JP7148226B2 - Red curable resin composition - Google Patents

Description

The present invention relates to a red curable resin composition.

Colored curable resin compositions are used in the production 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 colored curable resin composition containing a compound represented by the following formula as a coloring agent is known (for example, Patent Document 1).

JP 2016-027075 A

Conventionally known colored curable resin compositions have room for improvement in terms of the presence or absence of foreign matter on the surface of the resulting color filter.

The present invention includes the following inventions.
[1] A colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D) and a solvent (E), wherein the colorant (A) has a silicon atom and a dye (A1) having a maximum absorption wavelength in chloroform of 500 nm to 600 nm, and a red pigment (P),
The solvent (E) contains propylene glycol monomethyl ether acetate, and
A red curable resin composition in which the content of propylene glycol monomethyl ether acetate is 10% by mass or more and 78% by mass or less in the total amount of the solvent (E).
[2] The red curable resin composition according to [1] above, which contains a solvent having an SP value higher than that of propylene glycol monomethyl ether acetate in an amount of 22% by mass or more based on the total amount of the solvent (E).
[3] selected from the group consisting of propylene glycol monomethyl ether, ethylene glycol monobutyl ether, diacetone alcohol, ethyl lactate, 3-methoxy-1-butanol, ethyl 3-ethoxypropionate, cyclohexanone, γ-butyrolactone, and N-methylpyrrolidone; The red curable resin composition according to [1] or [2], which contains 22% by mass or more of the solvent (E) in the total amount.
[4] The red curable resin composition according to any one of [1] to [3], wherein the dye (A1) is a compound having a xanthene skeleton.
[5] The red curable resin composition according to any one of [1] to [4], further comprising a metal complex salt azo dye as a coloring agent (A).
[6] A color filter formed from the red curable resin composition according to any one of [1] to [5].
[7] A display device including the color filter described in [6] above.

In the color filter formed from the red curable resin composition of the present invention, generation of foreign matter on the surface is suppressed.

The red curable resin composition of the present invention contains a coloring agent (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D).
In addition, the compounds and functional groups exemplified in this specification can be used singly or in combination unless otherwise specified.

The red curable resin composition of the present invention includes, as a coloring agent (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 red pigment (P). 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 maximum absorption wavelength of 500 nm to 560 nm is particularly preferable.

As the dye (A1), a dye having a silicon atom and having an imidazole skeleton, a triarylmethane skeleton, a cyanine skeleton, or a xanthene skeleton is preferable. Dyes having a silicon atom and having an imidazole skeleton include, for example, compounds represented by formula (IA) disclosed in Japanese Patent Publication No. 2010-526897.

[In Formula (IA), R ¹ is a group represented by 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. ]]
As the compound represented by formula (IA), a compound represented by the following formula is preferably exemplified.

Among the dyes (A1), dyes having a silicon atom and at least one skeleton selected from the group consisting of a triarylmethane skeleton, a cyanine skeleton and a xanthene skeleton are preferred, and have a silicon atom and a xanthene Dyes having a backbone are more preferred. As the dye having a silicon atom and a xanthene skeleton, a dye having a xanthene skeleton having an organosilicon group as a substituent is preferable. 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, those having a xanthene skeleton having a silylalkyl group such as a trimethylsilylalkyl group, a triethylsilylalkyl group, a trimethoxysilylalkyl group, and a triethoxysilylalkyl group as a substituent A dye is preferable, and a compound represented by formula (IB) (hereinafter sometimes referred to as "compound (IB)") is more preferable. Compound (IB) also includes its tautomer.

[In the formula (IB), R ²¹ to R ²⁴ are each independently a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, a phenyl group which may have a substituent, or the formula ( represents a group represented by ib); At least one of R ²¹ to R ²⁴ is a group represented by formula (ib).
* ^-R50 -Si ⁽ R29) 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. Plural 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 -- are 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 -- are not substituted at the same time, and terminal --CH ₂ -- is not substituted.
R ²⁵ and R ²⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
R ²⁷ and R ²⁸ each independently represent -OH, -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z ⁺ , -CO ₂ ^- , -CO ₂ H, -CO ₂ ^- Z ⁺ , -CO ^{2R 10} , --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 a 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.
Each R ¹³ independently represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.
p represents an integer of 0 to 4; ]

Compounds represented by formula (IB) also include compounds represented by formula (IC) (hereinafter sometimes referred to as "compound (IC)") and tautomers thereof.

[In the formula (IC), R ³¹ to R ³⁴ are each independently a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, a phenyl group which may have a substituent, or the formula ( ic) represents a group. At least one of R ³¹ to R ³⁴ is a group represented by 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 to 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 -- are 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 each independently represent -OH, -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z ⁺ , -CO ₂ ^- , -CO ₂ H, -CO ₂ ^- Z ⁺ , -CO ^{2R 10} , --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 a 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.
Each R ¹³ independently represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.
m represents an integer of 0 to 4; ]

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

Preferred monovalent saturated hydrocarbon groups having 1 to 10 carbon atoms represented by R ²¹ to R ²⁴ and R ³¹ to R ³⁴ are methyl group, ethyl group, propyl group and butyl group.

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

—CH ₂ — contained in the monovalent saturated hydrocarbon groups 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 -- are not substituted at the same time, and terminal --CH ₂ -- is not substituted.
Examples of monovalent saturated hydrocarbon groups 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 branched-chain alkyl groups having 3 to 20 carbon atoms such as group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group and 2-ethylhexyl group; cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, Alicyclic saturated hydrocarbon groups having 3 to 20 carbon atoms such as cyclooctyl group and tricyclodecyl group can be mentioned.

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

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

Examples of groups 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 formulae (* denotes represents a bond).

—CH ₂ — contained in the monovalent saturated hydrocarbon groups having 1 to 10 carbon atoms represented by R ²¹ to R ²⁴ and R ³¹ to R ³⁴ are —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 -- are not substituted at the same time, and terminal --CH ₂ -- is not substituted.

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

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

Examples of groups 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 formulae (* denotes a bond hand).

Examples of groups 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 formulae (* denotes a bond hand).

Examples of groups 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 formulae (* denotes a bond hand).

The phenyl groups represented by R ²¹ to R ²⁴ and R ³¹ to R ³⁴ may have substituents. The substituents include halogen atoms, -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 .

Examples of monovalent saturated hydrocarbon groups having 1 to 20 carbon atoms represented by R ¹⁰ to R ¹³ include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group and n-hexyl group. , n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-dodecyl group, n-hexadecyl group and n-icosyl group, linear alkyl groups having 1 to 20 carbon atoms; isopropyl branched-chain alkyl groups having 3 to 20 carbon atoms such as group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group and 2-ethylhexyl group; cyclopropyl group, cyclopentyl group, cyclohexyl group, cyclo Alicyclic saturated hydrocarbon groups having 3 to 20 carbon atoms such as heptyl group, cyclooctyl group and tricyclodecyl group can be mentioned.

—OR ¹⁰ includes, for example, methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy and icosyloxy groups.

—SO ₃ ⁻ Z ⁺ is preferably —SO ₃ ⁻ N ⁺ (R ¹³ ) ₄ .

—CO ₂ R ¹⁰ includes, for example, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a tert-butoxycarbonyl group, a hexyloxycarbonyl group and an icosyloxycarbonyl group.

—SR ¹⁰ includes, for example, a methylsulfanyl group, an ethylsulfanyl group, a butylsulfanyl group, a hexylsulfanyl group, a decylsulfanyl group and an icosylsulfanyl group.

—SO ₂ R ¹⁰ includes, for example, methylsulfonyl, ethylsulfonyl, butylsulfonyl, hexylsulfonyl, decylsulfonyl and icosylsulfonyl groups.

—SO ₃ R ¹⁰ includes, for example, 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-cyclopentylsulfamoyl 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-1-substituted sulfamoyl groups such as N-(2-ethylhexyl)sulfamoyl group, N-(1,5-dimethyl)hexylsulfamoyl group and 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-isopropylmethylsulfamoyl group moyl group, N,N-tert-butylmethylsulfamoyl group, N,N-butylethylsulfamoyl group, N,N-bis(1-methylpropyl)sulfamoyl group, N,N-heptylmethylsulfamoyl group and N,N-2 substituted sulfamoyl groups such as groups.

The substituents of the phenyl groups represented by R ²¹ to R ²⁴ and R ³¹ to R ³⁴ are preferably —R ¹⁰ , more preferably monovalent saturated hydrocarbon groups having 1 to 10 carbon atoms.

At least one of R ²¹ to R ²⁴ is a group represented by formula (ib).
In the group represented by 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 methyl group, ethyl group, propyl group and butyl group.

The alkoxy group having 1 to 4 carbon atoms represented by R ²⁹ includes methoxy, ethoxy, propoxy, tert-butoxy and the like.

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

The alkanediyl groups having 1 to 10 carbon atoms represented by R ⁵⁰ include methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, isopropylene, isobutylene, 2-methyltri Examples include methylene group, isopentylene group, isohexylene group, isooctylene group, 2-ethylhexylene group, etc. Among them, alkanediyl groups having 1 to 6 carbon atoms are preferred, and alkanediyl groups having 1 to 4 carbon atoms are more preferred.

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

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

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

In the formula (ib), the group in which —CH ₂ — constituting R ⁵⁰ is substituted with —NR ¹¹ — includes, for example, the following groups (* represents a bond).

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

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

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

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

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

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

At least one of R ³¹ to R ³⁴ is preferably a group represented by formula (ic).
In formula (ic), examples of the alkyl group having 1 to 4 carbon atoms represented by R ³⁹ include methyl group, ethyl group, propyl group and 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 formula (ic) include groups represented by the following formulas (i-1) to (i-12). As the group represented by formula (ic), groups represented by formula (i-2), formula (i-3), formula (i-5) and formula (i-6) are preferable.

Examples of alkyl groups 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, tert-butyl, isopentyl and neopentyl groups.

—SO ₃ ⁻ Z ⁺ represented by R ²⁷ , R ²⁸ , R ³⁷ and R ³⁸ is preferably —SO ₃ Na or —SO ₃ K.

—CO ₂ ⁻ Z ⁺ represented by R ²⁷ , R ²⁸ , R ³⁷ and R ³⁸ is preferably —CO ₂ Na or —CO ₂ K.

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

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

—SO ₂ NR ¹¹ R ¹² represented by R ²⁷ , R ²⁸ , R ³⁷ and R ³⁸ are, 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-pentylsulfamoyl group 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)sulfamoyl group, N-cyclopentylsulfamoyl 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, N-(1,1,2,2) -N-1 substituted sulfamoyl groups such as tetramethylbutyl)sulfamoyl group;
N,N-dimethylsulfamoyl group, N,N-ethylmethylsulfamoyl group, N,N-diethylsulfamoyl group, N,N-propylmethylsulfamoyl group, N,N-isopropylmethylsulfamoyl group moyl group, N,N-tert-butylmethylsulfamoyl group, N,N-butylethylsulfamoyl group, N,N-bis(1-methylpropyl)sulfamoyl group, N,N-heptylmethylsulfamoyl group and N,N-2 substituted sulfamoyl groups such as groups.

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.

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

Z ⁺ is preferably ⁺ N(R ¹³ ) ₄ .
All four R ¹³ in ⁺ N(R ¹³ ) ₄ are preferably the same. The total number of carbon atoms of the four R ¹³ is preferably 20-80, more preferably 20-60.

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, more preferably a methyl group, an ethyl group or a propyl group.

At least one of R ²¹ to R ²⁴ is a group represented by formula (ib), and other R ²¹ to R ²⁴ are preferably a methyl group, an ethyl group, a propyl group and the following groups ( * represents a bond with a nitrogen atom),

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

At least one of R ³¹ to R ³⁴ is a group represented by formula (ic), and the other R ³¹ to R ³⁴ are preferably a methyl group, an ethyl group, a propyl group and the following groups,

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

^R25 , ^R26 , ^R35 and ^R36 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 be.

R ¹⁰ is preferably methyl, ethyl, propyl or butyl.

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

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

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

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

Specific examples of compound (IB) include those shown below. Compounds (IB) include (I-1) ~ (I-4), (I-13) ~ (I-16), (I-25) ~ (I-28), (I-37) ~ ( I-40), (I-49) ~ (I-54), (I-55) ~ (I-62), (I-87) ~ (I-94), (I-117) ~ (I- 123) are preferred, and (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 preferred.

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

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 above. ^X2 represents a halogen atom or a trifluoromethylsulfonyloxy group. ] (hereinafter sometimes referred to as "compound (IV)"), and the formula (V)

[In the formula, R ²³ and R ²⁴ each have the same meaning as above. ]
It can be produced by mixing and reacting a compound represented by (hereinafter sometimes referred to as "compound (V)") in an organic solvent.

The halogen atom represented by X ² includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a chlorine atom.
X ² is preferably a halogen atom, 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, per 1 mol of compound (IV). be.

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

[In the formula, R ²⁵ , R ²⁶ , R ²⁸ and p have the same meanings as above.
X ¹ and X ² each independently represent a halogen atom or a trifluoromethylsulfonyloxy group.
R ⁴⁰ represents -SO ₂ - or -CO-. ]
A compound represented by (hereinafter sometimes referred to as "compound (VI)"), and formula (III)

[In the formula, R ²¹ and R ²² have the same meanings as above. ]
The compound represented by (hereinafter sometimes referred to as "compound (III)") is mixed and reacted in an organic solvent, and then the formula (V)

[In the formula, R ²³ and R ²⁴ each have the same meaning as above. ]
can be produced by mixing and reacting the compound represented by in an organic solvent.

The halogen atom represented by X ¹ includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, 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, 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, per 1 mol of compound (VI). more preferably 1 mol or more and 3 mol or less, and particularly preferably 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, per 1 mol of compound (VI). more preferably 1 mol or more and 3 mol or less, and particularly preferably 1 mol or more and 2 mol or less.

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, per 1 mol of compound (VI). more preferably 1 mol or more and 3 mol or less, and particularly preferably 1 mol or more and 2 mol or less.

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

Compound (IB) is useful as a dye. Due to its high solubility in organic solvents, it is particularly useful as a coloring agent for colored curable resin compositions used for 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 0.2% by mass or more, and 30% by mass or less, based on 100% by mass of the total solid content of the red curable resin composition. is preferred, and 20% by mass or less is more preferred.
Here, the "total amount of solid content" in this specification refers to the amount obtained by subtracting the content of the solvent from the total amount of the red 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.

The content of the dye (A1) is preferably 0.01% by mass or more and 80% by mass or less, more preferably 0.1% by mass or more and 60% by mass or less, based on 100% by mass of the total amount of the colorant (A). % or more and 40 mass % or less is more preferable.
Furthermore, the content of 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 dye (A1).
The content of the dye (A1) is preferably 10% by mass or more, more preferably 20% by mass or more, more preferably 100% by mass, more preferably 100% by mass in total of the dyes. It may be 80% by mass or less.

<Red Pigment (P)>
The red curable resin composition of the present invention contains a red pigment (P) as a coloring agent (A) in addition to the dye (A1).
Examples of the red pigment (P) include red compounds among compounds classified as pigments in the Color Index (published by The Society of Dyers and Colourists).
Specifically, C.I. I. Pigment Red 9 (hereinafter, the description of CI Pigment Red is omitted and only the number is described), 97, 105, 122, 123, 144, 149, 166, 168, 175, 176, 177, 180 , 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, etc.; I. Pigment Red 254, 255 are preferred.

The content of the red pigment (P) is preferably 0.1% by mass or more, more preferably 10% by mass or more, and still more preferably 30% by mass or more in 100% by mass of the colorant (A), It is preferably 99% by mass or less, more preferably 95% by mass or less.

Furthermore, the total content of the dye (A1) and the red pigment (P) 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). be.

In addition, the content ratio of the dye (A1) and the red pigment (P) (dye (A1)/red pigment (P)) is preferably 1/99 to 99/1, more preferably 1/99 to 99/1 on a mass basis. is 2/98 to 95/5.

<Pigment (Q)>
The red curable resin composition of the present invention may contain a pigment (Q) other than the red pigment (P) as the colorant (A) to the extent that the performance of the resulting color filter is not impaired. The pigment (Q) is not particularly limited, and known pigments can be used. Examples thereof include compounds classified as pigments in the Color Index (published by The Society of Dyers and Colourists).

The pigment (Q) (which is different from the red pigment (P)) is not particularly limited, and known pigments can be used. compounds that are

Examples of the pigment (Q) include C.I. I. Pigment Yellow 1 (hereinafter, the description of C.I. 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;
C. I. Orange pigments such as Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;
C. I. Blue pigments such as Pigment Blue 15, 15:3, 15:4, 15:6, 60, 80;
C. I. Violet color pigments such as Pigment Violet 1, 19, 23, 29, 32, 36, 38;
C. I. Green pigments such as Pigment Green 7, 36, 58;
C. I. Brown pigments such as Pigment Brown 23, 25;
C. I. Black pigments such as Pigment Black 1 and 7 are included.
These pigments may be used alone or in combination of two or more.

As the pigment (Q), a yellow pigment or an orange pigment is preferred.

The total pigment content is preferably 0.1% by mass or more, more preferably 10% by mass or more, still more preferably 30% by mass or more, and even more preferably 30% by mass or more, based on 100% by mass of the total amount of the colorant (A). It is preferably 50% by mass or more, preferably 99% by mass or less, and more preferably 95% by mass or less.

<Dye (A2)>
The red curable resin composition of the present invention may contain a dye (A2) other than the dye (A1) as the colorant (A) to the extent that the performance of the resulting color filter is not impaired. Dye (A2) (but different from dye (A1)) includes oil-soluble dyes, acid dyes, basic dyes, direct dyes, mordant dyes, amine salts of acid dyes, sulfonamide derivatives and metal complex salts of acid dyes. Examples include dyes such as dyes, for example, compounds classified as dyes in the Color Index (published by The Society of Dyers and Colorists) and known dyes described in Stain Note (Shikisensha). Further, according to the chemical structure, azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes other than the dye (A1), phthalocyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, squarylium dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes and nitro dyes; Among 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 Blue 4, 5, 37, 67, 70, 90;
C. I. 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 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. Acid Green 1, 3, 5, 9, 16, 50, 58, 63, 65, 80, 104, 105, 106, 109 and the like. I. acid dye,
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; 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 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, 245, 246, 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293;
C. I. Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82 and the like. I. direct dye,
C. I. C.I. I. disperse dyes,
C. I. Basic Red 1, 10;
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. Basic Green 1; I. basic dye,
C. I. Reactive Yellow 2,76,116;
C. I. Reactive Orange 16;
C. I. C.I. Reactive Red 36; I. reactive dyes,
C. I. Mordant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;
C. I. Modern Tread 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. Mordant 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. Mordant Violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;
C. I. Modant 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
C. I. C.I. I. modant dye,
C. I. C.I. I. vat dye,
etc.
Among them, red dyes, orange dyes and yellow dyes are preferred.
These dyes may be appropriately selected according to the spectral spectrum of the desired color filter. These dyes may be used alone or in combination of two or more.

As the dye (A2), a metal complex dye is preferred. A metal complex salt dye is a dye complexed with a metal atom using a dye molecule containing a group capable of forming a complex with a metal atom in the molecule as a ligand. Examples of dyes that serve as ligands include azo dyes and methine dyes, with azo dyes being preferred. In other words, metal complex salt dyes include metal complex salt azo dyes, metal complex salt methine dyes, and the like, and metal complex salt azo dyes are preferred. Examples of the metal atom include chromium, cobalt, and nickel, with chromium and cobalt being preferred.

Examples of the metal complex dye include C.I. I. Solvent Yellow 13, 19, 21, 25, 25:1, 62, 79, 81, 82, 83, 83:1, 88, 89, 90, 151, 161; C.I. I. Solvent Orange 5, 11, 20, 40:1, 41, 45, 54, 56, 58, 62, 70, 81, 99; C.I. I. Solvent Red 8, 35, 83:1, 84:1, 90, 90:1, 91, 92, 118, 119, 122, 124, 125, 127, 130, 132, 160, 208, 212, 214, 225, 233, 234, 243; I. Solvent Violet 2, 21, 21:1, 46, 49, 58, 61; C.I. I. Solvent Blue 137; C.I. I. Solvent Brown 28, 42, 43, 44, 53, 62, 63, C.I. I. Acid Yellow 59, 121; C.I. I. Acid Orange 74, 162; C.I. I. Examples include Acid Red 211 and metal complex salt dyes described in JP-A-2010-170117. These metal complex dyes may be used alone or in combination of two or more.
Among these, the metal complex dye preferably has a maximum absorption wavelength in the range of 410 nm or more and 580 nm or less, and more preferably has a maximum absorption wavelength in the range of 490 nm or more and 580 nm or less.

The ratio of the content of the dye (A1) and the metal complex salt dye (dye (A1)/metal complex salt dye) is preferably 0.1 or more, more preferably 0.2 or more, on a mass basis, and 10 is preferably 4 or less, more preferably 4 or less.

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

The content of the coloring agent (A) is preferably 1% by mass or more and 70% by mass or less, more preferably 1% by mass or more and 60% by mass or less, and still more preferably 1% by mass, relative to the total amount of solids. % or more and 50 mass % or less. When the content of the coloring agent (A) is within the above range, the 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 contains at least one monomer (a) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (hereinafter "( A copolymer having a structural unit derived from (sometimes referred to as "a)") is more preferred.
A copolymer having a structural unit derived from (a) is a monomer (b) having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b)" ) and a structural unit having an ethylenically unsaturated bond. The copolymer may further have other structural units.
Other structural units are derived from (a) and copolymerizable monomer (c) (but different from (a) and (b)) (hereinafter sometimes referred to as "(c)") A structural unit that

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-vinyl phthalic acid, 4-vinyl phthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexenedicarboxylic 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 [2.2.1]hept-2-ene, 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene and other bicyclounsaturated compounds containing a carboxy group;
Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6- Unsaturated dicarboxylic acid anhydrides such as tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride;
Unsaturated mono[(meth)acryloyloxyalkyl] esters of divalent or higher polyvalent carboxylic acids such as mono[2-(meth)acryloyloxyethyl] succinate, mono[2-(meth)acryloyloxyethyl] phthalate kind;
Examples include unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α-(hydroxymethyl)acrylic acid.
Among these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferable from the viewpoint of copolymerization reactivity and the solubility of the resulting resin in an alkaline aqueous solution.

(b) is, for example, a polymerizable compound having a cyclic ether structure having 2 to 4 carbon atoms (eg, 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 cyclic ether having 2 to 4 carbon atoms and a (meth)acryloyloxy group.
In this 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.

(b) includes, for example, a monomer having an oxiranyl group and an ethylenically unsaturated bond, a monomer having an oxetanyl group and an ethylenically unsaturated bond, a tetrahydrofuryl group and an ethylenically unsaturated bond A monomer etc. are mentioned.
Examples of (b) include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, vinylbenzyl glycidyl ether, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3,4-epoxytricyclo[5. 2.1.0 ^2,6 ]decyl acrylate, 3-ethyl-3-(meth)acryloyloxymethyloxetane, tetrahydrofurfuryl (meth)acrylate.

As (b), a monomer having an oxiranyl group and an ethylenically unsaturated bond is preferable in that the resulting color filter can have higher reliability such as heat resistance and chemical resistance. .

(c) includes, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth) Acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]Decan-8-yl (meth)acrylate (in the technical field, it is commonly referred to as “dicyclopentanyl (meth)acrylate”. In the case of “tricyclodecyl (meth)acrylate” ), tricyclo[5.2.1.0 ^2,6 ]decen-8-yl (meth)acrylate (in the art, it is commonly called “dicyclopentenyl (meth)acrylate”. ), dicyclopentanyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, benzyl (meth) acrylic acid esters such as (meth) acrylate;
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, and diethyl itaconate;
bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5- Hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2′-hydroxyethyl)bicyclo[2.2.1] Hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2 .1]hept-2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-di(2′-hydroxyethyl)bicyclo[2.2. 1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy -5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2 .2.1] bicyclounsaturated compounds such as 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 maleimidopropionate, N-(9-acridinyl)maleimide;
Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, 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 them, styrene, vinyltoluene, benzyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decan-8-yl (meth)acrylate, N -phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo[2.2.1]hept-2-ene are preferred.

A structural unit having an ethylenically unsaturated bond is preferably a structural unit having a (meth)acryloyl group in its side chain. A resin having such a structural unit is a polymer having a structural unit derived from (a) or (b), a group capable of reacting with the groups of (a) or (b), and an ethylenically unsaturated bond. It is obtained by adding a monomer having
Examples of such structural units include structural units in which glycidyl (meth)acrylate is added to (meth)acrylic acid units, structural units in which 2-hydroxyethyl (meth)acrylate is added to maleic anhydride units, glycidyl (meth)acrylate units, and glycidyl (meth)acrylate units. ) structural units obtained by adding (meth)acrylic acid to acrylate units, and the like. Moreover, when these structural units have a hydroxy group, a structural unit to which a carboxylic acid anhydride is further added is also included as a structural unit having 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 copolymer; glycidyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid Copolymer, glycidyl (meth)acrylate/styrene/(meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decyl (meth)acrylate/(meth)acrylic acid/ N-cyclohexylmaleimide copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decyl (meth)acrylate/(meth)acrylic acid/vinyltoluene copolymer, 3-methyl-3-( Copolymers having structural units derived from (a), (b) and (c) such as meth)acryloyloxymethyloxetane/(meth)acrylic acid/styrene copolymer; benzyl (meth)acrylate/(meth) ) acrylic acid copolymer, styrene / (meth) acrylic acid copolymer, benzyl (meth) acrylate / tricyclodecyl (meth) acrylate / (meth) acrylic acid copolymer; benzyl (meth) acrylate / (meth) Resin obtained by adding glycidyl (meth)acrylate to acrylic acid copolymer, resin obtained by adding glycidyl (meth)acrylate to tricyclodecyl (meth)acrylate/styrene/(meth)acrylic acid copolymer, tricyclodecyl A copolymer having structural units derived from (a) and (c), such as a resin obtained by adding glycidyl (meth)acrylate to a (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer; ( meth) A copolymer having a structural unit obtained by adding (a) to a structural unit derived from (b), such as a resin reacted with acrylic acid, and a structural unit derived from (c); tricyclodecyl (meth) Resin obtained by reacting (meth)acrylic acid with a copolymer of acrylate/glycidyl (meth)acrylate and further reacting tetrahydrophthalic anhydride ( Examples include a copolymer having a structural unit obtained by adding (a) to a structural unit derived from b) and further adding a carboxylic anhydride, and a structural unit derived from (c).

The above resin is, for example, the method described in the document "Experimental Method for Polymer Synthesis" (written by Takayuki Otsu, Published by Kagaku Dojin, 1st Edition, 1st Edition, March 1, 1972) and described in the document. It can be manufactured with reference to the cited document.

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); It is one selected from the group consisting of copolymers having structural units derived from (a) and (c).

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. When the molecular weight is within the above range, when forming a colored pattern, the residual film ratio before and after development is high, the solubility of the unexposed area in the developer is good, and the resolution of the colored pattern tends to be improved.
The molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the resin (B) is preferably 1.1-6, more preferably 1.2-4.

The acid value (solid content conversion) of the resin (B) is preferably 10 to 200 mg-KOH/g, more preferably 20 to 180 mg-KOH/g. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of resin (B), and can be determined by titration with an aqueous potassium hydroxide solution, for example.

The content of resin (B) is preferably 7 to 75% by mass, more preferably 10 to 70% by mass, still more preferably 13 to 70% by mass, based on the total solid content. When the content of the resin (B) is within the above range, a colored pattern can be formed, and the resolution and film retention rate of the colored pattern 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). is a (meth)acrylic acid ester compound.

Examples of polymerizable compounds having one ethylenically unsaturated bond include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, and N-vinylpyrrolidone. etc., as well as (a), (b) and (c) above.

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

Among them, the polymerizable compound is preferably a polymerizable compound having 3 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 and the like can be mentioned, among which dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate are preferred.

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

The content of the polymerizable compound (C) is preferably 4-65% by mass, more preferably 7-60% by mass, based on the total solid content.
In addition, the content ratio of the resin (B) and the polymerizable compound (C) [resin (B):polymerizable compound (C)] is preferably 20:80 to 80:20, more preferably 20:80 to 80:20, on a mass basis. is 35:65 to 80:20.
When the content of the polymerizable compound (C) is within the above range, there is a tendency that the residual film ratio and the chemical resistance of the color filter are improved when the colored pattern is formed.

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

Examples of O-acyloxime compounds 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-benzoyloxy-1-[9-ethyl-6- (2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-one-2-imine and other O-acyloxime compounds having an N-benzoyloxy group; N-acetoxy-1-[ 9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethan-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3, 3-dimethyl-2,4-dioxacyclopentanylmethyloxy)benzoyl}-9H-carbazol-3-yl]ethan-1-imine, N-acetoxy-1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-imine, N-acetoxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropan-1-one-2-imine, [11 -(2-ethylhexyl)-5-(2,4,6-trimethylbenzoyl)-11H-benzo[a]carbazol-8-yl]-[2-(2,2,3,3-tetrafluoropropoxy)phenyl ] and O-acyl oxime compounds having an N-acetoxy group such as methanone oxime O-acetate. Commercially available products such as Irgacure (registered trademark) OXE01, OXE02 (manufactured by BASF) and N-1919 (manufactured by ADEKA) may also be used.

Among them, 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-cyclopentylpropan-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2 -methylbenzoyl)-9H-carbazol-3-yl]ethan-1-imine, N-acetoxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropan-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]meth At least one selected from the group consisting of nonoxime O-acetates is preferred, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethan-1-imine and N-acetoxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropan-1-one-2-imine is more preferred.

Examples of alkylphenone compounds 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-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl- 1-(4-isopropenylphenyl)propan-1-one oligomers, α,α-diethoxyacetophenone, benzyl dimethyl ketal and the like. Commercially available products such as Irgacure (registered trademark) 369, 907, 379 (manufactured by BASF) may also be used.

Biimidazole compounds include, for example, 2,2′-bis(2-chlorophenyl)-4,4′,5,5′-tetraphenylbiimidazole, 2,2′-bis(2,3-dichlorophenyl)-4 ,4'5,5'-tetraphenylbiimidazole (see, for example, JP-A-6-75372 and JP-A-6-75373), 2,2'-bis(2-chlorophenyl)-4,4 ',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimidazole, 2,2'-bis(2 -chlorophenyl)-4,4',5,5'-tetra(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl ) Biimidazole (see, for example, JP-B-48-38403, JP-A-62-174204, etc.), the phenyl groups at the 4,4′,5,5′-positions are substituted with carboalkoxy groups Examples thereof include imidazole compounds (see, for example, JP-A-7-10913).

Examples of triazine compounds 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)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine, etc. mentioned.

Acylphosphine oxide compounds include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like.

Furthermore, the polymerization initiator (D) includes benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and 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, quinone compounds such as 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compounds and the like.

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, more preferably. is a polymerization initiator containing an O-acyloxime compound.
The content of the O-acyl compound in the polymerization initiator (D) is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more.

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

<Polymerization initiation aid (D1)>
The red curable resin composition of the present invention may further contain a polymerization initiation aid (D1). The polymerization initiation aid (D1) is a compound or a sensitizer used to accelerate the polymerization of the polymerizable compound whose polymerization has been initiated by the polymerization initiator. When the polymerization initiation aid (D1) is included, it is usually used in combination with the polymerization initiator (D).
Examples of the polymerization initiation aid (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds and carboxylic acid compounds.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4 -2-ethylhexyl dimethylaminobenzoate, N,N-dimethyl p-toluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, 4,4'-bis (Ethylmethylamino)benzophenone and the like can be mentioned, and 4,4′-bis(diethylamino)benzophenone is particularly preferable. Commercially available products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) may also be used.

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

The thioxanthone compounds include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone and the like.

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

Among them, a thioxanthone compound is preferable as the polymerization initiation aid (D1).

When using these polymerization initiation aids (D1), the content is preferably 0.01 to 30 parts by mass, with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). It is preferably 0.1 to 20 parts by mass. When the amount of the polymerization initiation aid (D1) is within this range, a colored pattern can be formed with higher sensitivity, and the productivity of color filters tends to improve.

In addition, the ratio of the contents of the polymerization initiation aid (D1) and the polymerization initiator (D) (polymerization initiation aid (D1)/polymerization initiator (D)) is 0.1 or more on a mass basis. is preferably 0.3 or more, still more preferably 0.5 or more, and preferably 2 or less, more preferably 1.2 or less, still more preferably 0.8 or less.

<Antioxidant (J)>
The red curable resin composition of the present invention preferably further contains an antioxidant (J). Antioxidants (J) include phenolic antioxidants, amine antioxidants, phosphorus antioxidants and sulfur antioxidants, with phenolic antioxidants and phosphorus antioxidants being preferred.

A phenolic antioxidant is an antioxidant having a phenolic hydroxy group in the molecule, preferably having a branched alkyl group at the ortho-position of the phenolic hydroxy group. Antioxidants having both a phenolic hydroxy group and a phosphate or phosphite structure are classified herein as phosphorus antioxidants.

Phenolic antioxidants include, for example, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 4,4′-butylidene-bis(3-methyl-6- tert-butylphenol), 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 2-tert-butyl-6-(3-tert -butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, (tetrakis [methylene-3-(3,5-di-tet-butyl-4-hydroxyphenyl) propionate] methane, pentaerythritol tetrakis [ 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 3,3′,3′ ',5,5',5''-hexa-tert-butyl-a,a',a''-(mesitylene-2,4,6-triyl)tri-p-cresol, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1,3,5-tris((4 -tert-butyl-3-hydroxy-2,6-xylyl)methyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, thiodiethylenebis[3-(3, 5-di-tert-butyl-4-hydroxyphenyl)propionate], benzenepropanoic acid, 3,5-bis(1,1-dimethylethyl)-4-hydroxy, C7-C9 side chain alkyl ester, 4,6- Bis(octylthiomethyl)-o-cresol, Irganox (registered trademark) 3125 (manufactured by BASF), 2,4-bis(n-octylthio)-6-(4-hydroxy 3',5'-di-tert- Butylanilino)-1,3,5-triazine, 3,9-bis(2-(3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy)-1,1-dimethylethyl)- 2,4,8,10-tetraoxaspiro(5,5)undecane, Sumilizer (registered trademark) BHT (manufactured by Sumitomo Chemical Co., Ltd.), Sumilizer (registered trademark) GA-80 (manufactured by Sumitomo Chemical Co., Ltd.), Sumilizer (registered trademark) GS (manufactured by Sumitomo Chemical Co., Ltd.), Cyanox (registered trademark) 1790 (Cytec Co., Ltd.) (manufactured by Eisai Co., Ltd.) and vitamin E (manufactured by Eisai Co., Ltd.).
When a phenol-based antioxidant is included, the content is preferably 1% by mass or more and 99% by mass or less in 100% by mass of the total amount of antioxidant (J) (100% by mass).

An amine-based antioxidant is an antioxidant having an amino group in its molecule.
Amine antioxidants include, for example, 1-naphthylamine, phenyl-1-naphthylamine, p-octylphenyl-1-naphthylamine, p-nonylphenyl-1-naphthylamine, p-dodecylphenyl-1-naphthylamine, phenyl-2 - naphthylamine-based antioxidants such as naphthylamine; N,N'-diisopropyl-p-phenylenediamine, N,N'-diisobutyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N,N' -di-β-naphthyl-p-phenylenediamine, N-phenyl-N'-isopropyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, N-1,3-dimethylbutyl-N Phenylenediamine antioxidants such as '-phenyl-p-phenylenediamine, dioctyl-p-phenylenediamine, phenylhexyl-p-phenylenediamine, phenyloctyl-p-phenylenediamine; dipyridylamine, diphenylamine, p,p'- di-n-butyldiphenylamine, p,p'-di-tert-butyldiphenylamine, p,p'-di-tert-pentyldiphenylamine, p,p'-dioctyldiphenylamine, p,p'-dinonyldiphenylamine, p, p'-didecyldiphenylamine, p,p'-didodecyldiphenylamine, p,p'-distyryldiphenylamine, p,p'-dimethoxydiphenylamine, 4,4'-bis(4-α,α-dimethylbenzoyl)diphenylamine , p-isopropoxydiphenylamine, dipyridylamine and other diphenylamine antioxidants; agents.
When an amine-based antioxidant is included, the content is preferably 1% by mass or more and 99% by mass or less in 100% by mass of the total amount of the antioxidant (J).

A phosphorus antioxidant is an antioxidant having a phosphate ester structure or a phosphite ester structure.
Examples of phosphorus antioxidants include 6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propyloxy]-2,4,8,10-tetra-tert-butyldibenz[d , f][1,3,2]dioxaphosphepine, tris(2,4-di-tert-butylphenyl)phosphite, diphenylisooctylphosphite, 2,2′-methylenebis(4,6-di -tert-butylphenyl)octylphosphite, diphenylisodecylphosphite, diphenylisodecylphosphite, triphenylphosphate, tributylphosphate, distearylpentaerythritol diphosphite, cyclic neopentanetetraylbis(2,6-di -tert-butyl-4-methylphenyl)phosphite, 6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propyloxy]-2,4,8,10-tetra-tert- Butylbenzo[d,f][1,3,2]dioxaphosphepine, tris(nonylphenyl)phosphite, tris(mono- & dinonylphenyl mixed)phosphite, diphenylmono(tridecyl)phosphite, 2 ,2′-ethylidenebis(4,6-di-tert-butylphenol)fluorophosphite, phenyldiisodecylphosphite, tris(2-ethylhexyl)phosphite, tris(isodecyl)phosphite, tris(tridecyl)phosphite, tetrakis (2,4-di-tert-butylphenyl)-4,4′-biphenylene-di-phosphonite, 4,4′-isopropylidenediphenyltetraalkyl (C12-C15) diphosphite, 4,4′-butylidenebis(3- methyl-6-tert-butylphenyl)-ditridecylphosphite, bis(nonylphenyl)pentaerythritol diphosphite, bis(2,4-di-t-butylphenyl)pentaerythritol-di-phosphite, cyclic neo Pentanetetraylbis(2,6-di-tert-butyl-4-methylphenyl-phosphite), 1,1,3-tris(2-methyl-4-ditridecylphosphite-5-tert-butylphenyl) butane, tetrakis(2,4-di-tert-butyl-5-methylphenyl)-4,4'-biphenylenediphosphonite, tri-2-ethylhexylphosphite, triisodecylphosphite phosphite, tristearylphosphite, phenyldiisodecylphosphite, trilauryltrithiophosphite, distearylpentaerythritol diphosphite, tris(nonylatedophenyl)phosphite tris[2-[[2,4,8,10-tetra -tert-butyldibenzo[d,f][1,3,2]dioxaphosphine-6-yl]oxy]ethyl]amine, bis(2,4-bis(1,1-dimethylethyl)-6-methyl Phenyl) ethyl ester phosphorous acid, ADEKA STAB (registered trademark) 329K (manufactured by ADEKA Corporation), ADEKA STAB (registered trademark) PEP36 (manufactured by ADEKA Corporation), ADEKA STAB (registered trademark) PEP-8 (manufactured by ADEKA Corporation) ), Sandstab (registered trademark) P-EPQ (manufactured by Clariant), Weston (registered trademark) 618 (manufactured by GE), Weston (registered trademark) 619G (manufactured by GE), Ultranox (registered trademark) 626 (manufactured by GE) ), 6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propyloxy]-2,4,8,10-tetra-tert-butyldibenz[d,f][1,3 , 2] dioxaphosphepin) and the like.
When the phosphorus-based antioxidant is included, the content is preferably 1% by mass or more and 99% by mass or less in 100% by mass of the total amount of the antioxidant (J).

A sulfur-based antioxidant is an antioxidant having a sulfur atom in the molecule.
Examples of sulfur-based antioxidants include dialkylthiodipropionate compounds such as dilauryl thiodipropionate, dimyristyl or distearyl, and β-alkylmercaptopropionates of polyols such as tetrakis[methylene(3-dodecylthio)propionate]methane. Examples include ester compounds.
When a sulfur-based antioxidant is included, its content is preferably 1% by mass or more and 99% by mass or less in 100% by mass of the total amount of antioxidant (J).

GPA-5001 (manufactured by ADEKA Corporation) or the like may be used as the antioxidant (J).

Among them, the antioxidant (J) is preferably at least one of a phenolic antioxidant and a phosphorus antioxidant, and preferably contains both a phenolic antioxidant and a phosphorus antioxidant.

When the red curable resin composition of the present invention contains an antioxidant (J), its content is preferably 0.01 to 20% by mass, more preferably 0.01 to 20% by mass, based on the total amount of solids. 05 to 10% by mass. When the content of the antioxidant (J) is within the above range, the obtained color filter tends to be excellent in heat resistance.

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

<Solvent (E)>
The solvent (E) in the present invention contains propylene glycol monomethyl ether acetate at a content of 10% by mass or more and 78% by mass or less in the total amount of the solvent (E). The content of propylene glycol monomethyl ether acetate is preferably 20% by mass or more and 78% by mass or less, more preferably 30% by mass or more and 78% by mass or less, based on the total amount of the solvent (E).
Solvents other than propylene glycol monomethyl ether acetate are not particularly limited, and solvents commonly used in the field can be used. For example, ester solvent (solvent containing -COO- in the molecule but not containing -O-), ether solvent (solvent containing -O- in the molecule but not containing -COO-), ether ester solvent (solvent containing -COO- in the molecule 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-, - solvents containing no CO- and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide and the like.

Ester solvents include 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, and 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, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetol, methylanisole and the like.

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.

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.

Alcohol solvents include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerin and the like.
Aromatic hydrocarbon solvents include benzene, toluene, xylene, mesitylene and the like.
Amide solvents 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, ethyl 3-ethoxypropionate, N-methylpyrrolidone and the like are preferred, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethylene glycol monobutyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol, ethyl 3-ethoxypropionate, 4-hydroxy-4- More preferred are methyl-2-pentanone and N-methylpyrrolidone.

Solvents other than propylene glycol monomethyl ether acetate may be used alone or in combination of two or more. Among them, a solvent having a higher SP value (solubility parameter) than propylene glycol monomethyl ether acetate is preferred. As a solvent other than propylene glycol monomethyl ether acetate, only a solvent having a larger SP value than propylene glycol monomethyl ether acetate may be used.

The SP value is, for example, J.P. Brandrup, E. H. Immergut, POLYMER HANDBOOK 3rd edition, John Wiley & Sons, Solubility Parameter Value section, Hansen parameters for liquids at 25°C can be applied. Solvents having a higher SP value than the (SP value (=9.0 (cal/cm ³ ) ^1/2 ) of propylene glycol monomethyl ether acetate obtained by the Hildebrand method from Hansen parameters include, for example, propylene glycol monomethyl ether (10.7 (cal/cm ³ ) ^1/2 ), ethylene glycol monobutyl ether (10.2 (cal/cm ³ ) ^1/2 ), diacetone alcohol (10.2 (cal/cm ³ ) ) ^1/2 ), ethyl lactate (10.0 (cal/cm ³ ) ^1/2 ), 3-methoxy-1-butanol (10.9 (cal/cm ³ ) ^1/2 ), 3-ethoxy Ethyl propionate (9.1 (cal/cm ³ ) ^1/2 ), cyclohexanone (9.3 (cal/cm ³ ) ^1/2 ), γ-butyrolactone (12.8 (cal/cm ³ ) ^1/2 ), and N-methylpyrrolidone (11.2 (cal/cm ³ ) ^1/2 ) are preferable.These solvents having a higher SP value than propylene glycol monomethyl ether acetate may be used alone or in combination with two solvents. The above may be combined.

The difference in SP value between propylene glycol monomethyl ether acetate and solvents other than propylene glycol monomethyl ether acetate is preferably 0.1 (cal/cm ³ ) ^1/2 or more, more preferably 0.3 (cal /cm ³ ) ^1/2 or more, more preferably 0.5 (cal/cm ³ ) ^1/2 or more, still more preferably 0.7 (cal/cm ³ ) ^1/2 or more, and 4 (cal/cm 3 ) 1/2 or more. cm ³ ) ^1/2 or less, more preferably 3 (cal/cm ³ ) ^1/2 or less, and even more preferably 2 (cal/cm ³ ) ^1/2 or less.

When using a solvent having a larger SP value than propylene glycol monomethyl ether acetate, the content is, for example, 22% by mass or more, preferably 28% by mass or more, for example, 60% by mass, in the total amount of the solvent (E). % or less, preferably 52 mass % or less.

The content of the solvent (E) is preferably 50-95% by mass, more preferably 55-92% by mass, relative to the total amount of the red curable resin composition. In other words, the solid content of the red curable resin composition is preferably 5-50% by mass, more preferably 8-45% by mass. When the content of the solvent (E) is within the above range, flatness during coating is improved, and when a color filter is formed, the color density is not insufficient, so display characteristics tend to be improved.

<Leveling agent (F)>
The red curable resin composition of the present invention may contain a leveling agent (F). Examples of the leveling agent (F) include silicone-based surfactants, fluorine-based surfactants, and silicone-based surfactants having fluorine atoms. These may have a polymerizable group in the side chain.
Examples of silicone-based surfactants include surfactants having a siloxane bond in the molecule. Specifically, Toray Silicone DC3PA, Toray SH7PA, Toray DC11PA, Toray SH21PA, Toray SH28PA, Toray SH29PA, Toray SH30PA, Toray Toray SH8400 (manufactured by Dow Corning Toray Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460 (manufactured by Momentive Performance Materials Japan LLC) and the like.

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

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

When the leveling agent (F) is contained, its content is preferably 0.001% by mass or more and 3% by mass or less, more preferably 0.002% by mass, relative to the total amount of the red curable resin composition. 2% by mass or more, more preferably 0.005% by mass or more and 1% by mass or less.
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 red curable resin composition of the present invention may optionally contain polymerization initiation aids, fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, chain transfer agents and the like. may contain known additives.

<Method for producing red curable resin composition>
The red curable resin composition of the present invention includes, for example, a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D), a solvent (E), and if necessary It can be prepared by mixing the leveling agent (F) and other ingredients.
The red pigment (P) and optionally used pigment (Q) are mixed in advance with part or all of the solvent (E), and are subjected to a bead mill or the like until the average particle size of the pigment is about 0.2 μm or less. It is preferable to use and disperse. At this time, if necessary, a pigment dispersant and a part or all of the resin (B) may be blended.
The desired red curable resin composition can be prepared by mixing the pigment dispersion thus obtained with the remaining components so as to have a predetermined concentration.
Compound (IB) is preferably dissolved in advance in part or all of solvent (E) to prepare a solution. It is preferable to filter the solution through a filter having a pore size of about 0.01 to 1 μm.
It is preferable to filter the mixed red curable resin composition through a filter having a pore size of about 0.01 to 10 μm.

<Manufacturing method of color filter>
Examples of the method for producing a colored pattern from the red curable resin composition of the present invention include a photolithography method, an inkjet method, a printing method, and the like. Among them, the photolithographic method is preferred. The photolithographic method is a method in which the red curable resin composition is applied to a substrate, dried to form a colored composition layer, exposed through a photomask, and developed. In the photolithographic method, a colored coating film, which is a cured product of the colored composition layer, can be formed by not using a photomask during exposure and/or not developing. The colored pattern or 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 appropriately adjusted according to the purpose and application. ˜6 μm.

Examples of the substrate include glass plates such as quartz glass, borosilicate glass, alumina silicate glass, and soda-lime glass whose surface is coated with silica; resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate; A thin film of aluminum, silver, silver/copper/palladium alloy, etc. is formed on the substrate. Other color filter layers, resin layers, transistors, circuits, and the like may be formed on these substrates.

The formation of each color pixel by the photolithographic method can be carried out using a known or commonly used apparatus and conditions. For example, it can be produced as follows.
First, a red curable resin composition is applied onto a substrate, dried by heating (pre-baking) and/or dried under reduced pressure to remove volatile components such as solvents, and dried to obtain a smooth colored composition layer.
Examples of coating methods include a spin coating method, a slit coating method, a slit and spin coating method, and the like.
The temperature for heat drying is preferably 30 to 120°C, more preferably 50 to 110°C. The heating time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes.
When drying under reduced pressure, it is preferably carried out at a pressure of 50 to 150 Pa and a temperature of 20 to 25°C.
The film thickness of the coloring composition layer is not particularly limited, and may be appropriately selected according to the desired film thickness of the color filter.

The colored composition layer is then exposed through a photomask to form the desired colored pattern. The pattern on the photomask is not particularly limited, and a pattern suitable for the intended use is used.
The light source used for exposure is preferably a light source that emits light with a wavelength of 250 to 450 nm. For example, light of less than 350 nm is cut using a filter that cuts this wavelength range, or light near 436 nm, 408 nm, and 365 nm is selectively extracted using a bandpass filter that extracts these wavelength ranges. You can Specifically, light sources include mercury lamps, light-emitting diodes, metal halide lamps, halogen lamps, and the like.
It is possible to uniformly irradiate the entire exposure surface with parallel light rays and to perform accurate alignment between the photomask and 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 development, the unexposed portion of the colored composition layer is dissolved in the developer and removed. As the developer, for example, aqueous solutions of alkaline compounds such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate and tetramethylammonium hydroxide are preferred. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. Furthermore, the developer may contain a surfactant.
The developing method may be any of a puddle method, a dipping method, a spray method, and the like. Furthermore, the substrate may be tilted at any angle during development. It is preferable to wash with water after development.

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

According to the red curable resin composition of the present invention, it is possible to form a color filter in which the generation of foreign matter is suppressed. The color filter is useful as a color filter for use in display devices (eg, liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state imaging devices.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited by the following examples, and can be modified appropriately within the scope that can conform to the gist of the above and later descriptions. It is of course possible to implement them, and all of them are included in the technical scope of the present invention. In the examples, percentages and parts representing contents or usage amounts are based on mass unless otherwise specified.

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

[Synthesis Example 1]

50 parts of the compound represented by Formula (VI) and 350 parts of isopropyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed at room temperature. To the resulting mixture, 18.1 parts of diethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise at a temperature not exceeding 20°C, and the mixture was stirred at 20°C for 3 hours. The resulting reaction mixture was added to 2100 parts of 10% hydrochloric acid to precipitate a solid. The precipitate was collected by filtration, and the resulting solid was washed with water and dried to obtain 23.6 parts of the compound represented by formula (I-1-A). Yield was 43%.

Identification of compound represented by formula (I-1-A) (mass spectrometry) ionization mode = ESI+: m/z = [M+H] ⁺ 442.1
Exact Mass: 441.1

30 parts of the compound represented by formula (I-1-A) and 150 parts of dehydrated chloroform (manufactured by Kanto Kagaku Co., Ltd.) were mixed at room temperature. To the resulting mixture, 26.3 parts of trimethoxy[3-(methylamino)propyl]silane (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added dropwise at a temperature not exceeding 40°C, and the mixture was stirred at 70°C for 3 hours. The resulting reaction mixture was cooled to room temperature. The resulting mixture was added to 825 parts of ethyl acetate to precipitate a solid. The resulting precipitate was filtered, and the obtained solid was washed with ethyl acetate and dried to obtain 35.5 parts of the compound represented by formula (I-1). Yield was 87%.

Identification of compound represented by formula (I-1) (mass spectrometry) ionization mode = ESI+: m/z = [M+H] ⁺ 599.2
Exact Mass: 598.2

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 deionized water to a volume of 100 cm ³ (concentration: 0.028 g/ L), the absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length: 1 cm). This compound had λmax=546 nm.

[Synthesis Example 2]
A flask equipped with a stirrer, dropping funnel, condenser, thermometer and gas inlet tube was filled with an appropriate amount of nitrogen to create a nitrogen atmosphere. Next, to a monomer mixture consisting of 7 parts of tricyclodecyl methacrylate, 27 parts of benzyl methacrylate, and 13 parts of methacrylic acid, Perbutyl O (manufactured by NOF Corporation) was added so as to be 1 part per 100 parts of the monomer mixture. The prepared mixed liquid was dropped into the flask from the dropping funnel over 2 hours. Further, the mixture was stirred at 120° C. for 2 hours to obtain a reaction liquid containing a copolymer. Next, an appropriate amount of air was flowed into the flask to replace the atmosphere with air, and 7 parts of glycidyl methacrylate, 0.34 parts of triphenylphosphine, and 0.07 parts of methylhydroquinone were introduced into the reaction containing the above copolymer, The reaction was continued at ℃, and when the solid content acid value reached 105 mg-KOH/g, the reaction was terminated by cooling to room temperature. A copolymer (resin B-1) solution was obtained by adding 32 parts of propylene glycol monomethyl ether acetate. The solids content of the resin B-1 solution was 30%. The weight average molecular weight of Resin B-1 was 3.0×10 ⁴ .

The polystyrene equivalent weight average molecular weight Mw and number average molecular weight Mn of the resin obtained in Synthesis Example 2 were measured by GPC under the following conditions.
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
Standard material for calibration; TSK STANDARD POLYSTYRENE
F-40, F-4, F-288, A-2500, A-500
(manufactured by Tosoh Corporation)
The ratio (Mw/Mn) of the polystyrene-equivalent weight-average molecular weight and the number-average molecular weight obtained above was defined as the molecular weight distribution.

[Preparation of red curable resin composition]
Each component was mixed so that it might become the composition shown in Table 1, and the red curable resin composition was obtained.

The pigment was previously dispersed by mixing with a pigment dispersant, resin B-1 described in section B-1 ¹⁾ and propylene glycol monomethyl ether acetate described in section E-1 ²⁾ .
Column B-1 ³⁾ represents the total resin B-1 content.
Column E-1 ⁴⁾ represents the total content of propylene glycol monomethyl ether acetate.

In addition, in Table 1, each component represents the following. In addition, resin (B) showed the number of parts of solid content conversion.
Dye (A-1): A-1: compound represented by formula (I-1) Dye (A-2): A-2: C.I. I. Solvent Red 130 (Orazol Red 330; manufactured by BASF; maximum absorption wavelength 495 nm; metal complex salt dye)

Pigment (A): A-3: C.I. I. pigment red 254
Pigment dispersant: acrylic pigment dispersant Resin (B): B-1: Resin B-1
Polymerizable compound (C): C-1: dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)
Polymerization initiator (D): D-1: N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethan-1-imine (Irgacure (registered trademark) OXE 02; manufactured by BASF; oxime compound)
Polymerization initiator (D): D-2: a compound represented by the following formula (TR-PBG-309; manufactured by Changzhou Yutaka Electronic New Materials Co., Ltd.)

Antioxidant (J): J-1: GPA-5001 (manufactured by ADEKA Co., Ltd.)
Solvent (E): E-1: Propylene glycol monomethyl ether acetate Solvent (E): E-2: Diacetone alcohol Solvent (E): E-3: Propylene glycol monomethyl ether Solvent (E): E-4: Cyclohexanone Solvent (E): E-5: Ethyl lactate Leveling agent (F): F-1: Polyether-modified silicone (Toray Silicone SH8400; manufactured by Dow Corning Toray Co., Ltd.)

[Formation of color filter (coloring pattern)]
On a 2-inch square glass substrate (Eagle XG; manufactured by Corning), the colored curable resin compositions obtained in Examples 1 to 10 were applied by spin coating, and then pre-baked at 100 ° C. for 3 minutes to color. A composition layer was obtained. After standing to cool, the distance between the glass substrate on which the colored composition layer was formed and the quartz glass photomask was set to 100 μm, and an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) was used in an air atmosphere at 50 mJ/ Light irradiation was performed with an exposure amount of cm ² (365 nm standard). A photomask having a 100 μm line-and-space pattern was used. The colored composition layer after light irradiation is immersed in an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 26 ° C. for 60 seconds. It was post-baked at 0 C for 20 minutes.
By the above operation, a colored pattern was obtained from each of the colored curable resin compositions of Examples 1 to 10.

[Film thickness measurement]
The film thickness of the obtained colored pattern was measured using a film thickness measuring device (DEKTAK3; manufactured by Japan Vacuum Engineering Co., Ltd.). Table 2 shows the results.

[Chromaticity evaluation]
For the resulting colored pattern on the glass substrate, the spectrum is measured using a colorimeter (OSP-SP-200; manufactured by Olympus Corporation), and the CIE XYZ color system is used using the color matching function of the C light source. The xy chromaticity coordinates (x, y) were measured. Table 2 shows the results. From the chromaticity coordinates, it was confirmed that the color of the obtained colored pattern on the glass substrate was red.

[Formation of color filter (colored coating film)]
After applying the colored curable resin compositions obtained in Examples 1 to 10 and Comparative Example 1 on a 2-inch square glass substrate (Eagle XG; manufactured by Corning) by a spin coating method, the coating was performed at 100° C. for 3 minutes. It was pre-baked to obtain a colored composition layer. After cooling, light irradiation was performed using an exposure machine (TME-150RSK; manufactured by Topcon Corporation) at an exposure dose of 50 mJ/cm ² (365 nm standard) in an air atmosphere without using a photomask. The colored composition layer after light irradiation is immersed in an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 26 ° C. for 60 seconds. A colored coating film was obtained by performing post-baking at °C for 20 minutes.

[Foreign matter evaluation]
Foreign matter on the surface of the colored coating film thus obtained was observed at a magnification of 50 times using an upright microscope (Axio Imager MAT; manufactured by Shimadzu Corporation).
If no foreign matter is observed, it can be said that the colored coating film has no practical problem as a color filter.

〇：観察部に異物なし
△：観察部に見える異物が１～９個
×：観察部に見える異物が１０個以上

○: No foreign matter in the observed area △: 1 to 9 foreign matter visible in the observed area ×: 10 or more foreign matter visible in the observed area

The color filter (colored coating film) formed from the colored curable resin composition containing the compound (A1) has a ratio of propylene glycol monomethyl ether acetate in the colored curable resin composition of 10% when the chromaticity is uniform. In the range of ~78%, no excessive contaminants were observed on the surface of the colored coating. On the other hand, when the ratio was 80%, foreign matter was observed on the surface of the colored coating film, which was unsuitable as a color filter.

According to the red curable resin composition of the present invention, by controlling the solvent ratio in the resist within a certain range, it is possible to form a color filter that does not generate foreign substances on its surface. The color filter is useful as a color filter for use in display devices (eg, liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state imaging devices.

Claims (6)

a coloring agent (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a solvent (E), wherein the coloring agent (A) has a silicon atom; , a dye (A1) having a maximum absorption wavelength in chloroform of 500 nm to 600 nm, and a red pigment (P),
The solvent (E) contains propylene glycol monomethyl ether acetate, and
The content of propylene glycol monomethyl ether acetate is 30% by mass or more and 78% by mass or less in the total amount of the solvent (E) ,
A red curable resin composition in which the dye (A1) is a compound represented by formula (IB) .

[In the formula (IB), R ²¹ to R ²⁴ are each independently a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, a phenyl group which may have a substituent, or the formula ( represents a group represented by ib); At least one of R ²¹ to R ²⁴ is a group represented by formula (ib).
*-R50 ^- Si ⁽ R29 ) 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. Plural 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 -- are 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 -- are not substituted at the same time, and terminal --CH ₂ -- is not substituted.
R ²⁵ and R ²⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
R ²⁷ and R ²⁸ each independently represent -OH, -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z ⁺ , -CO ₂ ^- , -CO ₂ H, -CO ₂ ^- Z ⁺ , -CO 2R ¹⁰ , --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 a 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.
Each R ¹³ independently represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.
p represents an integer of 0 to 4; ] 2. The red curable resin composition according to claim 1, which contains a solvent having an SP value higher than that of propylene glycol monomethyl ether acetate in an amount of 22% by mass or more based on the total amount of the solvent (E). a solvent selected from the group consisting of propylene glycol monomethyl ether, ethylene glycol monobutyl ether, diacetone alcohol, ethyl lactate, 3-methoxy-1-butanol, ethyl 3-ethoxypropionate, cyclohexanone, γ-butyrolactone, and N-methylpyrrolidone; 3. The red curable resin composition according to claim 1 or 2, containing 22% by mass or more of the total amount of the solvent (E). 4. The red curable resin composition according to any one of claims 1 to 3 , further comprising a metal complex salt azo dye as a coloring agent (A). A color filter formed from the red curable resin composition according to any one of claims 1 to 4 . A display device comprising the color filter according to claim 5 .