TWI794183B - Cyan curable resin composition, color filter and display device - Google Patents

Abstract

There is room for improvement in lightness of a color filter formed from a conventional colored curable resin composition. The cyan curable resin composition of the present invention contains a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D). As the colorant (A), the cyan curable resin composition The material contains a dye (A1) with a silicon atom whose maximum absorption wavelength is 500nm~600nm in chloroform and a cyan colorant. Moreover, this invention relates to the display device containing the color filter formed from the said cyan curable resin composition, and this color filter.

Description

Cyan curable resin composition, color filter and display device

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

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

現有技術文獻 專利文獻【Chemical 1】

Prior Art Documents Patent Documents

Patent Document 1: Japanese Patent Laid-Open No. 2011-118369

SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION There is room for improvement in lightness of a color filter formed from the above colored curable resin composition. means to solve the problem

The present invention includes the following inventions. [1] A cyan curable resin composition comprising a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D), as the colorant (A), the cyan curable The resin composition includes: a dye (A1) having a silicon atom whose maximum absorption wavelength in chloroform is 500 nm to 600 nm, and a cyan colorant. [2] The cyan curable resin composition according to [1], wherein the polymerization initiator (D) includes a polymerization initiator represented by the following formula (d1). 【Chemical 2】

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

The lightness of the color filter formed from the cyan curable resin composition of this invention is excellent.

BEST MODE FOR CARRYING OUT THE INVENTION The cyan curable resin composition of the present invention contains a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D). In addition, the compounds and functional groups exemplified in this specification can be used alone or in combination of multiple types unless otherwise specified.

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

【Chemical 3】

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

【Chemical 4】

[n represents an integer of 1 to 8, ^R represents a hydrogen atom or an alkyl group with 1 to 4 carbons, and * represents a bonding terminal with a nitrogen atom. ]] Examples of the compound represented by the formula (IA) preferably include compounds represented by the following formula.

【Chemical 5】

Among the dyes (A1), a dye having a silicon atom and at least one skeleton selected from a triarylmethane skeleton, a cyanine skeleton, and a xanthene skeleton is preferable, and a dye having a silicon atom and a xanthene skeleton is more preferable. As a dye having a silicon atom and a xanthene skeleton, a dye having a xanthene skeleton having an organosilicon group in a substituent is preferable. Wherein, the organosilicon group represents a group having a carbon-silicon bond. Among dyes having a xanthene skeleton having an organosilicon group in the substituent, those having a trimethylsilylalkyl group, a triethylsilylalkyl group, or a trimethoxysilylalkyl group in the substituent are preferable. , triethoxysilylalkyl and other dyes having a xanthene skeleton of a silylalkyl group, more preferably a compound represented by the formula (IB) (hereinafter sometimes referred to as "compound (IB)"). Its tautomers are also included in compound (IB).

【Chemical 6】

[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, at least one of R ²¹ to R ²⁴ is a group represented by the following formula (ib). *-R ⁵⁰ -Si(R ²⁹ ) ₃ (ib) [R ²⁹ represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbons, or an alkoxy group having 1 to 4 carbons, and * represents a bond to a nitrogen atom end. A plurality of R ²⁹ may be the same as or different from each other. R ⁵⁰ represents an alkylene group with 1 to 10 carbon atoms, and the -CH ₂ - constituting the alkylene group can be replaced by -O-, -CO-, -NR ¹¹ -, -OCO-, -COO-, -OCONH-, -CONH- or -NHCO- substitution. However, the adjacent -CH ₂ - in the alkylene group will not be replaced at the same time, nor will the terminal -CH ₂ - be replaced. ] In R ²¹ ~ R ²⁴ , the hydrogen atoms contained in the monovalent saturated hydrocarbon groups with 1 to 10 carbons can be replaced by halogen atoms, and the -CH ₂ - contained in the saturated hydrocarbon groups can be replaced by -O-, -CO -, -NR ¹¹ -, -OCO-, -COO-, -OCONH-, -CONH-, or -NHCO- substitution. However, adjacent -CH ₂ - in this saturated hydrocarbon group will not be substituted at the same time, nor will the terminal -CH ₂ - be substituted. R ²⁵ and R ²⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbons. R ²⁷ and _R ²⁸ each independently represent -OH, -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z ⁺ , -CO 2 ^- , -CO ₂ H, -CO ₂ ^- Z ⁺ , -CO ₂ R ¹⁰ , -SO ₃ R ¹⁰ or -SO ₂ NR ¹¹ R ¹² . R ¹⁰ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and hydrogen atoms contained in the saturated hydrocarbon group may be substituted with halogen atoms. 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 represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms. p represents an integer of 0 to 4. ]

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

【Chemical 7】

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

【chemical 8】

[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 bonding terminal with a nitrogen atom. ] In R ³¹ ~ R ³⁴ , the hydrogen atoms contained in the monovalent saturated hydrocarbon groups with 1 to 10 carbons can be replaced by halogen atoms, and the -CH ₂ - contained in the saturated hydrocarbon groups can be replaced by -O-, -CO -or-NR ¹¹ -replacement. However, adjacent -CH ₂ - in this saturated hydrocarbon group will not be substituted at the same time, nor will the terminal -CH ₂ - be substituted. R ³⁵ and R ³⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbons. R ³⁷ and _R ³⁸ each independently represent -OH, -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z ⁺ , -CO 2 ^- , -CO ₂ H, -CO ₂ ^- Z ⁺ , -CO ₂ R ¹⁰ , -SO ₃ R ¹⁰ or -SO ₂ NR ¹¹ R ¹² . R ¹⁰ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and hydrogen atoms contained in the saturated hydrocarbon group may be substituted with halogen atoms. 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 represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms. m represents an integer of 0 to 4. ]

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

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

The hydrogen atoms contained in the monovalent saturated hydrocarbon groups having 1 to 10 carbon atoms represented by R ²¹ to R ²⁴ and R ³¹ to R ³⁴ may be replaced by halogen atoms. Examples of the halogen include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Examples of the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms substituted with a halogen atom include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a perfluoroethyl group and a chlorobutyl group. -CH _{2 -} contained in the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms represented by R ²¹ to R ²⁴ and R ³¹ to R ³⁴ may be replaced by -O-, -CO- or -NR ¹¹ -. However, in this saturated hydrocarbon group, adjacent -CH ₂ -s are not simultaneously substituted, and terminal -CH ₂ - is not substituted either. Examples of monovalent saturated hydrocarbon groups having 1 to 10 carbon atoms represented by ^R include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, Linear alkyl groups with 1-20 carbons such as n-nonyl, n-decyl, n-dodecyl, n-hexadecyl and n-eicosyl; isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl and 2-ethylhexyl branched chain alkyl with 3~20 carbons; cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and tri Alicyclic saturated hydrocarbon groups with 3 to 20 carbon atoms such as cyclodecyl.

Examples of groups in which -CH ₂ - contained in the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms is replaced by -O- include groups represented by the following formula (* indicates a bonding terminal) .

【Chemical 9】

Examples of groups in which -CH ₂ - contained in the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms is replaced by -CO- include groups represented by the following formula (* indicates a bonding terminal) .

【chemical 10】

Examples of the group in which -CH ₂ - contained in the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms is replaced by -NR ¹¹ - include, for example, groups represented by the following formula (* indicates a bonding terminal ).

【chemical 11】

The -CH ₂ - contained in the monovalent saturated hydrocarbon group with 1 to 10 carbons represented by R ²¹ to R ²⁴ and R ³¹ to R ³⁴ can be selected from -OCO-, -COO-, -OCONH-, - At least one of CONH- and -NHCO- is replaced. However, in this saturated hydrocarbon group, adjacent -CH ₂ -s are not simultaneously substituted, and terminal -CH ₂ - is not substituted either.

Examples of the group in which -CH ₂ - contained in the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms is replaced by -OCO- include groups represented by the following formula (* indicates a bonding terminal) .

【Chemical 12】

Examples of groups in which -CH ₂ - contained in the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms is replaced by -COO- include groups represented by the following formula (* indicates a bonding terminal) .

【chemical 13】

Examples of groups in which -CH ₂ - contained in the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms is replaced by -OCONH- include groups represented by the following formula (* indicates a bonding terminal) .

【Chemical 14】

Examples of groups in which -CH ₂ - contained in the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms is replaced by -CONH- include groups represented by the following formula (* indicates a bonding terminal) .

【chemical 15】

Examples of groups in which -CH ₂ - contained in the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms is replaced by -NHCO- include groups represented by the following formula (* indicates a bonding terminal) .

【Chemical 16】

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

Examples of monovalent saturated hydrocarbon groups having 1 to 20 carbon atoms represented by R ¹⁰ to R ¹³ include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n- Octyl, n-nonyl, n-decyl, n-dodecyl, n-hexadecyl, n-eicosyl and other straight-chain alkyl groups with 1 to 20 carbons; isopropyl, isobutyl, sec Butyl, tert-butyl, isopentyl, neopentyl and 2-ethylhexyl branched chain alkyl with 3~20 carbons; cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl Alicyclic saturated hydrocarbon groups with 3 to 20 carbons such as tricyclodecanyl and tricyclodecanyl.

Examples of -OR ¹⁰ include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy and di Decyloxy.

-SO ₃ ^- Z ⁺ is preferably -SO ₃ ^- N ⁺ (R ¹³ ) ₄ .

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

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

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

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

Examples of -SO ₂ NR ¹¹ R ¹² include: N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl 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, N-(1,1-dimethylpropyl)sulfamoyl, N-(1,2-dimethylpropyl)sulfamoyl, N-(2,2-Dimethylpropyl)sulfamoyl, N-(1-methylbutyl)sulfamoyl, N-(2-methylbutyl)sulfamoyl, N- (3-Methylbutyl)sulfamoyl, N-cyclopentylsulfamoyl, N-hexylsulfamoyl, N-(1,3-dimethylbutyl)sulfamoyl, N -(3,3-Dimethylbutyl)sulfamoyl, N-heptylsulfamoyl, N-(1-methylhexyl)sulfamoyl, N-(1,4-dimethyl Amyl)sulfamoyl, N-octylsulfamoyl, N-(2-ethylhexyl)sulfamoyl, N-(1,5-dimethyl)hexylsulfamoyl, N- (1,1,2,2-Tetramethylbutyl)sulfamoyl and other N-1 substituted sulfamoyl groups; N,N-dimethylsulfamoyl, N,N-ethylmethylamine Sulfonyl, N,N-diethylsulfamoyl, N,N-propylmethylsulfamoyl, N,N-isopropylmethylsulfamoyl, N,N-tert-butylmethyl N , N-2 substituted sulfamoyl group.

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

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

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

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

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

Examples of the C1-C10 alkylene group represented by ^R50 include methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, and isopropylidene , isobutylene, 2-methyltrimethylene, isopentylene, isohexylene, isooctylene, 2-ethylhexylene, etc. Among them, alkylene groups with 1 to 6 carbon atoms are preferred, and more preferably An alkylene group with 1 to 4 carbon atoms.

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

【Chemical 17】

【chemical 18】

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

【chemical 19】

【chemical 20】

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

【Chemical 21】

【Chemical 22】

In the formula (ib), examples of the group in which —CH ₂ — constituting R ⁵⁰ is replaced by —NR ¹¹ — include groups shown below (* indicates a bonding terminal).

【Chemical 23】

【Chemical 24】

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

【Chemical 25】

【Chemical 26】

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

【Chemical 27】

【Chemical 28】

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

【Chemical 29】

【Chemical 30】

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

【Chemical 31】

【Chemical 32】

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

【Chemical 33】

【Chemical 34】

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

【Chemical 35】

【Chemical 36】

【Chemical 37】

【Chemical 38】

【Chemical 39】

【Chemical 40】

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

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

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

【Chemical 41】

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

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

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

Examples of -CO ₂ R ¹⁰ represented by R ²⁷ , R ²⁸ , R ³⁷ and R ³⁸ include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, tert-butoxycarbonyl, hexyloxycarbonyl and Eicosyloxycarbonyl.

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

Examples of -SO ₂ NR ¹¹ R ¹² represented by R ²⁷ , R ²⁸ , R ³⁷ and R ³⁸ include N-methylsulfamoyl, N-ethylsulfamoyl, N-propylamine Sulfonyl, N-isopropylsulfamoyl, N-butylsulfamoyl, N-isobutylsulfamoyl, N-sec-butylsulfamoyl, N-tert-butylsulfamoyl Acyl, N-pentylsulfamoyl, N-(1-ethylpropyl)sulfamoyl, N-(1,1-dimethylpropyl)sulfamoyl, N-(1, 2-Dimethylpropyl)sulfamoyl group, N-(2,2-dimethylpropyl)sulfamoyl group, N-(1-methylbutyl)sulfamoyl group, N-(2 -Methylbutyl)sulfamoyl, N-(3-methylbutyl)sulfamoyl, N-cyclopentylsulfamoyl, N-hexylsulfamoyl, N-(1,3 -Dimethylbutyl)sulfamoyl, N-(3,3-dimethylbutyl)sulfamoyl, N-heptylsulfamoyl, N-(1-methylhexyl)sulfamoyl Acyl, N-(1,4-dimethylpentyl)sulfamoyl, N-octylsulfamoyl, N-(2-ethylhexyl)sulfamoyl, N-(1,5 -Dimethyl)hexylsulfamoyl, N-(1,1,2,2-tetramethylbutyl)sulfamoyl and other N-1 substituted sulfamoyl groups; N,N-dimethylamine Sulfonyl, N,N-Ethylmethylsulfamoyl, N,N-Diethylsulfamoyl, N,N-Propylmethylsulfamoyl, N,N-Isopropylmethyl Aminosulfonyl, N,N-tert-butylmethylsulfamoyl, N,N-butylethylsulfamoyl, N,N-bis(1-methylpropyl)sulfamoyl, N , N-heptylmethylsulfamoyl and other N,N-2 substituted sulfamoyl groups.

The monovalent saturated hydrocarbon group having 1 to 20 carbon atoms represented by ^R10 is preferably a methyl group, an ethyl group, a propyl group, or a butyl group.

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

As Z ⁺ , ⁺ N(R ¹³ ) ₄ is preferred. The four R ^13s in ⁺ N(R ¹³ ) ₄ are preferably all the same. In addition, the total carbon number of four ^R13s is preferably 20-80, more preferably 20-60.

The monovalent saturated hydrocarbon group having 1 to 20 carbon atoms represented by ^R11 and ^R12 is preferably methyl, ethyl, propyl, butyl or 2-ethylhexyl.

The monovalent saturated hydrocarbon group having 1 to 20 carbon atoms represented by ^R13 is preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and more preferably a methyl group, an ethyl group, or a propyl group.

Among R ²¹ to R ²⁴ , at least one is a group represented by formula (ib), and other R ²¹ to R ²⁴ are preferably methyl, ethyl, propyl and the following groups (* represents the group with nitrogen atom bonding end).

【Chemical 42】

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

【Chemical 43】

Among R ³¹ to R ³⁴ , at least one is a group represented by formula (ic), and other R ³¹ to R ³⁴ are preferably methyl, ethyl, propyl or the following groups.

【Chemical 44】

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

【Chemical 45】

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

R ²⁷ , R ²⁸ , R ³⁷ and R ³⁸ are preferably -CO ₂ ^- , -CO ₂ H, -SO ₃ H, -SO ₃ ^- , more preferably -SO ₃ H, -SO ₃ ^- .

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

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

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

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

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

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

【Chemical 46】

【Chemical 47】

【Chemical 48】

【Chemical 49】

【Chemical 50】

【Chemical 51】

【Chemical 52】

【Chemical 53】

【Chemical 54】

【Chemical 55】

【Chemical 56】

【Chemical 57】

【Chemical 58】

【Chemical 59】

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

Compound (IB) can be obtained by formula (IV)

【Chemical 60】

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

【Chemical 61】

[wherein, R ²³ and R ²⁴ represent the same meanings as above, respectively. ] (hereinafter sometimes referred to as "compound (V)") is produced by mixing and reacting in an organic solvent.

Examples of the halogen atom represented by ^X2 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a chlorine atom. ^X2 is preferably a halogen atom, more preferably a chlorine atom. R ²⁷ is preferably -SO ₃ ^- .

The amount of compound (V) used is usually 1 mole to 10 moles, preferably 1 mole to 3 moles, more preferably 1 mole to 2 moles, based on 1 mole of compound (IV). .

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

【Chemical 62】

[In the formula, R ²⁵ , R ²⁶ , R ²⁸ and p represent the same meanings as above. ^X1 and ^X2 each independently represent a halogen atom or a trifluoromethylsulfonyloxy group. R ⁴⁰ represents -SO ₂ - or -CO-. ] Represented compound (hereinafter sometimes described as "compound (VI)".) and by the formula (III)

【Chemical 63】

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

【Chemical 64】

[wherein, R ²³ and R ²⁴ represent the same meanings as above, respectively. ] (hereinafter sometimes referred to as "compound (V)") is produced by mixing and reacting in an organic solvent.

Examples of the halogen atom represented by ^X1 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a chlorine atom. Preferably ^X1 and ^X2 are the same. ^X1 and ^X2 are each independently preferably a halogen atom, more preferably a chlorine atom. R ⁴⁰ is preferably -SO ₂ -.

The amount of compound (III) used is usually 1 mole to 30 moles, preferably 1 mole to 20 moles, more preferably 1 mole to 10 moles, relative to 1 mole of compound (VI). , more preferably 1 mol or more and 3 mol or less, particularly preferably 1 mol or more and 2 mol or less. The amount of compound (V) used is usually 1 mole to 30 moles, preferably 1 mole to 20 moles, more preferably 1 mole to 10 moles, relative to 1 mole of compound (VI). , more preferably 1 mol or more and 3 mol or less, particularly preferably 1 mol or more and 2 mol or less.

The amount of compound (V) used is usually 1 mole to 50 moles, preferably 1 mole to 30 moles, more preferably 1 mole to 20 moles relative to 1 mole of compound (III). .

Compound (IB) can be used as a dye. Since the solubility to an organic solvent is high, it can be used especially as a coloring agent of the colored curable resin composition used for the color filter of the display apparatuses, such as a liquid crystal display.

The content of the dye (A1) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and still more preferably 1% by mass, based on 100% by mass of the total solid content of the cyan curable resin composition. Above, preferably 40% by mass or less, more preferably 30% by mass or less, even more preferably 20% by mass or less. However, the "total amount of solid content" in this specification means the amount which removed the content of a solvent from the total amount of a cyan curable resin composition. The total amount of solid content and the content of each component relative thereto can be measured, for example, by known analytical means such as liquid chromatography or gas chromatography.

The content of the dye (A1) is preferably 0.01% by mass or more, more preferably 1% by mass or more, even more preferably 3% by mass or more, based on 100% by mass of the total amount of the colorant (A). Preferably it is 5 mass % or more, Preferably it is 90 mass % or less, More preferably, it is 80 mass % or less, More preferably, it is 60 mass % or less, More preferably, it is 50 mass % or less. Furthermore, the content of the compound (IB) is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more in 100% by mass of the dye (A1). In addition, the content of the dye (A1) is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and is also preferably 100% by mass in a total of 100% by mass of the dye. %, may be 100% by mass or less, may be 90% by mass or less.

<Cyan colorant (A2)> The cyan curable resin composition of this invention contains a cyan colorant (A2) as a colorant (A) other than the said dye (A1). Examples of cyan colorants include cyan compounds classified as dyes in the Excellence Index (cyan dye (A2-1)) or cyan compounds classified as pigments in the Color Index (published by The Society of Dyers and Colourists) compound (cyan pigment (A2-2)).

Examples of the cyan dye (A2-1) include C.I. Solvent Blue 4, 5, 37, 67, 70, 90; C.I. Acid Blue 1, 7, 9, 15, 18, 22, 29, 42, 59, 60 ,62,70,72,74,82,83,86,87,90,92,93,100,102,103,104,113,117,120,126,130,131,142,147,151,154 C.I. Direct Blue 1, 2, 6, 8, 15, 22, 25, 41, 57, 71, 76, 78, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196, 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 242, 243, 244, 245, 246, 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293; C.I. 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. Mordant Blue 1, 2, 3, 7, 9, 12, 13, 15, 16, 19, 20, 21, 22, 26, 30, 31, 39, 40, 41, 43, 44 , 49, 53, 61, 74, 77, 83, 84.

Specific examples of the cyan pigment (A2-2) include C.I. Pigment Blue (the description of C.I. Pigment Blue will be omitted below, and only the serial number will be described.) 15, 15:3, 15:4, 15:6, 16, 60, 75, 80, preferably C.I. Pigment Blue 15, 15:3, 15:4, 15:6, 16, 75, more preferably C.I. Pigment Blue 15, 15:3, 15:4, 15:6, especially C.I. Pigment Blue 15:6.

Among them, a cyan pigment (A2-2) is preferable, and a cyan pigment composed of a compound having a phthalocyanine skeleton (cyan phthalocyanine pigment) is more preferable. C.I. Pigment Blue 15, 15:3, 15:4, 15:6, 16, and 75 are mentioned as a cyan pigment which consists of the compound which has a phthalocyanine skeleton. The content of the cyan pigment (A2-2) is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more in 100% by mass of the cyan colorant (A2).

The content of the cyan colorant (A2) is preferably at least 0.1% by mass, more preferably at least 1% by mass, still more preferably at least 3% by mass, and still more preferably 100% by mass of the colorant (A). It is 5 mass % or more, Preferably it is 99 mass % or less, More preferably, it is 95 mass % or less, More preferably, it is 90 mass % or less.

Furthermore, the total content of the dye (A1) and the cyan colorant (A2) is preferably 80% by mass or more, more preferably 90% by mass, based on 100% by mass of the total amount of the colorant (A). above, more preferably 95% by mass or more.

In addition, the mass ratio of the content of the dye (A1) to the content of the cyan colorant (dye (A1)/cyan colorant (A2)) is preferably 0.01 or more, more preferably 0.05 or more, preferably 10 or less, more preferably 2 or less, particularly preferably 1.8 or less, may be 0.7 or less.

<Other coloring material (A3)> The cyan curable resin composition of this invention may contain the coloring material (A3) different from a dye (A1) or a cyan coloring agent (A2) as a coloring agent (A). Examples of other colorants (A3) include dyes (A3-1) (however, different from dyes (A1) or cyan colorants (A2)) and pigments (A3-2) (however, different from cyan colorants (A2) )different).

Examples of the aforementioned dye (A3-1) (however, it is different from the dye (A1) or the cyan colorant (A2)) include amines of oil-soluble dyes, acid dyes, basic dyes, direct dyes, mordant dyes, and acid dyes. Examples of dyes such as salts and sulfonamide derivatives of acid dyes include compounds classified as dyes in the Excellence Index (published by The Society of Dyers and Colourists), and known dyes described in Dyeing Notes (Yorsensha). In addition, depending on the chemical structure, azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes other than the dye (A1), phthalocyanine dyes, naphthoquinone dyes, quinone imine dyes, methine dyes, Azomethine dyes, squarylium dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes and nitro dyes, etc. 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 Green 1, 4, 5, 7, 34, 35, etc. C.I. Solvent Dye, C.I. Acid Yellow 1, 3, 7, 9, 11, 17, 23 ,25,29,34,36,38,40,42,54,65,72,73,76,79,98,99,111,112,113,114,116,119,123,128,134,135 ,138,139,140,144,150,155,157,160,161,163,168,169,172,177,178,179,184,190,193,196,197,199,202,203,204 , 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251; C.I. Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 195, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 289, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 388, 394, 401, 412, 417, 418, 422, 426; C.I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173; C.I. Acid Violet 6B, 7, 9, 17, 19, 30, 102; C.I. Acid Green 1, 3, 5, 9, 16, 50, 58, 63, 65, 80, 104, 105, 106, 109, etc. C.I. Acid dyes, C.I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141; C.I. Direct Red 79, 82, 83, 84, 91, 9 2, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250; C.I. Direct Orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107 ; C.I. Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104; C.I. Direct Green 25, 27, 31 , 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82, etc. C.I. Direct dyes, C.I. Disperse Yellow 54, 76, etc. C.I. Disperse dyes, C.I. Basic Red 1, 10; C.I. Basic Green 1 etc. C.I. Basic Dyes, C.I. Reactive Yellow 2, 76, 116; C.I. Reactive Orange 16; C.I. Reactive Red 36 etc. , 31, 33, 42, 43, 45, 56, 61, 62, 65; C.I. Mordant 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. Mordant Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48; C.I. Mordant Violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58; C.I. Mordant Green 1, 3, 4, 5, 10 , 15, 26, 29, 33, 34, 35, 41, 43, 53, etc. C.I. Mordant dyes, C.I. Vat Green 1, etc. C.I. Vat dyes, etc. Among them, purple dyes and red dyes are preferable. These dyes can be appropriately selected according to the desired spectral spectrum of the color filter.

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

The above-mentioned pigment (A3-2) (however, it is different from the cyan colorant (A2)) is not particularly limited, and known pigments can be used, for example, pigments classified in the excellent index (published by The Society of Dyers and Colourists) are listed compound of. Pigment (A3-2) includes, for example, C.I. Pigment Yellow 1 (hereinafter, the description of C.I. Pigment Yellow is omitted, and only the serial 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 and other yellow pigments; C.I. pigments Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments; C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149 , 166, 168, 175, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265 and other red pigments; C.I. Pigment Violet 1, 19, 23, 29, 32, 36 , 38 and other purple pigments; C.I. Pigment Green 7, 36, 58 and other green pigments; C.I. Pigment Brown 23, 25 and other brown pigments; C.I. Pigment Black 1, 7 and other black pigments, etc. These pigments may be used alone or in combination of two or more.

As pigments, yellow pigments such as C.I. Pigment Yellow 138, 139, and 150, red pigments such as C.I. Pigment Red 177, 242, and 254, and purple pigments such as C.I. Pigment Violet 1, 19, 23, 29, 32, 36, and 38 are preferable. By containing the above-mentioned pigment, the optimization of the transmission spectrum of the color filter using the cyan curable resin composition of this invention becomes easy, and the light resistance and chemical resistance of a color filter become favorable.

The total pigment content is preferably at least 1% by mass, more preferably at least 10% by mass, still more preferably at least 20% by mass, and still more preferably It is 30 mass % or more, Preferably it is 99 mass % or less, More preferably, it is 95 mass % or less, More preferably, it is 90 mass % or less. The content of the colorant (A) is preferably 1% by mass to 70% by mass, more preferably 3% by mass to 60% by mass, and still more preferably 3% by mass, based on the total amount of solid content. % or more and 50 mass % or less, particularly preferably 5 mass % or more and 35 mass % or less. When the content rate of the coloring agent (A) is within the above-mentioned range, desired light spectrum and color density can be obtained.

<Resin (B)> The resin (B) is not particularly limited, but is preferably an alkali-soluble resin, and more preferably has a monomer (a) derived from at least one selected from unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (hereinafter referred to as Copolymers of structural units referred to as "(a)"). The copolymer having a structural unit derived from (a) preferably has a monomer (b) derived from a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b)") ) and a copolymer of at least one selected from structural units having an ethylenically unsaturated bond. This copolymer may further have other structural units. Examples of other structural units include structures derived from monomer (c) that can be copolymerized with (a) (however, it is different from (a) and (b).) (hereinafter sometimes referred to as "(c)") unit.

As (a), specifically, unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid; maleic acid, fumaric acid, citraconic acid, etc.; acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6 -Unsaturated dicarboxylic acids such as tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, 1,4-cyclohexene dicarboxylic acid; methyl-5-norbornene-2,3-dicarboxylic acid Acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]heptene -2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6 -Ethylbicyclo[2.2.1]hept-2-ene and other carboxyl-containing bicyclic unsaturated compounds; maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinyl Phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5 ,6-Dicarboxybicyclo[2.2.1]hept-2-ene anhydride and other unsaturated dicarboxylic anhydrides; Succinic acid mono[2-(meth)acryloxyethyl]ester, phthalic acid mono[ 2-(meth)acryloxyethyl] unsaturated mono[(meth)acryloxyalkyl]esters of polybasic carboxylic acids with more than 2 valences; α-(hydroxymethyl)acrylic acid such Unsaturated acrylic esters containing hydroxyl and carboxyl groups in the same molecule, etc. Among these, acrylic acid, methacrylic acid, maleic anhydride, and the like are preferable from the viewpoint of copolymerization reactivity and the solubility of the obtained resin in an aqueous alkali solution.

When the copolymer contains a structural unit derived from (a), the ratio thereof is preferably 1 to 50% by mass, more preferably 5 to 30% by mass in 100% by mass of the copolymer.

(b) means, for example, a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and an ethylenically unsaturated bond polymeric compound. (b) A monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth)acryloxy group is preferable. In addition, in this specification, "(meth)acrylic acid" means at least 1 sort(s) chosen from acrylic acid and methacrylic acid. Expressions such as "(meth)acryl" and "(meth)acrylate" have the same meaning.

Examples of (b) include monomers having an oxiranyl group and an ethylenically unsaturated bond, monomers having an oxetanyl group and an ethylenically unsaturated bond, monomers having a tetrahydrofuryl group and an ethylenically unsaturated bond, Monomer etc. Examples of (b) include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, vinylbenzyl glycidyl ether, 3,4-cyclo(meth)acrylate Oxycyclohexyl methyl ester, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl acrylate, 3-ethyl-3-(meth)acryloxymethyloxetane, ( Tetrahydrofurfuryl Methacrylate.

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

When the copolymer contains a structural unit derived from (b), the ratio thereof is preferably 50 to 99 mass %, more preferably 60 to 95 mass % in 100 mass % of the copolymer.

Examples of (c) include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate ester, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate , (meth)cyclohexyl acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl (meth)acrylate (in this technical field Among them, as a common name, it is called "dicyclopentyl (meth)acrylate". In addition, it is sometimes called "tricyclodecanyl (meth)acrylate".), Tricyclo (meth)acrylate [5.2.1.0 ^2,6 ]decen-8-yl ester (in this technical field, it is called "dicyclopentenyl (meth)acrylate" as a common name.), dicyclopentyloxyethyl (meth)acrylate, ( Isobornyl methacrylate, Adamantyl (meth)acrylate, Allyl (meth)acrylate, Propargyl (meth)acrylate, Phenyl (meth)acrylate, Naphthyl (meth)acrylate (meth)acrylates such as benzyl (meth)acrylate; (meth)acrylates containing hydroxyl groups such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; Diethyl maleate, diethyl fumarate, diethyl itaconate and other dicarboxylic acid diesters; bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]heptane -2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2 -ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2 .1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-bis(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5 ,6-bis(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethyl Oxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept- 2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene and other bicyclic unsaturated compounds; N-phenylmaleimide, N-cyclohexylmaleimide Amine, N-Benzylmaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate , N-succinimidyl-6-maleimide hexanoate, N-succinimidyl-3-maleimide propionate, N-(9-acridinyl) maleate Dicarbonyl imine derivatives such as imide; Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene Styrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butyl Diene, isoprene, 2,3-dimethyl-1,3-butadiene, etc. Among these, styrene, vinyl toluene, benzyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decane-8-(meth)acrylate are preferable from the viewpoint of copolymerization reactivity and heat resistance. base ester, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo[2.2.1]hept-2-ene.

When the copolymer contains a structural unit derived from (c), the ratio thereof is preferably 1 to 99% by mass in 100% by mass of the copolymer.

The structural unit having an ethylenically unsaturated bond is preferably a structural unit having a (meth)acryloyl group in a side chain. A resin having such a structural unit is obtained by combining a polymer having a structural unit derived from (a), (b) with a group having a group reactive with (a), (b) and an ethylenically unsaturated bond. Obtained by monomer addition. Examples of such structural units include those obtained by adding glycidyl (meth)acrylate to (meth)acrylic acid units, and those obtained by adding 2-hydroxyethyl (meth)acrylate to maleic anhydride units. A structural unit obtained by adding (meth)acrylic acid to a glycidyl (meth)acrylate unit, etc. Moreover, when these structural units have a hydroxyl group, the structural unit which added carboxylic anhydride further can also be mentioned as a structural unit which has an ethylenically unsaturated bond.

Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth)acrylate/(meth)acrylic acid copolymer, 3,4-epoxycyclohexyl (meth)acrylate 5.2.1.0 ^2.6 ] Decyl ester/(meth)acrylic acid copolymer etc. copolymers with structural units from (a) and (b); glycidyl (meth)acrylate/benzyl (meth)acrylate/( Meth)acrylic acid copolymer, glycidyl (meth)acrylate/styrene/(meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decyl (meth)acrylate/( Meth)acrylic acid/N-cyclohexylmaleimide copolymer, (meth)acrylic acid 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decyl ester/(meth)acrylic acid/vinyltoluene copolymer , 3-methyl-3-(meth)acryloxymethyloxetane/(meth)acrylic acid/styrene copolymer etc. have structures derived from (a), (b) and (c) Copolymer of units; benzyl (meth)acrylate/(meth)acrylic acid copolymer, styrene/(meth)acrylic acid copolymer, benzyl (meth)acrylate/tricyclodecanyl (meth)acrylate/ (meth)acrylic acid copolymers; resins obtained by adding glycidyl (meth)acrylate to benzyl (meth)acrylate/(meth)acrylic acid copolymers, glycidyl (meth)acrylate and (meth)acrylic acid tricyclodecanyl/styrene/(meth)acrylic acid copolymer addition resin, the (meth)acrylate glycidyl and (meth)acrylic acid tricyclodecanyl/(meth)acrylic acid ) benzyl acrylate/(meth)acrylic acid copolymer addition resins etc. have structural units derived from (a) and (c) copolymers; make (meth)acrylic acid and (meth)acrylic acid tricyclodecane ester/glycidyl (meth)acrylate copolymer, a copolymer of (meth)acrylic acid and tricyclodecanyl (meth)acrylate/styrene/glycidyl (meth)acrylate Resins obtained by the reaction are copolymers having structural units derived from (b) added to structural units derived from (a) and structural units derived from (c); (meth)acrylic acid and (meth)acrylic acid tri A resin obtained by reacting a copolymer of cyclodecyl ester/glycidyl (meth)acrylate and tetrahydrophthalic anhydride, etc., has the ability to add (a), A structural unit obtained by further adding a carboxylic acid anhydride, a copolymer of a structural unit derived from (c), and the like.

The above-mentioned resin, for example, can refer to the method described in the document "Experimental Method for Polymer Synthesis" (Otsu Takayuki Publishing Co., Ltd. Chemical Doujin 1st Edition, 1st Printing Issue, March 1, 1972) and the method described in this document. Manufactured by citing literature.

The resin (B) is preferably selected from copolymers having structural units derived from (a) and (b); copolymers having structural units derived from (a), (b) and (c); and copolymers having structural units derived from (a) and one of the copolymers of structural units of (c), more preferably selected from copolymers having structural units from (a) and (b); and having from (a), (b) and (c) One of the copolymers of structural units is particularly preferably a copolymer having structural units derived from (a) and (b).

The polystyrene conversion weight average molecular weight of resin (B) becomes like this. Preferably it is 3,000-100,000, More preferably, it is 5,000-50,000, More preferably, it is 5,000-30,000. When the molecular weight is within the above-mentioned range, when forming a colored pattern, the remaining film rate before and after development is high, the solubility of the unexposed portion in the developing solution is good, and the resolution of the colored pattern tends to be improved. The molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the resin (B) is preferably 1.1-6, more preferably 1.2-4.

The acid value (in terms of solid content) of the resin (B) is preferably 40 to 170 mg-KOH/g, more preferably 50 to 150 mg-KOH/g, and even more preferably 60 to 135 mg-KOH/g. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (B), and can be determined, for example, by titration using an aqueous potassium hydroxide solution.

The content of the resin (B) is preferably 7 to 75% by mass, more preferably 13 to 70% by mass, still more preferably 17 to 70% by mass, and even more preferably 17 to 70% by mass relative to the total amount of solid content. 65% by mass. If the content of the resin (B) is within the above range, a colored pattern can be formed, and the resolution and residual film ratio of the colored pattern tend to increase.

<Polymerizable compound (C)> The polymerizable compound (C) is a compound that can be polymerized using active radicals and/or acids generated by the polymerization initiator (D), and examples thereof include polymerizable compounds having ethylenically unsaturated bonds Compounds, etc., are preferably (meth)acrylate compounds.

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

Examples of polymerizable compounds having two ethylenically unsaturated bonds include 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di( Meth)acrylate, triethylene glycol di(meth)acrylate, bis(acryloxyethyl)ether of bisphenol A, 3-methylpentanediol di(meth)acrylate, etc.

Among them, the polymerizable compound is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol penta(meth)acrylate. , dipentaerythritol hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tetrapentaerythritol deca(meth)acrylate, tetrapentaerythritol nona(meth)acrylate , Tris(2-(meth)acryloxyethyl)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 base) acrylate and the like, among which dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate are preferable.

The weight average molecular weight of the polymerizable compound (C) is preferably 150 to 2900, more preferably 250 to 1500.

The content of the polymerizable compound (C) is preferably 4 to 65% by mass, more preferably 7 to 60% by mass, and even more preferably 10 to 55% by mass based on the total amount of solid content. In addition, the content ratio of the resin (B) to the polymerizable compound (C) [resin (B):polymerizable compound (C)] is preferably 20:80 to 80:20, more preferably 35:65 on a mass basis ~80:20. When content of a polymeric compound (C) exists in the said range, there exists a tendency for the residual film rate at the time of color pattern formation and the chemical resistance of a color filter to improve.

<Polymerization initiator (D)> The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating active radicals, acids, etc. by the action of light or heat to initiate polymerization, and known polymerization initiators can be used. . Examples of the polymerization initiator (D) include O-acyl oxime compounds, alkyl phenone compounds, biimidazole compounds, triazine compounds, and acyl phosphine oxide compounds.

Examples of O-acyl oxime compounds include N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyl Oxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)- 3-cyclopentylpropan-1-one-2-imine, N-acetyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3 -yl]ethane-1-imine, N-acetyloxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-di Oxolanemethoxy)benzoyl}-9H-carbazol-3-yl]ethane-1-imine, N-acetyloxy-1-[9-ethyl-6-( 2-Methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-imine, N-benzoyloxy-1-[9-ethyl-6- (2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-one-2-imine, [11-(2-ethylhexyl)-5- (2,4,6-Trimethylbenzoyl)-11H-benzo[a]carbazol-8-yl]-[2-(2,2,3,3-tetrafluoropropoxy)benzene Base] Ketoxime O-acetate, etc. Commercially available items such as IRGACURE (registered trademark) OXE01 and OXE02 (manufactured by BASF Corporation), N-1919 (manufactured by ADEKA Corporation) can be used. Among them, the O-acyl oxime compound is preferably selected from N-benzoyloxy-1-(4-phenylsulfanylphenyl)butane-1-one-2-imine, N-benzoyloxy Base-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3 -Cyclopentylpropan-1-one-2-imine and [11-(2-ethylhexyl)-5-(2,4,6-trimethylbenzoyl)-11H-benzo[a At least one of ]carbazol-8-yl]-[2-(2,2,3,3-tetrafluoropropoxy)phenyl]ketone oxime O-acetate, more preferably selected from N- Benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine and [11-(2-ethylhexyl)-5-(2,4,6 -trimethylbenzoyl)-11H-benzo[a]carbazol-8-yl]-[2-(2,2,3,3-tetrafluoropropoxy)phenyl]methanone oxime O - at least one kind of acetate.

As the O-acyl oxime compound, a compound represented by the following formula (d1) (hereinafter may be referred to as "compound (d1)") is preferable.

【Chemical 65】

[In the formula (d1), R ^d1 represents an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent, a heterocyclic group having 3 to 36 carbon atoms which may have a substituent, or a heterocyclic group having 1 to 15 carbon atoms which may have a substituent A saturated hydrocarbon group or an aralkyl group with 7 to 33 carbon atoms that may have a substituent, and the methylene group (-CH ₂ -) contained in the above-mentioned saturated hydrocarbon group or aralkyl group can be replaced by -O-, -CO- , -S-, -SO ₂ - or -NR ^d5 -. In addition, "aromatic hydrocarbon group" in this specification means a group containing only an aromatic ring site. R ^d2 represents an aromatic hydrocarbon group with 6 to 18 carbons, a heterocyclic group with 3 to 36 carbons, or a saturated hydrocarbon group with 1 to 10 carbons. R ^d3 represents an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent, and a heterocyclic group having 3 to 36 carbon atoms which may have a substituent. R ^d4 represents an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent or an aliphatic hydrocarbon group having 1 to 15 carbon atoms which may have a substituent, and the methylene group (-CH ₂ -) contained in the above aliphatic hydrocarbon group Can be replaced by -O-, -CO- or -S-, the methine group (-CH<) contained in the above aliphatic hydrocarbon group can be replaced by -PO ₃ <, the hydrogen contained in the above aliphatic hydrocarbon group Atoms may be substituted by OH groups. R ^d5 represents a saturated hydrocarbon group having 1 to 10 carbon atoms, and the methylene group (-CH ₂ -) contained in the saturated hydrocarbon group may be replaced with -O- or -CO-. ]

The carbon number of the aromatic hydrocarbon group represented by R ^d1 is preferably 6-15, more preferably 6-12, and even more preferably 6-10. Examples of the aromatic hydrocarbon group include phenyl, naphthyl, anthracenyl, phenanthrenyl, biphenyl, terphenyl and the like, more preferably phenyl and naphthyl, particularly preferably phenyl. In addition, the aromatic hydrocarbon group represented by R ^d1 may have 1 or 2 or more substituents. The substituent is preferably substituted at the α-position and γ-position of the aromatic hydrocarbon group, more preferably substituted at the γ-position. Examples of the substituent include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl C1-15 saturated hydrocarbon groups such as tetradecyl, pentadecyl, etc.; halogen atoms such as fluorine atom, chlorine atom, iodine atom, bromine atom, etc. The carbon number of the saturated hydrocarbon group as the substituent is preferably 1-10, more preferably 1-7. The saturated hydrocarbon group as the substituent may be linear, branched or cyclic, or may be a combination of a chain group and a cyclic group. The methylene group (—CH ₂ —) contained in the saturated hydrocarbon group as the substituent may be replaced with —O— or —S—. In addition, the hydrogen atoms contained in the saturated hydrocarbon group may be substituted by halogen atoms such as fluorine atoms, chlorine atoms, iodine atoms, bromine atoms, and are preferably substituted by fluorine atoms. However, in the saturated hydrocarbon group as this substituent, adjacent methylene groups are not replaced at the same time, and terminal methylene groups are not replaced.

As a substituent of the aromatic hydrocarbon group represented by ^Rd1 , the group represented by the following formula etc. are mentioned, for example. In the formula, * represents a bonding terminal.

【Chemical 66】

【Chemical 67】

As the aromatic hydrocarbon group which may have a substituent represented by ^Rd1 , the group represented by the following formula etc. are mentioned. In the formula, * represents a bonding terminal.

【Chemical 68】

【Chemical 69】

As the aromatic hydrocarbon group which may have a substituent represented by ^Rd1 , the group represented by the following formula is preferable.

【chemical 70】

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

Examples of the saturated hydrocarbon group represented by R ^d6 include the same ones as the saturated hydrocarbon groups exemplified as substituents of the aromatic hydrocarbon group represented by R ^d1 . The carbon number of the saturated hydrocarbon group represented by R ^d6 is preferably 2 or more and 7 or less, more preferably 2 or more and 5 or less. In addition, the saturated hydrocarbon group of R ^d6 may be any of linear, branched and cyclic, and is preferably chain. Examples of the halogen atom which may be substituted for a hydrogen atom contained in R ^d6 include a fluorine atom, a chlorine atom, an iodine atom, and a bromine atom, and a fluorine atom is particularly preferable. In addition, preferably 2 or more and 10 or less hydrogen atoms contained in R ^d6 are substituted with halogen atoms, preferably 3 or more and 6 or less hydrogen atoms are substituted with halogen atoms. The substitution position of the R ^d6 O-group is preferably the ortho-position, the para-position, particularly preferably the para-position. In addition, m2 is preferably 1-2, particularly preferably 1.

The carbon number of the heterocyclic group represented by R ^d1 is preferably 3-20, more preferably 3-10, even more preferably 3-5. Examples of the heterocyclic group include pyrrolyl, furyl, thienyl, indolyl, benzofuryl, carbazolyl and the like. In addition, the heterocyclic group of R ^d1 may have 1 or 2 or more substituents. Examples of the substituent include the same groups as those exemplified as the substituent that the aromatic hydrocarbon group of R ^d1 may have.

The carbon number of the saturated hydrocarbon group represented by R ^d1 is preferably 1-12. Examples of the saturated hydrocarbon group represented by R ^d1 include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl , tridecyl, tetradecyl, pentadecyl, etc. These saturated hydrocarbon groups may be linear, branched or cyclic, and may be a combination of a chain group and a cyclic group. In addition, in the saturated hydrocarbon group of R ^d1 , the methylene group (-CH ₂ -) can be replaced by -O-, -CO-, -S-, -SO ₂ - or -NR ^d5 -, and the hydrogen atom can be replaced by OH Substituted by group or SH group. However, in this saturated hydrocarbon group, adjacent methylene groups are not replaced at the same time, and terminal methylene groups are not replaced.

R ^d5 represents a saturated hydrocarbon group with 1 to 10 carbons, preferably a saturated hydrocarbon group with 1 to 5 carbons, more preferably a saturated hydrocarbon group with 1 to 3 carbons. The saturated hydrocarbon group can be chain (straight chain or branched chain), also can be cyclic, can be any of straight chain, branched chain and cyclic, also can be the group of chain and ring A group formed by a combination of like groups. In addition, in the saturated hydrocarbon group of R ^d5 , the methylene group (-CH ₂ -) may be replaced by -O-, -CO-. However, in this saturated hydrocarbon group, adjacent methylene groups are not replaced at the same time, and terminal methylene groups are not replaced.

As the saturated hydrocarbon group which may have a substituent represented by ^Rd1 , the group represented by the following formula etc. are mentioned specifically,. *Indicates the bonding end.

【Chemical 71】

Furthermore, the optionally substituted aralkyl group represented by ^Rd1 is preferably a group obtained by combining an aromatic hydrocarbon group represented by ^Rd1 and an alkylene group derived from the saturated hydrocarbon group represented by ^Rd1 . The carbon number of the above-mentioned aralkyl group is preferably 7-33, more preferably 7-18, even more preferably 7-12. The aralkyl group may have one or more substituents, and examples of the substituents include those exemplified as the substituents that the aromatic hydrocarbon group represented by ^Rd1 and the saturated hydrocarbon group represented by ^Rd1 may have. same group. Specific examples of the group formed by combining the aromatic hydrocarbon group represented by R ^d1 and a divalent group derived from the saturated hydrocarbon group represented by R ^d1 above include groups represented by the following formula. In the formula, * represents a bonding terminal. The methylene group (-CH ₂ -) contained in the aralkyl group may be replaced by -O-, -CO-, -S-, -SO ₂ -, or -N(R ^d5 )-. However, in this aralkyl group, adjacent methylene groups are not simultaneously replaced, and terminal methylene groups are not replaced.

【Chemical 72】

Among them, R ^d1 is preferably an optionally substituted aromatic hydrocarbon group or an optionally substituted saturated hydrocarbon group, more preferably an optionally substituted aromatic hydrocarbon group.

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

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

The carbon number of the aromatic hydrocarbon group represented by R ^d3 is preferably 6-15, more preferably 6-12, even more preferably 6-10. Examples of the aromatic hydrocarbon group include phenyl, naphthyl, anthracenyl, phenanthrenyl, biphenyl, terphenyl and the like, more preferably phenyl and naphthyl. In addition, the aromatic hydrocarbon group represented by R ^d3 may have 1 or 2 or more substituents. The substituent is preferably substituted at the α-position and γ-position of the aromatic hydrocarbon group. As the substituent, an aliphatic hydrocarbon group having 1 to 15 carbon atoms is preferable, and specific examples thereof include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl Alkyl groups with 1 to 15 carbons; vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, nonenyl, decenyl and other alkenyls with 1 to 15 carbons. As for the carbon number of the aliphatic hydrocarbon group which is the said substituent, it is more preferable that it is 1-7. In addition, the aliphatic hydrocarbon group as the substituent may be any of linear, branched and cyclic, and may be a combination of a chain group and a cyclic group. In addition, in the aliphatic hydrocarbon group as the substituent, the methylene group (-CH ₂ -) may be replaced by -O-, -CO- or -S-, and the methine group (-CH<) may be replaced by -N<. However, in the aliphatic hydrocarbon group as this substituent, adjacent methylene groups are not replaced at the same time, and terminal methylene groups are not replaced.

As an aliphatic hydrocarbon group which is a substituent of the aromatic hydrocarbon group represented by ^Rd3 , the group represented by the following formula etc. are mentioned, for example. In the formula, * represents a bonding terminal.

【Chemical 73】

As the aromatic hydrocarbon group which may have a substituent represented by ^Rd3 , the group represented by the following formula etc. are mentioned, for example. In the formula, * represents a bonding terminal.

【Chemical 74】

The carbon number of the heterocyclic group represented by R ^d3 is preferably 3-20, more preferably 3-10, even more preferably 3-5. Examples of the heterocyclic group include pyrrolyl, furyl, thienyl, indolyl, benzofuryl, carbazolyl and the like. In addition, the heterocyclic group represented by ^Rd3 may have 1 or 2 or more substituents, and examples of the substituents include the same groups as those exemplified as substituents that the aromatic hydrocarbon group represented by ^Rd1 may have. group.

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

The carbon number of the aromatic hydrocarbon group represented by R ^d4 is preferably 6-15, more preferably 6-12, even more preferably 6-10. Examples of the aromatic hydrocarbon group include phenyl, naphthyl, anthracenyl, phenanthrenyl, biphenyl, terphenyl and the like, more preferably phenyl and naphthyl, particularly preferably phenyl. In addition, the aromatic hydrocarbon group represented by R ^d4 may have 1 or 2 or more substituents. Examples of the substituent include the same substituents that the aromatic hydrocarbon group of R ^d1 may have.

The carbon number of the aliphatic hydrocarbon group represented by R ^d4 is preferably 1-13, more preferably 2-10, and still more preferably 4-9. Examples of the ^aliphatic hydrocarbon group for R include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, Tridecyl, tetradecyl, pentadecyl and other alkyl groups; vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decene Alkenyl groups such as undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, etc. These aliphatic hydrocarbon groups may be chain (linear or branched) or cyclic, or may be a combination of a chain group and a cyclic group. In addition, in the aliphatic hydrocarbon group represented by R ^d4 , methylene (-CH ₂ -) may be replaced by -O-, -CO- or -S-, and methine (-CH<) may be replaced by -PO ₃ <. Hydrogen atoms contained in the above-mentioned aliphatic hydrocarbon group may be substituted with OH groups. However, in this aliphatic hydrocarbon group, adjacent methylene groups are not simultaneously replaced, and terminal methylene groups are not replaced.

As an aliphatic hydrocarbon group which may have a substituent represented by ^Rd4 , the group etc. which are represented by the following formula are mentioned, for example. In the formula, * represents a bonding terminal. 【Chemical 75】

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

Examples of the compound (d1) include compounds (d1-1) to (d1-67) represented by the formula (d1) as shown in the following Tables 1 to 7. In the table, * indicates a bonding terminal.

【Chemical 76】

【Table 1】

【Table 2】

【table 3】

【Table 4】

【table 5】

【Table 6】

【Table 7】

Among them, preferred compounds (d1-3)~(d1-6), (d1-18)~(d1-52), (d1-55), (d1-56), (d1-60), (d1-61 ), more preferably compounds (d1-3)~(d1-6), (d1-18)~(d1-41), more preferably compounds (d1-24), (d1-36)~(d1-40 ), particularly preferably compound (d1-24).

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

Examples of alkyl phenyl ketone compounds include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino- 1-(4-morpholinophenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1- [4-(4-morpholinyl)phenyl]butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1- [4-(2-Hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propane Oligomers of -1-ketone, α,α-diethoxyacetophenone, benzoyl dimethyl ketal, etc. Commercially available products such as IRGACURE (registered trademark) 369, 907, and 379 (the above are manufactured by BASF Corporation) can be used.

Examples of biimidazole compounds include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3- Dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (for example, refer to JP-A-6-75372, JP-A-6-75373, etc.), 2,2' -Bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'- Tetrakis(alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(dialkoxyphenyl)biimidazole, 2,2 '-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole (for example, refer to Japanese Patent Publication No. 48-38403, Japanese Patent Application Laid-Open No. 62 -174204, etc.), imidazole compounds in which the 4,4', 5,5'-position phenyl groups are substituted by alkoxycarbonyl groups (for example, refer to Japanese Patent Application Laid-Open No. 7-10913, etc.), and the like.

Examples of triazine compounds include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl) Methyl)-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)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl) Vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]- 1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine wait.

Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like.

Furthermore, examples of the polymerization initiator (D) include benzoin, such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether. Compound; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3', 4,4'-Tetra(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone and other benzophenone compounds; 9,10-phenanthrenequinone, 2-ethyl Quinone compounds such as anthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzoyl, methyl phenylglyoxylate, titanocene compounds, etc.

The polymerization initiator (D) is preferably a polymerization initiator comprising at least one selected from the group consisting of alkyl phenone compounds, triazine compounds, acyl phosphine oxide compounds, O-acyl oxime compounds and biimidazole compounds, more preferably A polymerization initiator comprising an O-acyl oxime compound.

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

The cyan curable resin composition of this invention may contain a solvent (E), a leveling agent (F), etc. further.

<Solvent (E)> The solvent (E) is not particularly limited, and solvents generally used in this field can be used. Examples include 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 ester solvents (solvents containing 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, not containing -O-, - CO- and -COO- solvents), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfide, etc.

Examples of ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate , Butyl propionate, Isopropyl butyrate, Ethyl butyrate, Butyl butyrate, Methyl pyruvate, Ethyl pyruvate, Propyl pyruvate, Methyl acetylacetate, Ethyl acetylacetate, Cyclo Hexyl alcohol acetate, γ-butyrolactone, etc.

Examples of ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol Monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3- Methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether , Diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, methyl anisole, etc.

Examples of ether ester solvents include methyl methoxy acetate, ethyl methoxy acetate, butyl methoxy acetate, methyl ethoxy acetate, ethyl ethoxy acetate, and 3-methoxypropionic acid Methyl ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, 2-methoxypropionate Ethyl ester, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, 2- Ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate Butyl ether acetate, dipropylene glycol methyl ether acetate, etc.

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

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

These solvents may be used alone or in combination of two or more. Among them, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diglycol Alcohol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol methyl ether acetate, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methanol Base-2-pentanone, N,N-dimethylformamide, N-methylpyrrolidone, etc., more preferably propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethylene glycol monobutyl ether, Dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol, ethyl 3-ethoxypropionate, N-methylpyrrolidone.

The content of the solvent (E) is preferably 50 to 95% by mass, more preferably 55 to 92% by mass, based on the total amount of the cyan curable resin composition. In other words, the solid content of the cyan 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 within the above-mentioned range, the flatness at the time of coating becomes favorable, and since the color density is not insufficient when the color filter is formed, there is a tendency for the display characteristics to become favorable.

<Leveling agent (F)> The cyan curable resin composition of this invention may contain a leveling agent (F). Examples of the leveling agent (F) include silicone-based surfactants, fluorine-based surfactants, silicone-based surfactants having fluorine atoms, and the like. These may have a polymerizable group in a side chain. Examples of the silicone-based surfactant include surfactants having a siloxane bond in the molecule, and the like. Specifically, TORAY SILICONE DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (trade name: manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (manufactured by MOMENTIBU PAFORMANS MATERIALS JAPAN CO., LTD.), etc.

As a fluorine-type surfactant, the surfactant etc. which have a fluorocarbon chain in a molecule|numerator are mentioned. Specific examples thereof include Floraldo (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megaface (registered trademark) F142D, F171, F172, F173, F177, F183, F554, R30, RS-718-K (manufactured by DIC Co., Ltd.), Eftop (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Corporation, Inc.), Surfulon (registered trademark) S381, S382, SC101, SC105 (Asahi Glass Co., Ltd.) Manufactured) and E5844 (manufactured by ダイキンファイン Chemical Research Institute), etc.

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

When the leveling agent (F) is contained, its content is preferably 0.001% by mass to 0.7% by mass, more preferably 0.002% by mass to 0.5% by mass, based on the total amount of the cyan curable resin composition. mass % or less, more preferably 0.005 mass % or more and 0.3 mass % or less. The flatness of a color filter can be made favorable that content of a leveling agent (F) exists in the said range.

<Other Components> The cyan curable resin composition of the present invention may contain, as necessary, polymerization initiation aids, fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, chain transfer agents, and the like. Additives known in the technical field.

<Method for Producing Cyan Curable Resin Composition> The cyan curable resin composition of the present invention can be prepared, for example, by mixing a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), and Prepared by mixing solvent (E), leveling agent (F) and other ingredients as needed. The cyan pigment (A2-2) and the optional pigment (A3-2) are preferably mixed with part or all of the solvent (E) in advance, and dispersed using a bead mill or the like until the average particle diameter of the pigment becomes about 0.2 μm or less. . At this time, part or all of the pigment dispersant and the resin (B) may be blended as needed. By mixing the remaining components with the pigment dispersion liquid thus obtained and mixing so as to have a predetermined concentration, a target cyan curable resin composition can be prepared. Compound (IB) is preferably dissolved in part or all of solvent (E) in advance to prepare a solution. The solution is preferably filtered with a filter having a pore diameter of about 0.01 to 1 μm. The mixed blue curable resin composition is preferably filtered through a filter having a pore diameter of about 0.01 to 10 μm.

<The manufacturing method of a color filter> As a method of manufacturing a colored pattern from the cyan curable resin composition of this invention, a photolithography method, an inkjet method, a printing method, etc. are mentioned. Among them, photolithography is preferable. The photolithography method is a method in which the above-mentioned cyan curable resin composition is applied to a substrate, dried to form a colored composition layer, and the colored composition layer is exposed through a photomask to be developed. In photolithography, a colored coating film that is a cured product of the above-mentioned colored composition layer can be formed by not using a photomask and/or not developing during exposure. The colored pattern and colored coating film formed in this way can be used as the color filter of this invention. The film thickness of the produced color filter is not particularly limited, and can be appropriately adjusted according to the purpose, use, etc., for example, 0.1-30 μm, preferably 0.1-20 μm, more preferably 0.5-6 μm.

As the substrate, glass plates such as quartz glass, borosilicate glass, aluminosilicate glass, soda-lime glass whose surface is coated with silica, polycarbonate, polymethyl methacrylate, polyparaphenylene, etc., can be used. Resin plates such as ethylene glycol diformate, silicon, aluminum, silver, and silver/copper/palladium alloy thin films are formed on the above-mentioned substrates. Additional color filter layers, resin layers, transistors, circuits, etc. may be formed on these substrates.

The formation of pixels of each color by photolithography can be performed under known or commonly used equipment and conditions. For example, it can be produced as follows. First, a cyan curable resin composition is coated on a substrate, and dried by heat drying (prebaking) and/or reduced pressure drying to remove volatile components such as solvents and obtain a smooth coloring composition layer. Examples of the coating method include a spin coating method, a slit coating method, a slit and spin coating method, and the like. The temperature at the time of heat drying is preferably 30 to 120°C, more preferably 50 to 110°C. In addition, the heating time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes. When performing reduced-pressure drying, it is preferable to carry out in the temperature range of 20-25 degreeC under the pressure of 50-150 Pa. The film thickness of a coloring composition layer is not specifically limited, According to the film thickness of the objective color filter, it can select suitably.

Next, the colored composition layer is exposed through a photomask for forming an intended colored pattern. The pattern on this photomask is not specifically limited, The pattern according to the intended use can be used. As a light source for exposure, a light source that generates light with a wavelength of 250 to 450 nm is preferable. For example, this wavelength range can be cut off using a filter that cuts off light below 350 nm, or these wavelength ranges can be selectively extracted using a bandpass filter that extracts light around 436 nm, around 408 nm, and around 365 nm. Specifically, as a light source, a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp, etc. are mentioned. Since it is possible to uniformly irradiate the entire exposure surface with parallel light rays and accurately align the photomask and the substrate on which the colored composition layer is formed, it is preferable to use an exposure device such as a mask aligner or a stepper.

A colored pattern is formed on a board|substrate by making the exposed coloring composition layer contact a developing solution, and developing. By image development, the unexposed part of a coloring composition layer dissolves in a developing solution, and is removed. As the developer, for example, an aqueous solution of a basic compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, tetramethylammonium hydroxide, or the like is preferable. The concentration in the aqueous solution of these basic compounds is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. Furthermore, the developer may contain a surfactant. The developing method may be any of spin-on-dip method, dipping method, spray method and the like. Furthermore, the substrate can be inclined at any angle during image development. Water washing is preferably performed after image development.

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

According to the cyan curable resin composition of this invention, the color filter excellent in lightness can be formed. This color filter can be used as a color filter for display devices (for example, liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state imaging elements. Example

The following examples are given to illustrate the present invention more specifically. The present invention is of course not limited by the following examples, and it is of course possible to appropriately modify and implement within the scope of adapting to the gist of the foregoing and the following, and these include Within the technical scope of the present invention. In the examples, % and parts indicating the content and usage amount are quality standards unless otherwise specified.

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

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

【Chemical 77】

Next, 44 parts of the compound represented by formula (I-1-A) and 21.4 parts of trimethoxy[3-(methylamino)propyl]silane (manufactured by Tokyo Chemical Industries, Ltd.) - In the presence of 50 parts of 2-pyrrolidone, it was heated at 100° C. for 5 hours. The obtained reaction liquid was cooled to room temperature, filtered, washed with 100 parts of water, and the obtained crystals were dried to obtain 52 parts of a compound represented by the formula (I-1).

【Chemical 78】

Identification of the compound represented by formula (I-1) (mass analysis) Ionization mode = ESI+: m/z = [M+H] ⁺ 599.2 Accurate mass: 598.1

Dissolve 0.35 g of the compound represented by formula (I-1) in chloroform to make a volume of 250 cm ³ , dilute 2 cm ³ of it with ion-exchanged water to make a volume of 100 cm ³ (concentration: 0.028 g/L), and use a spectrometer The absorption spectrum was measured with a photometer (quartz cell, optical path length: 1 cm). The maximum absorption wavelength λ _max of this compound is 546 nm.

[Synthesis of Resin] In a 1L flask equipped with a reflux cooler, a dropping funnel, and a stirrer, an appropriate amount of nitrogen was flowed in to replace it with a nitrogen atmosphere, and 280 parts by weight of propylene glycol monomethyl ether acetate was charged and stirred. Heat to 80°C. Next, 38 parts by weight of acrylic acid, 289 parts by weight of a mixture of 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decane-8 or/and 9-yl ester of acrylic acid, propylene glycol mono A mixed solution of 125 parts by weight of methyl ether acetate. On the other hand, a mixed solution in which 33 parts by weight of 2,2-azobis(2,4-dimethylvaleronitrile) was dissolved in 235 parts by weight of propylene glycol monomethyl ether acetate was dropped over 6 hours. After the dropping was completed, the same temperature was kept at the same temperature for 4 hours, and then cooled to room temperature to obtain a copolymer (resin B-1). The weight average molecular weight Mw of the produced copolymer was 9200, and the degree of dispersion was 2.08.

【Chemical 79】

The measurement of the polystyrene-equivalent weight average molecular weight Mw and the number average molecular weight Mn of the resin obtained by the said synthesis example was performed on the following conditions using the GPC method. Device: HLC-8120GPC (manufactured by Tosoh Co., Ltd.) Column: TSK-GELG2000HXL Column temperature: 40°C Solvent: THF Flow rate: 1.0mL/min Solid component concentration of test liquid: 0.001~0.01 Mass injection volume: 50μL Detector : Standard material for RI calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Co., Ltd.) The ratio (Mw/Mn) of the number average molecular weight was defined as the molecular weight distribution.

[Preparation of Cyan Curable Resin Composition] Each component was mixed so as to have the composition shown in Table 8, and a cyan curable resin composition was obtained.

【Table 8】

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

【Chemical 80】

(A) Colorant: A-3: 7.2 parts of dye (A-3) (mixture of compounds represented by formula (A3-1) ~ formula (A3-8)) and 92.7 parts of propylene glycol monomethyl ether acetate mixed solution

【Chemical 81】

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

【Chemical 82】

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

[Formation of 50 μm Square Hole Pattern] On a 2-inch-square glass substrate (EAGLE XG; manufactured by Corning Incorporated), the cyan curable resin composition was coated by spin coating, and prebaked at 100° C. for 3 minutes. After cooling, the substrate coated with the cyan curable resin composition was exposed to an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) through a mask pattern in which square holes of 50 μm were arranged, under air atmosphere, at 80 mJ /cm ² exposure amount (365nm reference) for light irradiation. After exposure, image development was performed at 23° C. for 60 seconds using a developing solution, followed by rinsing with running water for 20 seconds, and then spray-drying. Then, post-baking was performed at 230° C. for 30 minutes to form a 50 μm square hole pattern on the glass substrate.

[Measurement of Film Thickness] The film thickness of the obtained pattern was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.). The results are shown in Table 9.

由包含著色劑（A-1）和（A-2）的著色固化性樹脂組合物形成的圖案在使色度一致的情況下，與由比較例的著色固化性樹脂組合物形成的圖案相比，可知Y大，明度優異。[Chromaticity evaluation] The spectrum of the pattern on the obtained glass substrate was measured using a colorimeter (OSP-SP-200; manufactured by Olympus Co., Ltd.), and XYZ of CIE was measured using the equichromatic function of the C light source. The xy chromaticity coordinates (x, y) in the color system. The results are shown in Table 9. It was confirmed from the chromaticity coordinates that the color of the pattern on the obtained glass substrate was cyan. 【Table 9】

The pattern formed by the colored curable resin composition containing the colorants (A-1) and (A-2) is compared with the pattern formed by the colored curable resin composition of the comparative example when the chromaticity is made uniform , it can be seen that Y is large and lightness is excellent.

Industrial Applicability According to the cyan curable resin composition of the present invention, a color filter excellent in lightness can be formed. This color filter can be used as a color filter used in display devices (for example, liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state imaging elements.

(none)

Claims (4)

A cyan curable resin composition comprising a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D), as the colorant (A), the cyan curable resin composition The product comprises: a dye (A1) having a silicon atom whose maximum absorption wavelength is 500nm~600nm in chloroform, and a cyan colorant, wherein the cyan colorant comprises CI Pigment Blue 15, 15:3, 15:4 , and one or more cyan pigments of 15:6, wherein the mass ratio of the content of the dye (A1) to the content of the cyan colorant (dye (A1)/cyan colorant) is not less than 0.01 and not more than 2, And wherein, the polymerization initiator (D) comprises a polymerization initiator represented by the following formula (d1),

In the formula (d1), R ^d1 represents an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent, a heterocyclic group having 3 to 36 carbon atoms which may have a substituent, or a heterocyclic group having 1 to 15 carbon atoms which may have a substituent A saturated hydrocarbon group, or an aralkyl group with a carbon number of 7 to 33 that may have substituents, the methylene group (-CH ₂ -) contained in the saturated hydrocarbon group or aralkyl group can be replaced by -O-, -CO -, -S-, -SO ₂ -or -NR ^d5 -, R ^d2 represents an aromatic hydrocarbon group with 6 to 18 carbons, a heterocyclic group with 3 to 36 carbons or a saturated hydrocarbon group with 1 to 10 carbons, R ^d3 Represents an aromatic hydrocarbon group with a carbon number of 6 to 18 that may have a substituent, a heterocyclic group with a carbon number of 3 to 36 that may have a substituent, R ^d4 represents an aromatic hydrocarbon group with a carbon number of 6 to 18 that may have a substituent, or an aromatic hydrocarbon group that may have a substituent An aliphatic hydrocarbon group with 1 to 15 carbon atoms having a substituent, the methylene group (-CH ₂ -) contained in the aliphatic hydrocarbon group can be replaced by -O-, -CO- or -S-, the The methine group (-CH<) contained in the aliphatic hydrocarbon group can be replaced by -PO ₃ <, the hydrogen atom contained in the aliphatic hydrocarbon group can be replaced by an OH group, R ^d5 represents carbon number 1~10 In the saturated hydrocarbon group, the methylene group (-CH ₂ -) contained in the saturated hydrocarbon group may be replaced with -O- or -CO-. The cyan curable resin composition according to claim 1, wherein the content of the colorant (A) is 3% by mass or more and 60% by mass or less with respect to the total amount of solid content of the cyan curable resin composition. A color filter formed from the cyan curable resin composition according to claim 1 or 2. A display device comprising the color filter according to claim 3.