TW201819540A - Red curable resin composition, color filter formed of red curable resin composition, display device having the color filter comprising a colorant, a resin, a polymerizable compound, a polymerization initiator, and a solvent - Google Patents

Abstract

The present invention relates to a red curable resin composition, a color filter formed of the red curable resin composition, and a display device having the color filter. The red curable resin composition of the present invention contains a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a solvent (E), which can contain a dye (A1) having silicon atoms and chloroform having a maximum absorption wavelength of 500nm to 600nm and a red pigment (P) as a colorant (A), and contain the propylene glycol monomethyl ether acetate as a solvent (E), and the content of the propylene glycol monomethyl ether acetate in the total amount of the solvent is 10% by mass or more and 78% by mass or less.

Description

Red curable resin composition, color filter formed of red curable resin composition, display device including color filter

FIELD OF THE INVENTION The present invention relates to a red curable resin composition.

BACKGROUND OF THE INVENTION A colored curable resin composition can be used for producing a color filter used in a display device such as a liquid crystal display device, an electroluminescence display device, or a plasma display. 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).

[Chemical 1] Prior art document patent document

Patent Document 1: Japanese Laid-Open Patent Publication No. 2016-027075

Problem to be Solved by the Invention The colored curable resin composition known so far has room for improvement in the presence or absence of foreign matter on the surface of the obtained color filter. Means for solving problems

The present invention includes the following inventions. [1] A red curable resin composition comprising a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a solvent (E), having a ruthenium atom and being extremely large in chloroform A dye (A1) and a red pigment (P) having an absorption wavelength of 500 nm to 600 nm are contained as a colorant (A), propylene glycol monomethyl ether acetate is contained as a solvent (E), and the total amount in the solvent (E) The content of the medium propylene glycol monomethyl ether acetate is 10% by mass or more and 78% by mass or less. [2] The red curable resin composition according to the above [1], wherein the total amount of the solvent (E) is 22% by mass or more of a solvent having a higher SP value than propylene glycol monomethyl ether acetate. [3] The red curable resin composition according to the above [1], wherein the total amount of the solvent (E) is 22% by mass or more, and is selected from the group consisting of propylene glycol monomethyl ether and ethylene glycol. In butyl ether, diacetone alcohol, ethyl lactate, 3-methoxy-1-butanol, ethyl 3-ethoxypropionate, cyclohexanone, γ-butyrolactone, N-methylpyrrolidone Solvent. [4] The red curable resin composition according to any one of the above [1], 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 the colorant (A). [6] A color filter formed of the red curable resin composition according to any one of the above [1] to [5]. [7] A display device comprising the color filter according to [6] above. Effect of the invention

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

To solve the problem

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

The red curable resin composition of the present invention contains a dye (A1) having a maximum absorption wavelength of 500 nm to 600 nm and having a ruthenium atom in chloroform (hereinafter sometimes referred to as "dye (A1)") and a red pigment (P) as a coloring. Agent (A). As the dye (A1), a dye having a maximum absorption wavelength of 500 nm to 580 nm in chloroform is preferable, and a dye having a maximum absorption wavelength of 500 nm to 560 nm in chloroform is particularly preferable.

As the above dye (A1), a dye having a ruthenium atom and having an imidazole skeleton, a triarylmethane skeleton, a cyanine skeleton or a xanthene skeleton is preferable. As the dye having a ruthenium atom and having an imidazole skeleton, for example, a compound represented by the formula (IA) disclosed in JP-A-2010-526897 is contained.

[Chemical 2]

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

[Chemical 3]

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

[Chemical 4]

Among the dyes (A1), a dye having a ruthenium atom and having at least one skeleton selected from the group consisting of a triarylmethane skeleton, a cyanine skeleton, and a xanthene skeleton is preferable, and a dye having a ruthenium atom and having a xanthene skeleton is more preferable. As the dye having a germanium atom and having a xanthene skeleton, a dye having a xanthene skeleton having an organic mercapto group in the substituent is preferable. Among them, an organic fluorenyl group means a group having a carbon-fluorene bond. In the dye having a xanthene skeleton having an organic mercapto group in the substituent, it is preferred to have a trimethylcarbinylalkyl group, a triethylformamylalkyl group, a trimethoxyformamidine alkyl group in the substituent. The dye of the xanthene skeleton of a mercaptoalkyl group such as a benzyl group or a triethoxymethoxyalkylalkyl group is more preferably a compound represented by the formula (IB) (hereinafter sometimes referred to as "compound (IB)"). Its tautomer is also included in the compound (IB).

[Chemical 5]

In the formula (IB), R ²¹ to R ²⁴ each independently represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, a phenyl group which may have a substituent or a group represented by the formula (ib). However, at least one of R ²¹ to R ²⁴ is a group represented by the formula (ib). *-R ⁵⁰ -Si(R ²⁹ ) ₃ (ib) [R ²⁹ represents a hydrogen atom, a hydroxyl 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. end. The plurality of R ²⁹ may be the same as or different from each other. R ⁵⁰ represents an alkylene group having 1 to 10 carbon atoms, and -CH ₂ - constituting the alkylene group may be -O-, -CO-, -NR ¹¹ -, -OCO-, -COO-, -OCONH-, -CONH- or -NHCO- replacement. However, in the alkylene group, the adjacent -CH ₂ - will not be replaced at the same time, and the terminal -CH ₂ - will not be replaced. 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 by a halogen atom, and -CH ₂ - contained in the saturated hydrocarbon group may be -O-, -CO -, -NR ¹¹ -, -OCO-, -COO-, -OCONH-, -CONH- or -NHCO-. However, in the saturated hydrocarbon group, the adjacent -CH ₂ - will not be replaced at the same time, and the terminal -CH ₂ - will not be replaced. 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 ₂ R 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 by a halogen atom. Z ⁺ represents ⁺ N(R ¹³ ) ₄ , Na ⁺ or K ⁺ . R ¹¹ and R ¹² each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms. R ¹³ each independently represents a hydrogen atom and a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms. p represents an integer from 0 to 4. ]

The compound represented by the formula (IB) also includes a compound represented by the formula (IC) (hereinafter sometimes referred to as "compound (IC)"), and tautomers thereof.

[Chemical 6]

In the formula (IC), R ³¹ to R ³⁴ each independently represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, a phenyl group which may have a substituent, or a group represented by the formula (ic). However, at least one of R ³¹ to R ³⁴ is a group represented by the formula (ic).

[Chemistry 7]

[n represents an integer of 1 to 8, and R ³⁹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and * represents a bonding end with a nitrogen atom. In R ³¹ to R ³⁴ , a hydrogen atom contained in a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms may be substituted by a halogen atom, and -CH ₂ - contained in the saturated hydrocarbon group may be -O-, -CO -or-NR ¹¹ - Replace. However, in the saturated hydrocarbon group, the adjacent -CH ₂ - will not be replaced at the same time, and the terminal -CH ₂ - will not be replaced. 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 ₂ R 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 by a halogen atom. Z ⁺ represents ⁺ N(R ¹³ ) ₄ , Na ⁺ or K ⁺ . R ¹¹ and R ¹² each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms. R ¹³ each independently represents a hydrogen atom and a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms. m represents an integer from 0 to 4. ]

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

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

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

The -CH ₂ - contained in the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms represented by R ²¹ to R ²⁴ and R ³¹ to R ³⁴ may be replaced by -O-, -CO- or -NR ¹¹ -. However, in the saturated hydrocarbon group, the adjacent -CH ₂ - will not be replaced at the same time, and the terminal -CH ₂ - will not be replaced. Examples of the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms represented by R ¹¹ include a methyl group, an ethyl group, a n-propyl group, a n-butyl group, a n-pentyl group, a n-hexyl group, a n-heptyl group, and an n-octyl group. a linear alkyl group having 1 to 20 carbon atoms such as n-decyl, n-decyl, n-dodecyl, n-hexadecyl or n-icosyl; isopropyl, isobutyl, sec-butyl, a branched chain alkyl group having 3 to 20 carbon atoms such as t-butyl, isopentyl, neopentyl and 2-ethylhexyl; cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and tri An alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms such as a cyclic fluorenyl group.

The group in which -CH ₂ - contained in the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms is replaced by -O- includes, for example, a group represented by the following formula (* represents a bonding end). .

[化8]

The group in which -CH ₂ - contained in the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms is replaced by -CO- includes, for example, a group represented by the following formula (* represents a bonding end). .

[Chemistry 9]

The group in which -CH ₂ - contained in the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms is replaced by -NR ¹¹ - is, for example, a group represented by the following formula (* represents a bonding end) ).

[化10]

-CH ₂ - contained in the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms represented by R ²¹ to R ²⁴ and R ³¹ to R ³⁴ may be selected from -OCO-, -COO-, -OCONH-, - Replace at least one of CONH- and -NHCO-. However, in the saturated hydrocarbon group, the adjacent -CH ₂ - will not be replaced at the same time, and the terminal -CH ₂ - will not be replaced.

The group in which -CH ₂ - contained in the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms is replaced by -OCO- includes, for example, a group represented by the following formula (* represents a bonding end). .

[11]

Examples of the monovalent saturated hydrocarbon group having a carbon number of 1 to 10 contained in -CH ₂ - is replaced by -COO- group, and examples thereof include a group represented by the following formula (* represents a binding terminal) .

[化12]

The group in which -CH ₂ - contained in the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms is replaced by -OCONH- includes, for example, a group represented by the following formula (* represents a bonding end). .

[Chemistry 13]

The group in which -CH ₂ - contained in the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms is replaced by -CONH- includes, for example, a group represented by the following formula (* represents a bonding end). .

[Chemistry 14]

The group in which -CH ₂ - contained in the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms is replaced by -NHCO- includes, for example, a group represented by the following formula (* represents a bonding end). .

[化15]

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

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ¹⁰ to R ¹³ include a methyl group, an ethyl group, a n-propyl group, a n-butyl group, a n-pentyl group, a n-hexyl group, a n-heptyl group, and a positive group. a linear alkyl group having 1 to 20 carbon atoms such as octyl, n-decyl, n-decyl, n-dodecyl, n-hexadecyl and n-icosyl; isopropyl, isobutyl and sec a branched chain alkyl group having 3 to 20 carbon atoms such as butyl, tert-butyl, isopentyl, neopentyl and 2-ethylhexyl; cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl An alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms such as a group and a tricyclic fluorenyl group.

As -OR ^10, and examples thereof include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy and di Decaconoxy.

As -SO ₃ ^- Z ⁺ , -SO ₃ ^- N ⁺ (R ¹³ ) ₄ is preferred.

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

Examples of -SR ¹⁰ include a methylsulfanyl group, an ethylsulfanyl group, a butylsulfanyl group, a hexylsulfanyl group, a mercaptosulfanyl group, and an eicosylsulfanyl group.

Examples of -SO ₂ R ¹⁰ include a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group, a nonylsulfonyl group, and an eicosylsulfonyl group.

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

Examples of the -SO ₂ NR ¹¹ R ¹² include an N-methylaminesulfonyl group, an N-ethylaminesulfonyl group, an N-propylaminesulfonyl group, and an N-isopropylaminesulfonyl group. N-butylamine sulfonyl, N-isobutylamine sulfonyl, N-sec-butylamine sulfonyl, N-tert-butylamine sulfonyl, N-pentylamine sulfonyl, N- (1-Ethylpropyl)aminesulfonyl, N-(1,1-dimethylpropyl)aminesulfonyl, N-(1,2-dimethylpropyl)aminesulfonyl, N -(2,2-dimethylpropyl)aminesulfonyl, N-(1-methylbutyl)aminesulfonyl, N-(2-methylbutyl)aminesulfonyl, N-( 3-methylbutyl)amine sulfonyl, N-cyclopentylamine sulfonyl, N-hexylamine sulfonyl, N-(1,3-dimethylbutyl)amine sulfonyl, N- (3,3-dimethylbutyl)amine sulfonyl, N-heptylamine sulfonyl, N-(1-methylhexyl)amine sulfonyl, N-(1,4-dimethylpentyl) Aminesulfonyl, N-octylaminesulfonyl, N-(2-ethylhexyl)aminesulfonyl, N-(1,5-dimethyl)hexylaminesulfonyl, N-( N-1 substituted amine sulfonyl group such as 1,1,2,2-tetramethylbutylamine sulfonyl sulfhydryl; N,N-dimethylamine sulfonyl, N,N-ethylmethylamine sulfonate Mercapto, N,N-diethylamine sulfonyl, N,N-propylmethylamine sulfonate N,N-isopropylmethylamine sulfonyl, N,N-tert-butylmethylamine sulfonyl, N,N-butylethylamine sulfonyl, N,N-bis(1-A N,N-2 substituted amine sulfonyl group such as propylsulfonyl, N,N-heptylmethylamine sulfonyl.

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

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

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

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

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

Examples of the alkylene group having 1 to 10 carbon atoms represented by R ⁵⁰ include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, and an isopropylidene group. , isobutylene, 2-methyltrimethylene, isoisopentyl, isohexylene, isoisooctyl, 2-ethylhexylene, etc., of which an alkylene group having 1 to 6 carbon atoms is preferred, more preferably An alkylene group having 1 to 4 carbon atoms.

The group represented by the formula (ib) is, for example, a group represented by the following formula.

[Chemistry 16]

[化17]

In the formula (ib), examples of the group in which -CH ₂ - constituting R ⁵⁰ is replaced by -O- include the following groups (* indicates a bonding end).

[化18]

[Chemistry 19]

In the formula (ib), the group in which -CH ₂ - constituting R ⁵⁰ is replaced by -CO- includes, for example, the group shown below (* represents a bonding end).

[Chemistry 20]

[Chemistry 20]

In the formula (ib), the group in which -CH ₂ - constituting R ⁵⁰ is replaced by -NR ¹¹ - may, for example, be a group shown below (* represents a bonding end).

[化22]

[化23]

In the formula (ib), the group in which -CH ₂ - constituting R ⁵⁰ is replaced by -OCO- includes, for example, a group shown below (* represents a bonding end).

[Chem. 24]

[化25]

In the formula (ib), the group in which -CH ₂ - constituting R ⁵⁰ is replaced by -COO- includes, for example, a group shown below (* represents a bonding end).

[Chem. 26]

[化27]

In the formula (ib), the group in which -CH ₂ - constituting R ⁵⁰ is replaced by -OCONH- includes, for example, a group shown below (* represents a bonding end).

[化28]

[化29]

In the formula (ib), the group in which -CH ₂ - constituting R ⁵⁰ is replaced by -CONH- includes, for example, a group shown below (* represents a bonding end).

[化30]

[化31]

In the formula (ib), the group in which -CH ₂ - constituting R ⁵⁰ is replaced by -NHCO- includes, for example, a group shown below (* represents a bonding end).

[化32]

[化33]

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

[化34]

[化35]

[化36]

[化37]

[化38]

[39]

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

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

The group represented by the formula (ic) is, for example, a group represented by the following formula (i-1) to formula (i-12). The group represented by the formula (ic) is preferably a group represented by the formula (i-2), the formula (i-3), the formula (i-5), and the formula (i-6).

[化40]

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

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

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

Examples of -CO ₂ R ¹⁰ represented by R ²⁷ , R ²⁸ , R ³⁷ and R ³⁸ include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a tert-butoxycarbonyl group, and a hexyloxycarbonyl group. And eicosyloxycarbonyl.

Examples of -SO ₃ R ¹⁰ represented by R ²⁷ , R ²⁸ , R ³⁷ and R ³⁸ include a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, and a tert-butoxy group. Sulfonyl, hexyloxysulfonyl and eicosyloxysulfonyl.

Examples of -SO ₂ NR ¹¹ R ¹² represented by R ²⁷ , R ²⁸ , R ³⁷ and R ³⁸ include N-methylaminesulfonyl, N-ethylaminesulfonyl, and N-propylamine. Sulfonyl, N-isopropylaminesulfonyl, N-butylamine sulfonyl, N-isobutylamine sulfonyl, N-sec-butylamine sulfonyl, N-tert-butylamine sulfonate Sulfhydryl, N-pentylamine sulfonyl, N-(1-ethylpropyl)amine sulfonyl, N-(1,1-dimethylpropyl)amine sulfonyl, N-(1, 2-dimethylpropyl)aminesulfonyl, N-(2,2-dimethylpropyl)aminesulfonyl, N-(1-methylbutyl)aminesulfonyl, N-(2 -Methylbutyl)aminesulfonyl, N-(3-methylbutyl)aminesulfonyl, N-cyclopentylaminesulfonyl, N-hexylaminesulfonyl, N-(1,3 - dimethylbutyl)amine sulfonyl, N-(3,3-dimethylbutyl)amine sulfonyl, N-heptylamine sulfonyl, N-(1-methylhexyl)amine sulfonate Sulfhydryl, N-(1,4-dimethylpentyl)amine sulfonyl, N-octylamine sulfonyl, N-(2-ethylhexyl)amine sulfonyl, N-(1,5 -N-methyl hexylamine sulfonyl group, N-substituted sulfonyl group such as N-(1,1,2,2-tetramethylbutyl)amine sulfonyl group; N,N-dimethylamine Sulfonyl, N,N-ethylmethylaminesulfonyl, N,N-diethyl Aminesulfonyl, N,N-propylmethylaminesulfonyl, N,N-isopropylmethylaminesulfonyl, N,N-tert-butylmethylaminesulfonyl, N,N-butyl An N,N-2 substituted amine sulfonyl group such as ethylamine sulfonyl group, N,N-bis(1-methylpropyl)amine sulfonyl group or N,N-heptylmethylamine sulfonyl group.

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

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

As Z ⁺ , preferably ⁺ N(R ¹³ ) ₄ . The four R ¹³ in ⁺ N(R ¹³ ) ₄ are preferably all the same. Further, the total carbon number of the four R ¹³ is preferably 20 to 80, and more preferably 20 to 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, and 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 the formula (ib), and as other R ²¹ to R ²⁴ , a methyl group, an ethyl group, a propyl group and the following groups are preferable (* represents a nitrogen atom) Bonding end).

[化41]

More preferably, a methyl group, an ethyl group, a propyl group and the following groups (* represents a bonding end with a nitrogen atom).

[化42]

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

[化43]

More preferably, a methyl group, an ethyl group, a propyl group and the following groups (* represents a bonding end with a nitrogen atom).

[化44]

R ²⁵ , R ²⁶ , R ³⁵ and R ^{36 are} preferably a hydrogen atom, a methyl group or an ethyl group, and 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 ^- .

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

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

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

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

p and m are preferably an integer of 0 to 2, more preferably 0 or 1, further preferably 0.

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

[化45]

[Chem. 46]

[化47]

[48]

[化49]

[化50]

[化51]

[化52]

[化53]

[54]

[化55]

[化56]

[化57]

[化58]

Specific examples of the compound (IC) include a compound represented by the above formula (I-1) to (I-54), a compound represented by the formula (I-117) to the formula (I-119), and A compound represented by the formula (I-121), and a compound represented by the formula (I-123). The compound (IC) is preferably a compound represented by the formula (I-1) to the formula (I-4), a compound represented by the formula (I-13) to the formula (I-16), and a formula (I-25). a compound represented by the formula (I-28), a compound represented by the formula (I-37) to the formula (I-40), a compound represented by the formula (I-49) to the formula (I-54), and a formula ( I-117)~ a compound represented by the formula (I-119), more preferably a compound represented by the formula (I-1) to the formula (I-4), represented by the formula (I-13) to the formula (I-16) The compound represented by the formula (I-25) to the formula (I-28), the compound represented by the formula (I-117), and the compound represented by the formula (I-119).

Compound (IB) can pass by formula (IV)

[化59]

[wherein, R ²¹ , R ²² , R ²⁵ , R ²⁶ , R ²⁸ , R ²⁷ and p respectively have the same meanings as described above. X ² represents a compound represented by a halogen atom or a trifluoromethylsulfonyloxy group (hereinafter sometimes referred to as "compound (IV)")) and by the formula (V)

[60]

In the formula, a compound represented by R ²³ and R ^{24 in} the same meaning as described above (hereinafter sometimes referred to as "compound (V)") is produced by mixing and reacting in an organic solvent.

The halogen atom represented by X ² may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and is 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 the compound (V) to be used is usually 1 mol or more and 10 mol or less, preferably 1 mol or more and 3 mol or less, more preferably 1 mol, based on 1 mol of the compound (IV). Above the ear and below 2 moles.

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

[化61]

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

[化62]

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

[化63]

[wherein, R ²³ and R ²⁴ respectively have the same meanings as described above. The compound represented by the mixture is produced by mixing and reacting in an organic solvent.

The halogen atom represented by X ¹ may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and is preferably a chlorine atom. Preferably, X ¹ is the same as X ² . 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 the compound (III) to be used is usually 1 mol or more and 30 mol or less, preferably 1 mol or more and 20 mol or less, more preferably 1 mol, based on 1 mol of the compound (VI). The amount of the ear or more is 10 mol or less, 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 the compound (V) to be used is usually 1 mol or more and 30 mol or less, preferably 1 mol or more and 20 mol or less, more preferably 1 mol, based on 1 mol of the compound (VI). The amount of the ear or more is 10 mol or less, 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 the compound (III) to be used is usually 1 mol or more and 30 mol or less, preferably 1 mol or more and 20 mol or less, more preferably 1 mol, based on 1 mol of the compound (VI). The amount of the ear or more is 10 mol or less, 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 the compound (V) to be used is usually 1 mol or more and 50 mol or less, preferably 1 mol or more and 30 mol or less, more preferably 1 mol, based on 1 mol of the compound (III). Above the ear and below 20 m.

Compound (IB) can be used as a dye. The dissolving property in an organic solvent is high, and it is especially a coloring agent of the coloring curable resin composition used for the color filter of the display device of liquid-crystal display.

The content of the dye (A1) is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and preferably 30% by mass or less, more preferably 100% by mass based on the total amount of the solid content of the red curable resin composition. It is preferably 20% by mass or less. Here, the "total amount of solid content" in the present specification means the amount obtained by removing the content of the solvent from the total amount of the red curable resin composition. The total amount of the solid components and the content of each component with respect to the solid components can be measured, for example, by a 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, and further preferably 100% by mass or less based on 100% by mass of the total amount of the coloring agent (A). 1% by mass or more and 40% by mass or less. In addition, the content of the compound (IB) is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more, based on 100% by mass of the dye (A1). In addition, the content of the dye (A1) is preferably 10% by mass or more, more preferably 20% by mass or more, and also preferably 100% by mass, and more preferably 80% by mass based on 100% by mass of the total of the dyes. Below mass%.

<Red Pigment (P)> The red curable resin composition of the present invention contains a red pigment (P) as a colorant (A) in addition to the above dye (A1). As the red pigment (P), a red compound in a compound classified as a pigment in the excellent index (published by The Society of Dyers and Colourists) can be cited. Specifically, CI Pigment Red 9 (hereinafter, the description of CI Pigment Red is omitted, only the serial 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., preferably CI Pigment Red 254, 255.

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

Further, the total content of the dye (A1) and the red pigment (P) in the total amount of 100% by mass of the colorant (A) is preferably 80% by mass or more, and more preferably 90% by mass or more.

Further, the content ratio of the dye (A1) to the red pigment (P) (dye (A1) / red pigment (P)) is preferably 1/99 to 99/1, more preferably 2/98, on a mass basis. 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 obtained color filter is not impaired. As the pigment (Q), a known pigment can be used without particular limitation, and examples thereof include a compound classified as a pigment in an excellent index (published by The Society of Dyers and Colourists).

As the pigment (Q) (unlike the red pigment (P)), a known pigment can be used without particular limitation, and examples thereof include a compound classified as a pigment in an excellent index (published by The Society of Dyers and Colours).

Examples of the pigment (Q) include CI Pigment Yellow 1 (hereinafter, the description of CI Pigment Yellow is omitted, only the serial number is described), 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53 Yellow pigments such as 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214; CI Pigment Orange 13 , 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments; CI Pigment Blue 15, 15:3, 15:4, 15:6, 60 , 80 cyan pigments; CI pigment violet 1,19,23,29,32,36,38 and other purple pigments; CI pigment green 7,36,58 and other green pigments; CI pigment brown 23,25 and other brown pigments; CI pigments Black 1, 7 and other black pigments. These pigments may be used singly or in combination of two or more.

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

The content of the total of the pigments in the total amount of the coloring agent (A) is preferably 0.1% by mass or more, more preferably 10% by mass or more, further preferably 30% by mass or more, and still more preferably 50% by mass or more. It is 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 a colorant (A) to the extent that the performance of the obtained color filter is not impaired. Examples of the dye (A2) (except for the dye (A1)) include oil-soluble dyes, acid dyes, basic dyes, direct dyes, mordant dyes, amine salts of acid dyes, and sulfonamide derivatives of acid dyes. Examples of the dye such as a metal complex salt dye include a compound classified as a dye in the excellent index (published by The Society of Dyers and Colourists), and a known dye described in the dyeing note (color dyeing company). Further, examples of the chemical structure include an azo dye, a cyanine dye, a triphenylmethane dye, a xanthene dye other than the dye (A1), a phthalocyanine dye, a naphthoquinone dye, a quinone imine dye, and a methine dye. Azomethine dyes, squaric acid dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, and nitro dyes. Among these, an organic solvent-soluble dye is preferred.

Specifically, CI solvent yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162; CI solvent red 45, 49, 125, 130, 218; CI Solvent Orange 2, 7, 11, 15, 26, 56; CI Solvent Blue 4, 5, 37, 67, 70, 90; CI Solvent Green 1, 1, 5, 7, 34, 35, etc. CI Solvent Dye, CI Acid yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 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; CI 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; CI Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94 , 95, 107, 108, 169, 173; CI Acid Violet 6B, 7, 9, 17, 19, 30, 102; CI 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; CI Acidic green 1, 3, 5, 9, 16, 50, 58, 63, 65, 80, 104, 105, 106, 109 and other CI acid dyes, CI 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; CI Direct Red 79, 82, 83, 8 4, 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; CI direct orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97 , 106, 107; CI direct purple 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104; CI 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 ,2 74, 275, 293; CI direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82 and other CI direct dyes, CI dispersion yellow 54, 76 and other CI disperse dyes, CI basic red 1, 10; CI alkaline blue 1, 3, 5, 7, 9, 19, 24, 25, 26, 28, 29, 40, 41, 54, 58, 59, 64, 65, 66, 67, 68; CI alkaline green 1 and other CI basic dyes, CI active yellow 2, 76, 116; CI active orange 16; CI active red 36 and other CI reactive dyes, CI mordant yellow 5, 8 , 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65; CI mordant red 1, 2, 4, 9, 12, 14, 17, 18, 19, 22, 23, 25, 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; CI mordant orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43 , 47, 48; CI mordant purple 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58; 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 CI mord green 1, 3, 4, 5 CI mordant dyes such as 10, 15, 26, 29, 33, 34, 35, 41, 43, and 53, and CI reducing dyes such as CI-reduced green 1. Among them, a red dye, an orange dye, and a yellow dye are preferred. These dyes can be appropriately selected depending on the spectroscopic spectrum of the desired color filter. These dyes may be used singly or in combination of two or more.

As the dye (A2), a metal complex salt dye is preferred. The metal complex salt dye is a dye obtained by complexing a metal atom in a molecule containing a dye molecule capable of being salted with a metal atom as a ligand. Examples of the dye to be a ligand include an azo dye and a methine dye, and an azo dye is preferred. In other words, examples of the metal complex salt dye include a metal complex salt azo dye and a metal complex salt methine dye, and a metal complex salt azo dye is preferable. Examples of the metal atom include chromium, cobalt, nickel, and the like, and chromium or cobalt is preferable.

Examples of the metal complex salt dye include CI solvent yellow 13, 19, 21, 25, 25: 1, 62, 79, 81, 82, 83, 83: 1, 88, 89, 90, 151, and 161. ; CI Solvent Orange 5, 11, 20, 40: 1, 41, 45, 54, 56, 58, 62, 70, 81, 99; CI 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; CI solvent violet 2, 21, 21:1 46, 49, 58, 61; CI solvent blue 137; CI solvent brown 28, 42, 43, 44, 53, 62, 63, CI acid yellow 59, 121; CI acid orange 74, 162; CI acid red 211, Japan The metal complex salt dye described in JP-A-2010-170117. These metal complex salt dyes may be used singly or in combination of two or more. Among these, the metal complex salt dye preferably has a maximum absorption wavelength in a range of 410 nm or more and 580 nm or less, and more preferably has a maximum absorption wavelength in a range of 490 nm or more and 580 nm or less.

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

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

The content of the colorant (A) is preferably 1% by mass or more and 70% by mass or less, more preferably 1% by mass or more and 60% by mass or less, and still more preferably 1% by mass or more and 50% by mass based on the total amount of the solid content. Below mass%. When the content of the colorant (A) is within the above range, desired spectral and color concentrations can be obtained.

<Resin (B)> The resin (B) is not particularly limited, but is preferably an alkali-soluble resin, and more preferably has a monomer (a) derived from at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (hereinafter) A copolymer of structural units referred to as "(a)"). The copolymer having the structural unit derived from (a) preferably has a monomer (b) derived from a cyclic ether structure having a carbon number of 2 to 4 and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b)") a copolymer of at least one selected from the group consisting of structural units and structural units having ethylenically unsaturated bonds. The copolymer may further have other structural units. Examples of the other structural unit include a structural unit derived from a monomer (c) copolymerizable with (a) (although different from (a) and (b)) (hereinafter sometimes referred to as "(c)").

Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid; maleic acid, fumaric acid, and citraconic acid; , mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6- Unsaturated dicarboxylic acids such as tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, and 1,4-cyclohexene dicarboxylic acid; methyl-5-norbornene-2,3-dicarboxylic acid , 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]heptane- 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- a bicyclic unsaturated compound containing a carboxyl group such as ethylbicyclo[2.2.1]hept-2-ene; maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinyl neighbor Phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5, Unsaturated 6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride Carboxylic anhydrides; succinic acid mono [2-(methyl) propylene methoxyethyl] ester, phthalic acid mono [2-(methyl) propylene methoxyethyl] ester, etc. An acid unsaturated mono[(meth)acryloxyalkyl]ester; an unsaturated acrylate having a hydroxyl group and a carboxyl 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 solubility of the obtained resin in an aqueous alkali solution.

(b) means, for example, a cyclic ether structure having a carbon number of 2 to 4 (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and an ethylenically unsaturated bond. Polymeric compound. (b) A monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth)acryloxy group is preferred. In the present specification, "(meth)acrylic acid" means at least one selected from the group consisting of acrylic acid and methacrylic acid. The expressions "(meth)acryloyl" and "(meth)acrylate" have the same meaning.

As (b), for example, a monomer having an epoxyethyl group and an ethylenically unsaturated bond, a monomer having an oxetanyl group and an ethylenically unsaturated bond, a tetrahydrofuranyl group and an ethylenically unsaturated bond may be mentioned. Monomers, etc. Examples of (b) include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, vinylbenzyl glycidyl ether, and 3,4-cyclo(meth)acrylate. oxygen cyclohexyl methacrylate, 3,4-epoxy-tricyclo [5.2.1.0 ^2,6] decyl, 3-ethyl-3- (meth) oxymethyl Bing Xixi oxetane, ( Tetrahydrofurfuryl methacrylate.

(b) is preferably a monomer having an epoxy group and an ethylenically unsaturated bond, in that reliability of heat resistance and chemical resistance of the obtained color filter can be further improved.

Examples of (c) include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, and tert-butyl (meth)acrylate. Ester, 2-ethylhexyl (meth)acrylate, lauryl (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 ]decane-8-yl (meth)acrylate (in the technical field) In the conventional name, it is called "dicyclopentanyl (meth) acrylate." Further, it is sometimes called "tricyclodecyl (meth) acrylate"), tricyclo(meth) acrylate [5.2.1.0 ^{2 , 6]} dec-8-yl ester (the art, as a common name, referred to as "(meth) acrylate, dicyclopentenyloxyethyl"), (meth) acrylate, dicyclopentanyl oxyethyl (meth ) isobornyl acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, ( (meth) acrylates such as benzyl methacrylate; a hydroxyl group-containing (meth) acrylate such as 2-hydroxyethyl acrylate or 2-hydroxypropyl (meth) acrylate; diethyl maleate, diethyl fumarate, and itaconic acid Dicarboxylic acid diesters such as esters; bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2- Alkene, 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]g 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 a bicyclic unsaturated compound such as hept-2-ene; N-phenyl maleimine, N-cyclohexylmaleimide, N-benzyl maleimide, N-amber quinone imine -3-maleimide benzoate, N-succinimide -4-Malayimine butyrate, N-succinimide-6-maleimide caprate, N-succinimide-3-maleimide propionate, Dicarbonylimine derivatives such as 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 these, from the viewpoints of copolymerization reactivity and heat resistance, styrene, vinyl toluene, benzyl (meth)acrylate, and tricyclo(methyl)acrylate [5.2.1.0 ^2,6 ]decane-8- are preferable. Base ester, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo[2.2.1]hept-2-ene.

The structural unit having an ethylenically unsaturated bond is preferably a structural unit having a (meth)acrylonitrile group in a side chain. The resin having such a structural unit is obtained by reacting a polymer having structural units derived from (a), (b) with a group having a group reactive with (a), (b), and an ethylenically unsaturated bond. Obtained by monomer addition. Examples of such a structural unit include a structural unit obtained by adding (meth)acrylic acid unit to glycidyl (meth)acrylate, and adding a maleic anhydride unit to 2-hydroxyethyl (meth)acrylate. The structural unit is a structural unit obtained by adding (meth)acrylic acid to a glycidyl (meth)acrylate unit. Further, when these structural units have a hydroxyl group, a structural unit obtained by further adding a carboxylic acid anhydride may be exemplified 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 and (meth)acrylic acid 3,4-epoxytricyclo[5.2. .1.0 ^2.6 ] a copolymer of a structural unit derived from (a) and (b) such as an oxime ester/(meth)acrylic acid copolymer; glycidyl (meth)acrylate/benzyl benzyl (meth)acrylate/(A) Acrylic acid copolymer, glycidyl (meth)acrylate/styrene/(meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.4.1.0 ^2.6 ]decyl (meth)acrylate/(A) Acrylic acid/N-cyclohexylmaleimide copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decyl methacrylate/(meth)acrylic acid/vinyltoluene copolymer, 3-methyl-3-(meth)acryloxymethyloxybutane/(meth)acrylic acid/styrene copolymer or the like having structural units derived from (a), (b) and (c) Copolymer; benzyl (meth)acrylate/(meth)acrylic acid copolymer, styrene/(meth)acrylic acid copolymer, benzyl (meth)acrylate/tricyclodecyl (meth)acrylate/( Methyl)acrylic acid copolymer; making glycidyl (meth)acrylate and benzyl (meth)acrylate a resin obtained by adding a /(meth)acrylic acid copolymer, and a copolymer of glycidyl (meth)acrylate and tricyclodecyl (meth)acrylate/styrene/(meth)acrylic acid copolymer A resin, a resin obtained by adding a glycidyl (meth)acrylate to a tricyclodecyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer, etc., has (a) and a copolymer of a structural unit of (c); a resin obtained by reacting a copolymer of (meth)acrylic acid with tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate, and (meth)acrylic acid A resin obtained by reacting a copolymer of tricyclodecyl (meth) acrylate/styrene/glycidyl (meth) acrylate with a structural unit obtained by adding (a) a structural unit derived from (b) And a copolymer derived from the structural unit of (c); a resin obtained by reacting a copolymer of (meth)acrylic acid with tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate further with tetrahydrogen A resin obtained by reacting phthalic anhydride or the like has a structural unit obtained by adding (a) a structural unit derived from (b) and further adding a carboxylic anhydride; A copolymer or the like derived from the structural unit of (c).

The above-mentioned resin can be referred to, for example, the method described in the "Experimental Method for Polymer Synthesis" (produced by Otsu Takayuki Publishing Co., Ltd., the first edition of Chemicals, the first edition, issued on March 1, 1972) and the documents described in the literature. Manufactured by citing literature.

The resin (B) is preferably a copolymer selected from the group consisting of structural units derived from (a) and (b); a copolymer having structural units derived from (a), (b) and (c); and having (a) And one of the copolymers of the structural unit of (c).

The polystyrene-equivalent weight average molecular weight of the resin (B) is preferably from 3,000 to 100,000, and more preferably from 5,000 to 50,000. When the molecular weight is within the above range, when the colored pattern is formed, the residual film ratio before and after development is high, and the solubility of the unexposed portion 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 from 1.1 to 6, more preferably from 1.2 to 4.

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

The content of the resin (B) is preferably 7 to 75% by mass, more preferably 10 to 70% by mass, even more preferably 13 to 70% by mass, based on the total amount of the solid component. When the content of the resin (B) is within the above range, a colored pattern can be formed, and the resolution of the colored pattern and the residual film ratio tend to be improved.

<Polymerizable compound (C)> The polymerizable compound (C) is a compound which can be polymerized by an active radical and/or an acid generated by the polymerization initiator (D), and examples thereof include a polymerizable ethylenically unsaturated bond. The compound or the like is preferably a (meth) acrylate compound.

Examples of the polymerizable compound having one ethylenically unsaturated bond include mercaptophenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, and 2-ethylhexyl carbitol acrylic acid. Ester, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, and the like, and (a), (b), and (c) above.

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

Among them, the polymerizable compound is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such a polymerizable compound include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol penta(meth)acrylic acid. Ester, dipentaerythritol hexa(meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, pentaerythritol deca (meth) acrylate, pentaerythritol nin (meth) acrylate Ester, tris(2-(meth)acryloxyethyl)isocyanurate, ethylene glycol modified pentaerythritol tetra(meth)acrylate, ethylene glycol modified dipentaerythritol hexa(meth)acrylate Ester, propylene glycol modified pentaerythritol tetra(meth)acrylate, propylene glycol modified dipentaerythritol hexa(meth) acrylate, caprolactone modified pentaerythritol tetra(meth) acrylate, caprolactone modified dipentaerythritol hexa Methyl) acrylate or the like, among which dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferable.

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

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

<Polymerization Initiator (D)> The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating a living radical, an acid, or the like by the action of light or heat, and a known polymerization initiator can be used. . Examples of the polymerization initiator (D) include an O-indenyl hydrazine compound, an alkyl phenyl ketone compound, a biimidazole compound, a triazine compound, and a fluorenylphosphine oxide compound.

The O-indenyl hydrazine compound may, for example, be N-benzylideneoxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine or N-benzidine. Oxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine, N-benzylideneoxy-1-(4-phenylsulfanylphenyl)- 3-cyclopentylpropan-1-one-2-imine, N-benzylideneoxy-1-[9-ethyl-6-(2-methylbenzylidene)-9H-carbazole- O-mercaptopurine compound having N-benzylideneoxy group, such as 3-yl]-3-cyclopentylpropan-1-one-2-imine; N-acetoxy-1-[9-B -6-(2-methylbenzhydryl)-9H-indazol-3-yl]ethane-1-imine, N-ethyloxy-1-[9-ethyl-6-{ 2-methyl-4-(3,3-dimethyl-2,4-dioxolanylmethoxy)benzimidyl}-9H-indazol-3-yl]ethane-1- Imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzomethyl)-9H-indazol-3-yl]-3-cyclopentylpropane-1- Imine, N-acetoxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropan-1-one-2-imine, [11-(2-ethylhexyl)- 5-(2,4,6-trimethylbenzylidene)-11H-benzo[a]carbazol-8-yl]-[2-(2,2,3,3-tetrafluoropropoxy) O-mercapto group deuteration with N-acetoxy group, such as phenyl]methanone O-acetate And the like. Commercial products such as Irgacure (registered trademark) OXE01, OXE02 (above, manufactured by BASF Corporation), and N-1919 (made by ADEKA Co., Ltd.) can be used.

Wherein the O-indenyl hydrazine compound is preferably selected from the group consisting of N-benzylideneoxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzylformamide 1-(4-phenylsulfanylphenyl)octane-1-one-2-imine, N-benzylideneoxy-1-(4-phenylsulfanylphenyl)-3 -cyclopentylpropan-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzylidene)-9H-indazole-3- Ethyl]imine-1-imine, N-acetoxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropan-1-one-2-imine and [11-( 2-ethylhexyl)-5-(2,4,6-trimethylbenzylidene)-11H-benzo[a]carbazol-8-yl]-[2-(2,2,3, At least one of 3-tetrafluoropropoxy)phenyl]methanone O-acetate, more preferably selected from N-ethyloxy-1-[9-ethyl-6-(2-A) Benzomethane)-9H-indazol-3-yl]ethane-1-imine and N-ethoxycarbonyl-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropane At least one of 1-keto-2-imine.

Examples of the alkyl phenyl ketone compound include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one and 2-dimethylamino group- 1-(4-morpholinophenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1- [4-(4-morpholinyl)phenyl]butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1- [4-(2-Hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propane An oligomer of 1-ketone, α,α-diethoxyacetophenone, benzoin dimethyl ketal, and the like. Commercial products such as Irgacure (registered trademark) 369, 907, and 379 (above, manufactured by BASF Corporation) can be used.

Examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, and 2,2'-bis(2,3- Dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (for example, see JP-A-6-75372, JP-A-6-75373, etc.), 2, 2'- Bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-four (alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(dialkoxyphenyl)biimidazole, 2,2' - bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole (for example, refer to Japanese Patent Publication No. Sho 48-38403, JP-A-62-- An imidazole compound in which a phenyl group at the 4,4', 5, 5'-position is substituted with an alkoxycarbonyl group (for example, see JP-A-7-10913, etc.).

Examples of the triazine compound include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine and 2,4-bis(trichloro). Methyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperidin-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)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl) Vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]- 1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-triazine Wait.

The fluorenylphosphine oxide compound may, for example, be 2,4,6-trimethylbenzimidyldiphenylphosphine oxide.

Further, examples of the polymerization initiator (D) include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether. a compound; benzophenone, methyl o-benzhydrylbenzoate, 4-phenylbenzophenone, 4-benzylidene-4'-methyldiphenyl sulfide, 3,3', a benzophenone compound such as 4,4'-tetrakis(tert-butylperoxycarbonyl)benzophenone or 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, 2-ethyl Anthraquinone compounds such as sulfonium and camphorquinone; 10-butyl-2-chloroacridone, benzoin, methyl phenylglyoxylate, titanium titanate, and the like.

The polymerization initiator (D) is preferably a polymerization initiator containing at least one selected from the group consisting of an alkyl phenyl ketone compound, a triazine compound, a fluorenyl phosphine oxide compound, an O-mercapto fluorene compound, and a biimidazole compound, and more preferably A polymerization initiator comprising an O-indenyl ruthenium compound. In the polymerization initiator (D), the content of the O-thiol compound 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, and more preferably 1 to 30 parts by mass, based on 100 parts by mass of the total of the resin (B) and the polymerizable compound (C).

<Polymerization Initiator (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 for promoting polymerization of a polymerizable compound in which polymerization is initiated by a polymerization initiator. When the polymerization initiation aid (D1) is contained, it is usually used in combination with the polymerization initiator (D). Examples of the polymerization initiation aid (D1) include an amine compound, an alkoxy fluorene compound, a thioxanthone compound, and a carboxylic acid compound.

The amine compound may, for example, be triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate or 4-dimethyl Isoamyl benzoate benzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4, 4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, 4,4'-bis (ethyl group) Aminoamino)benzophenone or the like, among which, 4,4'-bis(diethylamino)benzophenone is preferred. Commercial products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can be used.

Examples of the alkoxyfluorene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl. -9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, and the like.

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

Examples of the carboxylic acid compound include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, and dimethylphenyl. Sulfoalkylacetate, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine , phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthyloxyacetic acid, and the like.

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

In the case of using the polymerization initiation aid (D1), the content thereof is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 20 parts by mass based on 100 parts by mass of the total of the resin (B) and the polymerizable compound (C). Share. When the amount of the polymerization initiation aid (D1) is within this range, the coloring pattern can be further formed with high sensitivity, and the productivity of the color filter tends to increase.

In addition, the ratio of the content of the polymerization initiation aid (D1) to the polymerization initiator (D) (polymerization initiation aid (D1) / polymerization initiator (D)) is preferably 0.1 or more, more preferably 0.3, on a mass basis. The above is more preferably 0.5 or more, 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). Examples of the antioxidant (J) include a phenol-based antioxidant, an amine-based antioxidant, a phosphorus-based antioxidant, and a sulfur-based antioxidant, and a phenol-based antioxidant and a phosphorus-based antioxidant are preferable.

The phenolic antioxidant is an antioxidant having a phenolic hydroxyl group in the molecule, and is preferably an alkyl group having a branch in the ortho position of the phenolic hydroxyl group. In the present specification, an antioxidant having both a phenolic hydroxyl group and a phosphate structure or a phosphite structure is classified into a phosphorus-based antioxidant.

Examples of the phenolic antioxidant include 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane and 4,4'-butylene-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-tert) Butyl-4-hydroxyphenyl)propionate]methane, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-( 3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 3,3',3'',5,5',5''-hexa-tert-butyl-a,a',a ''-(1,3,5-Trimethylbenzene-2,4,6-triyl)tri-p-cresol, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyl) Benzyl)-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, thiodiethylene bis[3-(3,5- Di-tert-butyl-4-hydroxyphenyl)propionate], phenylpropionic 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 Corporation) ), 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)propenyloxy)-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.), シアノックス (registered trademark) 1790 (manufactured by サイテック ザイ )), and vitamin E (manufactured by エーザイ), etc. In the case of phenolic antioxidants, antioxidants (J) The content of the total amount of 100% by mass is preferably 1% by mass or more and 99% by mass or less.

The amine-based antioxidant is an antioxidant having an amine group in the molecule. Examples of the amine-based antioxidant include 1-naphthylamine, phenyl-1-naphthylamine, p-octylphenyl-1-naphthylamine, p-nonylphenyl-1-naphthylamine, and p-tenth. Naphthylamine-based antioxidants such as dialkylphenyl-1-naphthylamine and phenyl-2-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 Base-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, N-1,3-dimethylbutyl-N'-phenyl-p-phenylenediamine, two a phenylenediamine antioxidant such as octyl-p-phenylenediamine, phenylhexyl-p-phenylenediamine, phenyloctyl-p-phenylenediamine; dipyridylamine, diphenylamine, p-, '- Di-n-butyldiphenylamine, p-p-'-di-tert-butyldiphenylamine, p-p-'-di-tert-pentyldiphenylamine, p-, p-dioctyldiphenylamine, p, pair '-Dimercaptodiphenylamine, p-p-'-didecyldiphenylamine, p-, p-di(dodecyl)diphenylamine, p-, p-bis(styryl)diphenylamine, p, '-Dimethoxydiphenylamine, 4,4'-bis(4-α,α-dimethylbenzylidene)diphenylamine, para-iso Diphenylamine-based antioxidants such as propoxydiphenylamine and dipyridylamine; phenothiazine, N-methylphenothiazine, N-ethylphenothiazine, 3,7-dioctylphenothiazine, phenothiazine A phenothiazine-based antioxidant such as a azine carboxylate or a leusene. When the amine-based antioxidant is contained, the content of the antioxidant (J) is preferably 1% by mass or more and 99% by mass or less based on 100% by mass of the total amount of the antioxidant (J).

The phosphorus-based antioxidant is an antioxidant having a phosphate structure or a phosphite structure. Examples of the phosphorus-based antioxidant include 6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyl. Dibenzo[d,f][1,3,2]dioxaphosphole, tris(2,4-di-tert-butylphenyl)phosphite, diphenylisooctyl Phosphate, 2,2'-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite, diphenylisodecyl phosphite, diphenylisodecyl phosphite , triphenyl phosphate, tributyl phosphate, distearyl pentaerythritol diphosphite, cyclic neopentyl tetrakis(2,6-di-tert-butyl-4-methylphenyl) Phosphate, 6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butylbenzo[d,f ][1,3,2]dioxaphosphole, tris(nonylphenyl)phosphite, tris(mono- and dinonylphenyl) phosphite, diphenyl mono(ten) Trialkyl) phosphite, 2,2'-ethylenebis(4,6-di-tert-butylphenol) fluorophosphite, phenyl diisodecyl phosphite, tris(2-ethyl Hexyl) phosphite, tris(isodecyl)phosphite, tris(tridecyl)phosphite, tetrakis(2,4-di-tert-butylphenyl)-4,4' -biphenylene-di-phosphonate, 4,4'-isopropylidene diphenyltetraalkyl (C12-C15) diphosphite, 4,4'-butylene bis(3-methyl -6-tert-butylphenyl)-ditridecyl phosphite, bis(nonylphenyl)pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol -di-phosphite, cyclic neopentyltetrakis(2,6-di-tert-butyl-4-methylphenyl-phosphite), 1,1,3-tris(2-methyl) -4-bis(tridecyl)phosphite-5-tert-butylphenyl)butane, tetrakis(2,4-di-tert-butyl-5-methylphenyl)-4,4'- Biphenylene diphosphonate, tris-2-ethylhexyl phosphite, triisodecyl phosphite, tristearyl phosphite, phenyl diisononyl phosphite, trilaurate III Thiophosphite, distearyl pentaerythritol diphosphite, tris(nonylphenyl)phosphite tris[2-[[2,4,8,10-tetra-tert-butyldibenzo[d] , f][1,3,2]dioxaphosphino-6-yl]oxy]ethyl]amine, bis(2,4-bis(1,1-dimethylethyl)-6-methylbenzene Ethyl ester phosphoric acid, Adekastab (registered trademark) 329K (manufactured by ADEKA Co., Ltd.), Adekastab (registered trademark) PEP36 (manufactured by ADEKA Co., Ltd.), Adekastab (note) Trademark) PEP-8 (manufactured by ADEKA Co., Ltd.), Sandstab (registered trademark) P-EPQ (manufactured by Sigma), ウェストン (registered trademark) 618 (manufactured by GE), ウェストン (registered trademark) 619G (manufactured by GE) , ウルトラノックス (registered trademark) 626 (manufactured by GE), 6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10- Tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphospholene) and the like. When the phosphorus-based antioxidant is contained, the content of the antioxidant (J) is preferably 1% by mass or more and 99% by mass or less based on 100% by mass of the total amount of the antioxidant (J).

A sulfur-based antioxidant is an antioxidant having a sulfur atom in a molecule. Examples of the sulfur-based antioxidant include dialkyl thiodipropionate compounds such as dilauryl thiodipropionate, dimyristyl ester or distearyl ester, and tetrakis [methylene (3- 12). Alkylthio)propionate] A β-alkylmercaptopropionate compound of a polyhydric alcohol such as methane. When a sulfur-based antioxidant is contained, the content of the antioxidant (J) is preferably 1% by mass or more and 99% by mass or less based on 100% by mass of the total amount of the antioxidant (J).

As the antioxidant (J), GPA-5001 (manufactured by ADEKA Co., Ltd.) or the like can be used.

In particular, 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 the antioxidant (J), the content thereof is preferably 0.01 to 20% by mass, and more preferably 0.05 to 10% by mass based on the total amount of the solid component. When the content rate 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) or the like.

<Solvent (E)> The solvent (E) in the present invention contains propylene glycol monomethyl ether acetate in a content ratio of 10% by mass or more and 78% by mass or less based on the total amount of the solvent (E). The content of propylene glycol monomethyl ether acetate in the total amount of the solvent (E) is preferably 20% by mass or more and 78% by mass or less, and more preferably 30% by mass or more and 78% by mass or less. The solvent other than propylene glycol monomethyl ether acetate is not particularly limited, and a solvent which is generally used in the field can be used. For example, an ester solvent (a solvent containing -COO- or a solvent containing no -O- in a molecule), an ether solvent (a solvent containing -O- in the molecule, a solvent containing no -COO-), an ether ester solvent (in the molecule) a solvent containing -COO- and -O-), a ketone solvent (a solvent containing -CO- in the molecule, a solvent not containing -COO-), an alcohol solvent (containing OH in the molecule, and containing no -O-, -CO) - and -COO-solvent), aromatic hydrocarbon solvent, guanamine solvent, dimethyl hydrazine, and the like.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl acetate, and isoamyl acetate. , butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, ring Hexanol acetate, γ-butyrolactone, and the like.

Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, and diethylene glycol. Monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3- Methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether , diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenethyl ether, methyl anisole and the like.

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

Examples of the ketone solvent include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, and 4-methyl-2- Pentanone, cyclopentanone, cyclohexanone, isophorone and the like.

Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin. Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, and 1,3,5-trimethylbenzene. Examples of the guanamine solvent include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

These solvents may be used singly 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, and digan are preferred. Alcohol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol methyl ether acetate, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl Further, keto-2-pentyl ketone, N,N-dimethylformamide, ethyl 3-ethoxypropionate, N-methylpyrrolidone, etc., more preferably 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, 3-ethoxypropionic acid Ethyl ester, 4-hydroxy-4-methyl-2-pentanone, N-methylpyrrolidone.

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

The SP value can be applied, for example, to the Hansen parameter of the liquid at 25 ° C described in J. Brandrup, EHImmergut, POLYMER HANDBOOK 3rd edition, Solubility Parameter Value of John Wiley & Sons. As a solvent having a higher SP value than the propylene glycol monomethyl ether acetate obtained by the Hildebrand method using the Hildebrand method (SP value (=9.0 (cal/cm ³ ) ^1/2 ), for example, propylene glycol monomethyl is preferable. Ether (SP value 10.7 (cal/cm ³ ) ^1/2 ), ethylene glycol monobutyl ether (SP value 10.2 (cal/cm ³ ) ^1/2 ), diacetone alcohol (SP value 10.2 (cal/cm) ³ ) ^1/2 ), ethyl lactate (SP value 10.0 (cal/cm ³ ) ^1/2 ), 3-methoxy-1-butanol (SP value 10.9 (cal/cm ³ ) ^1/2 ), Ethyl 3-ethoxypropionate (SP value 9.1 (cal/cm ³ ) ^1/2 ), cyclohexanone (SP value 9.3 (cal/cm ³ ) ^1/2 ), γ-butyrolactone (SP value) 12.8 (cal/cm ³ ) ^1/2 ), N-methylpyrrolidone (SP value 11.2 (cal/cm ³ ) ^1/2 ). These solvents having a higher SP value than propylene glycol monomethyl ether acetate can be used. It is also possible to combine two or more types.

The difference between the SP values of the solvent other than the propylene glycol monomethyl ether acetate and the propylene glycol monomethyl ether acetate is preferably 0.1 (cal/cm ³ ) ^1/2 or more, and 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 preferably 4 (cal/cm ³ ) ^1/2 or less. More preferably, it is 3 (cal/cm ³ ) ^1/2 or less, and further preferably 2 (cal/cm ³ ) ^1/2 or less.

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

The content of the solvent (E) is preferably 50 to 95% by mass, and more preferably 55 to 92% by mass based on the total amount of the red curable resin composition. In other words, the solid content of the red curable resin composition is preferably 5 to 50% by mass, and more preferably 8 to 45% by mass. When the content of the solvent (E) is within the above range, the flatness at the time of coating becomes good, and when the color filter is formed, the color density does not become insufficient, and thus the display characteristics tend to be good.

<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 an organic oxime-based surfactant, a fluorine-based surfactant, and an organic ruthenium-based surfactant having a fluorine atom. These may have a polymerizable group in the side chain. Examples of the organic oxime-based surfactant include surfactants having a decane bond in the molecule. Specifically, Toray Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (trade name: Toray-Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 ( It is manufactured by Shin-Etsu Chemical Co., Ltd., TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (manufactured by ジャパン・パフォーマンス・マテリアルズ・ジャパンContract Club).

The fluorine-based surfactant may, for example, be a surfactant having a fluorocarbon chain in the molecule. Specifically, フロラード (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), メガファック (registered trademark) F142D, F171, F172, F173, F177, F183, F554, R30, RS-718-K (manufactured by DIC Corporation), エフトップ (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Corporation, Ltd.), サーフロン (registered trademark) S381, S382, SC101, SC105 (Asahi Glass Co., Ltd.) Manufactured) and E5844 (manufactured by ダイキンファインケミカル Research Institute).

The organic ruthenium-based surfactant having a fluorine atom as described above includes a surfactant having a siloxane chain and a fluorocarbon chain in the molecule. Specifically, メガファック (registered trademark) R08, BL20, F475, F477, and F443 (manufactured by DIC Corporation) and the like are exemplified.

When the leveling agent (F) is contained, the content thereof is preferably 0.001% by mass or more and 3% by mass or less, and more preferably 0.002% by mass or more and 2% by mass or less based on the total amount of the red curable resin composition. More preferably, it is 0.005 mass % or more and 1 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 components> The red curable resin composition of the present invention may contain a polymerization initiation aid, a filler, another polymer compound, an adhesion promoter, an antioxidant, a light stabilizer, a chain transfer agent, etc., as needed. Additives well known in the art.

<Method for Producing Red Curable Resin Composition> The red curable resin composition of the present invention can be, for example, a coloring agent (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a solvent. (E), and if necessary, a leveling agent (F) and other components are used in combination to prepare. The red pigment (P) and the pigment (Q) to be used as needed are preferably mixed with a part or all of the solvent (E) in advance, and dispersed by using a bead mill or the like until the average particle diameter of the pigment is about 0.2 μm or less. At this time, a part or all of the pigment dispersant and the resin (B) may be blended as needed. By mixing the remaining components in the pigment dispersion liquid thus obtained and mixing them so as to have a predetermined concentration, the intended red curable resin composition can be prepared. The compound (IB) is preferably dissolved in a part or all of the solvent (E) to prepare a solution. The solution was filtered using a screening procedure having a pore size of about 0.01 to 1 μm. The mixed red curable resin composition is preferably filtered by a screening program having a pore diameter of about 0.01 to 10 μm.

<Method for Producing Color Filter> A method of producing a colored pattern from the red curable resin composition of the present invention includes a photolithography method, an inkjet method, a printing method, and the like. Among them, photolithography is preferred. The photolithography method is a method in which the red curable resin composition is applied onto a substrate, dried to form a colored composition layer, and the colored composition layer is exposed and developed through a photomask. In the photolithography method, a coloring coating film which is a cured product of the coloring composition layer can be formed by using a photomask and/or no development at the time of exposure. The colored pattern and the colored coating film thus formed can be used as the color filter of the present invention. The film thickness of the produced color filter is not particularly limited, and can be appropriately adjusted depending on the purpose, use, and the like, and is, for example, 0.1 to 30 μm, preferably 0.1 to 20 μm, and more preferably 0.5 to 6 μm.

As the substrate, quartz glass, borosilicate glass, aluminosilicate glass, a glass plate such as soda lime glass coated with cerium oxide on the surface, polycarbonate, polymethyl methacrylate, and polyparaphenyl may be used. A resin sheet such as ethylene glycol diester or ruthenium or the like, and a product of aluminum, silver, silver/copper/palladium alloy thin film or the like is formed on the substrate. Additional color filter layers, resin layers, transistors, circuits, and the like can be formed on these substrates.

The formation of the respective color elements by photolithography can be carried out under known or conventional devices and conditions. For example, it can be produced as follows. First, the red curable resin composition is applied onto a substrate, and dried by heating (prebaking) and/or drying under reduced pressure to remove a volatile component such as a solvent and dry it to obtain a smooth colored composition layer. Examples of the coating method include a spin coating method, a slit coating method, a slit, and a spin coating method. The temperature at the time of heat drying is preferably 30 to 120 ° C, more preferably 50 to 110 ° C. Further, the heating time is preferably from 10 seconds to 60 minutes, and more preferably from 30 seconds to 30 minutes. In the case of drying under reduced pressure, it is preferably carried out under a pressure of 50 to 150 Pa at a temperature of 20 to 25 °C. The film thickness of the coloring composition layer is not particularly limited, and can be appropriately selected depending on the film thickness of the target color filter.

Next, the colored composition layer is exposed through a photomask for forming a colored pattern of the target. The pattern on the photomask is not particularly limited, and a pattern matching the intended use can be used. As the light source for exposure, a light source that generates light having a wavelength of 250 to 450 nm is preferable. For example, the wavelength range can be cut off using a filter that cuts light of less than 350 nm, or these wavelength ranges can be selectively taken out using a band pass filter that takes out light at around 436 nm, near 408 nm, and around 365 nm. Specifically, examples of the light source include a mercury lamp, a light-emitting diode, a metal halide lamp, a halogen lamp, and the like. Since the parallel light rays can be uniformly irradiated to the entire exposed surface, and the correct alignment of the photomask and the substrate on which the colored composition layer is formed is performed, it is preferable to use an exposure apparatus such as a mask aligner and a stepper.

The colored composition layer after exposure is developed in contact with the developer to form a colored pattern on the substrate. By development, the unexposed portion of the colored composition layer is dissolved in the developer to be removed. As the developer, an aqueous solution of a basic compound such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate or tetramethylammonium hydroxide is preferable. The concentration in the aqueous solution of these basic compounds is preferably 0.01 to 10% by mass, and more preferably 0.03 to 5% by mass. Further, the developer may contain a surfactant. The developing method may be any one of a spin coating immersion method, a dipping method, and a spray method. Further, the substrate can be inclined at an arbitrary angle during development. It is preferred to carry out water washing after development.

Further, it is preferred to post-bait the obtained colored pattern. The post-baking temperature is preferably from 150 to 250 ° C, more preferably from 160 to 235 ° C. The post-baking time is preferably from 1 to 120 minutes, more preferably from 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 generation of foreign matter is suppressed. This color filter can be used as a color filter for a display device (for example, a liquid crystal display device, an organic EL device, an electronic paper, or the like) and a solid-state image pickup element. Example

The present invention is not limited by the following examples, and the present invention is of course not limited to the following examples, and it is of course possible to carry out the changes as appropriate and can be appropriately implemented in the scope of the present invention. It is within the technical scope of the present invention. In the examples, % and parts of the content or the amount used are shown as a mass basis unless otherwise specified.

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

[Synthesis Example 1]

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

[化64]

Identification (mass analysis) of the compound represented by the formula (I-1-A) Ionization mode = ESI+: m/z = [M+H] ⁺ 442.1 Accurate mass: 441.1

30 parts of the compound represented by the formula (I-1-A) and 150 parts of dehydrated chloroform (manufactured by Kanto Chemical Co., Ltd.) were mixed at room temperature. In the obtained mixture, 26.3 parts of trimethoxy[3-(methylamino)propyl]decane (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise at a temperature of not more than 40 ° C, and stirred at 70 ° C. hour. The resulting reaction mixture was cooled to room temperature. The obtained mixture was added to 825 parts of ethyl acetate to precipitate a solid. The obtained precipitate was filtered, and the obtained solid was washed with ethyl acetate and dried to give 35.5 parts of the compound of formula (I-1). The yield was 87%.

[化65]

Identification (mass analysis) of the compound represented by formula (I-1) Ionization mode = ESI+: m/z = [M+H] ⁺ 599.2 Accurate mass: 598.2

Compound 0.35g represented by the formula (I-1) was dissolved in chloroform, so that the volume becomes 250cm ^3, in which the dilution water 2cm ³ with ion exchange, so that the volume becomes 100cm ³ (concentration: 0.028g / L), spectrophotometric The absorption spectrum was measured (quartz cell, optical path length: 1 cm). This compound was λ max = 546 nm.

[Synthesis Example 2] An appropriate amount of nitrogen was poured into a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, and replaced with a nitrogen atmosphere, and 100 parts of propylene glycol monomethyl ether acetate was added thereto while stirring. Heat to 120 ° C while heating. Next, in a monomer mixture composed of 7 parts of tricyclodecyl methacrylate, 27 parts of benzyl methacrylate, and 13 parts of methacrylic acid, パーブチル was added in one part with respect to 100 parts of the monomer mixture. O (manufactured by Nippon Oil & Fat Co., Ltd.), and the prepared mixture 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 poured into the flask, and replaced with an air atmosphere, and 7 parts of glycidyl methacrylate, 0.34 parts of triphenylphosphine, and 0.07 parts of methylhydroquinone were put into the reaction containing the above copolymer, at 120. The reaction was continued at ° C, and was cooled to room temperature at a time when the acid value of the solid component became 105 mg-KOH/g, and the reaction was completed. A copolymer (resin B-1) solution was obtained by adding 32 parts of propylene glycol monomethyl ether acetate. The solid content of the resin B-1 solution was 30%. The weight average molecular weight of the resin B-1 was 3.0 × 10 ⁴ .

The measurement of the polystyrene-equivalent weight average molecular weight Mw and the number average molecular weight Mn of the resin obtained in the above Synthesis Example 2 was carried out under the following conditions using a GPC method. Device: HLC-8120GPC (manufactured by Tosoh Corporation) Column: TSK-GELG2000HXL Column temperature: 40 °C Solvent: THF Flow rate: 1.0 mL/min Solid content concentration of the test solution: 0.001 to 0.01% by mass Injection amount: 50 μL Detector : RI calibration standard material: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation) The polystyrene-equivalent weight average molecular weight obtained above and The ratio of number average molecular weight (Mw/Mn) is defined as a molecular weight distribution.

[Preparation of Red Curable Resin Composition] Each component was mixed so as to have the composition shown in Table 1, and a red curable resin composition was obtained.

The pigment is mixed with the propylene glycol monomethyl ether acetate described in the column of the resin dispersant and the resin B-1 and E-1 ²⁾ described in the column of B-1 ¹⁾ , and is dispersed in advance. Column B-1 ³⁾ indicates the total content of the resin B-1. Column E-1 ⁴⁾ indicates the total content of propylene glycol monomethyl ether acetate.

In addition, in Table 1, each component shows the following. In addition, resin (B) shows the fraction of solid content conversion. Dye (A-1): A-1: Compound dye represented by formula (I-1) (A-2): A-2: CI solvent red 130 (Aolisin red 330; manufactured by BASF Corporation; maximum absorption wavelength 495nm; metal complex salt dye)

Pigment (A): A-3: CI Pigment Red 254 Pigment Dispersant: Acrylic Pigment Dispersant Resin (B): B-1: Resin B-1 Polymerizable Compound (C): C-1: Dipentaerythritol Hexacrylic Acid Ester (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) Polymerization initiator (D): D-1: N-acetoxy-1-[9-ethyl-6-(2-methyl Benzyl hydrazino)-9H-carbazol-3-yl]ethane-1-imine (Irgacure (registered trademark) OXE 02; manufactured by BASF Corporation; hydrazine compound) Polymerization initiator (D): D-2: Compound represented by the following formula (TR-PBG-309; Changzhou Strong Electronic New Material (made))

[化66]

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 organic germanium (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.)

[Formation of Color Filters (Color Patterns)] After the color-developing resin compositions obtained in Examples 1 to 10 were applied by spin coating on a glass substrate (EAGLE XG; manufactured by Corning Incorporated) of 2 inches square, Prebaking at 100 ° C for 3 minutes gave a colored composition layer. After cooling, the distance between the glass substrate on which the colored composition layer was formed and the quartz glass photomask was 100 μm, and an exposure machine (TME-150RSK; manufactured by Konica Minolta Co., Ltd.) was used, and 50 mJ/cm was used in an air atmosphere. The exposure amount of ² (365 nm reference) was irradiated with light. As a photomask, a photomask in which a line and a gap pattern of 100 μm were formed was used. The colored composition layer after light irradiation was immersed and developed at 26 ° C for 60 seconds in an aqueous developing solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide, washed with water, and then dried in an oven at 230 ° C. Bake after 20 minutes. By the above operation, a colored pattern was obtained from all of the colored curable resin compositions of Examples 1 to 10.

[Measurement of film thickness] The film thickness of the obtained coloring pattern was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.). The results are shown in Table 2.

[Colorimetric evaluation] The coloring pattern on the obtained glass substrate was measured for spectroscopic using a color measuring machine (OSP-SP-200; manufactured by Olympus Co., Ltd.), and CIE was measured using an isochromatic function of a C light source. The xy chromaticity coordinate (x, y) in the XYZ color system. The results are shown in Table 2. It was confirmed from the chromaticity coordinates that the color of the colored pattern on the obtained glass substrate was red.

[Formation of Color Filter (Colored Coating Film)] The coloring curability obtained in Examples 1 to 10 and Comparative Example 1 was applied by spin coating on a 2 inch square glass substrate (EAGLE XG; manufactured by Corning Incorporated). After the resin composition, it was prebaked at 100 ° C for 3 minutes to obtain a colored composition layer. After the cooling, the exposure apparatus (TME-150RSK; manufactured by Konica Minolta Co., Ltd.) was used, and light irradiation was performed under an air atmosphere at an exposure amount of 50 mJ/cm ² (365 nm basis) without using a photomask. The colored composition layer after light irradiation was immersed and developed at 26 ° C for 60 seconds in an aqueous developing solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide, washed with water, and then dried in an oven at 230 ° C. After baking for 20 minutes, a colored coating film was obtained.

[Foreign material evaluation] The foreign matter on the surface of the colored coating film was observed at a magnification of 50 times using an erecting microscope (Axio Imager MAT; manufactured by Shimadzu Corporation). If no foreign matter is observed, the colored coating film can be said to have no problem in practical use as a color filter.

【Table 2】

【table 3】 〇: There is no foreign matter in the observation unit △: 1 to 9 foreign objects seen in the observation unit ×: 10 or more foreign objects seen in the observation unit

The ratio of the propylene glycol monomethyl ether acetate of the colored curable resin composition in the case of the chromaticity of the color filter (coloring coating film) which consists of the color-curable resin composition containing the compound (A1) In the range of 10% to 78%, no excessive foreign matter was observed on the surface of the colored coating film. On the other hand, when the ratio is 80%, foreign matter is observed on the surface of the colored coating film, and it is not suitable as a color filter. Industrial availability

According to the red curable resin composition of the present invention, by controlling the solvent ratio in the resist to a predetermined range, it is possible to form a color filter in which no foreign matter is generated on the surface. This color filter can be used as a color filter used in a display device (for example, a liquid crystal display device, an organic EL device, an electronic paper, etc.) and a solid-state image sensor.

Claims (7)

A red curable resin composition comprising a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a solvent (E) having a ruthenium atom and a maximum absorption wavelength in chloroform A dye (A1) and a red pigment (P) of 500 nm to 600 nm are contained as a colorant (A), propylene glycol monomethyl ether acetate is contained as a solvent (E), and propylene glycol is contained in the total amount of the solvent (E). The content of monomethyl ether acetate is 10% by mass or more and 78% by mass or less. The red curable resin composition of claim 1, wherein the total amount of the solvent (E) is 22% by mass or more of a solvent having a higher SP value than propylene glycol monomethyl ether acetate. The red curable resin composition of claim 1 or 2, wherein 22% by mass or more of the total amount of the solvent (E) is selected from the group consisting of propylene glycol monomethyl ether, ethylene glycol monobutyl ether, and diacetone alcohol A solvent in ethyl lactate, 3-methoxy-1-butanol, ethyl 3-ethoxypropionate, cyclohexanone, γ-butyrolactone, or N-methylpyrrolidone. The red curable resin composition of claim 1 or 2, wherein the dye (A1) is a compound having a xanthene skeleton. The red curable resin composition of claim 1 or 2, further comprising a metal complex salt azo dye as the colorant (A). A color filter formed of the red curable resin composition as claimed in claim 1 or 2. A display device comprising the color filter of claim 6.