JP2016027149A - Colored curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored curable resin composition that forms a color filter having excellent chemical resistance.SOLUTION: There is provided a colored curable resin composition comprising a blue dye, a resin, a polymerizable compound, a polymerization initiator and a silsesquioxane compound. In the colored curable resin composition, the content of the silsesquioxane compound is preferably 25-3000 pts. mass based on 100 pts.mass of the blue dye.SELECTED DRAWING: None

Description

  The present invention relates to a colored curable resin composition.

  Japanese Patent Application Laid-Open No. 2012-83652 describes a colored curable resin composition comprising a blue dye, a binder resin, a photopolymerizable monomer, a photopolymerization initiator, and a solvent.

JP 2012-83651 A

  The further improvement of the chemical resistance of the color filter formed from said colored curable resin composition was calculated | required.

The present invention includes the following inventions.
[1] A colored curable resin composition containing a blue dye, a resin, a polymerizable compound, a polymerization initiator, and a silsesquioxane compound.
[2] The colored curable resin composition according to [1], wherein the content of the silsesquioxane compound is 25 to 3000 parts by mass with respect to 100 parts by mass of the blue dye.
[3] The blue dye includes at least one dye selected from the group consisting of a phthalocyanine dye, a triarylmethane dye, an anthraquinone dye, a cyanine dye, a porphyrin dye, and a thiazole dye, according to [1] or [2] Colored curable resin composition.
[4] The colored curable resin according to [1] or [2], wherein the blue dye is a compound having an anion having at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus and an oxygen atom. Composition.
[5] The colored curable resin composition according to [1] or [2], wherein the blue dye includes a compound represented by the formula (AI).

[In formula (AI), [Y ² ] ^m− represents an arbitrary m-valent anion.
R ^{41 to} R ⁴⁴ each independently represents a hydrogen atom, an optionally substituted saturated hydrocarbon group having 1 to 20 carbon atoms, or an oxygen atom between carbon atoms constituting an alkyl group having 2 to 20 carbon atoms. It represents an inserted group, an optionally substituted aryl group, or an optionally substituted aralkyl group. R ⁴¹ and R ⁴² may be bonded to form a ring with the nitrogen atom to which they are bonded, or R ⁴³ and R ⁴⁴ may be bonded to form a ring with the nitrogen atom to which they are bonded.
R ^{45 to} R ⁵² each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, a saturated hydrocarbon group having 1 to 8 carbon atoms, or a carbon atom constituting an alkyl group having 2 to 8 carbon atoms. Represents a group in which an oxygen atom is inserted, or R ⁴⁶ and R ⁵⁰ may be bonded to each other to form —O—, —NH—, —S— or —SO ₂ —.
Y ¹ represents an optionally substituted aryl group or an optionally substituted heteroaryl group.
When the compound represented by the formula (AI) includes a plurality of cations, the plurality of cations may have the same structure or different structures.
m represents an arbitrary natural number. ]
[6] A color filter formed from the colored curable resin composition according to [1] or [2].
[7] A display device including the color filter according to [6].

  Provided is a colored curable resin composition capable of forming a color filter having good chemical resistance.

The colored curable resin composition of the present invention contains a blue dye, a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a silsesquioxane compound (H).
The colored curable resin composition of the present invention further contains a solvent (E), a thiol compound (T), an antioxidant (G), a polymerization initiation assistant (D1) and / or a leveling agent (F). Among them, it is preferable to contain a solvent (E), a thiol compound (T), an antioxidant (G) and / or a leveling agent (F).

<Blue dye (A)>
In the present invention, the blue dye means a dye having a maximum absorption wavelength in a range of 580 nm to 650 nm in a chloroform solution. The blue dye is preferably a dye having a maximum absorption wavelength in the range of 590 nm to 645 nm, and more preferably a dye having a maximum absorption wavelength in the range of 600 nm to 645 nm.
The blue dye in the present invention includes a compound converted from a dye having a maximum absorption wavelength in the range of 580 nm to 650 nm and having a polyacid anion described later.

If the maximum absorption wavelength of the dye is in the range of 580 nm or more and 650 nm or less, the dye is not particularly limited, and a known dye can be used.
Examples of blue dyes include compounds classified as having a hue other than pigment in the Color Index (published by The Society of Dyers and Colorists), and known dyes described in Dyeing Notes (Color Dye). Can be mentioned. In addition, according to the chemical structure, phthalocyanine dyes, diarylmethane dyes, triarylmethane dyes, anthraquinone dyes, polymethine dyes, azomethine dyes, cyanine dyes, porphyrin dyes, thiazole dyes, etc., preferably phthalocyanine dyes, triaryl dyes Methane dye, anthraquinone dye, cyanine dye, porphyrin dye and thiazole dye.

In particular,
C. I. Solvent Blue 2, 4, 5, 14, 18, 35, 36, 37, 43, 45, 58, 59, 59: 1, 63, 67, 68, 69, 70, 78, 79, 83, 90, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 124, 128, 132, 136, 139;
C. I. Acid Blue 1, 3, 5, 7, 9, 11, 13, 15, 17, 18, 22, 23, 24, 25, 26, 27, 29, 34, 38, 40, 41, 42, 43, 45, 48, 51, 54, 59, 60, 62, 70, 72, 74, 75, 78, 80, 82, 83, 86, 87, 88, 90, 90: 1, 91, 92, 93, 93: 1, 96, 99, 100, 102, 103, 104, 108, 109, 110, 112, 113, 117, 119, 120, 123, 126, 127, 129, 130, 131, 138, 140, 142, 143, 147, 150, 151, 154, 158, 161, 166, 167, 168, 170, 171, 175, 182, 183, 184, 187, 192, 199, 203, 204, 205, 210, 213, 29,234,236,242,243,249,256,259,267,269,278,280,285,290,296,315,324: 1,335,340;
C. I. Direct Blue 1, 2, 3, 6, 8, 15, 22, 25, 28, 29, 40, 41, 42, 47, 52, 55, 57, 71, 76, 77, 78, 80, 81, 84, 85, 86, 87, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196, 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226, 228, 29,236,237,238,242,243,244,245,246,247,248,249,250,251,252,256,257,259,260,268,274,275,293;
C. I. Disperse Blue 1, 14, 56, 60, etc. I. Disperse dyes,
C. I. Basic Blue 1, 3, 5, 7, 9, 19, 21, 22, 24, 25, 26, 28, 29, 40, 41, 45, 47, 54, 58, 59, 60, 64, 65, 66, 67, 68, 81, 83, 88, 89;
C. I. Modern Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43 44, 48, 49, 53, 61, 74, 77, 83, 84 and the like.

  As the blue dye, the blue dyes described in International Publication No. 2012/128318, Korean Published Patent No. 2014-0026284, Korean Published Patent No. 2013-0111024, Korean Published Patent No. 2013-0062510, etc. Can be mentioned.

  Examples of the blue dye (A) include a compound having an anion having at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and an oxygen atom. Examples of the anion containing oxygen and at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus include polyacid anions such as a heteropolyacid anion having the element and an isopolyacid anion having the element. .

Examples of the anion of heteropolyacid or isopolyacid containing tungsten as an essential element 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⁻ , and other examples include [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. As an anion of heteropolyacid or isopolyacid containing tungsten as an essential element, anions of phosphotungstic acid, silicotungstic acid and tungsten-based isopolyacid are preferable.

An anion containing at least one element selected from the group consisting of silicon and phosphorus and oxygen is also preferable, and examples of the anion include SiO ₃ ²⁻ and PO ₄ ³⁻ .

  The blue dye having an anion having at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and an oxygen atom has a cation having a phthalocyanine skeleton, a cation having a diarylmethane skeleton, and a triarylmethane skeleton Examples thereof include compounds having at least one cation selected from the group consisting of a cation, a cation having an anthraquinone skeleton, a cation having an azomethine skeleton, a cation having a cyanine skeleton, and a cation having a porphyrin skeleton and the anion. In the cation having the triarylmethane skeleton, at least one aryl may be a heteroaryl such as thiazole.

  As the blue dye, a compound represented by the formula (AI) is more preferable.

[In formula (AI), [Y ² ] ^m− represents an arbitrary m-valent anion.
R ^{41 to} R ⁴⁴ each independently represents a hydrogen atom, an optionally substituted saturated hydrocarbon group having 1 to 20 carbon atoms, or an oxygen atom between carbon atoms constituting an alkyl group having 2 to 20 carbon atoms. It represents an inserted group, an optionally substituted aryl group, or an optionally substituted aralkyl group. R ⁴¹ and R ⁴² may be bonded to form a ring with the nitrogen atom to which they are bonded, or R ⁴³ and R ⁴⁴ may be bonded to form a ring with the nitrogen atom to which they are bonded.
R ^{45 to} R ⁵² each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, a saturated hydrocarbon group having 1 to 8 carbon atoms, or a carbon atom constituting an alkyl group having 2 to 8 carbon atoms. Represents a group in which an oxygen atom is inserted, or R ⁴⁶ and R ⁵⁰ may be bonded to each other to form —O—, —NH—, —S— or —SO ₂ —.
Y ¹ represents an optionally substituted aryl group or an optionally substituted heteroaryl group.
When the compound represented by the formula (AI) includes a plurality of cations, the plurality of cations may have the same structure or different structures.
m represents an arbitrary natural number. ]

[Y ² ] ^m− represents an arbitrary m-valent anion. The anion represented by Y ² is not particularly limited as long as it is an anion capable of forming a counter ion with a dye cation, preferably a boron-containing anion, an aluminum-containing anion, a fluorine-containing anion, a halogen atom such as a chlorine atom, and the like An anion having at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and an oxygen atom.

  Examples of the boron-containing anion and the aluminum-containing anion include an anion represented by the formula (4).

[In Formula (4), W ¹ and W ² each independently represent a group having two monovalent proton-donating substituents. M represents boron or aluminum. ]

  Examples of the group having two monovalent proton-donating substituents include groups in which protons are released from compounds having at least two monovalent proton-donating substituents (for example, a hydroxy group, a carboxy group, etc.). Can be mentioned. As the compound, catechol which may have a substituent, 2,3-dihydroxynaphthalene which may have a substituent, 2,2′-biphenol which may have a substituent, a substituent 3-hydroxy-2-naphthoic acid which may have a substituent, 2-hydroxy-1-naphthoic acid which may have a substituent, 1-hydroxy-2-naphthoic acid which may have a substituent It may be an acid, an optionally substituted binaphthol, an optionally substituted salicylic acid, an optionally substituted benzylic acid or an optionally substituted mandelic acid. Is preferred.

  In each compound exemplified as the compound having at least two monovalent proton-donating substituents, examples of the substituent include saturated hydrocarbon groups (eg, alkyl groups, cycloalkyl groups, etc.), halogen atoms, hydroxy groups, amino groups. Group, nitro group, alkoxy group and the like.

  Examples of the salicylic acid which may have a substituent include salicylic acid, 3-methylsalicylic acid, 3-tert-butylsalicylic acid, 3-methoxysalicylic acid, 3-nitrosalicylic acid, 4-trifluoromethylsalicylic acid, 3,5-di- monoaminosalicylic acid such as tert-butylsalicylic acid, 3-aminosalicylic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid; 3-hydroxysalicylic acid (2,3-dihydroxybenzoic acid), 4-hydroxysalicylic acid (2 , 4-dihydroxybenzoic acid), 5-hydroxysalicylic acid (2,5-dihydroxybenzoic acid), monohydroxysalicylic acid such as 6-hydroxysalicylic acid (2,6-dihydroxybenzoic acid); 4,5-dihydroxysalicylic acid, 4, 6-Dihydroxysalicyl Dihalosalicylic acid such as 3-chlorosalicylic acid, 4-chlorosalicylic acid, 5-chlorosalicylic acid, 6-chlorosalicylic acid, 3-bromosalicylic acid, 4-bromosalicylic acid, 5-bromosalicylic acid, 6-bromosalicylic acid and the like; And dihalosalicylic acid such as 3,5-dichlorosalicylic acid, 3,5-dibromosalicylic acid and 3,5-diiodosalicylic acid; and trihalosalicylic acid such as 3,5,6-trichlorosalicylic acid.

  As benzylic acid which may have a substituent,

  As the mandelic acid which may have a substituent,

Etc.

  Among the anions represented by the formula (4), preferred anions are the anions represented by the following formulas, which have the substituents shown in Table 1 (BC-1) to anions (BC-24), In addition, anion (BC-25) to anion (BC-28) represented by formula (BC-25), formula (BC-26), formula (BC-27), and formula (BC-28), respectively, may be mentioned. .

(M represents boron or aluminum.)

(M represents boron or aluminum.)

(M represents boron or aluminum.)

(M represents boron or aluminum.)

(M represents boron or aluminum.)

  As an anion represented by Formula (4), an anion (BC-1), an anion (BC-2), an anion (BC-3), an anion (BC-25), an anion (BC-26), an anion (BC -27) is preferable, an anion (BC-1), an anion (BC-2), and an anion (BC-25) are more preferable, and an anion (BC-1) and an anion (BC-2) are still more preferable. A salt of any one of these anions and the compound represented by the formula (AI) tends to be excellent in solubility in an organic solvent.

  Examples of the fluorine-containing anion include groups represented by formulas (6), (7), (8), and (9).

[In Formula (6), W ³ and W ⁴ each independently represent a fluorine atom or a fluorinated alkyl group having 1 to 4 carbon atoms, or W ³ and W ⁴ together represent 1 carbon atom. Represents a fluorinated alkanediyl group of ~ 4. ]

Wherein (7), the W ⁵ to ^W-7 each independently represents a fluorine atom or a fluorinated alkyl group having 1 to 4 carbon atoms. ]

[In the formula (8), Y ^a represents a fluorinated alkanediyl group having 1 to 4 carbon atoms. ]

Wherein (9), Y ^b represents a fluorinated alkyl group having 1 to 4 carbon atoms. ]

In the formulas (6), (7) and (9), the fluorinated alkyl group having 1 to 4 carbon atoms is preferably a perfluoroalkyl group. Examples of the perfluoroalkyl group include —CF ₃ , —CF ₂ CF ₃ , —CF ₂ CF ₂ CF ₃ , —CF (CF ₃ ) ₂ , —CF ₂ CF ₂ CF ₂ CF ₃ , —CF ₂ CF (CF ₃ ) ₂ , —C (CF ₃ ) _{3 and the} like.
In the formulas (6) and (8), the fluorinated alkanediyl group having 1 to 4 carbon atoms is preferably a perfluoroalkanediyl group, —CF ₂ —, —CF ₂ CF ₂ —, —CF ₂ CF ₂ CF _{2. -, - C (CF 3)} 2 -, - CF 2 CF 2 CF 2 CF 2 - , and the like.

  As the anion represented by the formula (6) (hereinafter sometimes referred to as “anion (6)”), the anion represented by the formula (6-1) to the formula (6-6) (hereinafter referred to as “anion (6)”). -1) "to" anion (6-6) ").

  Examples of the anion represented by the formula (7) (hereinafter sometimes referred to as “anion (7)”) include an anion (7-1) represented by the following formula.

  As the anion represented by the formula (8) (hereinafter sometimes referred to as “anion (8)”), the anions represented by the formula (8-1) to the formula (8-4) (hereinafter referred to as “anion (8— 1) "to" anion (8-4) ").

  As the anion represented by the formula (9) (hereinafter sometimes referred to as “anion (9)”), the anion represented by the formula (9-1) to the formula (9-4) (hereinafter referred to as “anion (9−)”). 1) "to" anion (9-4) ").

[Y ² ] ^m- is preferably a fluorine-containing anion or a polyacid anion, more preferably an anion represented by the formula (6): [PW ₁₂ O ₄₀ ] ³⁻ , [P ₂ W ₁₈ O ₆₂ ] ^{6 -} , [SiW ₁₂ O ₄₀ ] ^4- or [W ₁₀ O ₃₂ ] ^4- is preferred, more preferably an anion represented by formula (6-1) to formula (6-5), [PW ₁₂ O ₄₀ ] ^3- , [P ₂ W ₁₈ O ₆₂ ] ^6- , particularly preferably an anion represented by the formula (6-2), [PW ₁₂ O ₄₀ ] ^3- .

m represents an arbitrary natural number and is equal to the negative charge of the anion [Y ² ] ^m− . The m on the cation side is determined so that the anion [Y ² ] ^m− and the cation charge are equal. m is preferably a natural number of 1 to 10.

The saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ^{41 to} R ⁴⁴ may be linear, branched or cyclic. The saturated hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 4 carbon atoms. is there.
Examples of the linear or branched saturated hydrocarbon group include a linear alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, a nonyl group, and a decyl group. A branched alkyl group such as an isopropyl group, an isobutyl group, and a 2-ethylhexyl group; The carbon number of the linear or branched saturated hydrocarbon is preferably 1-8, more preferably 1-6, and still more preferably 1-4.
The cyclic saturated hydrocarbon group may be monocyclic or polycyclic. Examples of the cyclic saturated hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and an adamantyl group. Carbon number of a cyclic saturated hydrocarbon group becomes like this. Preferably it is 3-10, More preferably, it is 6-10.

The hydrogen atom of the saturated hydrocarbon group of R ^{41 to} R ⁴⁴ may be substituted with a substituent. Examples of the substituent include a substituted or unsubstituted amino group or a halogen atom. Examples of the substituted amino group include a dialkylamino group such as a dimethylamino group, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the saturated hydrocarbon group in which a hydrogen atom is substituted with a substituted or unsubstituted amino group or a halogen atom include a group represented by the following formula. In the following formula, * represents a bond with a nitrogen atom.

Among the groups represented by R ^{41 to} R ⁴⁴ , examples of the group in which an oxygen atom is inserted between methylene groups (carbon atoms) constituting an alkyl group having 2 to 20 carbon atoms are represented by the following formulae. Group. In the following formula, * represents a bond with a nitrogen atom. Among them, the group having an oxygen atom inserted between the methylene groups constituting the alkyl group is preferably a group having 2 to 10 carbon atoms, and more preferably a group having 2 to 6 carbon atoms. The alkyl group into which the oxygen atom is inserted is preferably a linear alkyl group. Moreover, 1-4 are preferable and, as for carbon number between oxygen atoms, 2-3 are more preferable.

In R ^{41 to} R ⁴⁴ , the aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms, and the aralkyl group preferably has 7 to 20 carbon atoms, more preferably carbon atoms. It is several 7-10.
The aryl group R ⁴¹ to R ^44, a phenyl group, a naphthyl group, etc. toluyl group.
Examples of the aryl group in the aralkyl group represented by R ^{41 to} R ⁴⁴ include a phenyl group and a naphthyl group. Examples of the aralkyl group include a group in which a bond of these aryl groups and an alkanediyl group are bonded. It is preferable that carbon number of the said alkanediyl group is 1-10, More preferably, it is 1-5, and it is preferable that it is a linear alkanediyl group. Specific examples of the alkanediyl group include a methylene group, an ethylene group, a propylene group, a butanediyl group, a pentanediyl group, and the aralkyl group includes a benzyl group, a phenylethyl group, a naphthylmethyl group, and a naphthylethyl group. Etc.
Among the groups represented by R ^{41 to} R ⁴⁴ , in the aryl group and the aralkyl group, examples of the substituent include halogen atoms such as fluorine atom, chlorine atom and iodine atom; carbon numbers 1 to 6 such as methoxy group and ethoxy group Hydroxy group; alkylsulfonyl group having 1 to 6 carbon atoms such as methylsulfonyl group; alkoxycarbonyl group having 2 to 6 carbon atoms such as methoxycarbonyl group and ethoxycarbonyl group; and the like.
Specific examples of the aryl group which may be substituted include groups represented by the following formulas. In the following formula, * represents a bond with a nitrogen atom.

  Examples of the aralkyl group which may be substituted include a group in which an alkylene group such as a methylene group or an ethylene group is bonded to the bond of the aryl group.

The ring formed by combining R ⁴¹ and R ⁴² together with the nitrogen atom to which they are bonded, and the ring formed by combining R ⁴³ and R ⁴⁴ together with the nitrogen atom to which they are bonded include 5 pyrrolidine rings and the like. Member ring; 6-membered ring such as morpholine ring, piperidine ring, piperazine ring; and the like.

R ^{41 to} R ⁴⁴ are each independently an optionally substituted saturated hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aryl group, or a substituted group, from the viewpoint of ease of synthesis. It is preferably an aralkyl group which may be substituted, more preferably independently a saturated hydrocarbon group having 1 to 8 carbon atoms or an optionally substituted aryl group represented by the following formula. In the following formula, * represents a bond with a nitrogen atom.

The saturated hydrocarbon group having 1 to 8 carbon atoms represented by R ^{45 to} R ⁵² may be linear, branched or cyclic, and is preferably linear. Examples of the saturated hydrocarbon group having 1 to 8 carbon atoms of R ^{45 to} R ⁵² include groups having 1 to 8 carbon atoms among the groups exemplified as the saturated hydrocarbon group of R ^{41 to} R ⁴⁴ . The group having an oxygen atom inserted between the methylene groups (carbon atoms) constituting the alkyl group is more preferably an alkyl group having 2 to 8 carbon atoms. The alkyl group into which the oxygen atom is inserted is preferably a linear alkyl group, and the number of carbon atoms between the oxygen atoms is preferably 1 to 4, and more preferably 2 to 3. For example, the group represented by the following formula is mentioned. In the following formula, * represents a bond with a carbon atom.

R ^{45 to} R ⁵² are each independently preferably a hydrogen atom, a halogen atom, or a saturated hydrocarbon group having 1 to 8 carbon atoms, and each independently represents a hydrogen atom, It is more preferably a methyl group, a fluorine atom or a chlorine atom.

R ⁴⁶ and R ⁵⁰ may be bonded to each other to form —O—, —NH—, —S— or —SO ₂ —.

Y ¹ represents an optionally substituted aryl group or an optionally substituted heteroaryl group.
The aryl group may be either a single ring or a condensed ring, and has 6 to 20 carbon atoms such as a phenyl group, a tolyl group, a xylyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group, and a terphenyl group. An aromatic hydrocarbon group is mentioned.
A heteroaryl group is a substituent derived from an aromatic heterocycle. The aromatic heterocyclic ring may be either a single ring or a condensed ring, and is preferably a 5- to 10-membered ring, and more preferably a 5- to 9-membered ring.
As the monocyclic aromatic heterocycle, a 5-membered ring having a nitrogen atom such as a pyrrole ring, an oxazole ring, a pyrazole ring, an imidazole ring, a thiazole ring;
A 5-membered ring having an oxygen atom or sulfur atom, such as a furan ring or a thiophene ring;
A 6-membered ring having a nitrogen atom such as a pyridine ring, a pyrimidine ring, a pyridazine ring, or a pyrazine ring; As the condensed aromatic heterocyclic ring, a condensed ring having a nitrogen atom such as an indole ring, a benzimidazole ring, a benzothiazole ring, a quinoline ring;
And a ring having an oxygen atom or a sulfur atom such as a benzofuran ring. As the heteroaryl group which may be substituted, a group represented by the formula (Ab2-x1) is more preferable.

[Ring T ² represents an aromatic heterocyclic ring, preferably an aromatic heterocyclic ring having 2 to 9 carbon atoms.
R ⁵³ and R ⁵⁴ 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 be substituted with a substituted or unsubstituted amino group or a halogen atom. A group in which an oxygen atom is inserted between the constituent carbon atoms, an optionally substituted aryl group, an optionally substituted aralkyl group, or a hydrogen atom is represented.
R ⁵⁵ represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aryl group which may be substituted.
k1 represents 0 or 1.
* Represents a bond with a carbocation. ]
Details of R ^{53 to} R ⁵⁵ will be described later.

  As the blue dye, a compound represented by the formula (A-II) is more preferable.

[In the formula (A-II), [Y ² ] ^m− , R ^{41 to} R ⁵² , and m are the same as above.
R ⁵³ and R ⁵⁴ are each independently a hydrogen atom, an oxygen atom between carbon atoms constituting an optionally substituted saturated hydrocarbon group having 1 to 20 carbon atoms or an alkyl group having 2 to 20 carbon atoms. It represents an inserted group, an optionally substituted aryl group, or an optionally substituted aralkyl group.
R ⁵⁵ represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aryl group which may be substituted.
X represents an oxygen atom, —NR ⁵⁷ — or a sulfur atom.
R ⁵⁷ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
When the compound represented by the formula (A-II) includes a plurality of cations, the plurality of cations may have the same structure or different structures. ]

Examples of R ⁵³ , R ⁵⁴ and R ⁵⁷ include the same groups as those exemplified for R ^{41 to} R ⁴⁴ .

Examples of the saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ⁵⁵ include the same groups as those exemplified as the saturated hydrocarbon group for R ^{41 to} R ⁴⁴ . Among these, an alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, an alkyl group having 1 to 6 carbon atoms is further preferable, and an alkyl group having 1 to 4 carbon atoms is particularly preferable.

Examples of the group represented by R ⁵⁵ in which an oxygen atom is inserted between carbon atoms constituting the alkyl group include the same groups as those exemplified for R ^{41 to} R ⁴⁴ . The alkyl group into which the oxygen atom is inserted is preferably a linear alkyl group. Moreover, 1-4 are preferable and, as for carbon number between oxygen atoms, 2-3 are more preferable.

In ^R55 , the aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms.
The aryl group R ^55, include the same groups as exemplified for R ⁴¹ to R ^44, a phenyl group is preferable.
In the aryl group of R ⁵⁵ , the substituent includes a halogen atom such as a fluorine atom, a chlorine atom or an iodine atom; an alkoxy group having 1 to 6 carbon atoms such as a methoxy group or an ethoxy group; a hydroxy group; a sulfamoyl group; C1-C6 alkyl sulfonyl groups, such as methoxycarbonyl group, ethoxycarbonyl groups, etc., C2-C6 alkoxycarbonyl groups, etc. are mentioned.

R ⁵⁵ is preferably a saturated hydrocarbon group having 1 to 10 carbon atoms or an optionally substituted aryl group, more preferably an alkyl group having 1 to 8 carbon atoms, or from the viewpoint of ease of synthesis. , A halogen atom, an alkoxy group having 1 to 4 carbon atoms, a hydroxy group, or an aryl group which may be substituted with a methylsulfonyl group, more preferably a group represented by the following formula. In the following formula, * represents a bond with a carbon atom.

X represents an oxygen atom, —NR ⁵⁷ — or a sulfur atom. Examples of the cyclic structure containing X include a group represented by the following formula. In the formula, R ^{53 to} R ⁵⁵ are each as defined above, and * represents a bond with a carbocation. Among these, as X, an oxygen atom or a sulfur atom is preferable, and a sulfur atom is particularly preferable.

  Examples of the cation moiety of the formula (AI) include the cations 1 to 27 shown by the formula (A-I-1) shown in Table 2 below. Among them, the cations 1 to 6 and the cation 12 are preferable. .

  In Table 2, Ph1 to Ph12 mean groups represented by the following formulae.

  As the cation in the formula (AI), cation 1 to cation 6, cation 11 or cation 12 is preferable, and cation 1, cation 2 or cation 12 is particularly preferable.

  When the compound represented by the formula (A-II) includes a plurality of cations, the plurality of cations may have the same structure or different structures.

  The colored curable resin composition of the present invention may contain only one blue dye or two or more blue dyes.

  The blue dye is preferably a dye soluble in an organic solvent.

The colored curable resin composition of the present invention may contain a dye other than the blue dye. Examples of dyes other than blue dyes include azo dyes, cyanine dyes, xanthene dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, squarylium dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, and nitro dyes. .
The colored curable resin composition of the present invention includes, as a blue dye, in addition to a compound having an anion having at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and an oxygen atom, other blue dyes, A dye other than the blue dye may be included.

The colored curable resin composition of the present invention may contain a pigment, but preferably contains substantially no pigment. The phrase “substantially free of pigment” means that the pigment content is 0.5 mass% or less with respect to the blue dye, and preferably 0 mass%.
As the pigment, a known pigment can be used, and examples thereof include pigments classified as pigments according to a color index (published by The Society of Dyers and Colorists).
As a pigment, for example,
C. I. Blue pigments such as CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60; I. Violet color pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, 38;
C. I. 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, Yellow pigments such as 147, 148, 150, 153, 154, 166, 173, 194, 214;
C. I. Orange pigments such as CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;
C. I. Red pigments such as 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;
C. I. Green pigments such as CI Pigment Green 7, 36, 58;
C. I. Brown pigments such as CI Pigment Brown 23 and 25;
C. I. And black pigments such as CI Pigment Black 1 and 7.

  The pigment can be made into a pigment dispersion in a state where the pigment dispersant is uniformly dispersed in the solution by carrying out a dispersion treatment by containing the pigment dispersant. The pigments may be subjected to a dispersion treatment alone, or a plurality of types may be mixed and dispersed.

  Examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic pigment dispersants. These pigment dispersants may 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 Geneca Co., Ltd.), EFKA (manufactured by BASF), Ajispur (Ajinomoto Fine (Techno Co., Ltd.), Disperbyk (Bic Chemie) and the like.

The content of the blue dye is usually 1 to 100% by mass, preferably 10 to 100% by mass, more preferably 40 to 100% by mass, and further preferably 70 to 100% by mass with respect to the total amount of the colorant. 100% by mass.
When the blue dye contains a dye having an anion having at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and an oxygen atom, and another blue dye or a dye other than a blue dye, the anion The content of the dye having is preferably 10 to 100% by mass, more preferably 40 to 100% by mass, and still more preferably 70 to 100% by mass with respect to the total amount of the blue dye.

  The colored curable resin composition of the present invention may contain extender pigment (I). Examples of the extender pigment include at least one selected from the group consisting of silicon oxide, barium sulfate, titanium oxide, zinc oxide, aluminum oxide, magnesium oxide, and calcium carbonate. Moreover, it is preferable that the average particle diameter of an extender is 500 nm or less from a transparency point. Of these, silicon oxide is preferred from the viewpoint of reliability and tackiness.

  When the extender is included, the content of extender (I) is preferably 0.1 to 80 parts by mass, more preferably 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). 1 to 30 parts by mass. When the total amount of extender pigment is in this range, tackiness and solvent resistance tend to be good.

<Resin (B)>
The resin (B) is preferably an alkali-soluble resin. The alkali-soluble resin is a copolymer containing a structural unit derived from at least one monomer (a) selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride.
Examples of the resin (B) include the following resins [K1] to [K6].
Resin [K1] at least one monomer (a) selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic acid anhydride (hereinafter sometimes referred to as “(a)”), and having 2 to 4 carbon atoms A copolymer of a monomer (b) having a cyclic ether structure and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b)”);
Resin [K2] (a) and (b), monomer (c) copolymerizable with (a) (however, different from (a) and (b)) (hereinafter referred to as “(c)”) In some cases)
Resin [K3] Copolymer of (a) and (c);
Resin [K4] A resin obtained by reacting (b) with a copolymer of (a) and (c);
Resin [K5] A resin obtained by reacting (a) with a copolymer of (b) and (c);
Resin [K6] A resin obtained by reacting (a) with a copolymer of (b) and (c) and further reacting with a carboxylic acid anhydride.

Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid;
Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexene dicarboxylic acid;
Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo Bicyclounsaturated compounds containing a carboxy group such as [2.2.1] hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;
Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6- Unsaturated dicarboxylic acid anhydrides such as tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride;
Unsaturated mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] Kind;
Examples thereof include unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α- (hydroxymethyl) acrylic acid.
Of these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferable from the viewpoint of copolymerization reactivity and the solubility of the resulting resin in an alkaline aqueous solution.

(B) is, for example, a polymerizable compound having a C2-C4 cyclic ether structure (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring) and an ethylenically unsaturated bond. Say.
(B) is preferably a monomer having a C2-C4 cyclic ether and a (meth) acryloyloxy group.
In the present specification, “(meth) acrylic acid” represents at least one selected from the group consisting of acrylic acid and methacrylic acid. Notations such as “(meth) acryloyl” and “(meth) acrylate” have the same meaning.

  Examples of (b) include a monomer having an oxiranyl group and an ethylenically unsaturated bond, a monomer having an oxetanyl group and an ethylenically unsaturated bond, and a tetrahydrofuryl group and an ethylenically unsaturated bond. And monomers.

  (B) is preferably a monomer having an oxiranyl group and an ethylenically unsaturated bond in that the reliability of the obtained color filter such as heat resistance and chemical resistance can be further increased. .

Examples of (c) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, and 2-ethylhexyl (meth). Acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate (in this technical field, it is called “dicyclopentanyl (meth) acrylate” as a common name. In the case of “tricyclodecyl (meth) acrylate”) There is a bird) Black (in the art, it is said that "dicyclopentenyl (meth) acrylate" as trivial name.) [5.2.1.0 ^2,6] decene-8-yl (meth) acrylate, dicyclopenta Nyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, benzyl (meth) acrylate, etc. (Meth) acrylic acid esters of
Hydroxy group-containing (meth) acrylic acid esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;
Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, diethyl itaconate;
Bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5- Hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2′-hydroxyethyl) bicyclo [2.2.1] Hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2 .1] Hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (2′-hydroxyethyl) bicyclo [2.2. 1] hept-2-ene, 5,6-dimethoxybicyclo [2.2 1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5 -Hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, 5-tert-butoxycarbonylbicyclo [ 2.2.1] Hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5 , 6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene, etc. Bicyclounsaturated compounds;
N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3 -Dicarbonylimide derivatives such as maleimide propionate, N- (9-acridinyl) maleimide;
Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyl toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene , Isoprene, 2,3-dimethyl-1,3-butadiene and the like.
Among these, styrene, vinyltoluene, benzyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate, N from the viewpoint of copolymerization reactivity and heat resistance. -Phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hept-2-ene are preferred.

Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl. Resin [K1] such as (meth) acrylate / (meth) acrylic acid copolymer; glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / styrene / ( (Meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl (meth) acrylate / (meth) acrylic acid / N-cyclohexylmaleimide copolymer, 3,4-epoxy tricyclo [5.2.1.0 ^2.6] decyl (meth) acrylate / (meth) acrylic acid / vinyl toluene copolymer, 3-methyl-3- ( A) Resin such as acryloyloxymethyloxetane / (meth) acrylic acid / styrene copolymer [K2]; benzyl (meth) acrylate / (meth) acrylic acid copolymer, styrene / (meth) acrylic acid copolymer , Benzyl (meth) acrylate / tricyclodecyl (meth) acrylate / (meth) acrylic acid copolymer, etc. resin [K3]; benzyl (meth) acrylate / (meth) acrylic acid copolymer with glycidyl (meth) Resin with acrylate added, Resin with glycidyl (meth) acrylate added to tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer, Tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / Glycidyl (meth) acrylate on (meth) acrylic acid copolymer Resin [K4] such as added resin; resin obtained by reacting a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate with (meth) acrylic acid, tricyclodecyl (meth) acrylate / styrene / Resin [K5] such as a resin obtained by reacting a copolymer of glycidyl (meth) acrylate with (meth) acrylic acid; a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate (meth) acrylic acid And resin [K6] such as a resin obtained by further reacting tetrahydrophthalic anhydride with the resin reacted with.

  The resin (B) is preferably a kind selected from the group consisting of a resin [K1], a resin [K2] and a resin [K3], and more preferably from a group consisting of a resin [K2] and a resin [K3]. It is the kind chosen. When these resins are used, the colored curable resin composition is excellent in developability. Resin [K2] is more preferable from the viewpoint of adhesion between the coloring pattern and the substrate.

  For example, the resin [K1] can be obtained by, for example, a method described in the document “Experimental Method for Polymer Synthesis” (Takayuki Otsu, published by Kagaku Dojin Co., Ltd., First Edition, First Edition, issued March 1, 1972) and It can manufacture with reference to the cited reference described in the said literature.

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 further preferably 5,000 to 30,000. . When the molecular weight is in the above range, the coating film hardness is improved, the residual film ratio is high, the solubility of the unexposed area in the developer is good, and the resolution of the colored pattern tends to be improved.
The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B) is preferably 1.1 to 6, and more preferably 1.2 to 4.

  The acid value of the resin (B) is preferably 30 to 170 mg-KOH / g, more preferably 40 to 150 mg-KOH / g, and still more preferably 50 to 135 mg-KOH / g. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g of the resin (B), and can be determined by titration with an aqueous potassium hydroxide solution, for example.

  Content of resin (B) becomes like this. Preferably it is 7-65 mass% with respect to the total amount of solid content, More preferably, it is 13-60 mass%, More preferably, it is 17-55 mass%. Here, the “total amount of solid content” in this specification refers to an amount obtained by removing the content of the solvent from the total amount of the colored curable resin composition. The total amount of solids and the content of each component relative thereto can be measured by known analytical means such as liquid chromatography or gas chromatography, for example.

<Polymerizable compound (C)>
The polymerizable compound (C) is a compound that can be polymerized by an active radical and / or an acid generated from the polymerization initiator (D), and examples thereof include a compound having a polymerizable ethylenically unsaturated bond. Is a (meth) acrylic acid ester compound.

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

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

  Especially, it is preferable that a polymeric compound (C) is a polymeric compound which has 3 or more of 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, dipentaerythritol hexa ( (Meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tris (2- (meth) acryloyloxyethyl) ) Isocyanurate, ethylene glycol modified pentaerythritol tetra (meth) acrylate, ethylene glycol modified dipentaerythritol Hexa (meth) acrylate, propylene glycol modified pentaerythritol tetra (meth) acrylate, propylene glycol modified dipentaerythritol hexa (meth) acrylate, caprolactone modified pentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, etc. Among them, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferable.

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

The content of the polymerizable compound (C) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and further preferably 17 to 55% by mass with respect to the total amount of the solid content. is there.
Further, the content ratio of the resin (B) and the polymerizable compound (C) [resin (B): polymerizable compound (C)] is based on mass, preferably 20:80 to 80:20, more preferably. Is 35: 65-80: 20.
When the content of the polymerizable compound (C) is within the above range, the remaining film ratio at the time of forming the colored pattern and the chemical resistance of the color filter tend to be improved.

<Polymerization initiator (D)>
The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating an active radical, an acid or the like by the action of light or heat and initiating polymerization, and a known polymerization initiator can be used. Examples of the polymerization initiator that generates active radicals include alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, O-acyloxime compounds, and biimidazole compounds.

  Examples of the O-acyloxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane. -1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1- [9-ethyl-6- (2-Methylbenzoyl) -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2, 4-Dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-imine, N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) ) -9H-carbazol-3-yl] -3-cyclopentylpropan-1-one-2-imine and the like. Commercial products such as Irgacure (registered trademark) OXE01, OXE02 (above, manufactured by BASF), N-1919 (manufactured by ADEKA) may be used. Among these, O-acyloxime compounds include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1 At least one selected from the group consisting of -on-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan-1-one-2-imine is preferred, and N-benzoyloxy -1- (4-Phenylsulfanylphenyl) octane-1-one-2-imine is more preferred. When these O-acyloxime compounds are used, a color filter with high brightness tends to be obtained.

  Examples of the alkylphenone compound include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutane. -1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butan-1-one, 2-hydroxy-2-methyl- 1-phenylpropan-1-one, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl -1- (4-Isopropenylphenyl) propan-1-one oligomer, α, α-diethoxyacetophenone, benzyldi And methyl ketal. Commercial products such as Irgacure 369, 907, 379 (above, manufactured by BASF) may be used.

  Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4- Methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxy Styryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4 -Bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino- 2-methylpheny ) Ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

  Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Commercial products such as Irgacure (registered trademark) 819 (manufactured by BASF) may be used.

  Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,3-dichlorophenyl)- 4,4 ′, 5,5′-tetraphenylbiimidazole (see, for example, JP-A-6-75372 and JP-A-6-75373), 2,2′-bis (2-chlorophenyl) -4 , 4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (alkoxyphenyl) biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (dialkoxyphenyl) biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (trial Xylphenyl) biimidazole (for example, see JP-B-48-38403, JP-A-62-174204, etc.), and the phenyl group at the 4,4′5,5′-position is substituted with a carboalkoxy group. Examples thereof include imidazole compounds (for example, see JP-A-7-10913).

  Furthermore, as the polymerization initiator (D), benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl- Benzophenone compounds such as 4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, Examples include quinone compounds such as 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds. These are preferably used in combination with a polymerization initiation assistant (D1) (particularly amines) described later.

  Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenyl methyl. Onium salts such as benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, nitrobenzyl tosylate, Examples thereof include benzoin tosylate.

  The polymerization initiator (D) is preferably a polymerization initiator containing at least one selected from the group consisting of alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, O-acyloxime compounds and biimidazole compounds, and O-acyloxy compounds. More preferred is a polymerization initiator containing a sulfur compound.

  The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts per 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). Part by mass. When the content of the polymerization initiator (D) is within the above range, the sensitivity is increased and the exposure time tends to be shortened, so the productivity of the color filter is improved.

<Polymerization initiation aid (D1)>
The polymerization initiation assistant (D1) is a compound or a sensitizer used for accelerating the polymerization of the polymerizable compound that has been polymerized by the polymerization initiator. When the polymerization initiation assistant (D1) is included, it is usually used in combination with the polymerization initiator (D).
Examples of the polymerization initiation aid (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds.

  Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4 2-dimethylhexyl dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (Ethylmethylamino) benzophenone and the like can be mentioned, among which 4,4′-bis (diethylamino) benzophenone is preferable. Commercial products such as EAB-F (Hodogaya Chemical Co., Ltd.) may be used.

  Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10-di. Examples include butoxyanthracene and 2-ethyl-9,10-dibutoxyanthracene.

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

  Examples of the carboxylic acid compound include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid and the like can be mentioned.

  When using these polymerization initiation assistants (D1), the content thereof is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). Preferably it is 1-20 mass parts. When the amount of the polymerization initiation assistant (D1) is within this range, a colored pattern can be formed with higher sensitivity and the productivity of the color filter tends to be improved.

<Silsesquioxane compound (H)>
The silsesquioxane compound (H) means a compound represented by the formula (1) in which the main chain skeleton is composed of Si—O bonds.
[(RSiO _3/2 ) _n ] (1)
(In the formula, R represents an organic group, and n represents a natural number.)
R represents a monovalent organic group, and examples of the monovalent organic group include an optionally substituted monovalent hydrocarbon group.
Examples of the hydrocarbon group include an aliphatic hydrocarbon group and an aromatic hydrocarbon group. Examples of the aliphatic hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, sec. -C1-C20 aliphatic hydrocarbon group such as butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, 2-ethylhexyl group, octyl group, nonyl group, decyl group, undecyl group and dodecyl group Preferably, it is a C1-C12 alkyl group.
As an aromatic hydrocarbon group, C6-C20 aromatic hydrocarbon groups, such as a phenyl group, a naphthyl group, a benzyl group, a tolyl group, a styryl group, are mentioned.
Examples of the substituent that the monovalent hydrocarbon group may have include a monovalent substituent such as a (meth) acryloyl group, a hydroxy group, a sulfanyl group, a carboxy group, an isocyanato group, an amino group, and a ureido group. . In addition, —CH ₂ — contained in the monovalent hydrocarbon group may be replaced by —O—, —S—, a carbonyl group or the like.

The monovalent organic group represented by R preferably contains at least one reactive group. The reactive group means a group that can react with other sites by a chemical reaction.
Examples of reactive groups include vinyl, allyl, (meth) acryloyl, styryl, oxiranyl, oxetanyl, carboxy, hydroxy, thiacyclopropyl, sulfanyl, isocyanato, amino and ureido groups. And a (meth) acryloyl group, a sulfanyl group, and an oxiranyl group are preferable.

The silsesquioxane compound (H) includes a cage type, a ladder type, or a random type, and is preferably a random type.
The cage-type silsesquioxane compound may be a complete cage type or an incomplete cage-type silsesquioxane compound in which a part of the cage is open.
Examples of the silsesquioxane compound (H) include silsesquioxane, AC-SQ TA-100, MAC-SQ TM-100, AC-SQ SI-20, and MAC-SQ SI described in JP2011-128239A. -20, MAC-SQ HDM, OX-SQ TX-100, OX-SQ SI-20, OX-SQ ME-20, OX-SQ HDX (manufactured by Toa Gosei Co., Ltd.), Comporacene (registered trademark) SQ107, Comporacene (Registered Trademark) SQ109, Comporacene (Registered Trademark) SQ506, Comporacene (Registered Trademark) SQ502-6 (manufactured by Arakawa Chemical Industry Co., Ltd.), and the like.

The colored curable resin composition of the present invention may contain two or more silsesquioxane compounds (H).
The silsesquioxane compound (H) is preferably insoluble in an alkaline aqueous solution.
The content of the silsesquioxane compound (H) is usually 5 to 3000 parts by weight, preferably 15 to 3000 parts by weight, and more preferably 25 to 3000 parts by weight with respect to 100 parts by weight of the blue dye. Yes, more preferably 35 to 2500 parts by mass, particularly preferably 60 to 2000 parts by mass. The higher the content of silsesquioxane with respect to the blue dye, the more remarkable the chemical resistance improvement effect.

<Thiol compound (T)>
The thiol compound (T) is a compound having a sulfanyl group in the molecule.
Specific examples of the thiol compound (T) include, for example, hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, tri Methylolpropane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyl Tristhiopropionate, pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) buta Dipentaerythritol hexakisthiopropionate, dipentaerythritol hexakis (3-mercaptobutyrate), 1,3,5-trismercaptopropionate-1,3,5-triazine-2,4,6 ( 1H, 3H, 5H) -trione, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, etc. Can be mentioned.
Content of the thiol compound (T) in the colored curable resin composition of this invention is a mass fraction with respect to the polymerization initiator (D) whole quantity, Preferably it is 2-70 mass%, More preferably, it is 5-50 mass. %. When the content of the thiol compound (T) is in the above range, the sensitivity tends to be high and the developability tends to be good, which is preferable.

<Solvent (E)>
The solvent (E) is an ester solvent (a solvent containing —COO— in the molecule and not containing —O—), an ether solvent (a solvent containing —O— in the molecule and not containing —COO—), an ether ester. Solvent (solvent containing -COO- and -O- in the molecule), ketone solvent (solvent containing -CO- in the molecule and not containing -COO-), alcohol solvent (containing OH in the molecule,- And solvents that do not contain O-, -CO-, and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, and the like.

  As ester solvents, methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate And methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, propylene glycol diacetate, ethylene glycol diacetate, and γ-butyrolactone.

  Ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether , Propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethyl Glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, methyl anisole, and the like.

  Examples of ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Ethyl propionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, Ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate and the like.

  Examples of ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, and isophorone. Etc.

Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerin and the like.
Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, mesitylene and the like.
Examples of the amide solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like.

  The solvent (E) is preferably an ester solvent, an ether solvent, an ether ester solvent or a ketone solvent, and propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, More preferred are ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol or 4-hydroxy-4-methyl-2-pentanone, propylene glycol monomethyl ether acetate, propylene Glycol monomethyl ether, ethylene glycol monobutyl ether, dipropylene glycol methyl ether Ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol, ethyl 3-ethoxypropionate or 4-hydroxy-4-methyl-2-pentanone is more preferred.

A solvent (E) may be used independently or may use 2 or more types together.
When two or more solvents are used in combination, the colored curable resin composition of the present invention preferably contains at least one selected from the group consisting of an ether ester solvent and a ketone solvent, and both the ether ester solvent and the ketone solvent. It is more preferable to contain.

  The content of the solvent (E) is preferably 70 to 95% by mass and more preferably 75 to 92% by mass with respect to the total amount of the colored curable resin composition. In other words, the solid content of the colored curable resin composition is preferably 5 to 30% by mass, more preferably 8 to 25% by mass. When the content of the solvent (E) is in the above range, the flatness at the time of coating is good, and when the color filter is formed, the color density does not become insufficient and the display characteristics tend to be good.

<Leveling agent (F)>
Examples of the leveling agent (F) include silicone surfactants, fluorine surfactants, and silicone surfactants having a fluorine atom. These may have a polymerizable group in the side chain.
Examples of the silicone surfactant include a surfactant having a siloxane bond in the molecule. Specifically, Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (trade names: 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 (made by Momentive Performance Materials Japan GK) .

  Examples of the fluorosurfactant include surfactants having a fluorocarbon chain in the molecule. Specifically, Florard (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), MegaFac (registered trademark) F142D, F171, F172, F173, F177, F183, F183, F554, R30, RS-718-K (manufactured by DIC Corporation), Ftop (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals), Surflon (registered trademark) S381, S382, SC101, SC105 (Asahi Glass Co., Ltd.) and E5844 (Daikin Fine Chemical Laboratory Co., Ltd.).

  Examples of the silicone-based surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain in the molecule. Specifically, Megafac (registered trademark) R08, BL20, F475, F477, F443 (manufactured by DIC Corporation), and the like can be given.

  The content of the leveling agent (F) is preferably 0.001% by mass to 0.2% by mass, and preferably 0.002% by mass to 0.1%, based on the total amount of the colored curable resin composition. It is not more than mass%, more preferably not less than 0.01 mass% and not more than 0.05 mass%. This content does not include the content of the pigment dispersant. When the content of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.

<Antioxidant (G)>
Examples of the antioxidant (G) include phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants, and phenol-based antioxidants and phosphorus-based antioxidants are preferable.

  The phenolic antioxidant is an antioxidant having a phenolic hydroxy group in the molecule, and preferably has an alkyl group branched to the ortho position of the —OH group of the phenolic hydroxy group. In the present specification, an antioxidant having both a phenolic hydroxy group and a phosphate ester structure or a phosphite ester structure is classified as a phosphorus antioxidant.

  Examples of phenolic antioxidants include 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 4,4′-butylidene-bis (3-methyl-6- t-butylphenol), 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 2-tert-butyl-6- (3-tert -Butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, (tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4- Droxyphenyl) propionate, 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-t-butyl-a, a ′, a ″-(mesitylene-2,4,6-triyl) Tri-p-cresol, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -Trione, 1,3,5-tris ((4-tert-butyl-3-hydroxy-2,6-xylyl) methyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H ) -Trione, thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], benzenepropanoic acid, 3,5-bis (1,1-dimethylethyl) -4-hydroxy C7-C9 side chain alkyl ester, 4,6- Su (octylthiomethyl) -o-cresol, Irganox® 3125 (manufactured by BASF), 2,4-bis (n-octylthio) -6- (4-hydroxy 3 ′, 5′-di-t- Butylanilino) -1,3,5-triazine, 3,9-bis (2- (3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy) -1,1-dimethylethyl)- 2,4,8,10-tetraoxaspiro (5,5) undecane, Sumilizer (registered trademark) BHT (manufactured by Sumitomo Chemical Co., Ltd.), Sumilizer (registered trademark) GA-80 (manufactured by Sumitomo Chemical Co., Ltd.), Examples thereof include Sumilizer (registered trademark) GS (manufactured by Sumitomo Chemical Co., Ltd.), Cyanox (registered trademark) 1790 (manufactured by Cytec Co., Ltd.) and vitamin E (manufactured by Eisai Co., Ltd.).

An amine antioxidant is an antioxidant having an amino group in the molecule.
Examples of amine-based antioxidants include 1-naphthylamine, phenyl-1-naphthylamine, p-octylphenyl-1-naphthylamine, p-nonylphenyl-1-naphthylamine, p-dodecylphenyl-1-naphthylamine, and phenyl-2. -Naphthylamine antioxidants such as naphthylamine; N, N'-diisopropyl-p-phenylenediamine, N, N'-diisobutyl-p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine, N, N ' -Di-β-naphthyl-p-phenylenediamine, N-phenyl-N'-isopropyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, N-1,3-dimethylbutyl-N '-Phenyl-p-phenylenediamine, dioctyl-p-pheny Phenylenediamine antioxidants such as diamine diamine, phenylhexyl-p-phenylenediamine, phenyloctyl-p-phenylenediamine; dipyridylamine, diphenylamine, p, p'-di-n-butyldiphenylamine, p, p'-di- t-butyldiphenylamine, p, p'-di-t-pentyldiphenylamine, p, p'-dioctyldiphenylamine, p, p'-dinonyldiphenylamine, p, p'-didecyldiphenylamine, p, p'-didodecyl Diphenylamine oxidation such as diphenylamine, p, p'-distyryldiphenylamine, p, p'-dimethoxydiphenylamine, 4,4'-bis (4-α, α-dimethylbenzoyl) diphenylamine, p-isopropoxydiphenylamine, dipyridylamine Inhibitor; phenothia Examples thereof include phenothiazine antioxidants such as gin, N-methylphenothiazine, N-ethylphenothiazine, 3,7-dioctylphenothiazine, phenothiazinecarboxylic acid ester, and phenoselenadine.

The phosphorus antioxidant is an antioxidant having a phosphate ester structure or a phosphite ester structure.
Examples of the phosphorus-based antioxidant include 6- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-t-butyldibenz [d, f] [1,3,2] dioxaphosphine, tris (2,4-di-t-butylphenyl) phosphite, diphenylisooctyl phosphite, 2,2′-methylenebis (4,6-di-) tert-butylphenyl) octyl phosphite, diphenyl isodecyl phosphite, diphenyl isodecyl phosphite, triphenyl phosphate, tributyl phosphate, distearyl pentaerythritol diphosphite, cyclic neopentanetetrayl bis (2,6- Di-t-butyl-4-methylphenyl) phosphite, 6- [3 -(3-t-Butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-t-butylbenzo [d, f] [1,3,2] dioxaphosphine , Tris (nonylphenyl) phosphite, tris (mono- and dinonylphenyl mixed) phosphite, diphenyl mono (tridecyl) phosphite, 2,2'-ethylidenebis (4,6-di-t-butylphenol) fluoro Phosphite, phenyl diisodecyl phosphite, tris (2-ethylhexyl) phosphite, tris (isodecyl) phosphite, tris (tridecyl) phosphite, tetrakis (2,4-di-t-butylphenyl) -4,4'- Biphenylene-diphosphonite, 4,4'-isopropylidenediphenyl ester Laalkyl (C12-C15) diphosphite, 4,4′-butylidenebis (3-methyl-6-tert-butylphenyl) -ditridecyl phosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4 -Di-t-butylphenyl) pentaerythritol di-phosphite, cyclic neopentanetetraylbis (2,6-di-t-butyl-4-methylphenyl-phosphite), 1,1,3-tris (2-methyl-4-ditridecyl phosphite-5-t-butylphenyl) butane, tetrakis (2,4-di-t-butyl-5-methylphenyl) -4,4′-biphenylenediphosphonite, Tri-2-ethylhexyl phosphite, triisodecyl phosphite, tristearyl phosphite Ite, phenyl diisodecyl phosphite, trilauryl trithiophosphite, distearyl pentaerythritol diphosphite, tris (nonyl attedphenyl) phosphite tris [2-[[2,4,8,10-tetra-t-butyldibenzo [D, f] [1,3,2] dioxaphosphin-6-yl] oxy] ethyl] amine, bis (2,4-bis (1,1-dimethylethyl) -6-methylphenyl) ethyl ester Phosphorous acid, ADK STAB (registered trademark) 329K (manufactured by ADEKA), ADK STAB (registered trademark) PEP36 (manufactured by ADEKA), ADK STAB (registered trademark) PEP-8 (manufactured by ADEKA), Registered trademark) P-EPQ (manufactured by Clariant), Weston (registered trademark) 618 ( GE), Weston (registered trademark) 619G (manufactured by GE), Ultranox (registered trademark) 626 (manufactured by GE), 6- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) ) Propoxy] -2,4,8,10-tetra-t-butyldibenz [d, f] [1,3,2] dioxaphosphine.

The sulfur-based antioxidant is an antioxidant having a sulfur atom in the molecule.
Examples of the sulfur-based antioxidant include dialkylthiodipropionate compounds such as dilauryl thiodipropionate, dimyristyl or distearyl, and β-alkyl mercaptopropionic acid of polyols such as tetrakis [methylene (3-dodecylthio) propionate] methane. An ester compound etc. are mentioned.

The colored curable resin composition of the present invention may contain two or more antioxidants.
Content of antioxidant (G) in this invention is 0.1-10 mass% normally with respect to the total amount of solid content, Preferably it is 0.5-8 mass%, More preferably, it is 1-6 mass%. is there. Within the above-mentioned range, it is preferable in that it disperses well in the colored curable resin composition, the precipitation of unnecessary components is small, and the color characteristics of the obtained color filter are hardly affected.

<Other ingredients>
The colored curable resin composition of the present invention may contain additives known in the art, such as fillers, other polymer compounds, adhesion promoters, light stabilizers, chain transfer agents, and the like, if necessary. .

<Method for producing colored curable resin composition>
The colored curable resin composition of the present invention includes, for example, a blue dye (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), a silsesquioxane compound (H), and as necessary. It can be prepared by mixing the solvent (E), leveling agent (F), antioxidant (G), polymerization initiation assistant (D1), thiol compound (T), pigment and other components used accordingly.
When the pigment is included, the pigment is preferably mixed with a part or all of the solvent (E) in advance and dispersed using a bead mill or the like until the average particle size of the pigment is about 0.2 μm or less. Under the present circumstances, you may mix | blend a part or all of the said pigment dispersant and resin (B) as needed. The desired colored curable resin composition can be prepared by mixing the remaining components in the pigment dispersion thus obtained so as to have a predetermined concentration.
The dye may be dissolved in part or all of the solvent (E) to prepare a solution in advance, or may be dispersed in part or all of the solvent (E) to prepare a dye dispersion in advance. . When preparing the dye dispersion, a dispersant used in this field may be used. The solution is preferably filtered with a filter having a pore size of about 0.01 to 1 μm.
The colored curable resin composition after mixing is preferably filtered with a filter having a pore size of about 0.01 to 10 μm.

<Color filter manufacturing method>
Examples of the method for producing a colored pattern from the colored curable resin composition of the present invention include a photolithographic method, an inkjet method, and a printing method. Of these, the photolithographic method is preferable. The photolithographic method is a method in which the colored curable resin composition is applied to a substrate, dried to form a colored composition layer, and the colored composition layer is exposed through a photomask and developed. In the photolithography method, a colored coating film that is a cured product of the colored composition layer can be formed by not using a photomask and / or not developing during exposure. The colored pattern and the colored coating film thus formed are the color filter of the present invention.
The film thickness of the color filter to be produced is not particularly limited, and can be adjusted as appropriate according to the purpose and application. ~ 6 μm.

  As the substrate, quartz glass, borosilicate glass, alumina silicate glass, glass plate such as soda lime glass coated with silica on the surface, resin plate such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, silicon, on the substrate In addition, aluminum, silver, or a silver / copper / palladium alloy thin film is used. On these substrates, another color filter layer, a resin layer, a transistor, a circuit, and the like may be formed.

Formation of each color pixel by the photolithographic method can be performed by a known or commonly used apparatus and conditions. For example, it can be produced as follows.
First, a colored curable resin composition is applied on a substrate, dried by heating (pre-baking) and / or drying under reduced pressure to remove volatile components such as a solvent, and a smooth colored composition layer is obtained.
Examples of the coating method include spin coating, slit coating, and slit and spin coating.
30-120 degreeC is preferable and the temperature in the case of performing heat drying has more preferable 50-110 degreeC. In addition, the heating time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes.
When performing vacuum drying, it is preferable to carry out in the temperature range of 20-25 degreeC under the pressure of 50-150 Pa.
The film thickness of the coloring composition layer is not particularly limited, and may be appropriately selected according to the film thickness of the target color filter.

Next, the coloring composition layer is exposed through a photomask for forming a target coloring pattern. The pattern on the photomask is not particularly limited, and a pattern according to the intended use is used.
The light source used for exposure is preferably a light source that generates light having a wavelength of 250 to 450 nm. For example, light less than 350 nm can be cut using a filter that cuts this wavelength range, or light near 436 nm, 408 nm, and 365 nm can be selectively extracted using a bandpass filter that extracts these wavelength ranges. Or you may. Specific examples include mercury lamps, light emitting diodes, metal halide lamps, halogen lamps, and the like.
Use an exposure device such as a mask aligner or a stepper because the entire exposure surface can be illuminated with parallel rays uniformly, or the photomask can be accurately aligned with the substrate on which the colored composition layer is formed. Is preferred.

A colored pattern is formed on the substrate by developing the exposed colored composition layer in contact with a developer. By the development, the unexposed portion of the colored composition layer is dissolved in the developer and removed. As the developer, for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, tetramethylammonium hydroxide is preferable. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. Further, the developer may contain a surfactant.
The developing method may be any of paddle method, dipping method, spray method and the like. Further, the substrate may be tilted at an arbitrary angle during development.
After development, it is preferable to wash with water.

  Furthermore, it is preferable to post-bake the obtained colored pattern. The post-bake temperature is preferably 150 to 250 ° C, more preferably 160 to 235 ° C. The post-bake time is preferably 1 to 120 minutes, more preferably 10 to 60 minutes.

  According to the colored curable resin composition of the present invention, a color filter having particularly excellent brightness can be produced. The color filter is useful as a color filter used in display devices (for example, liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state image sensors. Among these, it is useful as a color filter for liquid crystal display devices.

Hereinafter, the colored curable resin composition of the present invention will be described in more detail by way of examples.
Unless otherwise specified, “%” and “parts” in the examples are% by mass and parts by mass.
In the following synthesis examples, the compounds were identified by mass spectrometry (LC; Agilent 1200 type, MASS; Agilent LC / MSD type) or elemental analysis (Elemental Co., Ltd. VARIO-EL).

[Synthesis Example 1]
The following reaction was performed in a nitrogen atmosphere. A flask equipped with a condenser and a stirrer was charged with 36.3 parts of potassium thiocyanate and 160 parts of acetone, and then stirred at room temperature for 30 minutes. Next, 50 parts of benzoic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 10 minutes, and the mixture was stirred at room temperature for 2 hours. After cooling the obtained reaction mixture with ice, 45.7 parts of N-ethyl-o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise and stirred at room temperature for 30 minutes. After cooling the obtained reaction mixture with ice, 34.2 parts of 30% aqueous sodium hydroxide solution was added dropwise, and the mixture was further stirred at room temperature for 30 minutes. To the obtained reaction mixture, 35.3 parts of chloroacetic acid was added dropwise at room temperature, stirred for 7 hours under heating to reflux, and allowed to cool to room temperature. The obtained reaction solution was added to 120 parts of water, 200 parts of toluene was further added, and the mixture was stirred for 30 minutes. The resulting solution was separated into an organic layer and an aqueous layer by a liquid separation operation, and the obtained organic layer was washed with 200 parts of 1N hydrochloric acid, then with water, and finally with a saturated saline solution. . An appropriate amount of bowsho was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was evaporated to give a pale yellow liquid. The resulting pale yellow liquid was purified by column chromatography. The purified pale yellow liquid was dried at 60 ° C. under reduced pressure to obtain 52.0 parts of a compound represented by the formula (BI-1). Yield 50%

  The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 9.3 parts of the compound represented by the formula (BI-1), 10 parts of 4,4′-bis (diethylamino) benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) Then, after adding 20 parts of toluene, 14.8 parts of phosphorus oxychloride was added and stirred at 95-100 ° C. for 3 hours. The resulting reaction mixture was cooled to room temperature and then diluted with 170 parts of isopropanol. The obtained diluted reaction solution was poured into 300 parts of saturated brine, and then 100 parts of toluene was added and stirred for 30 minutes. The obtained mixture was separated into an organic layer and an aqueous layer by a liquid separation operation, and the obtained organic layer was washed with saturated brine. An appropriate amount of bowsho was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was evaporated to obtain a blue-violet solid. The obtained blue-violet solid was dried at 60 ° C. under reduced pressure to obtain 19.8 parts of a compound represented by the formula (A-II-1). Yield 100%

Identification of compound represented by formula (A-II-1) (mass spectrometry) ionization mode = ESI +: m / z = 601.3 [M-Cl] ⁺
Exact Mass: 636.3

  The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 10 parts of the compound represented by the formula (A-II-1), 4.5 parts of bis (trifluoromethanesulfonyl) imide lithium (manufactured by Tokyo Chemical Industry Co., Ltd.), and After adding 100 parts of N, N-dimethylformamide, the mixture was stirred at 50 to 60 ° C. for 3 hours. The resulting reaction mixture was cooled to room temperature and then added dropwise to 2000 parts of water with stirring for 1 hour to obtain a dark blue suspension. The obtained suspension was filtered to obtain a blue-green solid. The obtained blue-green solid was dried at 60 ° C. under reduced pressure to obtain 11.3 parts of a compound represented by the formula (AI-1). Yield 82%

0.35 g of the compound represented by the formula (AI-1) was dissolved in chloroform to a volume of 250 cm ³ , 2 cm ^{3 of} which was diluted with chloroform to a volume of 100 cm ³ (concentration: 0.028 g / L), an absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length: 1 cm). This compound showed an absorbance of 2.9 (arbitrary unit) at λmax = 628 nm.

[Synthesis Example 2]
The following reaction was performed in a nitrogen atmosphere. A flask equipped with a condenser and a stirrer was charged with 32.2 parts of potassium thiocyanate and 160 parts of acetone, and then stirred at room temperature for 30 minutes. To the obtained mixture, 50 parts of 2-fluorobenzoic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 10 minutes, and the mixture was stirred at room temperature for 2 hours. The obtained reaction mixture was ice-cooled. To the obtained reaction mixture, 40.5 parts of N-ethyl-o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise and stirred at room temperature for 30 minutes. The resulting reaction mixture was ice-cooled, 34.2 parts of a 30% aqueous sodium hydroxide solution was added dropwise, and the mixture was further stirred at room temperature for 30 minutes. To the obtained mixture, 31.3 parts of chloroacetic acid was added dropwise at room temperature, and the mixture was heated to reflux with stirring for 7 hours. Subsequently, after allowing the reaction mixture to cool to room temperature, the reaction solution was poured into 120 parts of water, 200 parts of toluene was added, and the mixture was stirred for 30 minutes. The obtained mixture was separated into an organic layer and an aqueous layer by a liquid separation operation, and the obtained organic layer was washed with 1N hydrochloric acid, then with water, and finally with a saturated saline solution. An appropriate amount of bowsho was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was evaporated to give a pale yellow liquid. The resulting pale yellow liquid was purified by column chromatography. The purified pale yellow liquid was dried at 60 ° C. under reduced pressure to obtain 49.9 parts of a compound represented by the formula (BI-2). Yield 51%

  The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 9.9 parts of the compound represented by the formula (BI-2), 10 parts of 4,4′-bis (diethylamino) benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) Then, after adding 20 parts of toluene, 14.8 parts of phosphorus oxychloride was added and stirred at 95-100 ° C. for 3 hours. The resulting reaction mixture was cooled to room temperature and then diluted with 170 parts of isopropanol. The obtained diluted reaction solution was poured into 300 parts of saturated brine, and then 100 parts of toluene was added and stirred for 30 minutes. The obtained mixture was separated into an organic layer and an aqueous layer by a liquid separation operation, and the obtained organic layer was washed with saturated brine. An appropriate amount of bowsho was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was evaporated using an evaporator to obtain a blue-violet solid. The resulting blue-violet solid was purified by column chromatography. The purified blue-violet solid was dried at 60 ° C. under reduced pressure to obtain 17.2 parts of a compound represented by the formula (A-II-2). Yield 85%

Identification of compound represented by formula (A-II-2) (mass spectrometry) ionization mode = ESI +: m / z = 619.3 [M-Cl] ⁺
Exact Mass: 654.3

  The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 10 parts of the compound represented by the formula (A-II-2), 5.7 parts of bis (trifluoromethanesulfonyl) imide lithium (manufactured by Tokyo Chemical Industry Co., Ltd.), and After charging 30 parts of N, N-dimethylformamide, the mixture was stirred at 40 ° C. for 3 hours. The resulting reaction mixture was cooled to room temperature and then added dropwise to 500 parts of water with stirring for 1 hour to obtain a dark blue suspension. The obtained suspension was filtered to obtain a blue-green solid. The obtained blue-green solid was dried at 60 ° C. under reduced pressure to obtain 11.9 parts of a compound represented by the formula (A-I-2). Yield 86%

0.35 g of the compound represented by the formula (A-I-2) was dissolved in chloroform to a volume of 250 cm ³ , 2 cm ^{3 of} which was diluted with chloroform to a volume of 100 cm ³ (concentration: 0.028 g / L), an absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length: 1 cm). This compound showed an absorbance of 3.1 (arbitrary unit) at λmax = 630 nm.

[Synthesis Example 3]
The following reaction was performed in a nitrogen atmosphere. Into a flask equipped with a condenser and a stirrer was charged 23.3 parts of potassium thiocyanate and 160 parts of acetone, and the mixture was stirred at room temperature for 30 minutes. To the obtained mixture, 50 parts of 2-bromobenzoic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 10 minutes, and the mixture was further stirred at room temperature for 2 hours. After cooling the obtained reaction mixture with ice, 29.3 parts of N-ethyl-o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise to the obtained mixture, and the mixture was stirred at room temperature for 30 minutes. The resulting reaction mixture was ice-cooled, 34.2 parts of a 30% aqueous sodium hydroxide solution was added dropwise, and the mixture was stirred at room temperature for 30 minutes. To the obtained mixture, 22.6 parts of chloroacetic acid was added dropwise at room temperature, and the mixture was heated to reflux with stirring for 7 hours. After the resulting reaction mixture was allowed to cool to room temperature, the reaction solution was poured into 120 parts of water, 200 parts of toluene was added, and the mixture was stirred for 30 minutes. The obtained mixture was separated into an organic layer and an aqueous layer by a liquid separation operation, and the obtained organic layer was washed with 1N hydrochloric acid, washed with water, and finally washed with a saturated saline solution. An appropriate amount of bowsho was added to the obtained organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was evaporated to give a pale yellow liquid. The resulting pale yellow liquid was purified by column chromatography. The purified pale yellow liquid was dried at 60 ° C. under reduced pressure to obtain 41.6 parts of a compound represented by the formula (BI-3). Yield 45%

  The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 12.9 parts of the compound represented by the formula (BI-3), 10 parts of 4,4′-bis (diethylamino) benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) Then, after adding 20 parts of toluene, 14.8 parts of phosphorus oxychloride was added and stirred at 95-100 ° C. for 3 hours. The resulting reaction mixture was cooled to room temperature and then diluted with 170 parts of isopropanol. The obtained diluted reaction solution was poured into 300 parts of saturated brine, and then 100 parts of toluene was added and stirred for 30 minutes. The obtained mixture was separated into an organic layer and an aqueous layer by a liquid separation operation, and the obtained organic layer was washed with saturated brine. An appropriate amount of bowsho was added to the obtained organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was evaporated to obtain a blue-violet solid. The resulting blue-violet solid was purified by column chromatography. The purified blue-violet solid was dried at 60 ° C. under reduced pressure to obtain 17.6 parts of a compound represented by the formula (A-II-3). Yield 80%

Identification of compound represented by formula (A-II-3) (mass spectrometry) ionization mode = ESI +: m / z = 679.3 [M-Cl] ⁺
Exact Mass: 714.2

  The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 10 parts of the compound represented by the formula (A-II-3), 5.2 parts of bis (trifluoromethanesulfonyl) imide lithium (manufactured by Tokyo Chemical Industry Co., Ltd.), and After charging 30 parts of N, N-dimethylformamide, the mixture was stirred at 40 ° C. for 3 hours. The resulting reaction mixture was cooled to room temperature and then added dropwise to 500 parts of water with stirring for 1 hour to obtain a dark blue suspension. The resulting suspension was filtered to obtain a blue-green solid. The obtained blue-green solid was dried at 60 ° C. under reduced pressure to obtain 12.9 parts of a compound represented by the formula (AI-3). Yield 96%

0.35 g of the compound represented by the formula (AI-3) was dissolved in chloroform to a volume of 250 cm ³ , 2 cm ^{3 of} which was diluted with chloroform to a volume of 100 cm ³ (concentration: 0.028 g / L), an absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length: 1 cm). This compound showed an absorbance of 2.6 (arbitrary unit) at λmax = 632 nm.

[Synthesis Example 4]
The following reaction was performed in a nitrogen atmosphere. A flask equipped with a condenser and a stirrer was charged with 33 parts of potassium thiocyanate and 160 parts of acetone, and then stirred at room temperature for 30 minutes. To the obtained mixture, 50.0 parts of 2-methylbenzoic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 10 minutes, and the mixture was stirred at room temperature for 2 hours. After cooling the obtained reaction mixture with ice, 41.6 parts of N-ethyl-o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise to the obtained mixture, and the mixture was stirred at room temperature for 30 minutes. The resulting reaction mixture was ice-cooled, 34.2 parts of a 30% aqueous sodium hydroxide solution was added dropwise, and the mixture was stirred at room temperature for 30 minutes. To the obtained mixture, 32.1 parts of chloroacetic acid was added dropwise at room temperature, and the mixture was heated to reflux with stirring for 7 hours. The resulting reaction mixture was allowed to cool to room temperature, and the resulting solution was poured into 120 parts of water, and then 200 parts of toluene was added and stirred for 30 minutes. The obtained mixture was separated into an organic layer and an aqueous layer by a liquid separation operation, and the obtained organic layer was washed with 1N hydrochloric acid, washed with water, and finally washed with a saturated saline solution. An appropriate amount of bowsho was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was evaporated to give a pale yellow liquid. The resulting pale yellow liquid was purified by column chromatography. The purified pale yellow liquid was dried at 60 ° C. under reduced pressure to obtain 40.5 parts of a compound represented by the formula (BI-4). Yield 41%

  The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 9.7 parts of a compound represented by the formula (BI-4), 4,4′-bis (diethylamino) benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) 10 Then, 14.8 parts of phosphorus oxychloride was added and stirred at 95-100 ° C. for 3 hours. The resulting reaction mixture was cooled to room temperature and then diluted with 170 parts of isopropanol. The obtained diluted reaction solution was poured into 300 parts of saturated brine, and then 100 parts of toluene was added and stirred for 30 minutes. The obtained mixture was separated into an organic layer and an aqueous layer by a liquid separation operation, and the obtained organic layer was washed with saturated brine. An appropriate amount of bowsho was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was evaporated to obtain a blue-violet solid. The resulting blue-violet solid was purified by column chromatography. The purified blue-violet solid was dried at 60 ° C. under reduced pressure to obtain 15.1 parts of a compound represented by the formula (A-II-4). Yield 75%

Identification of compound represented by formula (A-II-4) (mass spectrometry) ionization mode = ESI +: m / z = 615.4 [M-Cl] ⁺
Exact Mass: 650.3

  The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 10 parts of a compound represented by the formula (A-II-4), 5.7 parts of bis (trifluoromethanesulfonyl) imide lithium (manufactured by Tokyo Chemical Industry Co., Ltd.), and After charging 30 parts of N, N-dimethylformamide, the mixture was stirred at 40 ° C. for 3 hours. The resulting reaction mixture was cooled to room temperature and then added dropwise to 500 parts of water with stirring for 1 hour to obtain a dark blue suspension. The obtained suspension was filtered to obtain a blue-green solid. The obtained blue-green solid was dried at 60 ° C. under reduced pressure to obtain 13.2 parts of a compound represented by the formula (AI-4). Yield 96%

0.35 g of the compound represented by formula (AI-4) was dissolved in chloroform to a volume of 250 cm ³ , 2 cm ^{3 of} which was diluted with chloroform to a volume of 100 cm ³ (concentration: 0.028 g / L), an absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length: 1 cm). This compound showed an absorbance of 2.7 (arbitrary unit) at λmax = 627 nm.

[Synthesis Example 5]
The following reaction was performed in a nitrogen atmosphere. Into a flask equipped with a condenser and a stirring device, 24.5 parts of potassium thiocyanate and 160 parts of acetone were added, followed by stirring at room temperature for 30 minutes. To the obtained mixture, 50 parts of 2-trifluoromethylbenzoic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 10 minutes, and the mixture was stirred at room temperature for 2 hours. After cooling the obtained reaction mixture with ice, 30.8 parts of N-ethyl-o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise to the obtained mixture, and the mixture was stirred at room temperature for 30 minutes. The obtained reaction mixture was ice-cooled. To the obtained mixture, 34.2 parts of 30% aqueous sodium hydroxide solution was added dropwise and stirred at room temperature for 30 minutes. To the obtained mixture, 23.8 parts of chloroacetic acid was added dropwise at room temperature, and the mixture was heated to reflux with stirring for 7 hours. The resulting reaction mixture was allowed to cool to room temperature, poured into 120 parts of water, 200 parts of toluene was added, and the mixture was stirred for 30 minutes. The obtained mixture was separated into an organic layer and an aqueous layer by a liquid separation operation, and the obtained organic layer was washed with 1N hydrochloric acid, washed with water, and finally washed with a saturated saline solution. An appropriate amount of bowsho was added to the obtained organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was evaporated to obtain a pale yellow liquid. The resulting pale yellow liquid was purified by column chromatography. The purified pale yellow liquid was dried at 60 ° C. under reduced pressure to obtain 31.1 parts of a compound represented by the formula (BI-5). Yield 36%

  The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 11.4 parts of a compound represented by the formula (BI-5), 4,4′-bis (diethylamino) benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) 10 And 20.0 parts of toluene were added, and then 14.8 parts of phosphorus oxychloride was added and stirred at 95-100 ° C. for 3 hours. The resulting reaction mixture was cooled to room temperature and then diluted with 170 parts of isopropanol. The obtained diluted reaction solution was poured into 300 parts of saturated brine, and then 100 parts of toluene was added and stirred for 30 minutes. The obtained mixture was separated into an organic layer and an aqueous layer by a liquid separation operation, and the obtained organic layer was washed with saturated brine. An appropriate amount of bowsho was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was evaporated to obtain a blue-violet solid. The resulting blue-violet solid was purified by column chromatography. The purified blue-violet solid was dried at 60 ° C. under reduced pressure to obtain 15.2 parts of a compound represented by the formula (A-II-5). Yield 70%

Identification of compound represented by formula (A-II-5) (mass spectrometry) ionization mode = ESI +: m / z = 669.3 [M-Cl] ⁺
Exact Mass: 704.3

  The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 10 parts of a compound represented by the formula (A-II-5), 4.1 parts of bis (trifluoromethanesulfonyl) imide lithium (manufactured by Tokyo Chemical Industry Co., Ltd.), Then, 30.0 parts of N, N-dimethylformamide was added, followed by stirring at 40 ° C. for 3 hours. The resulting reaction mixture was cooled to room temperature and then added dropwise to 500 parts of water with stirring for 1 hour to obtain a dark blue suspension. The resulting suspension was filtered to obtain a blue-green solid. The obtained blue-green solid was dried at 60 ° C. under reduced pressure to obtain 11.4 parts of a compound represented by the formula (AI-5). Yield 85%

0.35 g of the compound represented by the formula (AI-5) was dissolved in chloroform to a volume of 250 cm ³ , 2 cm ^{3 of} which was diluted with chloroform to a volume of 100 cm ³ (concentration: 0.028 g / L), an absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length: 1 cm). This compound showed an absorbance of 1.9 (arbitrary unit) at λmax = 631 nm.

[Synthesis Example 6]
The following reaction was performed in a nitrogen atmosphere. After charging 15.3 parts of N-methylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) and 60 parts of N, N-dimethylformamide into a flask equipped with a condenser and a stirrer, the mixed solution was ice-cooled. 5.7 parts of 60% sodium hydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added little by little over 30 minutes under ice cooling, and then stirred for 1 hour while warming to room temperature. 10.4 parts of 4,4′-difluorobenzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the reaction solution little by little and stirred at room temperature for 24 hours. The reaction solution was added little by little to 200 parts of ice water, and then allowed to stand at room temperature for 15 hours. When the water was removed by decantation, a viscous solid was obtained as a residue. After adding 60 parts of methanol to this viscous solid, it stirred at room temperature for 15 hours. The precipitated solid was filtered off and purified by column chromatography. The purified pale yellow solid was dried at 60 ° C. under reduced pressure to obtain 9.8 parts of a compound represented by the formula (C-I-18).

  The following reaction was performed in a nitrogen atmosphere. A flask equipped with a condenser and a stirrer is charged with 8.2 parts of the compound represented by the formula (BI-2), 10 parts of the compound represented by the formula (CI-18) and 20 parts of toluene. Then, 12.2 parts of phosphorus oxychloride was added and stirred at 95-100 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and diluted with 170 parts of isopropanol. Next, the diluted reaction solution was poured into 300 parts of saturated brine, and then 100 parts of toluene was added and stirred for 30 minutes. Next, stirring was stopped and the mixture was allowed to stand for 30 minutes, whereby it was separated into an organic layer and an aqueous layer. After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed with 300 parts of saturated brine. An appropriate amount of sodium sulfate was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was evaporated using an evaporator to obtain a blue-violet solid. Further, the blue-violet solid was dried at 60 ° C. under reduced pressure to obtain 18.4 parts of a compound represented by the formula (A-II-18).

The following reaction was performed in a nitrogen atmosphere. Into a flask equipped with a condenser and a stirrer, 8 parts of the compound represented by the formula (A-II-18) and 396 parts of methanol were added, followed by stirring at room temperature for 30 minutes to prepare a blue solution. Next, after adding 396 parts of water to the blue solution, the mixture was further stirred at room temperature for 30 minutes to obtain a reaction solution.
A beaker is charged with 53 parts of water, and 11.8 parts of Keggin-type phosphotungstic acid (manufactured by Aldrich) and 53 parts of methanol are poured into the water and mixed at room temperature in an air atmosphere to prepare a phosphotungstic acid solution. Prepared.
The obtained phosphotungstic acid solution was dropped into the previously prepared reaction solution over 1 hour. The mixture was further stirred at room temperature for 30 minutes and then filtered to obtain a blue solid. The obtained blue solid was put into 200 parts of methanol and dispersed for 1 hour, followed by filtration twice. The operation of filtering the blue solid obtained by this operation in 200 parts of water and dispersing for 1 hour was repeated twice. The blue solid obtained by this operation was dried at 60 ° C. under reduced pressure to obtain 17.1 parts of a compound represented by the formula (AI-18).

0.35 g of the compound represented by the formula (AI-18) was dissolved in chloroform to a volume of 250 cm ³ , 2 cm ^{3 of} which was diluted with chloroform to a volume of 100 cm ³ (concentration: 0.028 g / L), an absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length: 1 cm). This compound showed an absorbance of 1.1 (arbitrary unit) at λmax = 626 nm.

[Synthesis Example 7]
Nitrogen was flowed at 0.02 L / min into a flask equipped with a stirrer, thermometer, reflux condenser and dropping funnel to form a nitrogen atmosphere, 305 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 70 ° C. with stirring. did. Next, 60 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (a compound represented by formula (I-1) and a compound represented by formula (II-1)) 440 parts are dissolved in 140 parts of propylene glycol monomethyl ether acetate to prepare a solution, and the solution is added at 70 ° C. over 4 hours using a dropping funnel. It was dripped in the flask kept warm.

On the other hand, a solution prepared by dissolving 30 parts of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 225 parts of propylene glycol monomethyl ether acetate was placed in a flask using another dropping funnel over 4 hours. It was dripped. After completion of the dropwise addition of the polymerization initiator solution, the mixture was kept at 70 ° C. for 4 hours, and then cooled to room temperature. The weight average molecular weight (Mw) was 9.1 × 10 ³ , the molecular weight distribution was 2.16, A resin B1 solution having a solid content of 34.8% and an acid value in terms of solid content of 81 mg-KOH / g was obtained. Resin B1 has the structural units shown below.

[Synthesis Example 8]
An appropriate amount of nitrogen was passed through a flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace the nitrogen atmosphere, and 371 parts by weight of propylene glycol monomethyl ether acetate was added and heated to 85 ° C. with stirring. Next, 54 parts by weight of acrylic acid, 225 parts by weight of a mixture of 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8 and / or 9-yl acrylate, vinyltoluene (mixture of isomers) A mixed solution of 81 parts by weight and 80 parts by weight of propylene glycol monomethyl ether acetate was added dropwise over 4 hours.
On the other hand, a mixed solution prepared by dissolving 30 parts by weight of 2,2-azobis (2,4-dimethylvaleronitrile) in 160 parts by weight of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. After completion of dropping, the mixture was kept at the same temperature for 4 hours, and then cooled to room temperature. B2) was obtained. The weight average molecular weight Mw of the resin B2 was 1.1 × 10 ⁴ and the molecular weight distribution was 2.01. Resin B2 has the following structural units.

The weight average molecular weight (Mw) and number average molecular weight (Mn) of the resins obtained in Synthesis Examples 7 and 8 were measured using the GPC method under the following conditions.
Apparatus; K2479 (manufactured by Shimadzu Corporation)
Column; SHIMADZU Shim-pack GPC-80M
Column temperature: 40 ° C
Solvent; THF (tetrahydrofuran)
Flow rate: 1.0 mL / min
Detector; Standard material for RI calibration; TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)
The polystyrene-converted weight average molecular weight and number average molecular weight ratio (Mw / Mn) obtained above was defined as molecular weight distribution.

Preparation Example 1
<Preparation of dispersion (1)>
10 parts of a compound represented by the formula (AI-18), 2 parts of a dispersant (BYK (registered trademark) -LPN6919 (manufactured by Big Chemie Japan)), 4 parts of resin B2 (in terms of solid content) and propylene glycol monomethyl A dispersion (1) was obtained by mixing 84 parts of ether acetate and sufficiently dispersing the compound represented by the formula (AI-18) using a bead mill.

Examples 1 to 12 and Comparative Example 1
<Preparation of colored curable resin composition>
Each component of Table 3 and Table 4 was mixed to obtain a colored curable resin composition. In Table 3 and Table 4, the number of parts of resin indicates a value in terms of solid content.

In Tables 3 and 4, each component represents the following.
Blue dye (A):
A1; Compound represented by Formula (A-I-1) A2; Compound represented by Formula (A-I-2) A3; Compound represented by Formula (AI-3) A4; Formula (A -I-4) Compound A5; Compound represented by Formula (AI-5) Resin (B): Resin B1
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound)
Thiol compound (T): pentaerythritol tetrakisthiopropionate (PEMP; manufactured by SC Organic Chemical Co., Ltd.)
Antioxidant (G): 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-tert-butyldibenz [d, f] [ 1,3,2] Dioxaphosfepine (Sumilyzer (registered trademark) GP; manufactured by Sumitomo Chemical Co., Ltd.)
Silsesquioxane compound (H): H1; Composelan (registered trademark) SQ109; manufactured by Arakawa Chemical Industries, Ltd. Silsesquioxane compound (H): H2; AC-SQ TA-100; manufactured by Toa Gosei Co., Ltd. (E): E1: Propylene glycol monomethyl ether acetate Solvent (E): E2: 4-hydroxy-4-methyl-2-pentanone Leveling agent (F): Polyether-modified silicone oil (Toray Silicone SH8400; Toray Dow Corning Co., Ltd. ) Made)

<Preparation of colored pattern>
A colored curable resin composition was applied by spin coating on a 5 cm square glass substrate (Eagle XG; manufactured by Corning), and then pre-baked at 100 ° C. for 3 minutes to form a colored composition layer. After standing to cool, the distance between the substrate on which the colored composition layer is formed and the quartz glass photomask is set to 100 μm, and an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) is used in an air atmosphere at 150 mJ / cm. Light was irradiated with an exposure amount of ² (based on 365 nm). A photomask having a 100 μm line and space pattern was used. The colored composition layer after irradiation with light is immersed and developed in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 25 ° C. for 80 seconds, washed with water, A colored pattern was obtained by post-baking at 230 ° C. for 20 minutes.

<Film thickness measurement>
About the obtained coloring pattern, the film thickness was measured using the film thickness measuring apparatus (DEKTAK3; Nippon Vacuum Technology Co., Ltd. product). The results are shown in Table 5.

<Chemical resistance evaluation>
About the obtained coloring pattern, spectroscopy was measured using the colorimeter (OSP-SP-200; Olympus Co., Ltd.), and the xy chromaticity coordinate in the XYZ color system of CIE was used using the characteristic function of C light source. (X, y) and tristimulus value Y were measured.
The obtained colored pattern was immersed in N-methylpyrrolidone at 23 ° C. for 40 minutes. After the immersion, the xy chromaticity coordinates (x, y) and Y are measured in the same manner as before the immersion, and the color difference ΔEab * is measured from the measured values by the method described in JIS Z 8730: 2009 (7. Calculation method of color difference). Was calculated. Based on ΔEab * of the colored curable composition obtained in Comparative Example 1, the chemical resistance improvement rate was calculated according to the following formula. The results are shown in Table 5.
Improvement rate (%) = {(ΔEab * of Comparative Example 1−ΔEab * of Example) / ΔEab *} of Comparative Example 1 × 100

Examples 13 to 16 and Comparative Example 2
<Preparation of colored curable resin composition>
Each component of Table 6 was mixed to obtain a colored curable resin composition. In Table 6, the number of parts of resin indicates a value in terms of solid content.

In Table 6, each component represents the following.
Blue dye (A); A6: C.I. I. Basic Blue 7 (Tokyo Chemical Industry Co., Ltd., maximum absorption wavelength in chloroform solution; 631 nm)

Resin (B): Resin B1
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound)
Thiol compound (T): pentaerythritol tetrakisthiopropionate (PEMP; manufactured by SC Organic Chemical Co., Ltd.)
Antioxidant (G): 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-tert-butyldibenz [d, f] [ 1,3,2] Dioxaphosfepine (Sumilyzer (registered trademark) GP; manufactured by Sumitomo Chemical Co., Ltd.)
Silsesquioxane compound (H): H1; Composelan (registered trademark) SQ109; manufactured by Arakawa Chemical Industries, Ltd. Solvent (E): E1: Propylene glycol monomethyl ether acetate Solvent (E): E2: 4-hydroxy-4- Methyl-2-pentanone Leveling agent (F): Polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.)

A colored pattern was prepared in the same manner as in Example 1 and evaluated for chemical resistance. Based on ΔEab * of the colored curable composition obtained in Comparative Example 2, the chemical resistance improvement rate was calculated according to the following formula. The results are shown in Table 7.
Improvement rate (%) = {(ΔEab * of Comparative Example 2−ΔEab * of Example) / ΔEab *} of Comparative Example 2 × 100

Examples 17 to 20 and Comparative Example 3
<Preparation of colored curable resin composition>
Each component of Table 8 was mixed to obtain a colored curable resin composition. In Table 8, the number of parts of resin indicates a value in terms of solid content.

In Table 8, each component represents the following.
Blue dye (A);
A7: Mixture of compounds represented by formula (3-1), formula (3-2), formula (3-3) and formula (3-4) (prepared by a method according to the synthesis example of Japanese Patent No. 396178) (Maximum absorption wavelength in chloroform solution; 594 nm)

Resin (B): Resin B1
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound)
Thiol compound (T): pentaerythritol tetrakisthiopropionate (PEMP; manufactured by SC Organic Chemical Co., Ltd.)
Antioxidant (G): 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-tert-butyldibenz [d, f] [ 1,3,2] Dioxaphosfepine (Sumilyzer (registered trademark) GP; manufactured by Sumitomo Chemical Co., Ltd.)
Silsesquioxane compound (H): H1; Composelan (registered trademark) SQ109; manufactured by Arakawa Chemical Industries, Ltd. Solvent (E): E1: Propylene glycol monomethyl ether acetate Solvent (E): E2: 4-hydroxy-4- Methyl-2-pentanone Leveling agent (F): Polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.)

A colored pattern was prepared in the same manner as in Example 1 and evaluated for chemical resistance. Based on ΔEab * of the colored curable composition obtained in Comparative Example 3, the improvement rate of chemical resistance was calculated according to the following formula. The results are shown in Table 9.
Improvement rate (%) = {(ΔEab * of Comparative Example 3−ΔEab * of Example) / ΔEab *} of Comparative Example 3 × 100

Examples 21 to 24 and Comparative Example 4
<Preparation of colored curable resin composition>
Each component of Table 10 was mixed to obtain a colored curable resin composition. In Table 10, the number of parts of resin indicates a value in terms of solid content.

In Table 10, each component represents the following.
Blue dye (A): A8; CERAFIS BLUE 603 (manufactured by Orient Chemical Industry Co., Ltd., maximum absorption wavelength in chloroform solution; 611 nm)
Resin (B): Resin B1
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound)
Thiol compound (T): pentaerythritol tetrakisthiopropionate (PEMP; manufactured by SC Organic Chemical Co., Ltd.)
Antioxidant (G): 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-tert-butyldibenz [d, f] [ 1,3,2] Dioxaphosfepine (Sumilyzer (registered trademark) GP; manufactured by Sumitomo Chemical Co., Ltd.)
Silsesquioxane compound (H): H2; AC-SQTA-100; manufactured by Toagosei Co., Ltd.)
Solvent (E): E1: Propylene glycol monomethyl ether acetate Solvent (E): E2: 4-hydroxy-4-methyl-2-pentanone Leveling agent (F): Polyether-modified silicone oil (Toray Silicone SH8400; Toray Dow Corning ( Made by Co., Ltd.)

A colored pattern was prepared in the same manner as in Example 1 and evaluated for chemical resistance. Based on ΔEab * of the colored curable composition obtained in Comparative Example 4, the chemical resistance improvement rate was calculated according to the following formula. The results are shown in Table 11.
Improvement rate (%) = {(ΔEab * of Comparative Example 4−ΔEab * of Example) / ΔEab *} of Comparative Example 4 × 100

Examples 25-28 and Comparative Example 5
<Preparation of colored curable resin composition>
Each component of Table 12 was mixed to obtain a colored curable resin composition. In Table 12, the number of parts of resin indicates a value in terms of solid content.

In Table 12, each component represents the following.
Blue dye (A): A9; C.I. I. Solvent Blue 45 (Savinyl Blue RS; manufactured by Clariant, maximum absorption wavelength in chloroform solution: 625 nm)
Resin (B): Resin B1
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound)
Thiol compound (T): pentaerythritol tetrakisthiopropionate (PEMP; manufactured by SC Organic Chemical Co., Ltd.)
Antioxidant (G): 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-tert-butyldibenz [d, f] [ 1,3,2] Dioxaphosfepine (Sumilyzer (registered trademark) GP; manufactured by Sumitomo Chemical Co., Ltd.)
Silsesquioxane compound (H): H1; Composelan (registered trademark) SQ109; manufactured by Arakawa Chemical Industries, Ltd. Solvent (E): E1: Propylene glycol monomethyl ether acetate Solvent (E): E2: 4-hydroxy-4- Methyl-2-pentanone Leveling agent (F): Polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.)

A colored pattern was prepared in the same manner as in Example 1, and the obtained colored pattern was immersed in N-methylpyrrolidone at 40 ° C. for 30 minutes for chemical resistance evaluation. Based on ΔEab * of the colored curable composition obtained in Comparative Example 5, the improvement rate of chemical resistance was calculated according to the following formula. The results are shown in Table 13.
Improvement rate (%) = {(ΔEab * of Comparative Example 5−ΔEab * of Example) / ΔEab *} of Comparative Example 5 × 100

Examples 29-32 and Comparative Example 6
<Preparation of colored curable resin composition>
Each component of Table 14 was mixed to obtain a colored curable resin composition. In the table, the number of parts of the resin indicates a value in terms of solid content.

In Table 14, each component represents the following.
Dispersion (1): Dispersion (1) prepared in Preparation Example 1
Resin (B): Resin B2
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound)
Thiol compound (T): pentaerythritol tetrakisthiopropionate (PEMP; manufactured by SC Organic Chemical Co., Ltd.)
Silsesquioxane compound (H): H1; Composelan (registered trademark) SQ109; manufactured by Arakawa Chemical Industries, Ltd. Solvent (E): E1: Propylene glycol monomethyl ether acetate Solvent (E): E3: Propylene glycol monomethyl ether Leveling agent (F): Polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.)

<Chemical resistance evaluation>
About the obtained coloring pattern, spectroscopy was measured using the colorimeter (OSP-SP-200; Olympus Co., Ltd.), and the xy chromaticity coordinate in the XYZ color system of CIE was used using the characteristic function of C light source. (X, y) and tristimulus value Y were measured.
The obtained colored pattern was immersed in N-methylpyrrolidone at 23 ° C. for 30 minutes. After the immersion, the xy chromaticity coordinates (x, y) and Y are measured in the same manner as before the immersion, and the color difference ΔEab * is measured from the measured values by the method described in JIS Z 8730: 2009 (7. Calculation method of color difference). Was calculated. Based on ΔEab * of the colored curable composition obtained in Comparative Example 6, the improvement rate of chemical resistance was calculated according to the following formula. The results are shown in Table 15.
Improvement rate (%) = {(ΔEab * of Comparative Example 6−ΔEab * of Example) / ΔEab * of Comparative Example 6 × 100

Examples 33 to 36 and Comparative Example 7
<Preparation of colored curable resin composition>
Each component of Table 16 was mixed to obtain a colored curable resin composition. In the table, the number of parts of the resin indicates a value in terms of solid content.

In Table 16, each component represents the following.
Dispersion (1): Dispersion (1) prepared in Preparation Example 1
Blue dye (A); A7: Mixture of compounds represented by formula (3-1), formula (3-2), formula (3-3) and formula (3-4) Resin (B): Resin B2
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound)
Thiol compound (T): pentaerythritol tetrakisthiopropionate (PEMP; manufactured by SC Organic Chemical Co., Ltd.)
Silsesquioxane compound (H): H2; AC-SQ TA-100; manufactured by Toagosei Co., Ltd. Solvent (E): E1: Propylene glycol monomethyl ether acetate Solvent (E): E3: Propylene glycol monomethyl ether Leveling agent ( F): Polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.)

<Chemical resistance evaluation>
About the obtained coloring pattern, spectroscopy was measured using the colorimeter (OSP-SP-200; Olympus Co., Ltd.), and the xy chromaticity coordinate in the XYZ color system of CIE was used using the characteristic function of C light source. (X, y) and tristimulus value Y were measured.
The obtained colored pattern was immersed in N-methylpyrrolidone at 40 ° C. for 30 minutes. After the immersion, the xy chromaticity coordinates (x, y) and Y are measured in the same manner as before the immersion, and the color difference ΔEab * is measured from the measured values by the method described in JIS Z 8730: 2009 (7. Calculation method of color difference). Was calculated. Based on ΔEab * of the colored curable composition obtained in Comparative Example 7, the improvement rate of chemical resistance was calculated according to the following formula. The results are shown in Table 17.
Improvement rate (%) = {(ΔEab * of Comparative Example 7−ΔEab * of Example) / ΔEab *} of Comparative Example 7 × 100

Examples 37 to 40 and Comparative Example 8
<Preparation of colored curable resin composition>
Each component of Table 18 was mixed to obtain a colored curable resin composition. In the table, the number of parts of the resin indicates a value in terms of solid content.

In Table 18, each component represents the following.
Blue dye (A); A2: Compound represented by formula (AI-2) Xanthene dye (X); X1: Compound represented by formula (X-1) (implementation of JP2013-253168A) Synthesis by the method according to the example)

Resin (B): Resin B1
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound)
Thiol compound (T): pentaerythritol tetrakisthiopropionate (PEMP; manufactured by SC Organic Chemical Co., Ltd.)
Antioxidant (G): 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-tert-butyldibenz [d, f] [ 1,3,2] Dioxaphosfepine (Sumilyzer (registered trademark) GP; manufactured by Sumitomo Chemical Co., Ltd.)
Silsesquioxane compound (H): H2; AC-SQ TA-100; manufactured by Toa Gosei Co., Ltd. Solvent (E): E1: Propylene glycol monomethyl ether acetate Solvent (E): E2: 4-hydroxy-4-methyl -2-Pentanone Leveling agent (F): polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.)

<Chemical resistance evaluation>
About the obtained coloring pattern, spectroscopy was measured using the colorimeter (OSP-SP-200; Olympus Co., Ltd.), and the xy chromaticity coordinate in the XYZ color system of CIE was used using the characteristic function of C light source. (X, y) and tristimulus value Y were measured.
The obtained colored pattern was immersed in N-methylpyrrolidone at 40 ° C. for 30 minutes. After the immersion, the xy chromaticity coordinates (x, y) and Y are measured in the same manner as before the immersion, and the color difference ΔEab * is measured from the measured values by the method described in JIS Z 8730: 2009 (7. Calculation method of color difference). Was calculated. Based on ΔEab * of the colored curable composition obtained in Comparative Example 8, the improvement rate of chemical resistance was calculated according to the following formula. The results are shown in Table 19.
Improvement rate (%) = {(ΔEab * of Comparative Example 8−ΔEab * of Example) / ΔEab * of Comparative Example 8 × 100

  Provided is a colored curable resin composition capable of forming a color filter having good chemical resistance.

Claims (7)

  A colored curable resin composition containing a blue dye, a resin, a polymerizable compound, a polymerization initiator, and a silsesquioxane compound.   The colored curable resin composition according to claim 1, wherein the content of the silsesquioxane compound is 25 to 3000 parts by mass with respect to 100 parts by mass of the blue dye.   The colored curable resin composition according to claim 1 or 2, wherein the blue dye contains at least one dye selected from the group consisting of a phthalocyanine dye, a triarylmethane dye, an anthraquinone dye, a cyanine dye, a porphyrin dye, and a thiazole dye. object.   The colored curable resin composition according to claim 1 or 2, wherein the blue dye is a compound having an anion having at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and an oxygen atom. The colored curable resin composition according to claim 1 or 2, wherein the blue dye contains a compound represented by the formula (AI).

[In formula (AI), [Y ² ] ^m− represents an arbitrary m-valent anion.
R ^{41 to} R ⁴⁴ each independently represents a hydrogen atom, an optionally substituted saturated hydrocarbon group having 1 to 20 carbon atoms, or an oxygen atom between carbon atoms constituting an alkyl group having 2 to 20 carbon atoms. It represents an inserted group, an optionally substituted aryl group, or an optionally substituted aralkyl group. R ⁴¹ and R ⁴² may be bonded to form a ring with the nitrogen atom to which they are bonded, or R ⁴³ and R ⁴⁴ may be bonded to form a ring with the nitrogen atom to which they are bonded.
R ^{45 to} R ⁵² each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, a saturated hydrocarbon group having 1 to 8 carbon atoms, or a carbon atom constituting an alkyl group having 2 to 8 carbon atoms. Represents a group in which an oxygen atom is inserted, or R ⁴⁶ and R ⁵⁰ may be bonded to each other to form —O—, —NH—, —S— or —SO ₂ —.
Y ¹ represents an optionally substituted aryl group or an optionally substituted heteroaryl group.
When the compound represented by the formula (AI) includes a plurality of cations, the plurality of cations may have the same structure or different structures.
m represents an arbitrary natural number. ]   A color filter formed from the colored curable resin composition according to claim 1.   A display device comprising the color filter according to claim 6.