TWI842831B - Colored curable resin composition, color filter and display device - Google Patents

Abstract

The present disclosure relates to a colored curable resin composition, which is a colored curable resin composition having a high film thickness retention rate of a color filter before and after post-baking, and a color filter obtained after post-baking whose line width does not become thicker, and comprises a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a thiol compound (E), wherein the colorant (A) comprises a xanthate dye, and the thiol compound (E) comprises a thiol compound containing an ether bond.

Description

Colored curable resin composition, color filter and display device

The present invention relates to a colored curable resin composition, a color filter and a display device.

Japanese Patent Application Publication No. 2018-101015 (Patent Document 1) describes a coloring resin composition for a color filter containing a coloring material represented by the following formula, a binder component, and a solvent.

[Prior art literature] [Patent literature]

[Patent Document 1] Japanese Patent Publication No. 2018-101015

[The problem that the invention wants to solve]

Regarding the colored curable resin composition used in the production of the color filter, if the film thickness retention rate of the obtained color filter before and after post-baking is to be improved, the line width of the pattern of the color filter obtained after post-baking tends to become thicker.

The purpose of the present invention is to provide a coloring curable resin composition that has a high film thickness retention rate of a color filter before and after post-baking (hereinafter, sometimes referred to as "film thickness retention rate") and does not thicken the line width of the color filter obtained after post-baking. [Means for Solving the Problem]

[1] A colored curable resin composition comprising a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a thiol compound (E), wherein the colorant (A) comprises a xanthate dye and the thiol compound (E) comprises a thiol compound containing an ether bond. [2] The colored curable resin composition as described in [1], wherein the thiol compound containing an ether bond is a compound represented by formula (I). [In the formula, A represents a residue of a polyol having m hydroxyl groups, a plurality of ^R1s bonded to oxygen atoms derived from the m hydroxyl groups each independently represents an alkylene group having 1 to 10 carbon atoms, m is an integer greater than 2, n is an integer greater than 2, and m≧n.] [3] The coloring curable resin composition as described in [2], wherein m is 2 to 10. [4] The coloring curable resin composition as described in [2] or [3], wherein the polyol is pentaerythritol or trihydroxymethylpropane. [5] The coloring curable resin composition as described in any one of [1] to [4], wherein the xanthate dye comprises a compound represented by formula (1a).

[In the formula (1a), R ^1a to R ^4a each independently represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent, and -CH ₂ - contained in the saturated hydrocarbon group may be substituted by -O-, -CO- or -NR ^11a -; R ^1a and R ^2a may together form a ring containing a nitrogen atom, and R ^3a and R ^4a may together form a ring containing a nitrogen atom; R ^5a represents a halogen atom, -OH, -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Za ⁺ , -CO ₂ H, -CO ₂ ^- Za ⁺ , -CO ₂ R ^8a , -SO ₃ R ^8a , -NR ^9a R ^10a or -SO ₂ NR ^9a R ^10a ; R ^6a and R ^{R 7a} each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; m represents an integer of 0 to 5; when m is 2 or more, multiple R ^5a's may be the same or different; a represents an integer of 0 or 1; Xa ^- represents a counterion; Za ⁺ represents ⁺ N(R ^11a ) ₄ , Na ⁺ or K ⁺ , and the four R ^11a's may be the same or different; R ^8a represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted by a halogen atom; R ^9a and R ^10a each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and -CH ₂ - contained in the saturated hydrocarbon group may be substituted by -O-, -CO-, -NH- or -NR ^8a -, and R ^9a and R R ^10a may bond with each other to form a 3- to 10-membered heterocyclic ring containing a nitrogen atom; R ^11a represents a hydrogen atom, a monovalent saturated alkyl group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms. ] [6] The colored curable resin composition as described in [5], wherein the compound represented by formula (1a) is a compound represented by formula (2a).

[In the formula (2a), R ^21a to R ^24a each independently represent a hydrogen atom, -R ^26a , a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent; R ^21a and R ^22a may together form a ring containing a nitrogen atom, and R ^23a and R ^24a may together form a ring containing a nitrogen atom; R ^25a represents a halogen atom, -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Za1 ⁺ , -NR ^28a R ^29a or -SO ₂ NHR ^26a ; m1 represents an integer of 0 to 5; when m1 is 2 or more, a plurality of R ^25a may be the same or different; a1 represents an integer of 0 or 1; Xa1 ^- represents an antiion; R ^28a and R 29a represent an integer of 0 to 5; ^{R 29a} each independently represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, wherein -CH ₂ - contained in the saturated hydrocarbon group may be substituted by -O- or -CO-; R ^28a and R ^29a may be bonded to each other to form a 3- to 10-membered heterocyclic ring containing a nitrogen atom; R ^26a represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a halogen atom or a carboxyl group; Za1 ⁺ represents ⁺ N(R ^27a ) ₄ , Na ⁺ or K ⁺ , and the four R ^27a may be the same or different; R ^27a represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a benzyl group.] [7] A color filter formed from the colored curable resin composition as described in any one of [1] to [6]. [8] A display device comprising the color filter as described in [7]. [Effects of the invention]

According to the present invention, a colored curable resin composition can be provided in which the film thickness retention rate of a color filter before and after post-baking is high and the line width of the color filter obtained after post-baking does not become wider.

<Coloring Curable Resin Composition> [Xanton Dye] Xanton dye is a dye containing a compound having a xanton skeleton in the molecule. Examples of xanthate dyes include: Color Index (C.I.) acid red 51 (hereinafter, C.I. acid red is omitted and only the number is recorded. The same applies to the others), 52, 87, 92, 94, 289, 388; C.I. acid violet 9, 30, 102; C.I. basic red 1 (rhodamine 6G), 2, 3, 4, 8; C.I. basic red 10, 11; C.I. basic violet 10 (rhodamine B), 11; C.I. solvent red 218; C.I. mordant red 27; C.I. reactive red 36 (rose Bengal) bengal) B); sulforhodamine G; xanthate dyes described in Japanese Patent Publication No. 2010-32999 and xanthate dyes described in Japanese Patent Publication No. 4492760, etc. Preferably, the dye is soluble in an organic solvent.

Among these, the xanthate dye is preferably a dye containing a compound represented by formula (1a) (hereinafter, sometimes referred to as "compound (1a)"). Compound (1a) may also be a tautomer thereof. When compound (1a) is used, the content of compound (1a) in the xanthate dye is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 90% by mass or more. In particular, it is preferred to use only compound (1a) as the xanthate dye. The compound represented by formula (1a) also includes tautomers thereof.

[In the formula (1a), R ^1a to R ^4a each independently represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent, and -CH ₂ - contained in the saturated hydrocarbon group may be substituted by -O-, -CO- or -NR ^11a -; R ^1a and R ^2a may together form a ring containing a nitrogen atom, and R ^3a and R ^4a may together form a ring containing a nitrogen atom; R ^5a represents a halogen atom, -OH, -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Za ⁺ , -CO ₂ H, -CO ₂ ^- Za ⁺ , -CO ₂ R ^8a , -SO ₃ R ^8a , -NR ^9a R ^10a or -SO ₂ NR ^9a R ^10a ; R ^6a and R ^{R 7a} each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; m represents an integer of 0 to 5; when m is 2 or more, multiple R ^5a's may be the same or different; a represents an integer of 0 or 1; Xa ^- represents a counterion; Za ⁺ represents ⁺ N(R ^11a ) ₄ , Na ⁺ or K ⁺ , and the four R ^11a's may be the same or different; R ^8a represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted by a halogen atom; R ^9a and R ^10a each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and -CH ₂ - contained in the saturated hydrocarbon group may be substituted by -O-, -CO-, -NH- or -NR ^8a -, and R ^9a and R ^10a may be bonded to form a heterocyclic ring having 3 to 10 members including a nitrogen atom; R ^11a represents a hydrogen atom, a monovalent saturated alkyl group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms.]

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ^1a to R ^4a include phenyl, toluyl, xylyl, mesityl, propylphenyl and butylphenyl.

Examples of the substituent which the aromatic hydrocarbon group may have include a halogen atom, a carboxyl group, a group containing a silicon atom, -R ^8a , -OH, -OR ^8a , -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Za ⁺ , -CO ₂ H, -CO ₂ R ^8a , -SR ^8a , -SO ₂ R ^8a , -SO ₃ R ^8a , and -SO ₂ NR ^9a R ^10a . Among these, the substituent is preferably a group containing a silicon atom, -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Za ⁺ , and -SO ₂ NR ^9a R ^10a , and more preferably a group containing a silicon atom, -SO ₃ ^- Za ⁺ , and -SO ₂ NR ^9a R ^10a . In this case, -SO ₃ ^- Za ⁺ is preferably -SO ₃ ^-+ N(R ^11a ) ₄ . When R ^1a to R ^4a are these groups, a color filter having less generation of foreign matter and excellent heat resistance can be formed from the colored curable resin composition of the present invention containing compound (1a). The silicon atom-containing group refers to a group containing a silicon atom, and may be, for example, a group represented by formula (ii). [In the formula, R ^50a represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms; a plurality of R ^50a groups may be the same or different.] R ^50a is preferably an alkoxy group having 1 to 4 carbon atoms. Specific examples of the group containing a silicon atom include silanyl groups such as trimethylsilanyloxy and triethylsilanyloxy; trimethoxysilyl groups, triethoxysilyl groups, and the like.

Examples of the monovalent saturated alkyl group having 1 to 20 carbon atoms in R ^1a to R ^4a and R ^8a to R ^11a include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, hexadecyl and eicosyl; branched alkyl groups such as isopropyl, isobutyl, isopentyl, neopentyl and 2-ethylhexyl; and alicyclic saturated alkyl groups having 3 to 20 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclodecyl.

As the substituent that the saturated alkyl group in R ^1a to R ^4a may have, for example, a carboxyl group, an aromatic alkyl group having 6 to 10 carbon atoms, a group containing a silicon atom, and a halogen atom can be listed. Examples of the aromatic alkyl group having 6 to 10 carbon atoms are the same as those of the aromatic alkyl group in R ^1a to R ^4a . Examples and preferred ranges of the group containing a silicon atom are the same as those described as the substituent that the aromatic alkyl group in R ^1a to R ^4a may have. As the substituent that the saturated alkyl group in R ^1a to R ^4a may have, a carboxyl group and a group containing a silicon atom are preferred.

Examples of the substituent that the saturated hydrocarbon group in R ^9a and R ^10a may have include a hydroxyl group, a group containing a silicon atom, and a halogen atom. Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms are the same as those described above. Examples and preferred ranges of the group containing a silicon atom are the same as those described above.

Examples of the ring formed by R ^1a and R ^2a together and the ring formed by R ^3a and R ^4a together include the following.

Examples of -OR ^8a include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy, and eicosyloxy.

Examples of -CO ₂ R ^8a include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, t-butoxycarbonyl, hexyloxycarbonyl and eicosyloxycarbonyl.

Examples of -SR ^8a include methyl alkyl, ethyl alkyl, butyl alkyl, hexyl alkyl, decyl alkyl and eicosyl alkyl. Examples of -SO ₂ R ^8a include methyl sulfonyl, ethyl sulfonyl, butyl sulfonyl, hexyl sulfonyl, decyl sulfonyl and eicosyl sulfonyl. Examples of -SO ₃ R ^8a include methoxy sulfonyl, ethoxy sulfonyl, propoxy sulfonyl, t-butoxy sulfonyl, hexyl sulfonyl and eicosyl sulfonyl.

Examples of _-SO2NR9aR10a include ^{sulfonylamine} ; N-methylsulfonylamine, N ^- ethylsulfonylamine, N-propylsulfonylamine, N-isopropylsulfonylamine, N-butylsulfonylamine, N-tert-butylsulfonylamine, N-pentylsulfonylamine, N-(1,1-dimethylpropyl)sulfonylamine, N-(2,2-dimethylpropyl)sulfonylamine, N-(2-methylbutyl)sulfonylamine; N-monosubstituted sulfonylamine groups such as sulfonylamine, N-cyclopentylsulfonylamine, N-hexylsulfonylamine, N-(1,3-dimethylbutyl)sulfonylamine, N-heptylsulfonylamine, N-(1-methylhexyl)sulfonylamine, N-(2-ethylhexyl)sulfonylamine, and N-(1,1,2,2-tetramethylbutyl)sulfonylamine; N,N-disubstituted sulfonylamines such as N,N-dimethylsulfonylamine, N,N-ethylmethylsulfonylamine, N,N-diethylsulfonylamine, N,N-propylmethylsulfonylamine, N,N-isopropylmethylsulfonylamine, N,N-tert-butylmethylsulfonylamine, N,N-butylethylsulfonylamine, N,N-bis(1-methylpropyl)sulfonylamine, and N,N-heptylmethylsulfonylamine.

R ^5a is preferably a halogen atom, -CO ₂ H, -CO ₂ ^- Za ⁺ , -CO ₂ R ^8a , -SO ₃ ^- , -SO ₃ ^- Za ⁺ , -SO ₃ H or SO ₂ NHR ^9a , and more preferably -SO ₃ ^- , -SO ₃ ^- Za + , -SO ₃ H, -NR ^9a R ^10a or SO ₂ NHR ^9a . R ^9a and R ^10a are each independently preferably a saturated alkyl group having 1 to 6 carbon atoms which may have a substituent.

Examples of the alkyl group having 1 to 6 carbon atoms in R ^6a and R ^7a include methyl, ethyl, propyl, butyl, pentyl, hexyl, and heptyl.

Examples of the aralkyl group having 7 to 10 carbon atoms in R ^11a include benzyl, phenylethyl, and phenylbutyl.

Za ⁺ is ⁺ N(R ^11a ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N(R ^11a ) ₄ . As the ⁺ N(R ^11a ) ₄ , at least two of the four R ^11a are preferably monovalent saturated alkyl groups having 5 to 20 carbon atoms. The total carbon number of the four R ^11a is preferably 20 to 80, more preferably 20 to 60. When ⁺ N(R ^11a ) ₄ is present in compound (1a), if R ^11a is one of these groups, a color filter having less foreign matter can be formed from the colored curable resin composition of the present invention containing compound (1a). Examples of the anti-ion represented by ^Xa- include halide ions, and anti-ions represented by formula (y1) and formula (y2).

[In formula (y1), ^RB1 represents a fluorinated alkyl group having 1 to 12 carbon atoms; In formula (y2), ^RB2 and ^RB3 each independently represent a halogen atom or a fluorinated alkyl group having 1 to 12 carbon atoms.] Examples of the halide ion include fluoride ions, chloride ions, bromide ions, and iodide ions.

Specific examples of the fluorinated alkyl group having 1 to 12 carbon atoms represented by ^RB1 include fluoromethyl, difluoromethyl, trifluoromethyl, 1,1,2,2,2-pentafluoroethyl, 2,2,2-trifluoroethyl, 3-(trifluoromethyl)-3,4,4,4-pentafluorobutyl, perfluoroethyl, perfluoropropyl, perfluoroisopropyl, perfluorobutyl, perfluorosec-butyl, perfluorotert-butyl, perfluoropentyl and perfluorohexyl. Preferred examples include groups in which all hydrogen atoms are substituted with fluorine atoms (i.e., perfluoroalkyl groups), and more preferred examples include perfluoroalkyl groups having 1 to 4 carbon atoms.

Examples of the halogen atom represented by ^RB2 and ^RB3 include fluorine, chlorine, bromine and iodine, preferably fluorine. Examples of the fluorinated alkyl group having 1 to 12 carbon atoms represented by ^RB2 and ^RB3 include the same as the fluorinated alkyl group represented by ^RB1 , preferably a perfluoroalkyl group having 1 to 4 carbon atoms. ^RB2 and ^RB3 may be bonded to each other to form a ring including _-SO2 -N ^-- _SO2- .

As compound (1a), a compound represented by formula (2a) (hereinafter, sometimes referred to as "compound (2a)") is preferred. Compound (2a) may be a tautomeric isomer thereof.

[In formula (2a), R ^21a to R ^24a each independently represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent; R ^21a and R ^22a may together form a ring containing a nitrogen atom, and R ^23a and R ^24a may together form a ring containing a nitrogen atom; R ^25a represents a halogen atom, -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Za1 ⁺ , -NR ^28a R ^29a or -SO ₂ NHR ^26a ; m1 represents an integer of 0 to 5; when m1 is 2 or more, a plurality of R ^25a may be the same or different; a1 represents an integer of 0 or 1; Xa1 ^- represents an antiion; R ^28a and R 29a represent an integer of 0 to 5; ^{R 29a} each independently represents a hydrogen atom or a monovalent saturated alkyl group having 1 to 10 carbon atoms which may have a substituent, wherein -CH ₂ - contained in the saturated alkyl group may be substituted by -O- or -CO-, and R ^28a and R ^29a may be bonded to each other to form a 3- to 10-membered heterocyclic ring containing a nitrogen atom; R ^26a represents a monovalent saturated alkyl group having 1 to 20 carbon atoms which may have a halogen atom or a carboxyl group; Za1 ⁺ represents ⁺ N(R ^27a ) ₄ , Na ⁺ or K ⁺ , and the four R ^27a may be the same or different; R ^27a represents a monovalent saturated alkyl group having 1 to 20 carbon atoms or a benzyl group.]

As the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ^21a to R ^24a , there may be exemplified the same groups as those exemplified as the aromatic hydrocarbon groups in R ^1a to R ^4a . The hydrogen atom contained in the aromatic hydrocarbon group may be substituted by a carboxyl group, a silicon atom-containing group, -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Za1 ⁺ , -SO ₃ R ^26a or -SO ₂ NHR ^26a . As a combination of R ^21a to R ^24a , it is preferred that R ^21a and R ^23a are each independently a hydrogen atom or a saturated hydrocarbon group having 1 to 10 carbon atoms (the saturated hydrocarbon group may have a halogen atom, a group containing a silicon atom or a carboxyl group), and R ^22a and R ^24a are each independently a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms (the hydrogen atom contained in the aromatic hydrocarbon group may be substituted by a carboxyl group, a group containing a silicon atom, -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Za1 ⁺ , -SO ₃ R ^26a or -SO ₂ NHR ^26a ). A more preferred combination is that R ^21a and R ^23a are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms (the alkyl group may have a halogen atom, a group containing a silicon atom, or a carboxyl group), and R ^22a and R ^24a are monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms (the hydrogen atom contained in the aromatic hydrocarbon group may be substituted by a carboxyl group, a group containing a silicon atom, -SO ₃ ^- Za1 ⁺ , or -SO ₂ NHR ^26a ). When R ^21a to R ^24a are these groups, a color filter having excellent heat resistance can be formed from the colored curable resin composition of the present invention containing compound (2a). Examples and preferred ranges of the group containing a silicon atom are the same as those in the description of formula (1a).

As the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent in R ^21a to R ^24a , the same groups as those listed as the aromatic hydrocarbon groups in R ^1a to R ^4a may be cited. The hydrogen atom contained in the aromatic hydrocarbon group may be substituted by a group containing a silicon atom, -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Za1 ⁺ , -SO ₃ R ^26a or -SO ₂ NHR ^26a . Examples and preferred ranges of the group containing a silicon atom are the same as those in the description of formula (1a). Examples of R ^28a and R ^29a may be the same as those of R ^9a and R ^10a in formula (1a).

Examples of the ring containing a nitrogen atom formed by R ^21a and R ^22a and the ring containing a nitrogen atom formed by R ^23a and R ^24a include the same rings as those formed by R ^1a and R ^2a . Among them, an aliphatic heterocyclic ring is preferred. Examples of the aliphatic heterocyclic ring include the following.

As the monovalent saturated alkyl group having 1 to 20 carbon atoms in R ^26a and R ^27a , the same groups as those listed as the saturated alkyl group in R ^8a to R ^11a can be cited. When R ^21a to R ^24a are monovalent saturated alkyl groups having 1 to 20 carbon atoms which may have a substituent, R ^21a to R ^24a are each independently preferably a methyl group or an ethyl group. In addition, as R ^26a in -SO ₃ R ^26a and -SO ₂ NHR ^26a , a branched chain alkyl group having 3 to 20 carbon atoms is preferred, a branched chain alkyl group having 6 to 12 carbon atoms is more preferred, and a 2-ethylhexyl group is further preferred. When R ^26a is any of these groups, a color filter with less generation of foreign matter can be formed from the colored curable resin composition of the present invention containing the compound (2a).

Za1 ⁺ is ⁺ N(R ^27a ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N(R ^27a ) ₄ . As the ⁺ N(R ^27a ) ₄ , at least two of the four R ^27a are preferably monovalent saturated alkyl groups having 5 to 20 carbon atoms. The total carbon number of the four R ^27a is preferably 20 to 80, more preferably 20 to 60. When ⁺ N(R ^27a ) ₄ is present in compound (2a), if R ^27a is one of these groups, a color filter with less generation of foreign matter can be formed from the colored curable resin composition of the present invention containing compound (2a).

The counter ion represented by ^Xa1- is the same as the examples and preferred ranges in the above description of ^Xa- .

In addition, the compound (1a) is preferably a compound represented by the formula (3a) (hereinafter, sometimes referred to as "compound (3a)"). The compound (3a) may be a tautomeric isomer thereof.

[In formula (3a), R ^31a and R ^32a each independently represent a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, the hydrogen atom contained in the saturated hydrocarbon group may be substituted by an aromatic hydrocarbon group having 6 to 10 carbon atoms, a carboxyl group, a group containing a silicon atom or a halogen atom, the hydrogen atom contained in the aromatic hydrocarbon group may be substituted by ^{a group containing a silicon atom or an alkoxy group having 1 to 3 carbon atoms, and the -CH 2 - contained in the saturated hydrocarbon group may be substituted by -O-, -CO- or -NR 11a -; R 33a and} _R ^{34a each independently} represent ^a group containing a silicon atom, an alkyl group having 1 to 4 carbon atoms, an alkylalkyl group ^having 1 to 4 carbon atoms or an alkylsulfonyl group having 1 to 4 carbon atoms; R ^{31a and} R ^33a may together form a ring containing ^a nitrogen atom, R R ^32a and R ^34a may together form a ring containing a nitrogen atom; p and q each independently represent an integer of 0 to 5; when p is 2 or more, multiple R ^33a may be the same or different, and when q is 2 or more, multiple R ^34a may be the same or different; R ^11a has the same meaning as described above.]

Examples of the monovalent saturated alkyl group having 1 to 10 carbon atoms in R ^31a and R ^32a include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl. Examples of the aromatic alkyl group having 6 to 10 carbon atoms which may have a substituent include phenyl, toluyl, xylyl, mesityl, propylphenyl, and butylphenyl. Examples of the alkoxy group having 1 to 3 carbon atoms include methoxy, ethoxy, and propoxy. R ^31a and R ^32a are each independently preferably a monovalent saturated alkyl group having 1 to 3 carbon atoms (the saturated alkyl group may have a halogen atom or a carboxyl group). Examples and preferred ranges of the group containing a silicon atom are the same as those in the description of formula (1a).

Examples of the alkyl group having 1 to 4 carbon atoms in R ^33a and R ^34a include methyl, ethyl, propyl, butyl, isopropyl, isobutyl, sec-butyl, tert-butyl, and the like. Examples of the alkylalkyl group having 1 to 4 carbon atoms in R ^33a and R ^34a include methylalkyl, ethylalkyl, propylalkyl, butylalkyl, and isopropylalkyl. Examples of the alkylsulfonyl group having 1 to 4 carbon atoms in R ^{33a and R 34a include methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, and isopropylsulfonyl. R 33a and R 34a are each} independently preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group. Examples and preferred ranges of the silicon atom-containing group in R ^33a and R ^34a are the same as those in the description of the above formula (1a).

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

Examples of compound (1a) include compounds represented by formula (1-1) to formula (1-97). In the formula, R ^40a represents a monovalent saturated alkyl group having 1 to 20 carbon atoms, preferably a branched chain alkyl group having 6 to 12 carbon atoms, and more preferably a 2-ethylhexyl group. R ^26a has the same meaning as R ^26a in formula (2a).

Among the compounds, the compounds represented by formula (1-1) to formula (1-14), formula (1-27) to formula (1-75) and formula (1-92) to formula (1-97) are equivalent to compound (2a), and the compounds represented by formula (1-15) to formula (1-26) and formula (1-76) to formula (1-91) are equivalent to compound (3a).

The xanthate dye may be a commercially available xanthate dye (e.g., "Chugai Aminol Fast Pink R-H/C" manufactured by Chugai Chemical Co., Ltd., "Rhodamin 6G" manufactured by TAOKA Chemical Industry Co., Ltd.). Alternatively, the commercially available xanthate dye may be used as a starting material and synthesized with reference to Japanese Patent Publication No. 2010-32999.

The content of the xanthate dye in the coloring agent (A) based on the total amount of the solid components in the coloring agent (A) may be, for example, 0.1 mass % to 100 mass %, more preferably 0.1 mass % to 99.0 mass %, further preferably 0.5 mass % to 90.0 mass %, particularly preferably 1.0 mass % to 50.0 mass %, and even more preferably 1.5 mass % to 30.0 mass %.

In this specification, the "total amount of solid components in the coloring agent (A)" refers to the total amount of components after removing the solvent (F) from the coloring agent (A). In the present invention, the total amount of solid components and the content of each component relative to this can be measured by a known analytical method such as liquid chromatography or gas chromatography.

[1] Colorant (A) The content of the colorant (A) in the colorant curable resin composition is preferably 5% by mass or more and 80% by mass or less, more preferably 5% by mass or more and 70% by mass or less, and even more preferably 5% by mass or more and 60% by mass or less, relative to the total amount of solid components in the colorant curable resin composition. When the content of the colorant (A) is within the above range, the desired light distribution or color concentration can be obtained.

In this specification, the "total amount of solid components in the coloring curable resin composition" means the total amount of components after removing the solvent (F) from the coloring curable resin composition.

When the coloring curable resin composition contains a solvent (hereinafter, also referred to as solvent (F)), a coloring agent-containing liquid containing a coloring agent (A) and a solvent (F) may be prepared in advance, and the coloring agent-containing liquid may be used to prepare the coloring curable resin composition. When the coloring agent (A) is not dissolved in the solvent (F), the coloring agent-containing liquid may be prepared in the form of a dispersion by dispersing the coloring agent (A) in the solvent (F) and mixing the two. The coloring agent-containing liquid may contain a part or all of the solvent (F) contained in the coloring curable resin composition.

The content of the solid component in the colorant-containing liquid relative to the total amount of the colorant-containing liquid is preferably 0.1 mass % or more and 99.9 mass % or less, more preferably 1 mass % or more and 90 mass % or less, further preferably 1 mass % or more and 60 mass % or less, and particularly preferably 3 mass % or more and 50 mass % or less.

The content of the colorant (A) in the colorant-containing liquid is preferably 0.01 mass % or more and 100 mass % or less, more preferably 0.1 mass % or more and 99.9 mass % or less, further preferably 1 mass % or more and 99 mass % or less, and particularly preferably 10 mass % or more and 90 mass % or less, in the total amount of solid components in the colorant-containing liquid.

In this specification, the "total amount of solid components in the colorant-containing liquid" refers to the total amount of components after removing the solvent (F) from the colorant-containing liquid.

Regarding the colorant (A), the colorant (A) can be uniformly dispersed in the colorant-containing liquid by containing a dispersant and performing a dispersion treatment.

As the dispersant, there can be cited surfactants, which can be any of cationic, anionic, nonionic and amphoteric surfactants. Specifically, there can be cited polyester-based, polyamine-based and acrylic-based surfactants. These dispersants can be used alone or in combination of two or more. Dispersants that are indicated by trade names include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Flowlen (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (registered trademark) (manufactured by Zeneca Co., Ltd.), EFKA (registered trademark) (manufactured by BASF Co., Ltd.), Ajisper (registered trademark) (manufactured by Ajinomoto Fine-Techno Co., Ltd.), Disperbyk (registered trademark) (manufactured by BYK-Chemie Co., Ltd.), and BYK (registered trademark) (manufactured by BYK-Chemie Co., Ltd.).

In order to prepare the coloring agent-containing liquid, when a dispersant is used, the amount of the dispersant (solid content) used is preferably 5 parts by mass or more and 100 parts by mass or less, and more preferably 5 parts by mass or more and 50 parts by mass or less, relative to 100 parts by mass of the coloring agent (A). If the amount of the dispersant used is within the above range, there is a tendency to obtain a coloring agent-containing liquid in a more uniformly dispersed state.

The colorant (A) may further include a colorant other than the xanthate dye [hereinafter, sometimes referred to as the colorant (A1)]. The colorant (A1) may include at least one selected from the group consisting of dyes other than the xanthate dye and pigments.

As the dye contained in the coloring agent (A1), known dyes can be used, and solvent dyes, acid dyes, direct dyes, mordant dyes, etc. can be listed. For example, compounds of dyes classified as solvent, acid, basic, reactive, direct, disperse, mordant, or vat in the Dye Index (published by The Society of Dyers and Colourists) or known dyes listed in the Dyeing Notes (Dyeing Company) can be listed. The dye can be appropriately selected according to the spectral spectrum of the desired color filter. These dyes can be used alone or in combination of two or more. The dye is preferably an organic solvent-soluble dye.

Specific examples of dyes include: C.I. Solvent Yellow 4 (hereinafter, the number is omitted and only the number is recorded), 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 117, 162, 163, 167, 189, C.I. Solvent Red 45, 49, 111, 125, 130, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 218, 222, 227, 230, 245, 247, C.I. Solvent Orange orange) 2, 7, 11, 15, 26, 56, 77, 86, C.I. solvent violet (solvent violet) 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60, C.I. solvent blue (solvent blue) 4, 5, 14, 18, 35, 36, 37, 45, 58, 59, 59: 1, 63, 67, 68, 69, 70, 78, 79, 83, 90, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139, C.I. solvent green (solvent green) 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35 and other C.I. solvent dyes; C.I. acid yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 1 61, 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, 33, 34, 35, 37, 40, 42, 44, 50, 51, 52, 57, 66, 73, 76, 80, 87, 88, 91, 92, 94, 95, 97, 98, 103, 106, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 155, 158, 160, 172, 176, 182, 183, 195, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 68, 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, 15, 16, 17, 19, 21, 23, 24, 25, 30, 34, 38, 49, 72, 102, C.I. Acid Blue 1, 3, 5, 7, 9, 11, 13, 15, 17, 18, 22, 23, 24, 25, 26, 27, 29, 34, 38, 40, 41, 42, 43, 45, 48, 51, 54, 59, 60, 62, 70, 72, 74, 75, 78, 80, 82, 83, 86, 87, 88, 90, 90: 1, 91, 92 , 93, 93:1, 96, 99, 100, 102, 103, 104, 108, 109, 110, 112, 113, 117, 119, 120, 123, 126, 127, 129, 130, 131, 138, 140, 142, 143, 147, 150, 151, 154, 158, 161, 166, 167, 168, 170, 171, 175, 182, 183, 184, 187, 192, 199, 203, 204, 205 , 210, 213, 229, 234, 236, 242, 243, 256, 259, 267, 269, 278, 280, 285, 290, 296, 315, 324: 1, 335, 340, C.I. Acid Green 1, 3, 5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 22, 25, 27, 28, 41, 50, 50: 1, 58, 63, 65, 80, 104, 105, 106, 109 and other C.I. acid dyes; C.I. Direct Connect yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141, C.I. Direct red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213 、218、220、221、222、232、233、234、241、243、246、250， C.I. Direct Orange 26、34、39、41、46、50、52、56、57、61、64、65、68、70、96、97、106、107， C.I. Direct Purple 47、52、54、59、60、65、66、79、80、81、82、84、89、90、93、95、96、103、104， C.I. Direct Blue 1、 2, 3, 6, 8, 15, 22, 25, 28, 29, 40, 41, 42, 47, 52, 55, 57, 71, 76, 77, 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 3, 164, 165, 166, 167, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196, 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 242, 243, 244, 245, 246, 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293, C.I. Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82 and other C.I. Direct Dyes; C.I. Disperse Yellow 51, 54, 76, C.I. Disperse Violet 26, 27, C.I. Disperse Blue 1, 14, 56, 60 and other C.I. Disperse Dyes; C.I. Alkaline Red 1, 10, C.I. Alkaline Blue 1 , 3, 5, 7, 9, 19, 21, 22, 24, 25, 26, 28, 29, 40, 41, 45, 47, 54, 58, 59, 60, 64, 65, 66, 67, 68, 81, 83, 88, 89, C.I. Alkaline Violet 2, C.I. Alkaline Red 9, C.I. Alkaline Green 1 and other C.I. Alkaline Dyes; C.I. Reactive Yellow 2, 76, 116, C.I. Reactive Orange 16, C.I. Reactive Red 36 and other C.I. Reactive Dyes; C.I. Mordant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65, C.I. Media Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 27, 29, 30, 32, 33, 36, 37, 38, 39, 41, 42, 43, 45, 46, 48, 52, 53, 56, 62, 63, 71, 74, 76, 78, 85, 86, 88, 90, 94, 95, C.I. Media 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. Medium Violet 1, 1: 1, 2, 3, 4, 5, 6, 7, 8, 10, 11, 14, 15, 16, 17, 18, 19, 21, 22, 23, 24, 27, 28, 30, 31, 32, 33, 36, 37, 39, 40, 41, 44, 45, 47, 48, 49, 53, 58, C.I. .C.I. mordant blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, 84, C.I. mordant green 1, 3, 4, 5, 10, 13, 15, 19, 21, 23, 26, 29, 31, 33, 34, 35, 41, 43, 53 and other C.I. mordant dyes; C.I. vat green 1 and other C.I. vat dyes, etc.

In addition, as dyes, according to the chemical structure, there can be listed: triarylmethane dyes, azo dyes, cyanine dyes, triphenylmethane dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azo methine dyes, squarylium dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, nitro dyes, tetrazo porphyrin dyes, etc. In the coloring curable resin composition of the present invention, the coloring agent (A) preferably contains a triarylmethane dye as a dye. If the coloring agent (A) contains a triarylmethane dye, there is a tendency that the brightness of the obtained color filter is improved, so it is preferred.

Examples of the pigment contained in the coloring agent (A1) include organic pigments, inorganic pigments, and compounds classified as pigments in the Colour Index (published by The Society of Dyers and Colourists). The pigments may be used alone or in combination of two or more.

As the pigments mentioned above, there are: C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 179, 180, 192, 202, 208, 209, 215, 216, 224, 242, 254, 255, 264, 265, 266, 268, 269, 273, 291, C.I. Pigment Yellow 1, 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 , 180, 185, 194, 214, 231 and other yellow pigments; C.I. pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments; C.I. pigment blue 15, 15:3, 15:4, 15:6, 21, 28, 60, 64 and 76 and other blue pigments; C.I. pigment purple 1, 14, 19, 23, 29, 32, 33, 36, 37, 38 and other purple pigments; C.I. pigment green 7, 10, 15, 25, 36, 47, 58, 59 and other green pigments; C.I. pigment brown 23, 25, 28 and other brown pigments; C.I. pigment black 1, 7 and other black pigments, etc.

The pigment may be subjected to rosin treatment, surface treatment using pigment derivatives with acidic or alkaline groups, grafting treatment on the pigment surface using polymer compounds, micronization treatment using sulfuric acid micronization method, or cleaning treatment using organic solvents or water to remove impurities, or removal treatment of ionic impurities using ion exchange method, etc. The particle size of the pigment is preferably uniform.

By including a pigment dispersant and performing a dispersion treatment, a pigment dispersion liquid in which the pigment is uniformly dispersed in the pigment dispersant solution can be prepared. The pigments can be dispersed individually or a plurality of pigments can be mixed and dispersed.

Examples of pigment dispersants include cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic pigment dispersants. These pigment dispersants may be used alone or in combination of two or more. Examples of pigment dispersants include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Flowlen (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Zeneca Co., Ltd.), EFKA (manufactured by BASF Co., Ltd.), Ajisper (manufactured by Ajinomoto Fine-Techno Co., Ltd.), and Disperbyk (manufactured by BYK-Chemie Co., Ltd.).

When a pigment dispersant is used, its usage amount is preferably 100 parts by mass or less, more preferably 5 parts by mass or more and 50 parts by mass or less relative to 100 parts by mass of the pigment. If the usage amount of the pigment dispersant is within the above range, there is a tendency to obtain a uniformly dispersed pigment dispersion.

When the colorant (A) includes the colorant (A1), the content of the colorant (A1) in the colorant (A) may be, for example, 0.1% by mass or more and 99.9% by mass or less, more preferably 0.1% by mass or more and 99% by mass or less, and even more preferably 0.5% by mass or more and 97% by mass or less, based on the total amount of the solid components of the colorant (A). When the coloring agent (A) contains a triarylmethane dye, the content of the triarylmethane dye in the coloring agent (A) may be within the range of the content of the coloring agent (A1), preferably 98% by mass or less, more preferably 95% by mass or less, and more preferably 10% by mass or more, more preferably 20% by mass or more, based on the total amount of the solid content of the coloring agent (A). Furthermore, when the coloring agent (A) contains a triarylmethane dye, the coloring agent (A) may contain only xanthate dyes and triarylmethane dyes, and may also contain other coloring agents (A1).

[2] Resin (B) The coloring curable resin composition of the present invention contains one or more resins (B). The resin (B) is preferably an alkali-soluble resin. Alkali-solubility refers to the property of being soluble in an aqueous solution of an alkali compound, i.e., a developer. Examples of the resin (B) include the following resins [K1] to [K6].

Resin [K1]: A copolymer of at least one (a) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides [hereinafter, sometimes referred to as "(a)"], and a monomer (b) having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenic unsaturated bond [hereinafter, sometimes referred to as "(b)"]. Resin [K2]: A copolymer of (a) and (b), and a monomer (c) copolymerizable with (a) (which is different from (a) and (b)) [hereinafter, sometimes referred to as "(c)"]. Resin [K3]: A copolymer of (a) and (c). Resin [K4]: A resin obtained by reacting (b) with a copolymer of (a) and (c). Resin [K5]: A resin obtained by reacting a copolymer of (a), (b) and (c). Resin [K6]: A resin obtained by reacting a copolymer of (a), (b) and (c), and then reacting the copolymer with a carboxylic anhydride.

As (a), specifically, there can be listed: (meth)acrylic acid, crotonic acid, o-vinylbenzoic acid, m-vinylbenzoic acid, p-vinylbenzoic acid and other unsaturated monocarboxylic acids; cis-butenedioic acid, fumaric acid, citric acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, 1,4-cyclohexene dicarboxylic acid and other unsaturated dicarboxylic acids; methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy -5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene and other bicyclic unsaturated compounds containing a carboxyl group; Malic anhydride, Conic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic 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 (bicycloheptene dicarboxylic anhydride (himic anhydride)) and other unsaturated dicarboxylic anhydrides; unsaturated mono[(meth)acryloxyalkyl]esters of divalent or higher polycarboxylic acids such as mono[2-(meth)acryloxyethyl]succinate and mono[2-(meth)acryloxyethyl]phthalate; unsaturated (meth)acrylic acids containing hydroxyl and carboxyl groups in the same molecule such as α-(hydroxymethyl)(meth)acrylic acid. Among them, (a) is preferably (meth)acrylic acid, maleic anhydride, etc., and more preferably acrylic acid and maleic anhydride from the viewpoint of copolymerization reactivity or solubility in alkaline aqueous solution.

In this specification, the term "(meth)acrylic group" refers to at least one selected from the group consisting of acrylic group and methacrylic group. The same applies to "(meth)acryl" and "(meth)acrylate".

(b) refers to a polymerizable compound having a cyclic ether structure with 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxycyclopropane ring, an oxycyclobutane ring and a tetrahydrofuran ring (oxycyclopentane ring)) and an ethylenic unsaturated bond. (b) is preferably a monomer having a cyclic ether structure with 2 to 4 carbon atoms and a (meth)acryloyloxy group. Examples of (b) include a monomer (b1) having an oxycyclopropyl group and an ethylenic unsaturated bond [hereinafter, sometimes referred to as "(b1)"], a monomer (b2) having an oxycyclobutyl group and an ethylenic unsaturated bond [hereinafter, sometimes referred to as "(b2)"], and a monomer (b3) having a tetrahydrofuranyl group and an ethylenic unsaturated bond [hereinafter, sometimes referred to as "(b3)"].

Examples of (b1) include a monomer (b1-1) having a structure formed by oxidizing an unsaturated aliphatic hydrocarbon ring [hereinafter, sometimes referred to as "(b1-1)"] and a monomer (b1-2) having a structure formed by oxidizing an unsaturated alicyclic hydrocarbon ring [hereinafter, sometimes referred to as "(b1-2)"].

Examples of (b1-1) include: (meth) glycidyl acrylate, (meth) acrylate β-methyl glycidyl acrylate, (meth) acrylate β-ethyl glycidyl acrylate, glycidyl vinyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, α-methyl-o-vinyl benzyl glycidyl ether, α-methyl-m-vinyl benzyl glycidyl ether, α-methyl-p-vinyl benzyl glycidyl ether, 2,3-bis(glycidyloxymethyl)benzene Ethylene, 2,4-bis(glycidyloxymethyl)styrene, 2,5-bis(glycidyloxymethyl)styrene, 2,6-bis(glycidyloxymethyl)styrene, 2,3,4-tri(glycidyloxymethyl)styrene, 2,3,5-tri(glycidyloxymethyl)styrene, 2,3,6-tri(glycidyloxymethyl)styrene, 3,4,5-tri(glycidyloxymethyl)styrene, 2,4,6-tri(glycidyloxymethyl)styrene, and the like.

Examples of (b1-2) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (e.g., Celloxide 2000; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., Cyclomer A400; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., Cyclomer M100; manufactured by Daicel Chemical Industries, Ltd.), compounds represented by formula (B-I), compounds represented by formula (B-II), and the like.

[In formula (BI) and formula (B-II), ^Ra and ^Rb each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, wherein the hydrogen atom contained in the alkyl group may be substituted by a hydroxyl group; ^X1 and ^X2 each independently represent a single bond, * ^-Rc- , * ^-Rc -O-, *-Rc- ^S- , or * ^-Rc -NH-; ^Rc represents an alkanediyl group having 1 to 6 carbon atoms; and * represents a bond with O.]

Examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, etc. Examples of the alkyl group in which a hydrogen atom is substituted with a hydroxyl group include hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxy-1-methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, etc. ^Ra and ^Rb are preferably a hydrogen atom, methyl, hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, and more preferably a hydrogen atom or methyl. Examples of the alkanediyl group constituting R ^c include a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, and a hexane-1,6-diyl group.

^X1 and ^X2 are preferably a single bond, a methylene group, an ethylidene group, a * _-CH2 -O- (* represents a bond with O) group, and a * _{-CH2CH2 -} O- group, and more preferably a single bond and a * _{-CH2CH2 -} O- group. Specific examples of the compound represented by formula (BI) include compounds represented by formula (BI-1) to formula (BI-15), preferably compounds represented by formula (BI-1), formula (BI-3), formula (BI-5), formula (BI-7), formula (BI-9), and formula (BI-11) to formula (BI-15), and more preferably compounds represented by formula (BI-1), formula (BI-7), formula (BI-9), and formula (BI-15).

As specific examples of the compound represented by formula (B-II), there are compounds represented by formula (B-II-1) to formula (B-II-15), preferably compounds represented by formula (B-II-1), formula (B-II-3), formula (B-II-5), formula (B-II-7), formula (B-II-9), formula (B-II-11) to formula (B-II-15), and more preferably compounds represented by formula (B-II-1), formula (B-II-7), formula (B-II-9) and formula (B-II-15).

The compound represented by formula (B-I) and the compound represented by formula (B-II) can be used alone. They can be mixed in any ratio. When mixed, the mixing ratio is preferably 5:95 to 95:5, more preferably 10:90 to 90:10, and further preferably 20:80 to 80:20 in terms of formula (B-I): formula (B-II) [molar ratio]. The monomer (b2) having an oxocyclobutyl group and an ethylenic unsaturated bond is preferably a monomer having an oxocyclobutyl group and a (meth)acryloyloxy group. Preferred examples of (b2) include 3-methyl-3-(methyl)acryloyloxymethyloxycyclobutane, 3-ethyl-3-(methyl)acryloyloxymethyloxycyclobutane, 3-methyl-3-(methyl)acryloyloxyethyloxycyclobutane, and 3-ethyl-3-(methyl)acryloyloxyethyloxycyclobutane. The monomer (b3) having a tetrahydrofuranyl group and an ethylenic unsaturated bond is preferably a monomer having a tetrahydrofuranyl group and a (meth)acryloyloxy group. Preferred examples of (b3) include tetrahydrofurfuryl acrylate (e.g., Viscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

Specific examples of (c) include: methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl (meth)acrylate [in the technical field, it is commonly referred to as "dicyclopentyl (meth)acrylate"]. In addition, (meth)acrylates such as "tricyclodecyl (meth)acrylate"], tricyclo[5.2.1.0 ^2,6 ]decen-8-yl (meth)acrylate [in the technical field, it is commonly referred to as "dicyclopentenyl (meth)acrylate"], dicyclopentanyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, benzyl (meth)acrylate, etc.; (meth)acrylates containing a hydroxyl group such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconate; Bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxy 5,6-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-di(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-di(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene [2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, 5-tert-butoxycarbonylbicyclo[2 Bicyclic unsaturated compounds such as bis(cyclohexyloxycarbonyl)bis(cyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbis(cyclo[2.2.1]hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bis(cyclo[2.2.1]hept-2-ene and 5,6-bis(cyclohexyloxycarbonyl)bis(cyclo[2.2.1]hept-2-ene); Dicarbonyl imide derivatives such as N-phenyl cis-1-butenediamide, N-cyclohexyl cis-1-butenediamide, N-benzyl cis-1-butenediamide, N-succinimidyl-3-cis-1-butenediamide benzoate, N-succinimidyl-4-cis-1-butenediamide butyrate, N-succinimidyl-6-cis-1-butenediamide hexanoate, N-succinimidyl-3-cis-1-butenediamide propionate, and N-(9-acridinyl)cis-1-butenediamide; Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, etc. Among them, from the viewpoint of copolymerization reactivity and heat resistance, (c) is preferably benzyl (meth)acrylate, tricyclodecyl (meth)acrylate, styrene, N-phenyl cis-1-butylene diimide, N-cyclohexyl cis-1-butylene diimide, N-benzyl cis-1-butylene diimide, bicyclo[2.2.1]hept-2-ene, etc. Moreover, from the viewpoint of excellent developing property during pattern formation, (c) is more preferably benzyl (meth)acrylate and tricyclodecyl (meth)acrylate.

Among all the structural units constituting the resin [K1], the ratio of the structural units derived from each of them in the resin [K1] is preferably in the following range. Structural units derived from (a): 2 mol% to 50 mol% (preferably 10 mol% to 45 mol%); Structural units derived from (b), especially structural units derived from (b1): 50 mol% to 98 mol% (preferably 55 mol% to 90 mol%). If the ratio of the structural units of the resin [K1] is in the above range, there is a tendency that the storage stability, developability, and solvent resistance of the obtained pattern are excellent. The resin [K1] can be produced by referring to the method described in the document "Experimental Methods for Polymer Synthesis" (written by Takayuki Otsu, Kagaku Dojin Publishing Co., Ltd., first edition, first printing, issued on March 1, 1972) and the cited documents described in the document. Specifically, the method includes adding the specified amounts of (a) and (b) (especially (b1)), a polymerization initiator and a solvent, etc. into a reaction vessel, stirring, heating, and keeping warm in a deoxygenated environment. In addition, the polymerization initiator and solvent used here are not particularly limited, and those commonly used in this field can be used. As polymerization initiators, azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) or organic peroxides (benzoyl peroxide, etc.) can be listed. As solvents, any solvent that dissolves each monomer can be used, and solvents (F) described later as solvents for coloring curable resin compositions can be used. The obtained copolymer can be used directly as a solution after the reaction, or as a concentrated or diluted solution, or as a solid (powder) extracted by reprecipitation or the like. In particular, during the polymerization, by using solvent (F) described later as a solvent, the solution after the reaction can be used directly, which can simplify the production steps.

Among all the structural units constituting the resin [K2], the ratio of the structural units derived from each in the resin [K2] is preferably in the following range. Structural units derived from (a): 4 mol% to 45 mol%, preferably 10 mol% to 40 mol%, and more preferably 15 mol% to 35 mol%; Structural units derived from (b), especially structural units derived from (b1): 2 mol% to 95 mol%, preferably 3 mol% to 70 mol%, and more preferably 5 mol% to 45 mol%; Structural units derived from (c): 1 mol% to 94 mol%, preferably 20 mol% to 85 mol%, and more preferably 40 mol% to 80 mol%. If the ratio of the structural units of the resin [K2] is within the above range, the storage stability, developability, solvent resistance of the obtained pattern, heat resistance and mechanical strength tend to be excellent. The resin [K2] can be produced in the same manner as the method described as the method for producing the resin [K1]. Specifically, a method can be cited in which the specified amounts of (a), (b) (especially (b1)) and (c), a polymerization initiator and a solvent are added to a reaction vessel, and the mixture is stirred, heated and kept warm in a deoxygenated environment. The obtained copolymer can be used directly as a solution after the reaction, or as a concentrated or diluted solution, or as a solid (powder) extracted by a method such as reprecipitation.

Among all the structural units constituting the resin [K3], the ratio of the structural units derived from each of them in the resin [K3] is preferably in the following range. Structural units derived from (a): 2 mol% to 55 mol%, more preferably 10 mol% to 50 mol%, further preferably 15 mol% to 50 mol%, particularly preferably 25 mol% to 50 mol%; Structural units derived from (c): 45 mol% to 98 mol%, more preferably 50 mol% to 90 mol%, further preferably 50 mol% to 85 mol%, particularly preferably 50 mol% to 75 mol%. Resin [K3] can be manufactured in the same manner as the method described as the method for manufacturing resin [K1].

Resin [K4] can be produced by obtaining a copolymer of (a) and (c), and adding a cyclic ether structure having 2 to 4 carbon atoms in (b), particularly an oxycyclopropane in (b1), to the carboxylic acid and/or carboxylic anhydride in (a). Specifically, first, a copolymer of (a) and (c) is produced in the same manner as described as the method for producing resin [K1]. In this case, the ratio of the structural units derived from each of the structural units in all structural units constituting the copolymer of (a) and (c) is preferably within the following range. Structural units derived from (a): 5 mol% to 50 mol% (preferably 10 mol% to 45 mol%); Structural units derived from (c): 50 mol% to 95 mol% (preferably 55 mol% to 90 mol%).

Next, the cyclic ether structure with 2 to 4 carbon atoms possessed by (b), especially the cyclohexane ring possessed by (b1), and a part of the carboxylic acid and/or carboxylic anhydride derived from (a) in the copolymer are reacted. Specifically, after the copolymer of (a) and (c) is produced, the atmosphere in the flask is replaced from nitrogen to air, and (b) (especially (b1)), carboxylic acid or carboxylic anhydride and a reaction catalyst of the cyclic ether structure (such as tris(dimethylaminomethyl)phenol, etc.) and a polymerization inhibitor (such as hydroquinone, etc.) are added to the flask, and the reaction is carried out at 60°C to 130°C for 1 hour to 10 hours, thereby obtaining a resin [K4]. The amount of (b), especially (b1), used relative to 100 mol of (a) is preferably 5 mol to 80 mol, and more preferably 10 mol to 75 mol. By setting it within this range, there is a tendency for the balance of storage stability, developability, solvent resistance, heat resistance, mechanical strength and sensitivity to become better. In terms of the high reactivity of the cyclic ether structure and the difficulty of leaving unreacted (b), the (b) used in the resin [K4] is preferably (b1), and more preferably (b1-1). The amount of the reaction catalyst used relative to the total amount of (a), (b) (especially (b1)) and (c) is preferably 0.001 mass % to 5 mass %. The amount of the polymerization inhibitor used is preferably 0.001 mass % to 5 mass % relative to the total amount of (a), (b) and (c). The reaction conditions such as the method of adding, the reaction temperature and the time can be appropriately adjusted in consideration of the production equipment or the amount of heat generated by the polymerization. In addition, the method of adding or the reaction temperature can be appropriately adjusted in consideration of the production equipment or the amount of heat generated by the polymerization, similarly to the polymerization conditions.

Regarding resin [K5], as a first stage, a copolymer of (b) (particularly (b1)) and (c) is obtained in the same manner as the production method of the resin [K1]. As described above, the obtained copolymer may be used directly as a solution after the reaction, or may be used as a concentrated or diluted solution, or may be used as a solid (powder) extracted by a method such as reprecipitation. The ratio of the structural units derived from (b) (particularly (b1)) and (c) relative to the total molar number of all structural units constituting the copolymer is preferably in the following range. Structural units derived from (b), especially structural units derived from (b1): 5 mol% to 95 mol% (preferably 10 mol% to 90 mol%); Structural units derived from (c): 5 mol% to 95 mol% (preferably 10 mol% to 90 mol%).

Furthermore, under the same conditions as the method for producing resin [K4], the carboxylic acid or carboxylic anhydride contained in (a) and the cyclic ether structure derived from (b) contained in the copolymer of (b) (particularly (b1)) and (c) are reacted to obtain resin [K5]. The amount of (a) reacted with the copolymer is preferably 5 mol to 80 mol per 100 mol of (b) (particularly (b1)). In terms of the high reactivity of the cyclic ether structure and the difficulty in leaving unreacted (b), (b) used in resin [K5] is preferably (b1), and more preferably (b1-1).

Resin [K6] is a resin obtained by further reacting carboxylic acid anhydride and resin [K5]. Carboxylic acid anhydride and hydroxyl group generated by reaction of cyclic ether structure with carboxylic acid or carboxylic acid anhydride are reacted. Examples of carboxylic acid anhydride include maleic anhydride, conic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic 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 (bicycloheptene dicarboxylic anhydride), and the like.

Among the resins [K1] to [K6], the preferred resin as the resin (B) is [K1] or [K2]. The resin (B) may contain one type of resin or two or more types of resins.

The weight average molecular weight (Mw) of the resin (B) in terms of polystyrene is preferably 3,000 or more and 100,000 or less, more preferably 5,000 or more and 50,000 or less, further preferably 5,000 or more and 30,000 or less, and particularly preferably 10,000 or more and 30,000 or less. If the weight average molecular weight (Mw) is within the above range, the unexposed portion tends to have high solubility in the developer, and the film thickness retention rate or hardness of the obtained colored pattern tends to be high. The molecular weight distribution of the resin (B) [weight average molecular weight (Mw)/number average molecular weight (Mn)] is preferably 1.1 or more and 6 or less, and more preferably 1.2 or more and 4 or less.

The acid value of the resin (B) converted to solid content is preferably 5 mg-KOH/g or more and 200 mg-KOH/g or less, more preferably 50 mg-KOH/g or more and 180 mg-KOH/g or less, further preferably 80 mg-KOH/g or more and 150 mg-KOH/g or less, and particularly preferably 95 mg-KOH/g or more and 150 mg-KOH/g or less. The acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin, and can be obtained, for example, by titration using an aqueous potassium hydroxide solution.

In the solid content of the coloring curable resin composition of 100 mass%, the content of the resin (B) is preferably 1 mass% or more and 50 mass% or less, and more preferably 5 mass% or more and 45 mass% or less. If the content of the resin (B) is within the above range, the unexposed part tends to have high solubility in the developer.

[3] Polymerizable compound (C)

The polymerizable compound (C) is not particularly limited as long as it is a compound that can be polymerized by active radicals generated from the polymerization initiator (D) by light irradiation, etc., and examples thereof include polymerizable compounds having ethylenic unsaturated bonds. The weight average molecular weight of the polymerizable compound (C) is preferably 3,000 or less.

Among them, the polymerizable compound (C) is preferably a photopolymerizable compound having three or more ethylenically unsaturated bonds, and examples thereof include trihydroxymethylpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol poly(meth)acrylate, tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tetrapentaerythritol octa(meth)acrylate, and tetrapentaerythritol octa(meth)acrylate. Tetraol deca(meth)acrylate, pentaerythritol nona(meth)acrylate, tri(2-(meth)acryloyloxyethyl) isocyanurate, ethylene glycol-modified pentaerythritol tetra(meth)acrylate, ethylene glycol-modified dipentaerythritol hexa(meth)acrylate, propylene glycol-modified pentaerythritol tetra(meth)acrylate, propylene glycol-modified dipentaerythritol hexa(meth)acrylate, caprolactone-modified pentaerythritol tetra(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, etc. Among them, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. are preferred.

The coloring curable resin composition of the present invention may contain one or more polymerizable compounds (C). The content of the polymerizable compound (C) is preferably 20 parts by mass or more and 150 parts by mass or less, and more preferably 40 parts by mass or more and 110 parts by mass or less, relative to 100 parts by mass of the resin (B) in the coloring curable resin composition.

The content of the polymerizable compound (C) is preferably 7% by mass or more and 65% by mass or less, more preferably 10% by mass or more and 60% by mass or less, and still more preferably 10% by mass or more and 50% by mass or less, relative to the total amount of solid components in the coloring curable resin composition. When the content of the polymerizable compound (C) is within the above range, the film thickness retention rate during coloring pattern formation and the chemical resistance of the color filter tend to be improved.

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

The O-acyl oxime compound is a compound having a partial structure represented by formula (d1). Hereinafter, * represents a bond.

Examples of the O-acyl oxime compound include N-benzoyloxy-1-(4-phenylalkylphenyl)butane-1-one-2-imine, N-benzoyloxy-1-(4-phenylalkylphenyl)octane-1-one-2-imine, N-benzoyloxy-1-(4-phenylalkylphenyl)-3-cyclopentylpropane-1-one-2-imine, N-acetyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethane-1-imine, N-acetyloxy- 1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxacyclopentylmethoxy)benzyl}-9H-carbazol-3-yl]ethane-1-imine, N-acetyloxy-1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-imine, N-benzyloxy-1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-one-2-imine, and the like. Commercially available products such as Irgacure OXE01, Irgacure OXE02 (both manufactured by BASF), and N-1919 (manufactured by ADEKA) may also be used. Among them, the O-acyl oxime compound is preferably at least one selected from the group consisting of N-benzoyloxy-1-(4-phenylalkylphenyl)butane-1-one-2-imine, N-benzoyloxy-1-(4-phenylalkylphenyl)octane-1-one-2-imine, and N-benzoyloxy-1-(4-phenylalkylphenyl)-3-cyclopentylpropane-1-one-2-imine, and more preferably N-benzoyloxy-1-(4-phenylalkylphenyl)octane-1-one-2-imine. These O-acyl oxime compounds tend to provide a color filter having high brightness.

The alkylphenone compound is a compound having a partial structure represented by formula (d2) or a partial structure represented by formula (d3). In these partial structures, the benzene ring may have a substituent.

Examples of compounds having a partial structure represented by formula (d2) include 2-methyl-2-morpholinyl-1-(4-methylphenyl)propane-1-one, 2-dimethylamino-1-(4-morpholinylphenyl)-2-benzylbutane-1-one, and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butane-1-one. Commercially available products such as Irgacure 369, Irgacure 907, and Irgacure 379 (all manufactured by BASF) can also be used. Examples of compounds having a partial structure represented by formula (d3) include 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propane-1-one, 1-hydroxycyclohexylphenyl ketone, oligomers of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propane-1-one, α,α-diethoxyacetophenone, benzyl dimethyl ketal, and the like. In terms of sensitivity, the alkylphenone compound is preferably a compound having a partial structure represented by formula (d2).

Examples of the triazine compound include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, [2-(5-methylfuran-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-triazine, etc.

Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzyldiphenylphosphine oxide, etc. Commercially available products such as Irgacure (registered trademark) 819 (manufactured by BASF) can also be used.

Examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (see, for example, Japanese Patent Laid-Open No. 6-75372, Japanese Patent Laid-Open No. 6-75373, etc.), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 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, see Japanese Patent Publication No. 48-38403, Japanese Patent Laid-Open No. 62-174204, etc.), biimidazole compounds in which the phenyl groups at the 4,4',5,5'-positions are substituted with alkoxycarbonyl groups (for example, see Japanese Patent Laid-Open No. 7-10913, etc.), and the like.

Furthermore, the polymerization initiator (D) includes benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone compounds such as benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, and 2,4,6-trimethylbenzophenone; quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone, and camphorquinone; 10-butyl-2-chloroacridone, benzil, methyl phenylglyoxylate, and titaniumocene compounds. These are preferably used in combination with the polymerization initiator aid (D1) (particularly amines) described later.

Examples of the acid generator include onium salts such as 4-hydroxyphenyldimethylzincium p-toluenesulfonate, 4-hydroxyphenyldimethylzincium hexafluoroanticorbic acid salt, 4-acetoxyphenyldimethylzincium p-toluenesulfonate, 4-acetoxyphenyl-methyl-benzylzincium hexafluoroanticorbic acid salt, triphenylzincium p-toluenesulfonate, triphenylzincium hexafluoroanticorbic acid salt, diphenyliodonium p-toluenesulfonate, and diphenyliodonium hexafluoroanticorbic acid salt, nitrobenzyl toluenesulfonate salts, and benzoin toluenesulfonate salts.

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

The content of the polymerization initiator (D) is preferably 0.1 parts by mass or more and 30 parts by mass or less, and more preferably 2 parts by mass or more and 20 parts by mass or less, relative to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). When the content of the polymerization initiator (D) is within the above range, the sensitivity tends to be high and the exposure time tends to be shortened, so the productivity of the color filter tends to be improved.

[5] Polymerization initiator (D1) The polymerization initiator (D1) is a compound or sensitizer used to promote the polymerization of a polymerizable compound that starts polymerization by the polymerization initiator. When the polymerization initiator (D1) is included, it can be used in combination with the polymerization initiator (D). As the polymerization initiator (D1), amine compounds, alkoxyanthracene compounds, thioxanthrone compounds and carboxylic acid compounds can be listed. Among them, thioxanthrone compounds are preferred. Two or more polymerization initiators (D1) can also be used in combination.

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

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

Examples of the thioxanthrone compound include 2-isopropylthioxanthrone, 4-isopropylthioxanthrone, 2,4-diethylthioxanthrone, 2,4-dichlorothioxanthrone, and 1-chloro-4-propoxythioxanthrone.

Examples of the carboxylic acid compound include phenyl alkoxyacetic acid, methyl phenyl alkoxyacetic acid, ethyl phenyl alkoxyacetic acid, methyl ethyl phenyl alkoxyacetic acid, dimethyl phenyl alkoxyacetic acid, methoxy phenyl alkoxyacetic acid, dimethoxy phenyl alkoxyacetic acid, chloro phenyl alkoxyacetic acid, dichloro phenyl alkoxyacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, and the like.

The content of the polymerization initiator (D1) is preferably 0.1 parts by mass or more and 30 parts by mass or less, and more preferably 1 part by mass or more and 20 parts by mass or less, relative to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). When the content of the polymerization initiator (D1) is within the above range, a pattern can be formed with a higher sensitivity, and there is a tendency that the productivity of the color filter is improved.

[6] Thiol compound (E) The thiol compound (E) includes a thiol compound containing an ether bond. When the coloring curable resin composition includes a thiol compound containing an ether bond, the film thickness retention rate tends to be higher. The coloring curable resin composition of the present invention may include one or more thiol compounds containing an ether bond.

The thiol compound containing an ether bond may contain, for example, 2 or more and 6 or less hydroxyl groups (-SH), preferably 3 or more and 5 or less. The thiol compound containing an ether bond may have, for example, 2 or more and 6 or less ether bonds, preferably 3 or more and 5 or less.

The thiol compound containing an ether bond is preferably a compound represented by formula (I). [In the formula, A represents a residue of a polyol having m hydroxyl groups; the plurality of ^R1s bonded to the oxygen atoms derived from the m hydroxyl groups each independently represents an alkylene group having 1 to 10 carbon atoms; m is an integer greater than 2, n is an integer greater than 2, and m≧n.]

A represents a residue of a polyol having m hydroxyl groups. A residue of a polyol refers to a structure formed by removing a hydrogen atom (H) constituting at least one hydroxyl group (OH) from a polyol. In formula (I), an oxygen atom (O) bonded to the removed hydrogen atom, i.e., an oxygen atom derived from a hydroxyl group, is bonded to ^{n R1s} . All or part of the oxygen atoms derived from the hydroxyl groups in the polyol may be bonded to ^R1 .

The polyol is not particularly limited as long as it is a compound having two or more hydroxyl groups in one molecule. For example, aliphatic polyols, alicyclic polyols, polyols containing aromatic rings, sugars and their derivatives, etc. are listed. Among them, aliphatic polyols, alicyclic polyols and/or polyols containing aromatic rings are preferred. More preferred is aliphatic polyols.

The aliphatic polyol preferably has a carbon number of 2 to 30. Specifically, for example, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 1,6-hexanediol, 1,12-dodecanediol and other alkanediols; diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol and other polyalkanediols; (poly)glycerol, trihydroxymethylpropane, pentaerythritol, dipentaerythritol, sorbitol, sorbitan and other trivalent or higher polyols, and these may also be alkylene oxide adducts (for example, with an addition molar number of 1 to 50).

The alicyclic polyol preferably has, for example, 3 to 30 carbon atoms. Specifically, alicyclic diols such as 1,4-cyclohexanedimethanol and hydrogenated bisphenol A are exemplified.

The aromatic ring-containing polyol preferably has a carbon number of 6 to 30. Specifically, examples thereof include bisphenol A, bisphenol F, bisphenol S and other bisphenol alkylene oxide adducts (for example, the addition molar number is 2 to 30).

m may be 2 or more, preferably 2-10, more preferably 2-8, further preferably 2-6, particularly preferably 3-6.

The polyol in A is preferably a polyol having 3 to 6 hydroxyl groups, more preferably pentaerythritol, trihydroxymethylpropane or dipentaerythritol.

^R1's are the same or different and represent an alkylene group having 1 to 10 carbon atoms. The alkylene group may be a linear chain or a branched chain.

The carbon atom bonded to the alkylene group in the alkylene group represented by R ¹ may be a primary carbon atom, a secondary carbon atom, or a tertiary carbon atom, and is preferably a primary carbon atom or a secondary carbon atom from the viewpoint of reactivity.

^R1 may have one or more substituents, and preferably ^R1 has no substituents. Examples of substituents that ^R1 may have include halogen atoms, hydroxyl groups, carboxyl groups, sulfonic acid groups, amino groups, and phosphoric acid groups.

The molecular weight of the thiol compound containing an ether bond can be, for example, 50 to 700. From the viewpoint of reducing the viscosity, it is preferably 100 to 500, more preferably 150 to 380.

Examples of the thiol compound containing an ether bond include pentaerythritol tripropyl mercaptan and trihydroxymethylpropane dipropyl mercaptan.

The thiol compound containing an ether bond can be produced by a known production method. For example, it can be produced according to the method described in WO2016/171072.

The thiol compound (E) may contain one or more thiol compounds (E1) other than the thiol compound containing an ether bond. When the polymerization initiator (D) is an oxime compound such as an O-acyl oxime compound and/or a biimidazole compound, the thiol compound (E1) is particularly preferably used. The thiol compound (E1) is a compound having at least one hydroxyl group (-SH) in the molecule. The thiol compound (E1) is preferably a compound having one hydroxyl group in the molecule.

Examples of compounds having a hydroxyl group in the molecule include 2-hydroxyoxazole, 2-hydroxythiazole, 2-hydroxybenzimidazole, 2-hydroxybenzothiazole, 2-hydroxybenzoxazole, 2-hydroxynicotinic acid, 2-hydroxypyridine, 2-hydroxypyridin-3-ol, 2-hydroxypyridine-N-oxide, 4-amino-6-hydroxy-2-hydroxypyrimidine, 4-amino-6-hydroxy-2-hydroxypyrimidine, 4-amino-2-hydroxypyrimidine, 6-amino-5-nitroso-2-thiouracil, 4,5-diamino-6-hydroxy-2-hydroxypyrimidine, 4,6-diamino-2 -Benzyl pyrimidine, 2,4-diamino-6-benzene pyrimidine, 4,6-dihydroxy-2-benzene pyrimidine, 4,6-dimethyl-2-benzene pyrimidine, 4-hydroxy-2-benzene-6-methyl pyrimidine, 4-hydroxy-2-benzene-6-propyl pyrimidine, 2-benzene-4-methyl pyrimidine, 2-benzene pyrimidine, 2-thiouracil, 3,4,5,6-tetrahydropyrimidine-2-thiol, 4,5-diphenylimidazole-2-thiol, 2-benzene imidazole, 2-benzene-1-methylimidazole, 4-amino-3-hydrazino-5-benzene-1,2,4-triazole, 3-amino-5 2-Henyl-1,2,4-triazole, 2-methyl-4H-1,2,4-triazole-3-thiol, 4-methyl-4H-1,2,4-triazole-3-thiol, 3-Henyl-1H-1,2,4-triazole-3-thiol, 2-amino-5-benzene-1,3,4-thiadiazole, 5-amino-1,3,4-thiadiazole-2-thiol, 2,5-dibenzene-1,3,4-thiadiazole, (furan-2-yl) methyl mercaptan, 2-benzene-5-thiazolidinone, 2-benzene thiazoline, 2-benzene-4 (3H)-quinazolinone, 1-phenyl-1H-tetracycline, 2-benzene-5-thiazolidinone ...5-thiazolidinone, 2-benzene-4 (3H)-quinazolinone, 1-phenyl-1H-tetracycline, 2-benzene-5-thiazolidinone, 2-benzene-5-thiazolidinone, 2- oxadiazole-5-thiol, 2-quinolinethiol, 2-hydroxy-5-methylbenzimidazole, 2-hydroxy-5-nitrobenzimidazole, 6-amino-2-hydroxybenzothiazole, 5-chloro-2-hydroxybenzothiazole, 6-ethoxy-2-hydroxybenzothiazole, 6-nitro-2-hydroxybenzothiazole, 2-hydroxynaphthoimidazole, 2-hydroxynaphthooxazole, 3-hydroxy-1,2,4-triazole, 4-amino-6-hydroxypyrazolo[2,4-d]pyridine, 2-amino-6-purinethiol, 6-hydroxypurine and 4-hydroxy-1H-pyrazolo[2,4-d]pyrimidine, etc.

Examples of compounds having two or more alkyl groups in the molecule include hexanedithiol, decanedithiol, 1,4-bis(methylalkyl)benzene, butanediol di(3-alkylpropionate), butanediol di(3-alkyl acetate), ethylene glycol di(3-alkyl acetate), trihydroxymethylpropane tri(3-alkyl acetate), butanediol di(3-alkyl propionate), trihydroxymethylpropane tri(3-alkyl propionate), trihydroxymethylpropane tri(3-alkyl acetate), pentaerythritol tetra(3-alkyl propionate), pentaerythritol tetra(3-alkyl acetate), trihydroxyethyl tri(3-alkyl propionate), pentaerythritol tetra(3-alkyl butyrate), and 1,4-bis(3-alkylbutyloxy)butane.

The content of the thiol compound (E) is preferably 0.5 parts by mass or more and 50 parts by mass or less, more preferably 1 part by mass or more and 45 parts by mass or less, and further preferably 5 parts by mass or more and 40 parts by mass or less, relative to 100 parts by mass of the polymerization initiator (D). When the content of the thiol compound (E) is within the above range, the sensitivity tends to be high and the developing property tends to be good.

[7] Solvent (F) The colored curable resin composition of the present invention preferably contains one or more solvents (F). Examples of the solvent (F) include ester solvents (solvents containing -COO-), ether solvents other than ester solvents (solvents containing -O-), ether ester solvents (solvents containing -COO- and -O-), ketone solvents other than ester solvents (solvents containing -CO-), alcohol solvents, aromatic hydrocarbon solvents, amide solvents, and dimethyl sulfoxide.

As ester solvents, there can be listed: 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, cyclohexanol acetate and γ-butyrolactone, etc. As the ether solvent, there can be listed: 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, phenethyl ether and methyl anisole.

As the ether ester solvent, there can be mentioned methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate and dipropylene glycol methyl ether acetate.

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

Examples of alcohol solvents include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerol. Examples of aromatic hydrocarbon solvents include benzene, toluene, xylene, and mesitylene. Examples of amide solvents include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

From the viewpoint of coating properties and drying properties, the solvent (F) preferably contains an organic solvent having a boiling point of 120° C. or higher and 180° C. or lower at 1 atm. Among them, the solvent (F) preferably comprises at least one selected from the group consisting of propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone and N,N-dimethylformamide, and more preferably comprises at least one selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol and ethyl 3-ethoxypropionate.

In the coloring curable resin composition, the content of the solvent (F) is preferably 70 mass % or more and 95 mass % or less, more preferably 75 mass % or more and 92 mass % or less. In other words, the solid content of the coloring curable resin composition is preferably 5 mass % or more and 30 mass % or less, more preferably 8 mass % or more and 25 mass % or less. When the content of the solvent (F) is within the above range, the flatness during coating is improved, and the color density is not insufficient when forming a blue color filter, so there is a tendency that the display characteristics are improved.

[8] Leveling agent (G) As the leveling agent (G), there can be mentioned silicone-based surfactants (without fluorine atoms), fluorine-based surfactants, and silicone-based surfactants with fluorine atoms. These may also have polymerizable groups in the side chains.

Examples of silicone-based surfactants include surfactants having siloxane bonds in the molecule. Specifically, they include: Toray silicone DC3PA, Toray silicone SH7PA, Toray silicone DC11PA, Toray silicone SH21PA, Toray silicone SH28PA, Toray silicone SH29PA, Toray silicone SH30PA, Toray silicone SH8400 (trade name; Toray Dow Corning) (manufactured by Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452 and TSF4460 (manufactured by Momentive Performance Materials Japan Co., Ltd.), etc.

Examples of fluorine-based surfactants include surfactants having a fluorine-carbon chain in the molecule. Specifically, they include: Fluorad (registered trademark) FC430, Fluorad (registered trademark) FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megafac (registered trademark) F142D, Megafac F171, Megafac F172, Megafac F173, Megafac F177, Megafac F183, Megafac F554, Megafac R30, Megafac ) RS-718-K (manufactured by DIC Corporation), Eftop (registered trademark) EF301, Eftop EF303, Eftop EF351, Eftop EF352 (manufactured by Mitsubishi Materials Electronics Co., Ltd.), Surflon (registered trademark) S381, Surflon S382, Surflon SC101, Surflon SC105 (manufactured by Asahi Glass Co., Ltd.), and E5844 (manufactured by Daikin Fine Chemicals Laboratories Co., Ltd.), etc.

As silicone-based surfactants having fluorine atoms, surfactants having siloxane bonds and fluorocarbon chains in the molecule can be cited. Specifically, Megafac (registered trademark) R08, Megafac BL20, Megafac F475, Megafac F477, and Megafac F443 (manufactured by DIC Corporation) can be cited.

In the colored curable resin composition, the content of the leveling agent (G) is usually 0.0001 mass % or more and 0.6 mass % or less, preferably 0.0001 mass % or more and 0.4 mass % or less, and more preferably 0.0001 mass % or more and 0.2 mass % or less. This content does not include the content of the above-mentioned pigment dispersant.

[9] Other ingredients The colored curable resin composition of the present invention may contain one or more fillers, polymer compounds other than the resin (B), adhesion promoters, ultraviolet absorbers, anti-agglomeration agents, organic acids, curing agents and other additives as needed.

<Method for producing colored curable resin composition> The colored curable resin composition of the present invention can be prepared by mixing a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and, if necessary, a thiol compound (E), a solvent (F), a leveling agent (G), a polymerization initiator aid (D1), an antioxidant (H), and other components.

<Color filter, method for manufacturing the same, and display device> The coloring curable resin composition of the present invention can be effectively used as a material for a color filter. In addition, a color filter formed by the coloring curable resin composition of the present invention also belongs to the scope of the invention of this application. The color filter can also form a colored pattern. As a method for manufacturing a colored pattern from the coloring curable resin composition of the present invention, photolithography, inkjet method, printing method, etc. can be listed, and photolithography is preferred. Photolithography is a method of applying a coloring curable resin composition to a substrate, drying it to form a colored composition layer, and exposing and developing the colored composition layer through a photomask. In photolithography, a colored coating film can be formed as a cured product of the colored composition layer by not using a mask during exposure and/or not performing development. The colored pattern or colored coating film formed by the colored curable resin composition of the present invention is the color filter of the present invention. The color filter of the present invention can be typically used as a colored pixel.

As the substrate, glass plates such as quartz glass, borosilicate glass, alumina silicate glass, sodium calcium glass coated with silicon dioxide, or resin plates such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, silicon, or aluminum, silver, silver/copper/palladium alloy thin films, etc. can be used. Other color filter layers, resin layers, transistors, circuits, transparent electrodes, etc. can also be formed on these substrates.

The formation of colored pixels by photolithography can be carried out under known or conventional devices or conditions, for example, in the following manner. First, a colored curable resin composition is applied to a substrate, and then dried by heating and drying (pre-baking) and/or reducing pressure drying to remove volatile components such as solvents, thereby obtaining a smooth colored composition layer. Examples of coating methods include spin coating, slit coating, slit and spin coating, and the like.

The temperature for heat drying is preferably 30°C or higher and 120°C or lower, more preferably 50°C or higher and 110°C or lower. The heating time is preferably 10 seconds to 5 minutes, more preferably 30 seconds to 3 minutes. When performing reduced pressure drying, it is preferably performed at a pressure of 50 Pa or higher and 150 Pa or lower and at a temperature of 20°C or higher and 25°C or lower. The film thickness of the coloring composition layer is not particularly limited and can be appropriately selected according to the film thickness of the target color filter.

Next, the coloring composition layer is exposed through a photomask for forming a target coloring pattern. The pattern on the photomask is not particularly limited, and a pattern corresponding to the target application can be used. The light source used in the exposure is preferably a light source that generates light with a wavelength of more than 250 nm and less than 450 nm. For example, a filter that cuts off the wavelength range for light less than 350 nm can be used to cut off the light, or a bandpass filter that extracts the light in the wavelength range near 436 nm, near 408 nm, and near 365 nm can be used to selectively extract the light in these wavelength ranges. Specifically, as the light source, mercury lamps, light-emitting diodes, metal halide lamps, halogen lamps, etc. can be listed.

During exposure, in order to evenly irradiate the entire exposure surface with parallel light or to accurately align the mask with the substrate on which the colored component layer is formed, it is preferable to use an exposure device such as a mask aligner and a stepper.

The colored pattern is formed on the substrate by contacting the exposed colored composition layer with a developer for development. By development, the unexposed part of the colored composition layer is dissolved in the developer and removed. The developer is preferably an aqueous solution of alkaline compounds such as potassium hydroxide, sodium bicarbonate, sodium carbonate, and tetramethylammonium hydroxide. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01% by mass or more and 10% by mass or less, and more preferably 0.03% by mass or more and 5% by mass or less. Furthermore, the developer may also contain a surfactant.

The developing method may be any of a coating method, an immersion method, a spray method, etc. Furthermore, the substrate may be tilted at any angle during the developing process. After the developing process, it is preferably washed with water.

The colored curable resin composition of the present invention has little residue on the substrate where the unexposed portion of the colored composition layer is dissolved in a developer and removed.

Furthermore, it is preferred to post-bake the obtained colored pattern. The post-bake temperature is preferably 150° C. or higher and 250° C. or lower, more preferably 160° C. or higher and 235° C. or lower. The post-bake time is preferably 1 minute to 120 minutes, more preferably 10 minutes to 60 minutes.

Regarding the colored curable resin composition of the present invention, the ratio of the film thickness of the colored composition layer after exposure, development and post-baking to the film thickness of the colored composition layer before exposure [after heat drying (pre-baking) and/or reduced pressure drying] is high, for example, can be 50% or more.

The thickness of the colored coating or colored pattern formed by the colored curable resin composition will affect the adjacent pixels, so it is better to be as thin as possible. Especially in the case of a thick film, when making a liquid crystal panel, the light from the light source sometimes leaks through two or more colors of pixels, and when the panel is observed from an oblique angle, there is a risk that the vividness of the color will disappear. The thickness of the colored coating or colored pattern after post-baking is usually preferably less than 3 μm, and more preferably less than 2.8 μm. The lower limit of the film thickness of the colored coating or colored pattern is not particularly limited, and is usually more than 1 μm, and can also be more than 1.5 μm. The colored coating or colored pattern can show excellent developing properties, and therefore is excellent as a color filter.

Generally, when the film thickness retention rate of the colored coating or colored pattern before and after post-baking is low, in order to ensure a predetermined film thickness in the colored coating or colored pattern after post-baking, it is necessary to increase the film thickness of the colored coating or colored pattern before post-baking, thereby using a large amount of curable resin composition. In contrast, the colored curable resin composition of the present invention has a high film thickness retention rate of the colored coating or colored pattern before and after post-baking, so a predetermined film thickness can be obtained even with a relatively small amount of curable resin composition. The film thickness retention rate of the colored curable resin composition of the present invention is higher than that of the conventional colored curable resin composition, and the difference between the film thickness retention rate of the colored curable resin composition of the present invention and the conventional colored curable resin composition can be, for example, 2% or more. When the film thickness retention rate is higher than 2%, the amount of the colored curable resin composition used in the preparation of the colored coating film or the colored pattern can be significantly reduced.

The color filter of the present invention can be effectively used as a color filter used in display devices (liquid crystal display devices, organic electroluminescence (EL) devices, electronic paper, etc.) and solid-state imaging devices. [Example]

The following is a description of the coloring curable resin composition of the present invention by way of specific examples, but the present invention is not limited to the following examples unless otherwise specified. Unless otherwise specified, "parts" means "parts by mass" and "%" means "% by mass". In addition, unless otherwise specified, the reaction is carried out in a nitrogen atmosphere.

Hereinafter, the structures of the compounds were confirmed by mass analysis (liquid chromatography (LC); Agilent 1200 model, MASS; Agilent liquid chromatography/mass selective detection (LC/MSD) model).

The polystyrene-equivalent weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin were determined by gel permeation chromatography (GPC) under the following conditions. Apparatus: HLC-8120GPC (manufactured by Tosoh Co., Ltd.) Column: TSK-GELG2000HXL Column temperature: 40°C Solvent: tetrahydrofuran (THF) Flow rate: 1.0 mL/min Test liquid solid content concentration: 0.001 mass% to 0.01 mass% Injection volume: 50 μL Detector: RI Calibration standard substance: TSK standard polystyrene F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Co., Ltd.) The ratio (Mw/Mn) of the weight average molecular weight and the number average molecular weight of the polystyrene obtained in the above was set as the dispersion degree.

The acid value of the resin in terms of solid content is a value obtained by titrating a solution containing the resin with an aqueous potassium hydroxide solution to determine the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin.

(Synthesis Example 1) 17.4 parts of tert-amyl alcohol and 2.22 parts of metallic sodium reacted at 130°C in a nitrogen environment to synthesize sodium tert-amyl alcohol. It was heated to 60°C, and 9.1 parts of 4-bromobenzonitrile, 7.105 parts of di-tert-amyl succinate, and 10.89 parts of tert-amyl alcohol were added, and stirred for 2 hours in a manner such that the liquid temperature was below 85°C. The suspension was further stirred for more than 18 hours, and then added to a mixed solution of 20 parts of methanol, 100 parts of water, and 4.921 parts of sulfuric acid cooled to -10°C. After the addition of the suspension was completed, it was kept at 0°C and stirred for 5 hours. After the reaction was completed, the solid component was filtered. The solid component was repeatedly washed with methanol and water alternately until the filtrate was free of color and salt precipitation. Thereafter, the solid component was dried in a vacuum dryer at 80° C. for 18 hours to obtain 10.7 parts of the target red pigment 1.

(Synthesis Example 2) According to the method described in Example 1 of Japanese Patent Laid-Open No. 2016-277075, 52 parts of the compound represented by formula (1-34) were obtained.

Identification (mass analysis) of the compound represented by formula (1-34): Ionization mode = electrospray ionization (ESI) +: m/z = [M+H] ⁺ 599.2 Exact mass: 598.1

(Synthesis Example 3) According to the method described in Example 2 of Japanese Patent Laid-Open No. 2017-226814, 1.0 part of the compound represented by formula (1-87) was obtained.

Identification (mass analysis) of the compound represented by formula (1-87): Ionization mode = ESI+: m/z = [M+H] ⁺ 747.5 Exact mass: 746.3

(Synthesis Example 4) According to the method described in Synthesis Example 2 of Japanese Patent Laid-Open No. 2016-176075, 24 parts of the compound represented by formula (1-22) were obtained. The yield was 80%.

Identification (mass analysis) of the compound represented by formula (1-22): Ionization mode = ESI+: m/z = [M+H] ⁺ 659.9 Exact mass: 658.9

(Synthesis Example 5) The following reaction is carried out in a nitrogen environment. In a flask equipped with a cooling tube and a stirring device, 26.4 parts of potassium thiocyanate and 156 parts of acetonitrile are added, and stirred at room temperature for 30 minutes. 40.0 parts of 2,6-difluorobenzyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) are added dropwise to the flask over 30 minutes, and stirred at room temperature for 1 hour. 30.6 parts of N-ethyl-o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) are added dropwise to the flask over 30 minutes, and stirred at room temperature for 1 hour. In the flask, an aqueous solution obtained by dissolving 79.2 parts of sodium monochloroacetate in 120 parts of ion-exchange water and 60.4 parts of a 30% aqueous sodium hydroxide solution were added, and the mixture was stirred at room temperature for 18 hours. After further adding 600 parts of ion-exchange water to the flask, the mixture was stirred for 1 hour, and the precipitated yellow-white solid was filtered. The obtained yellow-white solid was washed with 120 parts of acetonitrile and then washed with 560 parts of ion-exchange water. The washed yellow-white solid, 156 parts of ion-exchange water, 35.0 parts of 99% acetic acid (manufactured by Wako Junyaku Industries Co., Ltd.) and 156 parts of toluene were added to a flask equipped with a stirring device, and the mixture was stirred at room temperature for 2 hours. 80.8 parts of a 30% aqueous sodium hydroxide solution were added dropwise over 10 minutes, stirred for 5 minutes, and the aqueous layer was removed by liquid separation. 156 parts of ion exchange water were added to the obtained organic layer and the mixture was washed by liquid separation, and then 156 parts of ion exchange water and 0.1 parts of 35% hydrochloric acid were added and washed by liquid separation. The obtained organic layer was concentrated by an evaporator and dried under reduced pressure at 35°C to obtain the compound represented by formula (t-1) as a white solid. The yield was 43.4 parts and the yield was 58.0%.

The following reaction was carried out in a nitrogen environment. In a flask equipped with a cooling tube and a stirring device, 13.2 parts of the compound represented by formula (t-1), 19.0 parts of the compound represented by formula (t-2) and 38 parts of toluene were added, and then 9.2 parts of phosphinoyl chloride were added and stirred at 100°C for 7 hours. The reaction mixture was then cooled to room temperature and diluted with 29 parts of methyl ethyl ketone. A mixed solution of 114 parts of ion exchange water and 10 parts of a 35% hydrochloric acid aqueous solution was then injected into the diluted reaction mixture, and the water layer was removed by liquid separation. The obtained organic layer was freed of solvent using an evaporator and then dried at 60° C. under reduced pressure to obtain a compound represented by formula (t-3) as a bluish purple solid. The amount of the bluish purple solid obtained was 39.4 parts.

The following reaction was carried out in a nitrogen atmosphere. In a flask equipped with a cooling tube and a stirring device, 38.4 parts of the compound represented by formula (t-3) and 112 parts of dichloromethane were added and stirred for 30 minutes. The reaction solution was cooled in an ice bath and the internal temperature was maintained at 10°C. In this state, 31.6 parts of chlorosulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the reaction solution was heated to room temperature and stirred for 9 hours. The reaction solution was then cooled in an ice bath and the internal temperature was maintained at 10°C. In this state, it was diluted with a mixed solution of 64 parts of N,N-dimethylformamide and 4.9 parts of ion exchange water. After the diluted reaction solution was injected into 1120 parts of toluene, a viscous solid was precipitated when stirred for 30 minutes. After the oil layer was discharged by decantation, 320 parts of toluene were added to the obtained viscous solid and stirred for 30 minutes. After the oil layer was discharged by decantation, 832 parts of 20% saline solution were added to the obtained viscous solid and stirred for 1 hour, and then a blue solid was filtered out. The obtained blue solid was washed with 576 parts of 20% saline solution and dried under reduced pressure at 35°C. The obtained solid and 128 parts of methanol were added to a flask equipped with a stirrer and stirred for 30 minutes, followed by filtration to separate into a solid and a filtrate. The filtrate was designated as filtrate A. The filtered solid was washed with 192 parts of methanol and separated into a solid and a filtrate by filtration. The filtrate was designated as filtrate B. Filters A and B were mixed and the solvent was removed by an evaporator, followed by reduced pressure drying at 40°C to obtain a compound represented by formula (t-4) as a bluish purple solid. The amount of bluish purple solid obtained was 38.3 parts.

In a flask equipped with a cooling tube and a stirring device, add 28.0 parts of the compound represented by formula (t-4), 43.2 parts of barium chloride dihydrate and 356 parts of ion exchange water, stir at 40°C for 2 hours, and then filter the reaction suspension. In a flask equipped with a stirring device, add the filtered solid and 350 parts of ion exchange water and stir for 30 minutes, then filter the suspension. After washing the obtained solid with 280 parts of ion exchange water, dry it under reduced pressure at 60°C to obtain the compound represented by formula (t-5) as a blue-purple solid. The amount obtained is 24.5 parts, and the yield is 81.7%.

Identification (mass analysis) of the compound represented by formula (t-5): Ionization mode = ESI-: m/z = 949.5 [M-Ba + 2H] ^- Exact mass [M-Ba]: 947.28

(Synthesis Example 6) A nitrogen atmosphere was replaced by flowing an appropriate amount of nitrogen in a flask equipped with a reflux cooler, a dropping funnel and a stirrer, and 151 parts of ethyl lactate and 178 parts of propylene glycol monomethyl ether acetate were added, and the mixture was heated to 85° C. while stirring. Subsequently, a mixed solution of 38 parts of acrylic acid, 25 parts of a mixture of 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decane-8-yl acrylate and 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decane-9-yl acrylate (containing ratio of 1:1 in molar ratio), 137 parts of N-cyclohexyl cis-butylenediamide, 50 parts of 2-hydroxyethyl methylpropionate, and 338 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. On the other hand, a solution obtained by dissolving 5 parts of 2,2-azobisisobutyronitrile in 88 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After the addition was completed, the mixture was kept at 85°C for 4 hours and then cooled to room temperature to obtain a copolymer (resin B1) solution having a viscosity of 23 mPas and a solid content of 25.4% as measured by a B-type viscometer (23°C). The weight average molecular weight Mw of the generated copolymer was 8.0×10 ³ , the degree of dispersion was 2.1, and the acid value converted to solid content was 109 mg-KOH/g. Resin B1 has the following structural units.

In the following examples, in the preparation of the colored curable resin composition, any of the following is used as each component. Resin (B): Resin B1 obtained in the above (Synthesis Example 6) Polymerizable compound (C): Dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) Polymerization initiator (D): N-benzoyloxy-1-(4-phenylphenyl)octane-1-one-2-imide (Irgacure (registered trademark) OXE-01; manufactured by BASF; oxime compound) Mercapto compound (E): Pentaerythritol trispropanethiol (PEPT) Leveling agent (G): Polyether modified silicone oil (Toray silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.), recorded as "SH8400" in the embodiment

[Example 1] [Preparation of a coloring curable resin composition] The components shown below are mixed, and a pigment dispersion 1 in which the pigment is fully dispersed is prepared using a beads mill. The components shown below are mixed using the pigment dispersion 1 to obtain a coloring curable resin composition. ＜Pigment dispersion 1＞ Red pigment 1 obtained in (Synthesis Example 1)                           66.22 parts Acrylic pigment dispersant                                             14.17 parts Resin B1 obtained in (Synthesis Example 6) (based on solid content) 28.38 parts Propylene glycol monomethyl ether acetate                                                 361.87 parts ＜Coloring curable resin composition＞ Coloring agent (A): Pigment dispersion 1                                             471 parts Xanthone dye obtained in (Synthesis Example 2)               10 parts Resin (B): Resin B1 (based on solid content)                       37 parts Polymerizable compound (C): Dipentaerythritol hexaacrylate                  35 servings

The obtained colored curable resin composition was evaluated by the following method.

<Formation of color filters>

A coloring curable resin composition was applied by spin coating on a 2-inch square glass substrate (Eagle 2000; manufactured by Corning) and pre-baked at 100°C for 3 minutes to form a coloring composition layer. After cooling, the coloring composition layer was irradiated with light using an exposure machine (TME-150RSK; manufactured by Topcon) in an atmospheric environment at an exposure dose of 60 mJ/ ^cm2 (365 nm reference) using a mask (line width 100 μm) and a gap of 250 μm between the glass substrate and the mask. After light irradiation, the film was developed with a 0.04% potassium hydroxide solution at a spray pressure of 0.1 Pa for 60 seconds and then washed with water. After removing moisture with an air knife, the film thickness of the color filter (film thickness before post-baking) was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.). The color filter was post-baked at 230°C for 20 minutes in an oven to obtain a color filter. After cooling, the film thickness of the obtained color filter (film thickness after post-baking) was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.).

The film thickness retention rate was calculated by the following formula. The results are shown in Table 1. Film thickness retention rate [%] = (film thickness after post-baking [μm] / film thickness before post-baking [μm]) × 100

<Line width> The obtained color filter was measured for patterned line width using a scanning electron microscope (S-4000: manufactured by Hitachi, Ltd.) and its shape (cross section) was confirmed. The pattern line width [μm] of the color filter relative to the mask line width of 100 μm is shown in Table 1.

[Comparative Example 1] A colored curable resin composition and a color filter were prepared and evaluated in the same manner as in Example 1 except that trimethylolpropane tris(3-mercaptopropionate) (TMMP) was used instead of the thiol compound (E) pentaerythritol tripropylthiol (PEPT). The results are shown in Table 1.

[Comparative Example 2] A colored curable resin composition and a color filter were prepared and evaluated in the same manner as in Example 1 except that pentaerythritol tetrakis(3-mercaptopropionate) (PEMP) was used instead of the thiol compound (E) pentaerythritol tripropylthiol (PEPT). The results are shown in Table 1.

[Table 1] Table 1 Embodiment 1 Comparison Example 1 Comparison Example 2 Film thickness retention rate (%) 87 84 84 Line width (μm) 102 101 102

[Example 2] Pigment dispersion 2, coloring curable resin composition and color filter were prepared in the same manner as in Example 1 except that the following components were mixed, and then evaluated. The results are shown in Table 2. ＜Pigment dispersion 2＞ C.I. Pigment Blue 15:6                                                           22.12 parts Acrylic pigment dispersant                                                  7.76 parts Resin B1 obtained in (Synthesis Example 6) (based on solid content) 8.87 parts Propylene glycol monomethyl ether acetate                                                 182.91 parts ＜Coloring curable resin composition＞ Coloring agent (A): Pigment dispersion 2                                             222 parts                                         3 parts Resin (B): Resin B1 (based on solid content)                            56 parts Polymerizable compound (C): dipentaerythritol hexaacrylate                   35 parts Polymerization initiator (D): Yanjiagu (registered trademark) OXE-01          10 parts Thiol compound (E): PEPT                                                      3 parts Solvent (F): Ethyl lactate                                                       33 parts Diacetone alcohol                                                         71 parts Propylene glycol monomethyl ether acetate                                       424 parts Leveling agent (G): SH8400 (solid content conversion)                     0.1 parts

[Comparative Example 3] A colored curable resin composition and a color filter were prepared and evaluated in the same manner as in Example 2 except that trihydroxymethylpropane tri(3-butyl propionate) (TMMP) was used instead of the thiol compound (E) pentaerythritol tripropyl mercaptan (PEPT). The results are shown in Table 2.

[Table 2] Table 2 Embodiment 2 Comparison Example 3 Film thickness retention rate (%) 88 84 Line width (μm) 92 93

[Example 3] The components shown below were mixed to obtain a colored curable resin composition. A color filter was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 3. Coloring agent (A): Pigment dispersion 2                                             222 parts Xanton dye obtained in (Synthesis Example 4)           3 parts Resin (B): Resin B1 (solid content conversion)                         56 parts Polymerizable compound (C): Dipentaerythritol hexaacrylate                   35 parts Polymerization initiator (D): Yanjiagu (registered trademark) OXE-01          10 parts Thiol compound (E): PEPT                                                 3 parts Solvent (F): Ethyl lactate                                                 33 parts Diacetone alcohol                                                     11 parts Propylene glycol monomethyl ether acetate                                      485 parts Leveling agent (G): SH8400 (solid content conversion) 0.1 parts

[Example 4] A coloring curable resin composition was obtained in the same manner as in Example 3 except that the pigment dispersion 2 was changed to 218 parts, the thiol compound (E) was changed to 0.5 parts, and the propylene glycol monomethyl ether acetate was changed to 473 parts. A color filter was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 3.

[Comparative Example 4] A colored curable resin composition and a color filter were prepared and evaluated in the same manner as in Example 3 except that trihydroxymethylpropane tri(3-hydroxypropionate) (TMMP) was used instead of the thiol compound (E) pentaerythritol tripropyl mercaptan (PEPT). The results are shown in Table 3.

[Comparative Example 5] A colored curable resin composition and a color filter were prepared and evaluated in the same manner as in Example 3 except that pentaerythritol tetra(3-pentyl propionate) (PEMP) was used instead of the thiol compound (E) pentaerythritol tripropyl mercaptan (PEPT). The results are shown in Table 3.

[Table 3] Table 3 Embodiment 3 Embodiment 4 Comparison Example 4 Comparison Example 5 Film thickness retention rate (%) 88 86 82 84 Line width (μm) 94 94 94 95

[Example 5] Except for mixing the components shown below, a colored curable resin composition and a color filter were prepared in the same manner as in Example 1 and evaluated. The results are shown in Table 4. <Dispersion 3> Dispersion 3 was prepared by mixing the components shown below. Compound represented by formula (t-5) obtained in (Synthesis Example 5) 10 parts Acrylic pigment dispersant 8 parts Resin B1 obtained in (Synthesis Example 6) (solid content conversion) 3 parts Diacetone alcohol 12 parts Propylene glycol monomethyl ether acetate 91 parts <Coloring curable resin composition> Coloring agent (A): Dispersion 3 119 parts Pigment dispersion 2 134 parts Xanthone dye obtained in (Synthesis Example 4) 3 parts Resin (B): Resin B1 (solid content conversion) 57 parts Polymerizable compound (C): dipentaerythritol hexaacrylate                35 parts Polymerization initiator (D): Yanjiagu (registered trademark) OXE-01          10 parts Mercapto compound (E): PEPT                                                      3 parts Solvent (F): Ethyl lactate                                                       34 parts Diacetone alcohol                                                         11 parts Propylene glycol monomethyl ether acetate                                       481 parts Leveling agent (G): SH8400 (solid content conversion)                     0.1 parts

[Comparative Example 6] A colored curable resin composition and a color filter were prepared and evaluated in the same manner as in Example 5 except that trihydroxymethylpropane tri(3-butyl propionate) (TMMP) was used instead of the thiol compound (E) pentaerythritol tripropyl mercaptan (PEPT). The results are shown in Table 4.

[Table 4] Table 4 Embodiment 5 Comparative Example 6 Film thickness retention rate (%) 86 84 Line width (μm) 106 105

[Example 6] Except for mixing the following components, a colored curable resin composition and a color filter were prepared in the same manner as in Example 1 and evaluated. The results are shown in Table 5. Coloring agent (A): Xanthan dye obtained in (Synthesis Example 4)           23 parts Resin (B): Resin B1 (solid content conversion)                         65 parts Polymerizable compound (C): Dipentaerythritol hexaacrylate                    35 parts Polymerization initiator (D): Yanjiagu (registered trademark) OXE-01          10 parts Thiol compound (E): PEPT                                                     3 parts Solvent (F): Ethyl lactate                                                       38 parts Diacetone alcohol                                                         93 parts Propylene glycol monomethyl ether acetate                                   534 parts Leveling agent (G): SH8400 (solid content conversion)                    0.1 part

[Comparative Example 7] A colored curable resin composition and a color filter were prepared and evaluated in the same manner as in Example 6 except that trihydroxymethylpropane tri(3-hydroxypropionate) (TMMP) was used instead of the thiol compound (E) pentaerythritol tripropyl mercaptan (PEPT). The results are shown in Table 5.

[Comparative Example 8] A colored curable resin composition and a color filter were prepared and evaluated in the same manner as in Example 6 except that pentaerythritol tetra(3-pentyl propionate) (PEMP) was used instead of the thiol compound (E) pentaerythritol tripropyl mercaptan (PEPT). The results are shown in Table 5.

[Table 5] Table 5 Embodiment 6 Comparison Example 7 Comparative Example 8 Film thickness retention rate (%) 86 83 84 Line width (μm) 97 97 98

[Example 7] Except for mixing the following components, a colored curable resin composition and a color filter were prepared in the same manner as in Example 1 and evaluated. The results are shown in Table 6. Coloring agent (A): Dispersion 3                                                   227.1 parts Xanthan dye obtained in (Synthesis Example 3)    2.8 parts Resin (B): Resin B1 (solid content conversion)                       50.4 parts Polymerizable compound (C): Dipentaerythritol hexaacrylate             45.0 parts Polymerization initiator (D): Yanjiagu (registered trademark) OXE-01     5.0 parts Thiol compound (E): PEPT                                             1.0 parts Solvent (F): Diacetone alcohol                                                     137.1 parts Ethyl lactate                                                   29.5 parts Propylene glycol monomethyl ether acetate                                442.2 parts Leveling agent (G): SH8400 (solid content conversion) 0.1 parts

[Comparative Example 9] A colored curable resin composition and a color filter were prepared and evaluated in the same manner as in Example 7 except that trihydroxymethylpropane tri(3-hydroxypropionate) (TMMP) was used instead of the thiol compound (E) pentaerythritol tripropyl mercaptan (PEPT). The results are shown in Table 6.

[Comparative Example 10] A colored curable resin composition and a color filter were prepared and evaluated in the same manner as in Example 7 except that pentaerythritol tetra(3-pentyl propionate) (PEMP) was used instead of the thiol compound (E) pentaerythritol tripropyl mercaptan (PEPT). The results are shown in Table 6.

[Table 6] Table 6 Embodiment 7 Comparative Example 9 Comparative Example 10 Film thickness retention rate (%) 84 82 82 Line width (μm) 116 118 117

As shown in Tables 1 to 6, it was confirmed that when a color filter is produced using the color curable resin composition provided by the present invention, a high film thickness retention rate can be obtained and the line width can be maintained, compared with the case where a color filter is produced using a color curable resin composition other than the color filter provided by the present invention. [Industrial Applicability]

According to the colored curable resin composition of the present invention, the obtained color filter can obtain a high film thickness retention rate and maintain the line width, so it is extremely useful in the industry.

without

without

Claims (9)

A colored curable resin composition comprises a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a thiol compound (E), wherein the colorant (A) comprises a xanthone dye, the thiol compound (E) comprises a thiol compound containing an ether bond, wherein the thiol compound containing an ether bond comprises a compound represented by formula (I), A-( ^R1 -SH) _n (I) [wherein A represents a residue of a polyol having m hydroxyl groups, a plurality of ^R1s bonded to oxygen atoms derived from the m hydroxyl groups each independently represents an alkylene group having 1 to 10 carbon atoms, m is an integer greater than 2, n is an integer greater than 2, and m≧n]. The colored curable resin composition as described in claim 1, wherein m is 2 to 10. The colored curable resin composition as described in claim 1, wherein the polyol is pentaerythritol or trihydroxymethylpropane. The colored curable resin composition according to any one of claims 1 to 3, wherein the xanthate dye comprises a compound represented by formula (1a),

[In the formula (1a), R ^1a to R ^4a each independently represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent, and the -CH ₂ - contained in the saturated hydrocarbon group may be substituted by -O-, -CO- or -NR ^11a -; R ^1a and R ^2a may together form a ring containing a nitrogen atom, and R ^3a and R ^4a may together form a ring containing a nitrogen atom; R ^5a represents a halogen atom, -OH, -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Za ⁺ , -CO ₂ H, -CO ₂ ^- Za ⁺ , -CO ₂ R ^8a , -SO ₃ R ^8a , -NR ^9a R ^10a or -SO ₂ NR ^9a R ^10a ; R ^6a and R ^{R 7a} each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; m represents an integer of 0 to 5; when m is 2 or more, multiple R ^5a may be the same or different; a represents an integer of 0 or 1; Xa ^- represents a counterion; Za ⁺ represents ⁺ N(R ^11a ) ₄ , Na ⁺ or K ⁺ , and the four R ^11a may be the same or different; R ^8a represents a monovalent saturated alkyl group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated alkyl group may be substituted by a halogen atom; R ^9a and R ^10a each independently represent a hydrogen atom or a monovalent saturated alkyl group having 1 to 20 carbon atoms which may have a substituent, and -CH ₂ - contained in the saturated alkyl group may be substituted by -O-, -CO-, -NH- or -NR ^8a -, and R ^9a and R [0066] R 11a and R ^10a may bond to each other to form a 3- to 10-membered heterocyclic ring containing a nitrogen atom; R ^11a represents a hydrogen atom, a monovalent saturated alkyl group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms]. The colored curable resin composition according to claim 4, wherein the compound represented by the formula (1a) is a compound represented by the formula (2a),

[In formula (2a), R ^21a to R ^24a each independently represent a hydrogen atom, -R ^26a , a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent; R ^21a and R ^22a may together form a ring containing a nitrogen atom, and R ^23a and R ^24a may together form a ring containing a nitrogen atom; R ^25a represents a halogen atom, -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Za1 ⁺ , -NR ^28a R ^29a or -SO ₂ NHR ^26a ; m1 represents an integer of 0 to 5; when m1 is 2 or more, a plurality of R ^25a may be the same or different; a1 represents an integer of 0 or 1; Xa1 ^- represents an antiion; R ^28a and R 29a represent an integer of 0 to 5; ^{R 29a} each independently represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and -CH ₂ - contained in the saturated hydrocarbon group may be substituted by -O- or -CO-; R ^28a and R ^29a may bond to each other to form a 3-membered to 10-membered heterocyclic ring containing a nitrogen atom; R ^26a represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a halogen atom or a carboxyl group; Za1 ⁺ represents ⁺ N(R ^27a ) ₄ , Na ⁺ or K ⁺ , and the four R ^27a may be the same or different; R ^27a represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a benzyl group]. A color filter formed from a colored curable resin composition as described in any one of claims 1 to 3. A color filter formed from the colored curable resin composition as described in claim 4. A color filter formed from the colored curable resin composition as described in claim 5. A display device comprising a color filter as described in claim 6.