Colored resin composition, color filter, and display device

Abstract

The present invention relates to a colored resin composition, a color filter and a display device. The colored resin composition contains a colorant, a resin, a polymerizable compound and a polymerization initiator. The colorant contains a triarylmethane lake and a compound represented by formula (A1). In formula (A1), A 1a and A 2a Each independently represents a phenylene group which may have a substituent, L 1a and L 2a Each independently represents a divalent hydrocarbon group having 1 to 12 carbon atoms, wherein the -CH2- contained in the hydrocarbon group may be -O-, -SO2- or -NR 11a ‑substituted, R 1a ~R 6a Each independently represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 8 carbon atoms. 11a The hydrogen atom or the alkyl group having 1 to 8 carbon atoms makes the light resistance and heat resistance of the formed color filter better than those of the conventionally known colored resin composition, and also makes the heat resistance in a state where an overcoat layer is laminated better.

Description

Technical Field

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

[0002] Color filters used in display devices such as liquid crystal display devices, electroluminescent display devices, and plasma displays, and solid-state imaging devices such as CCD or CMOS sensors are manufactured from colored resin compositions. As such colored resin compositions, compositions containing only a triarylmethane compound represented by formula (A3-7) as a colorant are known (Patent Document 1).

[0003] [Chemistry 1]

[0004]

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application Publication No. 2018-127596 Summary of the invention

[0008] Problems to be solved by the invention

[0009] The object is to further improve the light resistance and heat resistance of the formed color filter compared with the above-mentioned conventionally known composition. Another object is to also improve the heat resistance in a state where an overcoat layer is laminated.

[0010] Solution to the problem

[0011] The gist of the present invention is as follows.

[0012] [1] A colored resin composition comprising a colorant, a resin, a polymerizable compound and a polymerization initiator,

[0013] The colorant contains a triarylmethane lake and a compound represented by formula (A1).

[0014] [Chemistry 2]

[0015]

[0016] [In formula (A1),

[0017] A 1a and A 2a Each independently represents a phenylene group which may have a substituent.

[0018] L 1a and L 2aEach independently represents a divalent hydrocarbon group having 1 to 12 carbon atoms, wherein the -CH 2 -Can be -O-, -SO 2 -or-NR 11a -replace.

[0019] R 1a ~R 6a Each independently represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 8 carbon atoms. 11a represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.]

[0020] [2] The colored resin composition according to [1], wherein the triarylmethane lake is at least one selected from the group consisting of a compound represented by formula (A2) and a compound represented by formula (A3).

[0021] [Chemistry 3]

[0022]

[0023] [In formula (A2),

[0024] R 11b ~R 14b Each independently represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent. In the saturated hydrocarbon group having 1 to 20 carbon atoms, the hydrogen atom contained in the saturated hydrocarbon group may be substituted by a substituted or unsubstituted amino group or a halogen atom. When the saturated hydrocarbon group has 2 to 20 carbon atoms, the -CH 2 - may be substituted with -O- or -CO-. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, the adjacent -CH 2 - will not be replaced by -O- at the same time. R 11b With R 12b can combine to form a ring with the nitrogen atom to which they are bound, R 13b With R 14b They may combine to form a ring together with the nitrogen atom to which they are bound.

[0025] R 17b ~R 24b Each independently represents a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, or an alkyl group having 1 to 8 carbon atoms, wherein -CH 2 - may be substituted by -O- or -CO-. 18b and R 22b Can combine with each other to form -NH-, -O-, -S- or -SO 2 -.

[0026] Ring T1b It represents an aromatic heterocyclic ring having 3 to 10 carbon atoms which may have a substituent, or an aromatic hydrocarbon ring having 6 to 10 carbon atoms which may have a substituent.

[0027] [Y] m- represents any m-valent anion containing at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus, and oxygen.

[0028] m represents an arbitrary natural number.

[0029] When a plurality of structures represented by the following formulae are contained in one molecule, they may be the same structure or different structures.

[0030] [Chemistry 4]

[0031]

[0032] [wherein, ring T 1b , R 11b ~R 14b and R 17b ~R 24b Each has the same meaning as above. ]]

[0033] [Chemistry 5]

[0034]

[0035] [In formula (A3),

[0036] R 41b ~R 44b Each independently represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, and the substituents which the aromatic hydrocarbon group and the aralkyl group may have may be -SO 3 - or -SO 2 -N - -SO 2 -R f The hydrogen atoms contained in the saturated hydrocarbon group may be substituted by substituted or unsubstituted amino groups or halogen atoms. When the number of carbon atoms in the saturated hydrocarbon group is 2 to 20, the -CH 2 - may be substituted with -O- or -CO-. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, the adjacent -CH 2 - will not be replaced by -O- at the same time. R 41b With R 42b can combine to form a ring with the nitrogen atom to which they are bound, R 43b With R 44bThey may combine to form a ring together with the nitrogen atom to which they are bound.

[0037] R 47b ~R 54b Each independently represents a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, -SO 3 - 、-SO 2 -N - -SO 2 -R f , or an alkyl group having 1 to 8 carbon atoms, wherein -CH 2 - can be substituted by -O- or -CO-, R 48b With R 52b Can combine with each other to form -NH-, -S-, or -SO 2 -. However, in this alkyl group, the adjacent -CH 2 - will not be replaced by -O- at the same time.

[0038] Ring T 2b represents an aromatic heterocyclic ring having 3 to 10 carbon atoms or an aromatic hydrocarbon ring having 6 to 10 carbon atoms, and the aromatic heterocyclic ring and the aromatic hydrocarbon ring may have a saturated hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted amino group, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent. The substituent that the aromatic hydrocarbon group may have may be -SO 3 - or -SO 2 -N - -SO 2 -R f .

[0039] M r+ It represents a metal ion with a valence of r.

[0040] k represents R 41b ~R 44b , R 47b ~R 54b and Ring T 2b All-SO 3 - The number and -SO 2 -N - -SO 2 -R f The sum of the number of .

[0041] r represents an integer of 1 or greater.

[0042] R f It represents a fluoroalkyl group having 1 to 12 carbon atoms.

[0043] Among them, R 41b ~R 44b , R47b ~R 54b and Ring T 2b Have at least one -SO 3 - or -SO 2 -N - -SO 2 -R f .

[0044] When a plurality of structures represented by the following formulae are contained in one molecule, they may be the same structure or different structures.

[0045] [Chemistry 6]

[0046]

[0047] [wherein, ring T 2b , R 41b ~R 44b and R 47b ~R 54b Each has the same meaning as above. ]]

[0048] [3] A color filter formed from the colored resin composition according to [1] or [2].

[0049] [4] A display device comprising the color filter described in [3].

[0050] Effects of the Invention

[0051] The color filter formed from the colored resin composition of the present invention is excellent in light resistance, heat resistance, and heat resistance in a state where an overcoat layer is laminated. DETAILED DESCRIPTION

[0052] The colored resin composition of the present invention contains a colorant (hereinafter, sometimes referred to as "colorant (A)"), a resin (hereinafter, sometimes referred to as "resin (B)"), a polymerizable compound (hereinafter, sometimes referred to as "polymerizable compound (C)"), and a polymerization initiator (hereinafter, sometimes referred to as "polymerization initiator (D)").

[0053] It is preferred that the colored resin composition of the present invention further contains a solvent (hereinafter, sometimes referred to as a solvent (E)).

[0054] The colored resin composition of the present invention may contain a leveling agent (hereinafter, sometimes referred to as a leveling agent (F)).

[0055] In the present specification, compounds exemplified as components may be used alone or in combination of two or more, unless otherwise specified.

[0056] <Colorant (A)>

[0057] The colored resin composition of the present invention contains a triarylmethane lake and a specific anthraquinone compound described below as a colorant (A).

[0058] <Triarylmethane Lake>

[0059] The triarylmethane lake of the present invention refers to an organic pigment that is insoluble in water or an organic solvent by precipitating a triarylmethane dye that is soluble in water or an organic solvent with a precipitant.

[0060] The triarylmethane lake may be a compound composed of a cation having a triarylmethane skeleton and an anion derived from a precipitant, or may be a compound composed of an anion having a triarylmethane skeleton and a cation derived from a precipitant. The triarylmethane skeleton refers to a skeleton in which three aromatic rings are bonded to one carbon, and among the three aromatic rings, preferably two are aromatic hydrocarbon rings and one is an aromatic heterocyclic ring.

[0061] The triarylmethane lake is preferably at least one selected from the group consisting of a compound represented by formula (A2) (hereinafter, sometimes referred to as compound (A2)) and a compound represented by formula (A3) (hereinafter, sometimes referred to as compound (A3)).

[0062] <<Compound (A2)>>

[0063] [Chemistry 7]

[0064]

[0065] [In formula (A2),

[0066] R 11b ~R 14b Each independently represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent. In the saturated hydrocarbon group having 1 to 20 carbon atoms, the hydrogen atom contained in the saturated hydrocarbon group may be substituted by a substituted or unsubstituted amino group or a halogen atom. When the saturated hydrocarbon group has 2 to 20 carbon atoms, the -CH 2 - may be substituted with -O- or -CO-. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, the adjacent -CH 2 - will not be replaced by -O- at the same time. R 11b With R 12b can combine to form a ring with the nitrogen atom to which they are bound, R 13b With R 14b They may combine to form a ring together with the nitrogen atom to which they are bound.

[0067] R 17b ~R24b Each independently represents a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, or an alkyl group having 1 to 8 carbon atoms, wherein -CH 2 - may be substituted by -O- or -CO-. 18b and R 22b Can combine with each other to form -NH-, -O-, -S- or -SO 2 -.

[0068] Ring T 1b It represents an aromatic heterocyclic ring having 3 to 10 carbon atoms which may have a substituent, or an aromatic hydrocarbon ring having 6 to 10 carbon atoms which may have a substituent.

[0069] [Y] m- represents any m-valent anion containing at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus, and oxygen.

[0070] m represents an arbitrary natural number.

[0071] When a plurality of structures represented by the following formulae are contained in one molecule, they may be the same structure or different structures.

[0072] [Chemistry 8]

[0073]

[0074] [wherein, ring T 1b , R 11b ~R 14b and R 17b ~R 24b Each has the same meaning as above. ]]

[0075] Ring T 1b The aromatic heterocyclic ring may be a monocyclic ring or a condensed ring.

[0076] As a ring T 1b The substituents that the aromatic heterocyclic ring may have include a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms that may have a substituent, an aromatic hydrocarbon group having 6 to 20 carbon atoms that may have a substituent, and an amino group that may have a substituent. 1b An amino group which may have a substituent such as an alkyl group having 1 to 10 carbon atoms is preferred.

[0077] Among them, ring T 1b The aromatic heterocycle of is preferably an aromatic heterocycle containing a nitrogen atom, and more preferably a 5-membered aromatic heterocycle containing a nitrogen atom.

[0078] Further, Ring T 1b The ring represented by formula (A2-t1) is particularly preferred.

[0079] [Chemistry 9]

[0080]

[0081] [In formula (A2-t1),

[0082] R 26b It represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group which may have a substituent.

[0083] X1b represents an oxygen atom, -NR 27b -, or a sulfur atom.

[0084] R 27b It represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

[0085] R 15b and R 16b Each independently represents a saturated hydrocarbon group having 1 to 20 carbon atoms or an alkyl group having 2 to 20 carbon atoms which may have a substituent, and the -CH 2 - a group which may be substituted with -O-, an aromatic hydrocarbon group which may have a substituent, an aralkyl group which may have a substituent, or a hydrogen atom. 15b With R 16b They may combine to form a ring together with the nitrogen atom to which they are bound.

[0086] However, the adjacent -CH 2 - will not be replaced by -O- at the same time. In addition, the -CH 2 - will not be replaced by -O-.

[0087] *Indicates the bond to the carbocation.]

[0088] As a ring T 1b The aromatic hydrocarbon ring includes a benzene ring, a naphthalene ring and the like.

[0089] As a ring T 1b The substituent that the aromatic hydrocarbon ring may have includes a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, and an amino group which may have a substituent.

[0090] R 11b ~R 16b and R 26bThe saturated hydrocarbon group having 1 to 20 carbon atoms may be any of straight chain, branched chain and cyclic. As the straight chain or branched chain saturated hydrocarbon group, there can be mentioned straight chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, dodecyl, hexadecyl, eicosyl, etc.; branched chain alkyl groups such as isopropyl, isobutyl, isopentyl, neopentyl, 2-ethylhexyl, etc. The saturated hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and further preferably 1 to 6 carbon atoms.

[0091] R 11b ~R 16b and R 26b The cyclic saturated hydrocarbon group represented may be monocyclic or polycyclic. Examples of the cyclic saturated hydrocarbon group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and adamantyl. The cyclic saturated hydrocarbon group preferably has 3 to 10 carbon atoms, and more preferably has 6 to 10 carbon atoms.

[0092] R 11b ~R 16b and R 26b The saturated hydrocarbon group may be substituted with a halogen atom or a substituted amino group. As the substituted amino group, for example, an amino group; an alkylamino group such as a methylamino group, a dimethylamino group, and a diethylamino group may be mentioned. In addition, as the halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. may be mentioned. In addition, when the halogen atom is a fluorine atom, it is preferably substituted with the halogen atom in a manner of forming a perfluoroalkyl unit such as a trifluoromethyl unit, a pentafluoroethyl unit, a heptafluoropropyl unit, etc.

[0093] As R 17b ~R 24b The alkyl group having 1 to 8 carbon atoms represented by R 11b The saturated hydrocarbon groups represented by are exemplified as linear or branched saturated hydrocarbon groups having 1 to 8 carbon atoms.

[0094] In addition, as R 27b The alkyl group having 1 to 10 carbon atoms represented by R is exemplified by 11b The saturated hydrocarbon groups represented by the above are linear or branched saturated hydrocarbon groups having 1 to 10 carbon atoms.

[0095] When R 11b ~R 16b When the number of carbon atoms of the saturated hydrocarbon group (preferably an alkyl group) represented by is 2 or more, the -CH 2 - may be substituted with -O- or -CO-, preferably with -O-. The saturated hydrocarbon group (preferably an alkyl group) preferably has 2 to 10 carbon atoms, more preferably 2 to 8. 2When - is substituted with -O- or -CO-, the number of carbon atoms between the terminal and -O- or -CO-, or between -O- or -CO- and -O- or -CO- is, for example, 1 to 5, preferably 2 to 3, and more preferably 2. However, the adjacent -CH 2 - will not be replaced by -O- at the same time.

[0096] In addition, as can have R 11b ~R 16b and R 26b The aromatic hydrocarbon group of the substituent represented by is preferably a group having 6 to 20 carbon atoms, more preferably a group having 6 to 15 carbon atoms, and further preferably a group having 6 to 12 carbon atoms. Examples of the aromatic hydrocarbon group include aryl groups such as phenyl, tolyl, xylyl, naphthyl, anthracenyl, phenanthryl, biphenyl, and terphenyl, and are preferably phenyl, naphthyl, tolyl, and xylyl, and are particularly preferably phenyl and tolyl. In addition, the aromatic hydrocarbon group preferably has one or more substituents, and examples of the substituent include: halogen atoms such as fluorine atoms, chlorine atoms, iodine atoms, and bromine atoms; alkoxy groups having 1 to 6 carbon atoms such as methoxy and ethoxy; hydroxyl groups; sulfamoyl groups; alkylsulfonyl groups having 1 to 6 carbon atoms such as methylsulfonyl; alkoxycarbonyl groups having 1 to 6 carbon atoms such as methoxycarbonyl and ethoxycarbonyl; and the like.

[0097] As can have R 11b ~R 16b Examples of the aralkyl group as the substituent include groups formed by bonding an alkanediyl group having 1 to 5 carbon atoms such as methylene, ethylene and propylene to the groups described above as the aromatic hydrocarbon group.

[0098] As R 11b With R 12b The nitrogen atoms to which they are bound form a ring, R 13b With R 14b The nitrogen atoms to which they are bound form a ring, and R 15b With R 16b Examples of the ring formed by combining with the nitrogen atom to which they are combined include nitrogen-containing non-aromatic 4- to 7-membered rings such as pyrrolidine ring, morpholine ring, piperidine ring, and piperazine ring. Preferred examples include 4- to 7-membered rings having only one nitrogen atom as a heteroatom such as pyrrolidine ring and piperidine ring.

[0099] Among them, as R 11b ~R 14b and R 26b , preferably a saturated hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group which may have a substituent, and each independently more preferably a saturated hydrocarbon group having 1 to 8 carbon atoms or a group represented by the following formula: In the following formula, * represents a bond, and Me represents a methyl group.

[0100] [Chemistry 10]

[0101]

[0102] R 11b and R 13b Each of R 12b and R 14b Each of them is independently preferably an aromatic hydrocarbon group which may have a substituent, R 26b An aromatic hydrocarbon group which may have a halogen atom is preferred.

[0103] R 11b and R 13b Each independently is more preferably a saturated hydrocarbon group having 1 to 6 carbon atoms, and R 12b and R 14b Each independently is more preferably an aromatic hydrocarbon group, R 26b More preferably, it is an aromatic hydrocarbon group which may have a fluorine atom.

[0104] R 11b and R 13b Each independently is further preferably a methyl group or an ethyl group, R 12b and R 14b Each independently is more preferably phenyl, R 26b More preferred is a phenyl group having a fluorine atom.

[0105] R 15b and R 16b Each of them is preferably independently a saturated hydrocarbon group having 1 to 20 carbon atoms, a group in which -O- is inserted between carbon atoms of an alkyl group having 2 to 20 carbon atoms, or an aromatic hydrocarbon group which may have a substituent, or R 15b With R 16b Combined with the nitrogen atom to which they are combined to form a ring. A more preferred embodiment is that R 15b and R 16b Each independently represents a saturated hydrocarbon group having 1 to 8 carbon atoms, an alkoxyalkyl group, or a group represented by the following formula, or R 15b With R 16b The 4- to 7-membered ring is formed by bonding to a nitrogen atom as a hetero atom. In the following formula, * represents a bond to a nitrogen atom, and Me represents a methyl group.

[0106] [Chemistry 11]

[0107]

[0108] In addition, as R 17b ~R 24b The -CH 2- The group substituted with -O- or -CO- can be exemplified by the group consisting of the above R 11b ~R 16b A group having 8 or less carbon atoms selected from the corresponding groups.

[0109] From the perspective of ease of synthesis, R 17b ~R 24b Each independently is preferably a hydrogen atom, a halogen atom or an alkyl group having 1 to 8 carbon atoms, each independently is more preferably a hydrogen atom, a methyl group, a fluorine atom or a chlorine atom, and each independently is further preferably a hydrogen atom.

[0110] X1b is preferably a sulfur atom.

[0111] Examples of the cation portion of the formula (A2) include cations 1 to cations 14 represented by the formula (I-1), as shown in Table 1 below.

[0112] [Chemistry 12]

[0113]

[0114] [Table 1]

[0115]

[0116] In Table 1, Ph1 to Ph9 represent groups represented by the following formula: In the formula, * represents a bond.

[0117] [Chemistry 13]

[0118]

[0119] Among them, as the cation part of formula (A2), cations 1 to 6 and cations 11 to 14 are preferred, cation 1, cation 2, or cations 12 to 14 are more preferred, and cation 12 is further preferred.

[0120] [Y] m- It is an arbitrary m-valent anion containing at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus, and oxygen. A compound containing such an anion tends to have good heat resistance and solvent resistance.

[0121] m is preferably 1-20, more preferably 1-14, further preferably 2-8, and further more preferably 2-6.

[0122] As [Y] m- The anion represented is preferably an anion of a heteropoly acid containing tungsten or an anion of an isopoly acid containing tungsten.

[0123] Examples of the anion of the heteropolyacid or isopolyacid containing tungsten include Keggin type phosphotungstate ion α-[PW 12 O 40 ] 3- 、Dawson type phosphotungstate ion α-[P 2 W 18 O 62 ] 6- β-[P 2 W 18 O 62 ] 6- 、Keggin type silicotungstate ion α-[SiW 12 O 40 ] 4- ,β-[SiW 12 O 40 ] 4- ,γ-[SiW 12 O 40 ] 4- , [P 2 W 17 O 61 ] 10- , [P 2 W 15 O 56 ] 12- , [H 2 P 2 W 12 O 48 ] 12- , [NaP 5 W 30 O 110 ] 14- ,α-[SiW 9 O 34 ] 10- ,γ-[SiW 10 O 36 ] 8- ,α-[SiW 11 O 39 ] 8- ,β-[SiW 11 O 39 ] 8- , [W 6 O 19 ] 2- , [W 10 O 32 ] 4- , WO 4 2- and mixtures thereof.

[0124] As [Y] m-The anion represented is also preferably an anion composed of at least one element selected from the group consisting of silicon and phosphorus and oxygen.

[0125] Examples of the anion composed of at least one element selected from the group consisting of silicon and phosphorus and oxygen include SiO 3 2- ,PO 4 3- .

[0126] From the perspective of ease of synthesis and post-treatment, phosphotungstate anions such as Keggin-type phosphotungstate ions and Dawson-type phosphotungstate ions; silicotungstate anions such as Keggin-type silicotungstate ions; [W 10 O 32 ] 4- Among them, Keggin type phosphotungstate anions and tungsten isopoly acid anions are particularly preferred.

[0127] Examples of the compound (A2) include compounds represented by formula (A2-1) to formula (A2-52) in Tables 2 to 3 below.

[0128] [Table 2]

[0129] Compound (A2) cation m Anions (A2-1) Cation 1 3 <![CDATA[[PW 12 THE 40 ] 3- ]]> (A2-2) Cation 1 6 <![CDATA[[P 2 W 18 O 62 ] 6- ]]> (A2-3) Cation 1 4 <![CDATA[[SiW 12 THE 40 ] 4- ]]> (A2-4) Cation 1 4 <![CDATA[[W 10 THE 32 ] 4- ]]> (A2-5) Cation 2 3 <![CDATA[[PW 12 THE 40 ] 3- ]]> (A2-6) Cation 2 6 <![CDATA[[P 2 W 18 O 62 ] 6- ]]> (A2-7) Cation 2 4 <![CDATA[[SiW 12 THE 40 ] 4- ]]> (A2-8) Cation 4 4 <![CDATA[[W 10 THE 32 ] 4- ]]> (A2-9) Cation 4 3 <![CDATA[[PW 12 THE 40 ] 3- ]]> (A2-10) Cation 4 6 <![CDATA[[P 2 W 18 O 62 ] 6- ]]> (A2-11) Cation 4 4 <![CDATA[[SiW 12 THE 40 ] 4- ]]> (A2-12) Cation 5 4 <![CDATA[[W 10 THE 32 ] 4- ]]> (A2-13) Cation 5 3 <![CDATA[[PW 12 THE 40 ] 3- ]]> (A2-14) Cation 5 6 <![CDATA[[P 2 W 18 O 62 ] 6- ]]> (A2-15) Cation 5 4 <![CDATA[[SiW 12 THE 40 ] 4- ]]> (A2-16) Cation 6 4 <![CDATA[[W 10 THE 32 ] 4- ]]> (A2-17) Cation 6 3 <![CDATA[[PW 12 THE 40 ] 3- ]]> (A2-18) Cation 6 6 <![CDATA[[P 2 W 18 O 62 ] 6- ]]> (A2-19) Cation 6 4 <![CDATA[[SiW 12 THE 40 ] 4- ]]> (A2-20) Cation 7 4 <![CDATA[[W 10 THE 32 ] 4- ]]> (A2-21) Cation 7 3 <![CDATA[[PW 12 THE 40 ] 3- ]]> (A2-22) Cation 7 6 <![CDATA[[P 2 W 18 O 62 ] 6- ]]> (A2-23) Cation 7 4 <![CDATA[[SiW 12 THE 40 ] 4- ]]> (A2-24) Cation 7 4 <![CDATA[[W 10 THE 32 ] 4- <!-- 11 --> ]]> (A2-25) Cation 8 3 <![CDATA[[PW 12 THE 40 ] 3- ]]> (A2-26) Cation 8 6 <![CDATA[[P 2 W 18 O 62 ] 6- ]]> (A2-27) Cation 8 4 <![CDATA[[SiW 12 THE 40 ] 4- ]]> (A2-28) Cation 8 4 <![CDATA[[W 10 THE 32 ] 4- ]]>

[0130] [Table 3]

[0131] Compound (A2) cation m Anions (A2-29) Cation 9 3 <![CDATA[[PW 12 THE 40 ] 3- ]]> (A2-30) Cation 9 6 <![CDATA[[P 2 W 18 O 62 ] 6- ]]> (A2-31) Cation 9 4 <![CDATA[[SiW 12 THE 40 ] 4- ]]> (A2-32) Cation 9 4 <![CDATA[[W 10 THE 32 ] 4- ]]> (A2-33) Cation 10 3 <![CDATA[[PW 12 THE 40 ] 3- ]]> (A2-34) Cation 10 6 <![CDATA[[P 2 W 18 O 62 ] 6- ]]> (A2-35) Cation 10 4 <![CDATA[[SiW 12 THE 40 ] 4- ]]> (A2-36) Cation 10 4 <![CDATA[[W 10 THE 32 ] 4- ]]> (A2-37) Cation 11 3 <![CDATA[[PW 12 THE 40 ] 3- ]]> (A2-38) Cation 11 6 <![CDATA[[P 2 W 18 O 62 ] 6- ]]> (A2-39) Cation 11 4 <![CDATA[[SiW 12 THE 40 ] 4- ]]> (A2-40) Cation 11 4 <![CDATA[[W 10 THE 32 ] 4- ]]> (A2-41) Cation 12 3 <![CDATA[[PW 12 THE 40 ] 3- ]]> (A2-42) Cation 12 6 <![CDATA[[P 2 W 18 O 62 ] 6- ]]> (A2-43) Cation 12 4 <![CDATA[[SiW 12 THE 40 ] 4- ]]> (A2-44) Cation 12 4 <![CDATA[[W 10 THE 32 ] 4- ]]> (A2-45) Cation 13 3 <![CDATA[[PW 12 THE 40 ] 3- ]]> (A2-46) Cation 13 6 <![CDATA[[P 2 W 18 O 62 ] 6- ]]> (A2-47) Cation 13 4 <![CDATA[[SiW 12 THE 40 ] 4- ]]> (A2-48) Cation 13 4 <![CDATA[[W 10 THE 32 ] 4- ]]> (A2-49) Cation 14 3 <![CDATA[[PW 12 THE 40 ] 3- ]]> (A2-50) Cation 14 6 <![CDATA[[P 2 W 18 O 62 ] 6- ]]> (A2-51) Cation 14 4 <![CDATA[[SiW 12 THE 40 ] 4- ]]> (A2-52) Cation 14 4 <![CDATA[[W 10 THE 32 ] 4- ]]>

[0132] As compound (A2), the compound represented by formula (A2-41) to formula (A2-44) is preferred, and the compound represented by formula (A2-41) is more preferred.

[0133] Compound (A2) can be produced according to the method described in JP-A-2015-28121.

[0134] <<Compound (A3)>>

[0135] [Chemistry 14]

[0136]

[0137] [In formula (A3),

[0138] R 41b ~R 44b Each independently represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, and the substituents which the aromatic hydrocarbon group and the aralkyl group may have may be -SO 3- or -SO 2 -N - -SO 2 -R f The hydrogen atoms contained in the saturated hydrocarbon group may be substituted by substituted or unsubstituted amino groups or halogen atoms. When the number of carbon atoms in the saturated hydrocarbon group is 2 to 20, the -CH 2 - may be substituted with -O- or -CO-. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, the adjacent -CH 2 - will not be replaced by -O- at the same time. R 41b With R 42b can combine to form a ring with the nitrogen atom to which they are bound, R 43b With R 44b They may combine to form a ring together with the nitrogen atom to which they are bound.

[0139] R 47b ~R 54b Each independently represents a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, -SO 3 - 、-SO 2 -N - -SO 2 -R f , or an alkyl group having 1 to 8 carbon atoms, wherein -CH 2 - can be substituted by -O- or -CO-, R 48b With R 52b Can combine with each other to form -NH-, -S-, or -SO 2 -. However, in this alkyl group, the adjacent -CH 2 - will not be replaced by -O- at the same time.

[0140] Ring T 2b represents an aromatic heterocyclic ring having 3 to 10 carbon atoms or an aromatic hydrocarbon ring having 6 to 10 carbon atoms, and the aromatic heterocyclic ring and the aromatic hydrocarbon ring may have a saturated hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted amino group, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent. The substituent that the aromatic hydrocarbon group may have may be -SO 3 - or -SO 2 -N - -SO 2 -R f .

[0141] M r+ It represents a metal ion with a valence of r.

[0142] k represents R 41b ~R 44b , R47b ~R 54b and Ring T 2b All-SO 3 - The number and -SO 2 -N - -SO 2 -R f The sum of the number of .

[0143] r represents an integer of 1 or greater.

[0144] R f It represents a fluoroalkyl group having 1 to 12 carbon atoms.

[0145] Among them, R 41b ~R 44b , R 47b ~R 54b and Ring T 2b Have at least one -SO 3 - or -SO 2 -N - -SO 2 -R f .

[0146] When a plurality of structures represented by the following formulae are contained in one molecule, these structures may be the same or different.

[0147] [Chemistry 15]

[0148]

[0149] [wherein, ring T 2b , R 41b ~R 44b and R 47b ~R 54b Each has the same meaning as above. ]]

[0150] Ring T 2b The aromatic heterocyclic ring represented by may be a monocyclic ring or a condensed ring. 2b The number of carbon atoms of the aromatic heterocyclic ring represented by is preferably 3 to 10, more preferably 3 to 8. In addition, the aromatic heterocyclic ring is preferably a 5- to 10-membered ring, more preferably a 5- to 9-membered ring. Examples of the monocyclic aromatic heterocyclic ring include pyrrole ring, A 5-membered ring containing a nitrogen atom such as an azole ring, a pyrazole ring, an imidazole ring, and a thiazole ring; a 5-membered ring not containing a nitrogen atom such as a furan ring and a thiophene ring; a 6-membered ring containing a nitrogen atom such as a pyridine ring, a pyrimidine ring, a pyridazine ring, and a pyrazine ring; as an aromatic heterocyclic ring as a condensed ring, there can be mentioned condensed rings containing nitrogen atoms such as an indole ring, a benzimidazole ring, a benzothiazole ring, and a quinoline ring; a condensed ring not containing a nitrogen atom such as a benzofuran ring; etc.

[0151] Among them, as ring T 2b It is an aromatic heterocycle containing a nitrogen atom, preferably an aromatic heterocycle containing a nitrogen atom, and more preferably a 5-membered aromatic heterocycle containing a nitrogen atom.

[0152] As a ring T 2b The substituents that the aromatic heterocyclic ring may have include halogen atoms, cyano groups, saturated hydrocarbon groups having 1 to 20 carbon atoms that may have a substituent, substituted or unsubstituted amino groups, or aromatic hydrocarbon groups having 6 to 20 carbon atoms that may have a substituent, and preferably include saturated hydrocarbon groups having 1 to 20 carbon atoms, substituted or unsubstituted amino groups, or aromatic hydrocarbon groups having 6 to 20 carbon atoms that may have a substituent. Ring T 2b It is preferably an amino group which may have a substituent, and the substituent which may have the amino group is preferably a saturated hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent, an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or the like.

[0153] Ring T 2b Preferred is a ring represented by formula (A3-t1).

[0154] [Chemistry 16]

[0155]

[0156] [In formula (A3-t1),

[0157] R 56b It represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.

[0158] X2b represents an oxygen atom, -N(R 57b )-, or a sulfur atom.

[0159] R 57b It represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

[0160] R 45b and R 46b Each independently represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent. When the saturated hydrocarbon group has 2 to 20 carbon atoms, the -CH 2 - may be substituted with -O- or -CO-. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, the adjacent -CH 2 - will not be replaced by -O- at the same time. R 45b With R 46bThey may combine to form a ring together with the nitrogen atom to which they are bound.

[0161] *Indicates the bond to the carbocation.]

[0162] In addition, the ring T 2b A ring represented by formula (A3-t2) is also preferred.

[0163] [Chemistry 17]

[0164]

[0165] [In formula (A3-t2),

[0166] R 59b It represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent.

[0167] R 60b It represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.

[0168] R 61b Represents hydrogen atom, -SO 3 - , or -SO 2 -N - -SO 2 -R f .

[0169] *Indicates the bond to the carbocation.]

[0170] As a ring T 2b Examples of the aromatic hydrocarbon ring represented by include a benzene ring and a naphthalene ring.

[0171] As a ring T 2b Examples of the substituent that the represented aromatic hydrocarbon ring may have include the substituent that the above-mentioned aromatic heterocyclic ring may have.

[0172] R 41b ~R 46b , R 56b and R 59b ~R 60b The saturated hydrocarbon group having 1 to 20 carbon atoms and the ring T 2bThe saturated hydrocarbon group having 1 to 20 carbon atoms that the amino group may have may be any of linear, branched, and cyclic. Examples of the linear or branched saturated hydrocarbon group include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, hexadecyl, and eicosyl; and branched alkyl groups such as isopropyl, isobutyl, isopentyl, neopentyl, and 2-ethylhexyl. The number of carbon atoms in the saturated hydrocarbon group is preferably 1 to 10, more preferably 1 to 8, and even more preferably 1 to 6.

[0173] R 41b ~R 46b , R 56b and R 59b ~R 60b The cyclic saturated hydrocarbon group represented by 2b The cyclic saturated hydrocarbon group which may have an amino group may be monocyclic or polycyclic. Examples of the cyclic saturated hydrocarbon group include alicyclic saturated hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and adamantyl. The number of carbon atoms in the cyclic saturated hydrocarbon group is preferably 3 to 10, more preferably 6 to 10.

[0174] R 41b ~R 46b , R 56b and R 59b ~R 60b The saturated hydrocarbon group and the ring T 2b The saturated hydrocarbon group that may have an amino group may have a substituted or unsubstituted amino group or a halogen atom as a substituent. As a substituted amino group, for example, alkylamino groups such as methylamino, dimethylamino, and diethylamino can be mentioned. In addition, as a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom can be mentioned. In addition, when the halogen atom is a fluorine atom, the saturated hydrocarbon group having a fluorine atom as a substituent is preferably a perfluoroalkyl group such as a trifluoromethyl group, a perfluoroethyl group, and a perfluoropropyl group.

[0175] As R 47b ~R 54b The alkyl group having 1 to 8 carbon atoms represented by R 41b The saturated hydrocarbon group represented by is exemplified by a linear or branched saturated hydrocarbon group having 1 to 8 carbon atoms.

[0176] In addition, as R 57b The alkyl group having 1 to 10 carbon atoms represented by R is exemplified by 41b The saturated hydrocarbon group represented by exemplifies a group having 1 to 10 carbon atoms in a linear or branched saturated hydrocarbon group.

[0177] When R 41b ~R 46bWhen the number of carbon atoms of the saturated hydrocarbon group represented by is 2 to 20, the -CH 2 - may be substituted with -O- or -CO-. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, the adjacent -CH 2 - is not substituted by -O- at the same time. In this case, the saturated hydrocarbon group is preferably a linear or branched saturated hydrocarbon group (i.e., a linear or branched alkyl group), and more preferably a linear saturated hydrocarbon group (i.e., a linear alkyl group). -CH 2 -The saturated hydrocarbon group which may be substituted with -O- or -CO- preferably has 2 to 10 carbon atoms, more preferably 2 to 8 carbon atoms. 2 When - is substituted with -O- or -CO-, the number of carbon atoms between the terminal and -O- or -CO-, or between -O- or -CO- and -O- or -CO- is preferably 1 to 5, more preferably 2 to 3, and even more preferably 2.

[0178] In addition, R 41b ~R 46b , R 56b and R 59b ~R 60b The aromatic hydrocarbon group and the ring T of the substituent represented by 2b The number of carbon atoms of the aromatic hydrocarbon group (wherein the aromatic hydrocarbon group may have a substituent) that the amino group may have is preferably 6 to 20, more preferably 6 to 15, and even more preferably 6 to 12. Examples of the aromatic hydrocarbon group include phenyl, tolyl, xylyl, naphthyl, anthracenyl, phenanthryl, biphenyl, terphenyl, etc., preferably phenyl, tolyl, xylyl, naphthyl, and particularly preferably phenyl, tolyl, and xylyl. In addition, the aromatic hydrocarbon group may have one or more substituents. Examples of the substituent include halogen atoms such as fluorine, chlorine, iodine, and bromine atoms; alkoxy groups having 1 to 6 carbon atoms such as methoxy and ethoxy; hydroxyl groups; sulfamoyl groups; alkylsulfonyl groups having 1 to 6 carbon atoms such as methylsulfonyl; alkoxycarbonyl groups having 1 to 6 carbon atoms such as methoxycarbonyl and ethoxycarbonyl; -SO 3 - ;-SO 2 -N - -SO 2 -R f ; etc., preferably a halogen atom such as a fluorine atom, a chlorine atom, an iodine atom, a bromine atom; -SO 3 - ;-SO 2 -N - -SO 2 -R f , more preferably a fluorine atom or -SO 3 - Among them, -SO 3- and-SO 2 -N - -SO 2 -R f It is preferred that the amine group directly bonds to the aromatic hydrocarbon ring of the aromatic hydrocarbon group, that is, that the hydrogen atom bonded to the aromatic hydrocarbon ring is substituted.

[0179] Specific examples of the aromatic hydrocarbon group which may have a substituent include groups represented by the following formulae: In the following formulae, * represents a bond.

[0180] [Chemistry 18]

[0181]

[0182] [Chemistry 19]

[0183]

[0184] As can have R 41b ~R 46b , R 59b The aralkyl group of the substituent represented by and the ring T 2b The aralkyl group (wherein the aralkyl group may have a substituent) which the amino group may have includes a group formed by combining an alkanediyl group having 1 to 10 carbon atoms (preferably 1 to 5 carbon atoms) such as methylene, ethylene, and propylene with the group described as the aromatic hydrocarbon group. The aralkyl group preferably has 7 to 30 carbon atoms, more preferably 7 to 20, and even more preferably 7 to 17 carbon atoms.

[0185] As R 41b With R 42b The nitrogen atoms to which they are bound form a ring, R 43b With R 44b The nitrogen atoms to which they are bound form a ring, and R 45b With R 46b Examples of the ring formed by combining with the nitrogen atom to which they are combined include nitrogen-containing non-aromatic 4- to 7-membered rings such as pyrrolidine ring, morpholine ring, piperidine ring, and piperazine ring. Preferred examples include 4- to 7-membered rings having only one nitrogen atom as a heteroatom such as pyrrolidine ring and piperidine ring.

[0186] Among them, as R 41b ~R 44b , R 56b , R 59b ~R 60b , each independently preferably is a saturated hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group which may have a substituent, and each independently more preferably is a saturated hydrocarbon group having 1 to 8 carbon atoms or a group represented by the following formula, R 41b and R43b Each of them is independently preferably a saturated hydrocarbon group having 1 to 20 carbon atoms, 42b and R 44b Each of them is independently an aromatic hydrocarbon group which may have a substituent, and R 56b More preferably, it is an aromatic hydrocarbon group which may have a substituent.

[0187] R 56b , R 59b ~R 60b More preferably, it is a group represented by the following formula: In the following formula, * represents a bond.

[0188] [Chemistry 20]

[0189]

[0190] [Chemistry 21]

[0191]

[0192] R 45b ~R 46b Each of the above is preferably independently a saturated hydrocarbon group having 1 to 20 carbon atoms, a -CH 2 - a group substituted by -O- or -CO-, or an aromatic hydrocarbon group which may have a substituent, or R 45b With R 46b Combined with the nitrogen atoms to which they are bound, they form a ring. 45b ~R 46b Each independently is more preferably a saturated hydrocarbon group having 1 to 8 carbon atoms, an alkoxyalkyl group, or a group represented by the following formula, or R 45b With R 46b They are combined to form a 4- to 7-membered ring having only one nitrogen atom as a heteroatom, and each is independently preferably a saturated hydrocarbon group having 1 to 8 carbon atoms, an alkoxyalkyl group, or a group represented by the following formula: 45b More preferably, it is a saturated hydrocarbon group having 1 to 4 carbon atoms, and R 46b More preferably, it is tolyl. In the following formulae, * represents a bond to a nitrogen atom.

[0193] [Chemistry 22]

[0194]

[0195] [Chemistry 23]

[0196]

[0197] In addition, as a component of R 47b ~R 54b-CH 2 - is substituted by -O- or -CO- (wherein, in the alkyl group, the adjacent -CH 2 - will not be substituted by -O- at the same time), the above R 41b ~R 46b -CH 2 - A group having 8 or less carbon atoms in a group substituted with -O- or -CO-.

[0198] R 47b ~R 54b Each independently is preferably a hydrogen atom, a halogen atom or an alkyl group having 1 to 8 carbon atoms, each independently is more preferably a hydrogen atom, a methyl group, a fluorine atom or a chlorine atom, and each independently is further preferably a hydrogen atom.

[0199] In addition, as R 57b , preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

[0200] As R 61b , preferably a hydrogen atom.

[0201] X2b is preferably -S-.

[0202] As M r+ The r-valent metal ions represented by the above-mentioned may include alkali metal ions such as lithium ion, sodium ion, potassium ion, etc.; alkaline earth metal ions such as beryllium ion, magnesium ion, calcium ion, strontium ion, barium ion, etc.; transition metal ions such as titanium ion, zirconium ion, chromium ion, manganese ion, iron ion, cobalt ion, nickel ion, copper ion, etc.; typical metal ions such as zinc ion, cadmium ion, aluminum ion, indium ion, tin ion, lead ion, bismuth ion, etc. r is 1 or more, preferably 2 or more, preferably 5 or less, more preferably 4 or less, and further preferably 3 or less.

[0203] As M r+ , more preferably alkaline earth metal ions, typical metal ions, etc., further preferably alkaline earth metal ions, zinc ions, and further preferably alkaline earth metal ions.

[0204] In formula (A3), M r+ The number of 41b ~R 44b , R 47b ~R 54b and Ring T 2b All-SO 3 - The number and -SO 2 -N - -SO 2 -R fThe sum of the numbers of (k) is less than 1. Therefore, the valence of compound (A3) becomes 0, that is, it becomes an electrically neutral compound.

[0205] As R f The fluoroalkyl group having 1 to 12 carbon atoms represented by the fluoroalkyl group may include monofluoromethyl, difluoromethyl, perfluoromethyl, monofluoroethyl, difluoroethyl, trifluoroethyl, tetrafluoroethyl, perfluoroethyl, monofluoropropyl, difluoropropyl, trifluoropropyl, tetrafluoropropyl, pentafluoropropyl, hexafluoropropyl, perfluoropropyl, monofluorobutyl, difluorobutyl, trifluorobutyl, tetrafluorobutyl, pentafluorobutyl, hexafluorobutyl, heptafluorobutyl, octafluorobutyl, and perfluorobutyl. f The fluoroalkyl group represented by is preferably a perfluoroalkyl group. f The fluoroalkyl group represented has preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and even more preferably 1 to 3 carbon atoms.

[0206] In formula (A3), R 41b ~R 44b , R 47b ~R 54b and Ring T 2b Have at least one -SO 3 - or -SO 2 -N - -SO 2 -R f , preferably with at least one -SO 3 - . R 41b ~R 44b , R 47b ~R 54b and Ring T 2b All-SO 3 - and-SO 2 -N - -SO 2 -R f The sum of the numbers of (k) is preferably 1 to 7, more preferably 2 to 7, further preferably 2 to 4, further preferably 2 or 3, and particularly preferably 2.

[0207] -SO 3 - or -SO 2 -N - -SO 2 -R f It is preferred that at least one condition selected from the following (Ia) to (Id) is satisfied, and it is more preferred that at least one condition selected from (Ia) and (Ib) is satisfied.

[0208] (Ia) as the above R47b ~R 54b Any of

[0209] (Ib) and can have R 41b ~R 44b Any of the aromatic hydrocarbon groups having 6 to 20 carbon atoms of the substituent represented by

[0210] (Ic) and can have R 41b ~R 44b Any of the aralkyl groups having 7 to 30 carbon atoms in the substituent represented by

[0211] (Id) and replace T 2b The hydrogen atom of the aromatic heterocyclic ring represented by is bonded to any one of the aromatic hydrocarbon groups having 6 to 20 carbon atoms

[0212] Among them, -SO is bonded to the aromatic hydrocarbon group or aralkyl group. 3 - or -SO 2 -N - -SO 2 -R f In case of -SO 3 - or -SO 2 -N - -SO 2 -R f It is preferably directly bonded to the aromatic hydrocarbon ring of the aromatic hydrocarbon group or aralkyl group. 3 - or -SO 2 -N - -SO 2 -R f It is preferred to substitute the hydrogen atoms bonded to the aromatic hydrocarbon ring.

[0213] In the case of R 41b ~R 44b The substituent represented by is an aromatic hydrocarbon group having 6 to 20 carbon atoms or may have R 41b ~R 44b In the aromatic hydrocarbon ring (e.g., benzene ring) of the aralkyl group having 7 to 30 carbon atoms represented by the substituent, -SO 3 - or -SO 2 -N - -SO 2 -R f It is preferably bonded to the para position relative to the bonding position of the nitrogen atom.

[0214] In compound (A3) containing multiple -SO 3 - or -SO2 -N - -SO 2 -R f In case of multiple-SO 3 - or -SO 2 -N - -SO 2 -R f They may be bonded to the same aromatic hydrocarbon ring or to different aromatic hydrocarbon rings.

[0215] The compound (A3) preferably has no ethylenically unsaturated bond.

[0216] The compound (A3) is preferably a compound represented by the following formula (II-1) (hereinafter, sometimes referred to as compound (II-1)).

[0217] [Chemistry 24]

[0218]

[0219] [In formula (II-1),

[0220] R 81b ~R 90b Each independently represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, -SO 3 - or -SO 2 -N - -SO 2 -R f .

[0221] k1 represents R 41b , R 43b , R 47b ~R 54b , R 81b ~R 90b and Ring T 2b All-SO 3 - The number and -SO 2 -N - -SO 2 -R f The sum of the number of .

[0222] R 41b , R 43b , R 47b ~R 54b 、T 2b 、M r+ , r, R f Synonymous with above.

[0223] Among them, R41b , R 43b , R 47b ~R 54b , R 81b ~R 90b and Ring T 2b Have at least one -SO 3 - or -SO 2 -N - -SO 2 -R f . ]

[0224] As R 81b ~R 90b The saturated hydrocarbon group having 1 to 20 carbon atoms represented by can be exemplified by 41b The same groups as those exemplified for the saturated hydrocarbon group represented by 81b ~R 90b , preferably a hydrogen atom, a saturated hydrocarbon group having 1 to 8 carbon atoms, -SO 3 - or -SO 2 -N - -SO 2 -R f , more preferably a hydrogen atom, a saturated hydrocarbon group having 1 to 4 carbon atoms, -SO 3 - or -SO 2 -N - -SO 2 -R f , more preferably a hydrogen atom, a saturated hydrocarbon group having 1 to 4 carbon atoms, or -SO 3 - .

[0225] -SO 3 - or -SO 2 -N - -SO 2 -R f It preferably satisfies at least one condition selected from (Ie) to (Ig), more preferably satisfies at least one condition selected from (If) and (Ig), and even more preferably satisfies the condition of (If).

[0226] (Ie) As R 47b ~R 54b Any of

[0227] (If) as R 81b ~R 90b Any of

[0228] (Ig) and substituted T2b The hydrogen atom of the aromatic heterocyclic ring represented by

[0229] -SO 3 - or -SO 2 -N - -SO 2 -R f It is more preferable to satisfy the condition (If').

[0230] (If') in R 86b and R 89b Either or both of

[0231] In formula (II-1), R 41b , R 43b , R 47b ~R 54b , R 81b ~R 90b and Ring T 2b All-SO 3 - and-SO 2 -N - -SO 2 -R f The sum of the numbers of (k1) is preferably 1 to 7, more preferably 1 to 4, and even more preferably 1 or 2.

[0232] Examples of the compound (A3) include the following compounds (compounds represented by formula (A3-1) to formula (A3-13)).

[0233] [Chemistry 25]

[0234]

[0235] [Chemistry 26]

[0236]

[0237] [Chemistry 27]

[0238]

[0239] [Chemistry 28]

[0240]

[0241] [Chemistry 29]

[0242]

[0243] [Chemistry 30]

[0244]

[0245] [Chemistry 31]

[0246]

[0247] [Chemistry 32]

[0248]

[0249] [Chemistry 33]

[0250]

[0251] [Chemistry 34]

[0252]

[0253] [Chemistry 35]

[0254]

[0255] [Chemistry 36]

[0256]

[0257] [Chemistry 37]

[0258]

[0259] Among the compounds represented by formula (A3-1) to formula (A3-13), preferred are compounds represented by formula (A3-7), formula (A3-11), or formula (A3-13), and particularly preferred are compounds represented by formula (A3-7).

[0260] The triarylmethane lake is preferably dispersed in a solvent to prepare a colored dispersion when producing the colored resin composition of the present invention. The colored dispersion can be mixed with the anthraquinone compound (A1), the resin (B), the polymerizable compound (C), the polymerization initiator (D), etc. to prepare the colored resin composition.

[0261] As the solvent for preparing the colored dispersion, any solvent can be used as long as it can be used as the solvent (E) of the colored resin composition. Examples of the solvent include ether ester solvents and ketone solvents described below.

[0262] In the colored dispersion, the content of the solvent is, for example, 1 to 50 parts by mass, preferably 2 to 30 parts by mass, and more preferably 3 to 20 parts by mass, relative to 1 part by mass of the triarylmethane lake.

[0263] When the triarylmethane lake is dispersed in a solvent to prepare a colored dispersion, a pigment dispersant is preferably used. As the pigment dispersant, surfactants such as cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic acid can be cited. These pigment dispersants can be used alone or in combination of two or more. As the pigment dispersant, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Zeneca Co., Ltd.), EFKA (manufactured by BASF Co., Ltd.), Ajispur (manufactured by Ajinomoto Fine-Techno Co., Ltd.), Disperbyk (manufactured by BYK Chemical Co., Ltd.), BYK (manufactured by BYK Chemical Co., Ltd.) and the like can be cited as trade names.

[0264] In the color dispersion, the content of the pigment dispersant is, for example, 1 to 1000 parts by mass, preferably 3 to 200 parts by mass, more preferably 5 to 100 parts by mass, and particularly preferably 5 to 50 parts by mass, based on 100 parts by mass of the triarylmethane lake.

[0265] The content of the triarylmethane lake in the total amount of the colorant (A) is, for example, 5 mass % or more, preferably 10 mass % or more, more preferably 20 mass % or more, and for example, 99 mass % or less, preferably 95 mass % or less, more preferably 90 mass % or less.

[0266] <Anthraquinone compound (A1)>

[0267] The anthraquinone compound used as the colorant (A) is a compound represented by the formula (A1) (hereinafter, sometimes referred to as “anthraquinone compound (A1)”).

[0268] [Chemistry 38]

[0269]

[0270] [In formula (A1),

[0271] A 1a and A 2a Each independently represents a phenylene group which may have a substituent.

[0272] L 1a and L 2a Each independently represents a divalent hydrocarbon group having 1 to 12 carbon atoms, wherein the -CH 2 -Can be -O-, -SO 2 -or-NR 11a -replace.

[0273] R 1a ~R 6aEach independently represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 8 carbon atoms. 11a represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.]

[0274] As A 1a and A 2a The substituent that the phenylene group represented by may have includes a halogen atom (chlorine atom, bromine atom, etc.), -R 21a 、-OH、-OR 21a 、-SO 3 H, -SO 3 - G + , -COOH, -COO - T + , -CO 2 R 21a 、-SR 21a 、-SO 2 R 21a 、-SO 3 R 21a or -SO 2 NR 12a R 13a The above R 21a represents a saturated hydrocarbon group having 1 to 20 carbon atoms, -R 21a R 21a It is preferably an alkyl group having 1 to 8 carbon atoms. 12a and R 13a Each independently represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms, and R 12a and R 13a They can combine to form a ring with the nitrogen atom to which they are bound. + for Na + , K + , or N + (R 15a ) 4 , T + for Na + , K + , or N + (R 16a ) 4 , 4 Rs 15a Can be the same or different, 4 R 16a Can be the same or different. 15a , R 16a It represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

[0275] Among the above substituents, -R 21a 、-SO 3 H, -SO3 - G + , -COOH, -COO - T + and-SO 2 NR 12a R 13a , as the-SO 3 - G + , preferably -SO 3 - N + (R 15a ) 4 The most preferred substituent is -R 21a .

[0276] As R 1a ~R 6a , R 11a , R 15a , R 16a and R 21a The alkyl group having 1 to 8 carbon atoms represented by can be, for example, a straight-chain alkyl group such as methyl, ethyl, propyl, butyl, pentyl, hexyl, etc.; a branched-chain alkyl group such as isopropyl, isobutyl, isopentyl, neopentyl, etc. 1a ~R 6a and R 11a , preferably a hydrogen atom.

[0277] As a component of L 1a and L 2a The hydrocarbon having 1 to 12 carbon atoms of the divalent group represented by , for example, aliphatic saturated hydrocarbon having 1 to 12 carbon atoms, benzene, benzene having an alkyl group having 1 to 8 carbon atoms, etc. Examples of the divalent aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms include methylene, straight-chain alkanediyl groups having bonds at both ends such as ethane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, and hexane-1,6-diyl, ethane-1,1-diyl, propane-1,1-diyl, propane-1,2-diyl, propane-2,2-diyl, butane-1,1-diyl, butane-1,2-diyl, butane-1,3-diyl, Butane-2,2-diyl, butane-2,3-diyl, 2-methylpropane-1,1-diyl, 2-methylpropane-1,2-diyl, 2-methylpropane-1,3-diyl, 2-methylpropane-1,4-diyl, 2-methylpropane-2,3-diyl, 2-methylpropane-2,4-diyl, 2-methylpropane-3,3-diyl, 2-methylpropane-3,4-diyl, 2-methylpropane-4,4-diyl and the like are preferably straight-chain alkanediyl groups having bonds at both ends.

[0278] Examples of benzene having an alkyl group with 1 to 8 carbon atoms include methylbenzene, dimethylbenzene, ethylbenzene, propylbenzene, ethyl(methyl)benzene, butylbenzene, and ethyl(dimethyl)benzene. The divalent group formed by the benzene having an alkyl group with 1 to 8 carbon atoms may have two bonds on the alkyl group, two bonds on the benzene ring, or one bond on the alkyl group and one bond on the benzene ring. Among them, the one bond on the alkyl group and one bond on the benzene ring is preferred.

[0279] As R 12a , R 13a and R 21a The saturated hydrocarbon group having 1 to 20 carbon atoms represented by the above-mentioned group includes, for example, a linear alkyl group such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, hexadecyl, eicosyl, a branched alkyl group such as isopropyl, isobutyl, isopentyl, neopentyl, 2-ethylhexyl, and an alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, tricyclodecyl, etc. The saturated hydrocarbon group more preferably has 1 to 10 carbon atoms.

[0280] As R 12a and R 13a Examples of the aralkyl group having 7 to 10 carbon atoms include benzyl, phenylethyl, and phenylbutyl.

[0281] As R 12a With R 13a Examples of the ring formed by bonding with the nitrogen atom to which they bond include the following rings. In the formula, * represents a bonding bond.

[0282] [Chemistry 39]

[0283]

[0284] As N + (R 15a ) 4 、N + (R 16a ) 4 , tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium and the like can be mentioned.

[0285] AS-OR 21a For example, there can be mentioned alkoxy groups such as methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy and eicosyloxy.

[0286] As -CO 2 R 21aFor example, there can be mentioned alkoxycarbonyl groups such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, tert-butoxycarbonyl, hexyloxycarbonyl and eicosyloxycarbonyl.

[0287] AS-SR 21a Examples of the alkylthio group include alkylthio groups such as methylthio, ethylthio, butylthio, hexylthio, decylthio and eicosylthio.

[0288] AS-SO 2 R 21a Examples of the alkylsulfonyl group include alkylsulfonyl groups such as methylsulfonyl, ethylsulfonyl, butylsulfonyl, hexylsulfonyl, decylsulfonyl and eicosylsulfonyl.

[0289] AS-SO 3 R 21a For example, there can be mentioned alkoxysulfonyl groups such as methoxysulfonyl, ethoxysulfonyl, propoxysulfonyl, tert-butoxysulfonyl, hexyloxysulfonyl and eicosyloxysulfonyl.

[0290] AS-SO 2 NR 12a R 13a For example, we can cite:

[0291] Sulfonamide;

[0292] N-methylsulfamoyl, N-ethylsulfamoyl, N-propylsulfamoyl, N-isopropylsulfamoyl, N-butylsulfamoyl, N-isobutylsulfamoyl, N-sec-butylsulfamoyl, N-tert-butylsulfamoyl, N-pentylsulfamoyl, N-(1-ethylpropyl)sulfamoyl, N-(1,1-dimethylpropyl)sulfamoyl, N-(1,2-dimethylpropyl)sulfamoyl, N-(2,2-dimethylpropyl)sulfamoyl, N-(1-methylbutyl)sulfamoyl, N-(2-methylbutyl)sulfamoyl, N N-1-substituted sulfamoyl groups such as -(3-methylbutyl)sulfamoyl, N-cyclopentylsulfamoyl, N-hexylsulfamoyl, N-(1,3-dimethylbutyl)sulfamoyl, N-(3,3-dimethylbutyl)sulfamoyl, N-heptylsulfamoyl, N-(1-methylhexyl)sulfamoyl, N-(1,4-dimethylpentyl)sulfamoyl, N-octylsulfamoyl, N-(2-ethylhexyl)sulfamoyl, N-(1,5-dimethylhexyl)sulfamoyl and N-(1,1,2,2-tetramethylbutyl)sulfamoyl;

[0293] N,N-2 substituted sulfamoyl groups such as 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 and N,N-heptylmethylsulfamoyl.

[0294] As R 1a ~R 6a The halogen atom represented by A 1a and A 2a Examples of the halogen atom which may be a substituent of the phenylene group represented by the above-mentioned group include a chlorine atom and a bromine atom.

[0295] As the anthraquinone compound (A1), *-L of the formula (A1) 1a -**(* indicates the same as A 1a The bond between CO 2 H bond) and *-L 2a -**(* indicates the same as A 2a The bond between CO 2 The bonds of H) are each independently preferably compounds that form structures represented by formulae (A1a) to (A1h).

[0296] [Chemistry 40]

[0297] *-OR 31a -**(A1a)

[0298] *-OR 32a -**(A1b)

[0299] *-OR 33a -R 32a -**(A1c)

[0300] *-OR 32a -R 33a -**(A1d)

[0301] [In formulas (A1a) to (A1h), R 31a represents an alkanediyl group having 1 to 10 carbon atoms, R 32a represents a phenylene group which may be bonded with an alkyl group having 1 to 4 carbon atoms, R 33a It represents an alkanediyl group having 1 to 4 carbon atoms. * represents 1a or A 2a The bond between CO 2 H bonding.]

[0302] Among the structures represented by formulae (A1a) to (A1h), structures represented by formulae (A1a) and (A1f) are preferred.

[0303] As anthraquinone compound (A1), for example, a compound represented by formula (A1X) (hereinafter, sometimes referred to as compound (A1X)) can be mentioned. As specific examples of the compound represented by formula (A1X), for example, compounds represented by formulas (A1X-1) to (A1X-36) in Table 4 below can be mentioned.

[0304] [Chemistry 41]

[0305]

[0306] [Table 4]

[0307] Compound (A1X) <![CDATA[R 41a ]]> <![CDATA[R 42a ]]> <![CDATA[R 43a ]]> <![CDATA[R 44a ]]> <![CDATA[R 45a ]]> (A1X-1) H H RX1 H H (A1X-2) H H RX2 H H (A1X-3) H H RX3 H H (A1X-4) H H RX4 H H (A1X-5) H H RX5 H H (A1X-6) H H RY1 H H (A1X-7) H H RY2 H H (A1X-8) H H RY3 H H (A1X-9) H H RY4 H H (A1X-10) Me H RX1 H Me (A1X-11) Me H RX2 H Me (A1X-12) Me H RX3 H Me (A1X-13) Me H RX4 H Me (A1X-14) Me H RX5 H Me (A1X-15) Me H RY1 H Me (A1X-16) Me H RY2 H Me (A1X-17) Me H RY3 H Me (A1X-18) Me H RY4 H Me (A1X-19) H H H RX1 H (A1X-20) H H H RX2 H (A1X-21) H H H RX3 H (A1X-22) H H H RX4 H (A1X-23) H H H RX5 H (A1X-24) H H H RY1 H (A1X-25) H H H RY2 H (A1X-26) H H H RY3 H (A1X-27) H H H RY4 H (A1X-28) Me H Me RX1 Me (A1X-29) Me H Me RX2 Me (A1X-30) Me H Me RX3 Me (A1X-31) Me H Me RX4 Me (A1X-32) Me H Me RX5 Me (A1X-33) Me H Me RY1 Me (A1X-34) Me H Me RY2 Me (A1X-35) Me H Me RY3 Me (A1X-36) Me H Me RY4 Me

[0308] In Table 4, Me represents a methyl group, and RX1 to RX5 and RY1 to RY4 each represent a group represented by the following formula: In the formula, * represents a bond.

[0309] [Chemistry 42]

[0310]

[0311] Among the compounds represented by formulae (A1X-1) to (A1X-36), compounds represented by formulae (A1X-28) to (A1X-36) are more preferred, and compounds represented by formula (A1X-36) are particularly preferred.

[0312] The content of the anthraquinone compound (A1) in the total amount of the colorant (A) is, for example, 1 mass % or more, preferably 3 mass % or more, more preferably 5 mass % or more, and for example, 70 mass % or less, preferably 60 mass % or less, more preferably 50 mass % or less.

[0313] Furthermore, the content of the anthraquinone compound (A1) in the total amount of the triarylmethane lake and the anthraquinone compound (A1) is, for example, 5% by mass or more, preferably 10% by mass or more, more preferably 13% by mass or more, and for example, 70% by mass or less, preferably 60% by mass or less, more preferably 50% by mass or less, and further preferably 40% by mass or less.

[0314] The anthraquinone compound (A1) can be produced by a known method. The compound represented by the formula (A1X2) can be produced, for example, according to the following synthesis scheme.

[0315] [Chemistry 43]

[0316]

[0317] [Where A 1a , A 2a , R 1a ~R 6a , R 31a Synonymous with above. 51a represents an alkyl group having 1 to 4 carbon atoms.]

[0318] More specifically, the 1,4,9,10-tetrahydroxyanthracene represented by the formula (A1Z) can be oxidized and the hydroxyl group can be substituted with a hydroxylamine compound (specifically H 2 NA 1a -OH, H 2 NA 2a -OH) to produce a compound represented by formula (A1Y), and the compound represented by formula (A1Y) and a compound represented by formula Br-R 31a -CO 2 R 51a The compound represented by the present invention is condensed by removing HBr to generate an ether compound, and then -CO 2 R 51a The target compound (A1X2) is produced by hydrolysis of the radical.

[0319] <Colorant(A4)>

[0320] The colored resin composition of the present invention may contain a dye (hereinafter sometimes referred to as dye (AA)) and / or a pigment (hereinafter sometimes referred to as pigment (AB)) other than the above triarylmethane lake and anthraquinone compound (A1) as a colorant (A4).

[0321] The dye (AA) is not particularly limited as long as it does not contain the anthraquinone compound (A1), and a known dye can be used. Examples of the dye include solvent dyes, acid dyes, direct dyes, and mordant dyes.

[0322] As dye (AA), for example, the known dye described in the compound of the dye with the hue other than the pigment, the dyeing handbook (color dyeing society) that can be enumerated in the color index (dyeing home association (The Society of Dyers and Colourists) publication) can be enumerated. In addition, according to chemical structure, azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, phthalocyanine dyes, anthraquinone dyes (but excluding anthraquinone compound (A1)), naphthoquinone dyes, quinoneimine dyes, methine dyes, azo methine dyes, squarylium dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes and nitro dyes etc. can be enumerated. Among them, preferably organic solvent soluble dyes.

[0323] The content of the compound classified as a dye in the anthraquinone compound (A1) is, for example, 30% by mass or more, preferably 60% by mass or more, more preferably 90% by mass or more, and may be 95% by mass or more or 100% by mass in all dyes.

[0324] The pigment (AB) is not particularly limited as long as it does not contain a triarylmethane lake and anthraquinone compound (A1), and known pigments can be used. For example, pigments classified as pigments in the Color Index (published by The Society of Dyers and Colourists) can be mentioned.

[0325] Examples of the pigment (AB) include:

[0326] CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214 and other yellow pigments;

[0327] CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments;

[0328] CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265 and other red pigments;

[0329] CI Pigment Blue 15, 15:3, 15:4, 15:6, 60 and other blue pigments;

[0330] CI Pigment Violet 1, 19, 23, 29, 32, 36, 38 and other purple pigments;

[0331] CI Pigment Green 7, 36, 58 and other green pigments;

[0332] CI Pigment Brown 23, 25 and other brown pigments;

[0333] Black pigments such as CI Pigment Black 1, 7, etc.

[0334] The pigment may also be subjected to the following treatments as necessary: ​​rosin treatment, surface treatment using a pigment derivative having an acidic or basic group introduced therein, grafting treatment of the pigment surface using a polymer compound, micronization treatment using a sulfuric acid micronization method, or cleaning treatment using an organic solvent or water for removing impurities, removal of ionic impurities using an ion exchange method, etc.

[0335] The pigment preferably has a uniform particle size, and can be dispersed by adding a pigment dispersant to obtain a pigment dispersion in which the pigment is uniformly dispersed in a solution.

[0336] Examples of the pigment dispersant include the same pigment dispersants as those that can be used when preparing a color dispersion by dispersing the above-mentioned triarylmethane lake in a solvent.

[0337] In the pigment dispersion, the content of the pigment dispersant is preferably 1% by mass or more and 100% by mass or less, and more preferably 5% by mass or more and 50% by mass or less relative to the total amount of the pigment. If the content of the pigment dispersant is within the above range, there is a tendency to obtain a pigment dispersion in a uniform dispersed state.

[0338] The content of the colorant (A) in the colored resin composition is preferably 2 to 60% by mass, more preferably 5 to 50% by mass, and further preferably 8 to 40% by mass in the total amount of the solid content. When the content of the colorant (A) is within the above range, the color density when the color filter is prepared is sufficient, and the composition can contain the necessary amount of resin and polymerizable compound, so that a pattern with sufficient mechanical strength can be formed.

[0339] Here, the "total amount of solid content" in this specification means the amount after excluding the content of the solvent from the total amount of the colored resin composition. The total amount of solid content and the content of each component can be measured by a known analysis method such as liquid chromatography or gas chromatography.

[0340] <Resin (B)>

[0341] The resin (B) is not particularly limited, but is preferably an alkali-soluble resin, and more preferably a resin having a structural unit derived from at least one monomer (a) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (hereinafter sometimes referred to as "monomer (a)"). The resin (B) further preferably has at least one structural unit selected from the group consisting of the following structural units: a structural unit derived from a monomer (b) having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond (hereinafter sometimes referred to as "monomer (b)"); a structural unit derived from a monomer (c) (which is different from monomer (a) and monomer (b)) (hereinafter sometimes referred to as "monomer (c)") copolymerizable with the monomer (a); and a structural unit having an ethylenically unsaturated bond in a side chain.

[0342] Specific examples of the monomer (a) include acrylic acid, methacrylic acid, maleic anhydride, itaconic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, and mono[2-(meth)acryloyloxyethyl]succinate. Preferred examples include acrylic acid, methacrylic acid, and maleic anhydride.

[0343] The monomer (b) is preferably a monomer having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and a (meth)acryloyloxy group.

[0344] In addition, in this specification, "(meth)acrylic acid" means at least one selected from the group consisting of acrylic acid and methacrylic acid. Expressions such as "(meth)acryloyl" and "(meth)acrylate" have the same meaning.

[0345] Examples of the monomer (b) include glycidyl (meth)acrylate, vinylbenzyl glycidyl ether, (meth)acrylate-3,4-epoxytricyclo[5.2.1.0 2,6 ] decyl ester, 3-ethyl-3-(meth)acryloyloxymethyloxetane, tetrahydrofurfuryl (meth)acrylate, etc., preferably glycidyl (meth)acrylate, (meth)acrylate-3,4-epoxytricyclo[5.2.1.0 2,6 ]decyl ester, 3-ethyl-3-(meth)acryloyloxymethyloxetane.

[0346] Examples of the monomer (c) include (meth)acrylates such as methyl (meth)acrylate, butyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.02,6]decane-8-yl (meth)acrylate, benzyl (meth)acrylate, and 2-hydroxyethyl (meth)acrylate; maleimides such as N-phenylmaleimide, N-cyclohexylmaleimide, and N-benzylmaleimide; styrene-based monomers such as styrene and vinyltoluene, and preferably styrene, vinyltoluene, 2-hydroxyethyl (meth)acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, and N-benzylmaleimide.

[0347] The above-mentioned (meth)acrylates, maleimides, styrene-based monomers and the like can be appropriately combined, and a combination of (meth)acrylates and maleimides is preferred.

[0348] The structural unit having an ethylenically unsaturated bond in the side chain can be constructed as follows: a monomer (b) is added to a copolymer structure of a monomer (a) and a monomer (c); a monomer (a) is added to a copolymer structure of a monomer (b) and a monomer (c); or a monomer (a) is added to a copolymer structure of a monomer (b) and a monomer (c), and a carboxylic anhydride is further reacted.

[0349] The polystyrene-equivalent weight average molecular weight of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and even more preferably 5,000 to 30,000.

[0350] 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.

[0351] The acid value of the resin (B) is preferably 20 to 170 mg-KOH / g, more preferably 30 to 150 mg-KOH / g, and further preferably 40 to 135 mg-KOH / g in terms of solid content. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (B), and can be obtained by titration using, for example, a potassium hydroxide aqueous solution.

[0352] The content of the resin (B) in the total solid content of the colored resin composition is preferably 5 to 70% by mass, more preferably 15 to 60% by mass, and even more preferably 20 to 50% by mass.

[0353] <Polymerizable compound (C)>

[0354] The polymerizable compound (C) is a compound that can be polymerized by active radicals and / or acids generated from the polymerization initiator (D), and examples thereof include compounds having a polymerizable ethylenically unsaturated bond, and are preferably (meth)acrylate compounds.

[0355] 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 tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate.

[0356] The weight average molecular weight of the polymerizable compound (C) is preferably from 150 to 2,900, and more preferably from 250 to 1,500.

[0357] The content of the polymerizable compound (C) in the total solid content of the colored resin composition is preferably 5 to 65% by mass, more preferably 15 to 60% by mass, and even more preferably 20 to 50% by mass.

[0358] <Polymerization initiator (D)>

[0359] The polymerization initiator (D) is not particularly limited as long as it is a compound that can generate active free radicals, acids, etc. by the action of light or heat to initiate polymerization, and a known polymerization initiator can be used. Examples of the polymerization initiator that generates active free radicals include: N-benzoyloxy-1-(4-phenylthiophenyl)butane-1-one-2-imine, N-benzoyloxy-1-(4-phenylthiophenyl)octane-1-one-2-imine, N-benzoyloxy-1-(4-phenylthiophenyl)-3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1-(4-phenylthiophenyl)-3-cyclohexylpropane-1-one- 2-imine, 2-methyl-2-morpholino-1-(4-methylthiophenyl)propane-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, etc.

[0360] 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). If the content of the polymerization initiator (D) is within the above range, there is a tendency to increase the sensitivity and shorten the exposure time, thereby improving the productivity of the color filter.

[0361] <Polymerization initiator aid (D1)>

[0362] The colored resin composition of the present invention may contain a polymerization initiator aid (D1). The polymerization initiator aid (D1) is a compound or a sensitizer for accelerating the polymerization of a polymerizable compound that initiates polymerization by a polymerization initiator.

[0363] Examples of the polymerization initiator aid (D1) include 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, 9,10-dimethoxyanthracene, 2,4-diethylthioxanthone, and N-phenylglycine.

[0364] When these polymerization initiator aids (D1) are used, the content thereof 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). If the content of the polymerization initiator aid (D1) is within the above range, a color filter can be formed with higher density, and there is a tendency to improve the productivity of the color filter.

[0365] <Solvent (E)>

[0366] The colored resin composition preferably contains a solvent (E). The solvent (E) is not particularly limited, and a solvent commonly used in the art can be used. For example, an ester solvent (a solvent containing -COO- but not containing -O- in the molecule), an ether solvent (a solvent containing -O- but not containing -COO- in the molecule), an ether ester solvent (a solvent containing -COO- and -O- in the molecule), a ketone solvent (a solvent containing -CO- but not containing -COO- in the molecule), an alcohol solvent (a solvent containing OH but not containing -O-, -CO- and -COO- in the molecule), an aromatic hydrocarbon solvent, an amide solvent, dimethyl sulfoxide, etc. can be cited.

[0367] As the solvent, there can be mentioned:

[0368] Ester solvents such as ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, n-butyl acetate, ethyl butyrate, butyl butyrate, ethyl pyruvate, methyl acetoacetate, cyclohexanol acetate and γ-butyrolactone (solvents containing -COO- but not -O- in the molecule);

[0369] Ether solvents such as ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, 3-methoxy-1-butanol, diethylene glycol dimethyl ether, and diethylene glycol methyl ethyl ether (solvents containing -O- but not -COO- in the molecule);

[0370] Ether ester solvents (solvents containing -COO- and -O- in the molecule) such as methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and diethylene glycol monoethyl ether acetate;

[0371] Ketone solvents such as 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), heptanone, 4-methyl-2-pentanone, and cyclohexanone (solvents containing -CO- but not -COO- in the molecule);

[0372] Alcohol solvents such as butanol, cyclohexanol, and propylene glycol (solvents containing OH but not -O-, -CO-, and -COO- in the molecule);

[0373] Amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone; etc.

[0374] As the solvent, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol) and ethyl lactate are more preferred.

[0375] When the solvent (E) is included, the content of the solvent (E) is preferably 60 to 95% by mass, more preferably 65 to 92% by mass, in the total amount of the colored resin composition of the present invention. In other words, the total amount of the solid content of the colored resin composition is preferably 5 to 40% by mass, more preferably 8 to 35% by mass, in the total amount of the colored resin composition of the present invention. When the content of the solvent (E) is within the above range, the flatness during coating becomes good, and the color density is not insufficient when forming a color filter, so there is a tendency for the display characteristics to be improved.

[0376] <Leveling agent (F)>

[0377] The colored resin composition may contain a leveling agent (F). Examples of the leveling agent (F) include silicone-based surfactants, fluorine-based surfactants, and silicone-based surfactants having fluorine atoms. These may have a polymerizable group in their side chains.

[0378] As the silicone surfactant, there can be mentioned surfactants having a siloxane bond in the molecule, etc. Specifically, there can be mentioned Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (trade name: manufactured by Toray Dow Corning Co., Ltd.); KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.); TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (manufactured by Momentive Advanced Materials Japan Co., Ltd.).

[0379] Examples of the fluorine-based surfactant 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), Eftop (registered trademark) EF301, Eftop EF303, Eftop EF351, Eftop EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Surflon (registered trademark) S381, Surflon S382, Surflon SC101, Surflon SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemicals Laboratories, Ltd.), etc.

[0380] Examples of the above-mentioned organosilicon-based surfactants having fluorine atoms 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) and the like.

[0381] When a leveling agent (F) is included, the content of the leveling agent (F) is preferably 0.001 to 0.2 mass %, more preferably 0.002 to 0.1 mass % in the total amount of the colored resin composition. It should be noted that the content does not include the content of the pigment dispersant. If the content of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.

[0382] <Other ingredients>

[0383] The colored resin composition of the present invention may contain additives known in the art, such as a filler, a polymer compound, an adhesion promoter, an antioxidant, a light stabilizer, and a chain transfer agent, as necessary.

[0384] <Method for producing colored resin composition>

[0385] The colored resin composition of the present invention can be prepared by mixing a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and, if necessary, a polymerization initiation aid (D1), a solvent (E), a leveling agent (F), and other components.

[0386] <Method for manufacturing color filter>

[0387] Examples of a method for producing a colored pattern (color filter) from the colored resin composition of the present invention include a photolithography method, an inkjet method, and a printing method. Among them, a photolithography method is preferred.

[0388] In order to correct the height difference between pixels and improve the flatness, the color filter may be laminated with an overcoat layer. As the curable composition for the overcoat layer, a known binder resin can be used.

[0389] Since the colored resin composition contains triarylmethane lake and anthraquinone compound (A1), the color filter produced from the colored resin composition has excellent light resistance and heat resistance, and also has excellent heat resistance when the overcoat layer is laminated. The color filter is useful as a color filter used in display devices (e.g., liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state imaging elements. Example

[0390] Hereinafter, the present invention will be described in more detail with reference to the following examples. Of course, the present invention is not limited to the following examples, and can be implemented by appropriately changing the scope of the present invention within the scope of the context, which are all included in the technical scope of the present invention. It should be noted that, unless otherwise specified below, "parts" means "parts by mass", and "%" means "% by mass".

[0391] In the following examples, the structures of the compounds were confirmed by mass spectrometry (LC: Model 1200 manufactured by Agilent, MASS: Model LC / MSD manufactured by Agilent).

[0392] [Synthesis example 1]

[0393] The following reaction was carried out under a nitrogen atmosphere. 50 parts of the compound represented by formula (CI-2) and 188 parts of N,N-dimethylformamide were added to a flask equipped with a condenser and a stirring device, and stirred for 30 minutes while cooling in an ice bath. 40 parts of potassium tert-butoxide (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to the flask, and further stirred for 1 hour while cooling in an ice bath. 55.6 parts of iodoethane (manufactured by Tokyo Chemical Industry Co., Ltd.) were added dropwise while keeping the reaction mixture ice-cold. The reaction mixture was heated to 35°C using an oil bath and stirred for 5 hours, then allowed to stand and cool to room temperature. 1000 parts of a 10% sodium chloride aqueous solution were added to another flask equipped with a stirring device, and the above reaction mixture was added dropwise while stirring. After stirring for 30 minutes, the solid was filtered. The obtained solid was washed 3 times with 500 parts of ion exchange water, dried at 60°C under reduced pressure, and 53.0 parts of the compound represented by formula (CI-3) were obtained. The yield was 93.5%.

[0394] [Chemistry 44]

[0395]

[0396] [Chemistry 45]

[0397]

[0398] The following reaction was carried out under a nitrogen atmosphere. After adding 26.4 parts of potassium thiocyanate and 156 parts of acetonitrile to a flask equipped with a condenser and a stirring device, stir at room temperature for 30 minutes. After 40.0 parts of 2,6-difluorobenzoyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was dripped into the above flask over 30 minutes, it was stirred at room temperature for 1 hour. After 30.6 parts of N-ethyl-o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was dripped into the above flask over 30 minutes, it was stirred at room temperature for 1 hour. Into the above flask, an aqueous solution prepared by dissolving 79.2 parts of sodium monochloroacetate in 120 parts of ion exchange water and 60.4 parts of a 30% sodium hydroxide aqueous solution were added, and stirred at room temperature for 18 hours. After further adding 600 parts of ion exchange water to the above flask, stir for 1 hour, and filter out the precipitated yellow-white solid. The obtained yellow-white solid was washed with 120 parts of acetonitrile and then washed with 560 parts of ion exchange water. In a flask equipped with a stirring device, the washed yellow-white solid, 156 parts of ion exchange water, 35.0 parts of 99% acetic acid (produced by Wako Pure Chemical Industries, Ltd.) and 156 parts of toluene were placed and stirred at room temperature for 2 hours. 80.8 parts of 30% sodium hydroxide aqueous solution were added dropwise over 10 minutes, stirred for 5 minutes, and the water layer was removed by liquid separation. 156 parts of ion exchange water were added to the obtained organic layer for liquid separation and washing, and then 156 parts of ion exchange water and 0.1 parts of 35% hydrochloric acid were added for liquid separation and washing. The obtained organic layer was concentrated using an evaporator and dried under reduced pressure at 35°C to obtain a compound represented by formula (BI-3) as a white solid. The yield was 43.4 parts, and the yield was 58.0%.

[0399] [Chemistry 46]

[0400]

[0401] The following reaction is carried out under a nitrogen atmosphere. After 13.2 parts of the compound represented by formula (BI-3), 19.0 parts of the compound represented by formula (CI-3) and 38 parts of toluene are added to a flask equipped with a condenser and a stirring device, 9.2 parts of phosphorus oxychloride are added and stirred at 100°C for 7 hours. Then, the reaction mixture is cooled to room temperature and diluted with 29 parts of methyl ethyl ketone. Then, a mixed solution of 114 parts of ion exchange water and 10 parts of 35% hydrochloric acid aqueous solution is injected into the diluted reaction mixture, and the water layer is removed by liquid separation. The obtained organic layer is subjected to solvent distillation using an evaporator and then dried at 60°C under reduced pressure to obtain a compound represented by formula (X-II-7) as a bluish purple solid. The yield of the bluish purple solid is 39.4 parts.

[0402] [Chemistry 47]

[0403]

[0404] The following reaction was carried out under a nitrogen atmosphere. 38.4 parts of the compound represented by formula (X-II-7) and 112 parts of dichloromethane were added to a flask equipped with a condenser and a stirring device and stirred for 30 minutes. The reaction mixture was cooled and 31.6 parts of chlorosulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were added while the internal temperature was maintained at 10°C, and then the reaction mixture was warmed to room temperature and stirred for 9 hours. The reaction mixture was then cooled and diluted with a mixed solution of 64 parts of N,N-dimethylformamide and 4.9 parts of ion exchange water while the internal temperature was maintained at 10°C. If the diluted reaction mixture is injected into 1120 parts of toluene and stirred for 30 minutes, a viscous solid will precipitate. After the oil layer was discharged by decantation, 320 parts of toluene were added to the obtained viscous solid and stirred for 30 minutes. After 832 parts of 20% brine was added to the viscous solid obtained after the oil layer was discharged by decantation and stirred for 1 hour, the blue solid was filtered out. The obtained blue solid was washed with 576 parts of 20% saline and dried under reduced pressure at 35°C. The obtained solid and 128 parts of methanol were added to a flask equipped with a stirring device and stirred for 30 minutes before filtering to separate the solid and the filtrate. The filtrate was set as filtrate I. The filtered solid was washed with 192 parts of methanol, and the solid and the filtrate were separated by filtration. The filtrate was set as filtrate II. Filtrate I and filtrate II were mixed and the solvent was removed by an evaporator, and then dried under reduced pressure at 40°C to obtain a compound represented by formula (XI-7) as a bluish purple solid. The yield of the bluish purple solid was 38.3 parts.

[0405] [Chemistry 48]

[0406]

[0407] In a flask equipped with a condenser and a stirring device, 28.0 parts of a compound represented by formula (XI-7), 43.2 parts of barium chloride dihydrate and 356 parts of ion exchange water were added, and after stirring at 40°C for 2 hours, the reaction mixture was filtered. After the filtered solid and 350 parts of ion exchange water were added to a flask equipped with a stirring device and stirred for 30 minutes, the suspension was filtered. After the obtained solid was washed with 280 parts of ion exchange water, it was dried under reduced pressure at 60°C to obtain a compound represented by formula (A3-7) as a bluish purple solid. The yield was 24.5 parts, and the yield was 81.7%.

[0408] [Chemistry 49]

[0409]

[0410] Identification of the compound represented by formula (A3-7)

[0411] (Mass analysis) Ionization mode = ESI+: m / z = 949.5 [M-Ba + 2H]+

[0412] Exact Mass [M-Ba]: 947.28

[0413] [Synthesis example 2]

[0414] The following reaction is carried out under a nitrogen atmosphere. After adding 32.2 parts of potassium thiocyanate and 160 parts of acetone into a flask equipped with a condenser and a stirring device, stir at room temperature for 30 minutes. Then, 50.0 parts of 2-fluorobenzoyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) are added dropwise over 10 minutes. After the addition is completed, stir further at room temperature for 2 hours. Then, after the reaction mixture is ice-cooled, 40.5 parts of N-ethyl-o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) are added dropwise. After the addition is completed, stir further at room temperature for 30 minutes. Then, after the reaction mixture is ice-cooled, 34.2 parts of a 30% aqueous sodium hydroxide solution are added dropwise. After the addition is completed, stir further at room temperature for 30 minutes. Then, 31.3 parts of chloroacetic acid are added dropwise at room temperature. After the addition is completed, stir for 7 hours under heating reflux. Then, after the reaction mixture is allowed to stand and cool to room temperature, the reaction mixture is injected into 120.0 parts of ion exchange water, and 200 parts of toluene are added and stirred for 30 minutes. Then stop stirring, let stand for 30 minutes, and separate the organic layer and the aqueous layer. After removing the aqueous layer by liquid separation operation, the organic layer is washed with 200 parts of 1N hydrochloric acid, then washed with 200 parts of ion exchange water, and finally washed with 200 parts of saturated brine. After adding an appropriate amount of sodium sulfate to the organic layer and stirring for 30 minutes, filter to obtain a dry organic layer. The obtained organic layer is subjected to solvent distillation using an evaporator to obtain a light yellow liquid. The obtained light yellow liquid is refined using column chromatography. The refined light yellow liquid is dried at 60°C under reduced pressure to obtain 49.9 parts of the compound represented by formula (B-II). The yield is 51%.

[0415] [Chemistry 50]

[0416]

[0417] The following reaction is carried out under a nitrogen atmosphere. After 15.3 parts of N-methylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) and 60 parts of N,N-dimethylformamide are added to a flask equipped with a condenser and a stirring device, the mixed solution is ice-cooled. After 5.7 parts of 60% sodium hydride (manufactured by Tokyo Chemical Industry Co., Ltd.) are added little by little over 30 minutes under ice cooling, the mixture is stirred for 1 hour while warming to room temperature. Next, 10.4 parts of 4,4'-difluorobenzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) are added little by little to the reaction mixture and stirred at room temperature for 24 hours. After the reaction mixture is added little by little to 200 parts of ice water, it is allowed to stand at room temperature for 15 hours, and the water is removed by decantation to obtain a sticky solid as a residue. After 60 parts of methanol are added to the sticky solid, it is stirred at room temperature for 15 hours. After filtering out the precipitated solid, it is purified by column chromatography. The purified light yellow solid was dried at 60°C under reduced pressure to obtain 9.8 parts of a compound represented by formula (C-II) with a yield of 53%.

[0418] [Chemistry 51]

[0419]

[0420] The following reaction is carried out under a nitrogen atmosphere. After 8.2 parts of the compound represented by formula (B-II), 10.0 parts of the compound represented by formula (C-II) and 20.0 parts of toluene are put into a flask equipped with a condenser and a stirring device, 12.2 parts of phosphorus oxychloride are added and stirred at 95-100°C for 3 hours. Then, the reaction mixture is cooled to room temperature and diluted with 170.0 parts of isopropanol. Then, after the diluted reaction mixture is injected into 300.0 parts of saturated brine, 100 parts of toluene are added and stirred for 30 minutes. Stop stirring, let stand for 30 minutes, and then separate the organic layer and the aqueous layer. After removing the aqueous layer by liquid separation operation, the organic layer is washed with 300 parts of saturated brine. After adding an appropriate amount of Glauber's salt to the organic layer and stirring for 30 minutes, filter to obtain a dry organic layer. The obtained organic layer is solvent distilled using an evaporator to obtain a bluish purple solid. Furthermore, the blue-purple solid was dried at 60° C. under reduced pressure to obtain 18.4 parts of a compound represented by the formula (YI-41). The yield was 100%.

[0421] [Chemistry 52]

[0422]

[0423] Identification of the compound represented by formula (YI-41)

[0424] (Mass analysis) Ionization mode = ESI+: m / z = 687.3 [M-Cl] +

[0425] Exact mass: 722.3

[0426] The following reaction was carried out under a nitrogen atmosphere. 8.0 parts of the compound represented by the formula (YI-41) and 396.0 parts of methanol were added to a flask equipped with a condenser and a stirring device, and stirred at room temperature for 30 minutes to prepare a blue solution. Then, 396.0 parts of ion exchange water were added to the blue solution, and further stirred at room temperature for 30 minutes to obtain a reaction mixture.

[0427] 53 parts of ion-exchanged water were placed in a beaker, and 11.8 parts of Keggin-type phosphotungstic acid (manufactured by Aldrich) and 53 parts of methanol were further placed in the ion-exchanged water, and the mixture was mixed at room temperature in an air atmosphere to prepare a phosphotungstic acid solution.

[0428] The obtained phosphotungstic acid solution was added dropwise to the pre-modulated reaction mixture over 1 hour. After further stirring at room temperature for 30 minutes, a blue solid was obtained by filtration. The obtained blue solid was put into 200.0 parts of methanol and dispersed for 1 hour, and the filtering operation was repeated twice. The blue solid obtained by the operation was put into 200.0 parts of ion exchange water and dispersed for 1 hour, and the filtering operation was repeated twice. The blue solid obtained by the operation was dried at 60 ° C under reduced pressure to obtain 17.1 parts of the compound represented by formula (A2-41). The yield was 94%.

[0429] [Chemistry 53]

[0430]

[0431] [Synthesis example 3]

[0432] 66.9 parts of chlorosulfonic acid were added to a flask equipped with a condenser and a stirring device, cooled to below 10°C, and 3.6 parts of CI Solvent Blue 104 (the compound represented by formula (A1Y-1)) were slowly added under stirring. Then, the reaction mixture was allowed to warm up to room temperature (25°C) on its own and stirred at the same temperature for 6 hours. The resulting reaction mixture was added dropwise to 108 parts of ice water to prepare a suspension, the precipitated crystals were filtered out, carefully washed with ion exchange water, and dried under reduced pressure at 60°C overnight to obtain 4.9 parts of a crude product of the compound represented by formula (A1Y-2). It was purified by silica gel column chromatography (solvent: chloroform) to obtain 3.4 parts of the compound represented by formula (A1Y-2).

[0433] [Chemistry 54]

[0434]

[0435] In a flask equipped with a condenser and a stirring device, 4.6 parts of methyl 3-amino-4-methylbenzoate and 16.5 parts of chloroform were added, cooled to below 10°C, and a solution of 2.4 parts of the compound represented by formula (A1Y-2) dissolved in 16.5 parts of chloroform and 2.2 parts of pyridine were added dropwise in sequence under stirring. Then, the reaction mixture was allowed to warm up to room temperature by itself and stirred at the same temperature for 5 hours. 150 parts of chloroform and 50 parts of 2N hydrochloric acid were added to the obtained reaction mixture and the liquid was separated, and the organic layer was washed twice with 50 parts of 2N hydrochloric acid. The obtained organic layer was dried with excess sodium sulfate, and chloroform was removed from the solution obtained after filtration under reduced pressure to obtain 3.4 parts of a crude product of the compound represented by formula (A1Y-3). It was purified by silica gel column chromatography (solvent: chloroform) to obtain 2.8 parts of the compound represented by formula (A1Y-3).

[0436] [Chemistry 55]

[0437]

[0438] Identification of the compound represented by formula (A1Y-3)

[0439] (Mass analysis) Ionization mode = ESI+: m / z = 929.2 [M+H] +

[0440] Exact mass: 928.3

[0441] In a flask equipped with a condenser and a stirring device, 2.5 parts of the compound represented by the formula (A1Y-3), 35 parts of N-methylpyrrolidone and 17 parts of an 8% sodium hydroxide aqueous solution were added and stirred at 50°C for 5 hours. After standing and cooling, the obtained reaction mixture was added to 175 parts of 2N hydrochloric acid to prepare a suspension, and the precipitated crystals were filtered out, carefully washed with ion exchange water, and dried under reduced pressure at 60°C overnight to obtain 2.1 parts of the compound represented by the formula (A1X-36).

[0442] [Chemistry 56]

[0443]

[0444] Identification of the compound represented by formula (A1X-36)

[0445] (Mass analysis) Ionization mode = ESI+: m / z = 901.2 [M+H] +

[0446] Exact mass: 900.3

[0447] [Synthesis example 4]

[0448] In a flask equipped with a reflux condenser, a dropping funnel, and a stirrer, a proper amount of nitrogen was introduced to replace the atmosphere with nitrogen, 141 parts of ethyl lactate and 178 parts of propylene glycol monomethyl ether acetate were added, and the mixture was heated to 85° C. while stirring. Then, 38 parts of acrylic acid and 3,4-epoxytricyclo[5.2.1.0 2,6 ]decane-8-yl ester and acrylate-3,4-epoxytricyclo[5.2.1.0 2,6 ] A mixed solution of 25 parts of a mixture of decane-9-yl ester (containing a molar ratio of 1:1), 137 parts of N-cyclohexylmaleimide, 50 parts of 2-hydroxyethyl methacrylate, and 338 parts of propylene glycol monomethyl ether acetate. On the other hand, a solution prepared by dissolving 5 parts of 2,2-azobisisobutyronitrile in 88 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After the addition was completed, the mixture was kept at 85°C for 4 hours and then cooled to room temperature to obtain a copolymer (resin B1) solution having a viscosity of 23 mPas and a solid content of 25.6% as measured by a B-type viscometer (23°C). The weight average molecular weight Mw of the resulting copolymer is 8.0×10 3 , a dispersion degree of 2.1, and an acid value of 111 mg-KOH / g in terms of solid content. Resin B1 has the following structural units.

[0449] [Chemistry 57]

[0450]

[0451] The weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin were measured using a GPC method under the following conditions.

[0452] Device: K2479 (manufactured by Shimadzu Corporation)

[0453] Column: SHIMADZU Shim-pack GPC-80M

[0454] Column temperature: 40°C

[0455] Solvent: THF (tetrahydrofuran)

[0456] Test solution concentration: 25 mg / mL (solvent: THF)

[0457] Flow rate: 1.0mL / min

[0458] Detector: RI

[0459] Calibration standard substances: TSK standard polystyrene F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)

[0460] The ratio of the polystyrene-equivalent weight average molecular weight and the number average molecular weight obtained above is defined as the dispersion degree (Mw / Mn).

[0461] [Example 1]

[0462] <Preparation of Colored Resin Composition 1>

[0463] (A) Coloring agent: 21 parts of the compound represented by formula (A3-7)

[0464] 9 parts of acrylic pigment dispersant

[0465] 264 parts of propylene glycol monomethyl ether acetate

[0466] The mixture was mixed and the compound represented by formula (A3-7) was fully dispersed using a bead mill.

[0467] (A) Colorant: 5 parts of a compound represented by formula (A1X-36)

[0468] (B) Resin: Resin B1 (solid content conversion) 50 parts

[0469] (C) Polymerizable compound: 50 parts of dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)

[0470] (D) Polymerization initiator: 7 parts of N-benzoyloxy-1-(4-phenylthiophenyl)octan-1-one-2-imine (IRGACURE (registered trademark) OXE 01; manufactured by BASF)

[0471] (F) Leveling agent: 0.1 part of polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Dow Corning Toray Corporation)

[0472] (E) Solvent: 517 parts of propylene glycol monomethyl ether acetate

[0473] (E) Solvent: 23 parts of ethyl lactate

[0474] The mixture was mixed to obtain a colored resin composition 1.

[0475] [Example 2]

[0476] <Preparation of Colored Resin Composition 2>

[0477] (A) Coloring agent: 11 parts of the compound represented by formula (A2-41)

[0478] 4 parts of acrylic pigment dispersant

[0479] Propylene glycol monomethyl ether acetate 129 parts

[0480] 5 parts of diacetone alcohol

[0481] Mix and fully disperse the compound represented by formula (A2-41) using a bead mill, and then

[0482] (A) Colorant: 5 parts of a compound represented by formula (A1X-36)

[0483] (B) Resin: Resin B1 (solid content conversion) 50 parts

[0484] (C) Polymerizable compound: 50 parts of dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)

[0485] (D) Polymerization initiator: 7 parts of N-benzoyloxy-1-(4-phenylthiophenyl)octan-1-one-2-imine (IRGACURE (registered trademark) OXE 01; manufactured by BASF Corporation)

[0486] (F) Leveling agent: 0.1 part of polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Dow Corning Toray Corporation)

[0487] (E) Solvent: 674 parts of propylene glycol monomethyl ether acetate

[0488] (E) Solvent: 26 parts of ethyl lactate

[0489] The colored resin composition 2 was obtained by mixing.

[0490] [Comparative Example 1]

[0491] <Preparation of Colored Resin Composition 3>

[0492] (A) Colorant: 20 parts of the compound represented by formula (A3-7)

[0493] 8 parts of acrylic pigment dispersant

[0494] 252 parts of propylene glycol monomethyl ether acetate

[0495] The mixture was mixed and the compound represented by formula (A3-7) was fully dispersed using a bead mill.

[0496] (B) Resin: 50 parts of Resin B1 (solid content conversion)

[0497] (C) Polymerizable compound: 50 parts of dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)

[0498] (D) Polymerization initiator: 7 parts of N-benzoyloxy-1-(4-phenylthiophenyl)octan-1-one-2-imine (IRGACURE (registered trademark) OXE01; manufactured by BASF)

[0499] (F) Leveling agent: 0.1 part of polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Dow Corning Toray Corporation)

[0500] (E) Solvent: 493 parts of propylene glycol monomethyl ether acetate

[0501] (E) Solvent: 23 parts of ethyl lactate

[0502] The mixture was mixed to obtain a colored resin composition 3.

[0503] <Production of color filters (coloring patterns)>

[0504] The colored resin composition was applied by spin coating on a 5 cm square glass substrate (Eagle 2000; manufactured by Corning Incorporated) and then pre-baked at 100°C for 3 minutes to obtain a colored resin composition layer. After cooling, the substrate on which the colored resin composition layer was formed and a quartz glass photomask were set to have a gap of 100 μ0, and an exposure machine (TME-150RSK; manufactured by Topcon) was used to expose the substrate at 150 mJ / cm 2 The light was irradiated with an exposure amount (365 nm reference). As a photomask, a photomask with a 100 μ0 line and space pattern was used. The colored resin composition layer after light irradiation was immersed in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 24°C for 60 seconds, and after washing with water, it was post-baked in an oven at 230°C for 20 minutes to obtain a color filter.

[0505] <Film thickness measurement>

[0506] The film thickness of the obtained color filter was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.)).

[0507] <Chroma Evaluation>

[0508] The obtained color filter was measured for spectroscopy using a colorimeter (OSP-SP-200; manufactured by Olympus Corporation), and the xy chromaticity coordinates (x, y) and the stimulus value Y in the XYZ colorimetric system of CIE were measured using the colorimetric function of the C illuminant. A larger Y value indicates higher brightness.

[0509] <Lightfastness Evaluation>

[0510] An ultraviolet cut filter (COLORED OPTICAL GLASS L38; manufactured by Hoya Co., Ltd.; cuts off light of 380 nm or less) was placed on the obtained color filter, and irradiated with xenon light for 48 hours using a light resistance tester (SUNTEST GPS+; manufactured by Toyo Seiki Seisaku-sho, Ltd.).

[0511] The xy chromaticity coordinates (x, y) and Y were measured before and after irradiation, and the color difference A (the color difference A is ΔE*ab before and after light irradiation) was calculated using the method described in JIS Z 8730:2009 (7. Color difference calculation method) from the measured values. The results are shown in Table 5. The smaller the color difference A, the smaller the color change.

[0512] [Table 5]

[0513] Color difference A Example 1 8.2 Example 2 3.1 Comparative Example 1 33.0

[0514] <Preparation of curable composition for outer cover layer>

[0515] A curable composition for an outer coating layer was prepared by mixing 60 parts of a styrene / methacrylic acid / glycidyl methacrylate copolymer (mass ratio of 30 / 20 / 50; synthesized by the method described in Japanese Patent Application Laid-Open No. 11-133600; molecular weight of 21,000), 40 parts of dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.), 6 parts of 2-methyl-2-morpholino-1-(4-methylthiophenyl)propane-1-one (IRGACURE (registered trademark) 907; manufactured by BASF), and 197 parts of diethylene glycol dimethyl ether.

[0516] <Evaluation of heat resistance of laminated film>

[0517] The above-mentioned curable composition for outer covering layer was applied to the obtained color filter by spin coating so that the film thickness after drying was 1.5 μ., and then the pre-baking was performed at 100° C. for 3 minutes and the post-baking was performed at 230° C. for 20 minutes in a clean oven to prepare a laminated film. The laminated film was heated at 230° C. for 2 hours in a clean oven, and the color difference B (the color difference B is ΔE*ab before and after heating when it is a laminated film) was calculated by the method described in JIS Z 8730: 2009 (7. Calculation method of color difference) from the xy chromaticity coordinates (x, y) and Y measurement values ​​before and after heating, and the improvement rate was further calculated, and the results are shown in Table 6. It should be noted that in the present invention, the improvement rate refers to the degree of improvement in heat resistance of the colored resin composition of the embodiment as a laminated film relative to the colored resin composition 3 of Comparative Example 1. That is, the improvement rate is represented by the following formula (i).

[0518] Improvement rate (%) = (color difference B of comparative example 1 / color difference B of example) × 100 (i)

[0519] A larger improvement rate value means a smaller color change.

[0520] [Table 6]

[0521]

[0522] Industrial Applicability

[0523] According to the colored resin composition of the present invention, a color filter having good light resistance, heat resistance, and heat resistance in a state where an overcoat layer is laminated can be formed. The color filter is useful as a color filter used in a display device (e.g., a liquid crystal display device, an organic EL device, an electronic paper, etc.) and a solid-state imaging element.

Claims

1. A colored resin composition comprising a colorant, a resin, a polymerizable compound and a polymerization initiator, The colorant comprises a triarylmethane lake and a compound represented by formula (A1), The triarylmethane lake is at least one selected from the group consisting of a compound represented by formula (A2) and a compound represented by formula (A3), In formula (A1), A 1a and A 2a each independently represents a phenylene group which may have a substituent, L 1a and L 2a Each independently represents -SO2NHR 32a -, R 32a represents a phenylene group which may be bonded to an alkyl group having 1 to 4 carbon atoms, R 1a ~R 6a Each independently represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 8 carbon atoms, and R 11a represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, In formula (A2), R 11b ~R 14b Each independently represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, wherein the hydrogen atom contained in the saturated hydrocarbon group having 1 to 20 carbon atoms may be substituted by a substituted or unsubstituted amino group or a halogen atom, and when the saturated hydrocarbon group has 2 to 20 carbon atoms, the -CH2- contained in the saturated hydrocarbon group may be substituted by -O- or -CO-, but in the saturated hydrocarbon group having 2 to 20 carbon atoms, adjacent -CH2- may not be substituted by -O- at the same time, and R 11b With R 12b can combine to form a ring with the nitrogen atom to which they are bound, R 13b With R 14b can combine to form a ring with the nitrogen atom to which they are bound, R 17b ~R 24b Each independently represents a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, or an alkyl group having 1 to 8 carbon atoms, wherein the -CH2- group constituting the alkyl group may be substituted by -O- or -CO-, and R 18b and R 22b Can combine with each other to form -NH-, -O-, -S- or -SO2-, Ring T 1b represents an aromatic heterocyclic ring having 3 to 10 carbon atoms which may have a substituent or an aromatic hydrocarbon ring having 6 to 10 carbon atoms which may have a substituent, [Y] m- represents any m-valent anion containing at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus, and oxygen, m represents any natural number, In addition, when a molecule contains a plurality of structures represented by the following formulae, they may be the same structure or different structures. Chemical formula 1 In Chemical Formula 1, ring T 1b , R 11b ~R 14b and R 17b ~R 24b Each has the same meaning as above, In formula (A3), R 41b ~R 44b Each independently represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, and the substituents which the aromatic hydrocarbon group and the aralkyl group may have may be -SO3 - or -SO2-N - -SO2-R f The hydrogen atoms contained in the saturated hydrocarbon group may be substituted by substituted or unsubstituted amino groups or halogen atoms. When the carbon number of the saturated hydrocarbon group is 2 to 20, the -CH2- contained in the saturated hydrocarbon group may be substituted by -O- or -CO-. However, in the saturated hydrocarbon group with 2 to 20 carbon atoms, adjacent -CH2- will not be substituted by -O- at the same time. R 41b With R 42b can combine to form a ring with the nitrogen atom to which they are bound, R 43b With R 44b can combine to form a ring with the nitrogen atom to which they are bound, R 47b ~R 54b Each independently represents a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, -SO3 - 、-SO2-N - -SO2-R f , or an alkyl group having 1 to 8 carbon atoms, wherein the -CH2- constituting the alkyl group may be substituted by -O- or -CO-, and R 48b With R 52b They can combine with each other to form -NH-, -S-, or -SO2-, but in the alkyl group, adjacent -CH2- will not be replaced by -O- at the same time. Ring T 2b represents an aromatic heterocyclic ring having 3 to 10 carbon atoms or an aromatic hydrocarbon ring having 6 to 10 carbon atoms, wherein the aromatic heterocyclic ring and the aromatic hydrocarbon ring may have a saturated hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted amino group, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, and the substituent which the aromatic hydrocarbon group may have may be -SO3 - or -SO2-N - -SO2-R f , M r+ represents a metal ion with a valence of r, k represents R 41b ~R 44b , R 47b ~R 54b and Ring T 2b -SO3 - The number and -SO2-N - -SO2-R f The sum of the number of r represents an integer greater than 1, R f represents a fluoroalkyl group having 1 to 12 carbon atoms, in, R 41b ~R 44b , R 47b ~R 54b and Ring T 2b With at least one -SO3 - or -SO2-N - -SO2-R f , In addition, when a molecule contains a plurality of structures represented by the following formulae, they may be the same structure or different structures. Chemical formula 2 In Chemical Formula 2, ring T 2b , R 41b ~R 44b and R 47b ~R 54b Each has the same meaning as above. 2 . A color filter formed from the colored resin composition according to claim 1 . A display device comprising the color filter according to claim 2 .

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