Colorant and colored curable resin composition

Abstract

The present invention addresses the problem of providing a colorant and a colored curable resin composition capable of forming a color filter having better red brightness. The colored curable resin composition contains a colorant, a resin, a polymerizable compound and a polymerization initiator, wherein the colorant contains C.I. Pigment violet 19, a compound represented by formula (I) and a compound represented by formula (II). [In formula (I), X1 represents a hydrogen atom, an aromatic hydrocarbon group which may have a substituent, or a heterocyclic group which may have a substituent, X2 represents a hydrogen atom, a halogen atom, a hydrocarbon group which may have a substituent and has 1-20 carbon atoms,-OR1 or-COOR2, X3 represents a halogen atom, a cyano group, a nitro group, a hydrocarbon group which may have a substituent and has 1-20 carbon atoms,-OR3,-COOR4,-CONR5R6 or-SO2NR7R8, and n represents 1 or 2. ] (In formula (II), L1 represents a divalent aromatic hydrocarbon group which may have a substituent, and X11-X14 represent a hydrogen atom or a hydrocarbon group having 1-20 carbon atoms which may have a substituent. ].

Description

Technical Field

[0001] The present invention relates to a colorant, a colored curable resin composition containing the colorant, a color filter formed from the colored curable resin composition, and a display device including the color filter. Background Art

[0002] Color filters used in display devices such as liquid crystal displays, electroluminescent displays, and plasma displays, and solid-state imaging devices such as CCDs and CMOS sensors are manufactured from colored resin compositions. Various colorants are used in such colored resin compositions. For example, CI Pigment Violet 19, CI Pigment Red 269, and CI Pigment Yellow 139 are known to be used as colorants (Patent Document 1).

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: Japanese Patent Application Laid-Open No. 2021-103295 Summary of the Invention

[0006] To improve color performance in color filters, it is necessary to increase brightness at the target chromaticity coordinates. For example, a red color filter preferably has high brightness when its chromaticity coordinates in the CIE XYZ colorimetric system, using the characteristic function of a C illuminant, are within the range of x = 0.640 to 0.720 and y = 0.280 to 0.360 (more specifically, at chromaticity coordinates of x = 0.680 and y = 0.320).

[0007] The present invention has been made in view of the above-mentioned circumstances, and an object of the present invention is to provide a colorant and a colored curable resin composition capable of forming a color filter having better red brightness.

[0008] The gist of the present invention is as follows.

[0009] [1] A colored curable resin composition comprising a colorant, a resin, a polymerizable compound, and a polymerization initiator,

[0010] The colorant contains CI Pigment Violet 19, a compound represented by formula (I), and a compound represented by formula (II).

[0011]

[0012] [In formula (I),

[0013] X 1 represents a hydrogen atom, an aromatic hydrocarbon group which may have a substituent, or a heterocyclic group which may have a substituent.

[0014] X 2represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, -OR 1 or -COOR 2 .

[0015] X 3 represents a halogen atom, a cyano group, a nitro group, a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, -OR 3 , -COOR 4 , -CONR 5 R 6 or -SO2NR 7 R 8 .

[0016] R 1 ~R 8 Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

[0017] n represents 1 or 2,

[0018] m represents any integer from 0 to 5,

[0019] The sum of m and n is an integer of 6 or less.

[0020] X 1 、X 2 or X 3 When there are multiple ones, they may be the same or different.]

[0021]

[0022] [In formula (II),

[0023] L 1 represents a divalent aromatic hydrocarbon group which may have a substituent.

[0024] X 11 ~X 14 Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.]

[0025] [2] The colored curable resin composition according to [1], further comprising a solvent.

[0026] [3] A color filter formed from the colored curable resin composition according to [1] or [2].

[0027] [4] A display device comprising the color filter described in [3].

[0028] [5] A colorant comprising CI Pigment Violet 19, a compound represented by formula (I), and a compound represented by formula (II).

[0029]

[0030] [In formula (I),

[0031] X 1 represents a hydrogen atom, an aromatic hydrocarbon group which may have a substituent, or a heterocyclic group which may have a substituent.

[0032] X 2 represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, -OR 1 or -COOR 2 .

[0033] X 3 represents a halogen atom, a cyano group, a nitro group, a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, -OR 3 , -COOR 4 , -CONR 5 R 6 or -SO2NR 7 R 8 .

[0034] R 1 ~R 8 Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

[0035] n represents 1 or 2,

[0036] m represents any integer from 0 to 5,

[0037] The sum of m and n is an integer of 6 or less.

[0038] X 1 、X 2 or X 3 When there are multiple ones, they may be the same or different.]

[0039]

[0040] [In formula (II),

[0041] L 1 represents a divalent aromatic hydrocarbon group which may have a substituent.

[0042] X 11 ~X 14 Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.]

[0043] The colorant and colored curable resin composition of the present invention can improve the brightness of the resulting color filter at specific chromaticity coordinates. Furthermore, in a preferred embodiment, the transmittance of the resulting color filter at 530 nm can be suppressed. Furthermore, in a preferred embodiment, the colorant content in the total solids content of the colored curable resin composition can be suppressed. DETAILED DESCRIPTION

[0044] The colorant of the present invention (hereinafter also referred to as colorant (A)) comprises CI Pigment Violet 19, a compound represented by the following formula (I) (hereinafter also referred to as compound (I)), and a compound represented by the following formula (II) (hereinafter also referred to as compound (II)). The colorant of the present invention can be included as a colorant component in the following colored curable resin composition.

[0045] The colored curable resin composition of the present invention contains a colorant (A), a resin (hereinafter also referred to as resin (B)), a polymerizable compound (hereinafter also referred to as polymerizable compound (C)), and a polymerization initiator (hereinafter also referred to as polymerization initiator (D)), wherein the colorant contains CI Pigment Violet 19, compound (I), and compound (II).

[0046] Moreover, it is preferable that the colored curable resin composition of this invention further contains a solvent (hereinafter also called a solvent (E)).

[0047] Moreover, the colored curable resin composition of this invention may further contain a polymerization initiation auxiliary agent (hereinafter also referred to as a polymerization initiation auxiliary agent (D1)).

[0048] Moreover, the colored curable resin composition of this invention may further contain a leveling agent (hereinafter also referred to as a leveling agent (F)).

[0049] In addition, in this specification, the compound illustrated as each component can be used individually or in combination of 2 or more types unless otherwise specified.

[0050] Colorant (A)

[0051] Colorant (A) includes: CI Pigment Violet 19, Compound (I) and Compound (II). By including CI Pigment Violet 19, Compound (I) and Compound (II) in the colorant (A), the brightness of the obtained color filter under specific chromaticity coordinates can be improved by using the colorant and the colored curable resin composition containing the colorant. Specifically, a color filter with good brightness can be formed with chromaticity coordinates of x = 0.640 to 0.720 and y = 0.280 to 0.360 in the XYZ color system of CIE using the characteristic function of the C light source (more specifically, at chromaticity coordinates of x = 0.680 and y = 0.320). Therefore, using the colorant and the colored curable resin composition containing the colorant, a color filter with particularly good red color characteristics can be obtained.

[0052] In addition, in the color filter, in order to improve the color performance, it is necessary to suppress the transmittance of a specific wavelength. For example, as a red color filter, it is preferred that the transmittance at 530nm is low. If the transmittance at 530nm is high, there is a concern that the desired color characteristics may not be obtained due to leakage of green light. By including CI Pigment Violet 19, compound (I) and compound (II) in the colorant (A), the colorant and the colored curable resin composition comprising the colorant are utilized, and it is preferably possible to suppress the transmittance at 530nm of the obtained color filter, so that a color filter with better color performance can be obtained.

[0053] In addition, in color filter, in order to realize desired color performance, it is generally known to have the colorant content rate in the total amount of the solid component of the colored curable resin composition being improved. However, if the content rate of the colorant in the colored curable resin composition is improved, the content rate of the curing component will be reduced, so there is a concern that residue or pattern shape will deteriorate when the color filter is formed. Therefore, from the aspect of the bad production when the color filter can be suppressed by the content rate of the component (for example, resin, polymerizable compound) other than the colorant and the aspect of the degree of freedom in the design of the colored curable resin composition being able to be improved, the colorant content rate in the total amount of the solid component of the preferably colored curable resin composition is low. CI Pigment Violet 19, compound (I) and compound (II) are included by colorant (A), so that the colored curable resin composition preferably including the colorant can form a color filter with desired color performance while suppressing the content rate of the colorant in the total amount of the solid component.

[0054] <<Compound (I)>>

[0055] Compound (I) has a predetermined chemical structure represented by the following formula (I). Although compound (I) is described in detail below, compound (I) also includes resonance structures of formula (I), tautomers of formula (I), and compounds obtained by rotating the groups in formula (I) around the bond axis of a single bond.

[0056]

[0057] [In formula (I),

[0058] X 1 represents a hydrogen atom, an aromatic hydrocarbon group which may have a substituent, or a heterocyclic group which may have a substituent.

[0059] X 2 represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, -OR 1 or -COOR 2 .

[0060] X 3 represents a halogen atom, a cyano group, a nitro group, a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, -OR 3 , -COOR 4 , -CONR 5 R 6 or -SO2NR 7 R 8 .

[0061] R 1 ~R 8 Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

[0062] n represents 1 or 2,

[0063] m represents any integer from 0 to 5,

[0064] The sum of m and n is an integer of 6 or less.

[0065] X 1 、X 2 or X 3 When there are multiple ones, they may be the same or different.]

[0066] As X 1Examples of the aromatic hydrocarbon group represented by include aryl groups such as phenyl, 1-naphthyl, 2-naphthyl, anthracenyl, phenanthrenyl, and biphenyl; alkylaryl groups such as o-tolyl, m-tolyl, p-tolyl, 2-ethylphenyl, 3-ethylphenyl, 4-ethylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2,4,6-trimethylphenyl, 2-methyl-6-ethylphenyl, 2,6-diethylphenyl, o-isopropylphenyl, m-isopropylphenyl, p-isopropylphenyl, 2-methyl-6-isopropylphenyl, 4-butylphenyl, o-tert-butylphenyl, m-tert-butylphenyl, and p-tert-butylphenyl; and alkenylaryl groups such as 4-vinylphenyl.

[0067] X 1 The number of carbon atoms in the aromatic hydrocarbon group represented by is preferably 6 to 20, more preferably 6 to 18, further preferably 6 to 12, and even more preferably 6 to 10.

[0068] X 1 The heterocyclic group represented by X may be a monocyclic or polycyclic ring, and may be a saturated or unsaturated ring. 1 The heterocyclic group represented by is preferably a heterocyclic group containing a heteroatom other than a carbon atom as a ring constituent. Examples of the heteroatom include a nitrogen atom, an oxygen atom, and a sulfur atom.

[0069] X 1 The heterocyclic group represented by is preferably 2 to 20, more preferably 3 to 18, and even more preferably 3 to 15.

[0070] Examples of the heterocyclic group containing only nitrogen atoms as heteroatoms include monocyclic heterocyclic groups such as pyrrolyl, imidazolyl, pyrazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, pyrrolidinyl, piperidinyl, and piperazinyl; and polycyclic heterocyclic groups such as indolizinyl, indolyl, 1H-indazolyl, isoquinolyl, quinolyl, phthalazinyl, carbazolyl, acridinyl, indolinyl, and isoindolinyl.

[0071] Examples of the heterocyclic group containing only oxygen atoms as heteroatoms include monocyclic heterocyclic groups such as furyl and pyranyl; and polycyclic heterocyclic groups such as isobenzofuranyl, chromenyl, xanthenyl and chromanyl.

[0072] Examples of the heterocyclic group containing only a sulfur atom as a heteroatom include monocyclic heterocyclic groups such as thienyl; and polycyclic heterocyclic groups such as benzo[b]thienyl and thianthrenyl.

[0073] Examples of the heterocyclic group containing a nitrogen atom and an oxygen atom as heteroatoms include Monocyclic heterocyclic groups such as oxazolyl; polycyclic heterocyclic groups such as benzimidazolinone; etc.

[0074] As X 1 The heterocyclic group represented by , among which a polycyclic heterocyclic group is preferred, and a polycyclic heterocyclic group having a benzene ring such as benzo[b]thienyl, thianthrenyl, isobenzofuranyl, chromenyl, xanthenyl, indolyl, 1H-indazolyl, isoquinolyl, quinolyl, phthalazinyl, carbazolyl, acridinyl, chromanyl, indolinyl, isoindolinyl, benzimidazolinone group is more preferred.

[0075] As X 2 、X 3 and R 1 ~R 8 The hydrocarbon group represented by includes aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The aliphatic hydrocarbon group may be saturated or unsaturated, and may be chain or alicyclic.

[0076] Examples of the saturated or unsaturated chain hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, an n-tridecyl group, an n-tetradecyl group, an n-pentadecyl group, an n-hexadecyl group, an n-heptadecyl group, an n-octadecyl group, an n-nonadecyl group, and an n-eicosyl group; an isopropyl group, a (1-ethyl)propyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a (1-ethyl)butyl group, a (2-ethyl)butyl group, a (1-propyl)butyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, a (2-methyl)pentyl group, a (1-ethyl)pentyl group, a (3- branched-chain alkyl groups such as (1-ethyl)pentyl, (1-propyl)pentyl, (1-butyl)pentyl, isohexyl, (2-methyl)hexyl, (5-methyl)hexyl, (2-ethyl)hexyl, (1-butyl)hexyl, (2-methyl)heptyl, (2-ethyl)heptyl, (3-ethyl)heptyl, (2-methyl)octyl, and (2-ethyl)octyl; and alkenyl groups such as vinyl, 1-propenyl, 2-propenyl (allyl), (1-methyl)vinyl, 2-butenyl, 3-butenyl, 1,3-butadienyl, (1-(2-propenyl))vinyl, (1,2-dimethyl)propenyl, and 2-pentenyl.

[0077] Examples of the saturated or unsaturated alicyclic hydrocarbon group include cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl; cycloalkenyl groups such as cyclohexenyl (e.g., cyclohex-2-ene, cyclohex-3-ene), cycloheptenyl, and cyclooctenyl; and norbornyl, adamantyl, and bicyclo[2.2.2]octyl.

[0078] Examples of the aromatic hydrocarbon group include the following: 1 The same groups as the aromatic hydrocarbon groups represented by .

[0079] The hydrocarbon group having 1 to 20 carbon atoms may be a group composed of two or more selected from the chain hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups listed above, as long as the upper limit of the number of carbon atoms is 20. Examples of such groups include aralkyl groups such as benzyl, phenethyl, and 1-methyl-1-phenylethyl; arylalkenyl groups such as phenylvinyl (phenylvinyl); arylalkynyl groups such as phenylethynyl; 1-methylcyclopropyl, 1-methylcyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 1,2-dimethylcyclohexyl, 1,3-dimethylcyclohexyl, 1,4-dimethylcyclohexyl, 2,3-dimethylcyclohexyl, 2,4-dimethylcyclohexyl, 2,5-dimethylcyclohexyl, 2,6-dimethylcyclohexyl, 3,4-dimethylcyclohexyl. alicyclic hydrocarbon groups to which one or more alkyl groups or alicyclic hydrocarbon groups are bonded, such as cyclopropylmethyl, cyclopropylethyl, cyclobutylmethyl, cyclobutylethyl, cyclopentylmethyl, cyclopentylethyl, cyclohexylmethyl, 2-methylcyclohexylmethyl, and cyclohexylethyl; and an alkyl group to which one or more alicyclic hydrocarbon groups are bonded, such as cyclopropylmethyl, cyclopropylethyl, cyclobutylmethyl, cyclobutylethyl, cyclopentylmethyl, cyclopentylethyl, cyclohexylmethyl, 2-methylcyclohexylmethyl, and cyclohexylethyl.

[0080] As X 1 Aromatic hydrocarbon groups and heterocyclic groups represented by X 2 A hydrocarbon group represented by X 3 The substituents that the hydrocarbon group represented by may have include a halogen atom, a hydroxyl group, an alkoxy group, an alkylsulfanyl group, a formyl group, a carboxyl group, a substituted or unsubstituted amino group, an N-acylamino group, a nitro group, a cyano group, a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted sulfamoyl group, and -SO3M. The above-mentioned M represents a hydrogen atom or an alkali metal atom (e.g., sodium or potassium).

[0081] Examples of the alkoxy group as a substituent include methoxy, ethoxy, propoxy, n-butoxy, tert-butoxy, etc. The number of carbon atoms in the alkoxy group is preferably 1 to 4, more preferably 1 or 2.

[0082] Examples of the alkylsulfanyl group as a substituent include methylsulfanyl, ethylsulfanyl, propylsulfanyl, n-butylsulfanyl, etc. The number of carbon atoms in the alkylsulfanyl group is preferably 1 to 4, more preferably 1 or 2.

[0083] Examples of substituted amino groups as substituents include amino groups having one or two hydrocarbon groups. Examples of the hydrocarbon groups include those exemplified above as hydrocarbon groups having 1 to 20 carbon atoms, preferably alkyl groups having 1 to 4 carbon atoms or aromatic hydrocarbon groups having 6 to 10 carbon atoms. Examples of substituted amino groups include N-monosubstituted amino groups such as N-methylamino, N-ethylamino, N-propylamino, N-isopropylamino, and N-phenylamino; and N,N-disubstituted amino groups such as N,N-dimethylamino, N,N-diethylamino, N,N-dipropylamino, N,N-diisopropylamino, N,N-diphenylamino, N,N-ethylmethylamino, N,N-methylphenylamino, and N,N-ethylphenylamino.

[0084] N-acylamino as a substituent refers to -NHCOR 9a The group represented by R 9a represents a hydrogen atom or a hydrocarbon group. 9a The hydrocarbon group represented by includes the groups exemplified as the above-mentioned hydrocarbon groups having 1 to 20 carbon atoms. 9a , preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms. Examples of the N-acylamino group include N-formylamino, N-acetylamino, N-propionylamino, N-butyrylamino, and N-benzoylamino.

[0085] The substituted or unsubstituted carbamoyl group as a substituent refers to -CONR 9b R 9c The group represented by R 9b 、R 9c Each independently represents a hydrogen atom or a hydrocarbon group. 9b 、R 9c The hydrocarbon group represented by includes the groups exemplified as the above-mentioned hydrocarbon groups having 1 to 20 carbon atoms. 9b 、R 9c , are each independently preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms. 9b R 9cFor example, there can be mentioned carbamoyl groups; N-monosubstituted carbamoyl groups such as N-methylcarbamoyl, N-ethylcarbamoyl, N-propylcarbamoyl, N-isopropylcarbamoyl, n-butylcarbamoyl, N-tert-butylcarbamoyl, and N-phenylcarbamoyl; and N,N-disubstituted carbamoyl groups such as N,N-dimethylcarbamoyl, N,N-ethylmethylcarbamoyl, N,N-diethylcarbamoyl, N,N-propylmethylcarbamoyl, N,N-dipropylcarbamoyl, N,N-butylmethylcarbamoyl, N,N-tert-butylmethylcarbamoyl, N,N-di-tert-butylcarbamoyl, N,N-phenylmethylcarbamoyl, and N,N-diphenylcarbamoyl.

[0086] The substituted or unsubstituted sulfamoyl group as a substituent refers to -SO2NR 9d R 9e The group represented by R 9d 、R 9e Each independently represents a hydrogen atom or a hydrocarbon group. 9d 、R 9e The hydrocarbon group represented by includes the groups exemplified as the above-mentioned hydrocarbon groups having 1 to 20 carbon atoms. 9d 、R 9e , are each independently preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms. 9d R 9e For example, there can be mentioned a sulfamoyl group; an N-monosubstituted sulfamoyl group such as an N-methylsulfamoyl group, an N-ethylsulfamoyl group, an N-propylsulfamoyl group, an N-isopropylsulfamoyl group, an n-butylsulfamoyl group, and an N-isobutylsulfamoyl group; and an N,N-disubstituted sulfamoyl group such as an N,N-dimethylsulfamoyl group, an N,N-ethylmethylsulfamoyl group, an N,N-diethylsulfamoyl group, an N,N-propylmethylsulfamoyl group, an N,N-isopropylmethylsulfamoyl group, an N,N-tert-butylmethylsulfamoyl group, an N,N-butylethylsulfamoyl group, and an N,N-dibutylsulfamoyl group.

[0087] As X 2 Indicates -OR 1 and X 3 Indicates -OR 3 For example, there can be mentioned hydroxyl groups; alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, and pentyloxy groups; and the like.

[0088] As X 2 Indicated by -COOR 2 and X 3 Indicated by -COOR 4Examples thereof include carboxyl; and alkoxycarbonyl groups such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, tert-butoxycarbonyl, butoxycarbonyl, and pentyloxycarbonyl.

[0089] As X 3 -CONR 5 R 6 For example, there can be mentioned carbamoyl; N-monosubstituted carbamoyl such as N-methylcarbamoyl, N-ethylcarbamoyl, N-propylcarbamoyl, N-isopropylcarbamoyl, n-butylcarbamoyl, N-isobutylcarbamoyl, N-sec-butylcarbamoyl, N-tert-butylcarbamoyl, and N-pentylcarbamoyl; N,N-dimethylcarbamoyl, N,N-ethylmethylcarbamoyl, N,N- N,N-disubstituted carbamoyl groups such as diethylcarbamoyl, N,N-propylmethylcarbamoyl, N,N-dipropylcarbamoyl, N,N-isopropylmethylcarbamoyl, N,N-diisopropylcarbamoyl, N,N-tert-butylmethylcarbamoyl, N,N-diisobutylcarbamoyl, N,N-di-sec-butylcarbamoyl, N,N-di-tert-butylcarbamoyl and N,N-butylmethylcarbamoyl.

[0090] As X 3 Represented by -SO2NR 7 R 8 For example, sulfamoyl; N-methylsulfamoyl, N-ethylsulfamoyl, N-propylsulfamoyl, N-isopropylsulfamoyl, n-butylsulfamoyl, N-isobutylsulfamoyl, N-pentylsulfamoyl, N-(1-ethylpropyl)sulfamoyl, N-(1,1-dimethylpropyl)sulfamoyl, N-cyclopentylsulfamoyl, N-hexylsulfamoyl and other N-monosubstituted sulfamoyl groups. N,N-disubstituted sulfamoyl groups; N,N-dimethylsulfamoyl, N,N-ethylmethylsulfamoyl, N,N-diethylsulfamoyl, N,N-propylmethylsulfamoyl, N,N-isopropylmethylsulfamoyl, N,N-tert-butylmethylsulfamoyl, N,N-butylethylsulfamoyl, N,N-bis(1-methylpropyl)sulfamoyl, N,N-heptylmethylsulfamoyl and the like.

[0091] As X 2 and X 3 Examples of the halogen atom represented by and the halogen atom as a substituent include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Among them, a fluorine atom, a chlorine atom or a bromine atom is preferred.

[0092] n represents 1 or 2, m represents any integer from 0 to 5, and the sum of m and n is an integer of 6 or less.

[0093] As X 1, preferably a hydrogen atom or an aromatic hydrocarbon group which may have a substituent, more preferably a hydrogen atom, an aryl group which may have a substituent, or an alkylaryl group which may have a substituent, further preferably a hydrogen atom, an aryl group which may have a substituent, or an alkylaryl group, further preferably a hydrogen atom or a phenyl group which may have a substituent, further preferably a hydrogen atom or a phenyl group, still more preferably a phenyl group.

[0094] As X 2 , preferably a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or -OR 1 , more preferably a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, or an alkoxy group having 1 to 20 carbon atoms, further preferably a hydrogen atom, a chain hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, or an alkoxy group having 1 to 10 carbon atoms, further preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms which may have a substituent, or an alkoxy group having 1 to 4 carbon atoms, further preferably an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and still more preferably an alkoxy group having 1 to 4 carbon atoms.

[0095] As X 3 , preferably a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, -OR 3 , -CONR 5 R 6 or -SO2NR 7 R 8 , more preferably a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, or -OR 3 , more preferably a halogen atom, a chain hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, or an alkoxy group having 1 to 20 carbon atoms, further preferably a halogen atom, an alkyl group having 1 to 4 carbon atoms which may have a substituent, or an alkoxy group having 1 to 10 carbon atoms, more preferably a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 4 carbon atoms which has a halogen atom as a substituent, or an alkoxy group having 1 to 4 carbon atoms, still more preferably a fluorine atom, a chlorine atom, a fluoroalkyl group having 1 to 4 carbon atoms (particularly a perfluoroalkyl group), or an alkoxy group having 1 to 4 carbon atoms, further more preferably a chlorine atom, a trifluoromethyl group, or an alkoxy group having 1 to 4 carbon atoms.

[0096] n is 1 or 2, preferably 1.

[0097] m is an integer of 0 to 5, preferably an integer of 0 to 2, more preferably 0 or 2, and even more preferably 2.

[0098] When m is 2, 2 X 3It may be bonded at any of the ortho, meta, and para positions, but is preferably bonded at the meta or para position, and more preferably at the para position.

[0099] Examples of compound (I) include compounds (Ia-1) to (Ia-600) identified by the following formula (Ia) and Tables 1 to 8, and compounds (Ib-1) to (Ib-588) identified by the following formula (Ib) and Tables 9 to 16. In Tables 1 to 16, "t1" to "t6" represent groups represented by the following formulas (t1) to (t6), respectively; "H" represents a hydrogen atom; "Me" represents a methyl group; "Et" represents an ethyl group; "OMe" represents a methoxy group; "OEt" represents an ethoxy group; "Cl" represents a chlorine atom; "F" represents a fluorine atom; "CF3" represents a trifluoromethyl group; and "-" represents the absence of the corresponding group.

[0100]

[0101] [Table 1]

[0102] Compound <![CDATA[X 1 ]]> <![CDATA[X 2 ]]> <![CDATA[X 3a ]]> <![CDATA[X 3b ]]> Compound <![CDATA[X 1 ]]> <![CDATA[X 2 ]]> <![CDATA[X 3a ]]> <![CDATA[X 3b ]]> (Ia-1) t1 Me Cl Cl (Ia-41) t1 Et OMe Cl (Ia-2) t1 Me Cl F (Ia-42) t1 Et OMe F (Ia-3) t1 Me Cl <![CDATA[CF3]]> (Ia-43) t1 Et OMe <![CDATA[CF3]]> (Ia-4) t1 Me Cl OMe (Ia-44) t1 Et OMe OMe (Ia-5) t1 Me Cl OEt (Ia-45) t1 Et OMe OEt (Ia-6) t1 Me F Cl (Ia-46) t1 Et OEt Cl (Ia-7) t1 Me F F (Ia-47) t1 Et OEt F (Ia-8) t1 Me F <![CDATA[CF3]]> (Ia-48) t1 Et OEt <![CDATA[CF3]]> (Ia-9) t1 Me F OMe (Ia-49) t1 Et OEt OMe (Ia-10) t1 Me F OEt (Ia-50) t1 Et OEt OEt (Ia-11) t1 Me <![CDATA[CF3]]> Cl (Ia-51) t1 OMe Cl Cl (Ia-12) t1 Me <![CDATA[CF3]]> F (Ia-52) t1 OMe Cl F (Ia-13) t1 Me <![CDATA[CF3]]> <![CDATA[CF3]]> (Ia-53) t1 OMe Cl <![CDATA[CF3]]> (Ia-14) t1 Me <![CDATA[CF3]]> OMe (Ia-54) t1 OMe Cl OMe (Ia-15) t1 Me <![CDATA[CF3]]> OEt (Ia-55) t1 OMe Cl OEt (Ia-16) t1 Me OMe Cl (Ia-56) t1 OMe F Cl (Ia-17) t1 Me OMe F (Ia-57) t1 OMe F F (Ia-18) t1 Me OMe <![CDATA[CF3]]> (Ia-58) t1 OMe F <![CDATA[CF3]]> (Ia-19) t1 Me OMe OMe (Ia-59) t1 OMe F OMe (Ia-20) t1 Me OMe OEt (Ia-60) t1 OMe F OEt (Ia-21) t1 Me OEt Cl (Ia-61) t1 OMe <![CDATA[CF3]]> Cl (Ia-22) t1 Me OEt F (Ia-62) t1 OMe <![CDATA[CF3]]> F (Ia-23) t1 Me OEt <![CDATA[CF3]]> (Ia-63) t1 OMe <![CDATA[CF3]]> <![CDATA[CF3]]> (Ia-24) t1 Me OEt OMe (Ia-64) t1 OMe <![CDATA[CF3]]> OMe (Ia-25) t1 Me OEt OEt (Ia-65) t1 OMe <![CDATA[CF3]]> OEt (Ia-26) t1 Et Cl Cl (Ia-66) t1 OMe OMe Cl (Ia-27) t1 Et Cl F (Ia-67) t1 OMe OMe F (Ia-28) t1 Et Cl <![CDATA[CF3]]> (Ia-68) t1 OMe OMe <![CDATA[CF3]]> (Ia-29) t1 Et Cl OMe (Ia-69) t1 OMe OMe OMe (Ia-30) t1 Et Cl OEt (Ia-70) t1 OMe OMe OEt (Ia-31) t1 Et F Cl (Ia-71) t1 OMe OEt Cl (Ia-32) t1 Et F F (Ia-72) t1 OMe OEt F (Ia-33) t1 Et F <![CDATA[CF3]]> (Ia-73) t1 OMe OEt <![CDATA[CF3]]> (Ia-34) t1 Et F OMe (Ia-74) t1 OMe OEt OMe (Ia-35) t1 Et F OEt (Ia-75) t1 OMe OEt OEt (Ia-36) t1 Et <![CDATA[CF3]]> Cl (Ia-76) t1 OEt Cl Cl (Ia-37) t1 Et <![CDATA[CF3]]> F (Ia-77) t1 OEt Cl F (Ia-38) t1 Et <![CDATA[CF3]]> <![CDATA[CF3]]> (Ia-78) t1 OEt Cl <![CDATA[CF3]]> (Ia-39) t1 Et <![CDATA[CF3]]> OMe (Ia-79) t1 OEt Cl OMe (Ia-40) t1 Et <![CDATA[CF3]]> OEt (Ia-80) t1 OEt Cl OEt

[0103] [Table 2]

[0104] Compound <![CDATA[X 1 ]]> <![CDATA[X 2 ]]> <![CDATA[X 3a ]]> <![CDATA[X 3b ]]> Compound <![CDATA[X 1 ]]> <![CDATA[X 2 ]]> <![CDATA[X 3a ]]> <![CDATA[X 3b ]]> (Ia-81) t1 OEt F Cl (Ia-121) t2 Me OEt Cl (Ia-82) t1 OEt F F (Ia-122) t2 Me OEt F (Ia-83) t1 OEt F <![CDATA[CF3]]> (Ia-123) t2 Me And <![CDATA[CF3]]> (Ia-84) t1 And F Oh my (Ia-124) t2 Me And Oh my (Ia-85) t1 And F And (Ia-125) t2 Me And And (Ia-86) t1 And <![CDATA[CF3]]> Cl (Ia-126) t2 And Cl Cl (Ia-87) t1 And <![CDATA[CF3]]> F (Ia-127) t2 And Cl F (Ia-88) t1 And <![CDATA[CF3]]> <![CDATA[CF3]]> (Ia-128) t2 And Cl <![CDATA[CF3]]> (Ia-89) t1 And <![CDATA[CF3]]> Oh my (Ia-129) t2 And Cl Oh my (Ia-90) t1 And <![CDATA[CF3]]> And (Ia-130) t2 And Cl And (Ia-91) t1 And Oh my Cl (Ia-131) t2 And F Cl (Ia-92) t1 And Oh my F (Ia-132) t2 And F F (Ia-93) t1 And Oh my <![CDATA[CF3]]> (Ia-133) t2 And F <![CDATA[CF3]]> (Ia-94) t1 And Oh my Oh my (Ia-134) t2 And F Oh my (Ia-95) t1 And Oh my And (Ia-135) t2 And F And (Ia-96) t1 And And Cl (Ia-136) t2 And <![CDATA[CF3]]> Cl (Ia-97) t1 And And F (Ia-137) t2 And <![CDATA[CF3]]> F (Ia-98) t1 And And <![CDATA[CF3]]> (Ia-138) t2 And <![CDATA[CF3]]> <![CDATA[CF3]]> (Ia-99) t1 And And Oh my (Ia-139) t2 And <![CDATA[CF3]]> Oh my (Ia-100) t1 And And And (Ia-140) t2 And <![CDATA[CF3]]> And (Ia-101) t2 Me Cl Cl (Ia-141) t2 And Oh my Cl (Ia-102) t2 Me Cl F (Ia-142) t2 And Oh my F (Ia-103) t2 Me Cl <![CDATA[CF3]]> (Ia-143) t2 And Oh my <![CDATA[CF3]]> (Ia-104) t2 Me Cl Oh my (Ia-144) t2 And Oh my Oh my (Ia-105) t2 Me Cl And (Ia-145) t2 And Oh my And (Ia-106) t2 Me F Cl (Ia-146) t2 And And Cl (Ia-107) t2 Me F F (Ia-147) t2 And And F (Ia-108) t2 Me F <![CDATA[CF3]]> (Ia-148) t2 And And <![CDATA[CF3]]> (Ia-109) t2 Me F Oh my (Ia-149) t2 And And Oh my (Ia-110) t2 Me F And (Ia-150) t2 And And And (Ia-111) t2 Me <![CDATA[CF3]]> Cl (Ia-151) t2 Oh my Cl Cl (Ia-112) t2 Me <![CDATA[CF3]]> F (Ia-152) t2 Oh my Cl F (Ia-113) t2 Me <![CDATA[CF3]]> <![CDATA[CF3]]> (Ia-153) t2 Oh my Cl <![CDATA[CF3]]> (Ia-114) t2 Me <![CDATA[CF3]]> Oh my (Ia-154) t2 Oh my Cl Oh my (Ia-115) t2 Me <![CDATA[CF3]]> And (Ia-155) t2 Oh my Cl And (Ia-116) t2 Me Oh my Cl (Ia-156) t2 Oh my F Cl (Ia-117) t2 Me Oh my F (Ia-157) t2 Oh my F F (Ia-118) t2 Me Oh my <![CDATA[CF3]]> (Ia-158) t2 Oh my F <![CDATA[CF3]]> (Ia-119) t2 Me Oh my Oh my (Ia-159) t2 Oh my F Oh my (Ia-120) t2 Me Oh my And (Ia-160) t2 Oh my F And

[0105] [Table 3]

[0106] compounds <![CDATA[X 1 ]]> <![CDATA[X 2 ]]> <![CDATA[X 3a ]]> <![CDATA[X 3b ]]> compounds <![CDATA[X 1 ]]> <![CDATA[X 2 ]]> <![CDATA[X 3a ]]> <![CDATA[X 3b ]]> (Ia-161) t2 Oh my <![CDATA[CF3]]> Cl (Ia-201) t3 Me Cl Cl (Ia-162) t2 Oh my <![CDATA[CF3]]> F (Ia-202) t3 Me Cl F (Ia-163) t2 Oh my <![CDATA[CF3]]> <![CDATA[CF3]]> (Ia-203) t3 Me Cl <![CDATA[CF3]]> (Ia-164) t2 Oh my <![CDATA[CF3]]> Oh my (Ia-204) t3 Me Cl Oh my (Ia-165) t2 Oh my <![CDATA[CF3]]> And (Ia-205) t3 Me Cl And (Ia-166) t2 Oh my Oh my Cl (Ia-206) t3 Me F Cl (Ia-167) t2 Oh my Oh my F (Ia-207) t3 Me F F (Ia-168) t2 Oh my Oh my <![CDATA[CF3]]> (Ia-208) t3 Me F <![CDATA[CF3]]> (Ia-169) t2 Oh my Oh my Oh my (Ia-209) t3 Me F Oh my (Ia-170) t2 Oh my Oh my And (Ia-210) t3 Me F And (Ia-171) t2 Oh my And Cl (Ia-211) t3 Me <![CDATA[CF3]]> Cl (Ia-172) t2 Oh my And F (Ia-212) t3 Me <![CDATA[CF3]]> F (Ia-173) t2 Oh my And <![CDATA[CF3]]> (Ia-213) t3 Me <![CDATA[CF3]]> <![CDATA[CF3]]> (Ia-174) t2 Oh my And Oh my (Ia-214) t3 Me <![CDATA[CF3]]> Oh my (Ia-175) t2 Oh my And And (Ia-215) t3 Me <![CDATA[CF3]]> And (Ia-176) t2 And Cl Cl (Ia-216) t3 Me Oh my Cl (Ia-177) t2 And Cl F (Ia-217) t3 Me Oh my F (Ia-178) t2 And Cl <![CDATA[CF3]]> (Ia-218) t3 Me Oh my <![CDATA[CF3]]> (Ia-179) t2 And Cl Oh my (Ia-219) t3 Me Oh my Oh my (Ia-180) t2 And Cl And (Ia-220) t3 Me Oh my And (Ia-181) t2 And F Cl (Ia-221) t3 Me And Cl (Ia-182) t2 And F F (Ia-222) t3 Me And F (Ia-183) t2 And F <![CDATA[CF3]]> (Ia-223) t3 Me And <![CDATA[CF3]]> (Ia-184) t2 And F Oh my (Ia-224) t3 Me And Oh my (Ia-185) t2 And F And (Ia-225) t3 Me And And (Ia-186) t2 And <![CDATA[CF3]]> Cl (Ia-226) t3 And Cl Cl (Ia-187) t2 And <![CDATA[CF3]]> F (Ia-227) t3 And Cl F (Ia-188) t2 And <![CDATA[CF3]]> <![CDATA[CF3]]> (Ia-228) t3 And Cl <![CDATA[CF3]]> (Ia-189) t2 And <![CDATA[CF3]]> Oh my (Ia-229) t3 And Cl Oh my (Ia-190) t2 And <![CDATA[CF3]]> And (Ia-230) t3 And Cl And (Ia-191) t2 And Oh my Cl (Ia-231) t3 And F Cl (Ia-192) t2 And Oh my F (Ia-232) t3 And F F (Ia-193) t2 And Oh my <![CDATA[CF3]]> (Ia-233) t3 And F <![CDATA[CF3]]> (Ia-194) t2 And Oh my Oh my (Ia-234) t3 And F Oh my (Ia-195) t2 And Oh my And (Ia-235) t3 And F And (Ia-196) t2 And And Cl (Ia-236) t3 And <![CDATA[CF3]]> Cl (Ia-197) t2 And And F (Ia-237) t3 And <![CDATA[CF3]]> F (Ia-198) t2 And And <![CDATA[CF3]]> (Ia-238) t3 And <![CDATA[CF3]]> <![CDATA[CF3]]> (Ia-199) t2 And And Oh my (Ia-239) t3 And <![CDATA[CF3]]> Oh my (Ia-200) t2 And And And (Ia-240) t3 And <![CDATA[CF3]]> And

[0107] [Table 4]

[0108] compounds <![CDATA[X 1 ]]> <![CDATA[X 2 ]]> <![CDATA[X 3a ]]> <![CDATA[X 3b ]]> compounds <![CDATA[X 1 ]]> <![CDATA[X 2 ]]> <![CDATA[X 3a ]]> <![CDATA[X 3b ]]> (Ia-241) t3 And Oh my Cl (Ia-281) t3 And F Cl (Ia-242) t3 And Oh my F (Ia-282) t3 And F F (Ia-243) t3 And Oh my <![CDATA[CF3]]> (Ia-283) t3 And F <![CDATA[CF3]]> (Ia-244) t3 And Oh my Oh my (Ia-284) t3 And F Oh my (Ia-245) t3 And Oh my And (Ia-285) t3 And F And (Ia-246) t3 And And Cl (Ia-286) t3 And <![CDATA[CF3]]> Cl (Ia-247) t3 And And F (Ia-287) t3 And <![CDATA[CF3]]> F (Ia-248) t3 And And <![CDATA[CF3]]> (Ia-288) t3 And <![CDATA[CF3]]> <![CDATA[CF3]]> (Ia-249) t3 And And Oh my (Ia-289) t3 And <![CDATA[CF3]]> Oh my (Ia-250) t3 And And And (Ia-290) t3 And <![CDATA[CF3]]> And (Ia-251) t3 Oh my Cl Cl (Ia-291) t3 And Oh my Cl (Ia-252) t3 Oh my Cl F (Ia-292) t3 And Oh my F (Ia-253) t3 Oh my Cl <![CDATA[CF3]]> (Ia-293) t3 And Oh my <![CDATA[CF3]]> (Ia-254) t3 Oh my Cl Oh my (Ia-294) t3 And Oh my Oh my (Ia-255) t3 Oh my Cl And (Ia-295) t3 And Oh my And (Ia-256) t3 Oh my F Cl (Ia-296) t3 And And Cl (Ia-257) t3 Oh my F F (Ia-297) t3 And And F (Ia-258) t3 Oh my F <![CDATA[CF3]]> (Ia-298) t3 And And <![CDATA[CF3]]> (Ia-259) t3 Oh my F Oh my (Ia-299) t3 And And Oh my (Ia-260) t3 Oh my F And (Ia-300) t3 And And And (Ia-261) t3 Oh my <![CDATA[CF3]]> Cl (Ia-301) t4 Me Cl Cl (Ia-262) t3 Oh my <![CDATA[CF3]]> F (Ia-302) t4 Me Cl F (Ia-263) t3 Oh my <![CDATA[CF3]]> <![CDATA[CF3]]> (Ia-303) t4 Me Cl <![CDATA[CF3]]> (Ia-264) t3 Oh my <![CDATA[CF3]]> Oh my (Ia-304) t4 Me Cl Oh my (Ia-265) t3 Oh my <![CDATA[CF3]]> And (Ia-305) t4 Me Cl And (Ia-266) t3 Oh my Oh my Cl (Ia-306) t4 Me F Cl (Ia-267) t3 Oh my Oh my F (Ia-307) t4 Me F F (Ia-268) t3 Oh my Oh my <![CDATA[CF3]]> (Ia-308) t4 Me F <![CDATA[CF3]]> (Ia-269) t3 Oh my Oh my Oh my (Ia-309) t4 Me F Oh my (Ia-270) t3 Oh my Oh my And (Ia-310) t4 Me F And (Ia-271) t3 Oh my And Cl (Ia-311) t4 Me <![CDATA[CF3]]> Cl (Ia-272) t3 Oh my And F (Ia-312) t4 Me <![CDATA[CF3]]> F (Ia-273) t3 Oh my And <![CDATA[CF3]]> (Ia-313) t4 Me <![CDATA[CF3]]> <![CDATA[CF3]]> (Ia-274) t3 Oh my And Oh my (Ia-314) t4 Me <![CDATA[CF3]]> Oh my (Ia-275) t3 Oh my And And (Ia-315) t4 Me <![CDATA[CF3]]> And (Ia-276) t3 And Cl Cl (Ia-316) t4 Me Oh my Cl (Ia-277) t3 And Cl F (Ia-317) t4 Me Oh my F (Ia-278) t3 And Cl <![CDATA[CF3]]> (Ia-318) t4 Me Oh my <![CDATA[CF3]]> (Ia-279) t3 And Cl Oh my (Ia-319) t4 Me Oh my Oh my (Ia-280) t3 And Cl And (Ia-320) t4 Me Oh my And

[0109] [Table 5]

[0110] compounds <![CDATA[X 1 ]]> <![CDATA[X 2 ]]> <![CDATA[X 3a ]]> <![CDATA[X 3b ]]> compounds <![CDATA[X 1 ]]> <![CDATA[X 2 ]]> <![CDATA[X 3a ]]> <![CDATA[X 3b ]]> (Ia-321) t4 Me And Cl (Ia-361) t4 Oh my <![CDATA[CF3]]> Cl (Ia-322) t4 Me And F (Ia-362) t4 Oh my <![CDATA[CF3]]> F (Ia-323) t4 Me And <![CDATA[CF3]]> (Ia-363) t4 Oh my <![CDATA[CF3]]> <![CDATA[CF3 <!-- 12 -->]]> (Ia-324) t4 Me And Oh my (Ia-364) t4 Oh my <![CDATA[CF3]]> Oh my (Ia-325) t4 Me And And (Ia-365) t4 Oh my <![CDATA[CF3]]> And (Ia-326) t4 And Cl Cl (Ia-366) t4 Oh my Oh my Cl (Ia-327) t4 And Cl F (Ia-367) t4 Oh my Oh my F (Ia-328) t4 And Cl <![CDATA[CF3]]> (Ia-368) t4 Oh my Oh my <![CDATA[CF3]]> (Ia-329) t4 And Cl Oh my (Ia-369) t4 Oh my Oh my Oh my (Ia-330) t4 And Cl And (Ia-370) t4 Oh my Oh my And (Ia-331) t4 And F Cl (Ia-371) t4 Oh my And Cl (Ia-332) t4 And F F (Ia-372) t4 Oh my And F (Ia-333) t4 And F <![CDATA[CF3]]> (Ia-373) t4 Oh my And <![CDATA[CF3]]> (Ia-334) t4 And F Oh my (Ia-374) t4 Oh my And Oh my (Ia-335) t4 And F And (Ia-375) t4 Oh my And And (Ia-336) t4 And <![CDATA[CF3]]> Cl (Ia-376) t4 And Cl Cl (Ia-337) t4 And <![CDATA[CF3]]> F (Ia-377) t4 And Cl F (Ia-338) t4 And <![CDATA[CF3]]> <![CDATA[CF3]]> (Ia-378) t4 And Cl <![CDATA[CF3]]> (Ia-339) t4 And <![CDATA[CF3]]> Oh my (Ia-379) t4 And Cl Oh my (Ia-340) t4 And <![CDATA[CF3]]> And (Ia-380) t4 And Cl And (Ia-341) t4 And Oh my Cl (Ia-381) t4 And F Cl (Ia-342) t4 And Oh my F (Ia-382) t4 And F F (Ia-343) t4 And Oh my <![CDATA[CF3]]> (Ia-383) t4 And F <![CDATA[CF3]]> (Ia-344) t4 And Oh my Oh my (Ia-384) t4 And F Oh my (Ia-345) t4 And Oh my And (Ia-385) t4 And F And (Ia-346) t4 And And Cl (Ia-386) t4 And <![CDATA[CF3]]> Cl (Ia-347) t4 And And F (Ia-387) t4 And <![CDATA[CF3]]> F (Ia-348) t4 And And <![CDATA[CF3]]> (Ia-388) t4 And <![CDATA[CF3]]> <![CDATA[CF3]]> (Ia-349) t4 And And Oh my (Ia-389) t4 And <![CDATA[CF3]]> Oh my (Ia-350) t4 And And And (Ia-390) t4 And <![CDATA[CF3]]> And (Ia-351) t4 Oh my Cl Cl (Ia-391) t4 And Oh my Cl (Ia-352) t4 Oh my Cl F (Ia-392) t4 And Oh my F (Ia-353) t4 Oh my Cl <![CDATA[CF3]]> (Ia-393) t4 And Oh my <![CDATA[CF3]]> (Ia-354) t4 Oh my Cl Oh my (Ia-394) t4 And Oh my Oh my (Ia-355) t4 Oh my Cl And (Ia-395) t4 And Oh my And (Ia-356) t4 Oh my F Cl (Ia-396) t4 And And Cl (Ia-357) t4 Oh my F F (Ia-397) t4 And And F (Ia-358) t4 OMe F <![CDATA[CF3]]> (Ia-398) t4 OEt OEt <![CDATA[CF3]]> (Ia-359) t4 OMe F OMe (Ia-399) t4 OEt OEt OMe (Ia-360) t4 OMe F OEt (Ia-400) t4 OEt OEt OEt

[0111] [Table 6]

[0112] Compound <![CDATA[X 1 ]]> <![CDATA[X 2 ]]> <![CDATA[X 3a ]]> <![CDATA[X 3b ]]> Compound <![CDATA[X 1 ]]> <![CDATA[X 2 ]]> <![CDATA[X 3a ]]> <![CDATA[X 3b <!-- 13 -->]]> (Ia-401) t5 Me Cl Cl (Ia-441) t5 Et OMe Cl (Ia-402) t5 Me Cl F (Ia-442) t5 Et OMe F (Ia-403) t5 Me Cl <![CDATA[CF3]]> (Ia-443) t5 Et OMe <![CDATA[CF3]]> (Ia-404) t5 Me Cl OMe (Ia-444) t5 Et OMe OMe (Ia-405) t5 Me Cl OEt (Ia-445) t5 [[ID=四十七]]Et [[ID=四十八]]OMe [[ID=四十九]]OEt (Ia-406) t5 Me F Cl (Ia-446) t5 Et OEt Cl (Ia-407) t5 Me F F (Ia-447) t5 Et OEt F (Ia-408) t5 Me F <![CDATA[CF3]]> (Ia-448) t5 Et OEt <![CDATA[CF3]]> (Ia-409) t5 Me F OMe (Ia-449) t5 Et OEt OMe (Ia-410) t5 Me F OEt (Ia-450) t5 Et OEt OEt (Ia-411) t5 Me <![CDATA[CF3]]> Cl (Ia-451) t5 OMe Cl Cl (Ia-412) t5 Me <![CDATA[CF3]]> F (Ia-452) t5 OMe Cl F (Ia-413) t5 Me <![CDATA[CF3]]> <![CDATA[CF3]]> (Ia-453) t5 OMe Cl <![CDATA[CF3]]> (Ia-414) t5 Me <![CDATA[CF3]]> OMe (Ia-454) t5 OMe Cl OMe (Ia-415) t5 Me <![CDATA[CF3]]> OEt (Ia-455) t5 OMe Cl OEt (Ia-416) t5 Me OMe Cl (Ia-456) t5 OMe F Cl (Ia-417) t5 Me OMe F (Ia-457) t5 OMe F F (Ia-418) t5 Me OMe <![CDATA[CF3]]> (Ia-458) t5 OMe F <![CDATA[CF3]]> (Ia-419) t5 Me OMe OMe (Ia-459) t5 OMe F OMe (Ia-420) t5 Me OMe OEt (Ia-460) t5 OMe F OEt (Ia-421) t5 Me OEt Cl (Ia-461) t5 OMe <![CDATA[CF3]]> Cl (Ia-422) t5 Me OEt F (Ia-462) t5 OMe <![CDATA[CF3]]> F (Ia-423) t5 Me OEt <![CDATA[CF3]]> (Ia-463) t5 OMe <![CDATA[CF3]]> <![CDATA[CF3]]> (Ia-424) t5 Me OEt OMe (Ia-464) t5 OMe <![CDATA[CF3]]> OMe (Ia-425) t5 Me OEt OEt (Ia-465) t5 OMe <![CDATA[CF3]]> OEt (Ia-426) t5 Et Cl Cl (Ia-466) t5 OMe OMe Cl (Ia-427) t5 Et Cl F (Ia-467) t5 OMe OMe F (Ia-428) t5 Et Cl <![CDATA[CF3]]> (Ia-468) t5 OMe OMe <![CDATA[CF3]]> (Ia-429) t5 ​ Cl ​ ​ t5 ​ ​ ​ ​ t5 ​ Cl ​ ​ t5 ​ ​ ​ ​ t5 ​ F Cl ​ t5 ​ ​ Cl ​ t5 ​ F F ​ t5 ​ ​ F ​ t5 ​ F <![CDATA[CF3]]> ​ t5 ​ ​ <![CDATA[CF3]]> ​ t5 ​ F ​ ​ t5 ​ ​ ​ ​ t5 ​ F ​ ​ t5 ​ ​ ​ ​ t5 And <![CDATA[CF3]]> Cl (Ia-476) t5 And Cl Cl (Ia-437) t5 And <![CDATA[CF3]]> F (Ia-477) t5 And Cl F (Ia-438) t5 And <![CDATA[CF3]]> <![CDATA[CF3]]> (Ia-478) t5 And Cl <![CDATA[CF3]]> (Ia-439) t5 And <![CDATA[CF3]]> Oh my (Ia-479) t5 And Cl Oh my (Ia-440) t5 And <![CDATA[CF3]]> And (Ia-480) t5 And Cl And

[0113] [Table 7]

[0114] compounds <![CDATA[X 1 ]]> <![CDATA[X 2 ]]> <![CDATA[X 3a ]]> <![CDATA[X 3b ]]> compounds <![CDATA[X 1 ]]> <![CDATA[X 2 ]]> <![CDATA[X 3a ]]> <![CDATA[X 3b ]]> (Ia-481) t5 And F Cl (Ia-521) t6 Me And Cl (Ia-482) t5 And F F (Ia-522) t6 Me And F (Ia-483) t5 And F <![CDATA[CF3]]> (Ia-523) t6 Me And <![CDATA[CF3]]> (Ia-484) t5 And F Oh my (Ia-524) t6 Me And Oh my (Ia-485) t5 And F And (Ia-525) t6 Me And And (Ia-486) t5 And <![CDATA[CF3]]> Cl (Ia-526) t6 And Cl Cl (Ia-487) t5 And <![CDATA[CF3]]> F (Ia-527) t6 And Cl F (Ia-488) t5 And <![CDATA[CF3]]> <![CDATA[CF3]]> (Ia-528) t6 And Cl <![CDATA[CF3]]> (Ia-489) t5 And <![CDATA[CF3]]> Oh my (Ia-529) t6 And Cl Oh my (Ia-490) t5 And <![CDATA[CF3]]> And (Ia-530) t6 And Cl And (Ia-491) t5 And Oh my Cl (Ia-531) t6 And F Cl (Ia-492) t5 And Oh my F (Ia-532) t6 And F F (Ia-493) t5 And Oh my <![CDATA[CF3]]> (Ia-533) t6 And F <![CDATA[CF3]]> (Ia-494) t5 And Oh my Oh my (Ia-534) t6 And F Oh my (Ia-495) t5 And Oh my And (Ia-535) t6 And F And (Ia-496) t5 And And Cl (Ia-536) t6 And <![CDATA[CF3]]> Cl (Ia-497) t5 And And F (Ia-537) t6 And <![CDATA[CF3]]> F (Ia-498) t5 And And <![CDATA[CF3]]> (Ia-538) t6 And <![CDATA[CF3]]> <![CDATA[CF3]]> (Ia-499) t5 And And Oh my (Ia-539) t6 And <![CDATA[CF3]]> Oh my (Ia-500) t5 And And And (Ia-540) t6 And <![CDATA[CF3]]> And (Ia-501) t6 Me Cl Cl (Ia-541) t6 And Oh my Cl (Ia-502) t6 Me Cl F (Ia-542) t6 And Oh my F (Ia-503) t6 Me Cl <![CDATA[CF3]]> (Ia-543) t6 And Oh my <![CDATA[CF3]]> (Ia-504) t6 Me Cl Oh my (Ia-544) t6 And Oh my Oh my (Ia-505) t6 Me Cl And (Ia-545) t6 And Oh my And (Ia-506) t6 Me F Cl (Ia-546) t6 And And Cl (Ia-507) t6 Me F F (Ia-547) t6 And And F (Ia-508) t6 Me F <![CDATA[CF3]]> (Ia-548) t6 And And <![CDATA[CF3]]> (Ia-509) t6 Me F Oh my (Ia-549) t6 And And Oh my (Ia-510) t6 Me F And (Ia-550) t6 And And And (Ia-511) t6 Me <![CDATA[CF3]]> Cl (Ia-551) t6 Oh my Cl Cl (Ia-512) t6 Me <![CDATA[CF3]]> F (Ia-552) t6 Oh my Cl F (Ia-513) t6 Me <![CDATA[CF3]]> <![CDATA[CF3]]> (Ia-553) t6 Oh my Cl <![CDATA[CF3]]> (Ia-514) t6 Me <![CDATA[CF3]]> Oh my (Ia-554) t6 Oh my Cl Oh my (Ia-515) t6 Me <![CDATA[CF3]]> And (Ia-555) t6 Oh my Cl And (Ia-516) t6 Me OMe Cl (Ia-556) t6 OMe F Cl (Ia-517) t6 Me OMe F (Ia-557) t6 OMe F F (Ia-518) t6 Me OMe <![CDATA[CF3]]> (Ia-558) t6 OMe F <![CDATA[CF3]]> (Ia-519) t6 Me OMe OMe (Ia-559) t6 OMe F OMe (Ia-520) t6 Me OMe OEt (Ia-560) t6 OMe F OEt

[0115] [Table 8]

[0116] Compound <![CDATA[X 1 ]]> <![CDATA[X 2 ]]> <![CDATA[X 3a ]]> <![CDATA[X 3b ]]> (Ia-561) t6 OMe <![CDATA[CF3]]> Cl (Ia-562) t6 OMe <![CDATA[CF3]]> F (Ia-563) t6 OMe <![CDATA[CF3]]> <![CDATA[CF3]]> (Ia-564) t6 OMe <![CDATA[CF3]]> OMe (Ia-565) t6 OMe <![CDATA[CF3]]> OEt (Ia-566) t6 OMe OMe Cl (Ia-567) t6 OMe OMe F (Ia-568) t6 OMe OMe <![CDATA[CF3]]> (Ia-569) t6 OMe OMe OMe (Ia-570) t6 OMe OMe OEt (Ia-571) t6 OMe OEt Cl (Ia-572) t6 OMe OEt F (Ia-573) t6 OMe OEt <![CDATA[CF3]]> (Ia-574) t6 OMe OEt OMe (Ia-575) t6 OMe OEt OEt (Ia-576) t6 OEt Cl Cl (Ia-577) t6 OEt Cl F (Ia-578) t6 OEt Cl <![CDATA[CF3]]> (Ia-579) t6 OEt Cl OMe (Ia-580) t6 OEt Cl OEt (Ia-581) t6 OEt F Cl (Ia-582) t6 OEt F F (Ia-583) t6 OEt F <![CDATA[CF3]]> (Ia-584) t6 OEt F OMe (Ia-585) t6 OEt F OEt ​ t6 ​ <![CDATA[CF3]]> Cl ​ t6 ​ <![CDATA[CF3]]> F ​ t6 ​ <![CDATA[CF3]]> <![CDATA[CF3]]> ​ t6 ​ <![CDATA[CF3]]> ​ ​ t6 ​ <![CDATA[CF3]]> ​ ​ t6 ​ ​ Cl ​ t6 ​ ​ F ​ t6 ​ ​ <![CDATA[CF3 <!-- 16 -->]]> ​ t6 ​ ​ ​ ​ t6 ​ ​ ​ ​ t6 ​ ​ Cl ​ t6 ​ ​ F ​ t6 ​ ​ <![CDATA[CF3]]> ​ t6 ​ ​ ​ ​ t6 ​ ​ ​

[0117]

[0118] [Table 9]

[0119] ​ <![CDATA[X 1c ,X 1d ]]> <![CDATA[X 2c ,X 2d ]]> <![CDATA[X 3c ]]> <![CDATA[X 3d ]]> ​ <![CDATA[X 1c ,X 1d ]]> <![CDATA[X 2c ,X 2d ]]> <![CDATA[X 3c ]]> <![CDATA[X 3d ]]> ​ t1 ​ Cl Cl ​ t1 ​ <![CDATA[CF3]]> ​ ​ t1 ​ Cl F ​ t1 ​ <![CDATA[CF3]]> ​ ​ t1 ​ Cl <![CDATA[CF3]]> ​ t1 ​ ​ ​ ​ t1 ​ Cl ​ ​ t1 ​ ​ ​ ​ t1 ​ Cl ​ ​ t1 ​ ​ ​ ​ t1 ​ F F ​ t1 ​ Cl Cl ​ t1 ​ F <![CDATA[CF3]]> ​ t1 ​ Cl F ​ t1 ​ F ​ ​ t1 ​ Cl <![CDATA[CF3]]> ​ t1 ​ F ​ ​ t1 ​ Cl ​ ​ t1 ​ <![CDATA[CF3]]> <![CDATA[CF3]]> ​ t1 ​ Cl ​ ​ t1 ​ <![CDATA[CF3]]> ​ ​ t1 ​ F F ​ t1 ​ <![CDATA[CF3]]> ​ ​ t1 ​ F <![CDATA[CF3]]> ​ t1 ​ ​ ​ ​ t1 ​ F ​ ​ t1 ​ ​ ​ (Ib-54) t1 And F And (Ib-15) t1 Me And And (Ib-55) t1 And <![CDATA[CF3]]> <![CDATA[CF3]]> (Ib-16) t1 And Cl Cl (Ib-56) t1 And <![CDATA[CF3]]> Oh my (Ib-17) t1 And Cl F (Ib-57) t1 And <![CDATA[CF3]]> And (Ib-18) t1 And Cl <![CDATA[CF3]]> (Ib-58) t1 And Oh my Oh my (Ib-19) t1 And Cl Oh my (Ib-59) t1 And Oh my And (Ib-20) t1 And Cl And (Ib-60) t1 And And And (Ib-21) t1 And F F (Ib-61) t2 Me Cl Cl (Ib-22) t1 And F <![CDATA[CF3]]> (Ib-62) t2 Me Cl F (Ib-23) t1 And F Oh my (Ib-63) t2 Me Cl <![CDATA[CF3]]> (Ib-24) t1 And F And (Ib-64) t2 Me Cl Oh my (Ib-25) t1 And <![CDATA[CF3]]> <![CDATA[CF3]]> (Ib-65) t2 Me Cl And (Ib-26) t1 And <![CDATA[CF3]]> Oh my (Ib-66) t2 Me F F (Ib-27) t1 And <![CDATA[CF3]]> And (Ib-67) t2 Me F <![CDATA[CF3]]> (Ib-28) t1 And Oh my Oh my (Ib-68) t2 Me F Oh my (Ib-29) t1 And Oh my And (Ib-69) t2 Me F And (Ib-30) t1 And And And (Ib-70) t2 Me <![CDATA[CF3]]> <![CDATA[CF3]]> (Ib-31) t1 Oh my Cl Cl (Ib-71) t2 Me <![CDATA[CF3]]> Oh my (Ib-32) t1 Oh my Cl F (Ib-72) t2 Me <![CDATA[CF3]]> And (Ib-33) t1 Oh my Cl <![CDATA[CF3]]> (Ib-73) t2 Me Oh my Oh my (Ib-34) t1 Oh my Cl Oh my (Ib-74) t2 Me Oh my And (Ib-35) t1 Oh my Cl And (Ib-75) t2 Me And And (Ib-36) t1 Oh my F F (Ib-76) t2 And Cl Cl (Ib-37) t1 Oh my F <![CDATA[CF3]]> (Ib-77) t2 And Cl F (Ib-38) t1 Oh my F Oh my (Ib-78) t2 And Cl <![CDATA[CF3]]> (Ib-39) t1 Oh my F And (Ib-79) t2 And Cl Oh my (Ib-40) t1 Oh my <![CDATA[CF3]]> <![CDATA[CF3]]> (Ib-80) t2 And Cl And

[0120] [Table 10]

[0121] compounds <![CDATA[X 1c ,X 1d ]]> <![CDATA[X 2c ,X 2d ]]> <![CDATA[X 3c ]]> <![CDATA[X 3d ]]> compounds <![CDATA[X 1c ,X 1d ]]> <![CDATA[X 2c ,X 2d ]]> <![CDATA[X 3c ]]> <![CDATA[X 3d ]]> (Ia-81) t2 And F F (Ib-121) t3 Me Cl Cl (Ia-82) t2 And F <![CDATA[CF3]]> (Ib-122) t3 Me Cl F (Ia-83) t2 And F Oh my (Ib-123) t3 Me Cl <![CDATA[CF3]]> (Ia-84) t2 And F And (Ib-124) t3 Me Cl Oh my (Ia-85) t2 And <![CDATA[CF3]]> <![CDATA[CF3]]> (Ib-125) t3 Me Cl And (Ia-86) t2 And <![CDATA[CF3]]> Oh my (Ib-126) t3 Me F F (Ia-87) t2 And <![CDATA[CF3]]> And (Ib-127) t3 Me F <![CDATA[CF3]]> (Ia-88) t2 And Oh my Oh my (Ib-128) t3 Me F Oh my (Ia-89) t2 And Oh my And (Ib-129) t3 Me F And (Ia-90) t2 And And And (Ib-130) t3 Me CF <![CDATA[CF3]]> (Ia-91) t2 Oh my Cl Cl (Ib-131) t3 Me <![CDATA[CF3]]> Oh my (Ia-92) t2 Oh my Cl F (Ib-132) t3 Me <![CDATA[CF3]]> And (Ia-93) t2 Oh my Cl <![CDATA[CF3]]> (Ib-133) t3 Me Oh my Oh my (Ia-94) t2 Oh my Cl Oh my (Ib-134) t3 Me Oh my And (Ia-95) t2 Oh my Cl And (Ib-135) t3 Me And And (Ia-96) t2 Oh my F F (Ib-136) t3 And Cl Cl (Ia-97) t2 Oh my F <![CDATA[CF3]]> (Ib-137) t3 And Cl F (Ia-98) t2 Oh my F Oh my (Ib-138) t3 And Cl <![CDATA[CF3]]> (Ia-99) t2 Oh my F And (Ib-139) t3 And Cl Oh my (Ia-100) t2 Oh my <![CDATA[CF3]]> <![CDATA[CF3]]> (Ib-140) t3 And Cl And (Ia-101) t2 Oh my <![CDATA[CF3]]> Oh my (Ib-141) t3 And F F (Ia-102) t2 Oh my <![CDATA[CF3]]> And (Ib-142) t3 And F <![CDATA[CF3]]> (Ia-103) t2 Oh my Oh my Oh my (Ib-143) t3 And F Oh my (Ia-104) t2 Oh my Oh my And (Ib-144) t3 And F And (Ia-105) t2 Oh my And And (Ib-145) t3 And <![CDATA[CF3]]> <![CDATA[CF3]]> (Ia-106) t2 And Cl Cl (Ib-146) t3 And CF Oh my (Ia-107) t2 And Cl F (Ib-147) t3 And <![CDATA[CF3]]> And (Ia-108) t2 And Cl <![CDATA[CF3]]> (Ib-148) t3 And Oh my Oh my (Ia-109) t2 And Cl Oh my (Ib-149) t3 And Oh my And (Ia-110) t2 And Cl And (Ib-150) t3 And And And (Ia-111) t2 And F F (Ib-151) t3 Oh my Cl Cl (Ia-112) t2 And F <![CDATA[CF3]]> (Ib-152) t3 Oh my Cl F (Ia-113) t2 And F Oh my (Ib-153) t3 Oh my Cl <![CDATA[CF3]]> (Ia-114) t2 And F And (Ib-154) t3 Oh my Cl Oh my (Ia-115) t2 And <![CDATA[CF3]]> <![CDATA[CF3]]> (Ib-155) t3 Oh my Cl And (Ia-116) t2 And <![CDATA[CF3]]> Oh my (Ib-156) t3 Oh my F F (Ia-117) t2 And <![CDATA[CF3]]> And (Ib-157) t3 Oh my F <![CDATA[CF3]]> (Ia-118) t2 And Oh my Oh my (Ib-158) t3 Oh my F Oh my (Ia-119) t2 And Oh my And (Ib-159) t3 Oh my F And (Ia-120) t2 And And And (Ib-160) t3 Oh my <![CDATA[CF3]]> <![CDATA[CF3]]>

[0122] [Table 11]

[0123] compounds <![CDATA[X 1c ,X 1d ]]> <![CDATA[X 2c ,X 2d ]]> <![CDATA[X 3c ]]> <![CDATA[X 3d ]]> compounds <![CDATA[X 1c ,X 1d ]]> <![CDATA[X 2c ,X 2d ]]> <![CDATA[X 3c ]]> <![CDATA[X 3d ]]> (Ib-161) t3 Oh my <![CDATA[CF3]]> Oh my (Ib-201) t4 And F F (Ib-162) t3 Oh my <![CDATA[CF3]]> And (Ib-202) t4 And F <![CDATA[CF3]]> (Ib-163) t3 Oh my Oh my Oh my (Ib-203) t4 And F Oh my (Ib-164) t3 Oh my Oh my And (Ib-204) t4 And F And (Ib-165) t3 Oh my And And (Ib-205) t4 And <![CDATA[CF3]]> <![CDATA[CF3]]> (Ib-166) t3 And Cl Cl (Ib-206) t4 And <![CDATA[CF3]]> Oh my (Ib-167) t3 And Cl F (Ib-207) t4 And <![CDATA[CF3]]> And (Ib-168) t3 And Cl <![CDATA[CF3]]> (Ib-208) t4 And Oh my Oh my (Ib-169) t3 And Cl Oh my (Ib-209) t4 And Oh my And (Ib-170) t3 And Cl And (Ib-210) t4 And And And (Ib-171) t3 And F F (Ib-211) t4 Oh my Cl Cl (Ib-172) t3 And F <![CDATA[CF3]]> (Ib-212) t4 Oh my Cl F (Ib-173) t3 And F Oh my (Ib-213) t4 Oh my Cl <![CDATA[CF3]]> (Ib-174) t3 And F And (Ib-214) t4 What? Cl What? (Ib-175) t3 Oet <![CDATA[CF3]]> <![CDATA[CF3]]> (Ib-215) t4 What? Cl Oet (Ib-176) t3 Oet <![CDATA[CF3]]> What? (Ib-216) t4 What? F F (Ib-177) t3 Oet <![CDATA[CF3]]> Oet (Ib-217) t4 What? F <![CDATA[CF3]]> (Ib-178) t3 Oet What? What? (Ib-218) t4 What? F What? (Ib-179) t3 Oet What? Oet (Ib-219) t4 What? F Oet (Ib-180) t3 Oet Oet Oet (Ib-220) t4 What? <![CDATA[CF3]]> <![CDATA[CF3]]> (Ib-181) t4 Do Cl Cl (Ib-221) t4 What? <![CDATA[CF3]]> What? (Ib-182) t4 Do Cl F (Ib-222) t4 What? <![CDATA[CF3]]> Oet (Ib-183) t4 Do Cl <![CDATA[CF3]]> (Ib-223) t4 What? What? What? (Ib-184) t4 Do Cl What? (Ib-224) t4 What? What? Oet (Ib-185) t4 Do Cl Oet (Ib-225) t4 What? Oet Oet (Ib-186) t4 Do F F (Ib-226) t4 Oet Cl Cl (Ib-187) t4 Do F <![CDATA[CF3]]> (Ib-227) t4 Oet Cl F (Ib-188) t4 Do F What? (Ib-228) t4 Oet Cl <![CDATA[CF3]]> (Ib-189) t4 Do F Oet (Ib-229) t4 Oet Cl What? (Ib-190) t4 Do <![CDATA[CF3]]> <![CDATA[CF3]]> (Ib-230) t4 Oet Cl Oet (Ib-191) t4 Do <![CDATA[CF3]]> What? (Ib-231) t4 Oet F F (Ib-192) t4 Do <![CDATA[CF3]]> Oet (Ib-232) t4 Oet F <![CDATA[CF3]]> (Ib-193) t4 Do What? What? (Ib-233) t4 Oet F What? (Ib-194) t4 Do What? Oet (Ib-234) t4 Oet F Oet (Ib-195) t4 Do Oet Oet (Ib-235) t4 Oet <![CDATA[CF3]]> <![CDATA[CF3]]> (Ib-196) t4 Etc. Cl Cl (Ib-236) t4 Oet <![CDATA[CF3]]> What? (Ib-197) t4 Etc. Cl F (Ib-237) t4 Oet <![CDATA[CF3]]> Oet (Ib-198) t4 Etc. Cl <![CDATA[CF3]]> (Ib-238) t4 Oet What? What? (Ib-199) t4 Etc. Cl What? (Ib-239) t4 Oet What? Oet (Ib-200) t4 Etc. Cl Oet (Ib-240) t4 Oet Oet Oet

[0124] [Table 12]

[0125] compound <![CDATA[X 1c ,X 1d ]]> <![CDATA[X 2c ,X 2d ]]> <![CDATA[X 3c ]]> <![CDATA[X 3d ]]> compound <![CDATA[X 1c ,X 1d ]]> <![CDATA[X 2c ,X 2d ]]> <![CDATA[X 3c ]]> <![CDATA[X 3d ]]> (Ib-241) t5 Do Cl Cl (Ib-281) t5 What? <![CDATA[CF3]]> What? (Ib-242) t5 Do Cl F (Ib-282) t5 What? <![CDATA[CF3]]> Oet (Ib-243) t5 Do Cl <![CDATA[CF3]]> (Ib-283) t5 What? What? What? (Ib-244) t5 Do Cl What? (Ib-284) t5 What? What? Oet (Ib-245) t5 Do Cl Oet (Ib-285) t5 What? Oet Oet (Ib-246) t5 Do F F (Ib-286) t5 Oet Cl Cl (Ib-247) t5 Do F <![CDATA[CF3]]> (Ib-287) t5 Oet Cl F (Ib-248) t5 Do F What? (Ib-288) t5 Oet Cl <![CDATA[CF3]]> (Ib-249) t5 Do F Oet (Ib-289) t5 Oet Cl What? (Ib-250) t5 Do <![CDATA[CF3]]> <![CDATA[CF3]]> (Ib-29O) t5 Oet Cl Oet (Ib-251) t5 Do <![CDATA[CF3]]> What? (Ib-291) t5 Oet F F (Ib-252) t5 Do <![CDATA[CF3]]> Oet (Ib-292) t5 Oet F <![CDATA[CF3]]> (Ib-253) t5 Do What? What? (Ib-293) t5 Oet F What? (Ib-254) t5 Do What? Oet (Ib-294) t5 Oet F Oet (Ib-255) t5 Do Oet Oet (Ib-295) t5 Oet <![CDATA[CF3]]> <![CDATA[CF3 <!-- 20 -->]]> (Ib-256) t5 Etc. Cl Cl (Ib-296) t5 Oet <![CDATA[CF3]]> What? (Ib-257) t5 Etc. Cl F (Ib-297) t5 Oet <![CDATA[CF3]]> Oet (Ib-258) t5 Etc. Cl <![CDATA[CF3]]> (Ib-298) t5 Oet What? What? (Ib-259) t5 Etc. Cl What? (Ib-299) t5 Oet What? Oet (Ib-260) t5 Etc. Cl Oet (Ib-300) t5 Oet Oet Oet (Ib-261) t5 Etc. F F (Ib-301) t6 Do Cl Cl (Ib-262) t5 Etc. F <![CDATA[CF3]]> (Ib-302) t6 Do Cl F (Ib-263) t5 Etc. F What? (Ib-303) t6 Do Cl <![CDATA[CF3]]> (Ib-264) t5 Etc. F Oet (Ib-304) t6 Do Cl What? (Ib-265) t5 Etc. <![CDATA[CF3]]> <![CDATA[CF3]]> (Ib-305) t6 Do Cl Oet (Ib-266) t5 Etc. <![CDATA[CF3]]> What? (Ib-306) t6 Do F F (Ib-267) t5 Etc. <![CDATA[CF3]]> Oet (Ib-307) t6 Do F <![CDATA[CF3]]> (Ib-268) t5 Etc. What? What? (Ib-308) t6 Do F What? (Ib-269) t5 Etc. What? Oet (Ib-309) t6 Do F Oet (Ib-270) t5 Etc. Oet Oet (Ib-310) t6 Do <![CDATA[CF3]]> <![CDATA[CF3]]> (Ib-271) t5 What? Cl Cl (Ib-311) t6 Do <![CDATA[CF3]]> What? (Ib-272) t5 What? Cl F (Ib-312) t6 Do <![CDATA[CF3]]> Oet (Ib-273) t5 What? Cl <![CDATA[CF3]]> (Ib-313) t6 Do What? What? (Ib-274) t5 What? Cl What? (Ib-314) t6 Do What? Oet (Ib-275) t5 What? Cl Oet (Ib-315) t6 Do Oet Oet (Ib-276) t5 What? F F (Ib-316) t6 Etc. Cl Cl (Ib-277) t5 What? F <![CDATA[CF3]]> (Ib-317) t6 Etc. Cl F (Ib-278) t5 What? F What? (Ib-318) t6 Etc. Cl <![CDATA[CF3]]> (Ib-279) t5 What? F Oet (Ib-319) t6 Etc. Cl What? (Ib-280) t5 What? <![CDATA[CF3]]> <![CDATA[CF3]]> (Ib-320) t6 Etc. Cl Oet

[0126] [Table 13]

[0127] compound <![CDATA[X 1c ,X 1d ]]> <![CDATA[X 2c ,X 2d ]]> <![CDATA[X 3c ]]> <![CDATA[X 3d ]]> (Ib-321) t6 Etc. F F (Ib-322) t6 Etc. F <![CDATA[CF3]]> (Ib-323) t6 Etc. F What? (Ib-324) t6 Etc. F Oet (Ib-325) t6 Etc. <![CDATA[CF3]]> <![CDATA[CF3]]> (Ib-326) t6 Etc. <![CDATA[CF3]]> What? (Ib-327) t6 Etc. <![CDATA[CF3]]> Oet (Ib-328) t6 Etc. What? What? (Ib-329) t6 Etc. What? Oet (Ib-330) t6 Etc. Oet Oet (Ib-331) t6 What? Cl Cl (Ib-332) t6 What? Cl F (Ib-333) t6 What? Cl <![CDATA[CF3]]> (Ib-334) t6 What? Cl What? (Ib-335) t6 What? Cl Oet (Ib-336) t6 What? F F (Ib-337) t6 What? F <![CDATA[CF3]]> (Ib-338) t6 What? F What? (Ib-339) t6 What? F Oet (Ib-340) t6 What? <![CDATA[CF3]]> <![CDATA[CF3]]> (Ib-341) t6 What? <![CDATA[CF3]]> What? (Ib-342) t6 OMe <![CDATA[CF3]]> OEt (Ib-343) t6 OMe OMe OMe (Ib-344) t6 OMe OMe OEt (Ib-345) t6 OMe OEt OEt (Ib-346) t6 OEt Cl Cl (Ib-347) t6 OEt Cl F (Ib-348) t6 OEt Cl <![CDATA[CF3]]> (Ib-349) t6 OEt Cl OMe (Ib-350) t6 OEt Cl OEt (Ib-351) t6 OEt F F (Ib-352) t6 OEt F <![CDATA[CF3]]> (Ib-353) t6 OEt F OMe (Ib-354) t6 OEt F OEt (Ib-355) t6 OEt <![CDATA[CF3]]> <![CDATA[CF3]]> (Ib-356) t6 OEt <![CDATA[CF3]]> OMe (Ib-357) t6 OEt <![CDATA[CF3]]> OEt (Ib-358) t6 OEt OMe OMe (Ib-359) t6 ​ ​ ​ ​ t6 ​ ​ ​

[0128] [Table 14]

[0129] ​ <![CDATA[X 1c ,X 1d ]]> <![CDATA[X 2c ,X 2c ]]> <![CDATA[X 3c ]]> <![CDATA[X 3c ]]> ​ <![CDATA[X 1c ,X 1c ]]> <![CDATA[X 2c ,X 2d ]]> <![CDATA[X 3c ]]> <![CDATA[X 3d ]]> ​ t1 ​ - Cl ​ t2 ​ - Cl ​ t1 ​ - F ​ t2 ​ - F ​ t1 ​ - <![CDATA[CF3]]> ​ t2 ​ - <![CDATA[CF3]]> ​ t1 ​ - ​ ​ t2 ​ - ​ ​ t1 ​ - ​ ​ t2 ​ - ​ ​ t1 ​ - - ​ t2 ​ - - ​ t1 ​ - Cl ​ t3 ​ - Cl ​ t1 ​ - F ​ t3 ​ - F ​ t1 ​ - <![CDATA[CF3]]> ​ t3 ​ - <![CDATA[CF3 <!-- 22 -->]]> ​ t1 ​ - ​ ​ t3 ​ - ​ ​ t1 ​ - ​ ​ t3 ​ - ​ ​ t1 ​ - - ​ t3 ​ - - ​ t1 ​ - Cl ​ t3 ​ - Cl ​ t1 ​ - F ​ t3 ​ - F ​ t1 ​ - <![CDATA[CF3]]> ​ t3 ​ - <![CDATA[CF3]]> ​ t1 ​ - ​ ​ t3 ​ - ​ ​ t1 ​ - ​ ​ t3 ​ - ​ ​ t1 ​ - - ​ t3 ​ - - ​ t1 ​ - Cl ​ t3 ​ - Cl ​ t1 ​ - F ​ t3 ​ - F ​ t1 ​ - <![CDATA[CF3]]> ​ t3 ​ - <![CDATA[CF3]]> ​ t1 ​ - ​ ​ t3 ​ - ​ ​ t1 ​ - ​ ​ t3 ​ - ​ ​ t1 ​ - - ​ t3 ​ - - ​ t2 ​ - Cl ​ t3 ​ - Cl ​ t2 ​ - F ​ t3 ​ - F ​ t2 ​ - <![CDATA[CF3]]> ​ t3 ​ - <![CDATA[CF3]]> ​ t2 ​ - ​ ​ t3 ​ - ​ ​ t2 ​ - ​ ​ t3 ​ - ​ ​ t2 ​ - - ​ t3 ​ - - ​ t2 ​ - Cl ​ t4 ​ - Cl ​ t2 ​ - F ​ t4 Me - F (Ib-393) t2 Et - <![CDATA[CF3]]> (Ib-435) t4 Me - <![CDATA[CF3]]> (Ib-394) t2 Et - OMe (Ib-436) t4 Me - OMe (Ib-395) t2 Et - OEt (Ib-437) t4 Me - OEt (Ib-396) t2 Et - - (Ib-438) t4 Me - - (Ib-397) t2 OMe - Cl (Ib-439) t4 Et - Cl (Ib-398) t2 OMe - F (Ib-440) t4 Et - F (Ib-399) t2 OMe - <![CDATA[CF3]]> (Ib-441) t4 Et - <![CDATA[CF3]]> (Ib-400) t2 OMe - OMe (Ib-442) t4 Et - OMe (Ib-401) t2 OMe - OEt (Ib-443) t4 Et - OEt (Ib-402) t2 OMe - - (Ib-444) t4 Et - -

[0130] [Table 15]

[0131] Compound <![CDATA[X 1c ,X 1d ]]> <![CDATA[X 2c ,X 2d ]]> <![CDATA[X 3c ]]> <![CDATA[X 3c ]]> Compound <![CDATA[X 1c ,X 1c ]]> <![CDATA[X 2c ,X 2d ]]> <![CDATA[X 3c ]]> <![CDATA[X 3d ]]> (Ib-445) t4 OMe - Cl (Ib-487) t6 Et - Cl (Ib-446) t4 OMe - F (Ib-488) t6 Et - F (Ib-447) t4 OMe - <![CDATA[CF3]]> (Ib-489) t6 Et - <![CDATA[CF3]]> (Ib-448) t4 OMe - OMe (Ib-490) t6 Et - OMe (Ib-449) t4 OMe - OEt (Ib-491) t6 Et - OEt (Ib-450) t4 OMe - - (Ib-492) t6 Et - - (Ib-451) t4 OEt - Cl (Ib-493) t6 OMe - Cl (Ib-452) t4 OEt - F (Ib-494) t6 OMe - F (Ib-453) t4 OEt - <![CDATA[CF3]]> (Ib-495) t6 OMe - <![CDATA[CF3]]> (Ib-454) t4 OEt - OMe (Ib-496) t6 OMe - OMe (Ib-455) t4 OEt - OEt (Ib-497) t6 OMe - OEt (Ib-456) t4 OEt - - (Ib-498) t6 OMe - - (Ib-457) t5 Me - Cl (Ib-499) t6 OEt - Cl (Ib-458) t5 Me - F (Ib-500) t6 OEt - F (Ib-459) t5 Me - <![CDATA[CF3]]> (Ib-501) t6 OEt - <![CDATA[CF3]]> (Ib-460) t5 Me - OMe (Ib-502) t6 OEt - OMe (Ib-461) t5 Me - OEt (Ib-503) t6 OEt - OEt (Ib-462) t5 Me - - (Ib-504) t6 OEt - - (Ib-463) t5 Et - Cl (Ib-505) H Me - Cl (Ib-464) t5 Et - F (Ib-506) H Me - F (Ib-465) t5 Et - <![CDATA[CF3]]> (Ib-507) H Me - <![CDATA[CF3]]> (Ib-466) t5 Et - OMe (Ib-508) H Me - OMe (Ib-46 t5 ​ - ​ ​ H ​ - ​ ​ t5 ​ - - ​ H ​ - - ​ t5 ​ - Cl ​ H ​ - Cl ​ t5 ​ - F ​ H ​ - F ​ t5 ​ - <![CDATA[CF3]]> ​ H ​ - <![CDATA[CF3]]> ​ t5 ​ - ​ ​ H ​ - ​ ​ t5 ​ - ​ ​ H ​ - ​ ​ t5 ​ - - ​ H ​ - - ​ t5 ​ - Cl ​ H ​ - Cl ​ t5 ​ - F ​ H ​ - F ​ t5 ​ - <![CDATA[CF3]]> ​ H ​ - <![CDATA[CF3]]> (Ib-478) t5 OEt - OMe (Ib-520) H OMe - OMe (Ib-479) t5 OEt - OEt (Ib-521) H OMe - OEt (Ib-480) t5 OEt - - (Ib-522) H OMe - - (Ib-481) t6 Me - Cl (Ib-523) H OEt - Cl (Ib-482) t6 Me - F (Ib-524) H OEt - F (Ib-483) t6 Me - <![CDATA[CF3]]> (Ib-525) H OEt - <![CDATA[CF3]]> (Ib-484) t6 Me - OMe (Ib-526) H OEt - OMe (Ib-485) t6 Me - OEt (Ib-527) H OEt - OEt (Ib-486) t6 Me - - (Ib-528) H OEt - -

[0132] [Table 16]

[0133] Compound <![CDATA[X 1c ,X 1d ]]> <![CDATA[X 2c ,X 2d ]]> <![CDATA[X 3 c]]> <![CDATA[X 3d ]]> Compound <![CDATA[X 1c ,X 1d ]]> <![CDATA[X 2c ,X 2d ]]> <![CDATA[X 3c ]]> <![CDATA[X 3d ]]> (Ib-529) H Me Cl Cl (Ib-559) H OMe Cl Cl (Ib-530) H Me Cl F ​ H ​ Cl F ​ H ​ Cl <![CDATA[CF3]]> ​ H ​ Cl <![CDATA[CF3]]> ​ H ​ Cl ​ ​ H ​ Cl ​ ​ H ​ Cl ​ ​ H ​ Cl ​ ​ H ​ F F ​ H ​ F F ​ H ​ F <![CDATA[CF3]]> ​ H ​ F <![CDATA[CF3]]> ​ H ​ F ​ ​ H ​ F ​ ​ H ​ F ​ ​ H ​ F ​ ​ H ​ <![CDATA[CF3]]> <![CDATA[CF3]]> ​ H ​ <![CDATA[CF3]]> <![CDATA[CF3]]> ​ H ​ <![CDATA[CF3]]> ​ ​ H ​ <![CDATA[CF3]]> ​ ​ H ​ <![CDATA[CF3]]> ​ ​ H ​ <![CDATA[CF3]]> ​ ​ H ​ ​ ​ ​ H ​ ​ ​ ​ H ​ ​ ​ ​ H ​ ​ ​ ​ H ​ ​ ​ ​ H ​ ​ ​ ​ H ​ Cl Cl ​ H ​ Cl Cl ​ H ​ Cl F ​ H ​ Cl F ​ H ​ Cl <![CDATA[CF3]]> ​ H ​ Cl <![CDATA[CF3]]> ​ H ​ Cl ​ ​ H ​ Cl ​ ​ H ​ Cl ​ ​ H ​ Cl ​ ​ H ​ F F ​ H ​ F F ​ H ​ F <![CDATA[CF3]]> ​ H ​ F <![CDATA[CF3]]> ​ H ​ F ​ ​ H ​ F ​ ​ H ​ F ​ ​ H ​ F ​ ​ H ​ <![CDATA[CF3]]> <![CDATA[CF3]]> ​ H ​ <![CDATA[CF3]]> <![CDATA[CF3]]> ​ H ​ <![CDATA[CF3]]> ​ ​ H ​ <![CDATA[CF3]]> ​ ​ H ​ <![CDATA[CF3]]> ​ ​ H ​ <![CDATA[CF3]]> ​ ​ H ​ ​ ​ ​ H ​ ​ ​ ​ H ​ ​ ​ ​ H ​ ​ ​ ​ H ​ ​ ​ ​ H ​ ​ ​

[0134]

[0135] [In formulas (t1) to (t6), * represents a bonding site.]

[0136] Among the compounds (I), preferred are compounds (Ia-1) to (Ia-600) and (Ib-505) to (Ib-588), more preferred are compounds (Ia-1) to (Ia-100) and (Ib-505) to (Ib-528), further preferred are compounds (Ia-51) to (Ia-100) and (Ib-517) to (Ib-528), and even more preferred are compounds (Ia-51) to (Ia-75) and (Ib-76). (Ib-522), compound (Ib-528), more preferably compounds (Ia-51) to (Ia-55), compounds (Ia-61) to (Ia-70), compound (Ib-522), even more preferably compounds (Ia-51) to (Ia-55), compound (Ia-61), compound (Ia-66), compound (Ib-522), further more preferably compounds (Ia-51) to (Ia-55), compound (Ia-61), and compound (Ia-66).

[0137] As a method for producing compound (I), a known method can be used. For example, it can be produced by a method of condensing the phosgene of an azo compound represented by the following formula (I-i) with an amine compound represented by the following formula (I-ii), or by a method of coupling the amine compound represented by the following formula (I-iii) with a naphthol compound represented by the following formula (I-iv). The obtained compound (I) can be purified as needed by a known method such as recrystallization. It should be noted that the above-mentioned condensation reaction and coupling reaction can be carried out by any known method.

[0138]

[0139] [In formula (I-i) ~ formula (I-iv), X 1 ~X 3 , n and m have the same meanings as above.]

[0140] The phosgene of the azo compound represented by the above formula (I-i) can be produced by chlorinating a carboxylic acid derivative of the azo compound obtained by a coupling reaction of a diazo compound of the amine compound represented by the above formula (I-iii) (a compound represented by the following formula (I-v)) with 2-hydroxy-3-naphthoic acid using a chlorinating agent such as phosphorus pentachloride, phosphorus trichloride, or thionyl chloride.

[0141]

[0142] [In formula (I-v), X 1 and X 2 Means the same as above, Z - represents an inorganic or organic anion.]

[0143] As Z - Examples of inorganic anions include fluoride ion, chloride ion, bromide ion, iodide ion, perchlorate ion, hypochlorite ion, and the like. Examples of organic anions include CH3COO - 、C6H5COO - wait.

[0144] <<Compound (II)>>

[0145] Compound (II) has a predetermined chemical structure represented by the following formula (II). Compound (II) is described in detail below. Compound (II) also includes resonance structures of formula (II), tautomers of formula (II), and compounds obtained by rotating the groups in formula (II) around the bond axis of a single bond.

[0146]

[0147] [In formula (II),

[0148] L 1 represents a divalent aromatic hydrocarbon group which may have a substituent.

[0149] X 11 ~X 14 Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.]

[0150] L 1 The divalent aromatic hydrocarbon group represented by is a group formed by replacing two hydrogen atoms directly bonded to carbon atoms constituting the aromatic hydrocarbon ring with bonding sites. The aromatic hydrocarbon ring constituting the divalent aromatic hydrocarbon group may be either a monocyclic ring or a polycyclic ring, and examples thereof include a benzene ring, a biphenyl ring, a naphthalene ring, an anthracene ring, and a structure in which at least one hydrogen atom possessed by these aromatic hydrocarbon rings is replaced with a hydrocarbon group. Examples of the above-mentioned hydrocarbon group include the following: 2 、X 3 and R 1 ~R 8 The group represented by "a" is preferably a hydrocarbon group having 1 to 20 carbon atoms, preferably a hydrocarbon group having 1 to 12 carbon atoms, more preferably a chain hydrocarbon group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, further preferably a chain hydrocarbon group having 1 to 10 carbon atoms, and even more preferably a saturated chain hydrocarbon group having 1 to 4 carbon atoms. The number of hydrocarbon groups bonded to the aromatic hydrocarbon ring is preferably 0 to 4, more preferably 0 to 2. The number of carbon atoms in the divalent aromatic hydrocarbon group is preferably 6 to 30, more preferably 6 to 20, even more preferably 6 to 18, and even more preferably 6 to 12.

[0151] As X 11 ~X 14 The hydrocarbon group represented by X may be exemplified by 2 、X 3 and R 1 ~R 8 The same groups are included as those for the hydrocarbon groups having 1 to 20 carbon atoms represented by .

[0152] As L 1 The divalent aromatic hydrocarbon group represented by X 11 ~X 14 The substituents that the hydrocarbon group represented by 1 Aromatic hydrocarbon groups and heterocyclic groups represented by X 2 A hydrocarbon group represented by X 3 The substituents that the hydrocarbon group represented may have are the same as those of the group represented by .

[0153] As L 1, preferably a divalent aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent, more preferably a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent. The aromatic hydrocarbon ring constituting the divalent aromatic hydrocarbon group is preferably a benzene ring, a biphenyl ring, a naphthalene ring, or a structure in which at least one hydrogen atom possessed by these rings is substituted with a saturated chain hydrocarbon group having 1 to 10 carbon atoms (preferably 1 to 4 carbon atoms). More preferably, it is a benzene ring, a biphenyl ring, or a structure in which at least one hydrogen atom possessed by these rings is substituted with a saturated chain hydrocarbon group having 1 to 4 carbon atoms, and even more preferably a benzene ring or a biphenyl ring. The substituent that the divalent aromatic hydrocarbon group may have is preferably a halogen atom, an alkoxy group, an alkylsulfanyl group, a carboxyl group, a substituted or unsubstituted amino group, an N-acylamino group, a cyano group, or a substituted or unsubstituted carbamoyl group; more preferably a halogen atom, an alkoxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, a carboxyl group, a substituted or unsubstituted amino group, an N-acylamino group, a cyano group, or a substituted or unsubstituted carbamoyl group; further preferably a halogen atom, an alkoxy group having 1 to 4 carbon atoms, or a cyano group; further preferably a chlorine atom, a fluorine atom, an alkoxy group having 1 to 4 carbon atoms, or a cyano group; and even more preferably a chlorine atom, an alkoxy group having 1 to 4 carbon atoms, or a cyano group.

[0154] As L 1 , preferably any one of the groups represented by the following formulas (ph1) to (ph16), more preferably any one of the groups represented by formulas (ph1) to (ph3) and (ph11) to (ph13), further preferably any one of the groups represented by formula (ph11), formula (ph12), formula (ph11) and formula (ph12).

[0155]

[0156] [In formulas (ph1) to (ph16), * and ** represent bonding sites.]

[0157] X 11 、X 13Each independently represents preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, a cycloalkyl group having 3 to 10 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent, more preferably an alkyl group having 1 to 10 carbon atoms which may have a substituent, a cycloalkyl group having 3 to 10 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent, further preferably an alkyl group having 1 to 10 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent, still more preferably an alkyl group having 1 to 4 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent, still more preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent, still more preferably a phenyl group which may have a substituent, and still more preferably a phenyl group. 11 、X 13 The substituents that the hydrocarbon group represented by may have are preferably a halogen atom, an alkoxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, a carboxyl group, a substituted or unsubstituted amino group, an N-acylamino group, a cyano group, or a substituted or unsubstituted carbamoyl group; more preferably a halogen atom, an alkoxy group having 1 to 4 carbon atoms, or a cyano group; further preferably a chlorine atom, a fluorine atom, an alkoxy group having 1 to 4 carbon atoms, or a cyano group; and even more preferably a chlorine atom or a fluorine atom.

[0158] As X 12 、X 14 , are each independently preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, a cycloalkyl group having 3 to 10 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent, more preferably an alkyl group having 1 to 10 carbon atoms which may have a substituent, a cycloalkyl group having 3 to 10 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent, further preferably an alkyl group having 1 to 10 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent, further preferably an alkyl group having 1 to 4 carbon atoms which may have a substituent, still more preferably an alkyl group having 1 or 2 carbon atoms which may have a substituent, further more preferably a methyl group or an ethyl group, and particularly preferably a methyl group. As X 12 、X 14The substituent that the hydrocarbon group represented by is optionally substituted is preferably a halogen atom, an alkoxy group having 1 to 4 carbon atoms, an alkylsulfanyl group having 1 to 4 carbon atoms, a carboxyl group, a substituted or unsubstituted amino group, an N-acylamino group, a cyano group, or a substituted or unsubstituted carbamoyl group; more preferably a halogen atom, an alkoxy group having 1 to 4 carbon atoms, or a cyano group; further preferably a chlorine atom, a fluorine atom, an alkoxy group having 1 to 4 carbon atoms, or a cyano group; and even more preferably a chlorine atom or a fluorine atom.

[0159] Examples of compound (II) include compounds (II-1) to (II-231) shown in Tables 17 to 19. In Tables 17 to 19, "ph1" to "ph6," "ph8," "ph10" to "ph13," "r1," and "r2" represent groups represented by the following formulas (ph1) to (ph6), (ph8), (ph10) to (ph13), (r1), and (r2), respectively; "Me" represents a methyl group; "Et" represents an ethyl group; and "CF3" represents a trifluoromethyl group.

[0160] [Table 17]

[0161] ​ <![CDATA[L 1 ]]> <![CDATA[X 11 ]]> <![CDATA[X 12 ]]> <![CDATA[X 13 ]]> <![CDATA[X 14 ]]> compounds <![CDATA[L 1 ]]> <![CDATA[X 11 ]]> <![CDATA[X 12 ]]> <![CDATA[X 13 ]]> <![CDATA[X 14 ]]> (II-1) ph1 r1 Me r1 Me (II-43) ph3 r1 Me r1 Me (II-2) ph1 r1 Me r1 And (II-44) ph3 r1 Me r1 And (II-3) ph1 r1 Me r1 <![CDATA[CF3]]> (II-45) ph3 r1 Me r1 <![CDATA[CF3]]> (II-4) ph1 r1 And r1 And (II-46) ph3 r1 And r1 And (II-5) ph1 r1 And r1 <![CDATA[CF3]]> (II-47) ph3 r1 And r1 <![CDATA[CF3]]> (II-6) ph1 r1 <![CDATA[CF3]]> r1 <![CDATA[CF3]]> (II-48) ph3 r1 <![CDATA[CF3]]> r1 <![CDATA[CF3]]> (II-7) ph1 r2 Me r2 Me (II-49) ph3 r2 Me r2 Me (II-8) ph1 r2 Me r2 And (II-50) ph3 r2 Me r2 And (II-9) ph1 r2 Me r2 <![CDATA[CF3]]> (II-51) ph3 r2 Me r2 <![CDATA[CF3]]> (II-10) ph1 r2 And r2 And (II-52) ph3 r2 And r2 And (II-11) ph1 r2 And r2 <![CDATA[CF3]]> (II-53) ph3 r2 And r2 <![CDATA[CF3]]> (II-12) ph1 r2 <![CDATA[CF3]]> r2 <![CDATA[CF3]]> (II-54) ph3 r2 <![CDATA[CF3]]> r2 <![CDATA[CF3]]> (II-13) ph1 r1 Me r2 Me (II-55) ph3 r1 Me r2 Me (II-14) ph1 r1 Me r2 Me (II-56) ph3 r1 Me r2 Me (II-15) ph1 r1 Me r2 Me (II-57) ph3 r1 Me r2 Me (II-16) ph1 r1 And r2 And (II-58) ph3 r1 And r2 And (II-17) ph1 r1 And r2 And (II-59) ph3 r1 And r2 And (II-18) ph1 r1 And r2 And (II-60) ph3 r1 And r2 And (II-19) ph1 r1 <![CDATA[CF3]]> r2 <![CDATA[CF3]]> (II-61) ph3 r1 <![CDATA[CF3]]> r2 <![CDATA[CF3]]> (II-20) ph1 r1 <![CDATA[CF3]]> r2 <![CDATA[CF3]]> (II-62) ph3 r1 <![CDATA[CF3]]> r2 <![CDATA[CF3]]> (II-21) ph1 r1 <![CDATA[CF3]]> r2 <![CDATA[CF3]]> (II-63) ph3 r1 <![CDATA[CF3]]> r2 <![CDATA[CF3]]> (II-22) ph2 r1 Me r1 Me (II-64) ph4 r1 Me r1 Me (II-23) ph2 r1 Me r1 And (II-65) ph4 r1 Me r1 And (II-24) ph2 r1 Me r1 <![CDATA[CF3]]> (II-66) ph4 r1 Me r1 <![CDATA[CF3]]> (II-25) ph2 r1 And r1 And (II-67) ph4 r1 And r1 And (II-26) ph2 r1 And r1 <![CDATA[CF3]]> (II-68) ph4 r1 And r1 <![CDATA[CF3]]> (II-27) ph2 r1 <![CDATA[CF3]]> r1 <![CDATA[CF3]]> (II-69) ph4 r1 <![CDATA[CF3]]> r1 <![CDATA[CF3]]> (II-28) ph2 r2 Me r2 Me (II-70) ph4 r2 Me r2 Me (II-29) ph2 r2 Me r2 And (II-71) ph4 r2 Me r2 And (II-30) ph2 r2 Me r2 <![CDATA[CF3]]> (II-72) ph4 r2 Me r2 <![CDATA[CF3]]> (II-31) ph2 r2 And r2 And (II-73) ph4 r2 And r2 And (II-32) ph2 r2 And r2 <![CDATA[CF3]]> (II-74) ph4 r2 And r2 <![CDATA[CF3]]> (II-33) ph2 r2 <![CDATA[CF3]]> r2 <![CDATA[CF3]]> (II-75) ph4 r2 <![CDATA[CF3]]> r2 <![CDATA[CF3]]> (II-34) ph2 r1 Me r2 Me (II-76) ph4 r1 Me r2 Me (II-35) ph2 r1 Me r2 Me (II-77) ph4 r1 Me r2 Me (II-36) ph2 r1 Me r2 Me (II-78) ph4 r1 Me r2 Me (II-37) ph2 r1 And r2 And (II-79) ph4 r1 And r2 And (II-38) ph2 r1 And r2 And (II-80) ph4 r1 And r2 And (II-39) ph2 r1 And r2 And (II-81) ph4 r1 And r2 And (II-40) ph2 r1 <![CDATA[CF3]]> r2 <![CDATA[CF3]]> (II-82) ph4 r1 <![CDATA[CF3]]> r2 <![CDATA[CF3]]> (II-41) ph2 r1 <![CDATA[CF3]]> r2 <![CDATA[CF3]]> (II-83) ph4 r1 <![CDATA[CF3]]> r2 <![CDATA[CF3]]> (II-42) ph2 r1 <![CDATA[CF3]]> r2 <![CDATA[C F3]]> (II-84) ph4 r1 <![CDATA[CF3]]> r2 <![CDATA[CF3]]>

[0162] [Table 18]

[0163] compounds <![CDATA[L 1 ]]> <![CDATA[X 11 ]]> <![CDATA[X 12 ]]> <![CDATA[X 13 ]]> <![CDATA[X 14 ]]> compounds <![CDATA[L 1 ]]> <![CDATA[X 11 ]]> <![CDATA[X 12 ]]> <![CDATA[X 12 ]]> <![CDATA[X 14 ]]> (II-85) ph5 r1 Me r1 Me (H-127) ph8 r1 Me r1 Me (II-86) ph5 r1 Me r1 And (II-128) ph8 r1 Me r1 And (II-87) ph5 r1 Me r1 <![CDATA[CF3]]> (II-129) ph8 r1 Me r1 <![CDATA[CF3]]> (II-88) ph5 r1 And r1 And (II-130) ph8 r1 And r1 And (II-89) ph5 r1 And r1 <![CDATA[CF3]]> (II-131) ph8 r1 And r1 <![CDATA[CF3]]> (II-90) ph5 r1 <![CDATA[CF3]]> r1 <![CDATA[CF3]]> (II-132) ph8 r1 <![CDATA[CF3]]> r1 <![CDATA[CF3]]> (II-91) ph5 r2 Me r2 Me (II-133) ph8 r2 Me r2 Me (II-92) ph5 r2 Me r2 And (II-134) ph8 r2 Me r2 And (II-93) ph5 r2 Me r2 <![CDATA[CF3]]> (II-135) ph8 r2 Me r2 <![CDATA[CF3]]> (II-94) ph5 r2 And r2 And (II-136) ph8 r2 And r2 And (II-95) ph5 r2 And r2 <![CDATA[CF3]]> (II-137) ph8 r2 And r2 <![CDATA[CF3]]> (II-96) ph5 r2 <![CDATA[CF3]]> r2 <![CDATA[CF3]]> (II-138) ph8 r2 <![CDATA[CF3]]> r2 <![CDATA[CF3]]> (II-97) ph5 r1 Me r2 Me (II-139) ph8 r1 Me r2 Me (II-98) ph5 r1 Me r2 Me (II-140) ph8 r1 Me r2 Me (II-99) ph5 r1 Me r2 Me (II-141) ph8 r1 Me r2 Me (II-100) ph5 r1 And r2 And (II-142) ph8 r1 And r2 And (II-101) ph5 r1 And r2 And (II-143) ph8 r1 And r2 And (II-102) ph5 r1 And r2 And (II-144) ph8 r1 And r2 And (II-103) ph5 r1 <![CDATA[CF3]]> r2 <![CDATA[CF3]]> (II-145) ph8 r1 <![CDATA[CF3]]> r2 <![CDATA[CF3]]> (II-104) ph5 r1 <![CDATA[CF3]]> r2 <![CDATA[CF3]]> (II-146) ph8 r1 <![CDATA[CF3]]> r2 <![CDATA[CF3]]> (II-105) ph5 r1 <![CDATA[CF3]]> r2 <![CDATA[CF3]]> (II-147) ph8 r1 <![CDATA[CF3]]> r2 <![CDATA[CF3]]> (II-106) ph6 r1 Me r1 Me (II-148) ph1O r1 Me r1 Me (II-107) ph6 r1 Me r1 And (II-149) ph1O r1 Me r1 And (II-108) ph6 r1 Me r1 <![CDATA[CF3]]> (II-150) ph10 r1 Me r1 <![CDATA[CF3 <!-- 30 -->]]> (II-109) ph6 r1 And r1 And (II-151) ph10 r1 And r1 And (II-110) ph6 r1 And r1 <![CDATA[CF3]]> (II-152) ph10 r1 And r1 <![CDATA[CF3]]> (II-111) ph6 r1 <![CDATA[CF3]]> r1 <![CDATA[CF3]]> (II-153) ph10 r1 <![CDATA[CF3]]> r1 <![CDATA[CF3]]> (II-112) ph6 r2 Me r2 Me (H-154) ph10 r2 Me r2 Me (II-113) ph6 r2 Me r2 And (H-155) ph10 r2 Me r2 And (II-114) ph6 r2 Me r2 <![CDATA[CF3]]> (II-1 56) ph10 r2 Me r2 <![CDATA[CF3]]> (II-1 15) ph6 r2 And r2 And (II-157) ph10 r2 And r2 And (II-116) ph6 r2 And r2 <![CDATA[CF3]]> (II-158) ph10 r2 And r2 <![CDATA[CF3]]> (II-117) ph6 r2 <![CDATA[CF3]]> r2 <![CDATA[CF3]]> (II-159) ph10 r2 <![CDATA[CF3]]> r2 <![CDATA[CF3]]> (II-118) ph6 r1 Me r2 Me (II-160) ph10 r1 Me r2 Me (II-119) ph6 r1 Me r2 Me (II-161) ph10 r1 Me r2 Me (II-120) ph6 r1 Me r2 Me (II-162) ph10 r1 Me r2 Me (II-121) ph6 r1 And r2 And (II-163) ph10 r1 And r2 And (II-122) ph6 r1 And r2 And (II-164) ph10 r1 And r2 And (II-123) ph6 r1 And r2 And (II-165) ph10 r1 And r2 And (II-124) ph6 r1 <![CDATA[CF3]]> r2 <![CDATA[CF3]]> (II-166) ph10 r1 <![CDATA[CF3]]> r2 <![CDATA[CF3]]> (II-125) ph6 r1 <![CDATA[CF3]]> r2 <![CDATA[CF3]]> (II-167) ph10 r1 <![CDATA[CF3]]> r2 <![CDATA[CF3]]> (II-126) ph6 r1 <![CDATA[CF3]]> r2 <![CDATA[CF3]]> (II-168) ph10 r1 <![CDATA[CF3]]> r2 <![CDATA[CF3]]>

[0164] [Table 19]

[0165]

[0166]

[0167] [Wherein, * and ** represent bonding sites.]

[0168] Among compound (II), preferred are compound (II-1) to compound (II-63) and compound (II-169) to compound (II-231), more preferred are compound (II-1) to compound (II-42) and compound (II-169) to compound (II-210), further preferred are compound (II-1) to compound (II-21) and compound (II-169) to compound (II-189), further preferred are compound (II-1) to compound (II-12) and compound (II-169) to compound (II-180), and even more preferred are compound (II-1) to compound (II-6) and compound (II-169) to compound (II-174).

[0169] As a method for producing compound (II), a known method can be adopted. For example, it can be produced by the following method. First, the amine compound represented by the following formula (II-i) is diazotized to obtain a diazo compound represented by the following formula (II-ii), and the diazo compound represented by the following formula (II-ii) is subjected to a coupling reaction with the compound represented by the following formula (II-iii) to produce the amine compound represented by the following formula (II-iv). Then, the amine compound represented by the following formula (II-iv) is diazotized to obtain a diazo compound represented by the following formula (II-v), and the diazo compound represented by the following formula (II-v) is subjected to a coupling reaction with the compound represented by the following formula (II-vi), thereby producing compound (II). The obtained compound (II) can be further purified by known methods such as recrystallization as needed. It should be noted that the above-mentioned diazotization and coupling reactions can be carried out by any known method.

[0170]

[0171] [Where, L 1 、X 11 ~X 14 Means the same as above, Q a- and Q b- independently represent inorganic or organic anions]

[0172] As Q a- , Q b- Examples of inorganic anions include fluoride ion, chloride ion, bromide ion, iodide ion, perchlorate ion, hypochlorite ion, and the like. Examples of organic anions include CH3COO - 、C6H5COO - wait.

[0173] Colorant (A1)

[0174] The colorant (A) may further contain a colorant different from CI Pigment Violet 19, compound (I), and compound (II) (hereinafter also referred to as colorant (A1)). The colorant (A1) may be any one of a dye (hereinafter also referred to as dye (A1-1)) and a pigment (hereinafter also referred to as pigment (A1-2)). The colorant (A1) may contain one or both of these dyes (A1-1) and pigments (A1-2).

[0175] As long as the dye (A1-1) does not contain compound (I) and compound (II), known dyes can be used without particular limitation, and examples thereof include solvent dyes, acid dyes, direct dyes, mordant dyes, and the like. As dyes, for example, compounds classified as substances having hues other than pigments in the Color Index (published by The Society of Dyers and Colourists), and known dyes described in the Dyeing Guide (Color Dyeing Company) can be cited. Based on the chemical structure, examples of dyes include azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, thiazole dyes, Oxazine dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinone imine dyes, methine dyes, azomethine dyes, square acid dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, perylene dyes, quinophthalone dyes, isoindoline dyes, nitro dyes, etc. Among these, organic solvent-soluble dyes are preferred as the dye (A1-1).

[0176] Specific examples of the dye (A1-1) include:

[0177] CI Solvent Yellow 4 (hereinafter, CI Solvent Yellow will be omitted and only the number will be described. The same applies to others), 14, 15, 23, 24, 25, 38, 62, 63, 68, 79, 81, 82, 83, 89, 94, 98, 99, 117, 162, 163, 167, 189;

[0178] CI Solvent Red 24, 45, 49, 90, 91, 111, 118, 119, 122, 124, 125, 127, 130, 132, 143, 145, 146, 150, 151, 155, 160, 168, 169, 172, 175, 181, 207, 218, 222, 227, 230, 245, 247;

[0179] CI Solvent Orange 2, 7, 11, 15, 26, 41, 54, 56, 77, 86, 99;

[0180] CI Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60;

[0181] CI Solvent Blue 4, 5, 14, 18, 35, 36, 37, 38, 44, 45, 58, 59, 59: 1, 63, 67, 68, 69, 70, 78, 79, 83, 90, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139;

[0182] CI solvent dyes such as CI solvent green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35,

[0183] CI Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 156 7, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;

[0184] CI Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 33, 34, 35, 37, 40, 42, 44, 50, 51, 52, 57, 66, 73, 76, 80, 87, 88, 91, 92, 94, 95, 97, 98, 103, 106, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 155, 158, 160, 172, 176, 182 , 183, 195, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 289, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, ​​383, 388, 394, 401, 412, 417, 418, 422, 426;

[0185] CI Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 149, 162, 169, 173;

[0186] CI Acid Violet 6B, 7, 9, 15, 16, 17, 19, 21, 23, 24, 25, 30, 34, 38, 49, 72, 102;

[0187] CI Acid Blue 1, 3, 5, 7, 9, 11, 13, 15, 17, 18, 22, 23, 24, 25, 26, 27, 29, 34, 38, 40, 41, 42, 43, 45, 48, 51, 54, 59, 60, 62, 70, 72, 74, 75, 78, 80, 82, 83, 86, 87, 88, 90, 90:1, 91, 92, 93, 93:1, 96, 99, 100, 102, 103, 104, 108, 109, 110, 112, 113, 117, 119, 120, 123, 1 26, 127, 129, 130, 131, 138, 140, 142, 143, 147, 150, 151, 154, 158, 161, 166, 167, 168, 170, 171, 175, 182, 183, 184, 187, 192, 199, 203, 204, 205, 210, 213, 229, 234, 236, 242, 243, 249, 256, 259, 267, 269, 278, 280, 285, 290, 296, 315, 324: 1, 335, 340;

[0188] CI acid green 1, 3, 5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 22, 25, 27, 28, 41, 50, 50: 1, 58, 63, 65, 80, 104, 105, 106, 109 and other CI acid dyes,

[0189] CI Direct Yellow 2, 4, 28, 33, 34, 35, 38, 39, 43, 44, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 132, 136, 138, 141;

[0190] CI Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;

[0191] CI Direct Orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;

[0192] CI Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;

[0193] CI Direct Blue 1, 2, 3, 6, 8, 15, 22, 25, 28, 29, 40, 41, 42, 47, 52, 55, 57, 71, 76, 77, 78, 80, 81, 84, 85, 86, 87, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166, 1 67, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196, 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 242, 243, 244, 245, 246, 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293;

[0194] CI direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82 and other CI direct dyes,

[0195] CI Disperse Yellow 51, 54, 76;

[0196] CI Disperse Violet 26, 27;

[0197] CI disperse blue 1, 14, 56, 60 and other CI disperse dyes,

[0198] CI Basic Red 1, 9, 10;

[0199] CI Basic Blue 1, 3, 5, 7, 9, 19, 21, 22, 24, 25, 26, 28, 29, 40, 41, 45, 47, 54, 58, 59, 60, 64, 65, 66, 67, 68, 81, 83, 88, 89;

[0200] CI Basic Violet 2;

[0201] CI Basic Red 9;

[0202] CI basic dyes such as CI basic green 1,

[0203] CI Reactive Yellow 2, 76, 116;

[0204] CI Reactive Orange 16;

[0205] CI reactive dyes such as CI Reactive Red 36,

[0206] CI Medium Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;

[0207] CI Medium Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 27, 29, 30, 32, 33, 36, 37, 38, 39, 41, 42, 43, 45, 46, 48, 52, 53, 56, 62, 63, 71, 74, 76, 78, 85, 86, 88, 90, 94, 95;

[0208] CI Medium Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;

[0209] CI Medium Violet 1, 1: 1, 2, 3, 4, 5, 6, 7, 8, 10, 11, 14, 15, 16, 17, 18, 19, 21, 22, 23, 24, 27, 28, 30, 31, 32, 33, 36, 37, 39, 40, 41, 44, 45, 47, 48, 49, 53, 58;

[0210] CI Medium Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, 84;

[0211] CI mordant green 1, 3, 4, 5, 10, 13, 15, 19, 21, 23, 26, 29, 31, 33, 34, 35, 41, 43, 53 and other CI mordant dyes,

[0212] CI Vat Green 1 and other CI Vat Dyes and other dyes with Color Index (CI) numbers.

[0213] These dyes (A1-1) may be appropriately selected according to the spectral spectrum of a desired color filter.

[0214] As the pigment (A1-2), any known pigment can be used without particular limitation as long as it does not contain CI Pigment Violet 19, Compound (I) and Compound (II). Examples thereof include pigments classified as pigments in the Color Index (published by The Society of Dyers and Colourists).

[0215] Specific examples of the pigment (A1-2) include:

[0216] CI Pigment Yellow 1, 3, 10, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 81, 83, 86, 93, 94, 109, 110, 117, 125, 128, 129, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 185, 194, 214, 231 and other yellow pigments;

[0217] CI Pigment Orange 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 62, 64, 65, 71, 72, 73 and other orange pigments;

[0218] CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 178, 179, 180, 190, 192, 202, 209, 215, 216, 224, 242, 254, 255, 264, 265, 266, 268, 272, 273, 291, 295, 296, 297 and other red pigments;

[0219] CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60 and other blue pigments;

[0220] CI Pigment Violet 1, 23, 29, 32, 36, 38 and other purple pigments;

[0221] CI Pigment Green 7, 36, 58, 59, 62, 63, 64, 65, 66, 67 and other green pigments;

[0222] Brown pigments such as CI Pigment Brown 23 and 25;

[0223] CI Pigment Black 1, 7, 31, 32 and other black pigments and other pigments with Color Index (CI) numbers.

[0224] These pigments (A1-2) may be appropriately selected according to the spectral spectrum of a desired color filter.

[0225] Compound (I), compound (II) and the pigment may be subjected to rosin treatment, surface treatment using a pigment derivative into which an acidic group or a basic group is introduced, grafting treatment on the pigment surface using a polymer compound, micronization treatment using a sulfuric acid micronization method, or washing treatment using an organic solvent, water, or the like for removing impurities, or removal treatment of ionic impurities using an ion exchange method, or the like, as needed.

[0226] The particle size of compound (I), compound (II) and pigment is preferably substantially uniform. By containing a dispersant for dispersion treatment, a dispersion liquid in which at least one selected from compound (I), compound (II) and pigment is uniformly dispersed in a solution can be obtained. It should be noted that compound (I), compound (II) and pigment can be dispersed separately, or at least two selected from compound (I), compound (II) and pigment can be dispersed simultaneously.

[0227] As above-mentioned dispersant, for example, can enumerate surfactants such as cationic, anionic, nonionic, amphoteric, polyester, polyamine, acrylic acid etc..These dispersants can be used alone or in combination of 2 or more uses.As dispersant, with trade name, can enumerate KP (Shin-Etsu Chemical Co., Ltd. system), FLOWLEN (Kyoeisha Chemical Co., Ltd. system), Solsperse (Zeneca Co., Ltd. system), EFKA (BASF Corporation system), AJISPER (Ajinomoto Fine Chemicals Co., Ltd. system), Disperbyk (BYK Corporation system), BYK LPN (BYK Corporation system) etc.

[0228] When a dispersant is used, its amount is preferably 1 to 150% by mass, more preferably 5 to 100% by mass, and even more preferably 10 to 80% by mass relative to the total amount of compound (I), compound (II), and pigment. If the amount of the dispersant used is within the above range, a uniformly dispersed dispersion tends to be obtained.

[0229] The content of the colorant (A) is preferably 0.1 to 70% by mass, more preferably 0.5 to 65% by mass, further preferably 1.0 to 62% by mass, further preferably 5.0 to 60% by mass, further preferably 10 to 58% by mass, and still further preferably 15 to 56% by mass, based on the total solid content. When the content of the colorant (A) is within the above range, the color density of the resulting color filter is sufficient, and the desired amounts of the resin (B) and the polymerizable compound (C) can be contained in the colored curable resin composition. This allows for the suppression of defects during development (e.g., the generation of residues and poor pattern shape), resulting in a color filter having excellent mechanical strength.

[0230] As used herein, the term "total solids content" refers to the amount obtained by subtracting the solvent content from the total amount of the colored curable resin composition. The total solids content and the content (content ratio) of each component relative to the total solids content can be measured using known analytical methods such as liquid chromatography or gas chromatography.

[0231] The content ratio of the colorant (A) to the resin (B) described below (colorant (A) / resin (B)) is preferably 0.8 to 5.0, more preferably 1.0 to 4.5, even more preferably 1.1 to 4.2, even more preferably 1.2 to 4.0, even more preferably 1.3 to 3.8, and even more preferably 1.4 to 3.6, on a mass basis. When the content ratio of the colorant (A) to the resin (B) is within the above range, the color density of the resulting color filter is sufficient, and the desired amount of resin (B) can be contained in the colored curable resin composition. Therefore, defects during development (e.g., the generation of residues and pattern shape defects) can be suppressed, and a color filter with excellent mechanical strength can be formed.

[0232] The content of CI Pigment Violet 19 in the total amount of the colorant (A) is preferably 0.1 to 10 mass %, more preferably 0.5 to 8.5 mass %, further preferably 0.8 to 8.0 mass %, further preferably 1.0 to 7.5 mass %, and even more preferably 1.2 to 7.0 mass %.

[0233] The content of compound (I) in the total amount of the colorant (A) is preferably 0.5 to 50% by mass, more preferably 1 to 45% by mass, further preferably 3 to 40% by mass, further preferably 5 to 37% by mass, and even more preferably 7 to 35% by mass.

[0234] The content of compound (II) in the total amount of the colorant (A) is preferably 30 to 97% by mass, more preferably 40 to 95% by mass, further preferably 45 to 93% by mass, further preferably 50 to 90% by mass, and even more preferably 55 to 87% by mass.

[0235] The content ratio of Compound (I) to CI Pigment Violet 19 (Compound (I) / CI Pigment Violet 19) is preferably 0.5 to 25, more preferably 0.8 to 20, further preferably 1.0 to 18, and even more preferably 1.2 to 16 on a mass basis.

[0236] The content ratio of Compound (II) to CI Pigment Violet 19 (Compound (II) / CI Pigment Violet 19) is preferably 5 to 50, more preferably 8 to 45, further preferably 10 to 40, and even more preferably 12 to 35 on a mass basis.

[0237] The content ratio of Compound (II) to Compound (I) (Compound (II) / Compound (I)) is preferably 0.3 to 20, more preferably 0.8 to 15, further preferably 1.2 to 12, and even more preferably 1.5 to 10 on a mass basis.

[0238] The content of CI Pigment Violet 19 is preferably 0.05 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, further preferably 0.5 to 12 parts by mass, further preferably 1.0 to 10 parts by mass, and even more preferably 1.5 to 8 parts by mass, relative to 100 parts by mass of the total of Compound (I) and Compound (II).

[0239] The total content of CI Pigment Violet 19, Compound (I) and Compound (II) is preferably 0.1 to 70% by mass, more preferably 0.5 to 65% by mass, further preferably 1.0 to 62% by mass, further preferably 2.0 to 60% by mass, further preferably 5.0 to 58% by mass, and further preferably 8.0 to 56% by mass in the total amount of the solid component. If the total content is within the above range, the brightness at specific chromaticity coordinates of the obtained color filter can be increased, and the transmittance at 530 nm of the obtained color filter can be preferably suppressed.

[0240] The total content of CI Pigment Violet 19, Compound (I), and Compound (II) in the total amount of the colorant (A) is preferably 30% by mass or more, more preferably 50% by mass or more, even more preferably 60% by mass or more, even more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, and may be 100% by mass. If the total content is within the above range, the brightness of the obtained color filter at specific chromaticity coordinates can be improved, and the transmittance of the obtained color filter at 530 nm and / or the content of the colorant (A) in the total solid content of the colored curable resin composition can be suppressed.

[0241] The ratio of the total content of CI Pigment Violet 19, Compound (I) and Compound (II) to the content of the resin (B) described later ((total content of CI Pigment Violet 19, Compound (I) and Compound (II)) / content of Resin (B)) is preferably 0.8 to 5.0, more preferably 1.0 to 4.5, further preferably 1.1 to 4.2, further preferably 1.2 to 4.0, further preferably 1.3 to 3.8, and even more preferably 1.4 to 3.6, on a mass basis.

[0242] When a colorant (A1) is included, its content is preferably 0.01 to 30% by mass, more preferably 0.1 to 20% by mass, and even more preferably 1 to 15% by mass, based on the total amount of the colorant (A). The content of the yellow pigment as the colorant (A1) is preferably 2% by mass or less, more preferably 1.0% by mass or less, even more preferably 0.5% by mass or less, and particularly preferably 0% by mass, based on the total amount of the colorant (A). When the yellow pigment content is within the above range, a color filter having excellent color performance can be formed while suppressing the content of the colorant relative to the total solid content of the colored curable resin composition.

[0243] Resin (B)

[0244] The resin (B) is not particularly limited, but is preferably an alkali-soluble resin. Examples of the resin (B) include the following resins [K1] to [K6], and preferably at least one selected from the resins [K1] to [K6].

[0245] Resin [K1]: A copolymer comprising structural units derived from at least one monomer (a) (hereinafter also referred to as "(a)") selected from unsaturated carboxylic acids and unsaturated carboxylic anhydrides, and structural units derived from a monomer (b) (hereinafter also referred to as "(b)") having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond;

[0246] Resin [K2]: A copolymer having structural units derived from the above-mentioned (a), structural units derived from the above-mentioned (b), and structural units derived from a monomer (c) copolymerizable with (a) (which is different from (a) and (b)) (hereinafter also referred to as "(c)");

[0247] Resin [K3]: a copolymer having a structural unit derived from the above-mentioned (a) and a structural unit derived from the above-mentioned (c);

[0248] Resin [K4]: a copolymer having a structural unit obtained by adding the above-mentioned (b) to the structural unit derived from the above-mentioned (a), and a structural unit derived from the above-mentioned (c);

[0249] Resin [K5]: a copolymer having a structural unit obtained by adding the structural unit derived from the above-mentioned (a) to the structural unit derived from the above-mentioned (b), and a structural unit derived from the above-mentioned (c);

[0250] Resin [K6]: A copolymer having a structural unit obtained by adding the above-mentioned (a) to the structural unit derived from the above-mentioned (b), further adding a carboxylic acid anhydride, and a structural unit derived from the above-mentioned (c).

[0251] Examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, and o-, m-, and p-vinylbenzoic acid;

[0252] Unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, and 1,4-cyclohexenedicarboxylic acid;

[0253] Bicyclic unsaturated compounds containing a carboxyl group, such as methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene, and 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene;

[0254] Unsaturated dicarboxylic anhydrides such as maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride;

[0255] Unsaturated mono(meth)acryloyloxyalkyl) esters of divalent or higher polycarboxylic acids such as mono(2-(meth)acryloyloxyethyl) succinate and mono(2-(meth)acryloyloxyethyl) phthalate;

[0256] Unsaturated acrylic acid esters containing a hydroxyl group and a carboxyl group in the same molecule, such as α-(hydroxymethyl)acrylic acid.

[0257] Among these, acrylic acid, methacrylic acid, maleic anhydride, and the like are preferred from the viewpoint of copolymerization reactivity and solubility of the resulting resin in a developer (particularly an aqueous alkaline solution).

[0258] In this specification, "(meth)acrylic acid" refers to at least one selected from acrylic acid and methacrylic acid. The expressions "(meth)acryloyl" and "(meth)acrylate" also have the same meaning.

[0259] Specifically, (b) refers to a polymerizable compound having a cyclic ether structure having 2 to 4 carbon atoms (e.g., at least one selected from an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and an ethylenically unsaturated bond. Preferred examples of (b) include monomers having a cyclic ether structure having 2 to 4 carbon atoms and a (meth)acryloyloxy group.

[0260] As (b), for example, a monomer (b1) having an oxirane group and an ethylenically unsaturated bond (hereinafter also referred to as "(b1)"), a monomer (b2) having an oxetane group and an ethylenically unsaturated bond (hereinafter also referred to as "(b2)"), a monomer (b3) having a tetrahydrofuran group and an ethylenically unsaturated bond (hereinafter also referred to as "(b3)"), etc. can be cited.

[0261] Examples of (b1) include a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter also referred to as "(b1-1)") and a monomer (b1-2) having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized (hereinafter also referred to as "(b1-2)").

[0262] As (b1-1), a monomer having a glycidyl group and an ethylenically unsaturated bond is preferred. Examples of (b1-1) include glycidyl (meth)acrylate, β-methyl glycidyl (meth)acrylate, β-ethyl glycidyl (meth)acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis(glycidyl) ether, styrene, 2,4-bis(glycidyloxymethyl)styrene, 2,5-bis(glycidyloxymethyl)styrene, 2,6-bis(glycidyloxymethyl)styrene, 2,3,4-tris(glycidyloxymethyl)styrene, 2,3,5-tris(glycidyloxymethyl)styrene, 2,3,6-tris(glycidyloxymethyl)styrene, 3,4,5-tris(glycidyloxymethyl)styrene, 2,4,6-tris(glycidyloxymethyl)styrene, etc.

[0263] Examples of (b1-2) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (e.g., Celloxide (registered trademark) 2000; manufactured by Daicel Co., Ltd.), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., Cyclomer (registered trademark) A400; manufactured by Daicel Co., Ltd.), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., Cyclomer (registered trademark) M100; manufactured by Daicel Co., Ltd.), 3,4-epoxytricyclo[5.2.1.0](meth)acrylate, and 1,2-epoxy-4-vinylcyclohexane (e.g., Celloxide (registered trademark) 2000; manufactured by Daicel Co., Ltd.). 2,6 ] decyl ester, a compound represented by formula (BI) and a compound represented by formula (BII), etc.

[0264]

[0265] [In formula (BI) and formula (BII),

[0266] R e and R f It represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted by a hydroxyl group.

[0267] X e and X f Indicates a single bond, *-R g -, *-R g -O-, *-R g -S- or *-R g -NH-.

[0268] R g It represents an alkanediyl group having 1 to 6 carbon atoms.

[0269] *Indicates the bonding site with O.]

[0270] As R e and R f Examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, and tert-butyl.

[0271] Examples of the alkyl group in which a hydrogen atom is substituted with a hydroxy group include hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxy-1-methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, and 4-hydroxybutyl.

[0272] As R e and R f Preferred examples include a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, and a 2-hydroxyethyl group, and more preferred examples include a hydrogen atom and a methyl group.

[0273] Examples of the alkanediyl group having 1 to 6 carbon atoms include methylene, ethylene, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, and hexane-1,6-diyl.

[0274] As X e and X f Preferred examples include a single bond, a methylene group, an ethylene group, *-CH2-O-, and *-CH2CH2-O-; more preferred examples include a single bond and *-CH2CH2-O- (* represents a bonding site to O).

[0275] Examples of the compound represented by formula (BI) include compounds represented by any one of formulas (BI-1) to (BI-15). Among them, preferred are compounds represented by formula (BI-1), formula (BI-3), formula (BI-5), formula (BI-7), formula (BI-9), or formulas (BI-11) to (BI-15), and more preferred are compounds represented by formula (BI-1), formula (BI-7), formula (BI-9), or formula (BI-15).

[0276]

[0277] Examples of the compound represented by formula (BII) include compounds represented by any one of formulas (BII-1) to (BII-15). Among them, preferred are compounds represented by formula (BII-1), formula (BII-3), formula (BII-5), formula (BII-7), formula (BII-9), or formulas (BII-11) to (BII-15), and more preferred are compounds represented by formula (BII-1), formula (BII-7), formula (BII-9), or formula (BII-15).

[0278]

[0279] The compound represented by formula (BI) and the compound represented by formula (BII) may be used alone or in combination of two or more. When the compound represented by formula (BI) and the compound represented by formula (BII) are used in combination, the content ratio [compound represented by formula (BI) : compound represented by formula (BII)] is preferably 5:95 to 95:5, more preferably 20:80 to 80:20 on a molar basis.

[0280] As (b2) having an oxetane group and an ethylenically unsaturated bond, a monomer having an oxetane group and a (meth)acryloyloxy group is more preferable. Examples of (b2) include 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3-ethyl-3-acryloyloxymethyloxetane, 3-methyl-3-methacryloyloxyethyloxetane, 3-methyl-3-acryloyloxyethyloxetane, 3-ethyl-3-methacryloyloxyethyloxetane, and 3-ethyl-3-acryloyloxyethyloxetane.

[0281] As (b3) having a tetrahydrofuranyl group and an ethylenically unsaturated bond, a monomer having a tetrahydrofuranyl group and a (meth)acryloyloxy group is more preferred. Specific examples of (b3) include tetrahydrofurfuryl acrylate (e.g., Viscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.) and tetrahydrofurfuryl methacrylate.

[0282] As (b), (b1) is preferred from the viewpoint of improving the reliability of the obtained color filter in terms of heat resistance, chemical resistance, etc. Furthermore, (b1-2) is more preferred from the viewpoint of excellent storage stability of the colored curable resin composition.

[0283] Examples of (c) include (meth)acrylate monomers, unsaturated carboxylates such as unsaturated dicarboxylates, and vinyl monomers having an unsaturated aliphatic hydrocarbon ring, an unsaturated heterocyclic ring, or an aromatic ring.

[0284] Examples of the (meth)acrylate monomer include

[0285] (Meth)acrylates having a linear or branched aliphatic saturated hydrocarbon group, such as methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, and cyclopentyl (meth)acrylate;

[0286] (Meth)acrylates having a linear or branched aliphatic unsaturated hydrocarbon group, such as allyl (meth)acrylate and propargyl (meth)acrylate;

[0287] (Meth) acrylate cyclohexyl, (meth) acrylate 2-methylcyclohexyl, (meth) acrylate tricyclo[5.2.1.0 2,6 (Meth)acrylates having a cyclic saturated hydrocarbon group, such as decane-8-yl acrylate (commonly known in the art as "dicyclopentanyl (meth)acrylate." Also, sometimes referred to as "tricyclodecyl (meth)acrylate"), isobornyl (meth)acrylate, and adamantyl (meth)acrylate;

[0288] (Meth) acrylic acid tricyclic [5.2.1.0 2,6 (Meth)acrylates having a cyclic unsaturated aliphatic hydrocarbon group, such as decen-8-yl acrylate (commonly known as "dicyclopentenyl (meth)acrylate" in this technical field) and dicyclopentyloxyethyl (meth)acrylate;

[0289] (Meth)acrylates having an aromatic ring, such as phenyl (meth)acrylate, naphthyl (meth)acrylate, benzyl (meth)acrylate, and phenoxybenzyl (meth)acrylate;

[0290] (Meth)acrylates containing a hydroxyl group, such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate.

[0291] Examples of the unsaturated dicarboxylic acid ester include dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconate.

[0292] Among these unsaturated carboxylic acid esters, from the viewpoint of copolymerization reactivity and heat resistance,

[0293] Preferably, it is a (meth)acrylate monomer,

[0294] More preferably, C 1-10 Alkyl (meth) acrylate; (meth) acrylate tricyclic [5.2.1.0 2,6 ] decane-8-yl ester and other cyclic saturated hydrocarbon groups (meth) acrylates; (meth) acrylic acid tricyclic [5.2.1.0 2,6 ] (Meth)acrylates having a cyclic unsaturated aliphatic hydrocarbon group such as decen-8-yl ester; (meth)acrylates having an aromatic ring such as benzyl (meth)acrylate and phenoxybenzyl (meth)acrylate; (meth)acrylates containing a hydroxyl group such as 2-hydroxyethyl (meth)acrylate,

[0295] More preferably, (meth)acrylic acid C such as methyl methacrylate and 2-ethylhexyl acrylate is used. 1-10 Alkyl ester; (meth) acrylic acid tricyclic [5.2.1.0 2,6 ] (meth)acrylates having a cyclic saturated hydrocarbon group such as decane-8-yl acrylate; (meth)acrylates having an aromatic ring such as benzyl (meth)acrylate and phenoxybenzyl (meth)acrylate.

[0296] Examples of the vinyl monomer having an unsaturated aliphatic hydrocarbon ring include bicyclo[2.2.1]hept-2-ene (also referred to as 2-norbornene), 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-bis(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(2'-hydroxyethyl)bicyclo[2.2 .1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, 5- Bicyclic unsaturated compounds such as tert-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, and 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene.

[0297] Examples of the vinyl monomer having an unsaturated heterocyclic ring include dicarbonyl imide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N-succinimidyl-3-maleimidopropionate, and N-(9-acridinyl)maleimide.

[0298] Examples of the vinyl monomer having an aromatic ring include styrene-based monomers such as styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, and p-methoxystyrene.

[0299] As other vinyl monomers, there can be mentioned monomers containing a nitrile group such as acrylonitrile and methacrylonitrile;

[0300] Monomers containing halogen atoms such as vinyl chloride and vinylidene chloride;

[0301] Acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, etc.

[0302] Among these vinyl monomers, preferred are styrene-based monomers such as styrene and vinyltoluene, dicarbonyl imide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide, and N-benzylmaleimide, and bicyclic unsaturated compounds such as bicyclo[2.2.1]hept-2-ene from the viewpoint of copolymerization reactivity and heat resistance.

[0303] (c) is preferably an unsaturated carboxylic acid ester, and more preferably a (meth)acrylate monomer.

[0304] The structural unit obtained by adding (b) to the structural unit derived from (a) refers to a unit formed by adding (b) to the structural unit derived from (a) constituting the main chain of the copolymer, and has a pendant unsaturated group derived from (b). In this structural unit, (a) can be any of the above examples, and (b) can also be any of the above examples. In this structural unit, as (a), an unsaturated monocarboxylic acid such as (meth)acrylic acid is preferred, and as (b), a monomer (b1) having an oxirane group and an ethylenically unsaturated bond is preferred, and a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized is more preferred.

[0305] The structural unit obtained by adding (a) to the structural unit derived from (b) is a unit formed by adding (a) to the structural unit derived from (b) constituting the main chain of the copolymer, and has a pendant unsaturated group derived from (a). In this structural unit, (b) can be any of the above examples, and (a) can also be any of the above examples. In this structural unit, as (b), preferably, a monomer (b1) having an oxirane group and an ethylenically unsaturated bond is used, and more preferably, a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized. As (a), preferably, an unsaturated monocarboxylic acid such as (meth)acrylic acid is used.

[0306] The structural unit obtained by adding (a) to the structural unit derived from (b) and further adding carboxylic anhydride refers to a structural unit synthesized by half-esterifying the hydroxyl group generated by the addition of (a) to the structural unit derived from (b) constituting the main chain of the copolymer with carboxylic anhydride, and having a pendant carboxyl group derived from the carboxylic anhydride and a pendant unsaturated group derived from (a). In this structural unit, (b) can be any of the above examples, and (a) can also be any of the above examples. In this structural unit, as (b), preferably, a monomer (b1) having an oxirane group and an ethylenically unsaturated bond is used, and more preferably, a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized. As (a), preferably, an unsaturated monocarboxylic acid such as (meth)acrylic acid is used.

[0307] Examples of the carboxylic acid anhydride include saturated aliphatic polycarboxylic acid anhydrides such as malonic anhydride, succinic anhydride, glutaric anhydride, and adipic anhydride; unsaturated aliphatic polycarboxylic acid anhydrides such as maleic anhydride, citraconic anhydride, and itaconic anhydride; aromatic polycarboxylic acid anhydrides such as 3-vinylphthalic anhydride and 4-vinylphthalic anhydride; and alicyclic polycarboxylic acid anhydrides such as 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride and 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride.

[0308] In the resin [K1], the ratio of the structural units derived from each compound is preferably 2 to 60 mol% of the structural units derived from (a) and 40 to 98 mol% of the structural units derived from (b) in all the structural units constituting the resin [K1]. More preferably, the structural units derived from (a) are 10 to 50 mol% and the structural units derived from (b) are 50 to 90 mol%.

[0309] When the ratio of the structural unit of the resin [K1] is within the above range, the storage stability of the colored curable resin composition, the developability when forming a colored pattern, and the solvent resistance of the obtained color filter tend to be excellent.

[0310] Resin [K1] can be produced, for example, by referring to the method described in the document "Experimental Methods for Polymer Synthesis" (Otsu Takayuki Publishing Co., Ltd., Chemical Dojin, 1st edition, 1st printing, published on March 1, 1972) and the cited documents described in the document.

[0311] Specifically, the following method can be used: predetermined amounts of (a) and (b), a polymerization initiator, and a solvent are placed in a reaction vessel, and a deoxygenated atmosphere is created, for example, by replacing oxygen with nitrogen. The mixture is then heated and maintained while stirring. The polymerization initiator and solvent used herein are not particularly limited, and those commonly used in this field can be used. For example, polymerization initiators include azo compounds (such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), and dimethyl 2,2'-azobis(2-methylpropionate)) and organic peroxides (such as benzoyl peroxide and tert-butyl peroxy-2-ethylhexanoate). The solvent can be any solvent that dissolves the monomers, and examples thereof include the solvents described below as solvent (E).

[0312] The resulting copolymer may be used directly as a post-reaction solution, after concentration or dilution, or in a solid (powder) form by reprecipitation or other methods. In particular, by using the solvent contained in the colored curable resin composition of the present invention as a solvent during the polymerization, the post-reaction solution can be used directly to prepare the colored curable resin composition of the present invention, thereby simplifying the production process of the colored curable resin composition of the present invention.

[0313] In the resin [K2], the ratio of the structural units derived from each compound is preferably 2 to 45 mol% of the structural units derived from (a), 2 to 90 mol% of the structural units derived from (b), and 5 to 75 mol% of the structural units derived from (c) in all the structural units constituting the resin [K2]. More preferably, the ratio is 5 to 40 mol% of the structural units derived from (a), 5 to 80 mol% of the structural units derived from (b), and 10 to 70 mol% of the structural units derived from (c).

[0314] When the ratio of the structural units of the resin [K2] is within the above range, the storage stability of the colored curable resin composition, the developability when forming a colored pattern, and the solvent resistance, heat resistance, and mechanical strength of the obtained color filter tend to be excellent.

[0315] In resin [K2], (a) is preferably an unsaturated monocarboxylic acid such as (meth)acrylic acid. (b) is preferably a monomer (b1) having an oxirane group and an ethylenically unsaturated bond, and more preferably a monomer (b1-2) having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized. (c) is preferably an unsaturated carboxylic acid ester, more preferably a (meth)acrylate monomer, and even more preferably a (meth)acrylate having an aromatic ring.

[0316] The resin [K2] can be produced, for example, in the same manner as described as the method for producing the resin [K1].

[0317] In the resin [K3], the ratio of the structural units derived from each compound is preferably 2 to 60 mol% of the structural units derived from (a) and 40 to 98 mol% of the structural units derived from (c) in all the structural units constituting the resin [K3]. More preferably, the structural units derived from (a) are 10 to 50 mol% and the structural units derived from (c) are 50 to 90 mol%.

[0318] The resin [K3] can be produced, for example, in the same manner as described as the method for producing the resin [K1].

[0319] In the resin [K4], the ratio of the structural units derived from each compound in all the structural units constituting the resin [K4] is preferably 1 to 60 mol% of the structural units derived from (a) (without addition of (b)), 1 to 50 mol% of the structural units obtained by adding (b) to the structural units derived from (a), and 30 to 90 mol% of the structural units derived from (c). More preferably, the ratio of the structural units derived from (a) (without addition of (b)) is 5 to 50 mol%, 5 to 40 mol% of the structural units obtained by adding (b) to the structural units derived from (a), and 35 to 80 mol% of the structural units derived from (c).

[0320] Resin [K4] can be produced by obtaining a copolymer of (a) and (c), and adding a cyclic ether having 2 to 4 carbon atoms contained in (b) to the carboxylic acid and / or carboxylic anhydride contained in (a).

[0321] First, a copolymer of (a) and (c) is produced in the same manner as described as the method for producing resin [K1]. In this case, the ratio of the structural units derived from each compound is preferably the same as that exemplified for resin [K3].

[0322] Next, the cyclic ether having 2 to 4 carbon atoms contained in (b) is reacted with a portion of the carboxylic acid and / or carboxylic anhydride derived from (a) in the above copolymer.

[0323] After producing the copolymer of (a) and (c), the atmosphere in the flask is replaced from nitrogen to air, and (b), a reaction catalyst for a carboxylic acid or carboxylic anhydride and a cyclic ether (e.g., tris(dimethylaminomethyl)phenol, triphenylphosphine, etc.), and a polymerization inhibitor (e.g., hydroquinone, methoquinone, etc.) are placed in the flask and reacted at, for example, 60 to 130° C. for 1 to 10 hours to produce resin [K4].

[0324] The amount of (b) used is preferably 5 to 100 mol, more preferably 10 to 80 mol, and even more preferably 10 to 75 mol relative to 100 mol of (a). Within this range, there is a tendency for the storage stability of the colored curable resin composition, the developability during pattern formation, and the balance of solvent resistance, heat resistance, mechanical strength, and sensitivity of the resulting pattern to be improved. From the perspective of the high reactivity of cyclic ethers and the difficulty of unreacted (b) remaining, (b1) is preferably used as the (b) in resin [K4], and more preferably (b1-1).

[0325] The amount of the reaction catalyst used is preferably 0.001 to 5 parts by mass relative to 100 parts by mass of the total amount of (a), (b), and (c). The amount of the polymerization inhibitor used is preferably 0.001 to 5 parts by mass relative to 100 parts by mass of the total amount of (a), (b), and (c).

[0326] The reaction conditions such as the charging method, reaction temperature and time can be appropriately adjusted in consideration of the production equipment, the calorific value based on the polymerization, etc. In addition, the charging method and reaction temperature can be appropriately adjusted in consideration of the production equipment, the calorific value based on the polymerization, etc., similarly to the polymerization conditions.

[0327] In the resin [K5], the ratio of the structural units derived from each compound in all the structural units constituting the resin [K5] is preferably 0 to 30 mol% of the structural units derived from (b) (without addition of (a)), 5 to 95 mol% of the structural units obtained by adding (a) to the structural units derived from (b), and 5 to 95 mol% of the structural units derived from (c). More preferably, the structural units derived from (b) (without addition of (a)) are 0 to 25 mol%, 15 to 90 mol% of the structural units obtained by adding (a) to the structural units derived from (b), and 10 to 85 mol% of the structural units derived from (c).

[0328] As a first step, the resin [K5] is subjected to the same method as for producing the resin [K1] to obtain a copolymer of (b) and (c). Similarly to the above, the obtained copolymer may be used as is after the reaction, after concentration or dilution, or after being obtained as a solid (powder) by reprecipitation or the like.

[0329] The ratio of the structural units derived from (b) and (c) relative to the total molar number of all structural units constituting the above-mentioned copolymer is preferably 5 to 95 mol% for the structural units derived from (b) and 5 to 95 mol% for the structural units derived from (c), and more preferably 10 to 90 mol% for the structural units derived from (b) and 10 to 90 mol% for the structural units derived from (c).

[0330] Furthermore, resin [K5] can be obtained by reacting the cyclic ether derived from (b) contained in the copolymer of (b) and (c) with the carboxylic acid or carboxylic anhydride contained in (a) under the same conditions as those in the method for producing resin [K4].

[0331] The amount of (a) reacted with the copolymer is preferably 5 to 100 mol per 100 mol of (b). Since the cyclic ether has high reactivity and is less likely to leave unreacted (b), (b1) is preferred, and (b1-1) is more preferred, as (b) used in the resin [K5].

[0332] In the resin [K6], the ratio of the structural unit derived from each compound in all the structural units constituting the resin [K6] is preferably 0 to 30 mol% of the structural unit derived from (b) (without addition of (a)), 3 to 85 mol% of the structural unit obtained by adding (a) to the structural unit derived from (b) (without addition of carboxylic anhydride), 3 to 55 mol% of the structural unit obtained by adding (a) to the structural unit derived from (b) and further adding carboxylic anhydride, and 10 to 80 mol% of the structural unit derived from (c). More preferably, 0 to 25 mol% of the structural unit derived from (b) (without addition of (a)), 5 to 80 mol% of the structural unit obtained by adding (a) to the structural unit derived from (b) (without addition of carboxylic anhydride), 5 to 50 mol% of the structural unit obtained by adding (a) to the structural unit derived from (b) and further adding carboxylic anhydride, and 15 to 75 mol% of the structural unit derived from (c).

[0333] As a first step, the resin [K6] is subjected to the same method as for producing the resin [K1] to obtain a copolymer of (b) and (c). Similarly to the above, the obtained copolymer may be used as is after the reaction, after concentration or dilution, or after being obtained as a solid (powder) by methods such as reprecipitation.

[0334] The ratio of the structural units derived from (b) and (c) relative to the total molar number of all structural units constituting the above-mentioned copolymer is preferably 5 to 95 mol% for the structural units derived from (b) and 5 to 95 mol% for the structural units derived from (c), and more preferably 10 to 90 mol% for the structural units derived from (b) and 10 to 90 mol% for the structural units derived from (c).

[0335] Furthermore, under the same conditions as those for the production of resin [K4], the cyclic ether derived from (b) in the copolymer of (b) and (c) is reacted with the carboxylic acid or carboxylic anhydride in (a). The amount of (a) used is preferably 60 to 100 mol per 100 mol of (b).

[0336] The carboxylic acid anhydride is reacted with the hydroxyl group generated by the reaction of the cyclic ether and the carboxylic acid or carboxylic acid anhydride contained in (a).

[0337] The amount of the carboxylic anhydride used is preferably 0.1 to 1 mol, more preferably 0.2 to 0.95 mol, and even more preferably 0.3 to 0.90 mol, relative to 1 mol of (a) (in other words, 1 mol of hydroxyl groups generated by using (a)).

[0338] Crop resin (B) includes, specifically,

[0339] (Meth) acrylate 3,4-epoxycyclohexyl methyl ester / (meth) acrylic acid copolymer, acrylate 3,4-epoxy tricyclo[5.2.1.0 2,6 ] Decyl ester / (meth)acrylic acid copolymer and other resins [K1];

[0340] Glycidyl (meth)acrylate / benzyl (meth)acrylate / (meth)acrylic acid copolymer, glycidyl (meth)acrylate / styrene / (meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6 ] decyl ester / (meth) acrylic acid / N-cyclohexyl maleimide copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6 ] decyl ester / (meth) acrylic acid / N-cyclohexyl maleimide / 2-hydroxyethyl (meth) acrylate copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6 ]Decanol / (meth)acrylate / N-cyclohexylmaleimide / (meth)acrylate tricyclic[5.2.1.0 2,6 ]Decenyl-8-yl ester copolymer, acrylic acid 3,4-epoxy tricyclic [5.2.1.0 2,6 ] decyl ester / (meth) acrylic acid / benzyl (meth) acrylate copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6 ] Decyl ester / (meth) acrylic acid / phenoxybenzyl (meth) acrylic acid copolymer, 3-methyl-3-(meth)acryloyloxymethyloxetane / (meth) acrylic acid / styrene copolymer and other resins [K2];

[0341] Resins such as benzyl (meth)acrylate / (meth)acrylic acid copolymer and styrene / (meth)acrylic acid copolymer [K3];

[0342] Benzyl (meth)acrylate / resin obtained by adding glycidyl (meth)acrylate to a (meth)acrylic acid copolymer, tricyclo (meth)acrylate [5.2.1.0 2,6 ] decane-8-yl ester / styrene / resin obtained by adding glycidyl (meth)acrylate to (meth)acrylic acid copolymer, tricyclo (meth)acrylate [5.2.1.0 2,6 ] Resins such as decane-8-yl ester / benzyl (meth)acrylate / resins obtained by adding glycidyl (meth)acrylate to a (meth)acrylic acid copolymer, norbornene / vinyltoluene / resins obtained by adding glycidyl (meth)acrylate to a (meth)acrylic acid copolymer, and norbornene / styrene / resins obtained by adding glycidyl (meth)acrylate to a (meth)acrylic acid copolymer [K4];

[0343] (Meth) acrylic acid tricyclic [5.2.1.0 2,6] decane-8-yl ester / resin obtained by reacting a copolymer of (meth)acrylic acid and glycidyl (meth)acrylate, tricyclo (meth)acrylate [5.2.1.0 2,6 ] decane-8-yl ester / styrene / resin obtained by reacting a copolymer of (meth)acrylic acid and glycidyl (meth)acrylate, tricyclo (meth)acrylate [5.2.1.0 2,6 ] decane-8-yl ester / 2-ethylhexyl (meth)acrylate / resin obtained by reacting a copolymer of (meth)acrylic acid and glycidyl (meth)acrylate, tricyclo (meth)acrylate [5.2.1.0 2,6 ] Resins such as a resin obtained by reacting a copolymer of 8-decane-8-yl ester / 2-ethylhexyl (meth)acrylate / methyl (meth)acrylate / (meth)acrylic acid and glycidyl (meth)acrylate [K5];

[0344] (Meth) acrylic acid tricyclic [5.2.1.0 2,6 ] decane-8-yl ester / a resin obtained by reacting a copolymer of (meth)acrylic acid and glycidyl (meth)acrylate with tetrahydrophthalic anhydride, 2-ethylhexyl (meth)acrylate / tricyclo[5.2.1.0 2,6 ] decane-8-yl ester / resin obtained by reacting a copolymer of (meth)acrylic acid and glycidyl (meth)acrylate with succinic anhydride, methyl (meth)acrylate / 2-ethylhexyl (meth)acrylate / tricyclo[5.2.1.0 2,6 ] Resins such as decane-8-yl ester / a resin obtained by reacting a copolymer of (meth)acrylic acid and glycidyl (meth)acrylate and further reacting it with succinic anhydride [K6] and the like.

[0345] Resins [K1] to [K6] may be used alone or in combination of two or more. Resin (B) preferably contains at least one selected from resin [K1], resin [K2], and resin [K6]. It is more preferred that the resin (B) contains at least resin [K6], and further preferably contains at least resin [K1] and resin [K6].

[0346] The polystyrene-equivalent weight average molecular weight of the resin (B) is preferably 3,000 to 100,000, more preferably 4,000 to 50,000, and even more preferably 5,000 to 30,000. When the molecular weight is within this range, the hardness of the color filter is improved, the residual film rate is high, the solubility of the unexposed portion in the developer is good, and the resolution of the colored pattern tends to be improved.

[0347] The dispersion degree [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B) is preferably 1.1-6, more preferably 1.2-4.

[0348] The acid value of resin (B) is preferably 20 to 170 mg-KOH / g, more preferably 25 to 150 mg-KOH / g, and even more preferably 30 to 135 mg-KOH / g, calculated on a solids basis. The acid value is measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of resin (B) and can be determined, for example, by titration with an aqueous potassium hydroxide solution.

[0349] The content of the resin (B) is preferably 5 to 70% by mass, more preferably 8 to 65% by mass, further preferably 10 to 60% by mass, and even more preferably 12 to 55% by mass, based on the total solid content of the colored curable resin composition. When the content of the resin (B) is within this range, a colored pattern can be formed, and the resolution and residual film rate of the colored pattern tend to be improved.

[0350] <Polymerizable compound (C)>

[0351] The polymerizable compound (C) is a compound that can be polymerized by active radicals and / or acids generated by the polymerization initiator (D). Examples thereof include compounds having a polymerizable ethylenically unsaturated bond, and are preferably (meth)acrylate compounds.

[0352] Examples of the polymerizable compound having one ethylenically unsaturated bond include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinyl pyrrolidone, and the above-mentioned monomers (a), (b), and (c).

[0353] Examples of the polymerizable compound having two ethylenically unsaturated bonds include 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, bis(acryloyloxyethyl) ether of bisphenol A, and 3-methylpentanediol di(meth)acrylate.

[0354] Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri(meth)acrylate, pentaerythritol poly(meth)acrylate (e.g., pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate), dipentaerythritol poly(meth)acrylate (e.g., dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate), tripentaerythritol poly(meth)acrylate (e.g., tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate), pentaerythritol poly(meth)acrylate (e.g., pentaerythritol deca(meth)acrylate, pentaerythritol nona(meth)acrylate), tris(2-(meth)acryloyloxyethyl)isocyanurate, alkoxylated pentaerythritol poly(meth)acrylate (e.g., ethoxylated pentaerythritol tri(meth)acrylate), and ethoxylated pentaerythritol poly(meth)acrylate.

[0045] Examples of the present invention include alkoxylated pentaerythritol poly(meth)acrylates (e.g., ethoxylated dipentaerythritol penta(meth)acrylate, ethoxylated dipentaerythritol hexa(meth)acrylate, propoxylated dipentaerythritol penta(meth)acrylate, propoxylated dipentaerythritol hexa(meth)acrylate), caprolactone-modified pentaerythritol poly(meth)acrylates (e.g., caprolactone-modified pentaerythritol tri(meth)acrylate, caprolactone-modified pentaerythritol tetra(meth)acrylate), caprolactone-modified dipentaerythritol poly(meth)acrylates (e.g., caprolactone-modified dipentaerythritol penta(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate), and the like.

[0355] Among these, it is preferred that at least one selected from trimethylolpropane tri(meth)acrylate and dipentaerythritol poly(meth)acrylate be contained, and it is more preferred that at least one selected from trimethylolpropane triacrylate and dipentaerythritol polyacrylate be contained.

[0356] The weight average molecular weight of the polymerizable compound (C) is preferably 50 to 4,000, more preferably 70 to 3,500, further preferably 100 to 3,000, further preferably 150 to 2,900, and particularly preferably 250 to 1,500.

[0357] The content of the polymerizable compound (C) can be, for example, 2 to 65% by mass, preferably 5 to 60% by mass, more preferably 8 to 55% by mass, and even more preferably 10 to 50% by mass of the total solid content of the colored curable resin composition. When the content of the polymerizable compound (C) is within the above range, the residual film rate during colored pattern formation and the chemical resistance of the color filter tend to improve.

[0358] <Polymerization initiator (D)>

[0359] The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating active free radicals, acids, etc. under the action of light or heat to initiate polymerization, and known polymerization initiators can be used. Examples of polymerization initiators (D) that generate active free radicals include O-acyl oxime compounds, alkylphenone compounds, biimidazole compounds, triazine compounds, and acylphosphine oxide compounds.

[0360] The O-acyl oxime compound is a compound having a partial structure represented by formula (d-1).

[0361] Wherein, * represents the bonding site.

[0362]

[0363] Examples of the O-acyl oxime compound include N-benzoyloxy-1-(4-phenylsulfanylphenyl)butane-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethane-1-imine, and N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxolanemethoxy)benzoyl}-9H-carbazol-3-yl]ethane. -1-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-imine, N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1-[4-(2-hydroxyethoxy)phenylsulfanylphenyl]propane-1-one-2-imine, N-acetoxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropane-1-one-2-imine, 2-[(acetoxy)imino]-3-cyclohexyl-1-[4-(phenylsulfanyl)phenyl]propane-1-one, and the like. Commercially available products such as Irgacure OXE01, OXE02, and OXE03 (all manufactured by BASF), N-1919 (manufactured by ADEKA), PBG-314, PBG-317, PBG-326, PBG-327, and PBG-329 (all manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.) may also be used. Among them, the O-acyl oxime compound is preferably selected from N-acetoxy-1-[4-(2-hydroxyethoxy)phenylsulfanylphenyl]propane-1-one-2-imine, N-acetoxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropane-1-one-2-imine, 2-[(acetoxy)imino]-3-cyclohexyl-1-[4-(phenylsulfanyl)phenyl]propane-1-one, N-benzoyloxy-1-(4-phenylsulfanylphenyl)butane-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)butane-1-one-2-imine, The present invention further comprises at least one selected from the group consisting of 2-[(acetyloxy)imino]-3-cyclohexyl-1-[4-(phenylsulfanyl)phenyl]propane-1-one, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine and N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropane-1-one-2-imine, and more preferably at least one selected from the group consisting of 2-[(acetyloxy)imino]-3-cyclohexyl-1-[4-(phenylsulfanyl)phenyl]propane-1-one, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine and N-acetyloxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropane-1-one-2-imine.These O-acyloxime compounds tend to provide a color filter having high brightness.

[0364] The alkylphenone compound is a compound having a partial structure represented by formula (d-2) or a partial structure represented by formula (d-3). In these partial structures, the benzene ring may have a substituent. In the formula, * represents a bonding site.

[0365]

[0366] Examples of the compound having a partial structure represented by formula (d-2) include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutan-1-one, and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butan-1-one. Commercially available products such as Irgacure 369, 907, and 379 (all manufactured by BASF) can also be used.

[0367] Examples of the compound having a partial structure represented by formula (d-3) include 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propane-1-one, 1-hydroxycyclohexylphenyl ketone, oligomers of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propane-1-one, α,α-diethoxyacetophenone, and benzyl dimethyl ketal.

[0368] From the viewpoint of excellent sensitivity, the alkylphenone compound is preferably a compound having a partial structure represented by formula (d-2).

[0369] Examples of the triazine compound include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, and 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine. [2-(5-methylfuran-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-triazine, etc.

[0370] Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, etc. Commercially available products such as Irgacure (registered trademark) 819 (manufactured by BASF) can also be used.

[0371] Examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (see, for example, Japanese Patent Application Laid-Open Nos. 6-75372 and 6-75373), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimidazole, and 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimidazole. (2-Chlorophenyl)-4,4',5,5'-tetrakis(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole (see, for example, Japanese Patent Publication No. 48-38403 and Japanese Patent Application Laid-Open No. 62-174204), and biimidazole compounds in which the phenyl groups at the 4,4',5,5'-positions are substituted with carboalkoxy groups (see, for example, Japanese Patent Application Laid-Open No. 7-10913). Among these, compounds represented by the following formulas and mixtures thereof are preferred.

[0372]

[0373] Furthermore, examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone compounds such as benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetrakis(tert-butylperoxycarbonyl)benzophenone, and 2,4,6-trimethylbenzophenone; quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone, and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds. These are preferably used in combination with the polymerization initiator aid (D1) (particularly amines) described below.

[0374] Examples of the acid-generating polymerization initiator (D) include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, and diphenyliodonium. p-Toluenesulfonate, diphenyliodonium Hexafluoroantimonate, etc. Salts, nitrobenzyl toluenesulfonates, benzoin toluenesulfonates, etc.

[0375] The polymerization initiator (D) preferably contains at least one selected from the group consisting of an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, an O-acyloxime compound, and a biimidazole compound. It more preferably contains an O-acyloxime compound and / or a biimidazole compound, and further preferably contains an O-acyloxime compound.

[0376] The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, relative to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). When the content of the polymerization initiator (D) is within the above range, there is a tendency for increased sensitivity and shortened exposure time, thereby improving the productivity of the color filter.

[0377] <Polymerization initiator aid (D1)>

[0378] The polymerization initiator aid (D1) is a compound or a sensitizer for accelerating the polymerization of the polymerizable compound (C) initiated by the polymerization initiator (D). When the polymerization initiator aid (D1) is included, it is usually used in combination with the polymerization initiator (D).

[0379] Examples of the polymerization initiation aid (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds.

[0380] Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, and 4,4'-bis(ethylmethylamino)benzophenone. Among these, 4,4'-bis(diethylamino)benzophenone is preferred. Commercially available amine compounds such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can be used.

[0381] Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, and 2-ethyl-9,10-dibutoxyanthracene.

[0382] Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.

[0383] Examples of the carboxylic acid compound include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

[0384] When using these polymerization initiator aids (D1), their content is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, relative to 100 parts by mass of the total amount of all resins (B) and polymerizable compounds (C) contained in the colored curable resin composition. When the amount of the polymerization initiator aid (D1) is within this range, a colored pattern can be formed with higher sensitivity, and there is a tendency for the productivity of the color filter to improve.

[0385] Solvent (E)

[0386] The solvent (E) is not particularly limited, and solvents commonly used in this field can be used.

[0387] Examples of the solvent (E) include ester solvents (solvents containing -COO- and not -O- in the molecule), ether solvents (solvents containing -O- and not -COO- in the molecule), ether ester solvents (solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- and not -COO- in the molecule), alcohol solvents (solvents containing -OH and not -O-, -CO-, and -COO- in the molecule), aromatic hydrocarbon solvents, amide solvents, and dimethyl sulfoxide. Two or more of these solvents may be used in combination.

[0388] Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, and γ-butyrolactone.

[0389] Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dimethoxy-1-butanol, 3-methoxy-3-methylbutanol ... Alkane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenethyl ether, methyl anisole, etc.

[0390] Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and dipropylene glycol methyl ether acetate.

[0391] Examples of the ketone solvent include 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, and isophorone.

[0392] Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.

[0393] Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, and mesitylene.

[0394] Examples of the amide solvent include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0395] The solvent (E) is preferably a solvent containing at least one selected from an ester solvent, an ether solvent, an ether ester solvent, and a ketone solvent, and more preferably a solvent containing at least one selected from an ester solvent, an ether ester solvent, and a ketone solvent. Particularly preferred is a solvent containing at least one selected from propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, and diacetone alcohol, and more preferably a solvent containing propylene glycol monomethyl ether acetate and / or propylene glycol monomethyl ether.

[0396] The content of the solvent (E) is generally 99.99% by mass or less, preferably 40 to 99% by mass, more preferably 50 to 97% by mass, further preferably 60 to 95% by mass, and even more preferably 70 to 90% by mass, of the total amount of the colored curable resin composition. In other words, the total amount of solids in the colored curable resin composition is generally 0.01% by mass or more, preferably 1 to 60% by mass, more preferably 3 to 50% by mass, further preferably 5 to 40% by mass, and even more preferably 10 to 30% by mass. When the content of the solvent (E) is within the above range, the flatness during coating is improved, and the color density is not insufficient when forming a color filter, so there is a tendency for the display characteristics to be improved.

[0397] <Leveling agent (F)>

[0398] Examples of the leveling agent (F) include silicone surfactants, fluorine-based surfactants, and silicone surfactants having fluorine atoms, etc. These may have a polymerizable group in a side chain.

[0399] Examples of the silicone-based surfactant include surfactants having a siloxane bond in the molecule. Specific examples include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (trade name: manufactured by Dow Corning Toray Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, and KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (manufactured by Momentive Performance Materials Japan Co., Ltd.).

[0400] Examples of fluorine-based surfactants include surfactants having a fluorine carbon chain in the molecule. Specific examples include FLUORAD (registered trademark) FC430, FLUORAD FC431 (manufactured by Sumitomo 3M Co., Ltd.), MEGAFAC (registered trademark) F142D, MEGAFAC F171, MEGAFAC F172, MEGAFAC F173, MEGAFAC F177, MEGAFAC F183, MEGAFAC F554, MEGAFAC R30, MEGAFAC RS-718-K (manufactured by DIC Corporation), F-top (registered trademark) EF301, F-top EF303, F-top EF351, F-top EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Surflon (registered trademark) S381, Surflon S382, Surflon SC101, Surflon SC105 (manufactured by AGC Corporation) and E5844 (manufactured by Daikin Fine Chemicals Laboratories, Ltd.), etc.

[0401] Examples of the organosilicon-based surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain in the molecule, and more specifically, MEGAFAC (registered trademark) R08, MEGAFAC BL20, MEGAFAC F475, MEGAFAC F477, and MEGAFAC F443 (manufactured by DIC Corporation).

[0402] When a leveling agent (F) is included, its content is preferably 0.0005 to 1% by mass, more preferably 0.001 to 0.5% by mass, and even more preferably 0.005 to 0.3% by mass, based on the total amount of the colored curable resin composition. This content does not include the content of the dispersant described above. When the content of the leveling agent (F) is within this range, the flatness of the color filter can be improved.

[0403] <Other ingredients>

[0404] The colored curable resin composition may contain additives known in the art, such as a filler, other polymer compounds, an adhesion promoter, a quencher, an antioxidant, a light stabilizer, and a chain transfer agent, as needed.

[0405] <Method for producing a colored curable resin composition>

[0406] The colored curable resin composition can be prepared by mixing, for example, CI Pigment Violet 19, compound (I), compound (II), resin (B), polymerizable compound (C), polymerization initiator (D), and, if necessary, solvent (E), colorant (A1), leveling agent (F), polymerization initiator aid (D1), and other components.

[0407] Mixing can be performed using known or customary devices and conditions.

[0408] The colorant (A) can be mixed with part or all of the solvent (E) in advance and dispersed using a bead mill or the like until the average particle size is about 0.2 μm or less to obtain a dispersion liquid, and is preferably used in the form of a dispersion liquid. In this case, part or all of the above-mentioned dispersant and resin (B) can be added as needed. It is preferred to prepare the target colored curable resin composition by mixing the remaining components in the dispersion liquid obtained in this manner to a predetermined concentration. When using a bead mill, the diameter of the grinding beads is preferably selected to be 0.05 mm to 0.5 mm, and the material of the grinding beads can be glass, ceramic, metal, etc.

[0409] When a dye is used as the colorant (A), the dye may be dissolved in part or all of the solvent (E) to prepare a solution. The solution is preferably filtered using a filter having a pore size of about 0.01 to 1 μm.

[0410] <Color filter manufacturing method>

[0411] A color filter that can also be a color conversion layer can be formed by the colored curable resin composition of the present invention. As a method for manufacturing a colored pattern, photolithography, inkjet method, printing method, etc. can be mentioned. Among them, photolithography is preferred. Photolithography is a method in which the above-mentioned colored curable resin composition is applied to a substrate and dried to form a colored composition layer, and the colored composition layer is exposed through a photomask and developed. In the photolithography method, by not using a photomask and / or not developing during exposure, a colored coating film as a cured product of the above-mentioned colored composition layer can be formed. The colored pattern and colored coating film thus formed are the color filter of the present invention.

[0412] The film thickness of the color filter (cured film) is not particularly limited and can be appropriately adjusted according to the purpose, application, etc., and is, for example, 30 μm or less, preferably 20 μm or less, more preferably 6 μm or less, further preferably 4.5 μm or less, further preferably 3.0 μm or less, and preferably 0.1 μm or more, more preferably 0.2 μm or more, further preferably 0.3 μm or more.

[0413] As substrates, glass plates such as quartz glass, borosilicate glass, aluminosilicate glass, soda-lime glass coated with silicon dioxide, resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate, silicon, and substrates having thin films of aluminum, silver, or silver / copper / palladium alloys formed thereon can be used. Other color filter layers, resin layers, transistors, circuits, and the like can be formed on these substrates. Alternatively, silicon substrates treated with HMDS (hexamethyldisilazane) can be used.

[0414] The formation of each color pixel by photolithography can be performed using known or customary equipment and conditions. For example, the formation can be performed as follows.

[0415] First, a colored curable resin composition is applied to a substrate and then dried by heating (prebaking) and / or drying under reduced pressure to remove volatile components such as the solvent and dry the composition to obtain a smooth colored composition layer. Examples of coating methods include spin coating, slit coating, and slit and spin coating. The temperature during heating and drying is preferably 30 to 120°C, more preferably 50 to 110°C. Furthermore, the heating time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes.

[0416] When drying under reduced pressure is performed, it is preferably performed at a pressure of 50 to 150 Pa and a temperature range of 20 to 25° C. The film thickness of the colored composition layer is not particularly limited and may be appropriately selected depending on the film thickness of the target color filter.

[0417] Next, the colored composition layer is exposed through a photomask formed with the desired colored pattern. The pattern on the photomask is not particularly limited; a pattern corresponding to the intended application is used. Furthermore, in order to uniformly illuminate the entire exposure surface with parallel light and accurately align the photomask with the substrate on which the colored composition layer is formed, it is preferable to use an exposure device such as a mask aligner or a stepper. When forming a colored coating film, exposure can be performed without using a photomask.

[0418] The light source used for exposure is preferably one that generates light with a wavelength of 250 to 450 nm. For example, a filter that cuts off wavelengths less than 350 nm can be used to block light, or bandpass filters that selectively filter out light near 436 nm, 408 nm, or 365 nm can be used to selectively filter out light in these wavelength ranges. Specific examples include mercury lamps, light-emitting diodes, metal halide lamps, and halogen lamps.

[0419] The exposed colored composition layer is brought into contact with a developer and developed to form a colored pattern on the substrate. By development, the unexposed portion of the colored composition layer is dissolved in the developer and removed. As a developer, for example, aqueous solutions of alkaline compounds such as potassium hydroxide, sodium bicarbonate, sodium carbonate, and tetramethylammonium hydroxide are preferred. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01% to 10% by mass, more preferably 0.03% to 5% by mass. Furthermore, the developer may also contain a surfactant. The development method may be any one of a paddle method, an immersion method, and a spray method. Furthermore, the substrate may be tilted at any angle during development.

[0420] The substrate after development is preferably washed with water.

[0421] Furthermore, the obtained colored pattern or colored coating film is preferably post-baked. The post-baking temperature is preferably 50 to 250° C., more preferably 90 to 245° C. The post-baking time is preferably 1 to 120 minutes, more preferably 2 to 30 minutes.

[0422] The colored pattern and colored coating film obtained in this manner are useful as a color filter.

[0423] <Display device>

[0424] The color filter is useful as a color filter for use in display devices (e.g., liquid crystal display devices, organic EL devices, etc.), electronic paper, solid-state imaging devices, etc. Among them, it is useful as a color filter for use in organic EL display devices using OLED (Organic Light Emitting Diode) and the like. Since organic EL display devices do not require a backlight, they can be lightweight and thinner than liquid crystal display devices, and can achieve high image quality such as fast response speed and high contrast, save power, and can be folded. Therefore, they are adopted in various fields such as mobile phones, portable information terminals, and televisions.

[0425] The color filter may be further subjected to surface coating treatment in order to impart various characteristics.

[0426] Example

[0427] The present invention will be described in more detail below with reference to the following examples. However, the present invention is not limited to the following examples. It is understood that the present invention can be implemented with appropriate modifications within the scope of the preceding and following descriptions, and all such modifications are encompassed within the technical scope of the present invention. It should be noted that, unless otherwise specified, "parts" means "parts by mass" and "%" means "% by mass."

[0428] The polystyrene-equivalent weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin were measured by GPC (gel permeation chromatography) under the following conditions.

[0429] Device: HLC-8120GPC (manufactured by Tosoh Corporation)

[0430] Column: TSK-GELG2000HXL

[0431] Column temperature: 40°C

[0432] Solvent: tetrahydrofuran

[0433] Flow rate: 1.0 mL / min

[0434] Solid content concentration of analysis sample: 0.001 to 0.01 mass%

[0435] Injection volume: 50 μL

[0436] Detector: RI

[0437] Calibration standard substances: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)

[0438] The ratio of the polystyrene-equivalent weight average molecular weight to the number average molecular weight (Mw / Mn) obtained above was defined as the degree of dispersion.

[0439] (Synthesis example 1)

[0440] <Synthesis of Compound (Ia-61)>

[0441] According to the description of Example 1 of JP-A-2013-161026, a compound represented by the following formula (Ia-61) (hereinafter also referred to as compound (Ia-61)) was synthesized.

[0442]

[0443] (Synthesis example 2)

[0444] <Synthesis of Compound (Ib-522)>

[0445] According to the description of Example 1 of JP-A-2017-142503, a compound represented by the following formula (Ib-522) (hereinafter also referred to as compound (Ib-522)) was synthesized.

[0446]

[0447] (Synthesis example 3)

[0448] <Synthesis of Compound (II-1)>

[0449] The compound represented by the following formula (II-1) (hereinafter also referred to as compound (II-1)) was synthesized according to the description of Synthesis Example 4 in International Publication No. 2022 / 065357.

[0450]

[0451] (Synthesis Example 4)

[0452] <Synthesis of Resin (B-1)>

[0453] A suitable amount of nitrogen was introduced into a flask equipped with a reflux cooler, a dropping funnel, and a stirrer to replace the atmosphere with nitrogen. 256 parts of propylene glycol monomethyl ether acetate was added and heated to 80°C while stirring. Subsequently, 3,4-epoxytricyclo[5.2.1.0 2,6 ]Decan-8-yl ester and 3,4-epoxytricyclic acrylate [5.2.1.0 2,6 A mixed solution of 44 parts of a mixture of 9-decane esters (containing a ratio of 1:1 by molar ratio), 57 parts of acrylic acid, 249 parts of 3-phenoxybenzyl acrylate, and 159 parts of propylene glycol monomethyl ether acetate was prepared. Separately, a mixed solution of 25 parts of a polymerization initiator, 2,2-azobis(2,4-dimethylvaleronitrile), dissolved in 210 parts of propylene glycol monomethyl ether acetate, was added dropwise over 5 hours. After the addition of the initiator solution was completed, the mixture was maintained at 80°C for 4 hours and then cooled to room temperature to obtain a copolymer (resin (B-1)) solution having a viscosity of 51 mPas and a solid content of 36.0% as measured by a B-type viscometer (23°C). The resulting resin (B-1) had a weight-average molecular weight Mw of 11,000 and a dispersity of 1.98. Resin (B-1) has the following structural units.

[0454]

[0455] (Synthesis Example 5)

[0456] <Synthesis of Resin (B-2)>

[0457] In a flask equipped with a stirring apparatus, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, 241 parts of propylene glycol monomethyl ether acetate were placed and stirred while nitrogen substitution was carried out. The temperature was then raised to 130°C. Next, a solution prepared by adding 33.5 parts of t-butyl peroxy-2-ethylhexanoate to a monomer mixture consisting of 72.6 parts of 2-ethylhexyl acrylate, 145.3 parts of glycidyl methacrylate, and 9.7 parts of dicyclopentanyl methacrylate was added dropwise to the flask over 2 hours using the dropping funnel. After the addition was complete, the mixture was stirred for a further 30 minutes to allow for copolymerization. The flask was then purged with air, and 73.7 parts of acrylic acid, 0.9 parts of triphenylphosphine, and 0.9 parts of quinone were added. The reaction was continued at 120°C for 10 hours. Subsequently, 65.2 parts of succinic anhydride was added to the reaction system, and the reaction was continued for a further 1.5 hours to obtain a copolymer (resin (B-2)). Finally, 300 parts of propylene glycol monomethyl ether was added to the reaction solution, followed by propylene glycol monomethyl ether acetate to a copolymer solids concentration of 40%, yielding a copolymer (resin (B-2)) solution. The resulting resin (B-2) had a weight-average molecular weight (Mw) of 6100 and an acid value (based on solids content) of 97 mg-KOH / g. Resin (B-2) had the following structural units.

[0458]

[0459] (Synthesis Example 6)

[0460] <Synthesis of Resin (B-3)>

[0461] A suitable amount of nitrogen was introduced into a flask equipped with a reflux cooler, a dropping funnel, and a stirrer to replace the atmosphere with nitrogen. 340 parts of propylene glycol monomethyl ether acetate was added and heated to 80°C while stirring. Subsequently, 57 parts of acrylic acid and 3,4-epoxytricyclo[5.2.1.0 2,6 ]Decan-8-yl ester and 3,4-epoxytricyclic acrylate [5.2.1.0 2 ,6A mixed solution of 54 parts of a mixture of 9-decane esters (containing a 1:1 molar ratio), 239 parts of benzyl methacrylate, and 73 parts of propylene glycol monomethyl ether acetate was prepared. Separately, a solution of 40 parts of the polymerization initiator 2,2-azobis(2,4-dimethylvaleronitrile) dissolved in 197 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After the initiator solution was added dropwise, the mixture was maintained at 80°C for 3 hours and then cooled to room temperature to obtain a copolymer (resin (B-3)) solution having a viscosity of 127 mPas as measured by a Brookfield viscometer (23°C) and a solids content of 37.0% by weight. The resulting copolymer (resin (B-3)) had a weight-average molecular weight (Mw) of 9400, a dispersity of 1.89, and an acid value (based on solids content) of 114 mg-KOH / g. Resin (B-3) has the following structural units.

[0462]

[0463] (Synthesis Example 7)

[0464] <Synthesis of Resin (B-4)>

[0465] A suitable amount of nitrogen was introduced into a flask equipped with a reflux cooler, a dropping funnel, and a stirrer to replace the atmosphere with nitrogen. 280 parts of propylene glycol monomethyl ether acetate was added and heated to 80°C while stirring. Subsequently, 38 parts of acrylic acid and 3,4-epoxytricyclo[5.2.1.0 2,6 ]Decan-8-yl ester and 3,4-epoxytricyclic acrylate [5.2.1.0 2 ,6 A mixed solution of 289 parts of a mixture of 9-decane esters (containing a molar ratio of 1:1) and 125 parts of propylene glycol monomethyl ether acetate was prepared. Separately, a solution of 33 parts of the polymerization initiator 2,2-azobis(2,4-dimethylvaleronitrile) dissolved in 235 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After the initiator solution was added dropwise, the mixture was maintained at 80°C for 4 hours and then cooled to room temperature to obtain a copolymer (resin (B-4)) solution having a viscosity of 125 mPas and a solids content of 35.1% as measured by a Brookfield viscometer (23°C). The resulting copolymer (resin (B-4)) had a weight-average molecular weight (Mw) of 9200, a dispersity of 2.08, and an acid value (based on solids content) of 77 mg-KOH / g. Resin (B-4) has the following structural units.

[0466]

[0467] (Synthesis Example 8)

[0468] <Synthesis of Resin (B-5)>

[0469] In a flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube, 178 parts of propylene glycol monomethyl ether acetate was placed and stirred while nitrogen substitution was carried out. The temperature was then raised to 100°C. Next, a solution containing 47.1 parts of dimethyl 2,2'-azobis(2-methylpropionate) added to a monomer mixture consisting of 115.2 parts of 2-ethylhexyl acrylate, 86.0 parts of glycidyl methacrylate, 72.7 parts of methyl methacrylate, and 13.3 parts of dicyclopentanyl methacrylate was added dropwise to the flask over 2 hours using the dropping funnel. After the addition was complete, the mixture was stirred at 100°C for a further 30 minutes to allow for a copolymerization reaction. The flask was then purged with air, and 43.8 parts of acrylic acid, 1.0 part of triphenylphosphine, and 1.0 part of dibutylhydroxytoluene were added. The reaction was continued at 120°C for 10 hours. Subsequently, 22.1 parts of succinic anhydride were added to the reaction system, and the reaction was continued for a further 1.5 hours to obtain a copolymer. Finally, 330 parts of propylene glycol monomethyl ether were added to the reaction solution, and then propylene glycol monomethyl ether acetate was added to obtain a copolymer solids concentration of 40%, thereby obtaining a copolymer (resin (B-5)) solution. The resulting resin (B-5) had a weight-average molecular weight (Mw) of 6500 and an acid value (based on solids) of 35 mg-KOH / g. Resin (B-5) had the following structural units.

[0470]

[0471] (Preparation Example 1)

[0472] <Preparation of Pigment Dispersion (A-1)>

[0473] The following components were mixed and the pigment was sufficiently dispersed using a bead mill to obtain a pigment dispersion (A-1).

[0474]

[0475] (Preparation Example 2)

[0476] <Preparation of Pigment Dispersion (A-2)>

[0477] The following components were mixed and the pigment was sufficiently dispersed using a bead mill to obtain a pigment dispersion (A-2). CI Pigment Red 269 corresponds to the above-mentioned compound (Ia-54).

[0478]

[0479] (Preparation Example 3)

[0480] <Preparation of Pigment Dispersion (A-3)>

[0481] The following components were mixed and the pigment was sufficiently dispersed using a bead mill to obtain a pigment dispersion (A-3).

[0482]

[0483]

[0484] (Preparation Example 4)

[0485] <Preparation of Pigment Dispersion (A-4)>

[0486] The following components were mixed and the pigment was sufficiently dispersed using a bead mill to obtain a pigment dispersion (A-4). In addition, CI Pigment Orange 13 corresponds to the above-mentioned compound (II-169).

[0487]

[0488] (Preparation Example 5)

[0489] <Preparation of Pigment Dispersion (A-5)>

[0490] The following components were mixed and the pigment was sufficiently dispersed using a bead mill to obtain a pigment dispersion (A-5).

[0491]

[0492] (Preparation Example 6)

[0493] <Preparation of Pigment Dispersion (A-6)>

[0494] The following components were mixed and the pigment was sufficiently dispersed using a bead mill to obtain a pigment dispersion (A-6).

[0495]

[0496]

[0497] (Preparation Example 7)

[0498] <Preparation of Pigment Dispersion (A-7)>

[0499] The following components were mixed and the pigment was sufficiently dispersed using a bead mill to obtain a pigment dispersion (A-7).

[0500]

[0501] (Examples 1 to 4, Comparative Example 1)

[0502] (1) Preparation of colored curable resin composition

[0503] The pigment dispersion and copolymer solution thus prepared were mixed with the following components in the amounts shown in Table 20 to prepare a colored curable resin composition.

[0504] When preparing the colored curable resin composition, propylene glycol monomethyl ether acetate was added so that the solids concentration of the colored curable resin composition was 16%. The amounts of each component in Table 20 are expressed in parts by mass, and the amounts of the colorant (A), dispersant (acrylic pigment dispersant), resin (B), polymerizable compound (C), polymerization initiator (D), and leveling agent (F) are expressed in terms of solids.

[0505] Polymerizable compound (C-1): trimethylolpropane triacrylate (NK ESTER A-TMPT; manufactured by Shin-Nakamura Chemical Co., Ltd.)

[0506] Polymerization initiator (D-1): N-acetoxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropane-1-one-2-imine (PBG-327; O-acyl oxime compound; manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.)

[0507] Leveling agent (F-1): polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Dow Corning Toray Co., Ltd.)

[0508] [Table 20]

[0509]

[0510] (2) Production of coloring pattern (color filter)

[0511] The colored curable resin composition was applied to a 5 cm square glass substrate (EAGLE 2000; manufactured by CORNING) by spin coating to a film thickness of 1.6 μm after post-baking. The composition was then pre-baked at 85°C for 2 minutes to form a colored composition layer. After cooling, the colored composition layer formed on the substrate was exposed to a quartz glass photomask at a distance of 100 μm using an exposure machine (TME-150RSK; manufactured by TOPCON Co., Ltd.) in an air atmosphere at a temperature of 50 mJ / cm 2 The photomask was irradiated with an exposure dose of 100 μm (365 nm reference). A mask with a 100 μm line and space pattern was used as a photomask. The irradiated colored composition layer was developed by immersing it in an aqueous developer containing 2.38% tetramethylammonium hydroxide (TMAH) at 23°C for 60 seconds. The layer was then post-baked on a hot plate at 90°C for 15 minutes to obtain a colored pattern.

[0512] (3) Film thickness measurement

[0513] The film thickness of the obtained colored pattern was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.).

[0514] (4) Chromaticity evaluation

[0515] The resulting colored pattern was measured for spectrum using a colorimeter (OSP-SP-200; manufactured by Olympus Corporation). The characteristic function of illuminant C was used to measure the xy chromaticity coordinates (x, y) and stimulus value Y in the CIE XYZ colorimetric system. A larger Y value indicates higher brightness. The results are shown in Table 21.

[0516] (5) Transmittance measurement

[0517] The resulting colored pattern was measured using a colorimeter (OSP-SP-200; manufactured by Olympus Corporation) to measure the spectrum and transmittance. Lower transmittance at 530 nm indicates less green light leakage, indicating a color filter with excellent color performance (particularly red). The results are shown in Table 21.

[0518] [Table 21]

[0519]

[0520] As shown in Table 21, Examples 1 to 4 exhibited higher brightness at the specified chromaticity coordinates than Comparative Example 1, while also being able to suppress the colorant content in the total solids content of the colored curable resin composition. Furthermore, the transmittance at 530 nm was low, suppressing green light leakage. Therefore, it can be said that the color filters obtained in Examples 1 to 4 exhibited superior color performance as red filters compared to the color filter of Comparative Example 1.

Claims

1. A colored curable resin composition comprising a colorant, a resin, a polymerizable compound, and a polymerization initiator, The colorant comprises CI Pigment Violet 19, a compound represented by formula (I) and a compound represented by formula (II), In formula (I), X 1 represents a hydrogen atom, an aromatic hydrocarbon group which may have a substituent, or a heterocyclic group which may have a substituent, X 2 represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, -OR 1 or -COOR 2 , X 3 represents a halogen atom, a cyano group, a nitro group, a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, -OR 3 , -COOR 4 , -CONR 5 R 6 or -SO2NR 7 R 8 , R 1 ~R 8 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, n represents 1 or 2, m represents any integer from 0 to 5, The sum of m and n is an integer less than 6, X 1 、X 2 or X 3 When there are multiple, they can be the same or different. In formula (II), L 1 represents a divalent aromatic hydrocarbon group which may have a substituent. X 11 ~X 14 Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.

2. The colored curable resin composition according to claim 1, wherein Further comprising a solvent. 3 . A color filter formed from the colored curable resin composition according to claim 1 . A display device comprising the color filter according to claim 3 .

5. A colorant comprising CI Pigment Violet 19, a compound represented by formula (I) and a compound represented by formula (II), In formula (I), X 1 represents a hydrogen atom, an aromatic hydrocarbon group which may have a substituent, or a heterocyclic group which may have a substituent, X 2 represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, -OR 1 or -COOR 2 , X 3 represents a halogen atom, a cyano group, a nitro group, a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, -OR 3 , -COOR 4 , -CONR 5 R 6 or -SO2NR 7 R 8 , R 1 ~R 8 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, n represents 1 or 2, m represents any integer from 0 to 5, The sum of m and n is an integer less than 6, X 1 、X 2 or X 3 When there are multiple, they can be the same or different. In formula (II), L 1 represents a divalent aromatic hydrocarbon group which may have a substituent, X 11 ~X 14 Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.

Images