JP2018021176A - Blue curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To solve the problem in which: there is room for improvement in color filters formed from conventional coloring curable resin compositions in terms of brightness.SOLUTION: A blue curable resin composition contains a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D). As the colorant (A), contained are: a dye (A1) that has a maximum absorption wavelength in chloroform of 500 nm-600 nm and includes a silicon atom; and a blue colorant.SELECTED DRAWING: None

Description

  The present invention relates to a blue curable resin composition.

  Colored curable resin compositions are used in the manufacture of color filters used in display devices such as liquid crystal display devices, electroluminescence display devices, and plasma displays. As such a colored curable resin composition, a mixture of compounds represented by formula (A1-1) to formula (A1-8) and C.I. I. A colored curable resin composition containing Pigment Blue 15: 6 is known (Patent Document 1).

JP 2011-118369 A

  The color filter formed from the above colored curable resin composition has room for improvement in terms of brightness.

The present invention includes the following inventions.
[1] It contains a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D), and the colorant (A) has a maximum absorption wavelength in chloroform of 500 nm to 600 nm. A blue curable resin composition comprising a silicon atom-containing dye (A1) and a blue colorant.
[2] The blue curable resin composition according to [1], wherein the polymerization initiator (D) includes a polymerization initiator represented by the following formula (d1).

[In the formula (d1),
R ^d1 has an optionally substituted aromatic hydrocarbon group having 6 to 18 carbon atoms, an optionally substituted heterocyclic group having 3 to 36 carbon atoms, and a substituent. Represents a saturated hydrocarbon group having 1 to 15 carbon atoms, or an aralkyl group having 7 to 33 carbon atoms which may have a substituent, and a methylene group (- CH ₂ —) may be replaced by —O—, —CO—, —S—, —SO ₂ — or —NR ^d5 —.
R ^d2 represents an aromatic hydrocarbon group having 6 to 18 carbon atoms, a heterocyclic group having 3 to 36 carbon atoms, or a saturated hydrocarbon group having 1 to 10 carbon atoms.
R ^d3 represents an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent and a heterocyclic group having 3 to 36 carbon atoms which may have a substituent.
R ^d4 represents an optionally substituted aromatic hydrocarbon group having 6 to 18 carbon atoms, or an optionally substituted aliphatic hydrocarbon group having 1 to 15 carbon atoms, The methylene group (—CH ₂ —) contained in the aliphatic hydrocarbon group may be replaced by —O—, —CO— or —S—, and the methine group (—CH 2) contained in the aliphatic hydrocarbon group. <) May be replaced with —PO ₃ <, and a hydrogen atom contained in the aliphatic hydrocarbon group may be substituted with an OH group.
R ^d5 represents a saturated hydrocarbon group having 1 to 10 carbon atoms, and the methylene group (—CH ₂ —) contained in the saturated hydrocarbon group may be replaced by —O— or —CO—. ]
[3] The blue color according to [1] or [2], wherein the content of the colorant (A) is 3% by mass to 60% by mass with respect to the total solid content of the blue curable resin composition. Curable resin composition.
[4] The blue curable resin composition according to any one of [1] to [3], wherein the blue colorant is a pigment having a phthalocyanine skeleton.
[5] The mass ratio of the content of the dye (A1) to the content of the blue colorant (dye (A1) / blue colorant) is 0.01 or more and 2 or less [1] to [4] The blue curable resin composition according to any one of the above.
[6] A color filter formed from the blue curable resin composition according to any one of [1] to [5].
[7] A display device including the color filter according to [6].

  The color filter formed from the blue curable resin composition of the present invention is excellent in brightness.

The blue curable resin composition of the present invention contains a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D).
Further, the compounds and functional groups exemplified in the present specification can be used alone or in combination of plural kinds unless otherwise specified.

The blue curable resin composition of the present invention has, as a colorant (A), a dye (A1) having a maximum absorption wavelength in chloroform of 500 nm to 600 nm and having a silicon atom (hereinafter referred to as “dye (A1)”). And a blue colorant (A2). As the dye (A1), a dye having a maximum absorption wavelength in chloroform of 500 nm to 580 nm is preferable, and a dye having a wavelength of 500 nm to 560 nm is particularly preferable.
The dye (A1) is preferably a dye having a silicon atom and having an imidazole skeleton, a triarylmethane skeleton, a cyanine skeleton, or a xanthene skeleton. Examples of the dye having a silicon atom and having an imidazole skeleton include compounds represented by the formula (IA) disclosed in JP-T 2010-526897.

[In formula (IA), R ¹ is a group represented by the following formula (ia), and X is a halogen atom.

[N represents an integer of 1 to 8, R ² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and * represents a bond with a nitrogen atom. ]]
The compound represented by the formula (IA) is preferably a compound represented by the following formula.

  Among the dyes (A1), a dye having a silicon atom and having at least one skeleton selected from the group consisting of a triarylmethane skeleton, a cyanine skeleton, and a xanthene skeleton is preferable. A dye having a skeleton is more preferable. The dye having a silicon atom and having a xanthene skeleton is preferably a dye having a xanthene skeleton having an organosilicon group as a substituent. Here, the organosilicon group represents a group having a carbon-silicon bond. Among dyes having a xanthene skeleton having an organosilicon group as a substituent, the dye has a xanthene skeleton having a silylalkyl group as a substituent such as a trimethylsilylalkyl group, a triethylsilylalkyl group, a trimethoxysilylalkyl group, or a triethoxysilylalkyl group. A dye is preferable, and a compound represented by the formula (IB) (hereinafter sometimes referred to as “compound (IB)”) is more preferable. Compound (IB) also includes tautomers thereof.

[In Formula (IB), R ^{21 to} R ²⁴ each independently represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, an optionally substituted phenyl group, or a formula ( It represents a group represented by ib). However, at least one of R ^{21 to} R ²⁴ is a group represented by the following formula (ib).
* -R ⁵⁰ -Si (R ²⁹ ) ₃ (ib)
[R ²⁹ represents a hydrogen atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and * represents a bond with a nitrogen atom. The plurality of R ²⁹ may be the same or different.
R ⁵⁰ represents an alkanediyl group having 1 to 10 carbon atoms, and —CH ₂ — constituting the alkanediyl group is —O—, —CO—, —NR ¹¹ —, —OCO—, —COO—, — It may be substituted with OCONH-, -CONH- or -NHCO-. However, in the alkanediyl group, adjacent —CH ₂ — is not substituted at the same time, and terminal —CH ₂ — is not substituted. ]
In R ^{21 to} R ²⁴ , a hydrogen atom contained in a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms may be substituted with a halogen atom, and —CH ₂ — contained in the saturated hydrocarbon group is It may be substituted with —O—, —CO—, —NR ¹¹ —, —OCO—, —COO—, —OCONH—, —CONH— or —NHCO—. However, in the saturated hydrocarbon group, adjacent —CH ₂ — is not substituted at the same time, and terminal —CH ₂ — is not substituted.
R ²⁵ and R ²⁶ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
R ²⁷ and R ²⁸ are each ^{_{independently, -OH, -SO 3 -, -SO}} 3 H, -SO 3 - Z +, -CO 2 -, -CO 2 H, -CO 2 - Z +, -CO ₂ R ^10, represents a -SO ₃ R ¹⁰ or -SO ₂ NR ¹¹ R ^12.
R ¹⁰ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom.
Z ⁺ represents ⁺ N (R ¹³ ) ₄ , Na ⁺ or K ⁺ .
R ¹¹ and R ¹² each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.
R < ¹³ > represents a hydrogen atom and a C1-C20 monovalent saturated hydrocarbon group each independently.
p represents an integer of 0 to 4. ]

  The compound represented by the formula (IB) includes a compound represented by the following formula (IC) (hereinafter sometimes referred to as “compound (IC)”) and tautomers thereof.

[In formula (IC), each of R ^{31 to} R ³⁴ independently represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, an optionally substituted phenyl group, or a formula ( ic). However, at least one of R ^{31 to} R ³⁴ is a group represented by the formula (ic).

[N represents an integer of 1 to 8, R ³⁹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and * represents a bond with a nitrogen atom. ]
In R ^{31 to} R ³⁴ , a hydrogen atom contained in a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms may be substituted with a halogen atom, and —CH ₂ — contained in the saturated hydrocarbon group is It may be substituted with —O—, —CO— or —NR ¹¹ —. However, in the saturated hydrocarbon group, adjacent —CH ₂ — is not substituted at the same time, and terminal —CH ₂ — is not substituted.
R ³⁵ and R ³⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
R ³⁷ and R ³⁸ are each ^{_{independently, -OH, -SO 3 -, -SO}} 3 H, -SO 3 - Z +, -CO 2 -, -CO 2 H, -CO 2 - Z +, -CO ₂ R ^10, represents a -SO ₃ R ¹⁰ or -SO ₂ NR ¹¹ R ^12.
R ¹⁰ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom.
Z ⁺ represents ⁺ N (R ¹³ ) ₄ , Na ⁺ or K ⁺ .
R ¹¹ and R ¹² each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.
R < ¹³ > represents a hydrogen atom and a C1-C20 monovalent saturated hydrocarbon group each independently.
m represents an integer of 0 to 4. ]

In formula (IB) and formula (IC), examples of the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms represented by R ^{21 to} R ²⁴ and R ^{31 to} R ³⁴ include a methyl group, an ethyl group, n- Propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, decyl, 1-methylbutyl, 1 1,3,3-tetramethylbutyl group, 1,5-dimethylhexyl group, 1,6-dimethylheptyl group, 2-ethylhexyl group, 1,1,5,5-tetramethylhexyl group and the like.

The monovalent saturated hydrocarbon group having 1 to 10 carbon atoms represented by R ^{21 to} R ²⁴ and R ^{31 to} R ³⁴ is preferably a methyl group, an ethyl group, a propyl group, or a butyl group.

The hydrogen atom contained in the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms represented by R ^{21 to} R ²⁴ and R ^{31 to} R ³⁴ may be substituted with a halogen atom. As this halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example.
Examples of the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms substituted with a halogen atom include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a perfluoroethyl group, and a chlorobutyl group.

—CH ₂ — contained in the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms represented by R ^{21 to} R ²⁴ and R ^{31 to} R ³⁴ is —O—, —CO—, or —NR ¹¹ —. May be substituted. However, in the saturated hydrocarbon group, adjacent —CH ₂ — is not substituted at the same time, and terminal —CH ₂ — is not substituted.
Examples of the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms represented by R ¹¹ include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n- Linear alkyl groups having 1 to 20 carbon atoms such as heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-dodecyl group, n-hexadecyl group and n-icosyl group; isopropyl group, isobutyl Group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group and 2-ethylhexyl group, etc., a branched alkyl group having 3 to 20 carbon atoms; cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, C3-C20 alicyclic saturated hydrocarbon groups, such as a cyclooctyl group and a tricyclodecyl group, are mentioned.

Examples of the group in which —CH ₂ — contained in the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms is substituted with —O— include a group represented by the following formula (* represents a bond). Represents hand).

Examples of the group in which —CH ₂ — contained in the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms is substituted with —CO— include a group represented by the following formula (* represents a bond). Represents hand).

Examples of the group in which —CH ₂ — contained in the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms is substituted with —NR ¹¹ — include groups represented by the following formulas (* denotes Represents a bond).

—CH ₂ — contained in the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms represented by R ^{21 to} R ²⁴ and R ^{31 to} R ³⁴ is —OCO—, —COO—, —OCONH—, — It may be substituted with at least one group selected from the group consisting of CONH- and -NHCO-. However, in the saturated hydrocarbon group, adjacent —CH ₂ — is not substituted at the same time, and terminal —CH ₂ — is not substituted.

Examples of the group in which —CH ₂ — contained in the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms is substituted with —OCO— include a group represented by the following formula (* represents a bond). Represents hand).

Examples of the group in which —CH ₂ — contained in the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms is substituted with —COO— include a group represented by the following formula (* represents a bond). Represents hand).

Examples of the group in which —CH ₂ — contained in the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms is substituted with —OCONH— include groups represented by the following formula (* represents a bond). Represents hand).

Examples of the group in which —CH ₂ — contained in the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms is substituted with —CONH— include groups represented by the following formula (* represents a bond). Represents hand).

Examples of the group in which —CH ₂ — contained in the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms is substituted with —NHCO— include groups represented by the following formula (* represents a bond). Represents hand).

The phenyl group represented by R ^{21 to} R ²⁴ and R ^{31 to} R ³⁴ may have a substituent. Examples of the substituent include a halogen ^{atom, -R 10, -OH, -OR 10} , -SO 3 H, -SO 3 - Z +, -CO 2 H, -CO 2 R 10, -SR 10, -SO 2 R ¹⁰ , —SO ₃ R ¹⁰ and —SO ₂ NR ¹¹ R ¹² may be mentioned.

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ^{10 to} R ¹³ include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, and an n-hexyl group. A linear alkyl group having 1 to 20 carbon atoms such as n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-dodecyl group, n-hexadecyl group and n-icosyl group; Group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group, 2-ethylhexyl group and other branched alkyl groups having 3 to 20 carbon atoms; cyclopropyl group, cyclopentyl group, cyclohexyl group, cyclo C3-C20 alicyclic saturated hydrocarbon groups, such as a heptyl group, a cyclooctyl group, and a tricyclodecyl group, are mentioned.

Examples of —OR ¹⁰ include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a 2-ethylhexyloxy group, and an icosyloxy group.

-SO ₃ ^- as Z ^{+ _{is, -SO 3 - N + (R}} 13) 4 are preferred.

Examples of —CO ₂ R ¹⁰ include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a tert-butoxycarbonyl group, a hexyloxycarbonyl group, and an icosyloxycarbonyl group.

Examples of —SR ¹⁰ include a methylsulfanyl group, an ethylsulfanyl group, a butylsulfanyl group, a hexylsulfanyl group, a decylsulfanyl group, and an icosylsulfanyl group.

Examples of —SO ₂ R ¹⁰ include a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group, a decylsulfonyl group, and an icosylsulfonyl group.

Examples of —SO ₃ R ¹⁰ include a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a tert-butoxysulfonyl group, a hexyloxysulfonyl group, and an icosyloxysulfonyl group.

—SO ₂ NR ¹¹ R ¹² includes, for example, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group. Group, N-isobutylsulfamoyl group, N-sec-butylsulfamoyl group, N-tert-butylsulfamoyl group, N-pentylsulfamoyl group, N- (1-ethylpropyl) sulfamoyl group, N -(1,1-dimethylpropyl) sulfamoyl group, N- (1,2-dimethylpropyl) sulfamoyl group, N- (2,2-dimethylpropyl) sulfamoyl group, N- (1-methylbutyl) sulfamoyl group, N- (2-methylbutyl) sulfamoyl group, N- (3-methylbutyl) sulfamoyl group, N-cyclopentylsulfa Moyl group, N-hexylsulfamoyl group, N- (1,3-dimethylbutyl) sulfamoyl group, N- (3,3-dimethylbutyl) sulfamoyl group, N-heptylsulfamoyl group, N- (1- Methylhexyl) sulfamoyl group, N- (1,4-dimethylpentyl) sulfamoyl group, N-octylsulfamoyl group, N- (2-ethylhexyl) sulfamoyl group, N- (1,5-dimethyl) hexylsulfamoyl group An N-1 substituted sulfamoyl group such as a group, N- (1,1,2,2-tetramethylbutyl) sulfamoyl group;
N, N-dimethylsulfamoyl group, N, N-ethylmethylsulfamoyl group, N, N-diethylsulfamoyl group, N, N-propylmethylsulfamoyl group, N, N-isopropylmethylsulfa Moyl group, N, N-tert-butylmethylsulfamoyl group, N, N-butylethylsulfamoyl group, N, N-bis (1-methylpropyl) sulfamoyl group, N, N-heptylmethylsulfamoyl And N, N-2 substituted sulfamoyl groups such as a group.

Examples of the substituent that the phenyl group represented by R ²¹ to R ²⁴ and R ³¹ to R ³⁴ have, preferably -R ^10, more preferably a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms.

At least one of R ^{21 to} R ²⁴ is a group represented by the formula (ib).
In the group represented by the formula (ib), R ²⁹ represents a hydrogen atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ²⁹ include a methyl group, an ethyl group, a propyl group, and a butyl group.

Examples of the alkoxy group having 1 to 4 carbon atoms represented by R ²⁹ include a methoxy group, an ethoxy group, a propoxy group, and a tert-butoxy group.

R ^{29 in the} group represented by the formula (ib) is preferably a methyl group, an ethyl group, a methoxy group, or an ethoxy group, and more preferably a methoxy group or an ethoxy group.

Examples of the alkanediyl group having 1 to 10 carbon atoms represented by R ⁵⁰ include methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, isopropylene group, isobutylene group, 2-methyltriene group. A methylene group, an isopentylene group, an isohexylene group, an isooctylene group, a 2-ethylhexylene group, and the like are raised. Among them, an alkanediyl group having 1 to 6 carbon atoms is preferable, and an alkanediyl group having 1 to 4 carbon atoms is more preferable.

  Examples of the group represented by the formula (ib) include a group represented by the following formula.

In the formula (ib), examples of the group in which —CH ₂ — constituting R ⁵⁰ is substituted with —O— include groups represented by the following (* represents a bond).

In the formula (ib), examples of the group in which —CH ₂ — constituting R ⁵⁰ is substituted with —CO— include groups represented by the following (* represents a bond).

In the formula (ib), examples of the group in which —CH ₂ — constituting R ⁵⁰ is substituted with —NR ¹¹ — include groups represented by the following (* represents a bond).

In the formula (ib), examples of the group in which —CH ₂ — constituting R ⁵⁰ is substituted with —OCO— include groups represented by the following (* represents a bond).

In the formula (ib), examples of the group in which —CH ₂ — constituting R ⁵⁰ is substituted with —COO— include the following groups (* represents a bond).

In the formula (ib), examples of the group in which —CH ₂ — constituting R ⁵⁰ is substituted with —OCONH— include groups represented by the following (* represents a bond).

In the formula (ib), examples of the group in which —CH ₂ — constituting R ⁵⁰ is substituted with —CONH— include groups represented by the following (* represents a bond).

In the formula (ib), examples of the group in which —CH ₂ — constituting R ⁵⁰ is substituted with —NHCO— include the following groups (* represents a bond).

  As the formula (ib), a group represented by the following formula is preferable.

At least one of R ^{31 to} R ³⁴ is a group represented by the formula (ic).
In the formula (ic), examples of the alkyl group having 1 to 4 carbon atoms represented by R ³⁹ include a methyl group, an ethyl group, a propyl group, and a butyl group.

R ³⁹ is preferably a hydrogen atom, a methyl group, an ethyl group or a propyl group, more preferably a hydrogen atom, a methyl group or an ethyl group.

  Examples of the group represented by the formula (ic) include groups represented by the following formulas (i-1) to (i-12). The group represented by formula (ic) is preferably a group represented by formula (i-2), formula (i-3), formula (i-5), or formula (i-6).

Examples of the alkyl group having 1 to 6 carbon atoms represented by R ²⁵ , R ²⁶ , R ³⁵ and R ³⁶ include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, isopropyl group, isobutyl group, Examples include sec-butyl group, tert-butyl group, isopentyl group and neopentyl group.

R ^27, R ^28, R ³⁷ and -SO ₃ represented by R ^{38 -} as Z ⁺ is, -SO ₃ Na or -SO ₃ K is preferable.

-CO ₂ represented by R ^27, R ^28, R ³⁷ and R ^{38 -} as Z ⁺ is, -CO ₂ Na or -CO ₂ K are preferable.

Examples of —CO ₂ R ¹⁰ represented by R ²⁷ , R ²⁸ , R ³⁷ and R ³⁸ include methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, tert-butoxycarbonyl group, hexyloxycarbonyl group and icosyl. An oxycarbonyl group is mentioned.

Examples of —SO ₃ R ¹⁰ represented by R ²⁷ , R ²⁸ , R ³⁷ and R ³⁸ include methoxysulfonyl group, ethoxysulfonyl group, propoxysulfonyl group, tert-butoxysulfonyl group, hexyloxysulfonyl group and icosyl. An oxysulfonyl group is mentioned.

As —SO ₂ NR ¹¹ R ¹² represented by R ²⁷ , R ²⁸ , R ³⁷ and R ³⁸ , for example, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group N-isopropylsulfamoyl group, N-butylsulfamoyl group, N-isobutylsulfamoyl group, N-sec-butylsulfamoyl group, N-tert-butylsulfamoyl group, N-pentylsulfa Moyl group, N- (1-ethylpropyl) sulfamoyl group, N- (1,1-dimethylpropyl) sulfamoyl group, N- (1,2-dimethylpropyl) sulfamoyl group, N- (2,2-dimethylpropyl) Sulfamoyl group, N- (1-methylbutyl) sulfamoyl group, N- (2-methylbutyl) sulfamoyl group, N- (3-methylbutyl) sulfa Yl group, N-cyclopentylsulfamoyl group, N-hexylsulfamoyl group, N- (1,3-dimethylbutyl) sulfamoyl group, N- (3,3-dimethylbutyl) sulfamoyl group, N-heptylsulfa Moyl group, N- (1-methylhexyl) sulfamoyl group, N- (1,4-dimethylpentyl) sulfamoyl group, N-octylsulfamoyl group, N- (2-ethylhexyl) sulfamoyl group, N- (1, N-1-substituted sulfamoyl groups such as 5-dimethyl) hexylsulfamoyl group, N- (1,1,2,2-tetramethylbutyl) sulfamoyl group;
N, N-dimethylsulfamoyl group, N, N-ethylmethylsulfamoyl group, N, N-diethylsulfamoyl group, N, N-propylmethylsulfamoyl group, N, N-isopropylmethylsulfa Moyl group, N, N-tert-butylmethylsulfamoyl group, N, N-butylethylsulfamoyl group, N, N-bis (1-methylpropyl) sulfamoyl group, N, N-heptylmethylsulfamoyl And N, N-2 substituted sulfamoyl groups such as a group.

The monovalent saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ¹⁰ is preferably a methyl group, an ethyl group, a propyl group, or a butyl group.

The hydrogen atom contained in the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ¹⁰ may be substituted with a halogen atom.
As this halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example.
Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms substituted with a halogen atom include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a perfluoroethyl group, and a chlorobutyl group.

Z ⁺ is preferably ⁺ N (R ¹³ ) ₄ .
It is preferred that all ⁺ N (R ¹³⁾ 4 single R ¹³ in ₄ are the same. The total number of carbon atoms of the four R ¹³ is preferably 20 to 80, 20 to 60 is more preferable.

The monovalent saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ¹¹ and R ¹² is preferably a methyl group, an ethyl group, a propyl group, a butyl group or a 2-ethylhexyl group.

The monovalent saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ¹³ is preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and more preferably a methyl group, an ethyl group, or a propyl group.

Of R ²¹ to R ^24, at least one is a group represented by the formula (ib), Other R ²¹ to R ^24, a methyl group, an ethyl group, a propyl group, and a group of preferably up ( * Represents a bond with a nitrogen atom)

  A methyl group, an ethyl group, a propyl group, and the following groups are more preferable (* represents a bond with a nitrogen atom).

Of R ³¹ to R ^34, at least one is a group represented by the formula (ics), Other R ³¹ to R ^34, a methyl group, an ethyl group, a propyl group, and a group of the following preferred,

  A methyl group, an ethyl group, a propyl group, and the following groups are more preferable (* represents a bond with a nitrogen atom).

R ²⁵ , R ²⁶ , R ³⁵ and R ³⁶ are preferably a hydrogen atom, a methyl group or an ethyl group, more preferably a hydrogen atom.

R ²⁷ , R ²⁸ , R ³⁷ and R ³⁸ are preferably —CO ₂ ⁻ , —CO ₂ H, —SO ₃ H, —SO ₃ ^— , more preferably —SO ₃ H, —SO ₃ ^— . is there.

R ¹⁰ is preferably a methyl group, an ethyl group, a propyl group, or a butyl group.

R ¹¹ is preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, or a 2-ethylhexyl group.

R ¹² is preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, or a 2-ethylhexyl group.

R ¹³ is preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, or a butyl group.

  p and m are preferably integers of 0 to 2, more preferably 0 or 1, and still more preferably 0.

  Specific examples of compound (IB) include those shown below. As the compound (IB), (I-1) to (I-4), (I-13) to (I-16), (I-25) to (I-28), (I-37) to (I I-40), (I-49) to (I-54), (I-55) to (I-62), (I-87) to (I-94), (I-117) to (I- 123) is preferred, (I-1) to (I-4), (I-13) to (I-16), (I-25) to (I-28), (I-55) to (I- 62), (I-87) to (I-94), (I-117), (I-119) to (I-123) are more preferable.

  Specific examples of the compound (IC) include those represented by the above formulas (I-1) to (I-54), those represented by the formula (I-117) to the formula (I-119), and the formula (I Those represented by formula (I-121) and those represented by formula (I-123). As the compound (IC), (I-1) to (I-4), (I-13) to (I-16), (I-25) to (I-28), (I-37) to (I I-40), (I-49) to (I-54), (I-117) to (I-119) are preferred, and (I-1) to (I-4), (I-13) to (I I-16), (I-25) to (I-28), (I-117), and (I-119) are more preferable.

  Compound (IB) has the formula (IV)

[Wherein R ²¹ , R ²² , R ²⁵ , R ²⁶ , R ²⁸ , R ²⁷ and p each have the same meaning as described above. X ² represents a halogen atom or a trifluoromethylsulfonyloxy group. ]
And a compound represented by formula (V) (hereinafter sometimes referred to as “compound (IV)”).

[Wherein, R ²³ and R ²⁴ each have the same meaning as described above. ]
Can be produced by mixing and reacting in a organic solvent (hereinafter sometimes referred to as “compound (V)”).

Examples of the halogen atom represented by X ² include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and preferably a chlorine atom.
X ² is preferably a halogen atom, and more preferably a chlorine atom.
R ²⁷ is preferably —SO ₃ ^— .

  The amount of compound (V) to be used is generally 1 mol or more and 10 mol or less, preferably 1 mol or more and 3 mol or less, more preferably 1 mol or more and 2 mol or less with respect to 1 mol of compound (IV). is there.

Compound (IB) in which R ²⁷ is —SO ₃ ^— or —CO ₂ ^— (hereinafter sometimes referred to as Compound (II-1)) is represented by the formula (VI)

[Wherein, R ²⁵ , R ²⁶ , R ²⁸ and p represent the same meaning as described above.
X ¹ and X ² each independently represent a halogen atom or a trifluoromethylsulfonyloxy group.
R ⁴⁰ represents —SO ₂ — or —CO—. ]
And a compound represented by formula (III) (hereinafter sometimes referred to as “compound (VI)”)

[Wherein R ²¹ and R ²² represent the same meaning as described above. ]
And a compound represented by formula (hereinafter sometimes referred to as “compound (III)”) in an organic solvent, reacted, and

[Wherein, R ²³ and R ²⁴ each have the same meaning as described above. ]
Can be produced by mixing and reacting in a organic solvent (hereinafter sometimes referred to as “compound (V)”).

Examples of the halogen atom represented by X ¹ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and preferably a chlorine atom.
X ¹ and X ² are preferably the same.
X ¹ and X ² are each independently preferably a halogen atom, and more preferably a chlorine atom.
R ⁴⁰ is preferably —SO ₂ —.

The amount of compound (III) to be used is generally 1 mol or more and 30 mol or less, preferably 1 mol or more and 20 mol or less, more preferably 1 mol or more and 10 mol or less with respect to 1 mol of compound (VI). More preferably, it is 1 mol or more and 3 mol or less, Most preferably, it is 1 mol or more and 2 mol or less.
The amount of compound (V) to be used is generally 1 mol or more and 30 mol or less, preferably 1 mol or more and 20 mol or less, more preferably 1 mol or more and 10 mol or less with respect to 1 mol of compound (VI). More preferably, it is 1 mol or more and 3 mol or less, Most preferably, it is 1 mol or more and 2 mol or less.

  The amount of compound (V) to be used is generally 1 mol to 50 mol, preferably 1 mol to 30 mol, more preferably 1 mol to 20 mol, per 1 mol of compound (III). is there.

  Compound (IB) is useful as a dye. Since it is highly soluble in organic solvents, it is particularly useful as a colorant for colored curable resin compositions used in color filters of display devices such as liquid crystal displays.

The content of the dye (A1) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and still more preferably 1% by mass in a total amount of 100% by mass of the solid content of the blue curable resin composition. Above, preferably 40% by mass or less, more preferably 30% by mass or less, and further preferably 20% by mass or less.
Here, the “total amount of solids” in this specification refers to an amount obtained by removing the solvent content from the total amount of the blue 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.

The content of the dye (A1) is preferably 0.01% by mass or more, more preferably 1% by mass or more, still more preferably 3% by mass or more, and still more preferably in the total amount of the colorant (A) of 100% by mass. It is 5% by mass or more, preferably 90% by mass or less, more preferably 80% by mass or less, still more preferably 60% by mass or less, and still more preferably 50% by mass or less.
Furthermore, the content of the compound (IB) is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more in 100% by mass of the dye (A1).
Further, the content of the dye (A1) is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, in 100% by mass of the total of the dyes. It is also preferable that it may be 100% by mass or less, or 90% by mass or less.

<Blue colorant (A2)>
The blue curable resin composition of this invention contains a blue coloring agent (A2) as a coloring agent (A) other than the said dye (A1).
Among the compounds classified as dyes by the color index, the blue colorant is a blue compound (blue dye (A2-1)) or a compound classified as a pigment by the color index (published by The Society of Dyers and Colourists) Among them, a blue compound (blue pigment (A2-2)) can be mentioned.

Examples of the blue dye (A2-1) include C.I. I. Solvent Blue 4, 5, 37, 67, 70, 90;
C. I. Acid Blue 1, 7, 9, 15, 18, 22, 29, 42, 59, 60, 62, 70, 72, 74, 82, 83, 86, 87, 90, 92, 93, 100, 102, 103, 104, 113, 117, 120, 126, 130, 131, 142, 147, 151, 154, 158, 161, 166, 167, 168, 170, 171, 184, 187, 192, 199, 210, 229, 234, 236, 242, 243, 256, 259, 267, 285, 296, 315, 335;
C. I. Direct Blue 1, 2, 6, 8, 15, 22, 25, 41, 57, 71, 76, 78, 80, 81, 84, 85, 86, 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, 229, 236, 237, 238, 242, 243, 244, 2 5,246,247,248,249,250,251,252,256,257,259,260,268,274,275,293;
C. I. Basic Blue 1, 3, 5, 7, 9, 19, 24, 25, 26, 28, 29, 40, 41, 54, 58, 59, 64, 65, 66, 67, 68;
C. I. Modern Blue 1, 2, 3, 7, 9, 12, 13, 15, 16, 19, 20, 21, 22, 26, 30, 31, 39, 40, 41, 43, 44, 49, 53, 61 74, 77, 83, 84.

  Specific examples of the blue pigment (A2-2) include C.I. I. Pigment Blue (hereinafter, CI Pigment Blue is omitted, and only the number is described) 15, 15: 3, 15: 4, 15: 6, 16, 60, 75, 80, and the like. C. I. Pigment Blue 15, 15: 3, 15: 4, 15: 6, 16, 75 are preferable. I. Pigment Blue 15, 15: 3, 15: 4, and 15: 6 are more preferable. I. Pigment Blue 15: 6 is particularly preferable.

Among these, a blue pigment (A2-2) is preferable, and a blue pigment (blue phthalocyanine pigment) made of a compound having a phthalocyanine skeleton is more preferable. Examples of blue pigments made of a compound having a phthalocyanine skeleton include C.I. I. Pigment Blue 15, 15: 3, 15: 4, 15: 6, 16, 75.
The content of the blue pigment (A2-2) is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more, in 100% by mass of the blue colorant (A2). .

  The content of the blue colorant (A2) is preferably 0.1% by mass or more, more preferably 1% by mass or more, further preferably 3% by mass or more, and still more preferably in 100% by mass of the colorant (A). It is 5% by mass or more, preferably 99% by mass or less, more preferably 95% by mass or less, and further preferably 90% by mass or less.

  Furthermore, the total content of the dye (A1) and the blue colorant (A2) is preferably 80% by mass or more, more preferably 90% by mass or more, in 100% by mass of the total amount of the colorant (A). More preferably, it is 95% by mass or more.

  The mass ratio of the content of the dye (A1) to the content of the blue colorant (dye (A1) / blue colorant (A2)) is preferably 0.01 or more, more preferably 0.00. 05 or more, preferably 10 or less, more preferably 2 or less, particularly preferably 1.8 or less, and may be 0.7 or less.

<Other color materials (A3)>
The blue curable resin composition of the present invention may contain a colorant (A3) different from the dye (A1) or the blue colorant (A2) as the colorant (A). As other coloring materials (A3), dye (A3-1) (however, different from dye (A1) or blue colorant (A2)) and pigment (A3-2) (however, blue colorant (A2)) Is different).

  The dye (A3-1) (but different from the dye (A1) or the blue colorant (A2)) is an oil-soluble dye, an acid dye, a basic dye, a direct dye, a mordant dye, an amine salt of an acid dye. And dyes such as sulfonamide derivatives of acid dyes, for example, compounds classified as dyes by Color Index (published by The Society of Dyers and Colorists), and publicly known dyeing notes (color dyeing company) Dyes. In addition, according to chemical structure, azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes other than dye (A1), phthalocyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, squarylium dyes, acridine dyes, styryl dyes And dyes, coumarin dyes, quinoline dyes, and nitro dyes. Of these, organic solvent-soluble dyes are preferred.

Specifically, C.I. I. Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162;
C. I. Solvent Red 45, 49, 125, 130, 218;
C. I. Solvent Orange 2, 7, 11, 15, 26, 56;
C. I. Solvent Green 1, 4, 5, 7, 34, 35, etc. I. Solvent dyes,
C. I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;
C. I. Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 195, 198, 206, 211, 215, 216, 217, 227,228,249,252,257,258,260,261,266,268,270,274,277,280,281,289,308,312,315,316,339,341,345,346,349, 382, 383, 388, 394, 401, 412, 417, 418, 422, 426;
C. I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173;
C. I. Acid Violet 6B, 7, 9, 17, 19, 30, 102;
C. I. Acid Green 1, 3, 5, 9, 16, 50, 58, 63, 65, 80, 104, 105, 106, 109, etc. I. Acid dyes,
C. I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141;
C. I. Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;
C. I. Direct Orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;
C. I. Direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;
C. I. Direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82, etc. I. Direct dyes,
C. I. C. such as Disperse Yellow 54, 76 I. Disperse dyes,
C. I. Basic Red 1, 10;
C. I. C. such as Basic Green 1; I. Basic dyes,
C. I. Reactive Yellow 2, 76, 116;
C. I. Reactive Orange 16;
C. I. Reactive Red 36; I. Reactive dyes,
C. I. Modern yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;
C. I. Modern Red 1, 2, 4, 9, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 27, 30, 32, 33, 36, 37, 38, 39, 41, 43 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95;
C. I. Modern orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;
C. I. Modern violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;
C. I. Modern Green 1, 3, 4, 5, 10, 15, 26, 29, 33, 34, 35, 41, 43, 53, etc. I. Modern dyes,
C. I. C. of Bat Green 1 etc. I. Vat dye,
Etc.
Of these, violet dye and red dye are preferable.
These dyes may be appropriately selected according to the desired spectral spectrum of the color filter.

  The total content of the dye (A3-1) is preferably 0.1% by mass or more, more preferably 1% by mass or more, and even more preferably 5% by mass or more in the total amount of the colorant (A) of 100% by mass. Yes, preferably 50% by mass or less, more preferably 40% by mass or less, and still more preferably 30% by mass or less.

The pigment (A3-2) (but different from the blue colorant (A2)) is not particularly limited, and a known pigment can be used. For example, the color index (published by The Society of Dyers and Colorists) Examples include compounds classified as pigments.
Examples of the pigment (A3-2) include C.I. I. Pigment Yellow 1 (hereinafter, CI Pigment Yellow is omitted and only the number is described) 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214, etc .;
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. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 175, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, etc. Pigments;
C. I. Violet color pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, 38;
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.
These pigments may be used alone or in combination of two or more.

  Examples of the pigment include C.I. I. Yellow pigments such as C.I. Pigment Yellow 138, 139 and 150; I. Red pigments such as CI Pigment Red 177, 242, and 254; I. Violet color pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, and 38 are preferred. By including the pigment, the transmission spectrum of the color filter using the blue curable resin composition of the present invention can be easily optimized, and the light resistance and chemical resistance of the color filter are improved.

The total content of the pigment is preferably 1% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, and still more preferably 30% by mass in the total amount of the colorant (A) of 100% by mass. Or more, preferably 99% by mass or less, more preferably 95% by mass or less, and still more preferably 90% by mass or less.
The content of the colorant (A) is preferably 1% by mass or more and 70% by mass or less, more preferably 3% by mass or more and 60% by mass or less, and further preferably 3% by mass with respect to the total amount of the solid content. % To 50% by mass, particularly preferably 5% to 35% by mass. When the content of the colorant (A) is within the above range, a desired spectrum and color density can be obtained.

<Resin (B)>
The resin (B) is not particularly limited, but is preferably an alkali-soluble resin, and at least one monomer (a) selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride (hereinafter referred to as “( A copolymer having a structural unit derived from a) may be more preferable.
The copolymer having a structural unit derived from (a) is a monomer (b) having a C2-C4 cyclic ether structure and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b)”). And a copolymer having at least one selected from the group consisting of structural units having an ethylenically unsaturated bond. The copolymer may further have other structural units.
Other structural units are derived from the monomer (c) copolymerizable with (a) (however, different from (a) and (b)) (hereinafter sometimes referred to as “(c)”). The structural unit to be mentioned.

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.

  When a copolymer contains the structural unit derived from (a), it is preferable that the ratio is 1-50 mass% in 100 mass% of copolymers, More preferably, it is 5-30 mass%.

(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.
Examples of (b) include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, vinylbenzyl glycidyl ether, 3,4-epoxycyclohexylmethyl (meth) acrylate, and 3,4-epoxytricyclo [5. 2.1.0 ^2,6 ] decyl acrylate, 3-ethyl-3- (meth) acryloyloxymethyl oxetane, and tetrahydrofurfuryl (meth) acrylate.

  (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. .

  When a copolymer contains the structural unit derived from (b), it is preferable that the ratio is 50-99 mass% in 100 mass% of copolymers, More preferably, it is 60-95 mass%.

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 -Bicyclounsaturated compounds such as hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene;
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.

  When a copolymer contains the structural unit derived from (c), it is preferable that the ratio is 1-99 mass% in 100 mass% of copolymers.

The structural unit having an ethylenically unsaturated bond is preferably a structural unit having a (meth) acryloyl group in the side chain. The resin having such a structural unit includes a group having a structural unit derived from (a) or (b) and a group capable of reacting with the group (a) or (b) and an ethylenically unsaturated bond. It is obtained by adding a monomer having it.
As such a structural unit, a structural unit obtained by adding glycidyl (meth) acrylate to a (meth) acrylic acid unit, a structural unit obtained by adding 2-hydroxyethyl (meth) acrylate to a maleic anhydride unit, glycidyl (meta And a structural unit obtained by adding (meth) acrylic acid to an acrylate unit. Moreover, when these structural units have a hydroxy group, the structural unit which further added the carboxylic acid anhydride is also mentioned as a structural unit which has an ethylenically unsaturated bond.

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. Copolymers having structural units derived from (a) and (b) such as (meth) acrylate / (meth) acrylic acid copolymers; 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- cyclohexyl maleimide copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6] decyl (meth) acrylate / (meth) acrylic acid / vinyl Having structural units derived from (a), (b) and (c) such as toluene copolymer, 3-methyl-3- (meth) acryloyloxymethyloxetane / (meth) acrylic acid / styrene copolymer, etc. Copolymer: benzyl (meth) acrylate / (meth) acrylic acid copolymer, styrene / (meth) acrylic acid copolymer, benzyl (meth) acrylate / tricyclodecyl (meth) acrylate / (meth) acrylic acid copolymer Polymer: Resin obtained by adding glycidyl (meth) acrylate to benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer) Resin added with (meth) acrylate, tricyclodecyl (meth) acrylate / benzyl (meth) acrylate A copolymer having structural units derived from (a) and (c), such as a resin in which glycidyl (meth) acrylate is added to a thio / (meth) acrylic acid copolymer; tricyclodecyl (meth) acrylate / glycidyl Resin in which (meth) acrylic acid is reacted with a copolymer of (meth) acrylate, and (meth) acrylic acid is reacted with a copolymer of tricyclodecyl (meth) acrylate / styrene / glycidyl (meth) acrylate A copolymer having a structural unit obtained by adding (a) to a structural unit derived from (b) and a structural unit derived from (c); a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate A structural unit derived from (b) such as a resin obtained by further reacting a polymer with (meth) acrylic acid and further reacting with tetrahydrophthalic anhydride. And a copolymer having a structural unit obtained by adding (a) to a position and further adding a carboxylic acid anhydride and a structural unit derived from (c).

  The resin is described in, for example, the method described in the document “Experimental Method for Polymer Synthesis” (published by Takayuki Otsu, published by Kagaku Dojin Co., Ltd., 1st edition, 1st edition, published on March 1, 1972). It can be produced with reference to the cited references.

  The resin (B) is preferably a copolymer having structural units derived from (a) and (b); a copolymer having structural units derived from (a), (b) and (c); and A type selected from the group consisting of copolymers having structural units derived from (a) and (c), more preferably copolymers having structural units derived from (a) and (b); and A copolymer having a structural unit derived from (a), (b) and (c); and a copolymer having a structural unit derived from (a) and (b), particularly preferably a copolymer selected from the group consisting of It is a polymer.

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, when a colored pattern is formed, the residual film ratio before and after development is high, the solubility in the unexposed portion of 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 (in terms of solid content) of the resin (B) is preferably 40 to 170 mg-KOH / g, more preferably 50 to 150 mg-KOH / g, and further preferably 60 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.

  The content of the resin (B) is preferably 7 to 75% by mass, more preferably 13 to 70% by mass, still more preferably 17 to 70% by mass, and still more preferably based on the total amount of solids. Is 17 to 65% by mass. When the content of the resin (B) is in the above range, a colored pattern can be formed, and the resolution of the colored pattern and the remaining film rate tend to be improved.

<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.

  Among these, the polymerizable compound is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, 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 4 to 65% by mass, more preferably 7 to 60% by mass, and still more preferably 10 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 (D) include O-acyloxime compounds, alkylphenone compounds, biimidazole compounds, triazine compounds, and acylphosphine oxide compounds.

  Examples of the O-acyloxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane- 1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan-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, [11- (2-ethylhexyl) -5- (2,4,6-trimethylbenzoyl) -11H-benzo [a] And carbazol-8-yl]-[2- (2,2,3,3-tetrafluoropropoxy) phenyl] methanone oxime O-acetate. 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 -On-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine and [11- (2-ethylhexyl) -5- (2,4 , 6-trimethylbenzoyl) -11H-benzo [a] carbazol-8-yl]-[2- (2,2,3,3-tetrafluoropropoxy) phenyl] methanone oxime O-acetate At least one is preferred, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane 1-one-2-imine and [11- (2-ethylhexyl) -5- (2,4,6-trimethylbenzoyl) -11H-benzo [a] carbazol-8-yl]-[2- (2,2 , 3,3-tetrafluoropropoxy) phenyl] methanone oxime O-acetate is more preferred.

  As the O-acyloxime compound, a compound represented by the following formula (d1) (hereinafter sometimes referred to as “compound (d1)”) is preferable.

[In the formula (d1),
R ^d1 has an optionally substituted aromatic hydrocarbon group having 6 to 18 carbon atoms, an optionally substituted heterocyclic group having 3 to 36 carbon atoms, and a substituent. Represents a saturated hydrocarbon group having 1 to 15 carbon atoms, or an aralkyl group having 7 to 33 carbon atoms which may have a substituent, and a methylene group (- CH ₂ —) may be replaced by —O—, —CO—, —S—, —SO ₂ — or —NR ^d5 —.
In the present specification, the “aromatic hydrocarbon group” means a group consisting only of an aromatic ring moiety.
R ^d2 represents an aromatic hydrocarbon group having 6 to 18 carbon atoms, a heterocyclic group having 3 to 36 carbon atoms, or a saturated hydrocarbon group having 1 to 10 carbon atoms.
R ^d3 represents an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent and a heterocyclic group having 3 to 36 carbon atoms which may have a substituent.
R ^d4 represents an optionally substituted aromatic hydrocarbon group having 6 to 18 carbon atoms, or an optionally substituted aliphatic hydrocarbon group having 1 to 15 carbon atoms, The methylene group (—CH ₂ —) contained in the aliphatic hydrocarbon group may be replaced by —O—, —CO— or —S—, and the methine group (—CH 2) contained in the aliphatic hydrocarbon group. <) May be replaced with —PO ₃ <, and a hydrogen atom contained in the aliphatic hydrocarbon group may be substituted with an OH group.
R ^d5 represents a saturated hydrocarbon group having 1 to 10 carbon atoms, and the methylene group (—CH ₂ —) contained in the saturated hydrocarbon group may be replaced by —O— or —CO—. ]

The number of carbon atoms of the aromatic hydrocarbon group represented by R ^d1 is preferably 6 to 15, more preferably 6 to 12, and still more preferably 6 to 10. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group, and a terphenyl group. A phenyl group and a naphthyl group are more preferable, and a phenyl group is particularly preferable.
The aromatic hydrocarbon group represented by R ^d1 may have one or more substituents. The substituent is preferably substituted at the α-position or γ-position of the aromatic hydrocarbon group, and more preferably substituted at the γ-position. Examples of the substituent include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, butadecyl, pentadecyl And a saturated hydrocarbon group having 1 to 15 carbon atoms such as halogen atom such as fluorine atom, chlorine atom, iodine atom and bromine atom.
The saturated hydrocarbon group as the substituent preferably has 1 to 10 carbon atoms, and more preferably 1 to 7 carbon atoms. The saturated hydrocarbon group as the substituent may be linear, branched, or cyclic, or may be a group that combines a chain group and a cyclic group. The methylene group (—CH ₂ —) contained in the saturated hydrocarbon group as the substituent may be replaced with —O— or —S—. Further, the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, an iodine atom, or a bromine atom, and is preferably substituted with a fluorine atom. However, in the saturated hydrocarbon group as the substituent, adjacent methylene groups are not substituted at the same time, and the terminal methylene group is not substituted.

Examples of the substituent of the aromatic hydrocarbon group represented by R ^d1 include a group represented by the following formula. In the formula, * represents a bond.

Examples of the aromatic hydrocarbon group which may have a substituent represented by R ^d1 include groups represented by the following formulas. In the formula, * represents a bond.

As the aromatic hydrocarbon group which may have a substituent represented by R ^d1 , a group represented by the following formula is preferable.

[Wherein R ^d6 represents a saturated hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a halogen atom, and the hydrogen atom contained in R ^d6 may be substituted with a halogen atom. m2 represents an integer of 1 to 5. ]

Examples of the saturated hydrocarbon group represented by R ^d6 include the same groups as the saturated hydrocarbon groups exemplified as the substituent for the aromatic hydrocarbon group represented by R ^d1 . The saturated hydrocarbon group represented by R ^d6 has preferably 2 or more and 7 or less carbon atoms, and more preferably 2 or more and 5 or less. The saturated hydrocarbon group for R ^d6 may be linear, branched, or cyclic, and is preferably linear.
Examples of the halogen atom that may substitute the hydrogen atom contained in R ^d6 include a fluorine atom, a chlorine atom, an iodine atom, and a bromine atom, and a fluorine atom is particularly preferable. In addition, 2 or more and 10 or less of hydrogen atoms contained in R ^d6 are preferably substituted with halogen atoms, and 3 or more and 6 or less are preferably substituted with halogen atoms. The substitution position of the R ^d6 O— group is preferably the ortho position or the para position, and particularly preferably the para position.
M2 is preferably 1 to 2, particularly preferably 1.

The number of carbon atoms in the heterocyclic group represented by R ^d1 is preferably 3-20, more preferably 3-10, and even more preferably 3-5. Examples of the heterocyclic group include a pyrrolyl group, a furyl group, a thienyl group, an indolyl group, a benzofuryl group, and a carbazolyl group.
The heterocyclic group for R ^d1 may have one or more substituents. Examples of the substituent include the same groups as those exemplified as the substituent that the aromatic hydrocarbon group represented by R ^d1 may have.

The saturated hydrocarbon group represented by R ^d1 preferably has 1 to 12 carbon atoms. Examples of the saturated hydrocarbon group represented by R ^d1 include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group. Group, butadecyl group, pentadecyl group and the like. These saturated hydrocarbon groups may be linear, branched or cyclic, or may be a group in which a chain group and a cyclic group are combined. In the saturated hydrocarbon group for R ^d1 , the methylene group (—CH ₂ —) may be replaced by —O—, —CO—, —S—, —SO ₂ — or —NR ^d5 — The atom may be substituted with an OH group or an SH group. However, in the saturated hydrocarbon group, adjacent methylene groups are not substituted at the same time, and the terminal methylene group is not substituted.

R ^d5 represents a saturated hydrocarbon group having 1 to 10 carbon atoms, preferably a saturated hydrocarbon group having 1 to 5 carbon atoms, and more preferably a saturated hydrocarbon group having 1 to 3 carbon atoms. The saturated hydrocarbon group may be linear (linear or branched) or cyclic, and may be linear, branched, or cyclic. The group which combined the group and cyclic group may be sufficient. In the saturated hydrocarbon group for R ^d5 , the methylene group (—CH ₂ —) may be replaced by —O— or —CO—. However, in the saturated hydrocarbon group, adjacent methylene groups are not substituted at the same time, and the terminal methylene group is not substituted.

Specific examples of the saturated hydrocarbon group which may have a substituent represented by R ^d1 include groups represented by the following formulas. * Represents a bond.

Further, aralkyl group which may have a substituent, alkanediyl group derived from a saturated hydrocarbon group represented by an aromatic hydrocarbon group and the R ^d1 represented by R ^d1 represented by R ^d1 It is preferable that it is group which combined. The aralkyl group preferably has 7 to 33 carbon atoms, more preferably 7 to 18 carbon atoms, and still more preferably 7 to 12 carbon atoms. The aralkyl group may have one or more substituents, examples of the substituent, the aromatic hydrocarbon group represented by R ^d1, and saturated hydrocarbon group represented by R ^d1 The same group as the group illustrated as a substituent which may have may be mentioned. The group formed by combining a divalent group derived from a saturated hydrocarbon group represented by the R aromatic represented by ^d1 hydrocarbon group and the R ^d1, specifically, represented by the following formula The group can be mentioned. In the formula, * represents a bond. The methylene group (—CH ₂ —) contained in the aralkyl group may be replaced by —O—, —CO—, —S—, —SO ₂ — or —N (R ^d5 ) —. However, in the aralkyl group, adjacent methylene groups are not substituted simultaneously, and the terminal methylene group is not substituted.

Among them, as R ^d1 , an aromatic hydrocarbon group which may have a substituent or a saturated hydrocarbon group which may have a substituent is preferable, and an aromatic which may have a substituent A group hydrocarbon group is more preferred.

The number of carbon atoms of the aromatic hydrocarbon group represented by R ^d2 is preferably 6 to 15, more preferably 6 to 12, and still more preferably 6 to 10. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group, and a terphenyl group.
The number of carbon atoms of the heterocyclic group represented by R ^d2 is preferably 3-20, more preferably 3-10, and even more preferably 3-5. Examples of the heterocyclic group include a pyrrolyl group, a furyl group, a thienyl group, an indolyl group, a benzofuryl group, and a carbazolyl group.
The saturated hydrocarbon group represented by R ^d2 preferably has 1 to 7 carbon atoms, more preferably 1 to 5 carbon atoms, and particularly preferably 1 to 3 carbon atoms. Examples of the saturated hydrocarbon group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and the like. The saturated hydrocarbon group may be linear, branched, or cyclic, or may be a group that combines a linear group and a cyclic group.

Among them, R ^d2 is preferably a chain saturated hydrocarbon group, more preferably a chain saturated hydrocarbon group having 1 to 5 carbon atoms, and still more preferably a chain saturated hydrocarbon group having 1 to 3 carbon atoms. And is particularly preferably a methyl group.

The aromatic hydrocarbon group represented by R ^d3 preferably has 6 to 15 carbon atoms, more preferably 6 to 12 carbon atoms, and still more preferably 6 to 10 carbon atoms. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group, a terphenyl group, and the like, and a phenyl group and a naphthyl group are more preferable.
The aromatic hydrocarbon group represented by R ^d3 may have one or more substituents. The substituent is preferably substituted at the α-position or γ-position of the aromatic hydrocarbon group. The substituent is preferably an aliphatic hydrocarbon group having 1 to 15 carbon atoms, specifically, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl. An alkyl group having 1 to 15 carbon atoms such as a group and a decyl group; an alkenyl group having 1 to 15 carbon atoms such as an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, a nonenyl group, and a decenyl group; Is mentioned.
As for the said aliphatic hydrocarbon group as a substituent, it is more preferable that it is 1-7. In addition, the aliphatic hydrocarbon group as the substituent may be any of linear, branched, and cyclic, and may be a group in which a linear group and a cyclic group are combined. In the aliphatic hydrocarbon group as the substituent, the methylene group (—CH ₂ —) may be replaced by —O—, —CO— or —S—, and the methine group (—CH <) is , -N <may be substituted. However, in the aliphatic hydrocarbon group as the substituent, adjacent methylene groups are not substituted at the same time, and the terminal methylene group is not substituted.

Examples of the aliphatic hydrocarbon group as a substituent for the aromatic hydrocarbon group represented by R ^d3 include groups represented by the following formulas. In the formula, * represents a bond.

Examples of the aromatic hydrocarbon group which may have a substituent represented by R ^d3 include a group represented by the following formula. In the formula, * represents a bond.

The number of carbon atoms of the heterocyclic group represented by R ^d3 is preferably 3 to 20, more preferably 3 to 10, and further preferably 3 to 5. Examples of the heterocyclic group include a pyrrolyl group, a furyl group, a thienyl group, an indolyl group, a benzofuryl group, and a carbazolyl group.
Further, the heterocyclic group represented by R ^d3 may have one or more substituents, and the substituent includes an aromatic hydrocarbon group represented by R ^d1. Examples thereof include the same groups as those exemplified as the good substituent.

Among these, R ^d3 is preferably an aromatic hydrocarbon group having a substituent, and the substituent is preferably a chain alkyl group having 1 to 7 carbon atoms (more preferably 1 to 3 carbon atoms), The number of substituents is preferably 2 or more and 5 or less.

The number of carbon atoms of the aromatic hydrocarbon group represented by R ^d4 is preferably 6 to 15, more preferably 6 to 12, and still more preferably 6 to 10. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group, and a terphenyl group. A phenyl group and a naphthyl group are more preferable, and a phenyl group is particularly preferable.
Moreover, the aromatic hydrocarbon group represented by R ^d4 may have one or more substituents. Examples of the substituent include the same groups as the substituent that the aromatic hydrocarbon group represented by R ^d1 may have.

The number of carbon atoms of the aliphatic hydrocarbon group represented by R ^d4 is preferably 1-13, more preferably 2-10, more preferably from 4 to 9. Examples of the aliphatic hydrocarbon group for R ^d4 include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, Alkyl groups such as butadecyl and pentadecyl; ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl Alkenyl groups such as groups; and the like. These aliphatic hydrocarbon groups may be chain (linear or branched), cyclic, or a combination of a chain group and a cyclic group. In the aliphatic hydrocarbon group represented by R ^d4 , the methylene group (—CH ₂ —) may be replaced by —O—, —CO— or —S—, and a methine group (—CH <) it may be replaced by -PO ₃ <. A hydrogen atom contained in the aliphatic hydrocarbon group may be substituted with an OH group. However, in the aliphatic hydrocarbon group, adjacent methylene groups are not substituted at the same time, and the terminal methylene group is not substituted.

Examples of the aliphatic hydrocarbon group which may have a substituent represented by R ^d4 include a group represented by the following formula. In the formula, * represents a bond.

R ^d4 is preferably a chain aliphatic hydrocarbon group which may have a substituent, more preferably a chain alkyl group having no substituent, and still more preferably no substituent. It is a branched alkyl group.

  Examples of the compound (d1) include compounds (d1-1) to (d1-67) represented by the formula (d1) as shown in Tables 1 to 7 below. In the table, * represents a bond.

  Among them, compounds (d1-3) to (d1-6), (d1-18) to (d1-52), (d1-55), (d1-56), (d1-60), (d1-61) Are more preferable, and compounds (d1-3) to (d1-6) and (d1-18) to (d1-41) are more preferable, and compounds (d1-24) and (d1-36) to (d1) are more preferable. d1-40), particularly preferably compound (d1-24).

  The content of the polymerization initiator represented by the formula (d1) is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass in 100% by mass of the polymerization initiator (D). % Or more, particularly preferably 95% by mass or more.

  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, benzyldimethyl And luketal. Commercial products such as Irgacure (registered trademark) 369, 907, 379 (above, manufactured by BASF) may be used.

  Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and 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 (trialkoxy) Phenyl) biimidazole (for example, see JP-B-48-38403, JP-A-62-174204, etc.), a phenyl group at the 4,4 ′, 5,5′-position is substituted with a carboalkoxy group. Imidazole compounds (see, for example, JP-A-7-10913).

  Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxy Naphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) ) -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) -Methylphenyl) Thenyl] -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.

  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.

  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 more preferably. Is a polymerization initiator containing an O-acyloxime compound.

  The content of the polymerization initiator (D) is preferably 0.1 to 40 parts by mass, more preferably 1 to 30 parts per 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). Part by mass.

  The blue curable resin composition of the present invention may further contain a solvent (E), a leveling agent (F) and the like.

<Solvent (E)>
A solvent (E) is not specifically limited, The solvent normally used in the said field | area can be used. For example, 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 (intramolecular) Solvent containing -COO- and -O-), ketone solvent (solvent containing -CO- in the molecule and not containing -COO-), alcohol solvent (containing OH in the molecule, -O-,- A solvent not containing CO- and -COO-), an aromatic hydrocarbon solvent, an amide solvent, 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 , Methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, γ-butyrolactone and the like.

  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.

These solvents may be used alone or in combination of two or more.
Among them, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol methyl ether acetate, 3 -Methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, N, N-dimethylformamide, N-methylpyrrolidone, etc. are preferable, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether , Ethylene glycol monobutyl ether, dipropylene glycol Ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol, ethyl 3-ethoxypropionate, N- methylpyrrolidone is more preferred.

  Content of a solvent (E) becomes like this. Preferably it is 50-95 mass% with respect to the total amount of a blue curable resin composition, More preferably, it is 55-92 mass%. In other words, the solid content of the blue curable resin composition is preferably 5 to 50% by mass, more preferably 8 to 45% 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)>
The blue curable resin composition of the present invention may contain a 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 a surfactant 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.

  When the leveling agent (F) is contained, the content thereof is preferably 0.001% by mass or more and 0.7% by mass or less, more preferably 0.002%, based on the total amount of the blue curable resin composition. It is 0.005 mass% or more and 0.3 mass% or less more preferably. When the content of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.

<Other ingredients>
The blue curable resin composition of the present invention includes, as necessary, a polymerization initiation aid, a filler, another polymer compound, an adhesion promoter, an antioxidant, a light stabilizer, a chain transfer agent, and the like in the technical field. And may contain known additives.

<Method for producing blue curable resin composition>
The blue curable resin composition of the present invention includes, for example, a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a solvent (E) used as necessary. It can be prepared by mixing the leveling agent (F) and other components.
The blue pigment (A2-2) and the pigment (A3-2) used as necessary are mixed in advance with a part or all of the solvent (E) until the average particle diameter of the pigment is about 0.2 μm or less. It is preferable to disperse using a bead mill or the like. Under the present circumstances, you may mix | blend a pigment dispersant and some or all of resin (B) as needed.
The target blue curable resin composition can be prepared by mixing the remaining components in the pigment dispersion thus obtained so as to have a predetermined concentration.
It is preferable to prepare a solution by dissolving compound (IB) in part or all of the solvent (E) in advance. The solution is preferably filtered with a filter having a pore size of about 0.01 to 1 μm.
It is preferable to filter the blue curable resin composition after mixing with a filter having a pore diameter of about 0.01 to 10 μm.

<Color filter manufacturing method>
Examples of the method for producing a colored pattern from the blue 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 blue curable resin composition is applied to a substrate, dried to form a colored composition layer, and the colored composition layer is exposed and developed through a photomask. 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 can be used as 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, for example, 0.1 to 30 μm, preferably 0.1 to 20 μm, more preferably 0.5. ~ 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 blue 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. Specifically, examples of the light source include a mercury lamp, a light emitting diode, a metal halide lamp, and a halogen lamp.
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 blue curable resin composition of the present invention, a color filter having excellent brightness can be formed. 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.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by the following examples, but may be appropriately modified within a range that can meet the purpose described above and below. Of course, it is possible to implement them, and they are all included in the technical scope of the present invention. In the examples, “%” and “part” representing the content or amount used are based on mass unless otherwise specified.

  In the following examples, the structure of the compound was confirmed by mass spectrometry (LC; Agilent 1200 type, MASS; Agilent LC / MSD type).

[Synthesis Example 1]
40.6 parts of compound (VI) and 8 parts of diethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) as compound (III) were mixed in the presence of 50 parts of 1-methyl-2-pyrrolidone under light-shielding conditions at 30 ° C. For 3 hours. The obtained reaction solution was cooled to room temperature, then added to a mixed solution of 400 parts of water and 20 parts of 35% hydrochloric acid and stirred at room temperature for 1 hour, whereby crystals were deposited. The precipitated crystals were obtained as a suction filtration residue and then dried to obtain 44 parts of a compound represented by the formula (I-1-A).

  Next, 44 parts of the compound represented by the formula (I-1-A) and 21.4 parts of trimethoxy [3- (methylamino) propyl] silane (manufactured by Tokyo Chemical Industry Co., Ltd.) are combined with 1-methyl-2- Heated at 100 ° C. for 5 hours in the presence of 50 parts of pyrrolidone. The obtained reaction solution was cooled to room temperature, filtered, washed with 100 parts of water, and the obtained crystal was dried to obtain 52 parts of a compound represented by the formula (I-1).

Identification of compound represented by formula (I-1) (mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 599.2
Exact Mass: 598.1

0.35 g of the compound represented by the formula (I-1) was dissolved in chloroform to a volume of 250 cm ³ , 2 cm ^{3 of} which was diluted with ion-exchanged water 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). The maximum absorption wavelength λ _max of this compound was 546 nm.

(Synthesis of resin)
An appropriate amount of nitrogen was passed through a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace the nitrogen atmosphere, and 280 parts by weight of propylene glycol monomethyl ether acetate was added and heated to 80 ° C. with stirring. Next, 38 parts by weight of acrylic acid, 289 parts by weight of a mixture of 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8 and / or 9-yl acrylate, 125 parts of propylene glycol monomethyl ether acetate Part of the mixed solution was added dropwise over 5 hours. On the other hand, a mixed solution prepared by dissolving 33 parts by weight of 2,2-azobis (2,4-dimethylvaleronitrile) in 235 parts by weight of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After completion of dropping, the mixture was kept at the same temperature for 4 hours, and then cooled to room temperature. B-1) was obtained. The produced copolymer had a weight average molecular weight Mw of 9,200 and a dispersity of 2.08.

About the measurement of polystyrene conversion weight average molecular weight Mw and number average molecular weight Mn of resin obtained by said synthesis example, it carried out on condition of the following using GPC method.
Apparatus: HLC-8120GPC (manufactured by Tosoh Corporation)
Column; TSK-GELG2000HXL
Column temperature: 40 ° C
Solvent: THF
Flow rate: 1.0 mL / min
Test liquid solid content concentration: 0.001 to 0.01% by mass
Injection volume: 50 μL
Detector; RI
Reference material for 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 of blue curable resin composition)
Each component was mixed so that it might become a composition shown in Table 8, and the blue curable resin composition was obtained.

In Table 8, each component represents the following.
(A) Colorant: A-1: C.I. I. Pigment Blue 15: 6 (pigment) 12.0 parts, acrylic pigment dispersant 2.0 parts and propylene glycol monomethyl ether acetate 80.5 parts mixed and dispersed in advance (A) Colorant: A-2: A solution obtained by mixing 5.0 parts of the compound represented by the formula (I-1) and 89.9 parts of propylene glycol monomethyl ether acetate

  (A) Colorant: A-3: Dye (A-3) (mixture of compounds represented by formula (A3-1) to formula (A3-8)) 7.2 parts and propylene glycol monomethyl ether acetate 92. 7 parts mixed solution

(B) Resin: B-1: Resin B-1 solution (C) Polymerizable compound: C-1: Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd .; KAYARAD (registered trademark) DPHA)
(D) Polymerization initiator: D-1:

(E) Solvent: E-1: Propylene glycol monomethyl ether acetate (F) Leveling agent: F-1: Polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.)

[Formation of 50 μm square hole pattern]
A blue curable resin composition was applied on a 2-inch square glass substrate (Eagle XG; manufactured by Corning) by spin coating, and then prebaked at 100 ° C. for 3 minutes. After cooling, the substrate coated with the blue curable resin composition is exposed to the atmosphere using an exposure machine (TME-150RSK; manufactured by Topcon Corporation) through a mask pattern in which 50 μm square holes are arranged. In the atmosphere, light was irradiated with an exposure amount of 80 mJ / cm ² (365 nm standard). After the exposure, development was performed using a developer at 23 ° C. for 60 seconds, followed by rinsing with running water for 20 seconds and then spray drying. Thereafter, post-baking was performed at 230 ° C. for 30 minutes to form a 50 μm square hole pattern on the glass substrate.

[Film thickness measurement]
About the obtained 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 9.

[Chromaticity evaluation]
About the pattern on the obtained glass substrate, spectroscopy was measured using the colorimeter (OSP-SP-200; Olympus Co., Ltd.), and in the XYZ color system of CIE using the color matching function of C light source. The xy chromaticity coordinates (x, y) were measured. The results are shown in Table 9. From the chromaticity coordinates, it was confirmed that the color of the pattern on the obtained glass substrate was blue.

  The pattern formed from the colored curable resin composition containing the colorants (A-1) and (A-2) is the pattern formed from the colored curable resin composition of the comparative example when the chromaticity is uniform. It was found that Y was large compared to, and the brightness was excellent.

  According to the blue curable resin composition of the present invention, a color filter having excellent brightness can be formed. 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.

Claims (7)

  It contains a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D). As the colorant (A), the maximum absorption wavelength in chloroform is 500 nm to 600 nm, and a silicon atom A blue curable resin composition comprising a dye (A1) having a colorant and a blue colorant. The blue curable resin composition of Claim 1 in which the said polymerization initiator (D) contains the polymerization initiator represented by a following formula (d1).

[In the formula (d1),
R ^d1 has an optionally substituted aromatic hydrocarbon group having 6 to 18 carbon atoms, an optionally substituted heterocyclic group having 3 to 36 carbon atoms, and a substituent. Represents a saturated hydrocarbon group having 1 to 15 carbon atoms, or an aralkyl group having 7 to 33 carbon atoms which may have a substituent, and a methylene group (- CH ₂ —) may be replaced by —O—, —CO—, —S—, —SO ₂ — or —NR ^d5 —.
R ^d2 represents an aromatic hydrocarbon group having 6 to 18 carbon atoms, a heterocyclic group having 3 to 36 carbon atoms, or a saturated hydrocarbon group having 1 to 10 carbon atoms.
R ^d3 represents an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent and a heterocyclic group having 3 to 36 carbon atoms which may have a substituent.
R ^d4 represents an optionally substituted aromatic hydrocarbon group having 6 to 18 carbon atoms, or an optionally substituted aliphatic hydrocarbon group having 1 to 15 carbon atoms, The methylene group (—CH ₂ —) contained in the aliphatic hydrocarbon group may be replaced by —O—, —CO— or —S—, and the methine group (—CH 2) contained in the aliphatic hydrocarbon group. <) May be replaced with —PO ₃ <, and a hydrogen atom contained in the aliphatic hydrocarbon group may be substituted with an OH group.
R ^d5 represents a saturated hydrocarbon group having 1 to 10 carbon atoms, and the methylene group (—CH ₂ —) contained in the saturated hydrocarbon group may be replaced by —O— or —CO—. ]   The blue curable resin composition according to claim 1 or 2, wherein the content of the colorant (A) is 3% by mass or more and 60% by mass or less with respect to the total solid content of the blue curable resin composition. .   The blue curable resin composition according to any one of claims 1 to 3, wherein the blue colorant is a blue phthalocyanine pigment.   The mass ratio of the content of the dye (A1) to the content of the blue colorant (dye (A1) / blue colorant) is 0.01 or more and 2 or less. Blue curable resin composition.   The color filter formed from the blue curable resin composition in any one of Claims 1-5.   A display device comprising the color filter according to claim 6.