye according to any one of (1. to 8.).

[0022] 10. A color filter coloring agent containing the coloring composition according to (9.).

[0023] 11. A color filter using the color filter coloring agent according to (10.).

Advantages of the Invention

[0024] The triarylmethane dye of the present invention is excellent in heat resistance, and the coloring composition containing the dye is useful as a color filter coloring agent.

Embodiments for Carrying Out the Invention

[0025] Hereinafter, embodiments of the present invention will be described in detail. The present invention is not limited to the following embodiments and can be implemented with various modifications within the scope of the gist. First, the triarylmethane dye represented by the general formula (1) will be described.

[0026] In the general formula (1), R 1 ~R 14 In the "linear, branched or cyclic alkyl group having 1 to 12 carbon atoms which may have a substituent" represented by, as the "linear, branched or cyclic alkyl group having 1 to 12 carbon atoms", specifically, linear 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, 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 group, 3-methylpentyl group, 4-methylpentyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, 1-ethyl-1-methylpropyl group, isooctyl group, 2-ethylhexyl group and other branched alkyl groups; cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, 2-methylcyclohexyl group, 2-ethylcyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group and other cyclic alkyl groups (cycloalkyl groups), norbornyl group, 1-adamantyl group, 2-adamantyl group and the like can be mentioned. Here, for the "branched or cyclic alkyl group", it is understood by those skilled in the art that the lower limit of the number of carbon atoms is the number of carbon atoms capable of taking a branched or cyclic structure (that is, 3 carbon atoms).

[0027] In the general formula (1), R 1 ~R5 , R 11 ~R 14 In the “aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent” represented by, specific examples of the “aromatic hydrocarbon group having 6 to 20 carbon atoms” include aromatic hydrocarbon groups such as phenyl group, biphenylyl group, terphenylyl group, naphthyl group, azulenyl group, anthryl group, tetracenyl group, phenanthryl group, fluorenyl group, indenyl group, pyrenyl group, perylenyl group, fluoranthenyl group, triphenylenyl group, etc. (The “aromatic hydrocarbon group” in the present invention also includes an aryl group or a condensed polycyclic aromatic group).

[0028] In general formula (1), R 1 ~R 5In the "heterocyclic group having 2 to 20 carbon atoms which may have a substituent" represented by [formula], specific examples of the "heterocyclic group having 2 to 20 carbon atoms" include a pyridyl group, a pyrimidinyl group, a quinolyl group, an isoquinolyl group, a pyrazinyl group, a triazinyl group, a naphthyridinyl group, an acridinyl group, a phenanthrolinyl group, a carbolinyl group, a purinyl group, a phthalazinyl group, a quinoxalinyl group, a quinazolinyl group, a cinnolinyl group, a pteridinyl group, a phenanthridinyl group, a perimidinyl group, an anti-ridinyl 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 aza-indolyl group, an aza-indazolyl 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 benzoisoxazolyl group, a benzothiazolyl group, a benzoisothiazolyl group, a benzothiadiazolyl group, a phenoxathiinyl group, an oxazolopyridyl group, an oxazolopyrazyl group, a benzo[1,2-b:4,5-b']dithiophenyl group, a bipyridinyl group and other heterocyclic groups (or heteroaromatic hydrocarbon groups).

[0029] In general formula (1), R 6 ~R 10 Examples of the "halogen atom" represented by [formula] include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like. As the "halogen atom", a fluorine atom or a chlorine atom is preferable.

[0030] In general formula (1), R 6 ~R 10In the "linear, branched or cyclic alkoxy group having 1 to 12 carbon atoms which may have a substituent" represented by , the "linear, branched or cyclic alkoxy group having 1 to 12 carbon atoms" specifically includes linear alkoxy groups such as methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group; branched alkoxy groups such as isopropoxy group, isobutoxy group, s-butoxy group, t-butoxy group, isooctyloxy group; cyclic alkoxy groups (cycloalkoxy groups) such as cyclopropoxy group, cyclobutoxy group, cyclopentyloxy group, cyclohexyloxy group, cycloheptyloxy group, cyclooctyloxy group, cyclononyloxy group, cyclodecyloxy group; 1-adamantyloxy group, 2-adamantyloxy group, and the like.

[0031] In general formula (1), R 1 ~R 14 represented by any one of "linear, branched or cyclic alkyl group having 1 to 12 carbon atoms which may have a substituent", "aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent", "heterocyclic group having 2 to 20 carbon atoms which may have a substituent", or the "substituent" in the "linear, branched or cyclic alkoxy group having 1 to 12 carbon atoms which may have a substituent" specifically deuterium atom, hydroxy group (―OH), thiol group (―SH), cyano group (―CN), nitro group (―NO 2 )), trifluoromethyl group (―CF 3 )); halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom; linear, branched or cyclic alkyl group having 1 to 20 carbon atoms; linear or branched alkenyl group having 2 to 20 carbon atoms; linear or branched alkynyl group having 2 to 20 carbon atoms; A linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms; 1-adamantyloxy group, 2-adamantyloxy group; An acyl group having 1 to 20 carbon atoms; An 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; An unsubstituted amino group; a mono- or di-substituted amino group having 1 to 20 carbon atoms; —COOH, —COOM, or a carbonyl group, ester group or amide group having 1 to 20 carbon atoms which may have a substituent, —SO 3 H, —SO 3 M, or a sulfonyl group or sulfonamide group having 0 to 20 carbon atoms which may have a substituent (wherein M represents an inorganic cation or an organic cation). Examples include the above. These "substituents" may contain only one, or may contain a plurality. When a plurality are contained, they may be the same or different from each other. Further, in the group having these "substituents", when there are a plurality of positions where the "substituent" can be bonded, such as any of the four carbons in the n-butyl group, the para-position, meta-position, or ortho-position in the phenyl group, it may be substituted at any of those positions. When there are a plurality of positions where the "substituent" can be a bonding site, such as in a pyridyl group or a naphthyl group, it may be bonded at any of those positions. Further, these "substituents" may further have the substituents exemplified above. Therefore, these "substituents" may be represented, for example, as "a linear or branched unsubstituted or substituted alkyl group having 1 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 amide 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", and the like. When the "substituent" contains a carbon atom, the carbon atom is included in the above "1 to 20 carbon atoms" and "6 to 20 carbon atoms". Further, 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.

[0032] In General Formula (1), when there is a "monosubstituted or disubstituted amino group having 1 to 20 carbon atoms", "―NR 15 R 16 " represents the "substituent R 15 and R 16It includes an "amino group having" and examples thereof include a mono-substituted amino group, a di-substituted amino group, etc. "Substituent R" 15 and R 16 in the "amino group having", R 15 and R 16 As the "substituent" represented by, the same ones as the "substituents" in each group represented by R 1 ~R 14 are applicable. Examples of the mono-substituted amino group include an ethylamino group, a butylamino group, an acetylamino group, a phenylamino group, etc. Examples of the di-substituted 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; a dialkenylamino group having 4 to 20 carbon atoms such as a diallylamino group; a diphenylamino group, an N-acetyl-N-phenylamino group, a (n-butyl)-N-phenylamino group, etc.

[0033] In the general formula (1), when an "inorganic cation" or an "organic cation" represented by "M" exists, as the "organic cation", specifically, an ammonium ion represented by the formula of R 17 R 18 R 19 R 20 N + is mentioned. R 17 ~R 20 each independently represents 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. In the above formula, the details of the "substituent", the "linear or branched alkyl group having 1 to 20 carbon atoms" and the "aromatic hydrocarbon group having 6 to 20 carbon atoms" in R 17 ~R 20 are the same as those of R 1 ~R 14The same applies. Examples of the "inorganic cation" 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. As M, an alkali metal ion is preferred.

[0034] In the general formula (1), when there is a "carbonyl group, ester group, or amide group having 1 to 20 carbon atoms which may have a substituent", they are respectively represented by "―(C=O)―R 21 ", "―(C=O)―O―R 21 ", or "―(C=O)―NR 15 R 16 ". R 21 and "―NR 15 R 16 " are applied with the same ones as the "substituents" in each group represented by R 1 ~R 14 .

[0035] In the general formula (1), when there is a "sulfonyl group or sulfonamide group having 0 to 20 carbon atoms which may have a substituent", it means a group represented by "―SO 2 ―R 21 " (or "―S(=O) 2 ―R 21 ") or "―S(=O) 2 ―NR 15 R 16 ". R 21 and "―NR 15 R 16 " are applied with the same ones as the "substituents" in each group represented by R 1 ~R 14 .

[0036] In the general formula (1), in each of the above various "groups" having a "substituent" represented by R 1 ~R 14 , the "substituents" listed as the "substituents" "linear, branched, or cyclic alkyl group having 1 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, branched or cyclic alkoxy group having 1 to 20 carbon atoms", "an acyl group having 1 to 20 carbon atoms", "an 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", or "a monosubstituted or disubstituted amino group having 1 to 20 carbon atoms", specifically, 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, decyl group; cyclic alkyl groups (cycloalkyl groups) such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, cyclononyl group, cyclodecyl group; alkenyl groups such as vinyl group, 1-propenyl group, allyl group, 1-butenyl group, 2-butenyl group, 1-pentenyl group, 1-hexenyl group, isopropenyl group, isobutenyl group, or linear or branched alkenyl groups formed by multiple bonding of these; alkynyl groups such as ethynyl group, propargyl group, butynyl group, or linear or branched alkynyl groups formed by multiple bonding of these; mixed groups of alkenyl groups and alkynyl groups such as penta-3-en-1-ynyl group, hexa-2-en-4-ynyl group; linear or branched alkoxy groups such as methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, isopropoxy group, isobutoxy group, s-butoxy group, t-butoxy group, isooctyloxy group; Cyclic alkoxy groups having 3 to 20 carbon atoms such as cyclopropoxy group, cyclobutoxy group, cyclopentyloxy group, cyclohexyloxy group, cycloheptyloxy group, cyclooctyloxy group, cyclononyloxy group, cyclodecyloxy group (cycloalkoxy group); Acyl groups such as formyl group, acetyl group, propionyl group, acrylyl group, benzoyl group; Aromatic hydrocarbon groups or condensed polycyclic aromatic groups such as phenyl group, biphenylyl group, terphenylyl group, naphthyl group, anthracenyl group (anthryl group), tetracenyl group, phenanthryl group, fluorenyl group, indenyl group, pyrenyl group, perylenyl 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, benzoxazolyl group, benzimidazolyl group, benzotriazolyl group, purinyl group, carbazolyl group, dibenzothienyl group, dibenzofuranyl group, pyridyl group, pyrimidinyl group, triazinyl group, bipyridinyl group, quinolyl group, isoquinolyl group, naphthyridinyl group, acridinyl group, phenanthrolinyl group, carbolinyl group; Aryloxy groups such as phenyloxy group, tolyloxy group, biphenylyloxy group, naphthyloxy group, anthracenyloxy group, phenanthrenyloxy group; Aralkyloxy groups such as benzyl group, phenethyl group; Linear or branched monoalkylamino groups such as methylamino group, ethylamino group, isopropylamino group; linear or branched dialkylamino groups such as dimethylamino group, diethylamino group, ethylmethylamino group, dipropylamino group, dibutylamino group, di(2-ethylhexyl) group, di-t-butylamino group; monoarylamino groups such as phenylamino group, 1-naphthylamino group, 2-naphthylamino group; diarylamino groups such as diphenylamino group, N-phenyl-1-naphthylamino group; alkylarylamino groups such as N-methyl-phenylamino group; and other monosubstituted or disubstituted amino groups having a linear or branched alkyl group or an aromatic hydrocarbon group, etc. can be mentioned.

[0037] In general formula (1), R 1 and R 3 are preferably a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, more preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, and particularly preferably a phenyl group or a naphthyl group which may have a substituent. R 1 and R 3 may be the same or different from each other, but are more preferably the same.

[0038] In general formula (1), R 2 and R 4 are preferably -H, a linear, branched or cyclic alkyl group having 1 to 12 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 -H or a linear, branched or cyclic alkyl group having 1 to 3 carbon atoms which may have a substituent.

[0039] In general formula (1), R 5is preferably -H, a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, more preferably a linear, branched or cyclic alkyl group having 1 to 3 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, and particularly preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.

[0040] In the general formula (1), R 5 When having a substituent, the substituent is preferably a cyano group (―CN), a nitro group (―NO 2 ), a trifluoromethyl group (―CF 3 ), a carbonyl group (―(C=O)―), a halogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and more preferably an electron-withdrawing group such as a nitro group (―NO 2 ), a trifluoromethyl group (―CF 3 ), a halogen atom.

[0041] In the general formula (1), R 8 , R 12 ~R 14 is preferably a linear, branched or cyclic alkyl group having 1 to 12 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 alkyl group having 1 to 3 carbon atoms which may have a substituent. R 6 , R 7 , R 9 ~R 11 is each independently as defined above, but preferably all are hydrogen. In a particularly preferred embodiment, the triarylmethane dye has R 11 being ―H in the general formula (1), and R 8 , R 12 ~R 14 being a compound of a linear alkyl group having 1 to 3 carbon atoms which may have a substituent.

[0042] In general formula (1), An is not particularly limited, and examples thereof include halide ions or organic anions. Specifically, Cl - 、Br - 、I - ;(CF 3 SO 2 ) 2 N - (or Tf 2 N - ), (CF 3 SO 2 ) 3 C - (or Tf 3 C - ), (C 2 F 5 SO 2 ) 2 N - 、(C 4 F 9 SO 2 ) 2 N - 、(C 6 F 5 SO 2 ) 2 N - 、 (C 2 F 5 ) 3 F 3 P - 、 (CN) 2 N - 、(CN) 3 C - 、NC―S - 、; (C 6 H 4 SO 3 - )O(C 6 H 3 (C 12 H 25 )(SO 3 - ))、 C 6 H 4 (C 12 H25 )(SO 3 - );PF 6 - 、BF 4 - ; (PW 12 O 40 ) 3- 、(P 2 W 18 O 62 ) 6- 、 (SiW 12 O 40 ) 4- 、(PMo 12 O 40 ) 3- 、(SiMo 12 O 40 ) 3- 、 (PW 12-x Mo x O 40 ) 3- 、(SiW 12-x Mo x O 40 ) 4- 、 (P 2 W 18-y Mo y O 40 ) 6- (x represents an integer from 1 to 11, and y represents an integer from 1 to 17), and other heteropoly acid anions; Or, anions represented by the structural formulas of the following formulas (Z-1) to (Z-16) can be mentioned.

[0043]

Chem.

[0044]

Chem.

[0045]

Chem.

[0046] [Chemical formula]

[0047] In general formula (1), An may be single or a combination of two or more different ones, and is preferably a single one or any combination of two or three selected from the exemplified anions, more preferably a perfluoroalkylsulfonic acid anion (more preferably a perfluoroalkylsulfonic acid anion having 1 to 24 carbon atoms), a perfluoroalkylsulfonimide anion (more preferably a perfluoroalkylsulfonimide anion having 1 to 24 carbon atoms), a tris(trifluoromethanesulfonyl)methide anion, or any combination of single, two, or three selected from heteropolyacid anions. Therefore, "m" in general formula (1) is an arbitrary natural number selected so that formula (1) is electrically neutral as a whole according to the valence of the entire [An] in formula (1) and the valence of the cation of the structure of the triarylmethane skeleton in [ ]. It is preferable that m is an integer of 1 to 6, and more preferably an integer of 1 to 3.

[0048] Hereinafter, specific examples of preferred compounds of the triarylmethane dye of the present invention represented by general formula (1) are shown, but the present invention is not limited to these compounds. The following formulas (B-1) to (B-24) represent the triarylmethane dye portion in the general formula (1), and the anion portion represented by [An] is omitted. In the following structural formulas, some hydrogen atoms are omitted, including all possible stereoisomers and tautomers, and planar structural formulas are described.

[0049] [Chemical formula]

[0050] [Chemical formula]

[0051] [Chemistry]

[0052] [Chemistry]

[0053] [Chemistry]

[0054] [Chemistry]

[0055] [Chemistry]

[0056] [Chemistry]

[0057] The method for producing a compound which is a triarylmethane dye represented by the general formula (1) is not particularly limited, and known methods (for example, Non-Patent Document 1) can be applied, and it can be produced using reagents having various corresponding groups of the general formula (1) and other appropriate reagents. Hereinafter, one embodiment of the method for producing the compound of the present invention will be described. However, the present invention is not limited thereto.

[0058] The triarylmethane dye represented by the general formula (1) can be obtained by subjecting a benzophenone derivative having a corresponding substituent and a tetrahydroquinoline having a corresponding substituent to a condensation reaction. Further, the triarylmethane dye represented by the general formula (1) can be produced by salt exchange with a salt having a corresponding structure, if necessary. The chemical reaction in this production may be carried out in the presence of an organic solvent or without a solvent.

[0059] 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 ordinary organic synthesis, for example, purification by column chromatography; adsorption purification using silica gel, activated carbon, activated clay, etc.; recrystallization with a solvent or crystallization methods. In addition, for the identification, analysis, evaluation of optical properties, thermal physical properties, and other physical properties of these compounds, nuclear magnetic resonance analysis (NMR), absorbance measurement with a spectrophotometer, ultraviolet-visible absorption spectrum (UV-Vis) measurement, thermogravimetric measurement-differential thermal analysis (TG-DTA), etc. can be performed. These analysis methods can also be used for the solubility, color evaluation, and heat resistance evaluation of the obtained compounds.

[0060] The triarylmethane dyes of the present invention may be used (for example, mixed) by combining one kind or two or more kinds having different molecular structures. When using two or more kinds, in the mass concentration ratio in the total triarylmethane dyes, the mass concentration ratio of the least one kind of triarylmethane dye is 0.1 to 50% by mass. It is preferable that the number of types of triarylmethane dyes is one or two.

[0061] The triarylmethane dyes of the present invention, the coloring compositions containing such dyes, and the colorant for color filters containing such dyes or such coloring compositions need to be well dissolved or dispersed in an organic solvent containing a resin or the like in the manufacturing processes of the colorant and the color filter. Therefore, it is preferable that they have high solubility and dispersibility in the organic solvent. The organic solvent is not particularly limited, but specifically, 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; 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); dimethyl sulfoxide (DMSO), etc. are mentioned. PGME, PGMEA, cyclohexanone, or DAA is preferable, and PGME or PGMEA is particularly preferable from the viewpoint of achieving both the solubility of the resin and the solubility of the triarylmethane dye. These solvents may be used alone or in combination of two or more.

[0062] The triarylmethane dyes of the present invention show a maximum absorbance in the visible light region (for example, in the wavelength range of 350 to 800 nm) of the ultraviolet-visible absorption spectrum measured at around room temperature (for example, 23 to 27 °C) using a solution prepared by dissolving the dye in an organic solvent, and a maximum absorption wavelength is observed. In the present invention, it is preferable that the maximum absorption wavelength in the PGME solution is 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 of the ultraviolet-visible absorption spectrum does not shift significantly depending on the dissolution conditions, and PGME is preferable.

[0063] The triarylmethane dye of the present invention can be mixed with various resin solutions and applied onto a glass substrate to form a coating film. Color evaluation can be performed on the obtained coating film by measuring the color using a spectrophotometer and obtaining the color values of the coating film. The color values are CIE L * a * b * color systems and the like are generally used. Specifically, the color values L * , a * , b * of the film sample are measured, and the heat resistance can be determined from the color difference (ΔE * ab ) of the color values before and after heating at an appropriate temperature. When applied to a color filter, the color difference at a temperature around 230 °C can be used as an index of heat resistance. The smaller the value of ΔE * ab , the less discoloration due to thermal decomposition and the higher the heat resistance. A value of 20 or less is preferable, 12 or less is more preferable, and 10 or less is even more preferable. Further, as a method for comparing the heat resistance of the dyes, it may be evaluated by thermogravimetric measurement. For example, using a thermogravimetric-differential thermal analyzer, the 5% mass loss temperature can be measured by thermogravimetric measurement in an inert gas atmosphere such as nitrogen. As the 5% mass loss temperature, 270 °C or higher is preferable, 300 °C or higher is more preferable, and the higher the decomposition temperature, the more preferable.

[0064] The colorant for a color filter of the present invention includes a triarylmethane dye represented by the general formula (1), or a coloring composition containing at least one kind of the triarylmethane dye, and components generally used in the manufacture of color filters. A general color filter is obtained, for example, in the case of a method using a photolithography process, by mixing a liquid prepared by mixing a dye such as a dye or a pigment with a resin component (including monomers and oligomers) and a solvent, applying it onto a substrate such as glass or resin, exposing it through a photomask, creating a colored pattern of a dye-resin composite film soluble / insoluble in the solvent, and heating it after washing. Also, in the electrodeposition method and the printing method, a colored pattern is created using a mixture of a dye and a resin or other components. Therefore, specific components in the colorant for a color filter of the present invention include at least one triarylmethane dye represented by the general formula (1), other dyes such as other dyes and pigments, a resin component, an organic solvent, and other additives such as a photopolymerization initiator. Also, these components may be selected as appropriate, and other components may be added as necessary.

[0065] When the triarylmethane dye of the present invention or the coloring composition containing the triarylmethane dye is used as a colorant for a color filter, it may be used for each color color filter, but it is preferably used as a colorant for a blue or green color filter.

[0066] The colorant for a color filter of the present invention may use one or more triarylmethane dyes alone, or may be mixed with known dyes such as other dyes or pigments in order to adjust the color tone, that is, to adjust the spectral characteristics.

[0067] When used as a colorant for a cyan color filter, although not particularly limited, basic dyes such as C.I. Basic Blue 3, 7, 9, 54, 65, 75, 77, 99, 129, C.I. Basic Violet 10; acidic dyes such as C.I. Acid Blue 9, 74, C.I. Acid Red 52, 289; disperse dyes such as Disperse Blue 3, 7, 377; spiron dyes; cyanine-based, indigo-based, phthalocyanine-based, anthraquinone-based, methine-based, triarylmethane-based, indanthrene-based, oxazine-based, dioxazine-based, azo-based, xanthene-based dyes that do not belong to the present invention; other blue-based lake pigments, etc., blue-based or red-based dyes or pigments can be mentioned. When used as a colorant for a green color filter, although not particularly limited, green pigments such as C.I. Pigment Green 7, 10, 36, 47, 58, 59, 62, 63; yellow pigments such as C.I. 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, quinophthalone-based dyes that do not belong to the present invention; other lake pigments, etc., blue-based, yellow-based or green-based dyes or pigments can be mentioned.

[0068] In the present invention, as the dyes to be mixed for color tone adjustment, when used as a colorant for a blue color filter, triarylmethane dyes not belonging to the present invention such as C.I. Basic Blue 7, C.I. Basic Violet 10, C.I. Acid Red 52, 289 and other xanthene dyes, phthalocyanine dyes such as C.I. Pigment Blue 15:3, or dioxazine dyes such as C.I. Pigment Violet 23 are preferred. When used as a colorant for a green color filter, quinophthalone dyes such as C.I. Pigment Yellow 138, isoindoline dyes such as C.I. Pigment Yellow 185, azo dyes such as C.I. Pigment Yellow 150, or phthalocyanine pigments such as C.I. Pigment Green 58 are preferred. By using these dyes and the triarylmethane dyes belonging to the present invention, it is easy to optimize the transmittance spectrum, and a blue or green color filter excellent in light resistance and chemical resistance can be obtained.

[0069] The pigment may be subjected to surface treatment using rosin treatment, a pigment derivative having an acidic group or a basic group introduced, graft treatment on the pigment surface with a polymer compound, etc., micronization treatment by the sulfuric acid fine particle method, or cleaning treatment with an organic solvent or water for removing impurities, removal treatment by an ion exchange method for ionic impurities, etc. The particle size of the pigment is preferably uniform.

[0070] The mixing ratio of other dyes in the colorant for a color filter of the present invention is preferably 5 to 2000% by mass, more preferably 10 to 1000% by mass, based on the triarylmethane dye (the total thereof in the case of two or more kinds). The mixing ratio of a dye or other pigment component in the liquid colorant for a color filter is preferably 0.5 to 70% by mass, more preferably 1 to 50% by mass, based on the whole colorant.

[0071] As the resin component in the colorant for color filters of the present invention, known resins can be used as long as they have the manufacturing method of the color filter resin film formed using them and the properties required during use. Specifically, for example, acrylic resins, olefin resins, styrene resins, polyimide resins, urethane resins, polyester resins, epoxy resins, vinyl ether resins, phenol (novolak) resins, other transparent resins, photocurable resins or thermosetting resins can be mentioned, and these monomer or oligomer components can be used in appropriate combinations. Also, copolymers of these resins can be used in combination. The content of the resin in these colorants for color filters is preferably 5 to 95% by mass, more preferably 10 to 50% by mass in the case of liquid colorants.

[0072] In order to enhance the performance as a colorant for color filters, the color composition of the present invention can add organic compounds such as surfactants, dispersants, defoaming agents, leveling agents, antioxidants, ultraviolet absorbers, and other additives to be mixed during the production of colorants for color filters as other components of the compound. However, the content of these additives in the color composition is preferably an appropriate amount, and it is preferably a content within a range that does not reduce the solubility of the color composition of the present invention in the solvent or improve it more than necessary, and also does not affect the effects of other similar additives used during the production of color filters. These additives can be added at any timing during the preparation of the color composition.

[0073] 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, and also surfactants and dispersants necessary for stabilizing the properties of the components in the liquid colorant for color filters. Any of these can be known ones for color filter production 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, more preferably 10 to 40% by mass.

Examples

[0074] Hereinafter, embodiments of the present invention will be specifically described with reference to examples, but the present invention is not limited to the following examples. The reagents described in the synthesis examples were those manufactured by Tokyo Chemical Industry Co., Ltd., Sigma-Aldrich, Alfa Aesar, Duksan, Daejung, etc. In addition, all reactions in the synthesis examples were carried out under a nitrogen stream using a reaction vessel equipped with a condenser, a stirrer, and a thermometer, unless otherwise specified. The identification of the compounds in the following synthesis examples was 1 performed by 1H-NMR analysis (Bruker nuclear magnetic resonance apparatus, model: Ascend (registered trademark) 400 MHz).

[0075] [Synthesis Example 1] Synthesis of Compound (C-1) Into a reaction vessel, 40.0 g (211 mmol) of 1,2,3,4-tetrahydro-2,2,4,7-tetramethylquinoline, 65.9 g (423 mmol) of iodoethane, 52.6 g (380 mmol) of potassium carbonate, and 160 mL of DMF were added, and the mixture was stirred at 75 °C for 7 hours. After cooling, 200 mL of ethyl acetate and 200 mL of heptane were added to the reaction solution, and the mixture was stirred at room temperature (23 - 28 °C) and then filtered. 300 mL of water was added to the filtrate, and the organic layer was extracted. After further washing twice with 300 mL of water, the organic layer was extracted. Anhydrous magnesium sulfate was added, and the organic layer was dried and then filtered. The filtrate was concentrated under reduced pressure. The residue was dissolved in 350 mL of heptane, 45 g of silica gel was added, and the mixture was stirred at room temperature for 30 minutes and then filtered. By concentrating the filtrate under reduced pressure, the following (Intermediate 100) was obtained (42.5 g, yield 92%).

[0076]

Chemical formula

[0077] Subsequently, 5.60 g (25.8 mmol) of the above (Intermediate 100), 8.36 g (25.8 mmol) of 4,4'-bis(diethylamino)benzophenone, and 30 mL of toluene were placed in a reaction vessel and stirred at room temperature (23 - 28 °C). 5.01 g (51.5 mmol) of phosphorus oxychloride was added dropwise thereto, and the mixture was stirred at 100 °C for 5 hours. After the reaction solution was cooled to room temperature, 50 mL of dichloromethane and 50 mL of water were added, and the organic layer was extracted. Anhydrous magnesium sulfate was added, the organic layer was dried, filtered, and the filtrate was concentrated under reduced pressure. The obtained residue was purified by column chromatography (carrier: silica gel, solvent: dichloromethane / methanol = 100 / 0 - 90 / 10 (volume ratio)), and the solvent was distilled off under reduced pressure. The residue was dried under reduced pressure at 60 °C to obtain the following (Intermediate 101) (13.1 g, yield 91%).

[0078]

Chemical formula

[0079] Subsequently, 3.48 g (6.21 mmol) of the above (Intermediate 101) and 50 mL of methanol were placed in a reaction vessel. After the solid was dissolved, a solution prepared by dissolving 8.49 g of phosphotungstic acid hydrate in 100 mL of methanol was added dropwise. After this solution was stirred at 40 °C for 4 hours, the reaction solution was filtered. The obtained solid was suspended and washed with 100 mL of methanol, the solid was collected by filtration, and then dried under reduced pressure at 60 °C to obtain the target compound (C-1) as a blue solid (8.30 g, yield 92%).

[0080] NMR measurement of the obtained blue solid was performed, and the following 150 hydrogen signals were detected and identified as the structure of the compound represented by the following formula (C-1).

[0081] 1 H-NMR (400 MHz, DMSO-d 6 ): δ (ppm) = 7.24 (12H), 6.98 (12H), 6.83 (3H), 6.66 (3H), 3.61 (30H), 2.84 (3H), 1.86 (3H), 1.50 (3H), 1.42 (9H), 1.28 (9H), 1.19 (54H), 1.13 (9H).

[0082] [Chemical formula]

[0083] [Synthesis Example 2] Synthesis of Compound (C-2) Into a reaction vessel, 25.0 g (132 mmol) of 1,2,3,4-tetrahydro-2,2,4,7-tetramethylquinoline, 24.9 g (145 mmol) of 4-bromotoluene, 22.2 g (198 mmol) of potassium t-butoxide, 88 mL of toluene, 1.48 g (6.60 mmol) of palladium acetate, and 5.34 g (13.2 mmol) of tri-t-butylphosphine (50 wt% toluene solution) were added, and the mixture was stirred under reflux for 72 hours. After cooling, the reaction solution was filtered, the filtrate was washed with 200 mL of water, and the organic layer was extracted. Anhydrous magnesium sulfate was added, the organic layer was dried, filtered, and the filtrate was concentrated under reduced pressure. The residue was dissolved in 350 mL of heptane, 35 g of silica gel was added, the mixture was stirred at room temperature (23 - 28 °C) for 30 minutes, and then filtered. By concentrating the filtrate under reduced pressure, the following (Intermediate 102) was obtained (34.6 g, yield 94%).

[0084] [Chemical formula]

[0085] Into a reaction vessel, 49.1 g (458 mmol) of N-methylaniline and 175 mL of N,N-dimethylformamide (DMF) were added, and the mixture was cooled to 5 °C while stirring. 51.4 g (458 mmol) of potassium t-butoxide was added in 4 portions to this solution. Further, a solution prepared by dissolving 25.0 g (114 mmol) of 4,4'-difluorobenzophenone in 100 mL of DMF was added dropwise to this solution. After the dropwise addition, the temperature was raised to room temperature and the mixture was stirred for 3 hours. The reaction solution was poured into 600 mL of water, and the precipitated solid was collected by filtration. The obtained solid was added to 200 mL of methanol, suspended and washed at room temperature, and then the solid was collected by filtration. The obtained solid was dried under reduced pressure at 60 °C to obtain the following (Intermediate 103) (42.7 g, yield 95%).

[0086] [Chem.]

[0087] Subsequently, in the synthesis of (Intermediate 101) in Synthesis Example 1, except that (Intermediate 100) was changed to the said (Intermediate 102) and 4,4'-bis(diethylamino)benzophenone was changed to the said (Intermediate 103), the following (Intermediate 104) was obtained by the same method (8.69 g, yield 99%).

[0088] [Chem.]

[0089] Subsequently, 3.50 g (5.07 mmol) of the said (Intermediate 104) and 17 mL of methanol were placed in a reaction vessel and stirred. After the solid was dissolved, 1.53 g (5.32 mmol) of lithium bis(trifluoromethanesulfonyl)imide (LiN(SO 2 CF 3 )) 2 ) was added. After stirring at 45°C for 1 hour, it was cooled, 85 mL of water was added, and the precipitated solid was collected by filtration. The obtained solid was dried under reduced pressure at 80°C to obtain the target compound (C-2) as a purple solid (4.31 g, yield 91%).

[0090] NMR measurement of the obtained purple solid was carried out, and the signals of the following 48 hydrogens were detected and identified as the structure of the compound represented by the following formula (C-2).

[0091] 1 1H-NMR (400 MHz, DMSO-d 6 ): δ (ppm) = 7.58 (4H), 7.41 (8H), 7.24 (4H), 7.16 (1H), 7.12 (1H), 6.97 (1H), 6.92 (4H), 5.82 (1H), 3.52 (6H), 3.06 (1H), 2.40 (3H), 2.02 (1H), 1.71 (1H), 1.53 (3H), 1.34 (3H), 1.23 (3H), 1.07 (3H).

[0092] [Chemical formula]

[0093] [Synthesis Example 3] Synthesis of Compound (C-3) In the synthesis of Compound (C-1) in Synthesis Example 1, except that (Intermediate 101) was changed to the said (Intermediate 104), the target Compound (C-3) was obtained as a blue-violet solid by the same method (6.06 g, yield 91%).

[0094] NMR measurement of the obtained blue-violet solid was carried out, and signals of the following 144 hydrogens were detected, and the structure of the compound represented by the following formula (C-3) was identified.

[0095] 1 H-NMR (400 MHz, DMSO-d 6 ): δ (ppm) = 7.58 (12H), 7.41 (24H), 7.24 (12H), 7.16 (3H), 7.13 (3H), 6.98 (3H), 6.93 (12H), 5.82 (3H), 3.52 (18H), 3.06 (3H), 2.40 (9H), 2.02 (3H), 1.72 (3H), 1.52 (9H), 1.34 (9H), 1.23 (9H), 1.07 (9H).

[0096] [Chemical formula] [Synthesis Example 4] Synthesis of Compound (C-4) Into a reaction vessel, 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 were added. 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 the mixture was stirred at 110 °C for 3 hours. The reaction solution was cooled to room temperature, 200 mL of water and 50 mL of isopropanol were added, and after stirring, the solid was collected by filtration. The obtained solid was suspended and washed with 200 mL of water, and then the solid was collected by filtration. The obtained solid was dried under reduced pressure at 80 °C to obtain the following (Intermediate 105) (55.0 g, yield 94%).

[0097]

Chemical formula

[0098] Subsequently, in the synthesis of (Intermediate 102) in Synthesis Example 2, the following (Intermediate 106) was obtained (27.3 g, yield 88%) in the same manner except that 4-bromotoluene was changed to bromobenzene.

[0099]

Chemical formula

[0100] Subsequently, in the synthesis of (Intermediate 101) in Synthesis Example 1, the following (Intermediate 107) was obtained (5.10 g, yield 76%) in the same manner except that (Intermediate 100) was changed to the above (Intermediate 106) and 4,4'-bis(diethylamino)benzophenone was changed to the above (Intermediate 105).

[0101]

Chemical formula

[0102] Subsequently, in the synthesis of the compound (C-2) of Synthesis Example 2, the target compound (C-4) was obtained as a purple solid (5.10 g, yield 76%) in the same manner except that (Intermediate 104) was changed to the said (Intermediate 107).

[0103] NMR measurement of the obtained purple solid was carried out, and the signals of the following 49 hydrogens were detected and identified as the structure of the compound represented by the following formula (C-4).

[0104] 1 H-NMR (400 MHz, DMSO-d 6 ): δ (ppm) = 9.55 (2H), 7.58 (2H), 7.50 (1H), 7.35 - 7.09 (16H), 6.94 (1H), 5.75 (1H), 3.07 (1H), 2.15 (12H), 2.00 (1H), 1.72 (1H), 1.51 (3H), 1.34 (3H), 1.25 (3H), 1.12 (3H).

[0105]

Chemical formula

[0106] [Synthesis Example 5] Synthesis of Compound (C-5) To a reaction vessel, 150 g (357 mmol) of the said (Intermediate 105) and 500 mL of DMF were added, and the mixture was cooled to 5°C with stirring. To this solution, 120 g (1.07 mol) of potassium t-butoxide was added in 4 portions, and after that, while maintaining 5°C, 167 g (1.07 mol) of iodoethane was added dropwise. After the dropwise addition, the temperature was raised to 35°C and the mixture was stirred for 3 hours. This reaction solution was added dropwise to 3.0 L of 10% aqueous sodium chloride solution, and the precipitated solid was collected by filtration. The obtained solid was suspended and washed with 1.5 L of water, and then the solid was collected by filtration. The obtained solid was suspended and washed with 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 108) (152 g, yield 89%).

[0107]

Chemical formula

[0108] Subsequently, in the synthesis of (Intermediate 101) of Synthesis Example 1, except that 4,4'-bis(diethylamino)benzophenone was changed to the said (Intermediate 108), the following (Intermediate 109) was obtained in the same manner (14.1 g, yield 98%).

[0109]

Chemical formula

[0110] Subsequently, in the synthesis of Compound (C-1) of Synthesis Example 1, except that (Intermediate 101) was changed to the said (Intermediate 109), the target compound (C-5) was obtained as a blue solid in the same manner (13.7 g, yield 79%).

[0111] NMR measurement of the obtained blue solid was carried out, and signals of 174 hydrogens below were detected and identified as the structure of the compound represented by the following formula (C-5).

[0112] 1 H-NMR (400 MHz, DMSO-d 6 ): δ (ppm) = 7.36 (6H), 7.33 - 7.19 (24H), 7.08 (6H), 6.83 (3H), 6.69 (3H), 6.03 (6H), 3.83 (12H), 3.68 (3H), 3.46 (3H), 2.80 (3H), 2.10 (36H), 1.85 (3H), 1.77 (9H), 1.48 (3H), 1.41 (9H), 1.37 (9H), 1.22 (27H), 1.12 (9H).

[0113]

Chemical formula

[0114] [Synthesis Example 6] Synthesis of Compound (C-6) In the synthesis of (Intermediate 101) of Synthesis Example 1, except that the (Intermediate 100) was changed to 1-(2-hydroxyethyl)-1,2,3,4-tetrahydro-2,2,4,7-tetramethylquinoline and 4,4'-bis(diethylamino)benzophenone was changed to the (Intermediate 108), the following (Intermediate 110) was obtained by a similar method (6.81 g, yield 85%).

[0115] [Chemical Formula]

[0116] Subsequently, in the synthesis of Compound (C-2) of Synthesis Example 2, except that the (Intermediate 104) was changed to the (Intermediate 110), the target compound (C-6) was obtained as a blue-violet solid by a similar method (7.98 g, yield 87%).

[0117] NMR measurement of the obtained blue-violet solid was performed, and the signals of the following 57 hydrogens were detected and identified as the structure of the compound represented by the following formula (C-6).

[0118] 1 H-NMR (400 MHz, DMSO-d 6 ): δ (ppm) = 7.40 (2H), 7.29 (8H), 7.12 (2H), 6.84 (1H), 6.67 (1H), 6.05 (2H), 3.99 - 3.56 (8H), 2.83 (1H), 2.11 (12H), 1.88 (1H), 1.76 (3H), 1.48 (1H), 1.40 (3H), 1.31 - 1.16 (9H), 1.13 (3H).

[0119] [Chemical Formula]

[0120] [Synthesis Example 7] Synthesis of Compound (C-7) In the synthesis of (Intermediate 101) of Synthesis Example 1, except that the (Intermediate 100) was changed to the (Intermediate 102) and 4,4'-bis(diethylamino)benzophenone was changed to the (Intermediate 108), the following (Intermediate 111) was obtained in the same manner (8.82 g, yield 74%).

[0121] [Chemical Formula]

[0122] Subsequently, in the synthesis of Compound (C-2) of Synthesis Example 2, except that the (Intermediate 104) was changed to the (Intermediate 111), the target compound (C-7) was obtained as a blue-violet solid in the same manner (9.77 g, yield 85%).

[0123] NMR measurement of the obtained blue-violet solid was performed, and the following 60 hydrogen signals were detected and identified as the structure of the compound represented by the following formula (C-7).

[0124] 1 H-NMR (400 MHz, DMSO-d 6 ): δ (ppm) = 7.38 (4H), 7.26 (8H), 7.28 - 7.13 (4H), 6.94 (1H), 6.05 (2H), 5.80 (1H), 3.82 (4H), 3.05 (1H), 2.40 (3H), 2.09 (12H), 2.01 (1H), 1.70 (1H), 1.49 (3H), 1.33 (3H), 1.30 (9H), 1.14 (3H).

[0125] [Chemical Formula]

[0126] [Synthesis Example 8] Synthesis of Compound (C-8) In the synthesis of Compound (C-1) of Synthesis Example 1, except that the (Intermediate 101) was changed to the (Intermediate 111), the target compound (C-8) was obtained as a blue solid in the same manner (9.77 g, yield 85%).

[0127] NMR measurement of the obtained blue solid was carried out, and the signals of the following 180 hydrogens were detected and identified as the structure of the compound represented by the following formula (C-8).

[0128] 1 H-NMR(400 MHz, DMSO-d 6 ): δ(ppm) = 7.38(12H), 7.26(24H), 7.28 - 7.13(12H), 6.94(3H), 6.05(6H), 5.80(3H), 3.82(12H), 3.05(3H), 2.40(9H), 2.09(36H), 2.01(3H), 1.70(3H), 1.49(9H), 1.33(9H), 1.30(27H), 1.14(9H).

[0129]

Chemical formula

[0130] [Synthesis Example 9] Synthesis of Compound (C-9) In the synthesis of (Intermediate 101) in Synthesis Example 1, except that (Intermediate 100) was changed to the said (Intermediate 106) and 4,4'-bis(diethylamino)benzophenone was changed to the said (Intermediate 108), the following (Intermediate 112) was obtained by the same method (9.02 g, yield 90%).

[0131]

Chemical formula

[0132] Subsequently, in the synthesis of Compound (C-2) in Synthesis Example 2, except that (Intermediate 104) was changed to the said (Intermediate 112), the target compound (C-9) was obtained as a blue-violet solid by the same method (10.0 g, yield 84%).

[0133] NMR measurement of the obtained blue-violet solid was carried out, and the signals of the following 58 hydrogens were detected and identified as the structure of the compound represented by the following formula (C-9).

[0134] 1H-NMR (400 MHz, DMSO-d 6 ): δ (ppm) = 7.59 (2H), 7.50 (1H), 7.38 (2H), 7.28 (10H), 7.11 (2H), 6.95 (1H), 6.05 (2H), 5.76 (1H), 3.82 (4H), 3.06 (1H), 2.09 (12H), 2.01 (1H), 1.72 (1H), 1.43 (3H), 1.35 (3H), 1.20 (9H), 1.14 (3H).

[0135] [Chemical formula]

[0136] [Synthesis Example 10] Synthesis of Compound (C-10) In the synthesis of (Intermediate 102) in Synthesis Example 2, the following (Intermediate 113) was obtained (2.19 g, yield 45%) by the same method except that 4-bromotoluene was changed to 1-bromo-4-nitrobenzene.

[0137] [Chemical formula] Subsequently, in the synthesis of (Intermediate 101) in Synthesis Example 1, the following (Intermediate 114) was obtained (1.91 g, yield 33%) by the same method except that (Intermediate 100) was changed to the above (Intermediate 113) and 4,4'-bis(diethylamino)benzophenone was changed to the above (Intermediate 108).

[0138] [Chemical formula]

[0139] Subsequently, in the synthesis of Compound (C-2) in Synthesis Example 2, the target Compound (C-10) was obtained as a blue-violet solid (2.12 g, yield 85%) by the same method except that (Intermediate 104) was changed to the above (Intermediate 114).

[0140] NMR measurement of the obtained blue-violet solid was carried out, and the signals of the following 57 hydrogens were detected and identified as the structure of the compound represented by the following formula (C-10).

[0141] 1 H-NMR (400 MHz, DMSO-d 6 ): δ (ppm) = 8.40 (2H), 7.55 (2H), 7.41 (2H), 7.29 (9H), 7.14 (2H), 6.98 (1H), 6.06 (2H), 3.84 (4H), 3.08 (1H), 2.09 (12H), 2.02 (1H), 1.74 (1H), 1.51 (3H), 1.35 (3H), 1.21 (9H), 1.11 (3H).

[0142]

Chemical formula

[0143] [Synthesis of Comparative Example Compound (D-1)] According to the method described in paragraph

[0067] Example 2 of Patent Document 2 (Japanese Patent Application Laid-Open No. 2011-186043), the comparative example compound (D-1) represented by the following formula was obtained as a dark blue solid.

[0144] NMR measurement of the obtained dark blue solid was carried out, and the signals of the following 120 hydrogens were detected and identified as the structure of the compound represented by the following formula (D-1).

[0145] 1 H-NMR (400 MHz, DMSO-d 6 ): δ (ppm) = 8.34 (3H), 8.02 (3H), 7.60 - 7.11 (24H), 6.94 (12H), 6.81 (3H), 3.58 (30H), 1.34 (9H), 1.20 (36H).

[0146]

Chemical formula

[0147] [Synthesis of Comparative Example Compound (D-2)] By the method described in Synthesis Example 1 of Patent Document 3 (Japanese Patent Application Laid-Open No. 2012-83652), Comparative Example Compound (D-2) represented by the following formula was obtained as a brown solid.

[0148] NMR measurement of the obtained brown solid was performed, and signals of the following 40 hydrogens were detected and identified as the structure of the compound represented by the following formula (D-2).

[0149] 1 H-NMR (400 MHz, DMSO-d 6 ): δ (ppm) = 8.34 (1H), 8.02 (1H), 7.60 - 7.11 (8H), 6.94 (4H), 6.81 (1H), 3.58 (10H), 1.34 (3H), 1.20 (12H).

[0150]

Chemical formula

[0151] [Synthesis of Comparative Example Compound (D-3)] Into a reaction vessel, 5.00 g (25.9 mmol) of 4-diethylaminobenzoic acid and 30 mL of toluene were placed, 4.62 g (38.8 mmol) of thionyl chloride was added, and the mixture was stirred at 80 °C for 1 hour. After cooling the reaction solution, the solvent was concentrated under reduced pressure, and the residue was dissolved in 10 mL of dichloromethane. This solution was added dropwise to a solution prepared by mixing 4.14 g (31.1 mmol) of aluminum chloride and 30 mL of dichloromethane and cooled to 5 °C. Further, 4.22 g (25.9 mmol) of N,N-diethyl-m-toluidine was added dropwise to this solution, and after the addition, the mixture was stirred at room temperature (23 - 28 °C) for 1 hour. After pouring this solution into water, a 48% aqueous sodium hydroxide solution was added to adjust the pH to 10. After diluting with 50 mL of water, 50 mL of dichloromethane was added, and the organic layer was extracted. After concentrating the organic layer under reduced pressure, the residue was purified by column chromatography (carrier: silica gel, solvent: heptane / ethyl acetate = 90 / 10 (volume ratio)), and the solvent was distilled off under reduced pressure to obtain the following (Intermediate 200) (2.50 g, yield 29%).

[0152]

Chemical formula

[0153] Subsequently, 2.50 g (7.39 mmol) of N-ethyl-1-naphthylamine, 1.26 g (7.39 mmol) of the above (Intermediate 200), and 25 mL of toluene were placed in a reaction vessel, and 3.40 g (22.2 mmol) of phosphorus oxychloride was added. After stirring this solution at 100 °C for 5 hours, it was cooled to room temperature (23 - 28 °C). 24 mL of 1M aqueous hydrochloric acid solution and 50 mL of dichloromethane were added to this solution, and the organic layer was extracted. After concentrating the organic layer under reduced pressure, the residue was purified by column chromatography (carrier: silica gel, solvent: dichloromethane / methanol = 100 / 0 - 90 / 10 (volume ratio)), and the solvent was distilled off under reduced pressure. The residue was dried under reduced pressure at 80 °C to obtain the following (Intermediate 201) (2.50 g, yield 64.1%).

[0154]

Chemical formula

[0155] Subsequently, in the synthesis of the compound (C-2) in Synthesis Example 2, except that (Intermediate 104) was changed to the above (Intermediate 201), the comparative example compound (D-3) represented by the following formula was obtained as a purple solid (2.70 g, yield 92%) in the same manner.

[0156] The obtained purple solid was subjected to NMR measurement, and the signals of the following 42 hydrogens were detected and identified as the structure of the compound represented by the following formula (D-3).

[0157] 1 H-NMR (400 MHz, CDCl 3 ): δ (ppm) = 8.07 (1H), 7.51 (2H), 7.32 (4H), 7.09 (1H), 6.74 (3H), 6.59 (3H), 3.65 - 3.48 (10H), 1.75 (3H), 1.49 (3H), 1.30 (12H).

[0158]

Chemical formula

[0159] [Synthesis of Comparative Example Compound (D-4)] 44.4 g (367 mmol) of N-ethylaniline and 140 mL of DMF were placed in a reaction vessel and cooled to 5°C with stirring. 41.1 g (367 mmol) of potassium t-butoxide was added to this solution in 4 portions. Further, a solution prepared by dissolving 20.0 g (91.7 mmol) of 4,4'-difluorobenzophenone in 80 mL of DMF was added dropwise to this solution. After the addition, the temperature was raised to room temperature and the mixture was stirred for 18 hours. 400 mL of water, 400 mL of ethyl acetate, and 100 mL of heptane were added to the reaction solution, and the organic layer was extracted. The organic layer was washed twice with 300 mL of water. Anhydrous magnesium sulfate was added to the organic layer, dried, and then filtered. The filtrate was concentrated under reduced pressure, and the residue was dissolved in 300 mL of dichloromethane and 15 mL of ethyl acetate. 60 g of silica gel was added, and the mixture was stirred at room temperature for 30 minutes. This solution was filtered, and after the filtrate was concentrated under reduced pressure, heptane was added for crystallization. The solid was collected by filtration and dried under reduced pressure at 60°C to obtain the following (Intermediate 202) (27.4 g, yield 71%).

[0160] [Chemical formula]

[0161] Subsequently, in the synthesis of (Intermediate 201) in the synthesis of Comparative Example Compound (D-3), the following (Intermediate 203) was obtained (2.50 g, yield 34%) in the same manner except that (Intermediate 200) was changed to the above (Intermediate 202).

[0162] [Chemical formula]

[0163] In the synthesis of Compound (C-2) in Synthesis Example 2, the target compound (D-4) was obtained as a purple solid (1.92 g, yield 91%) in the same manner except that (Intermediate 104) was changed to the above (Intermediate 203).

[0164] The NMR measurement of the obtained purple solid was carried out, and the signals of the following 40 hydrogens were detected and identified as the structure of the compound represented by the following formula (D-4).

[0165] 1 H-NMR(400MHz, CDCl 3 ): δ(ppm) = 8.14(1H), 7.56 - 7.22(19H), 6.71(5H), 3.93(4H), 3.63(2H), 1.48(3H), 1.35(6H).

[0166]

Chemical formula

[0167] [Synthesis of Comparative Example Compound (D-5)] Into a reaction vessel, 20.0 g (150 mmol) of 1,2,3,4-tetrahydroquinoline, 33.7 g (180 mmol) of 1-iodobutane, 41.5 g (300 mmol) of potassium carbonate, and 100 mL of DMF were added, and the mixture was stirred at 80 °C for 15 hours. After the reaction solution was cooled, 200 mL of ethyl acetate was added, and the mixture was stirred at room temperature (23 - 28 °C) and then filtered. 100 mL of heptane and 300 mL of water were added to the filtrate, and the organic layer was extracted. After further washing twice with 300 mL of water, the organic layer was extracted. Anhydrous magnesium sulfate was added, and the organic layer was dried and then filtered. The filtrate was concentrated under reduced pressure. After the residue was dissolved in 300 mL of heptane, 30 g of silica gel was added, and the mixture was stirred at room temperature (23 - 28 °C) for 30 minutes and then filtered. By concentrating the filtrate under reduced pressure, the following (Intermediate 204) was obtained (23.9 g, yield 84%).

[0168]

Chemical formula

[0169] Subsequently, 3.00 g (16.9 mmol) of 4-diethylaminobenzaldehyde, 6.50 g (34.4 mmol) of the above (Intermediate 204), 0.51 g (8.46 mmol) of urea, 2.8 mL (33.9 mmol) of concentrated hydrochloric acid, and 45 mL of ethyl cellosolve were placed in a reaction vessel and stirred at 90 °C for 4 hours. After pouring the reaction solution into 250 mL of water, 3.50 g of sodium carbonate was added and stirred at room temperature (23 - 28 °C). After removing the supernatant, the residue was dissolved in dichloromethane, magnesium sulfate was added and dried. This solution was filtered, and after concentrating the filtrate under reduced pressure, the residue was purified by column chromatography (carrier: silica gel, solvent: dichloromethane / heptane = 60 / 40 - 100 / 0 (volume ratio)), and the solvent was distilled off under reduced pressure. The residue was dried under reduced pressure at 60 °C to obtain the following (Intermediate 205) (5.12 g, yield 56%).

[0170]

Chemical formula

[0171] Subsequently, 5.10 g (9.48 mmol) of the above (Intermediate 205) and 51 mL of dichloromethane were placed in a reaction vessel and stirred. After dissolving the solid, 3.50 g (14.2 mmol) of p-chloranil was added. After stirring at room temperature (23 - 28 °C) for 1 hour, 1.0 mL of concentrated hydrochloric acid was added and stirred for an additional 30 minutes. The reaction solution was filtered, and after concentrating the filtrate under reduced pressure, the residue was purified by column chromatography (carrier: silica gel, solvent: dichloromethane / methanol = 100 / 1 - 10 / 1 (volume ratio)), and the solvent was distilled off under reduced pressure. The residue was suspended and washed with heptane, and after filtering the solid, it was dried under reduced pressure at 80 °C to obtain the following (Intermediate 206) (4.53 g, yield 83%).

[0172]

Chemical formula

[0173] Subsequently, 3.50 g (6.12 mmol) of the above (Intermediate 206), 42 mL of water, and 21 mL of methanol were placed in a reaction vessel and stirred at 60 °C. After dissolving the solid, LiN(SO 2CF 3 ) 2 1.76 g (6.12 mmol) was added. After stirring at 60 °C for 1 hour, it was cooled, and the precipitated solid was collected by filtration. 50 mL of water was added to the obtained solid, and it was washed by suspension at 50 °C and then the solid was collected by filtration. The obtained solid was dried under reduced pressure at 80 °C to obtain the comparative example compound (D-5) represented by the following formula as a blue solid (4.63 g, yield 93%).

[0174] NMR measurement of the obtained blue solid was performed, and the signals of the following 50 hydrogens were detected and identified as the structure of the compound represented by the following formula (D-5).

[0175] 1 H-NMR (400 MHz, CDCl 3 ): δ (ppm) = 7.29 (2H), 7.18 (2H), 7.04 (2H), 6.78 (2H), 6.70 (2H), 3.56 (8H), 3.47 (4H), 2.77 (4H), 2.02 (4H), 1.69 (4H), 1.44 (4H), 1.32 (6H), 1.00 (6H).

[0176]

Chemical formula

[0177] [Synthesis of Comparative Example Compound (D-6)] In the synthesis of (Intermediate 201) in the synthesis of Comparative Example Compound (D-3), except that N-ethyl-1-naphthylamine was changed to (Intermediate 204) and the said (Intermediate 200) was changed to 4,4'-bis(diethylamino)benzophenone, the following (Intermediate 207) was obtained in the same manner (5.15 g, yield 53%).

[0178]

Chemical formula

[0179] Subsequently, in the synthesis of the compound (C-2) of Synthesis Example 2, except that (Intermediate 104) was changed to the said (Intermediate 207), in the same manner, the comparative example compound (D-6) represented by the following formula was obtained as a dark green solid (4.91 g, yield 75%).

[0180] NMR measurement was performed on the obtained dark green solid, and signals of the following 46 hydrogens were detected and identified as the structure of the compound represented by the following formula (D-6).

[0181] 1 H-NMR (400 MHz, DMSO-d 6 ): δ (ppm) = 7.25 (4H), 7.15 (1H), 7.05 (1H), 6.95 (5H), 3.59 - 3.50 (12H), 2.73 (2H), 1.90 (2H), 1.62 (2H), 1.38 (2H), 1.20 (12H), 0.95 (3H).

[0182]

Chemical formula

[0183] [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. Using an ultraviolet-visible spectrophotometer (manufactured by JASCO Corporation, model: V-650), the ultraviolet-visible absorption spectrum (wavelength range of 350 - 800 nm) was measured at room temperature (25 °C) as the spectral characteristic, and the maximum absorption wavelength in the measurement wavelength range was measured. The measurement results are shown in Table 1.

[0184] (Measurement of 5% mass loss temperature) Regarding the compound (C-1) obtained in Synthesis Example 1, using a thermogravimetric measurement-differential thermal analyzer (manufactured by Mac Science Co., Ltd., model: TG-DTA 2000S), under a nitrogen stream, TG-DTA measurement (sample mass: 5.0 - 6.0 mg, heating rate: 10 °C / min) was performed to measure the 5% mass loss temperature. The measurement results are shown in Table 1.

[0185] (Evaluation of heat resistance) 20 mg of the 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 stirred for 30 minutes to mix. The obtained colored resin solution was filtered through a syringe filter, and 1 g of the filtrate was applied onto a glass substrate (spin coating method, 1000 rpm - 6 seconds), and then heated and dried at 100 °C for 2 minutes to prepare a thin film. For the obtained film, color values were measured using a spectrophotometer (manufactured by Konica Minolta, Inc., model: CM-5). Then, heating was performed at 230 °C for 20 minutes, and the color values were measured in the same manner. The color difference (ΔE * ab ) before and after heating at 230 °C was used as an index of heat resistance, and the results are shown in Table 1.

[0186] [Examples 2 to 10] In Example 1, except that the compounds (C-2) to (C-10) obtained in Synthesis Examples 2 to 10 were used instead of the compound (C-1), the measurement of the maximum absorption wavelength, the measurement of the 5% mass loss temperature, and the evaluation of heat resistance were carried out in the same manner as in Example 1. The results are summarized in Table 1.

[0187] [Comparative Examples 1 to 6] For comparison, except that the comparative example compounds (D-1) to (D-6), which are triarylmethane dyes not belonging to the present invention, were used instead of the compound (C-1) in the examples, the measurement of the maximum absorption wavelength, the measurement of the 5% mass loss temperature, and the evaluation of heat resistance were carried out in the same manner as in Example 1. The results are summarized in Table 1.

[0188]

Table 1

[0189] As shown in Table 1, the triarylmethane dye, which is a compound of an example of the present invention, is excellent in that the 5% mass loss temperature and heat resistance during film formation are high as compared with the triarylmethane dyes of the comparative examples. From the comparison with Comparative Examples 1 to 5, it is understood that having a tetrahydroquinoline skeleton, and from the comparison with Comparative Example 6, having a substituent on the tetrahydroquinoline skeleton bring about high heat resistance.

Industrial Applicability

[0190] The coloring composition containing the triarylmethane dye according to the present invention has high heat resistance and can be used as a dye material for various applications such as a coloring agent for a color filter. Further, by using the coloring composition as a coloring agent for a color filter, it is possible to produce a color filter excellent in color characteristics (color gamut, luminance, contrast ratio, etc.).

Claims

1. A triarylmethane dye represented by the following general formula (1). 【Chemical 1】 [In formula (1), R １ ~R ５ are each independently, -H, A linear, branched or cyclic alkyl group having 1 to 12 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or A heterocyclic group having 2 to 20 carbon atoms which may have a substituent, R １ and R ２ 、R ３ and R ４ may be combined with each other to form a ring. R ６ ~R １０ are each independently, -H, a halogen atom, -OH, -CF ３ , -NO ２ , -CN, A linear, branched or cyclic alkyl group having 1 to 12 carbon atoms which may have a substituent, or A linear, branched or cyclic alkoxy group having 1 to 12 carbon atoms which may have a substituent, R １１ to R １４ each independently represents -H, A linear, branched or cyclic alkyl group having 1 to 12 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, R ８ and R １２ ~R １４ At least one of them represents a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent. An represents an anion, and m represents a natural number. ]

2. In the general formula (1), R １ and R ３ are each independently an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, The triarylmethane dye according to claim 1.

3. In the general formula (1), R １ and R ３ are the same. The triarylmethane dye according to claim 2.

4. In the general formula (1), R ５ is a linear alkyl group having 1 to 3 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, The triarylmethane dye according to claim 1.

5. In the general formula (1), R １１ is -H, and R ８ , R １２ to R １４ are linear alkyl groups having 1 to 3 carbon atoms which may have substituents, the triarylmethane dye according to claim 1.

6. In the general formula (1), An is The triarylmethane dye according to claim 1, which is a perfluoroalkylsulfonic acid anion, a perfluoroalkylsulfonimide anion, a tris(trifluoromethanesulfonyl)methide anion, or a heteropolyacid anion.

7. The triarylmethane dye of the general formula (1), wherein, using a propylene glycol monomethyl ether (PGME) solution, measured at 23 to 27 °C, in the ultraviolet-visible absorption spectrum (wavelength range of 350 to 800 nm), the maximum absorption wavelength of the absorption band is 570 nm or more and 640 nm or less. The triarylmethane dye according to claim 1.

8. The triarylmethane dye of the general formula (1), wherein, using a thermogravimetric-differential thermal analyzer, performed under a nitrogen stream (nitrogen flow rate: 50 mL / min), the 5% mass loss temperature of the TG-DTA measurement (sample mass: 5.0 to 6.0 mg, heating rate: 10 °C / min) is 270 °C or higher. The triarylmethane dye according to claim 1.

9. A coloring composition containing the triarylmethane dye according to any one of claims 1 to 8.

10. A colorant for a color filter containing the coloring composition according to claim 9.

11. A color filter using the colorant for a color filter according to claim 10.

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