KR102114956B1 - Red curable resin composition - Google Patents

Abstract

The red curable resin composition of the present invention includes a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a solvent (E), and as the colorant (A), Contains a dye (A1) having a silicon atom and a maximum absorption wavelength in chloroform of 500 nm to 600 nm, a red pigment (P), and propylene glycol monomethyl ether acetate as a solvent (E). Moreover, the content rate of propylene glycol monomethyl ether acetate is 10 mass% or more and 78 mass% or less in the total amount of a solvent (E).

Description

Red curable resin composition {RED CURABLE RESIN COMPOSITION}

The present invention relates to a red curable resin composition.

The colored curable resin composition is used for the production of color filters used in display devices such as liquid crystal display devices, electroluminescence display devices, and plasma displays. As such a color curable resin composition, a color curable resin composition containing a compound represented by the following formula as a colorant is known (for example, Patent Document 1).

(Formula 1)

(Patent Document 1) Japanese Patent Publication No. 2016-027075

The colored curable resin composition known conventionally has room for improvement in the presence or absence of foreign matter on the surface of the obtained color filter.

The present invention includes the following inventions.

[1] It includes a coloring agent (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D) and a solvent (E), and has a silicon atom as the coloring agent (A), A dye (A1) having a maximum absorption wavelength in chloroform of 500 nm to 600 nm and a red pigment (P) are included,

The red curable resin composition containing propylene glycol monomethyl ether acetate as a solvent (E), and the content rate of propylene glycol monomethyl ether acetate being 10 mass% or more and 78 mass% or less in the total amount of the solvent (E).

[2] The red curable resin composition according to [1] above, wherein the SP value contains at least 22% by mass of the total amount of the solvent (E) in a solvent having a higher SP value than propylene glycol monomethyl ether acetate.

[3] Propylene glycol monomethyl ether, ethylene glycol monobutyl ether, diacetone alcohol, ethyl lactate, 3-methoxy-1-butanol, 3-ethoxypropionic acid ethyl, cyclohexanone, γ-butyrolactone, N- The red curable resin composition as described in said [1] or [2], which contains 22 mass% or more of the solvent selected from the group which consists of methyl pyrrolidone in the whole amount of a solvent (E).

[4] The red curable resin composition according to any one of [1] to [3], wherein the dye (A1) is a compound having a xanthene skeleton.

[5] The red curable resin composition according to any one of [1] to [4], further comprising a metal complex salt azo dye as a colorant (A).

[6] A color filter formed of the red curable resin composition according to any one of [1] to [5] above.

[7] A display device comprising the color filter according to [6] above.

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

The red curable resin composition of the present invention includes a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D).

In addition, the compound and functional group illustrated in this specification can be used individually or in combination of multiple types, unless otherwise specified.

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

The dye (A1) is preferably a dye having a silicon atom and having an imidazole skeleton, a triarylmethane skeleton, a cyanine skeleton, or a xanthene skeleton. As a dye having a silicon atom and having an imidazole skeleton, for example, a compound represented by formula (IA) disclosed in JP 2010-526897 A is included.

(Formula 2)

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

(Formula 3)

[N represents an integer of 1 to 8, R ² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and * represents a bond with a nitrogen atom.]]

As a compound represented by Formula (IA), the compound preferably represented by the following formula is mentioned.

(Formula 4)

Among the dyes (A1), dyes having a silicon atom and having at least one skeleton selected from the group consisting of a triarylmethane skeleton, a cyanine skeleton, and a xanthene skeleton are preferred, have a silicon atom, and also have xanthene Dye having a skeleton is more preferable. As a dye having a silicon atom and having a xanthene skeleton, a dye having a xanthene skeleton having an organic silicon group as a substituent is preferable. Here, the organic silicon group refers to a group having a carbon-silicon bond. Among the dyes having a xanthene skeleton having an organic silicon group as a substituent, dyes having a xanthene skeleton having a silylalkyl group such as trimethylsilylalkyl group, triethylsilylalkyl group, trimethoxysilylalkyl group, and triethoxysilylalkyl as a substituent are preferred. The compound represented by formula (IB) (hereinafter, also referred to as "compound (IB)") is more preferable. The tautomer is also contained in the compound (IB).

(Formula 5)

[In formula (IB), R ²¹ to R ²⁴ each independently represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, a phenyl group which may have a substituent, or a group represented by formula (ib). However, R ²¹ ~ R ²⁴ and at least one of which is a group represented by the formula (ib).

* -R ⁵⁰ -Si (R ²⁹ ) ₃ (ib)

[R ²⁹ represents a hydrogen atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and * represents a bond with a nitrogen atom. The plurality of R ²⁹ may be the same or different, respectively.

R ⁵⁰ represents an alkanediyl group having 1 to 10 carbon atoms, and -CH ₂ -constituting the alkanediyl group is -O-, -CO-, -NR ^11- , -OCO-, -COO-, -OCONH It may be substituted with-, -CONH- or -NHCO-. However, in the alkanediyl group, adjacent -CH ₂ -is not simultaneously substituted, and terminal -CH ₂ -is not substituted.]

In R ²¹ to R ²⁴ , a hydrogen atom contained in a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms may be substituted with a halogen atom, and —CH ₂ — contained in the saturated hydrocarbon group is —O—, —CO—, It may be substituted with -NR ^11- , -OCO-, -COO-, -OCONH-, -CONH- or -NHCO-. However, in the saturated hydrocarbon group, adjacent -CH ₂ -is not substituted at the same time, and the terminal -CH ₂ -is not substituted.

R ²⁵ and R ²⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

R ²⁷ and R ²⁸ are, each ^{_{independently, -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 the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom.

Z ⁺ represents ⁺ N (R ¹³ ) ₄ , Na ⁺ or K ⁺ .

R ¹¹ and R ¹² each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.

R ¹³ each independently represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.

p represents the integer of 0-4.]

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

(Formula 6)

[In 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 formula (ic). However, at least 1 of R ³¹ -R ³⁴ is a group represented by formula (ic).

(Formula 7)

[n represents an integer of 1 to 8, R ³⁹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and * represents a bond with a nitrogen atom.]

In R ³¹ to R ³⁴ , a hydrogen atom contained in a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms may be substituted with a halogen atom, and -CH ₂ -contained in the saturated hydrocarbon group is -O-, -CO-, or It may be substituted with -NR ^11- . However, in the saturated hydrocarbon group, adjacent -CH ₂ -is not substituted at the same time, and the terminal -CH ₂ -is not substituted.

R ³⁵ and R ³⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

R ³⁷ and R ³⁸ are, each independently, -OH, -SO _3- , -SO ₃ H, -SO ₃ ^- Z ⁺ , -CO _2- , -CO ₂ H, -CO ₂ ^- Z ⁺ , -CO ₂ R ¹⁰ , -SO ₃ R ¹⁰ or -SO ₂ NR ¹¹ R ¹² .

R ¹⁰ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom.

Z ⁺ represents ⁺ N (R ¹³ ) ₄ , Na ⁺ or K ⁺ .

R ¹¹ and R ¹² each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.

R ¹³ each independently represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.

m represents the integer of 0-4.]

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

As the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms represented by R ²¹ to R ²⁴ and R ³¹ to R ³⁴ , a methyl group, an ethyl group, a propyl group, and a butyl group are preferable.

The hydrogen atom contained in the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms represented by R ²¹ to R ²⁴ and R ³¹ to R ³⁴ may be substituted with a halogen atom. As said halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom is mentioned, for example.

Examples of the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms substituted with halogen atoms 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 substituted with -O-, -CO- or -NR ^11- . However, in the saturated hydrocarbon group, adjacent -CH ₂ -are not simultaneously substituted, and terminal -CH ₂ -is not substituted at all.

Examples of the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms represented by R ¹¹ include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, and n-octyl group, linear alkyl groups having 1 to 20 carbon atoms such as n-nonyl group, n-decyl group, n-dodecyl group, n-hexadecyl group and n-icosyl group; isopropyl group, isobutyl group, sec-butyl group, tert A branched alkyl group having 3 to 20 carbon atoms, such as a butyl group, isopentyl group, neopentyl group, and 2-ethylhexyl group; cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, and tricyclo And an alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms such as a decyl group.

-CH ₂ groups which contain a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms in the art - is, there may be mentioned as the substituted group by -O-, for example, a group represented by the following formula (* represents a bonding hand).

(Formula 8)

Examples of the group substituted with -CH ₂ -valent and -CO- contained in the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms include groups represented by the following formula (* represents a bond) .

(Formula 9)

Examples of the group substituted with -CH ₂ -that is contained in the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms with -NR ¹¹ -include groups represented by the following formula (* represents a bond).

(Formula 10)

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

-CH ₂ groups which contain a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms in the art - The group substituted by a, -OCO-, there may be mentioned, for example, a group represented by the following formula (* represents a bonding hand).

(Formula 11)

Examples of the group substituted with -CH ₂ -that is included in the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms with -COO- include, for example, a group represented by the following formula (* represents a bond).

(Formula 12)

As a group substituted with -CH ₂ -valent and -OCONH- contained in the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, for example, a group represented by the following formula can be mentioned (* represents a bond).

(Formula 13)

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

(Formula 14)

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

(Formula 15)

The phenyl group represented by R ²¹ to R ²⁴ and R ³¹ to R ³⁴ may have a substituent. As the substituent, 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 methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, and n- Straight-chain alkyl groups having 1 to 20 carbon atoms such as octyl group, n-nonyl group, n-decyl group, n-dodecyl group, n-hexadecyl group and n-icosyl group; isopropyl group, isobutyl group, sec-butyl Branched alkyl group having 3 to 20 carbon atoms such as group, tert-butyl group, isopentyl group, neopentyl group and 2-ethylhexyl group; cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group And an alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms such as a tricyclodecyl group.

Examples of -OR ¹⁰ include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, and isoxyloxy group. Can be.

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

Examples of -CO ₂ R ¹⁰ include methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, tert-butoxycarbonyl group, hexyloxycarbonyl group, and isoxyloxycarbonyl group.

Examples of -SR ¹⁰ include methylsulfanyl group, ethylsulfanyl group, butylsulfanyl group, hexylsulfanyl group, decylsulfanyl group and isosilsulfanyl group.

Examples of -SO ₂ R ¹⁰ include methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, hexylsulfonyl group, decylsulfonyl group, and isosilsulfonyl group.

Examples of -SO ₃ R ¹⁰ include methoxysulfonyl group, ethoxysulfonyl group, propoxysulfonyl group, tert-butoxysulfonyl group, hexyloxysulfonyl group, and isoxyloxysulfonyl group.

As -SO ₂ NR ¹¹ R ¹² , for example, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group, N -Isobutylsulfamoyl group, N-sec-butylsulfamoyl group, N-tert-butylsulfamoyl group, N-pentylsulfamoyl group, N- (1-ethylpropyl) sulfamoyl group, N- (1,1 -Dimethylpropyl) sulfamoyl group, N- (1,2-dimethylpropyl) sulfamoyl group, N- (2,2-dimethylpropyl) sulfamoyl group, N- (1-methylbutyl) sulfamoyl group, N- (2-methylbutyl) sulfamoyl group, N- (3-methylbutyl) sulfamoyl group, N-cyclopentylsulfamoyl group, N-hexylsulfamoyl group, N- (1,3-dimethylbutyl) sulfamoyl group , N- (3,3-dimethylbutyl) sulfamoyl group, N-heptyl sulfamoyl group, N- (1-methylhexyl) sulfamoyl group, N- (1,4-dimethylpentyl) sulfamoyl group, N- Octyl sulfamoyl group, N- (2-ethylhexyl) sulfamoyl group, N- (1,5-dimethyl) hexyl sulfamoyl group, N- (1,1,2,2-tetramethylbutyl) sulfamoyl group, etc. N-1 substituted sulfamoyl group of;

N, N-dimethylsulfamoyl group, N, N-ethylmethylsulfamoyl group, N, N-diethylsulfamoyl group, N, N-propylmethylsulfamoyl group, N, N-isopropylmethylsulfamoyl group, N, such as N, N-tert-butylmethylsulfamoyl group, N, N-butylethylsulfamoyl group, N, N-bis (1-methylpropyl) sulfamoyl group, N, N-heptylmethylsulfamoyl group, And an N-2 substituted sulfamoyl group.

Examples of R ²¹ ~ R is a phenyl group having a substituent represented by ²⁴ and R ³¹ ~ R ^34, -R ¹⁰ are preferred, more preferably a univalent saturated hydrocarbon group having 1 to 10 carbon atoms.

At least one of R ²¹ to R ²⁴ is a group represented by formula (ib).

In the group represented by formula (ib), R ²⁹ represents a hydrogen atom, a 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 methyl group, ethyl group, propyl group and butyl group.

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

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

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

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

(Formula 16)

(Formula 17)

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

(Formula 18)

(Formula 19)

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

(Formula 20)

(Formula 21)

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

(Formula 22)

(Formula 23)

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

(Formula 24)

(Formula 25)

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

(Formula 26)

(Formula 27)

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

(Formula 28)

(Formula 29)

In the formula (ib), as the group in which -CH ₂ -constituting R ⁵⁰ is substituted with -CONH-, for example, a group represented by the following (* represents a bond).

(Formula 30)

(Formula 31)

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

(Formula 32)

(Formula 33)

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

(Formula 34)

(Formula 35)

(Formula 36)

(Formula 37)

(Formula 38)

(Formula 39)

At least one of R ³¹ to R ³⁴ is preferably a group represented by 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.

As R ³⁹ , a hydrogen atom, a methyl group, an ethyl group and a propyl group are preferable, and a hydrogen atom, a methyl group and an ethyl group are more preferable.

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

(Formula 40)

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

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

^{R 27, R 28, R -CO} 2 indicated by ^37, and R ^{38 -} Examples of Z ^+, is -CO ₂ Na, or -CO ₂ K are preferred.

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

As -SO ₃ R ¹⁰ represented by R ²⁷ , R ²⁸ , R ³⁷ and R ³⁸ , for example, methoxysulfonyl group, ethoxysulfonyl group, propoxysulfonyl group, tert-butoxysulfonyl group, hexyloxysul And a phenyl group and an isoxyloxysulfonyl group.

Examples of -SO ₂ NR ¹¹ R ¹² represented by R ²⁷ , R ²⁸ , R ³⁷ and R ³⁸ are, for example, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-iso Propyl sulfamoyl group, N-butyl sulfamoyl group, N-isobutyl sulfamoyl group, N-sec-butyl sulfamoyl group, N-tert-butyl sulfamoyl group, N-pentyl sulfamoyl group, N- (1- Ethylpropyl) sulfamoyl group, N- (1,1-dimethylpropyl) sulfamoyl group, N- (1,2-dimethylpropyl) sulfamoyl group, N- (2,2-dimethylpropyl) sulfamoyl group, N -(1-methylbutyl) sulfamoyl group, N- (2-methylbutyl) sulfamoyl group, N- (3-methylbutyl) sulfamoyl group, N-cyclopentyl sulfamoyl group, N-hexylsulfamoyl group, N- (1,3-dimethylbutyl) sulfamoyl group, N- (3,3-dimethylbutyl) sulfamoyl group, N-heptylsulfamoyl group, N- (1-methylhexyl) sulfamoyl group, N- ( 1,4-dimethylpentyl) sulfamoyl group, N-octylsulfamoyl group, N- (2-ethylhexyl) sulfamoyl group, N- (1,5-dimethyl) hexylsulfamoyl group, N- (1,1 N-2 substituted sulfamoyl groups such as, 2,2-tetramethylbutyl) sulfamoyl group;

N, N-dimethylsulfamoyl group, N, N-ethylmethylsulfamoyl group, N, N-diethylsulfamoyl group, N, N-propylmethylsulfamoyl group, N, N-isopropylmethylsulfamoyl group, N, such as N, N-tert-butylmethylsulfamoyl group, N, N-butylethylsulfamoyl group, N, N-bis (1-methylpropyl) sulfamoyl group, N, N-heptylmethylsulfamoyl group, And an N-2 substituted sulfamoyl group.

As the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ¹⁰ , a methyl group, an ethyl group, a propyl group and a butyl group are preferable.

The hydrogen atom contained in the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ¹⁰ may be substituted with a halogen atom.

As said halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom is mentioned, for example.

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms substituted with halogen atoms include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a perfluoroethyl group, and a chlorobutyl group.

As Z ^{+, +} N (R ¹³ ) ₄ is preferable.

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

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

As the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ¹³ , a methyl group, an ethyl group, a propyl group, and a butyl group are preferable, and a methyl group, an ethyl group, and a propyl group are more preferable.

At least one of R ²¹ to R ²⁴ is a group represented by formula (ib), and as the other R ²¹ to R ²⁴ , a methyl group, an ethyl group, a propyl group, and the following groups are preferable (* is a nitrogen atom) Represents a bonding hand),

(Formula 41)

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

(Formula 42)

At least one of R ³¹ to R ³⁴ is a group represented by 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,

(Formula 43)

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

(Formula 44)

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

R ^27, R ^28, R ³⁷ and R ³⁸ is preferably _{^{-CO 2 -, -CO 2 H,}} -SO 3 H, -SO - 3 , more preferably -SO ₃ H, -SO ^- ₃ to be.

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

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

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

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

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

As a specific example of a compound (IB), what appears below, for example is mentioned. As the compound (IB), (I-1) to (I-4), (I-13) to (I-16), (I-25) to (I-28), (I-37) to (I -40), (I-49)-(I-54), (I-55)-(I-62), (I-87)-(I-94), (I-117)-(I-123 ) Is preferred, (I-1) to (I-4), (I-13) to (I-16), (I-25) to (I-28), (I-55) to (I- 62), (I-87) to (I-94), (I-117), (I-119) to (I-123) are more preferable.

(Formula 45)

(Formula 46)

(Formula 47)

(Formula 48)

(Chemical Formula 49)

(Formula 50)

(Formula 51)

(Formula 52)

(Formula 53)

(Formula 54)

(Formula 55)

(Formula 56)

(Formula 57)

(Formula 58)

As a specific example of a compound (IC), what is represented by said Formula (I-1)-Formula (I-54), what is represented by Formula (I-117)-Formula (I-119), Formula (I), for example What is represented by -121) and what is represented by Formula (I-123) are mentioned. As a compound (IC), what is represented by Formula (I-1)-Formula (I-4), what is represented by Formula (I-13)-Formula (I-16), Formula (I-25)-Formula (I) -28), Expressions (I-37) to Expression (I-40), Expressions (I-49) to Expression (I-54), Expressions (I-117) to Expression ( It is preferably represented by I-119), represented by formulas (I-1) to (I-4), represented by formulas (I-13) to (I-16), and formulas (I-25) It is more preferable that it is represented by ~ formula (I-28), formula (I-117), or formula (I-119).

Compound (IB) is represented by formula (IV)

(Formula 59)

[In the formula, R ²¹ , R ²² , R ²⁵ , R ²⁶ , R ²⁸ , R ²⁷ and p each have the same meaning as described above. X ² represents a halogen atom or a trifluoromethylsulfonyloxy group.] (Hereinafter sometimes referred to as "compound (IV)") and formula (V)

(Formula 60)

[In the formula, R ²³ and R ²⁴ each have the same meaning as described above.]

Compounds represented by (hereinafter, sometimes referred to as "compound (V)") can be produced by mixing and reacting in an organic solvent.

Examples of the halogen atom represented by X ² include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and preferably a chlorine atom.

X ² is preferably a halogen atom, and more preferably a chlorine atom.

R ²⁷ is, -SO ₃ ^- is preferably.

The use amount of compound (V) is usually 1 mol or more and 10 mol or less, preferably 1 mol or more and 3 mol or less, and more preferably 1 mol or more and 2 mol or less, per 1 mol of compound (IV).

R ²⁷ is -SO ₃ ^- or -CO ₂ ^- (. Is sometimes referred to as compound (II-1)) of compound (IB) is the formula (VI)

(Formula 61)

[Wherein, R ²⁵ , R ²⁶ , R ²⁸ and p have the same meaning as described above.

X ¹ and X ² each independently represent a halogen atom or a trifluoromethylsulfonyloxy group.

R ⁴⁰ represents -SO ₂ -or -CO-.]

in The compound (hereinafter, sometimes referred to as "compound (VI)") and formula (III)

(Formula 62)

[In the formula, R ²¹ and R ²² have the same meaning as described above.]

The compound represented by (hereinafter, sometimes referred to as "compound (III)") is mixed and reacted in an organic solvent, and then formula (V)

(Formula 63)

[In the formula, R ²³ and R ²⁴ each have the same meaning as described above.]

The compound represented by can be prepared by mixing and reacting in an organic solvent.

Examples of the halogen atom represented by X ¹ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and preferably a chlorine atom.

It is preferable that X ¹ and X ² are the same.

X ¹ and X ² are each independently preferably a halogen atom, and more preferably a chlorine atom.

R ⁴⁰ is preferably -SO _2- .

The amount of the compound (III) 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 or more and 10 mol or less, and more per 1 mol of the compound (VI), further Preferably it is 1 mol or more and 3 mol or less, Especially preferably, it is 1 mol or more and 2 mol or less.

The use amount of the compound (V) 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 or more and 10 mol or less, and more per 1 mol of the compound (VI), further Preferably it is 1 mol or more and 3 mol or less, Especially preferably, it is 1 mol or more and 2 mol or less.

The use amount of compound (III) 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 or more and 10 mol or less, and more per 1 mol of compound (VI), further Preferably it is 1 mol or more and 3 mol or less, Especially preferably, it is 1 mol or more and 2 mol or less.

The use amount of compound (V) is usually 1 mol or more and 50 mol or less, preferably 1 mol or more and 30 mol or less, and more preferably 1 mol or more and 20 mol or less, per 1 mol of compound (III).

Compound (IB) is useful as a dye. It is useful as a coloring agent of the coloring curable resin composition used for the color filter of display apparatuses, such as a liquid crystal display, because it has high solubility in an organic solvent.

The content ratio 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, and 20% by mass, out of 100% by mass of the total amount of solid content of the red curable resin composition. The following are more preferable.

Here, the "total amount of solid content" in the present specification refers to an amount excluding the content of the solvent from the total amount of the red curable resin composition. The total amount of the solid content and the content of each component thereof can be measured by known analytical means such as liquid chromatography or gas chromatography.

The content rate of the dye (A1) is preferably 0.01 mass% or more and 80 mass% or less, more preferably 0.1 mass% or more and 60 mass% or less, and more preferably 1 mass% or more and 40 mass% in 100 mass% of the total amount of the colorant (A). % Or less is more preferable.

The content of the compound (IB) is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more in 100% by mass of the dye (A1).

The content of the dye (A1) is preferably 10% by mass or more, more preferably 20% by mass or more, and preferably 100% by mass, more preferably 80% by mass, out of 100% by mass of the total dye. You may do this.

<Red pigment (P)>

The red curable resin composition of this invention contains a red pigment (P) as a coloring agent (A) other than the said dye (A1).

As a red pigment (P), the red compound is mentioned among the compounds classified as a pigment by the color index (published by The Society of Dyers and Colourists).

Specifically, CI Pigment Red 9 (hereinafter, description of CI Pigment Red is omitted, and only the number is described.), 97, 105, 122, 123, 144, 149, 166, 168, 175, 176 , 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, and the like, and CI pigment red 254, 255 is preferred.

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

Moreover, it is preferable that the content rate of the total of the said dye (A1) and a red pigment (P) is 80 mass% or more in 100 mass% of the total amount of a coloring agent (A), More preferably, it is 90 mass% or more.

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

<Pigment (Q)>

The red curable resin composition of this invention may contain the pigment (Q) other than a red pigment (P) as a coloring agent (A) to the extent that the performance of the obtained color filter is not impaired. The pigment (Q) is not particularly limited, and a known pigment can be used, and examples thereof include compounds classified as pigments in a color index (published by The Society of Dyers and Colourists).

The pigment (Q) (however, it is different from the red pigment (P)) is not particularly limited, and a known pigment can be used. And compounds.

As the pigment (Q), for example, CI Pigment Yellow 1 (hereinafter, the description of CI Pigment Yellow is omitted, and only the number is described.), 3, 12, 13, 14, 15, 16, 17 , 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214 Yellow pigments such as;

Orange pigments such as C.I. pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;

Blue pigments such as C.I. pigment blue 15, 15: 3, 15: 4, 15: 6, 60, 80;

Violet pigments such as C.I. pigment violet 1, 19, 23, 29, 32, 36, 38;

Green pigments such as C.I. pigment green 7, 36, 58;

Brown pigments such as C.I. pigment brown 23, 25;

And black pigments such as C.I. pigment black 1 and 7.

These pigments may be used alone or in combination of two or more.

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

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

<Dye (A2)>

The red curable resin composition of this invention may contain the dye (A2) other than the dye (A1) as a coloring agent (A) to the extent that the performance of the obtained color filter is not impaired. Examples of the dye (A2) (but different from the dye (A1)) include oil-soluble dyes, acid dyes, basic dyes, direct dyes, mordant dyes, amine salts of acid dyes, sulfonamide derivatives of acid dyes, metal complex dyes, etc. And dyes, for example, compounds classified as dyes in the color index (published by The Society of Dyers and Colourists), and known dyes described in dyeing notes (dyeing yarns). In addition, according to the chemical structure, azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes other than dye (A1), phthalocyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, scwarrillium Dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, and nitro dyes. Of these, organic solvent-soluble dyes are preferred.

Specifically, C.I. solvent yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162;

C.I. Solvent red 45, 49, 125, 130, 218;

C.I. Solvent orange 2, 7, 11, 15, 26, 56;

C.I. Solvent blue 4, 5, 37, 67, 70, 90;

C.I. C.I. of Solvent Green 1, 4, 5, 7, 34, 35, etc. Solvent dyes,

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;

C.I. acid orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173;

C.I. acid violet 6 B, 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;

C.I.acid dyes such as Acid Green 1, 3, 5, 9, 16, 50, 58, 63, 65, 80, 104, 105, 106, 109, etc.

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, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;

C.I.Direct Orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;

C.I. Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;

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, 274, 275, 293;

C.I.direct dyes such as C.I.Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82,

C.I.disperse dyes such as C.I.disperse yellow 54, 76,

C.I.Basic Red 1, 10;

C.I. Basic Blue 1, 3, 5, 7, 9, 19, 24, 25, 26, 28, 29, 40, 41, 54, 58, 59, 64, 65, 66, 67, 68;

C.I.Basic Green 1; C.I.Basic Dye, etc.,

C.I. Reactive Yellow 2, 76, 116;

C.I.Reactive Orange 16;

C.I. reactive red 36; C.I. reactive dyes, etc.

C.I. modern yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;

CI Modern Red 1, 2, 4, 9, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 27, 30, 32, 33, 36, 37, 38, 39, 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95;

C.I. modern orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;

C.I. modern violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;

CI Modern Blue 1, 2, 3, 7, 9, 12, 13, 15, 16, 19, 20, 21, 22, 26, 30, 31, 39, 40, 41, 43, 44, 49, 53, 61, 74, 77, 83, 84

C.I.Modern dyes such as C.I.Modern Green 1, 3, 4, 5, 10, 15, 26, 29, 33, 34, 35, 41, 43, 53,

C.I.Bat dyes such as C.I.Bat Green 1,

And the like.

Among them, red dyes, orange dyes, and yellow dyes are preferred.

These dyes may be appropriately selected according to the spectral spectrum of the desired color filter. These dyes may be used alone or in combination of two or more.

As the dye (A2), a metal complex dye is preferable. The metal complex dye is a dye complex complexed with a metal atom using a dye molecule containing a metal atom and a group capable of complexing in the molecule as a ligand. Azo dye, methine dye, etc. are mentioned as a dye which consists as a ligand, and azo dye is preferable. In other words, a metal complex salt azo dye, a metal complex salt methine dye, etc. are mentioned as a metal complex salt dye, and a metal complex salt azo dye is preferable. Examples of the metal atom include chromium, cobalt, and nickel, and chromium and cobalt are preferable.

As said metal complex salt dye, C.I. solvent yellow 13, 19, 21, 25, 25: 1, 62, 79, 81, 82, 83, 83: 1, 88, 89, 90, 151, 161; C.I. Solvent Orange 5, 11, 20, 40: 1, 41, 45, 54, 56, 58, 62, 70, 81, 99; C.I. Solvent Red 8, 35, 83: 1, 84: 1, 90, 90: 1, 91, 92, 118, 119, 122, 124, 125, 127, 130, 132, 160, 208, 212, 214, 225, 233, 234, 243; CI Solvent Violet 2, 21, 21: 1, 46, 49, 58, 61; C.I. Solvent Blue 137; C.I. Solvent Brown 28, 42, 43, 44, 53, 62, 63, CI Acid Yellow 59, 121; CI Acid Orange 74, 162; CI Acid Red 211, and the metal complex dyes described in Japanese Patent Application Publication No. 2010-170117 Can be. These metal complex dyes may be used alone or in combination of two or more.

Among these, it is preferable that a metal complex dye has a maximum absorption wavelength in the range of 410 nm or more and 580 nm or less, and more preferably a maximum absorption wavelength in the range of 490 nm or more and 580 nm or less.

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

The total content of the dye is preferably 0.1% by mass or more, more preferably 1% by mass or more, more preferably 5% by mass or more, and 50% by mass or less, out of 100% by mass of the total amount of the colorant (A). It is preferable, More preferably, it is 40 mass% or less, More preferably, it is 30 mass% or less.

The content rate 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 more preferably 1% by mass or more and 50% by mass with respect to the total amount of the solid content. It is less than mass%. If the content rate of the colorant (A) is within the above range, desired spectroscopy or color density can be obtained.

<Resin (B)>

The resin (B) is not particularly limited, but is preferably an alkali-soluble resin, and at least one monomer (a) (hereinafter referred to as "(a)") selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides. In some cases, a copolymer having a structural unit derived from) is more preferable.

The copolymer having a structural unit derived from (a) is a structure derived from a monomer (b) (hereinafter sometimes referred to as "(b)") having a C2-C4 cyclic ether structure and an ethylenically unsaturated bond. It is preferably a copolymer having at least one kind selected from the group consisting of units and structural units having ethylenically unsaturated bonds. The copolymer may further have other structural units.

As another structural unit, the structural unit derived from the monomer (c) copolymerizable with (a) (however, (a) and (b) are different) (hereinafter sometimes referred to as "(c)"). Can be lifted.

As (a), specifically, unsaturated monocarboxylic acids, such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinyl benzoic acid;

Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetra Unsaturated dicarboxylic acids such as hydrophthalic acid and 1,4-cyclohexene dicarboxylic acid;

Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hepto-2-ene, 5,6-dicarboxybicyclo [2.2.1] hepto-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hepto-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hepto-2-ene, 5-carboxy-6-methylbicyclo [ 2.2.1] bicyclo-unsaturated compounds containing carboxy groups such as hepto-2-ene and 5-carboxy-6-ethyl bicyclo [2.2.1] hepto-2-ene;

Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, Unsaturated dicarboxylic acid anhydrides such as dimethyltetrahydrophthalic anhydride and 5,6-dicarboxybicyclo [2.2.1] hepto-2-ene anhydride;

Unsaturated monovalent polyvalent or higher carbonic acid mono ((meth) acryloyloxyalkyl) such as succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl] Esters;

and unsaturated acrylates containing hydroxy groups and carboxy groups in the same molecule, such as α- (hydroxymethyl) acrylic acid.

Of these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferred from the viewpoint of copolymerization reactivity and solubility of the resulting resin in an aqueous alkali solution.

(b) has, for example, a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and an ethylenically unsaturated bond. Refers to a polymerizable compound.

(b) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth) acryloyloxy group.

In addition, in this specification, "(meth) acrylic acid" represents at least 1 sort (s) selected from the group which consists of acrylic acid and methacrylic acid. Notations such as "(meth) acryloyl" and "(meth) acrylate" also have the same meaning.

Examples of (b) include a monomer having an oxiranyl group and an ethylenically unsaturated bond, a monomer having an oxetanyl group and an ethylenically unsaturated bond, a monomer having a tetrahydropril group and an ethylenically unsaturated bond, and the like.

As (b), for example, glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, vinylbenzyl glycidyl ether, 3,4-epoxycyclohexylmethyl (meth) acrylate , 3,4-epoxycitcyclo [5.2.1.0 ^2,6 ] decylacrylate, 3-ethyl-3- (meth) acryloyloxymethyloxetane, and tetrahydrofurfuryl (meth) acrylate. .

As (b), it is preferable that it is a monomer which has an oxiranyl group and an ethylenic unsaturated bond from the point which can make reliability, such as heat resistance and chemical resistance, of the obtained color filter higher.

Examples of (c) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, and tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) acrylate (in the art, it is called "dicyclopentanyl (meth) acrylate" In addition, it may be referred to as "tricyclodecyl (meth) acrylate"), tricyclo [5.2.1.0 ^2,6 ] decene-8-yl (meth) acrylate (in the technical field, it is a common name. It is called as "dicyclopentenyl (meth) acrylate"), dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) (Meth) acrylic acid esters such as acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, and benzyl (meth) acrylate;

Hydroxy group-containing (meth) acrylic acid esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;

Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconic acid;

Bicyclo [2.2.1] hepto-2-ene, 5-methylbicyclo [2.2.1] hepto-2-ene, 5-ethylbicyclo [2.2.1] hepto-2-ene, 5-hydroxy ratio Cyclo [2.2.1] hepto-2-ene, 5-hydroxymethyl bicyclo [2.2.1] hepto-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] hepto-2 -En, 5-methoxybicyclo [2.2.1] hepto-2-ene, 5-ethoxybicyclo [2.2.1] hepto-2-ene, 5,6-dihydroxybicyclo [2.2.1] hepto -2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hepto-2-ene, 5,6-di (2'-hydroxyethyl) bicyclo [2.2.1] hepto- 2-ene, 5,6-dimethoxybicyclo [2.2.1] hepto-2-ene, 5,6-diethoxybicyclo [2.2.1] hepto-2-ene, 5-hydroxy-5-methyl Bicyclo [2.2.1] hepto-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hepto-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] Bicyclo unsaturated compounds such as hepto-2-ene;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl- Dicarbonylimide derivatives such as 6-maleimide caproate, N-succinimidyl-3-maleimide propionate, and N- (9-acridinyl) maleimide;

Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, acetic acid Vinyl, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and the like.

Among them, from the viewpoint of copolymerization reactivity and heat resistance, styrene, vinyl toluene, benzyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) acrylate, -phenylmaleimide, N -Cyclohexylmaleimide, N-benzylmaleimide, Bicyclo [2.2.1] hepto-2-ene is preferred.

The structural unit having an ethylenically unsaturated bond is preferably a structural unit having a (meth) acryloyl group on the side chain. The resin having such a structural unit is obtained by adding a monomer having an ethylenically unsaturated group and a group capable of reacting with a group of (a) or (b) to a polymer having a structural unit derived from (a) or (b). Lose.

As such a structural unit, the structural unit which added the glycidyl (meth) acrylate to the (meth) acrylic acid unit, the structural unit which added the 2-hydroxyethyl (meth) acrylate to the maleic anhydride unit, glycidyl (meth) A structural unit etc. which added (meth) acrylic acid to the acrylate unit are mentioned. Moreover, when these structural units have a hydroxy group, the structural unit which added carbonic anhydride is also mentioned as a structural unit which has an ethylenic unsaturated bond.

As the resin (B), specifically, 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer, 3,4-epoxycyclocyclo [5.2.1.0 ^2.6 ] decyl (meth) acrylate / Copolymers having structural units derived from (a) and (b), such as (meth) acrylic acid copolymers; glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymers, glycies Di (meth) acrylate / styrene / (meth) acrylic acid copolymer, 3,4-epoxycitcyclo [5.2.1.0 ^2.6 ] decyl (meth) acrylate / (meth) acrylic acid / N-cyclohexylmaleimide copolymer, 3,4-epoxycyclo [5.2.1.0 ^2.6 ] decyl (meth) acrylate / (meth) acrylic acid / vinyl toluene copolymer, 3-methyl-3- (meth) acryloyloxymethyloxetane / (meth) Copolymers having structural units derived from (a), (b), and (c), such as acrylic acid / styrene copolymers; benzyl (meth) acrylate / (meth) acrylic acid copolymers, styrene / (meth) acrylic acid copolymers , Benzyl (meth) acrylate / tricyclodecyl (meth) acrylate / (meth) acrylic acid copolymer; resin obtained by adding glycidyl (meth) acrylate to benzyl (meth) acrylate / (meth) acrylic acid copolymer , Tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer added with glycidyl (meth) acrylate resin, tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) ) A copolymer having structural units derived from (a) and (c), such as a resin in which glycidyl (meth) acrylate is added to an acrylic acid copolymer; tricyclodecyl (meth) acrylate / glycidyl (metha) (Resin that reacts (meth) acrylic acid to copolymer of acrylate, resin that reacts (meth) acrylic acid to copolymer of tricyclodecyl (meth) acrylate / styrene / glycidyl (meth) acrylate, etc. A copolymer having a structural unit derived from (a) and a structural unit derived from (c) added to the structural unit derived from b); a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate (Meth) acrylic acid in addition to the resin reacted A copolymer having a structural unit derived from (c) and a structural unit obtained by adding (a) to a structural unit derived from (b), such as a resin reacted with lahydrophthalic anhydride, and further adding a carbonic anhydride. Can be heard.

The resin is, for example, the method described in the literature "Experiment for Polymer Synthesis" (Otsutayuki Yuki Chemical Co., Ltd. First Edition First Printing-March 1, 1972) and cited documents described in the document It can be prepared for reference.

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

The weight average molecular weight in terms of polystyrene in the resin (B) is preferably 3,000 to 100,000, and more preferably 5,000 to 50,000. When the molecular weight is in the above range, when forming a colored pattern, the residual film ratio before and after development is high, the solubility in the developer of the unexposed portion is good, and the resolution of the colored pattern tends to be improved.

The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B) is preferably 1.1 to 6, and more preferably 1.2 to 4.

The acid value (in terms of solid content) of the resin (B) is preferably 10 to 200 mg-KOH / g, and more preferably 20 to 180 mg-KOH / g. Here, the acid value is a value measured as the amount of potassium hydroxide (mg) required to neutralize 1 g of the resin (B), and can be obtained by titration using, for example, 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, and even more preferably 13 to 70% by mass, based on the total amount of solids. When the content of the resin (B) is within the above range, a colored pattern can be formed, and the resolution and the residual film rate of the colored pattern tend to improve.

<Polymerizable compound (C)>

The polymerizable compound (C) is a compound capable of polymerizing with an active radical and / or acid generated from the polymerization initiator (D), and examples thereof include compounds having a polymerizable ethylenically unsaturated bond, and the like. It is a (meth) acrylic acid ester compound.

As a polymerizable compound having one ethylenically unsaturated bond, for example, nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxy Ethyl acrylate, N-vinyl pyrrolidone, and the like (a), (b) and (c) described above.

As a polymerizable compound having two ethylenically unsaturated bonds, for example, 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, tri And ethylene glycol di (meth) acrylate, bis (acryloyloxyethyl) ether of bisphenol A, and 3-methylpentanediol di (meth) acrylate.

Especially, it is preferable that a polymerizable compound is a polymerizable compound which has three or more ethylenically unsaturated bonds. As such a polymerizable compound, for example, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate , Dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritolhepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol nona (Meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, ethylene glycol-modified pentaerythritol tetra (meth) acrylate, ethylene glycol-modified dipentaerythritol hexa (meth) acrylate , Propylene glycol modified pentaerythritol tetra (meth) acrylate, propylene glycol modified dipentaerythritol hexa (meth) acrylate, caprolactone modified pentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol hexa ( Meth) acrylate and the like, among them, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferable.

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

The content of the polymerizable compound (C) is preferably 4 to 65% by mass, more preferably 7 to 60% by mass, based on the total amount of solid content.

The content ratio [resin (B): polymerizable compound (C)] of the resin (B) and the polymerizable compound (C) is preferably 20:80 to 80:20 on a mass basis, more preferably It is 35: 65-80: 20.

When the content of the polymerizable compound (C) is within the above range, the residual film rate at the time of forming the colored pattern and the chemical resistance of the color filter tend to improve.

<Polymerization initiator (D)>

The polymerization initiator (D) generates active radicals, acids, and the like by the action of light or heat, and any known polymerization initiator can be used without particular limitation as long as it is a compound capable of initiating polymerization.

Examples of the polymerization initiator (D) include O-acyloxime compounds, alkyl phenone compounds, biimidazole compounds, triazine compounds, and acylphosphine oxide compounds.

Examples of the O-acyloxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butane-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl ) Octane-1-one-2-imine, N-benzoyloxy-1-1 (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine, N-benzoyloxy-1-1 [9 O-acyloxime compounds having N-benzoyloxy groups such as -ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] -3-cyclopentylpropan-1-one-2-imine; N -Acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- ｛ 2-methyl-4- (3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy) benzoyl｝ -9H-carbazole-3-yl] ethane-1-imine, N-acetoxy-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] -3-cyclopentylpropane-1-imine, N-acetoxy-1- (4-phenylsulfanylphenyl) -3 -Cyclohexylpropane-1-one-2-imine, [11- (2-ethylhexyl) -5- (2,4,6-trimethylbenzoyl) -11H-benzo [a] carbazole-8-yl]- [2- (2,2,3,3-tetrafluoropropoxy) phenyl] O-acyloxime compounds having an N-acetoxy group such as methaneone oxime O-acetate. You may use commercial items, such as Irgacure (registered trademark) OXE01, OXE02 (above, manufactured by BASF), and N-1919 (made by ADEKA).

Especially, the O-acyloxime compound is N-benzoyloxy-1-1 (4-phenylsulfanylphenyl) butane-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) Octane-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1-1 [9- Ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] ethane-1-imine, N-acetoxy-1-1 (4-phenylsulfanylphenyl) -3-cyclohexylpropane-1- On-2-imine and [11- (2-ethylhexyl) -5- (2,4,6-trimethylbenzoyl) -11H-benzo [a] carbazole-8-yl]-[2- (2,2 , 3,3-tetrafluoropropoxy) phenyl] methanone oxime-O-acetate is preferably at least one selected from the group consisting of N-acetoxy-1- [9-ethyl-6- (2-methyl Benzoyl) -9H-carbazole-3-yl] ethane-1-imine and N-acetoxy-1- (4-phenylsulfanylphenyl) -3-cyclohexylpropane-1-on-2-imine At least 1 type selected from is more preferable.

As an alkyl phenone compound, 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propane-1-one, 2-dimethylamino-1- (4-morpholinophenyl), for example -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-1-1 [4- (2-hydroxyethoxy) phenyl] propane-1-one, 1-hydroxy And cyclohexylphenyl ketones, 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propane-1-one oligomers, α, α-diethoxyacetophenone, and benzyldimethyl ketal. You may use commercial items, such as Irgacure (registered trademark) 369, 907, 379 (above, manufactured by BASF).

Examples of the biimidazole compound include, for example, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-) Dichlorophenyl) -4,4 ＇, 5,5＇-tetraphenylbiimidazole (see, for example, Japanese Patent Application Laid-open No. Hei 6-75372, Japanese Patent Laid-Open No. Hei 6-75373, etc.), 2, 2＇-bis (2-chlorophenyl) -4,4 ＇, 5,5＇-tetraphenylbiimidazole, 2,2＇-bis (2-chlorophenyl) -4,4＇, 5,5＇- Tetra (alkoxyphenyl) biimidazole, 2,2＇-bis (2-chlorophenyl) -4,4 ＇, 5,5＇-tetra (dialkoxyoxyphenyl) biimidazole, 2,2＇-bis ( 2-chlorophenyl) -4,4 ＇, 5,5＇-tetra (trialkoxyphenyl) biimidazole (for example, Japanese Patent Publication No. 48-38403, Japanese Patent Publication No. 62-174204, etc.) Reference.), An imidazole compound in which the phenyl group at 4,4 ', 5,5'1 is substituted by a carboalkoxy group (for example, see JP-A No. 7-10913, etc.) and the like. have.

As the triazine compound, for example, 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl)- 6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4- Bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2 -Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-tri Azin, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloro Methyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine and the like.

As an acylphosphine oxide compound, 2,4,6- trimethylbenzoyl diphenylphosphine oxide etc. are mentioned.

Further, as the polymerization initiator (D), benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, and 4-phenyl Benzophenone, 4-benzoyl-4＇-methyldiphenyl sulfide, 3,3 ＇, 4,4＇-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, etc. Benzophenone compounds; quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone, camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compounds, etc. Can be.

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

In the polymerization initiator (D), the content of the O-acyl compound is preferably 80% by mass or more, more preferably 90% by mass or more, and even 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 amount of the resin (B) and the polymerizable compound (C).

<Polymerization start aid (D1)>

The red curable resin composition of the present invention may further include a polymerization initiation aid (D1). The polymerization initiation aid (D1) is a compound or a sensitizer used to accelerate polymerization of the polymerizable compound in which polymerization is initiated by the polymerization initiator. When a polymerization start adjuvant (D1) is included, it is usually used in combination with a polymerization initiator (D).

Examples of the polymerization initiation assistant (D1) include an amine compound, an alkoxyanthracene compound, a thioxanthone compound, and a carbonic acid compound.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoic acid, and 4-dimethylamino Benzoic acid 2-ethylhexyl, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as mihirazketone), 4,4'-bis (diethylamino) benzophenone, 4, And 4'-bis (ethylmethylamino) benzophenone. Among them, 4,4'-bis (diethylamino) benzophenone is preferable. You may use commercial items, such as EAB-F (made by Hodogaya Chemical Industry Co., Ltd.).

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

As said thioxanthone compound, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4- diethyl thioxanthone, 2,4- dichloro thioxanthone, 1-chloro-4-propoxy And city oxanthone.

Examples of the carbonic acid compound include phenylsulfanyl acetic acid, methylphenylsulfanyl acetic acid, ethylphenylsulfanyl acetic acid, methylethylphenylsulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, methoxyphenylsulfanyl acetic acid, dimethoxyphenylsulfanyl acetic acid, and chloro And phenylsulfanyl acetic acid, dichlorophenylsulfanyl acetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

Especially, as a polymerization start adjuvant (D1), a thioxanthone compound is preferable.

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

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

<Antioxidant (J)>

It is preferable that the red curable resin composition of this invention contains antioxidant (J) further. Examples of the antioxidant (J) include phenolic antioxidants, amine antioxidants, phosphorus antioxidants, and sulfur antioxidants, and phenolic antioxidants and phosphorus antioxidants are preferred.

The phenolic antioxidant is an antioxidant having a phenolic hydroxyl group in the molecule, and preferably has an alkyl group branched to the ortho position of the phenolic hydroxyl group. In this specification, an antioxidant having a phenolic hydroxyl group and a phosphoric acid ester structure or a phosphorous acid ester structure is classified as a phosphorus-based antioxidant.

As a phenolic antioxidant, for example, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 4,4'-butylidenebis (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-methylphenylacrylate, (tetrakis [methylene-3- (3,5-di-tet-butyl-4-hydroxyphenyl) pro Cypionate] Methane, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl -4-hydroxyphenyl) propionate, 3,3 ＇, 3", 5, 5 ＇, 5" -hexa-tert-butyl-a, a ＇, a"-(mesitylene-2,4,6 -Toluyl) tri-p-cresol, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 ( 1H, 3H, 5H) -trione, 1,3,5-tris ((4-tert-butyl-3-hydroxy-2,6-xylyl) methyl) -1,3,5-triazine-2 , 4,6 (1H, 3H, 5H) -trione, thiodiethylene bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], benzenepropanoic acid, 3, 5-bis (1,1-dimethylethyl) -4-hydroxy, C7-C9 side chain alkyl ester, 4,6-bis (octylthiomethyl) -o-cresol, Irganox (registered trademark) # 3125 (manufactured by BASF) , 2,4-bis (n-octylthio) -6- (4-hydroxy3 ＇, 5＇-di-tert-butylanilino) -1,3,5-triazine, 3,9-bis ( 2- (3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy) -1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro (5,5) Undecane, Sumiizer (registered trademark) BHT (Sumitomo Chemical Co., Ltd.), Sumiizer (registered trademark) GA-80 (Sumitomo Chemical Co., Ltd.), Sumiizer (registered trademark) GS (Sumitomo Chemical Co., Ltd.) And Cyanox (registered trademark) 1790 (manufactured by Cytec Co., Ltd.) and vitamin E (manufactured by Ezai Co., Ltd.).

When a phenolic antioxidant is included, the content is preferably 1% by mass or more and 99% by mass or less in 100% by mass or 100% by mass in the total amount of the antioxidant (J).

The amine-based antioxidant is an antioxidant having an amino 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-dodecyl Naphthylamine-based antioxidants such as phenyl-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-p-phenylene Diamine, N-cyclohexyl-N＇-phenyl-p-phenylenediamine, N-1,3-dimethylbutyl-N＇-phenyl-p-phenylenediamine, dioctyl-p-phenylenediamine, phenylhexyl Phenylenediamine-based antioxidants such as -p-phenylenediamine and phenyloctyl-p-phenylenediamine; dipyridylamine, diphenylamine, p, p＇-di-n-butyldiphenylamine, p, p ＇-Di-tert-butyldiphenylamine, p, p＇-di-tert-pentyldiphenylamine, p, p＇-dioctyldiphenylamine, p, p＇-dinonyldiphenylamine, p, p＇- Didecyldiphenylamine, p, p＇-didodecyldiphenylamine, p, p＇-distyryldiphenylamine, p, p＇-dimethoxydiphenylamine, 4,4＇-bis (4-α, α- Diphenylamine-based antioxidants such as dimethylbenzoyl) diphenylamine, p-isopropoxydiphenylamine, and dipyridylamine; phenothiazine, N-methylphenothiazine, N-ethylphenothiazine, 3,7 -Phenothiazine-based antioxidants, such as dioctylphenothiazine, phenothiazine carboxylic acid ester, and phenoserrenadine.

When the amine-based antioxidant is included, the content thereof is preferably 1% by mass or more and 99% by mass or less out of 100% by mass of the total amount of the antioxidant (J).

The phosphorus antioxidant is an antioxidant having a phosphoric acid ester structure or a phosphorous acid ester structure.

As a phosphorus antioxidant, for example, 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propyloxy] -2,4,8,10-tetra-tert-butyldibenz [ d, f] [1,3,2] dioxaphosphine, tris (2,4-di-tert-butylphenyl) phosphite, diphenylisooctylphosphite, 2,2'-methylenebis (4,6 -Di-tert-butylphenyl) octylphosphite, diphenylisodecylphosphite, diphenylisodecylphosphite, triphenylphosphate, tributylphosphate, distearylpentaerythritol diphosphite, cyclic neopentanetetraylbis (2,6-di-tert-butyl-4-methylphenyl) phosphite, 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propyloxy] -2,4,8,10 -Tetra-tert-butylbenzo [d, f] [1,3,2] dioxaphosphine, tris (nonylphenyl) phosphite, tris (mono- & dinonylphenylmixed) phosphite, diphenylmono ( Tridecyl) phosphite, 2,2＇-ethylidenebis (4,6-di-tert-butylphenol) fluorophosphite, phenyldiisodecylphosphite, tris (2-ethylhexyl) phosphite, tris ( Isodecyl) phosphite, tris (tridecyl) phosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite, 4,4'-isopropylidenedi Phenyltetraalkyl (C12-C15) diphosphite, 4,4＇-butylidenebis (3-methyl-6-tert-butylphenyl) -ditridecylphosphite, bis (nonylphenyl) pentaerythritol diphosphite, Bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, cyclic neopentane tetraylbis (2,6-di-tert-butyl-4-methylphenylphosphite), 1,1,3- Tris (2-methyl-4-ditridecylphosphite-5-tert-butylphenyl) butane, tetrakis (2,4-di-tert-butyl-5-methylphenyl) -4,4＇-biphenylenedipo Sponite, tri-2-ethylhexylphosphite, triisodecylphosphite, tristearylphosphite, phenyldiisodecylphosphite, trilauryl trithiophosphite, distearylpentaerythritol diphosphite, tris ( Nonyl atephenyl) phosphite tris [2-[[2,4,8,10-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphine -6-yl] oxy] ethyl] amine, bis (2,4-bis (1,1-dimethylethyl) -6-methylphenyl) ethyl ester phosphorous acid, Adekastab (registered trademark) 329K (manufactured by Adeka) , Adekastab (registered trademark) PEP36 (manufactured by ADEKA Corporation), Adekastab (registered trademark) PEP-8 (manufactured by ADEKA Corporation), Sandstab (registered trademark) P-EPQ (manufactured by Curarian) Weston (registered trademark) 618 (manufactured by GE), Weston (registered trademark) 619G (manufactured by GE), Ultranox (registered trademark) 626 (manufactured by GE), 6- [3- (3-tert-butyl -4-hydroxy-5-methylphenyl) propyloxy] -2,4,8,10-tetra-tert-butyldibenz [d, f] [1,3,2] dioxaphosphine). have.

When the phosphorus-based antioxidant is included, the content thereof is preferably 1% by mass or more and 99% by mass or less, out of 100% by mass of the total amount of the antioxidant (J).

The sulfur-based antioxidant is an antioxidant having a sulfur atom in its molecule.

Examples of sulfur-based antioxidants include dialkylthidipropionate compounds such as dilauryl thiodipropionic acid, dimyristyl or distearyl, and tetrakis [methylene (3-dodecylthio) propionate] methane And β-alkyl mercaptopropionic acid ester compounds of polyols.

When a sulfur-based antioxidant is included, the content thereof is preferably 1% by mass or more and 99% by mass or less, out of 100% by mass of the total amount of the antioxidant (J).

As the antioxidant (J), GPA-5001 (manufactured by ADEKA Corporation) may be used.

Especially, as antioxidant (J), at least 1 type of phenolic antioxidant and phosphorus antioxidant is preferable, and it is preferable to contain both a phenolic antioxidant and phosphorus antioxidant.

When the red curable resin composition of the present invention contains an antioxidant (J), the content thereof is preferably 0.01 to 20% by mass, more preferably 0.05 to 10% by mass relative to the total amount of solids. When the content of the antioxidant (J) is within the above range, the color filter obtained tends to be excellent in heat resistance.

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

<Solvent (E)>

In the solvent (E) in the present invention, propylene glycol monomethyl ether acetate is contained in a content of 10% by mass or more and 78% by mass or less in the total amount of the solvent (E). The content rate of propylene glycol monomethyl ether acetate 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, with respect to the total amount of the solvent (E).

The solvent other than propylene glycol monomethyl ether acetate is not particularly limited, and a solvent commonly used in the art can be used. For example, ester solvents (solvents containing -COO- in the molecule and not containing -O-), ether solvents (solvents containing -O- in the molecule, and not containing -COO-), ether esters Solvents (solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- in the molecule and not containing -COO-), alcohol solvents (containing OH in the molecule,- And solvents that do not contain O-, -CO-, and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, and the like.

As an ester solvent, methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, Butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, γ-butyrolactone, and the like.

As the ether solvent, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene Glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenitol, methyl anisole And the like.

As the ether ester solvent, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate , 3-ethyl ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionic acid, methyl 2-ethoxypropionic acid, ethyl 2-ethoxypropionic acid, 2-methoxy-2-propionate Methyl methyl propionate, 2-ethoxy-2-methyl ethyl propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono Propyl 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.

As a ketone solvent, 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclo Fentanone, cyclohexanone, isophorone, and the like.

Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.

Benzene, toluene, xylene, mesitylene, etc. are mentioned as an aromatic hydrocarbon solvent.

Examples of the amide solvent include N, N-dimethylformamide, N, N-dimethylacetoamide, and N-methylpyrrolidone.

These solvents may be used alone or in combination of two or more.

Among them, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, 3-ethoxypropionic acid ethyl, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl Ether, dipropylene glycol methyl ether acetate, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, N, N-dimethylformamide, 3-e Ethoxy propionate, N-methylpyrrolidone, etc. are preferable, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethylene glycol monobutyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate , 3-methoxy-1-butanol, 3-ethyl ethoxypropionate, 4-hydroxy-4-methyl-2-pentanone, and N-methylpyrrolidone are more preferred.

As for the solvent other than propylene glycol monomethyl ether acetate, only 1 type may be sufficient and 2 or more types may be used together. Among them, a solvent having a large SP value (dissolution parameter) is preferable compared to propylene glycol monomethyl ether acetate. As a solvent other than propylene glycol monomethyl ether acetate, only a solvent having a larger SP value than propylene glycol monomethyl ether acetate may be used.

For the SP value, the Hansen parameter of the liquid at 25 described in the Solubility Parameter Value section of J.Brandrup, EHImmergut, POLYMERHANDBOOK 3rd edition, John Wiley & Sons can be applied, for example. As a solvent having a high SP value in comparison with (SP value (= 9.0 (cal / cm 3) ^1/2 ) of propylene glycol monomethyl ether acetate obtained using the Hildebrand method from the Hansen parameter, for example, propylene glycol monomethyl ether ( Copper 10.7 (cal / cm 3) ^1/2 ), ethylene glycol monobutyl ether (copper 10.2 (cal / cm 3) ^1/2 ), diacetone alcohol (copper 10.2 (cal / cm 3) ^1/2 ), ethyl lactate (copper 10.0 (cal / cm 3) ^1/2 ), 3-methoxy-1-butanol (copper 10.9 (cal / cm 3) ^1/2 ), 3-ethoxypropionic acid ethyl (copper 9.1 (cal / cm 3) ^1/2 ) , Cyclohexanone (copper 9.3 (cal / cm 3) ^1/2 ), γ-butyrolactone (copper 12.8 (cal / cm 3) ^1/2 ), N-methylpyrrolidone (copper 11.2 (cal / cm 3) ^{1 / 2} ) is preferable The solvent having a higher SP value than propylene glycol monomethyl ether acetate may be used alone or in combination of two or more.

The difference between the SP values of the propylene glycol monomethyl ether acetate and the solvent other than the propylene glycol monomethyl ether acetate is preferably 0.1 (cal / cm 3) ^1/2 or more, more preferably 0.3 (cal / cm 3) ^1/2 or more , More preferably 0.5 (cal / cm 3) ^1/2 or more, even more preferably 0.7 (cal / cm 3) ^1/2 or more, and 4 (cal / cm 3) ^1/2 or less, more preferably Is 3 (cal / cm 3) ^1/2 or less, more preferably 2 (cal / cm 3) ^1/2 or less.

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

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

<Leveling agent (F)>

The red curable resin composition of the present invention may contain a leveling agent (F). Examples of the leveling agent (F) include silicone-based surfactants, fluorine-based surfactants, and silicone-based surfactants having fluorine atoms. These may have a polymerizable group in the side chain.

As a silicone surfactant, surfactant etc. which have a siloxane bond in a molecule | numerator are mentioned. Specifically, Torrey Silicon DC3PA, Copper SH7PA, Copper DC11PA, Copper SH21PA, Copper SH28PA, Copper SH29PA, Copper SH30PA, Copper SH8400 (Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340 , KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460 (manufactured by Momentive Performance Materials, Japan, etc.).

As a fluorine-type surfactant, surfactant etc. which have a fluorocarbon chain in a molecule | numerator are mentioned. Specifically, Florad (registered trademark) FC430, copper FC431 (Sumitomo 3M Co., Ltd.), Megapak (registered trademark) F142D, copper F171, copper F172, copper F173, copper F177, copper F183, copper F554, copper R30, Dong RS-718-K (manufactured by DIC Corporation), F-Top (registered trademark) EF301, Dong EF303, Dong EF351, Dong EF352 (Mitsubishi Material Electronics Co., Ltd.), SUPRON (registered trademark) S381, copper S382, copper SC101, copper SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Chemical Products Research Institute).

As said silicone type surfactant which has the said fluorine atom, surfactant etc. which have a siloxane bond and a fluorocarbon chain in a molecule | numerator are mentioned. Specifically, Megapak (trademark) R08, copper BL20, copper F475, copper F477, copper F443 (made by DIC Corporation) etc. are mentioned.

When the leveling agent (F) is contained, its content is preferably 0.001% by mass or more and 3% by mass or less, more preferably 0.002% by mass or more and 2% by mass or less, more preferably with respect to the total amount of the red curable resin composition. 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 ingredients>

If necessary, the red curable resin composition of the present invention may contain additives known in the art, such as polymerization initiation aids, fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, chain transfer agents, and the like.

<Method for producing red curable resin composition>

The red curable resin composition of the present invention includes, for example, a coloring agent (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D), a solvent (E), and a leveling agent used as necessary ( It can be prepared by mixing F) and other components.

The red pigment (P) and the pigment (Q) used as necessary are mixed with a part or all of the solvent (E) in advance, using a beads mill or the like until the average particle diameter of the pigment is about 0.2 μm or less. It is preferred to disperse. At this time, part or all of the pigment dispersant and the resin (B) may be blended as necessary.

The desired red curable resin composition can be prepared by mixing the remaining components in the pigment dispersion thus obtained to a predetermined concentration.

It is preferable to prepare a solution by dissolving the compound (IB) in part or all of the solvent (E) in advance. It is preferable to filter the solution with a filter having a pore size of about 0.01 to 1 μm.

It is preferable to filter the red curable resin composition after mixing with a filter having a pore size of about 0.01 to 10 µm.

<Manufacturing method of color filter>

As a method for producing a colored pattern from the red curable resin composition of the present invention, there may be mentioned a photolithography method, an inkjet method, a printing method and the like. Among them, the potolisograph method is preferred. The photolithography method is a method of applying the red curable resin composition to a substrate, drying it to form a colored composition layer, and exposing and developing the colored composition layer through a photomask. In the photolithography method, a colored coating film that is a cured product of the colored composition layer can be formed by not using and / or developing a photomask during exposure. The colored pattern or colored coated film thus formed can be used as the color filter of the present invention.

The film thickness of the color filter to be produced is not particularly limited, and can be appropriately adjusted depending on the purpose or application, 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, glass plates such as quartz glass, borosilicate glass, alumina silicate glass, and soda lime glass with silica coating on the surface, resin plates such as polycarbonate, methyl polymethacrylate, polyethylene terephthalate, silicon, and aluminum on the substrate , Silver, silver / copper / palladium alloy thin films and the like are used. Other color filter layers, resin layers, transistors, circuits, and the like may be formed on these substrates.

The formation of each color pixel by the photolithography method can be carried out by a known or common apparatus or condition. For example, it can be produced as follows.

First, a red curable resin composition is applied onto a substrate, and volatile components such as a solvent are removed and dried by heat drying (pre-baking) and / or drying under reduced pressure to obtain a smooth colored composition layer.

As a coating method, a spin coating method, a slit coating method, a slit and spin coating method, etc. are mentioned.

30-120 is preferable and 50-110 is more preferable as temperature in the case of performing heat drying. Moreover, as heating time, it is preferable that it is 10 to 60 minutes, and it is more preferable that it is 30 to 30 minutes.

When drying under reduced pressure, it is preferable to carry out in a temperature range of 20 to 25 under a pressure of 50 to 150 Pa.

The thickness of the colored composition layer is not particularly limited, and may be appropriately selected depending on the thickness of the target color filter.

Next, the colored composition layer is exposed through a photomask for forming a desired colored pattern. The pattern on the said photomask is not specifically limited, The pattern according to the intended use is used.

The light source used for exposure is preferably a light source that generates light having a wavelength of 250 to 450 nm. For example, light having a wavelength of less than 350 nm is cut using a filter that cuts this wavelength range, or a band pass filter that extracts light near 436 nm, near 408 nm, and around 365 nm is used. It may be taken out selectively. Specifically, a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp, etc. are mentioned as a light source.

It is preferable to use an exposure apparatus such as a mask aligner and a stepper, because it is possible to uniformly irradiate parallel light beams over the entire exposure surface or to precisely position the substrate on which the photomask and the colored composition layer are formed.

A coloring pattern is formed on a board | substrate by making the coloring composition layer after exposure contact with a developing solution and developing. By development, the unexposed portion of the colored composition layer is dissolved in the developer and removed. As the developing solution, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, or tetramethylammonium hydroxide is preferable. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. In addition, the developer may contain a surfactant.

The developing method may be any of a puddle method, a dipping method, and a spray method. Further, the substrate may be tilted at an arbitrary angle during development. After development, it is preferable to wash with water.

Moreover, it is preferable to perform post-baking on the obtained coloring pattern. The post-baking temperature is preferably 150 to 250, and more preferably 160 to 235. The post-baking time is preferably 1 to 120 minutes, more preferably 10 to 60 minutes.

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

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited by the following Examples from the beginning, and is carried out by appropriately changing it within a range suitable for the purpose of before and after. Of course, it is possible, and they are all included in the technical scope of the present invention. In the example,% and parts indicating the content to the amount used are on a mass basis unless otherwise specified.

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

(Synthesis Example 1)

50 parts of the compound represented by formula (VI) and 350 parts of isopropyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed at room temperature. To the obtained mixture, 18.1 parts of diethylamine (manufactured by Tokyo Chemical Industries, Ltd.) was added dropwise to a temperature not exceeding 20, and stirred for 20 to 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%.

(Formula 64)

Identification of the compound represented by formula (I-1A)

(Mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 442.1

Exact Mass ： 441.1

30 parts of the compound represented by formula (I-1A) and 150 parts of dehydrated chloroform (manufactured by Kanto Chemical Co., Ltd.) were mixed at room temperature. To the obtained mixture, 26.3 parts of trimethoxy [3- (methylamino) propyl] silane (manufactured by Tokyo Chemical Industries, Ltd.) was added dropwise to a temperature not exceeding 40, and stirred at 70 to 3 hours. The obtained 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 obtain 35.5 parts of the compound represented by formula (I-1). The yield was 87%.

(Formula 65)

Identification of the compound represented by formula (I-1)

(Mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 599.2

Exact Mass ： 598.2

0.35 g of the compound represented by formula (I-1) was dissolved in chloroform to make the volume 250 cm 3, 2 cm 3 of which was diluted with ion-exchanged water to make the volume 100 cm 3 (concentration: 0.028 g / L), spectroscopic The absorption spectrum was measured using a photometer (quartz cell, optical path length; 1 cm). This compound was λmax = 546 nm.

(Synthesis Example 2)

The flask was equipped with a stirrer, a dropping lot, a condenser, a thermometer, and a gas introduction tube, and nitrogen was flowed in an appropriate amount to replace it with a nitrogen atmosphere, and 100 parts of propylene glycol monomethyl ether acetate was added and heated to 120 while stirring. Next, to a monomer mixture consisting of 7 parts of tricyclodecyl methacrylate, 27 parts of benzyl methacrylate, and 13 parts of methacrylic acid, 1 part of perbutyl O (manufactured by Nippon Oil Co., Ltd.) is added to 100 parts of monomer mixture. The mixed solution prepared by addition was dropped from the dropping lot into the flask over 2 hours. Further, the mixture was stirred at 120 for 2 hours to obtain a reaction solution containing a copolymer. Subsequently, an appropriate amount of air is flowed into the flask to replace it with an air atmosphere, and 7 parts of glycidyl methacrylate, 0.34 parts of triphenylphosphine, and 0.07 parts of methylhydroquinone are introduced during the reaction including the copolymer, 120 The reaction was continued, and the reaction was terminated by cooling to room temperature where the solid acid value reached 105 mg-KOH / g. By adding 32 parts of propylene glycol monomethyl ether acetate, a copolymer (resin B-1) solution was obtained. The solid content of the resin B-1 solution was 30%. The weight average molecular weight of Resin B-1 was 3.0 × 10 ⁴ .

About the measurement of the weight average molecular weight Mw and number average molecular weight Mn of polystyrene conversion of the resin obtained by the said synthesis example 2, it carried out on condition of the following using GPC method.

Device; HLC-8120 GPC (manufactured by Tosoh Corporation)

Column @ TSK-GELG2000HXL

Column temperature ； 40

Solvent; THF

Flow rate; 1.0 mL / min

Concentration of solid content in test solution; 0.001 to 0.01 mass%

Injection volume; 50 µl

Detector; RI

Standard material for calibration ； TSK STANDARD POLYSTYRENE

F-40, F-4, F-288, A-2500, A-500

(Made by Tosoh Corporation)

The ratio (Mw / Mn) of the weight average molecular weight and number average molecular weight in terms of polystyrene obtained above was 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 to obtain a red curable resin composition.

(Table 1)

The pigment was pre-dispersed by mixing with a pigment dispersant, the resins B-1 and E-1 described in the B-1 ¹⁾ column, and the propylene glycol monomethyl ether acetate described in the ²⁾ column.

B-1 ³⁾ column shows the total of resin B-1 content.

E-1 ⁴⁾ column shows the sum of propylene glycol monomethyl ether acetate content.

In addition, in Table 1, each component shows the following. Moreover, resin (B) showed the number of solid content conversion.

Dye (A-1): A-1: Compound represented by formula (I-1)

Dye (A-2): A-2: C.I. Solvent Red 130 (Orazole Red 330; manufactured by BASF; Maximum absorption wavelength: 495 nm; Metal complex salt dye)

Pigment (A): A-3: C.I. Pigment Red 254

Pigment Dispersant: Acrylic pigment dispersant

Resin (B): B-1: Resin B-1

Polymerizable compound (C): C-1: dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Chemical Industries, Ltd.)

Polymerization initiator (D): D-1: N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] ethane-1-imine (irgacure ( Trademark) OXE 02; manufactured by BASF; oxime compound)

Polymerization initiator (D): D-2: Compound represented by the following formula (TR-PBG-309; manufactured by resident strong electronic material (oil))

(Formula 66)

Antioxidant (J): J-1: GPA-5001 (made by ADEKA Corporation)

Solvent (E): E-1: Propylene glycol monomethyl ether acetate

Solvent (E): E-2: Diacetone alcohol

Solvent (E): E-3: Propylene glycol monomethyl ether

Solvent (E): E-4: Cyclohexanone

Solvent (E): E-5: Ethyl lactate

Leveling agent (F): F-1: Polyether-modified silicone (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.)

(Formation of color filter (colored pattern))

After coating the colored curable resin compositions obtained in Examples 1 to 10 on a 2 inch edge glass substrate (Egle XG; manufactured by Corning) by spin coating, pre-baking at 100 for 3 minutes to obtain a colored composition layer. After cooling, the distance between the glass substrate on which the colored composition layer was formed and the photomask made of quartz glass was set to 100 µm, and an exposure amount of 365 mJ / cm 2 (365) in an air atmosphere using an exposure machine (TME-150RSK; manufactured by Topcon Corporation) Light irradiation). As the photomask, a 100 µm line and space pattern was formed. The colored composition layer after light irradiation was immersed in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide for 26 to 60 seconds, and after water washing, post-baking was performed in an oven at 230 to 20 minutes.

By the above operation, in the colored curable resin compositions of Examples 1 to 10, all colored patterns were obtained.

〔Measurement of film thickness〕

About the obtained coloring pattern, the film thickness was measured using the film thickness measuring apparatus (DEKTAK3; manufactured by Japan Vacuum Technology Co., Ltd.). Table 2 shows the results.

(Chromaticity evaluation)

About the colored pattern on the obtained glass substrate, spectroscopy was measured using a colorimeter (OSP-SP-200; manufactured by Olympus Co., Ltd.), and the xy chromaticity coordinates in the XYZ colorimeter of the CIE using the isochromatic function of the C light source ( x, y) was measured. Table 2 shows the results. From the chromaticity coordinates, it was confirmed that the color of the colored pattern on the obtained glass substrate was red.

(Formation of color filter (colored coating film))

After coating the colored curable resin compositions obtained in Examples 1 to 10 and Comparative Example 1 on a 2 inch edge glass substrate (Egle XG; manufactured by Corning) by spin coating, pre-baking at 100 for 3 minutes to form a colored composition layer. Got After cooling, light was irradiated with an exposure amount of 50 mJ / cm 2 (based on 365 nm) in an atmospheric atmosphere without using a photomask using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.). The colored composition layer after light irradiation was immersed in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide for 26 to 60 seconds, and after washing with water, post-baking was performed in the oven at 230 to 20 minutes. , To obtain a colored coating film.

(Foreign body evaluation)

The obtained colored coating film was observed for foreign matter on the surface of the colored coating film at a magnification of 50 times using an upright microscope (Axio®Imager®MAT; manufactured by Shimadzu Corporation).

If the foreign material is unobserved, it can be said that the colored coating film is practically no problem as a color filter.

(Table 2)

(Table 3)

○: No foreign matter in the observation part

△: 1 to 9 foreign objects in the observation area

×: 10 or more foreign objects in the observation area

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

According to the red curable resin composition of the present invention, by controlling the solvent ratio in the resist to a certain range, a color filter that does not generate foreign matter on the surface can be formed. The color filter is useful as a color filter used in display devices (for example, liquid crystal display devices, organic EL devices, electronic papers, etc.) and solid-state imaging devices.

Claims (7)

It contains a coloring agent (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a solvent (E), has a silicon atom as the coloring agent (A), and is in chloroform. Dye (A1) having a maximum absorption wavelength of 500 nm to 600 nm, and a red pigment (P),
As the solvent (E), a solvent having a higher SP value than propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate is included,
The solvent having a higher SP value than the propylene glycol monomethyl ether acetate is propylene glycol monomethyl ether, ethylene glycol monobutyl ether, diacetone alcohol, ethyl lactate, 3-methoxy-1-butanol, 3-ethoxypropionate ethyl, γ -It contains at least one member selected from the group consisting of butyrolactone and N-methylpyrrolidone,
The content ratio of the propylene glycol monomethyl ether acetate is 10% by mass or more and 78% by mass or less in the total amount of the solvent (E),
The red curable resin composition in which the content of the solvent having a higher SP value than the propylene glycol monomethyl ether acetate is 22% by mass or more in the total amount of the solvent (E). delete delete According to claim 1,
The red curable resin composition in which the dye (A1) is a compound having a xanthene skeleton. According to claim 1,
A red curable resin composition further comprising a metal complex salt azo dye as colorant (A). A color filter formed of the red curable resin composition according to claim 1. A display device comprising the color filter according to claim 6.