KR20210127982A - Colored curable resin composition, color filter and display device - Google Patents

Abstract

The present disclosure is a colored curable resin composition that has a high film thickness retention in a color filter before and after post-bake, and does not have a thick line width of a color filter obtained after post-bake, a colorant (A) and A colored curable resin composition comprising a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a thiol compound (E), wherein the colorant (A) contains a xanthene dye, The said thiol compound (E) relates to the colored curable resin composition containing an ether bond containing thiol compound.

Description

Colored curable resin composition, color filter and display device

[0001] The present invention relates to a colored curable resin composition, a color filter, and a display device.

[0002] Japanese Patent Application Laid-Open No. 2018-101015 (Patent Document 1) describes a colored resin composition for color filters containing a colorant represented by the following formula, a binder component, and a solvent.

[0003]

[0004] 1. Japanese Patent Laid-Open No. 2018-101015

[0005] When it is attempted to increase the film thickness retention before and after post bake in the color filter obtained with respect to the colored curable resin composition used for manufacturing the color filter, the line width ( line) tends to be thicker.

[0006] An object of the present invention is that the film thickness retention rate in the color filter before and after post-baking (hereinafter, it may be abbreviated as "film thickness maintenance ratio") is high, and the line width of the color filter obtained after post-baking is thick. It is to provide the colored curable resin composition which does not lose.

[0007] [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) contains a xanthene dye, and the said thiol compound (E) contains an ether bond containing thiol compound, Colored curable resin composition.

[2] The colored curable resin composition according to [1], wherein the ether bond-containing thiol compound is a compound represented by formula (I).

A-(R^One-SH)_n (I)

[Wherein, A represents a residue of a polyhydric alcohol having m hydroxyl groups,

^{A plurality of R 1} bonded to an oxygen atom derived from the m hydroxyl groups, each independently represent an alkylene group having 1 to 10 carbon atoms,

m is an integer of 2 or more, n is an integer of 2 or more, and m≥n.]

[3] The colored curable resin composition according to [2], wherein m is 2 to 10.

[4] The colored curable resin composition according to [2] or [3], wherein the polyhydric alcohol is pentaerythritol or trimethylolpropane.

[5] The colored curable resin composition according to any one of [1] to [4], wherein the xanthene dye contains a compound represented by the formula (1a).

[0008]

[0009] [In formula (1a), R ^1a to R ^4a are each independently a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a carbon number which may have a substituent A monovalent aromatic hydrocarbon group of 6 to 10 is represented, and -CH ₂ - contained in the saturated hydrocarbon group may be substituted with -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 is 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 ^7a each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

m represents the integer of 0-5. When m is 2 or more, a plurality of R ^5a may be the same or different.

a represents the integer of 0 or 1.

Xa ⁻ represents a counter ion.

Za ⁺ represents ⁺ N(R ^11a ) ₄ , Na ⁺ or K ⁺ , and four R ^11a 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 with 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, -CH ₂ - contained in the saturated hydrocarbon group is -O-, -CO- , -NH- or -NR ^8a - may be substituted, and R ^9a and R ^10a may be bonded 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 hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms.]

[6] The colored curable resin composition according to [5], wherein the compound represented by the formula (1a) is a compound represented by the formula (2a).

[0010]

[0011] In formula (2a), R ^21a to R ^24a are each independently a hydrogen atom, -R ^26a , a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a substituent which may have a substituent It represents a C6-C10 monovalent|monohydric aromatic hydrocarbon group. 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 the integer of 0-5. When m1 is 2 or more, a plurality of R ^25a may be the same or different.

a1 represents the integer of 0 or 1.

Xa1 ^- represents a counter ion.

R ^28a and R ^29a each independently represent 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 is -O- or -CO It may be substituted with -, 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 halogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a carboxy group.

Za1 ⁺ represents ⁺ N(R ^27a ) ₄ , Na ⁺ or K ⁺ , and 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 according to any one of [1] to [6].

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

ADVANTAGE OF THE INVENTION According to this invention, the film thickness retention in the color filter before and behind post-baking is high, and the colored curable resin composition in which the line|wire width of the color filter obtained after post-baking does not spread can be provided.

[0013] <Colored curable resin composition>

[Xanthene Dyes]

A xanthene dye is a dye containing the compound which has a xanthene skeleton in a molecule|numerator. As the xanthene dye, for example, C.I. Acid Red 51 (hereinafter, the description of C.I. Acid Red will be omitted and only the number will be described. The same applies to 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 B), sulforhodamine G, the xanthene dye described in Japanese Patent Application Laid-Open No. 2010-32999, and the chromium described in Japanese Patent Publication No. 4492760 Santhene dye etc. are mentioned. It is preferable to dissolve in an organic solvent.

Among these, as the xanthene dye, a dye containing the compound represented by the formula (1a) (hereinafter sometimes referred to as “compound (1a)”) is preferable. Compound (1a) may be a tautomer thereof. When using compound (1a), content of compound (1a) in xanthene dye becomes like this. Preferably it is 50 mass % or more, More preferably, it is 70 mass % or more, More preferably, it is 90 mass % or more. In particular, it is preferable to use only compound (1a) as the xanthene dye. The compound represented by the formula (1a) also includes a tautomer thereof.

[0015]

[0016] In formula (1a), R ^1a to R ^4a are each independently a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or 6 to 10 carbon atoms which may have a substituent A monovalent aromatic hydrocarbon group is represented, and -CH ₂ - contained in the saturated hydrocarbon group may be substituted with -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 is 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 ^7a each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

m represents the integer of 0-5. When m is 2 or more, a plurality of R ^5a may be the same or different.

a represents the integer of 0 or 1.

Xa ^- represents a counter ion.

Za ⁺ represents ⁺ N(R ^11a ) ₄ , Na ⁺ or K ⁺ , and four R ^11a 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 with 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, -CH ₂ - contained in the saturated hydrocarbon group is -O-, -CO- , -NH- or -NR ^8a - may be substituted, and R ^9a and R ^10a may be bonded 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 hydrocarbon 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 a phenyl group, a toluyl group, a xylyl group, a mesityl group, a propylphenyl group, and a butylphenyl group.

[0018] Examples of the substituent that the aromatic hydrocarbon group may have include a halogen atom, a carboxy group, a silicon atom-containing group, -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, as the substituent, a group containing a silicon _{^{atom, -SO 3 -, -SO 3 H}} , -SO 3 - Za +, -SO 2 NR 9a R 10a groups are preferred, and containing a silicon atom, -SO ₃ ^- Za ⁺ and -SO ₂ NR ^9a R ^10a are more preferable. As -SO ₃ ^- Za ^{+ in} this case, -SO ₃ ^{- +} N(R ^11a ) ₄ is preferable. When R ^1a to R ^4a are these groups, from the colored curable resin composition of the present invention containing the compound (1a), it is possible to form a color filter with little foreign matter and excellent heat resistance. The silicon atom-containing group refers to a group containing a silicon atom, for example, a contribution represented by the formula (ii) may also be used.

-Si(R^50a)₃ (ii)

[In the formula, R ^50a represents a hydrogen atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. A plurality of R ^50a may be the same or different.]

R ^50a is preferably an alkoxy group having 1 to 4 carbon atoms. Specific examples of the silicon atom-containing group include a silyloxy group such as trimethylsilyloxy group, triethylsilyloxy group, trimethoxysilyl group, triethoxysilyl and the like.

[0019] ^{Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R 1a} to R ^4a and R ^8a to R ^11a include, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, straight-chain alkyl groups such as octyl group, nonyl group, decyl group, dodecyl group, hexadecyl group and icosyl group; branched alkyl groups such as isopropyl group, isobutyl group, isopentyl group, neopentyl group and 2-ethylhexyl group; and alicyclic saturated hydrocarbon groups having 3 to 20 carbon atoms, such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and a cyclodecyl group.

[0020] ^{Examples of the substituent which the saturated hydrocarbon group in R 1a} to R ^4a may have include a carboxy group, an aromatic hydrocarbon group having 6 to 10 carbon atoms, a silicon atom-containing group, and a halogen atom. Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms are the same as the aromatic hydrocarbon group in ^{R 1a} to R ^4a. Examples and preferable ranges of the silicon atom-containing group are the same as those described as the substituents which the aromatic hydrocarbon group in ^{R 1a} to R ^{4a may have.}

As ^{a substituent which the said saturated hydrocarbon group in R 1a} to R ^4a may have, it is preferable that they are a carboxy group and a silicon-atom containing group.

[0021] ^{Examples of the substituent which the saturated hydrocarbon group may have in R 9a} and R ^10a include a hydroxyl group, a silicon atom-containing group, and a halogen atom. Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms are the same as described above. Examples and preferred ranges of the silicon atom-containing group are the same as described above.

[0022] 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.}

[0023]

[0024] As -OR ^8a , for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a 2-ethylhexyloxy group, an icosyloxy group, etc. can be heard

[0025] _{Examples of -CO 2} R ^8a include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a tert-butoxycarbonyl group, a hexyloxycarbonyl group, and an icosyloxycarbonyl group.

[0026] ^{Examples of -SR 8a} include a methylsulfanyl group, an ethylsulfanyl group, a butylsulfanyl group, a hexylsulfanyl group, a decylsulfanyl group, and an icosylsulfanyl group.

Examples of -SO ₂ R ^8a include a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group, a decylsulfonyl group, and an icosylsulfonyl group.

Examples of -SO ₃ R ^8a include a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a tert-butoxysulfonyl group, a hexyloxysulfonyl group, and an icosyloxysulfonyl group.

[0027] -SO ₂ NR ^{9a As} R ^10a , for example, a sulfamoyl group;

N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group, N-tert-butylsulfamoyl group, N-pentylsulfamo group diyl, N-(1,1-dimethylpropyl)sulfamoyl group, N-(2,2-dimethylpropyl)sulfamoyl group, N-(2-methylbutyl)sulfamoyl group, N-cyclopentylsulfamoyl group, N-hexylsulfamoyl group, N-(1,3-dimethylbutyl)sulfamoyl group, N-heptylsulfamoyl group, N-(1-methylhexyl)sulfamoyl group, N-(2-ethylhexyl)sulfamo group N-1 substituted sulfamoyl groups, such as a diyl and N-(1,1,2,2-tetramethylbutyl) sulfamoyl group;

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

R ^5a is 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 Preferably, SO ₃ ^- , -SO ₃ ^- Za ⁺ , -SO ₃ H, -NR ^9a R ^10a or SO ₂ NHR ^9a is more preferable.

It is preferable that R ^9a and R ^10a are each independently a C1-C6 saturated hydrocarbon group which may have a substituent.

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

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

[0031] Za ⁺ is ⁺ N(R ^11a ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N(R ^11a ) ₄ .

As said ⁺ N(R ^11a ) ₄ , it is preferable that at least 2 among four R ^11a are C5-C20 monovalent|monohydric saturated hydrocarbon groups. Moreover, 20-80 are preferable and, as for total carbon number of ^{four R11a, 20-60 are more preferable.} When ⁺ N(R ^11a ) ₄ is present in the ^{compound (1a), if R 11a} is these groups, a color filter with few foreign substances can be formed from the colored curable resin composition of the present invention containing the compound (1a). .

Examples of ^{the counter ion represented by Xa −} include a halide ion and a counter ion represented by the formulas (y1) and (y2).

[0032]

[0033] In the formula (y1), R ^B1 represents a fluorinated alkyl group having 1 to 12 carbon atoms.

In formula (y2), R ^B2 and R ^B3 each independently represent a halogen atom or a fluorinated alkyl group having 1 to 12 carbon atoms.]

Examples of the halide ion include a fluoride ion, a chloride ion, a bromide ion and an iodide ion.

[0034] As ^{the C1-C12 fluorinated alkyl group represented by R B1} , specifically, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 1,1,2,2,2-pentafluoroethyl group, 2,2,2-trifluoroethyl group, 3-(trifluoromethyl)-3,4,4,4-pentafluorobutyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group group, perfluorobutyl group, perfluorosec-butyl group, perfluorotert-butyl group, perfluoropentyl group and perfluorohexyl group, preferably all hydrogen atoms are substituted with fluorine atoms group (that is, a perfluoroalkyl group), and more preferably a perfluoroalkyl group having 1 to 4 carbon atoms.

[0035] Examples of ^{the halogen atom represented by R B2} and R ^B3 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable.

Examples of the fluorinated alkyl group having 1 to 12 carbon atoms represented by R ^B2 and R ^{B3 include the same groups as the fluorinated alkyl group represented by R B1} , and preferably a perfluoroalkyl group having 1 to 4 carbon atoms.

R ^B2 and R ^B3 may combine with each other to form a ring containing _{-SO 2} -N ^- -SO _{2 -.}

As the compound (1a), a compound represented by the formula (2a) (hereinafter sometimes referred to as “compound (2a)”) is preferable. Compound (2a) may be a tautomer thereof.

[0037]

[0038] In formula (2a), R ^21a to R ^24a are each independently a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or 6 to 10 carbon atoms which may have a substituent Phosphorus represents a monovalent aromatic hydrocarbon group. 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 the integer of 0-5. When m1 is 2 or more, a plurality of R ^25a may be the same or different.

a1 represents the integer of 0 or 1.

Xa1 ^- represents a counter ion.

R ^28a and R ^29a each independently represent 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 is -O- or -CO It may be substituted with -, 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 halogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a carboxy group.

Za1 ⁺ represents ⁺ N(R ^27a ) ₄ , Na ⁺ or K ⁺ , and 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.]

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ^21a to R ^24a include the same groups as those exemplified as the aromatic hydrocarbon group for ^{R 1a} to R ^4a. A hydrogen atom contained in the aromatic hydrocarbon group may be substituted with a carboxy 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 , 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 silicon atom-containing group or a carboxy group. ), and R ^22a and R ^24a are each independently a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms (a hydrogen atom contained in the aromatic hydrocarbon group is a carboxy group, a silicon atom-containing group, -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Za1 ⁺ , -SO ₃ R ^26a or -SO ₂ NHR ^26a may be substituted.). A more preferable 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 silicon atom-containing group or a carboxy group.), R ^22a and R ^24a is a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms (a hydrogen atom contained in the aromatic hydrocarbon group may be substituted with a _{carboxy group, a silicon atom-containing group, -SO 3} ^- Za1 ⁺ or -SO ₂ NHR ^26a.) . If ^R21a - ^R24a are these groups, the color filter excellent in heat resistance can be formed from the colored curable resin composition of this invention containing a compound (2a). Examples and preferred ranges of the silicon atom-containing group are the same as the examples and preferred ranges in the description of Formula (1a) described above.

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent in R ^21a to R ^24a include the same groups as those exemplified as the aromatic hydrocarbon group for ^{R 1a} to R ^{4a above.} A hydrogen atom contained in the aromatic hydrocarbon group may be substituted with a _{silicon atom-containing group, -SO 3} ^- , -SO ₃ H, -SO ₃ ^- Za1 ⁺ , -SO ₃ R ^26a or -SO ₂ NHR ^26a. Examples and preferred ranges of the silicon atom-containing group are the same as the examples and preferred ranges in the description of Formula (1a) described above.

^{Examples of} R 28a and R ^29a are the same as those ^{of R 9a} and R ^10a in Formula (1a).

[0041] As ^{a ring containing a nitrogen atom formed together by R 21a} and R ^22a , and a ring containing a nitrogen atom formed together by R ^23a and R ^24a , the same as the ring formed by R ^1a and R ^{2a together} thing can be heard Especially, an aliphatic heterocyclic ring is preferable. Examples of the aliphatic heterocycle include the following.

[0042]

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ^26a and R ^27a include the same groups as those exemplified as the saturated hydrocarbon group in ^{R 8a} to R ^11a.

When R ^21a to R ^24a are a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, it ^{is preferable that R 21a} to R ^24a each independently represent a methyl group or an ethyl group. In addition, as the -SO ₃ R ^26a, and -SO ₂ NHR ^26a R ^26a in, having 3 to 20 carbon atoms of branched chain-like alkyl group is preferred, and a carbon number of 6 to 12 branched alkyl group and more preferably a shape of 2-ethyl A hexyl group is more preferable. If R ^26a is these groups, a color filter with little generation|occurrence|production of a foreign material can be formed from the colored curable resin composition of this invention containing a compound (2a).

[0044] Za1 ⁺ is ⁺ N(R ^27a ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N(R ^27a ) ₄ .

As said ⁺ N( ^R27a ) ₄ , ^{it is preferable that at least 2 of four R27a} are C5-C20 monovalent|monohydric saturated hydrocarbon groups. Moreover, 20-80 are preferable and, as for total carbon number of ^{four R27a, 20-60 are more preferable.} When ⁺ N(R ^27a ) ₄ is present in ^{compound (2a), if R 27a} is these groups, from the colored curable resin composition of the present invention containing compound (2a), a color filter with less generation of foreign matter can be formed. can

[0045] Xa1 ^- is the same as illustrated and a preferred range in the description ^of-the counter ion is represented by the Xa.

[0046] Further, as the compound (1a), a compound represented by the formula (3a) (hereinafter sometimes referred to as “compound (3a)”) is also preferable. Compound (3a) may be a tautomer thereof.

[0047]

[0048] In [Formula (3a), R ^31a and R ^32a each independently represent a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group is an aromatic hydrocarbon having 6 to 10 carbon atoms. A group, a carboxy group, a silicon atom-containing group or a halogen atom may be substituted, and the hydrogen atom contained in the aromatic hydrocarbon group may be substituted with a silicon atom-containing group or an alkoxy group having 1 to 3 carbon atoms, and contained in the saturated hydrocarbon group - CH ₂ - may be substituted with -O-, -CO- or -NR ^{11a -.}

R ^33a and R ^34a each independently represent a silicon atom-containing group, an alkyl group having 1 to 4 carbon atoms, an alkylsulfanyl 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, and R ^32a and R ^34a may together form a ring containing a nitrogen atom.

p and q each independently represent the integer of 0-5. When p is 2 or more, some R ^33a may be same or different, and when q is 2 or more, some R ^34a may be same or different.

R ^11a has the same meaning as above.]

Examples of the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms in R ^31a and R ^32a include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. and the like.

A phenyl group, a toluyl group, a xylyl group, a mesityl group, a propylphenyl group, a butylphenyl group, etc. are mentioned as a C6-C10 aromatic hydrocarbon group which you may have as a substituent.

As a C1-C3 alkoxy group, a methoxy group, an ethoxy group, a propoxy group, etc. are mentioned.

It is preferable that R ^31a and R ^32a each independently represent a monovalent saturated hydrocarbon group having 1 to 3 carbon atoms (the saturated hydrocarbon group may have a halogen atom or a carboxy group).

Examples and preferred ranges of the silicon atom-containing group are the same as the examples and preferred ranges in the description of Formula (1a) described above.

Examples of the alkyl group having 1 to 4 carbon atoms in R ^33a and R ^34a include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. have.

Examples of the alkylsulfanyl group having 1 to 4 carbon atoms in R ^33a and R ^34a include a methylsulfanyl group, an ethylsulfanyl group, a propylsulfanyl group, a butylsulfanyl group and an isopropylsulfanyl group.

Examples of the alkylsulfonyl group having 1 to 4 carbon atoms in R ^33a and R ^34a include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, a butylsulfonyl group and an isopropylsulfonyl group.

R ^33a and R ^34a are each independently preferably an alkyl group having 1 to 4 carbon atoms, 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 the examples and preferred ranges in the description of Formula (1a) described above.

[0051] As for p and q, an integer of 0 to 2 is preferable, and 0 or 1 is preferable.

[0052] Examples of the compound (1a) include compounds represented by formulas (1-1) to (1-97). In the formula, R ^40a represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, preferably a branched alkyl group having 6 to 12 carbon atoms, and more preferably a 2-ethylhexyl group. R ^26a has the same meaning as in Formula (2a).

[0053]

[0054]

[0055]

[0056]

[0057]

[0058]

[0059]

[0060]

[0061]

[0062]

[0063]

[0064]

[0065]

[0066]

[0067]

[0068]

[0069]

[0070]

[0071]

[0072] Among the compounds, represented by formulas (1-1) to (1-14), (1-27) to (1-75) and (1-92) to (1-97), The compound represented by Formulas (1-15) to Formula (1-26) and Formulas (1-76) to Formula (1-91) corresponds to Compound (2a), and the compound represented by Formulas (1-76) to Formula (1-91) corresponds to Compound (3a). .

As the xanthene dye, a commercially available xanthene dye (eg, “Chugai Aminol Fast Pink RH/C” manufactured by Chugai Kasei Company, Limited, “Rhodamin 6G” manufactured by Taoka Chemical Company, Limited) may be used. can In addition, it is also possible to synthesize a commercially available xanthene dye as a starting material with reference to Japanese Patent Application Laid-Open No. 2010-32999.

[0074] The content of the xanthene dye in the colorant (A) may be, for example, 0.1 mass% or more and 100 mass% or less, more preferably 0.1 mass%, based on the total amount of solid content in the colorant (A). It is more than 99.0 mass %, More preferably, it is 0.5 mass % or more and 90.0 mass % or less, Especially preferably, it is 1.0 mass % or more and 50.0 mass % or less, Especially preferably, it is 1.5 mass % or more and 30.0 mass % or less.

[0075] In the present specification, "total amount of solid content in the colorant (A)" refers to the total amount of components excluding the solvent (F) from the colorant (A). In this invention, the total amount of solid content and content of each component with respect to this can be measured by well-known analytical means, such as liquid chromatography or gas chromatography, for example.

[0076] [1] Colorant (A)

With respect to the total amount of solid content in colored curable resin composition, the content rate of the coloring agent (A) in colored curable resin composition becomes like this. Preferably it is 5 mass % or more and 80 mass % or less, More preferably, it is 5 mass % or more and 70 mass %. It is less than, More preferably, it is 5 mass % or more and 60 mass % or less. If the content rate of a coloring agent (A) is in said range, desired spectroscopy and color density can be obtained.

[0077] In the present specification, "the total amount of solid content in the colored curable resin composition" refers to the total amount of components excluding the solvent (F) from the colored curable resin composition.

[0078] When the colored curable resin composition contains a solvent (hereinafter also referred to as a solvent (F)), after preparing a colorant-containing liquid containing the colorant (A) and the solvent (F) in advance, the You may prepare colored curable resin composition using a coloring agent containing liquid. When a coloring agent (A) does not melt|dissolve in a solvent (F), a coloring agent containing liquid can be prepared as a dispersion liquid by disperse|distributing and mixing a coloring agent (A) in a solvent (F). The coloring agent containing liquid may contain a part or all of the solvent (F) contained in colored curable resin composition.

[0079] The content of solids in 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, with respect to the total amount of the colorant-containing liquid, more preferably They are 1 mass % or more and 60 mass % or less, Especially preferably, they are 3 mass % or more and 50 mass % or less.

The content rate of the colorant (A) in the colorant-containing liquid is preferably 0.01% by mass or more and 100% by mass or less, more preferably 0.1% by mass or more and 99.9% by mass or less of the total amount of solid content in the colorant-containing liquid, , More preferably, they are 1 mass % or more and 99 mass % or less, Especially preferably, they are 10 mass % or more and 90 mass % or less.

[0081] In the present specification, "total amount of solid content in the colorant-containing liquid" refers to the total amount of components excluding the solvent (F) from the colorant-containing liquid.

[0082] The colorant (A) can be uniformly dispersed in the colorant-containing liquid by subjecting the colorant (A) to a dispersion treatment containing a dispersing agent.

[0083] Examples of the dispersing agent include surfactants, and any surfactants of cationic, anionic, nonionic and amphoteric surfactants may be used. Specifically, surfactants, such as a polyester type, a polyamine type, and an acryl type, etc. are mentioned. You may use these dispersing agents individually or in combination of 2 or more type. As a dispersing agent, if represented by a brand name, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Florene (manufactured by KYOEISHA CHEMICAL Co., LTD.), Solsperse (registered trademark) (manufactured by Zeneca Co., Ltd.), EFKA ( (registered trademark) (manufactured by BASF Co., Ltd.), Azispa (registered trademark) (manufactured by Ajinomoto Fine-Techno Co., Inc.) and Disperbyk (registered trademark) (manufactured by BYK-Chemie Co., Ltd.), BYK (registered trademark) (BYK-Chemie Co., Ltd. product) etc. are mentioned.

[0084] When a dispersant is used to prepare the colorant-containing liquid, the amount of the dispersant (solid content) used is preferably 5 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the colorant (A), More preferably, they are 5 mass parts or more and 50 mass parts or less. When the usage-amount of this dispersing agent exists in said range, there exists a tendency for the colorant containing liquid in a more uniformly dispersed state to be obtained.

[0085] The colorant (A) may further contain a colorant (hereinafter also referred to as a colorant (A1)) other than the above-described xanthene dye.

The coloring agent (A1) may contain at least 1 sort(s) chosen from the group which consists of dyes and pigments other than the above-mentioned xanthene dye.

[0086] As the dye included in the colorant (A1), a known dye may be used, and solvent dyes, acid dyes, direct dyes, mordant dyes, and the like may be mentioned, for example, color index (The Society of Dyers and Colorists published). ) as solvent, acid, basic, reactive, direct, disperse, mordant, or vat, etc.色染社])) and the known dyes described in the present invention. What is necessary is just to select dye suitably according to the spectral spectrum of a desired color filter. These dyes may be used independently and may use 2 or more types together. The dye is preferably an organic solvent-soluble dye.

[0087] As a specific example of the dye, C.I. Solvent Yellow 4 (hereinafter, description of CI solvent yellow etc. will be omitted and only numbers will be described.), 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 2, 7, 11, 15, 26, 56, 77, 86;

C.I. Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60;

C.I. 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 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35, etc. 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, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;

C.I. Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 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, 268, 270, 274, 277, 280, 281, 289, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 388, 394, 401, 412, 417, 418, 422, 426;

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

C.I. Acid Violet 6B, 7, 9, 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, CIs of 104, 105, 106, 109, etc. acid dye,

C.I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141;

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

C.I. Direct Blue 1, 2, 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, 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, etc. C.I. direct dye,

C.I. Disperse Yellow 51, 54, 76;

C.I. Disperse Violet 26, 27;

C.I. Disperse Blue 1, 14, 56, 60, etc. C.I. dispers dye,

C.I. Basic Red 1, 10;

C.I. Basic 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. Basic Violet 2;

C.I. Basic Red 9;

C.I. Basic Green 1, etc. C.I. basic dye,

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. Modern 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. Mordant Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;

C.I. Mordant Violet 1, 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. Modern 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, etc. C.I. modern dye,

C.I. Bat Green 1, etc. C.I. Vat dye etc. are mentioned.

In addition, as the dye, according to the chemical structure, a triarylmethane dye, azo dye, cyanine dye, triphenylmethane dye, phthalocyanine dye, anthraquinone dye, naphthoquinone dye, quinoneimine dye, methine dye, azo methine dye, squarylium dye, acridine dye, styryl dye, coumarin dye, quinoline dye, nitro dye, tetraazaporphyrin dye, etc. are mentioned.

As for the colored curable resin composition of this invention, it is preferable that a coloring agent (A) contains a triarylmethane type dye as dye. When a coloring agent (A) contains a triarylmethane type dye, since there exists a tendency for the brightness of the color filter obtained to improve, it is preferable.

[0089] Examples of the pigment included in the colorant (A1) include organic pigments and inorganic pigments, and compounds classified as pigments in the Color Index (published by The Society of Dyers and Colorists). A pigment can be used individually or in combination of 2 or more types.

[0090] As the pigment, 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 yellow pigments;

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

C.I. blue pigments such as pigment blue 15, 15:3, 15:4, 15:6, 21, 28, 60, 64 and 76;

C.I. Violet pigments, such as pigment violet 1, 14, 19, 23, 29, 32, 33, 36, 37, 38;

C.I. Green pigments, such as pigment green 7, 10, 15, 25, 36, 47, 58, 59;

C.I. Brown pigments, such as Pigment Brown 23, 25, and 28;

C.I. Black pigments, such as Pigment Black 1 and 7, etc. are mentioned.

[0091] Pigments, if necessary, rosin treatment, surface treatment using a pigment derivative into which an acidic group or basic group is introduced, graft treatment to the pigment surface with a polymer compound, etc., sulfuric acid atomization method Atomization treatment by such as, washing treatment with an organic solvent or water for removing impurities, removal treatment by ion exchange method of ionic impurities, etc. may be performed. It is preferable that the particle diameters of a pigment are respectively uniform.

[0092] The pigment can be made into a pigment dispersion in a state uniformly dispersed in a pigment dispersant solution by containing a pigment dispersant and performing a dispersion treatment. A pigment may be disperse|distributed independently, respectively, and may mix and disperse|distribute multiple types.

[0093] Examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic pigment dispersants. These pigment dispersants may be used independently and may be used in combination of 2 or more type. As a pigment dispersant, as a trade name, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Florene (manufactured by KYOEISHA CHEMICAL Co., LTD.), Solsperse (manufactured by Zeneca Co., Ltd.), EFKA (manufactured by BASF Co., Ltd.) ), Ajispar (manufactured by Ajinomoto Fine-Techno Co., Inc.), Disperbyk (manufactured by BYK-Chemie), and the like.

[0094] When a pigment dispersant is used, the amount used is preferably 100 parts by mass or less, and more preferably 5 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the pigment. When the usage-amount of a pigment dispersant exists in said range, there exists a tendency for the pigment dispersion liquid of a uniformly dispersed state to be obtained.

When the colorant (A) contains the colorant (A1), the content of the colorant (A1) in the colorant (A) is, for example, 0.1% by mass or more and 99.9% by mass based on the total amount of solid content of the colorant (A). It may be less than, More preferably, they are 0.1 mass % or more and 99 mass % or less, More preferably, they are 0.5 mass % or more and 97 mass % or less.

When the colorant (A) contains a triarylmethane-based dye, the content rate of the triarylmethane-based dye in the colorant (A) may be within the range of the content rate of the colorant (A1), but more preferably the content of the colorant (A) It is 98 mass % or less based on the total amount of solid content, More preferably, it is 95 mass % or less, More preferably, it is 10 mass % or more, More preferably, it is 20 mass % or more. In addition, when a coloring agent (A) contains a triarylmethane type dye, a coloring agent (A) may contain only a xanthene dye and a triarylmethane type dye, and may contain another coloring agent (A1) in addition to these.

[0096] [2] Resin (B)

The colored curable resin composition of this invention contains 1 type, or 2 or more types of resin (B). It is preferable that resin (B) is alkali-soluble resin. Alkali solubility means the property to melt|dissolve in the developing solution which is the aqueous solution of an alkali compound. Examples of the resin (B) include the following resins [K1] to [K6].

[0097] Resin [K1]: at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride (a) [hereinafter sometimes referred to as “(a)”], and 2 to carbon atoms A copolymer of a monomer (b) (hereinafter, sometimes referred to as “(b)”) having a 4-membered cyclic ether structure and an ethylenically unsaturated bond.

Resin [K2]: (a) and (b) and a monomer (c) copolymerizable with (a) (however, different from (a) and (b).) [hereinafter referred to as “(c)” Yes.] of copolymers.

Resin [K3]: a copolymer of (a) and (c).

Resin [K4]: A resin obtained by reacting (b) with the copolymer of (a) and (c).

Resin [K5]: A resin obtained by reacting (a) with the copolymer of (b) and (c).

Resin [K6]: Resin obtained by making (a) react with the copolymer of (b) and (c), and also making carboxylic anhydride react.

As (a), specifically,

unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid;

Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexenedicarboxylic acid;

Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene , 5-Carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo Bicyclo unsaturated compounds containing a carboxy group, such as [2.2.1]hept-2-ene and 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene;

Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride , unsaturated dicarboxylic acid anhydrides such as dimethyltetrahydrophthalic anhydride and 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride (himic acid anhydride);

Unsaturated mono[(meth)acryloyloxyalkyl of divalent or higher polyhydric carboxylic acid such as monosuccinic acid mono[2-(meth)acryloyloxyethyl] and phthalic acid mono[2-(meth)acryloyloxyethyl] 〕ester;

and unsaturated (meth)acrylic acid containing a hydroxyl group and a carboxyl group in the same molecule such as α-(hydroxymethyl)(meth)acrylic acid.

Among them, from the viewpoint of copolymerization reactivity and solubility in aqueous alkali solution, (a) is preferably (meth)acrylic acid, maleic anhydride, or the like, and more preferably acrylic acid and maleic anhydride.

In addition, in this specification, "(meth)acryl" refers to at least one selected from the group consisting of acryl and methacryl. The same applies to descriptions such as “(meth)acryloyl” and “(meth)acrylate”.

[0100] (b) is a cyclic ether structure having 2 to 4 carbon atoms (eg, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring (oxolane ring)) and ethylenic It refers to a polymerizable compound having an unsaturated bond. (b) is preferably a monomer having a cyclic ether structure having 2 to 4 carbon atoms and a (meth)acryloyloxy group.

As (b), a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond [hereinafter sometimes referred to as "(b1)"], a monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond [hereinafter referred to as "(b1)") .

[0101] As (b1), a monomer (b1-1) having a structure in which an unsaturated aliphatic hydrocarbon is epoxidized [hereinafter sometimes referred to as "(b1-1)"], an unsaturated alicyclic hydrocarbon is epoxidized The monomer (b1-2) [hereinafter, sometimes referred to as “(b1-2)”] having a structure is mentioned.

[0102] As (b1-1), glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethyl glycidyl (meth) acrylate, glycidyl vinyl ether, o -vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl Ether, α-methyl-p-vinylbenzylglycidyl ether, 2,3-bis(glycidyloxymethyl)styrene, 2,4-bis(glycidyloxymethyl)styrene, 2,5-bis(glycidyl) Cydyloxymethyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene, 2,3,5-tris (glycidyloxymethyl) ) Styrene, 2,3,6-tris(glycidyloxymethyl)styrene, 3,4,5-tris(glycidyloxymethyl)styrene, 2,4,6-tris(glycidyloxymethyl)styrene and the like.

[0103] As (b1-2), vinylcyclohexene monoxide, 1,2-epoxy 4-vinylcyclohexane (eg, Seroxide 2000; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl (meth)acrylate (eg, cyclomer A400; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl (meth)acrylate (eg, cyclomer M100; manufactured by Daicel Chemical Industries, Ltd.); The compound represented by Formula (BI), the compound represented by Formula (B-II), etc. are mentioned.

[0104]

[0105] [In formulas (BI) and (B-II), R ^a and R ^b each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is, It may be substituted with a hydroxyl group. X ¹ and X ² each independently represent a single bond, *-R ^c -, *-R ^c -O-, *-R ^c -S-, or *-R ^c -NH-. R ^c represents an alkanediyl group having 1 to 6 carbon atoms. * indicates a bond with O.]

Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group.

Examples of the alkyl group in which a hydrogen atom is substituted with hydroxy include a hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, and 1-hydroxy group. and a hydroxy-1-methylethyl group, a 2-hydroxy-1-methylethyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group and a 4-hydroxybutyl group.

R ^a and R ^b are preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group or a 2-hydroxyethyl group, and more preferably a hydrogen atom or a methyl group.

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, and a pentane-1,5-diyl group. diyl, a hexane-1,6-diyl group, etc. are mentioned.

[0107] X ¹ and X ² are preferably a single bond, a methylene group, an ethylene group, *-CH ₂ -O- (* represents a bond with O) group, *-CH ₂ CH ₂ -O- It is a group, More preferably, it is a single bond, *-CH ₂ CH ₂ -O- group.

Specific examples of the compound represented by formula (BI) include compounds represented by formulas (BI-1) to (BI-15), preferably formulas (BI-1) and (BI-3) ), a compound represented by a formula (BI-5), a formula (BI-7), a formula (BI-9), a formula (BI-11) to a formula (BI-15), and more preferably a formula (BI-1), a compound represented by a formula (BI-7), a formula (BI-9), and a formula (BI-15) is mentioned.

[0108]

[0109]

[0110] Specific examples of the compound represented by formula (B-II) include compounds represented by formulas (B-II-1) to (B-II-15), preferably formula (B- II-1), formula (B-II-3), formula (B-II-5), formula (B-II-7), formula (B-II-9), formula (B-II-11)~ The compound represented by Formula (B-II-15) is mentioned, More preferably, Formula (B-II-1), Formula (B-II-7), Formula (B-II-9), Formula ( B-II-15);

[0111]

[0112]

[0113] The compound represented by the formula (B-I) and the compound represented by the formula (B-II) can be used alone, respectively. These can be mixed in arbitrary ratios. When mixing, the mixing ratio is the formula (BI): formula (B-II) [molar ratio], preferably 5:95 to 95:5, more preferably 10:90 to 90:10, still more preferably Usually it is 20:80~80:20.

It is preferable that the monomer (b2) which has an oxetanyl group and an ethylenically unsaturated bond is a monomer which has an oxetanyl group and a (meth)acryloyloxy group.

Preferred examples of (b2) include 3-methyl-3-(meth)acryloyloxymethyloxetane, 3-ethyl-3-(meth)acryloyloxymethyloxetane, 3-methyl-3-(meth) ) Acryloyloxyethyloxetane and 3-ethyl-3-(meth)acryloyloxyethyloxetane are mentioned.

It is preferable that the monomer (b3) which has a tetrahydrofuryl group and an ethylenically unsaturated bond is a monomer which has a tetrahydrofuryl group and a (meth)acryloyloxy group.

Preferred examples of (b3) include tetrahydrofurfuryl acrylate (eg, Viscote V#150, manufactured by OSAKA ORGANIC CHEMICAL INDUSTRY LTD), tetrahydrofurfuryl methacrylate, and the like.

[0114] As a specific example of (c),

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) acrylic rate, tricyclo[5.2.1.0 ^2,6 ]decan-8-yl(meth)acrylate [In the technical field, it is called "dicyclofentanyl(meth)acrylate" as a common name. Also, sometimes referred to as “tricyclodecyl (meth)acrylate.”], tricyclo[5.2.1.0 ^2,6 ]decen-8-yl (meth)acrylate [in the technical field, as a common name, “ Dicyclopentenyl (meth) acrylate.], dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate , (meth)acrylic acid esters such as propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, and benzyl (meth)acrylate;

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

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

Bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybi Cyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2 -ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept -2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-di(2'-hydroxyethyl)bicyclo[2.2.1]hept- 2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methyl Bicyclo[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[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxy Cycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(cyclohexylox bicyclo unsaturated compounds such as cycarbonyl)bicyclo[2.2.1]hept-2-ene;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-4-maleimidebutyrate, N-succinimidyl- dicarbonylimide derivatives such as 6-maleimide caproate, N-succinimidyl-3-maleimide propionate, and N-(9-acridinyl)maleimide;

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

Among them, from the viewpoint of copolymerization reactivity and heat resistance, as (c), benzyl (meth)acrylate, tricyclodecyl (meth)acrylate, styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N -benzylmaleimide, bicyclo[2.2.1]hept-2-ene, etc. are preferable. Moreover, as (c), benzyl (meth)acrylate and tricyclodecyl (meth)acrylate are more preferable at the point which is excellent in the developability at the time of pattern formation.

[0115] In the resin [K1], the ratio of the structural units derived from each is preferably in the following range among all the structural units constituting the resin [K1].

a structural unit derived from (a); 2-50 mol% (more preferably 10-45 mol%),

the structural unit derived from (b), particularly the structural unit derived from (b1); 50 to 98 mol% (more preferably 55 to 90 mol%).

When the ratio of the structural unit of resin [K1] exists in the said range, there exists a tendency excellent in storage stability, developability, and solvent resistance of the pattern obtained.

Resin [K1] is the method described in the document "Experimental Method of Polymer Synthesis" (published by Takayuki Otsu, Kagaku-Dojin Publishing Company, INC. 1st Edition 1st Edition March 1, 1972) and the method described in the document It can be prepared with reference to the cited references described.

Specifically, a method in which predetermined amounts of (a) and (b) (especially (b1)), a polymerization initiator, a solvent, etc. are put into a reaction vessel, and stirred, heated, and kept warm in a deoxygenated atmosphere. can In addition, the polymerization initiator, a solvent, etc. used here are not specifically limited, Any of those normally used in the said field|area can be used. Examples of the polymerization initiator include azo compounds (such as 2,2'-azobisisobutyronitrile and 2,2'-azobis(2,4-dimethylvaleronitrile)) and organic peroxides (such as benzoyl peroxide). have. As a solvent, what is necessary is just to melt|dissolve each monomer, The solvent (F) etc. which are mentioned later can be used as a solvent of colored curable resin composition.

As for the obtained copolymer, the solution after reaction may be used as it is, a concentrated or diluted solution may be used, Even if it uses what was extracted as a solid (powder) by methods, such as re-precipitation, do. In particular, by using the below-mentioned solvent (F) as a solvent at the time of this polymerization, the solution after reaction can be used as it is, and a manufacturing process can be simplified.

[0116] In the resin [K2], the proportion of the structural units derived from each is preferably in the following range among all the structural units constituting the resin [K2].

a structural unit derived from (a); 4 to 45 mol%, more preferably 10 to 40 mol%, still more preferably 15 to 35 mol%,

the structural unit derived from (b), particularly the structural unit derived from (b1); 2-95 mol%, more preferably 3-70 mol%, still more preferably 5-45 mol%,

a structural unit derived from (c); 1-94 mol%, More preferably, 20-85 mol%, More preferably, 40-80 mol%.

When the ratio of the structural unit of the resin [K2] is within the above range, it tends to be excellent in storage stability, developability, solvent resistance, heat resistance, and mechanical strength of the pattern obtained.

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 in which predetermined amounts of (a), (b) (especially (b1)) and (c), a polymerization initiator, and a solvent are put into a reaction vessel, and stirred, heated, and kept warm in a deoxidized atmosphere. can The obtained copolymer may use the solution after reaction as it is, may use the concentrated or diluted solution, and may use what was extracted as solid (powder) by methods, such as reprecipitation.

[0117] In the resin [K3], the ratio of the structural units derived from each is preferably in the following range among all the structural units constituting the resin [K3].

a structural unit derived from (a); 2 to 55 mol%, more preferably 10 to 50 mol%, still more preferably 15 to 50 mol%, particularly preferably 25 to 50 mol%,

a structural unit derived from (c); 45-98 mol%, More preferably, 50-90 mol%, More preferably, 50-85 mol%, Especially preferably, 50-75 mol%.

The resin [K3] can be produced in the same manner as the method described as the method for producing the resin [K1].

[0118] Resin [K4] obtains a copolymer of (a) and (c), and (b) has a cyclic ether structure having 2 to 4 carbon atoms, in particular (b1) has an oxirane ring (a) It can be prepared by adding to the carboxylic acid and/or carboxylic acid anhydride having Specifically, first, the copolymer of (a) and (c) is produced in the same manner as described as the method for producing the resin [K1]. In this case, it is preferable that the ratio of the structural unit derived from each exists in the following range among all the structural units which comprise the copolymer of (a) and (c).

a structural unit derived from (a); 5-50 mol% (more preferably 10-45 mol%),

a structural unit derived from (c); 50 to 95 mol% (more preferably 55 to 90 mol%).

[0119] Next, in a part of the carboxylic acid and/or carboxylic acid anhydride derived from (a) in the copolymer, (b) has a cyclic ether structure having 2 to 4 carbon atoms, particularly (b1) The branches react with the oxirane ring. Specifically, following the preparation of the copolymer of (a) and (c), the atmosphere in the flask is substituted with air from nitrogen, and (b) (particularly (b1)), a carboxylic acid or a carboxylic acid anhydride and a ring A reaction catalyst (such as tris(dimethylaminomethyl)phenol) and a polymerization inhibitor (such as hydroquinone) having a shape ether structure are placed in a flask, and reacted at 60 to 130° C. for 1 to 10 hours, whereby the resin [K4 ] can be obtained.

The usage-amount of (b), especially the usage-amount of (b1) becomes like this with respect to (a) 100 mol, Preferably it is 5-80 mol, More preferably, it is 10-75 mol. By setting it as this range, there exists a tendency for the balance of storage stability, developability, solvent resistance, heat resistance, mechanical strength, and a sensitivity to become favorable. Since the reactivity of the cyclic ether structure is high and unreacted (b) hardly remains, (b1) is preferable as (b) used for the resin [K4], and (b1-1) is more desirable.

It is preferable that the usage-amount of the said reaction catalyst is 0.001-5 mass % with respect to the total amount of (a), (b) (particularly (b1)) and (c). It is preferable that the usage-amount of the said polymerization inhibitor is 0.001-5 mass % with respect to the total amount of (a), (b), and (c).

Reaction conditions, such as the preparation method, reaction temperature, and time, can be suitably adjusted in consideration of manufacturing equipment, the amount of heat generated by polymerization, and the like. In addition, similarly to polymerization conditions, the preparation method and reaction temperature can be adjusted suitably in consideration of manufacturing equipment, the calorific value by polymerization, etc.

[0120] The resin [K5] is the first step, in the same manner as the above-described method for producing the resin [K1], to obtain a copolymer of (b) (particularly (b1)) and (c). As for the obtained copolymer, the solution after the reaction may be used as it is, a concentrated or diluted solution may be used, and the obtained copolymer may use what was extracted as a solid (powder) by methods, such as reprecipitation.

It is preferable that the ratio of the structural unit derived from (b) (especially (b1)) and (c) exists in the following range with respect to the total number of moles of all the structural units which comprise the said copolymer.

the structural unit derived from (b), particularly the structural unit derived from (b1); 5-95 mol% (more preferably 10-90 mol%),

a structural unit derived from (c); 5-95 mol% (more preferably 10-90 mol%).

[0121] In addition, under the same conditions as in the production method of the resin [K4], (a) Resin [K5] can be obtained by reacting the carboxylic acid or carboxylic acid anhydride of It is preferable that the usage-amount of (a) made to react with said copolymer is 5-80 mol with respect to 100 mol of (b) (particularly (b1)). Since the reactivity of the cyclic ether structure is high and unreacted (b) hardly remains, as (b) used for the resin [K5], (b1) is preferable, and (b1-1) is more preferable.

[0122] The resin [K6] is a resin in which a carboxylic acid anhydride is further reacted with the resin [K5]. A carboxylic acid anhydride is reacted with the hydroxyl group which arises by reaction of a cyclic ether structure and carboxylic acid or carboxylic acid anhydride.

Examples of the carboxylic acid anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3, 6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride (hymic acid anhydride), etc. are mentioned.

[0123] Among the resins [K1] to [K6], a preferable resin as the resin (B) is [K1] or [K2]. Resin (B) may consist of 1 type of resin, and may contain 2 or more types of resin.

[0124] The weight average molecular weight (Mw) in terms of polystyrene of the resin (B) is preferably 3,000 or more and 100,000 or less, more preferably 5,000 or more and 50,000 or less, still more preferably 5,000 or more and 30,000 or less, and particularly preferably Usually 10,000 or more and 30,000 or less. When a weight average molecular weight (Mw) exists in the said range, the solubility with respect to the developing solution of an unexposed part is high, and the film thickness retention and hardness of the coloring pattern obtained also tend to be high. The molecular weight distribution (weight average molecular weight (Mw)/number average molecular weight (Mn)) of resin (B) becomes like this. Preferably it is 1.1 or more and 6 or less, More preferably, they are 1.2 or more and 4 or less.

Acid value in conversion of solid content of resin (B) becomes like this. Preferably they are 5 mg-KOH/g or more and 200 mg-KOH/g or less, More preferably, they are 50 mg-KOH/g or more and 180 mg-KOH/gmg-KOH. /g, more 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. An acid value is a value measured as the quantity (mg) of potassium hydroxide required to neutralize 1 g of resin, For example, it can obtain|require by titration using potassium hydroxide aqueous solution.

[0125] The content of the resin (B) is preferably 1% by mass or more and 50% by mass or less, and 5% by mass or more and 45% by mass or less of the solid content of 100% by mass of the colored curable resin composition. When content of resin (B) exists in the said range, there exists a tendency for the solubility with respect to the developing solution of an unexposed part to be high.

[0126] [3] Polymeric 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 irradiation with light or the like, and examples thereof include compounds having a polymerizable ethylenically unsaturated bond. . It is preferable that the weight average molecular weight of a polymeric compound (C) is 3,000 or less.

Especially, as a polymeric compound (C), it is preferable that it is a photopolymerizable compound which has three or more ethylenically unsaturated bonds, Trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaeryth Ritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol poly (meth) acrylate, tripentaerythritol octa (meth) acrylic Late, tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocy Anurate, 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. are mentioned. Especially, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. are preferable.

[0127] The colored curable resin composition of the present invention may contain one or more polymerizable compounds (C). To [ content of a polymeric compound (C) ] 100 mass parts of resin (B) in colored curable resin composition, Preferably they are 20 mass parts or more and 150 mass parts or less, More preferably, they are 40 mass parts or more and 110 mass parts or less. am.

[0128] The content of the polymerizable compound (C) is preferably 7% by mass or more and 65% by mass or less with respect to the total amount of solid content in the colored curable resin composition, more preferably 10% by mass or more and 60% by mass or less, More preferably, they are 10 mass % or more and 50 mass % or less. When the content rate of a polymeric compound (C) exists in said range, there exists a tendency for the film thickness retention at the time of coloring pattern formation and the chemical-resistance of a color filter to improve.

[0129] [4] polymerization initiator (D)

The polymerization initiator (D) is not particularly limited as long as it is a compound capable of initiating polymerization by generating active radicals, acids, etc. by the action of light or heat, and a known polymerization initiator can be used. As a polymerization initiator which generate|occur|produces an active radical, an O-acyl oxime compound, an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, and a biimidazole compound are mentioned, for example.

[0130] The O-acyloxime compound is a compound having a partial structure represented by Formula (d1). Hereinafter, * represents a bond.

[0131]

[0132] Examples of the O-acyloxime compound include N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfa). Nylphenyl) octan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine, N-acetoxy-1- [9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4- (3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy)benzoyl}-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6- (2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-imine, N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H- and carbazol-3-yl]-3-cyclopentylpropan-1-one-2-imine. You may use commercial items, such as Irgacure OXE01, OXE02 (above, BASF make), and N-1919 (made by ADEKA). Among them, the O-acyloxime compound is N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl) At least one selected from the group consisting of octan-1-one-2-imine and N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine is preferable , N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine is more preferable. If it is these O-acyl oxime compounds, there exists a tendency for the color filter with high brightness to be obtained.

[0133] 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.

[0134]

[0135] Examples of the compound having a partial structure represented by formula (d2) include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino- 1-(4-morpholinophenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl) phenyl]butan-1-one; and the like. You may use commercial items, such as Irgacure 369, 907, 379 (above, BASF Corporation make).

As the compound having a partial structure represented by formula (d3), for example, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4-(2) -Hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexylphenylketone, an oligomer of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one; α,α-diethoxyacetophenone, benzyl dimethyl ketal, and the like.

From a viewpoint of a sensitivity, as an alkylphenone compound, the compound which has a partial structure represented by Formula (d2) is preferable.

[0136] As the triazine compound, for example, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl) )-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2, 4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran) -2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5 -triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine, 2,4-bis( and trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine.

[0137] Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide. You may use commercial items, such as Irgacure (trademark) 819 (made by BASF).

[0138] 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 Application Laid-Open Nos. H06-75372 and H06-75373), 2,2' -bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra( Alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chloro Phenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole (see, for example, Japanese Patent Publication Nos. S48-38403 and S62-174204), 4,4 and a biimidazole compound in which the phenyl group at the '5,5'-position is substituted with a carboalkoxy group (see, for example, Japanese Patent Application Laid-Open No. H07-10913, etc.) and the like.

[0139] Examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; Benzophenone, o-benzoyl methyl benzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, benzophenone compounds such as 2,4,6-trimethylbenzophenone; quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compound, etc. are mentioned. It is preferable to use these in combination with the polymerization initiation adjuvant (D1) (especially amines) mentioned later.

[0140] As the acid generator, for example, 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluene Sulfonate, 4-acetoxyphenyl methyl benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluene Onium salts, such as sulfonate and diphenyliodonium hexafluoroantimonate, nitrobenzyl tosylate, benzointosylate, etc. are mentioned.

[0141] The polymerization initiator (D) is preferably a polymerization initiator containing at least one selected from the group consisting of O-acyloxime compounds, alkylphenone compounds, triazine compounds, acylphosphine oxide compounds and biimidazole compounds. And the polymerization initiator containing an O- acyl oxime compound is more preferable.

[0142] The content of the polymerization initiator (D) is preferably 0.1 parts by mass or more and 30 parts by mass or less, more preferably 2 parts by mass, based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). It is more than part and 20 mass parts or less. When content of a polymerization initiator (D) exists in the said range, since there exists a tendency for it to become highly sensitive and exposure time to shorten, there exists a tendency for productivity of a color filter to improve.

[0143] [5] polymerization initiation aid (D1)

A polymerization initiation adjuvant (D1) is a compound used in order to accelerate|stimulate superposition|polymerization of the polymeric compound which superposition|polymerization was started by a polymerization initiator, or a sensitizer. When a polymerization initiator auxiliary (D1) is included, it is used in combination with a polymerization initiator (D).

Examples of the polymerization initiation auxiliary (D1) include an amine compound, an alkoxyanthracene compound, a thioxanthone compound, and a carboxylic acid compound. Especially, a thioxanthone compound is preferable. You may use together 2 or more types of polymerization initiation adjuvant (D1).

[0144] As the amine compound, triethanolamine, methyldiethanolamine, triisopropanolamine, 4-dimethylamino methyl benzoate, 4-dimethylamino ethyl benzoate, 4-dimethylamino benzoate isoamyl, benzoate 2-dimethylaminoethyl, 4 -Dimethylaminobenzoic acid 2-ethylhexyl, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone etc. are mentioned, Especially, 4,4'-bis(diethylamino)benzophenone is preferable. You may use commercial items, such as EAB-F (made by HODOGAYA CHEMICAL CO., LTD.).

[0145] 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, 2-ethyl-9,10-dibutoxyanthracene, etc. are mentioned.

[0146] As the thioxanthone compound, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4- Propoxythioxanthone etc. are mentioned.

[0147] As the carboxylic acid compound, phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanyl Acetic acid, chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, etc. are mentioned.

[0148] The content of the polymerization initiation auxiliary (D1) is preferably 0.1 parts by mass or more and 30 parts by mass or less, more preferably 1 mass parts, based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). It is more than part and 20 mass parts or less. When content of a polymerization initiation adjuvant (D1) exists in the said range, a pattern can be formed more highly sensitively, and there exists a tendency for productivity of a color filter to improve.

[0149] [6] Thiol compound (E)

The thiol compound (E) includes an ether bond-containing thiol compound. When colored curable resin composition contains an ether bond containing thiol compound, there exists a tendency for a film thickness retention to become high. The colored curable resin composition of this invention may contain 1 type(s) or 2 or more types of ether bond containing thiol compounds.

[0150] The ether bond-containing thiol compound may contain, for example, 2 or more and 6 or less of a sulfanyl group (-SH), and preferably contains 3 or more and 5 or less.

The ether bond-containing thiol compound may have, for example, 2 or more and 6 or less, preferably 3 or more and 5 or less.

[0151] The ether bond-containing thiol compound is preferably a compound represented by formula (I).

A-(R^One-SH)_n (I)

[Wherein, A represents a residue of a polyhydric alcohol having m hydroxyl groups,

^{A plurality of R 1} bonded to an oxygen atom derived from the m number of hydroxyl groups, each independently represents an alkylene group having 1 to 10 carbon atoms,

m is an integer of 2 or more, n is an integer of 2 or more, and m≥n.]

[0152] A represents a residue of a polyhydric alcohol having m hydroxyl groups. The residue of a polyhydric alcohol refers to the structure from which the hydrogen atom (H) which comprises at least 1 hydroxyl group (OH) was removed from the polyhydric alcohol. In Formula (I), the oxygen atom (O) couple|bonded with the removed hydrogen atom, ie, the oxygen atom derived from the hydroxyl group, couple|bonded with ^{n pieces of R<1>.} Even to reach the oxygen derived from the hydroxyl group of the alcohol valence bond and both R ¹ are, or may combine with R ¹ to a part.

[0153] The polyhydric alcohol is not particularly limited as long as it is a compound having two or more hydroxyl groups in one molecule. Examples thereof include aliphatic polyhydric alcohols, alicyclic polyhydric alcohols, aromatic ring-containing polyhydric alcohols, saccharides and derivatives thereof. Especially, an aliphatic polyhydric alcohol, an alicyclic polyhydric alcohol, and/or an aromatic ring containing polyhydric alcohol is preferable. More preferably, it is an aliphatic polyhydric alcohol.

[0154] The aliphatic polyhydric alcohol preferably has 2 to 30 carbon atoms. Specifically, for example, alkylene such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 1,6-hexanediol, and 1,12-dodecamethylene glycol glycol; polyalkylene glycols such as diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol and polypropylene glycol; (poly) polyhydric alcohols having trivalence or higher, such as glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, sorbitol, and sorbitan; etc. are mentioned, These alkylene oxide adducts (for example, added mole number 1-50) may be sufficient.

[0155] As the alicyclic polyhydric alcohol, for example, one having 3 to 30 carbon atoms is preferable. Specific examples thereof include alicyclic diols such as 1,4-cyclohexanedimethanol and hydrogenated bisphenol A.

[0156] The aromatic ring-containing polyhydric alcohol preferably has 6 to 30 carbon atoms. Specific examples thereof include alkylene oxide adducts of bisphenols such as bisphenol A, bisphenol F and bisphenol S (eg, 2 to 30 added moles).

[0157] m may be 2 or more, but is preferably 2 to 10, more preferably 2 to 8, still more preferably 2 to 6, particularly preferably 3 to 6.

[0158] The polyhydric alcohol in A is preferably a polyhydric alcohol having 3 to 6 hydroxyl groups, more preferably pentaerythritol, trimethylolpropane, and dipentaerythritol.

[0159] R ¹ is the same or different and represents an alkylene group having 1 to 10 carbon atoms. The alkylene group may be linear or branched.

[0160] ^{Among the alkylene groups represented by R 1} , the carbon atom bonded to the mercapto group may be a primary carbon atom, a secondary carbon atom, or a tertiary carbon atom, preferably from the viewpoint of reactivity. preferably a primary carbon atom or a secondary carbon atom.

[0161] R ¹ may have 1 or 2 or more substituents, but ^{it is preferable that R 1} does not include a substituent. As a substituent which R<^1> may have, a halogen atom, a hydroxyl group, a carboxyl group, a sulfonic acid group, an amino group, a phosphoric acid group, etc. are mentioned, for example.

[0162] The molecular weight of the ether bond-containing thiol compound may be, for example, 50 or more and 700 or less, preferably 100 or more and 500 or less, more preferably 150 or more and 380 or less from the viewpoint of reducing the viscosity.

[0163] Examples of the ether bond-containing thiol compound include pentaerythritol trispropanethiol and trimethylolpropanedipropanethiol.

[0164] The thiol compound containing an ether bond can be produced by a known production method. For example, it can be prepared according to the method described in WO2016/171072.

[0165] The thiol compound (E) may contain one or two or more thiol compounds (E1) other than the above-mentioned ether bond-containing thiol compounds. A thiol compound (E1) is used especially preferably when a polymerization initiator (D) is an oxime type compound, such as an O-acyl oxime compound, and/or a biimidazole compound. A thiol compound (E1) is a compound which has at least 1 sulfanyl group (-SH) in a molecule|numerator. The thiol compound (E1) is preferably a compound having one sulfanyl group in the molecule.

[0166] Examples of the compound having one sulfanyl group in the molecule include 2-sulfanyloxazole, 2-sulfanylthiazole, 2-sulfanylbenzimidazole, 2-sulfanylbenzothiazole, and 2-sulfanylbenzooxa. Sol, 2-sulfanylnicotinic acid, 2-sulfanylpyridine, 2-sulfanylpyridin-3-ol, 2-sulfanylpyridine-N-oxide, 4-amino-6-hydroxy-2-sulfanylpyrimidine, 4-Amino-6-hydroxy-2-sulfanylpyrimidine, 4-amino-2-sulfanylpyrimidine, 6-amino-5-nitroso-2-thiouracil, 4,5-diamino-6- Hydroxy-2-sulfanylpyrimidine, 4,6-diamino-2-sulfanylpyrimidine, 2,4-diamino-6-sulfanylpyrimidine, 4,6-dihydroxy-2-sulfanyl Pyrimidine, 4,6-dimethyl-2-sulfanylpyrimidine, 4-hydroxy-2-sulfanyl-6-methylpyrimidine, 4-hydroxy-2-sulfanyl-6-propylpyrimidine, 2- Sulfanyl-4-methylpyrimidine, 2-sulfanylpyrimidine, 2-thiouracil, 3,4,5,6-tetrahydropyrimidine-2-thiol, 4,5-diphenylimidazole-2- Thiol, 2-sulfanylimidazole, 2-sulfanyl-1-methylimidazole, 4-amino-3-hydrazino-5-sulfanyl-1,2,4-triazole, 3-amino-5 -sulfanyl-1,2,4-triazole, 2-methyl-4H-1,2,4-triazole-3-thiol, 4-methyl-4H-1,2,4-triazole-3-thiol , 3-sulfanyl 1H-1,2,4-triazole-3-thiol, 2-amino-5-sulfanyl-1,3,4-thiadiazole, 5-amino-1,3,4-thia Diazole-2-thiol, 2,5-disulfanyl-1,3,4-thiadiazole, (furan-2-yl)methanethiol, 2-sulfanyl-5-thiazolidone, 2-sulfanyl Thiazoline, 2-sulfanyl-4(3H)-quinazolinone, 1-phenyl-1H-tetrazole-5-thiol, 2-quinolinethiol, 2-sulfanyl-5-methylbenzimidazole, 2-sulfa Nyl-5-nitrobenzimidazole, 6-amino-2-sulfanylbenzothiazole, 5-chloro-2-sulfanylbenzothiazole, 6-ethoxy-2-sulfanylbenzothiazole, 6-nitro- 2-sulfanylbenzothiazole, 2-sulfanylnaphthoimidazole, 2-sulfanylnaphthooxazole, 3-sulfanyl-1,2,4-triazole, 4-amino-6-sulfanylpyrazolo[ 2,4-d]pyridine, 2-amino-6-purinethiol, 6-sulfanylpurine and 4-sulfanyl-1H-pyrazolo[2, 4-d]pyrimidine etc. are mentioned.

[0167] Examples of the compound having two or more sulfanyl groups in the molecule include hexanedithiol, decanedithiol, 1,4-bis(methylsulfanyl)benzene, butanediolbis(3-sulfanylpropionate), butanediolbis( 3-sulfanyl acetate), ethylene glycol bis (3-sulfanyl acetate), trimethylol propane tris (3-sulfanyl acetate), butanediol bis (3-sulfanyl propionate), trimethylol propane tris (3-sulfa) nyl propionate), trimethylolpropane tris (3-sulfanyl acetate), pentaerythritol tetrakis (3-sulfanyl propionate), pentaerythritol tetrakis (3-sulfanyl acetate), trishydroxyethyl tris(3-sulfanylpropionate), pentaerythritoltetrakis(3-sulfanylbutyrate), 1,4-bis(3-sulfanylbutyloxy)butane, etc. are mentioned.

[0168] 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, further preferably based on 100 parts by mass of the polymerization initiator (D). Preferably, it is 5 mass parts or more and 40 mass parts or less. When content of a thiol compound (E) exists in the said range, there exists a tendency for a sensitivity to become high and developability to become favorable.

[0169] [7] Solvent (F)

It is preferable that the colored curable resin composition of this invention contains 1 type, or 2 or more types of solvent (F). As the solvent (F), an ester solvent (a solvent containing -COO-), an ether solvent other than an ester solvent (a solvent containing -O-), an ether ester solvent (a solvent containing -COO- and -O-) , ketone solvents other than ester solvents (solvents containing -CO-), alcohol solvents, aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, and the like.

[0170] As the ester solvent, methyl lactate, ethyl lactate, butyl lactate, 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, γ-butyrolactone, and the like.

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

[0171] As the ether ester solvent, methyl methoxy acetate, ethyl methoxy acetate, butyl methoxy acetate, methyl ethoxy acetate, ethyl ethoxy acetate, 3-methoxy methyl propionate, 3-methoxy ethyl propionate, 3-e Methyl oxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-methoxy -2-methylpropionate, 2-ethoxy-2-methylpropionate ethyl, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate; Propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate, etc. are mentioned.

[0172] As the ketone solvent, 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentane on, cyclopentanone, cyclohexanone, isophorone, and the like.

[0173] Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol and glycerin. Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene and mesitylene. Examples of the amide solvent include N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone.

[0174] The solvent (F) preferably contains an organic solvent having a boiling point of 120° C. or more and 180° C. or less at 1 atm from the viewpoint of applicability and drying properties. Among them, the solvent (F) is 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 containing at least one selected from the group consisting of ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone and N,N-dimethylformamide propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol and 3-ethoxypropionate ethyl It is more preferable to include at least one selected from the group consisting of.

[0175] The content of the solvent (F) in the colored curable resin composition is preferably 70% by mass or more and 95% by mass or less, and more preferably 75% by mass or more and 92% by mass or less. In other words, solid content of colored curable resin composition becomes like this. Preferably they are 5 mass % or more and 30 mass % or less, More preferably, they are 8 mass % or more and 25 mass % or less. When content of a solvent (F) exists in the said range, since the flatness at the time of application|coating becomes favorable and color density does not run short when a color filter is formed, there exists a tendency for a display characteristic to become favorable.

[0176] [8] Leveling agent (G)

As a leveling agent (G), the silicone type surfactant (which does not have a fluorine atom), a fluorine type surfactant, and the silicone type surfactant which has a fluorine atom, etc. are mentioned. These may have a polymeric group in a side chain.

[0177] Examples of the silicone-based surfactant include surfactants having a siloxane bond in the molecule. Specifically, 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: manufactured by Dow Corning Toray Co., Ltd.), KP321 , KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452 and TSF4460 (Momentive Performance Materials Japan LLC) manufacture) and the like.

[0178] Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain in the molecule. Specifically, Fluorad (registered trademark) FC430, Fluorad FC431 (manufactured by Sumitomo 3M Limited), Megapac (registered trademark) F142D, Megapac F171, Megapac F172, Megapac F173, Megapac F177, Megapac F183, Megapac F554, Megapac R30, Megapac RS-718-K (manufactured by DIC CORPORATION), eftop (registered trademark) EF301, eftop EF303, eftop EF351, eftop EF352 (Mitsubishi Materials Electronic Chemicals Co., Ltd. manufacture), Suplon (trademark) S381, Sufflon S382, Sufflon SC101, Sufflon SC105 (manufactured by Asahi Glass Co., Ltd.), and E5844 (manufactured by Daikin Fine Chemical Genkyusho), and the like.

[0179] Examples of the silicone-based surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain in the molecule. Specific examples thereof include Megapac (registered trademark) R08, Megapac BL20, Megapac F475, Megapac F477, and Megapac F443 (manufactured by DIC CORPORATION).

The content of the leveling agent (G) in the colored curable resin composition 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, more preferably 0.0001 mass % or more and 0.2 mass % or more. mass% or less. In addition, content of the said pigment dispersant is not contained in this content.

[0181] [9] Other ingredients

If necessary, the colored curable resin composition of the present invention may contain one or more additives such as fillers, polymer compounds other than the resin (B), adhesion promoters, ultraviolet absorbers, aggregation inhibitors, organic acids, and curing agents. .

[0182] <Method for producing colored curable resin composition>

The colored curable resin composition of this invention is a coloring agent (A), resin (B), a polymeric compound (C), and a polymerization initiator (D), and as needed, a thiol compound (E), a solvent (F), a leveling agent It can prepare by mixing (G), polymerization initiation adjuvant (D1), antioxidant (H), and other components.

[0183] <Color filter, manufacturing method thereof, and display device>

The colored curable resin composition of this invention is useful as a material of a color filter. A color filter formed from the colored curable resin composition of the present invention also falls within the scope of the present invention. The color filter may form the coloring pattern.

As a method of manufacturing a colored pattern from the colored curable resin composition of this invention, the photolithographic method, the inkjet method, the printing method, etc. are mentioned, Preferably it is the photolithographic method. A photolithographic method is a method of apply|coating a colored curable resin composition to a board|substrate, drying it, forming a coloring composition layer, exposing this coloring composition layer through a photomask, and developing. The photolithographic method WHEREIN: The colored coating film which is hardened|cured material of the said coloring composition layer can be formed by not using a photomask at the time of exposure and/or not developing. The colored pattern and colored coating film formed from the colored curable resin composition of this invention are the color filter of this invention. The color filter which concerns on this invention is typically used as a color pixel.

[0184] As the substrate, a glass plate such as quartz glass, borosilicate glass, alumina silicate glass, and soda lime glass coated with silica, a resin plate such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, silicone, the substrate Those in which aluminum, silver, silver/copper/palladium alloy thin films, etc. were formed on it are used. On these board|substrates, another color filter layer, a resin layer, a transistor, a circuit, a transparent electrode, etc. may be formed.

[0185] Formation of a colored pixel by the photolithography method can be performed under a known or customary apparatus or condition, and can be produced, for example, as follows. First, a colored curable resin composition is apply|coated on a board|substrate, and volatile components, such as a solvent, are removed and dried by heat-drying (pre-bake) and/or drying under reduced pressure, and a smooth coloring composition layer is obtained. Examples of the coating method include a spin coating method, a slit coating method, and a slit-and-spin coating method.

As a temperature in the case of heat-drying, 30 degreeC or more and 120 degrees C or less are preferable, and 50 degrees C or more and 110 degrees C or less are more preferable. Moreover, as heating time, 10 second - 5 minutes are preferable, and 30 second - 3 minutes are more preferable. When performing reduced-pressure drying, it is preferable to carry out under the pressure of 50 Pa or more and 150 Pa or less, and to carry out in the temperature range of 20 degreeC or more and 25 degrees C or less. The film thickness of the coloring composition layer is not specifically limited, What is necessary is just to select suitably according to the film thickness of the color filter made into the objective.

[0187] Next, the coloring composition layer is exposed through a photomask for forming a desired coloring pattern. The pattern on this photomask is not specifically limited, The pattern according to the intended use is used. As a light source used for exposure, the light source which generate|occur|produces the light whose wavelength is 250 nm or more and 450 nm or less is preferable. For example, light of less than 350 nm is cut using a filter that cuts this wavelength range, or light around 436 nm, 408 nm, or 365 nm is selectively extracted using a bandpass filter that extracts these wavelength ranges. do. Specific examples of the light source include a mercury lamp, a light emitting diode, a metal halide lamp, and a halogen lamp.

[0188] For exposure, an exposure apparatus such as a mask aligner and a stepper is used because it is possible to uniformly irradiate parallel rays to the entire exposure surface or to perform accurate alignment between the photomask and the substrate on which the coloring composition layer is formed. It is preferable to do

[0189] A colored pattern is formed on the substrate by developing the colored composition layer after exposure in contact with a developer. By image development, the unexposed part of a coloring composition layer melt|dissolves in a developing solution, and is removed.

The developer is preferably an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate, or 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. Moreover, the developing solution may contain surfactant.

[0190] The developing method may be any of a puddle method, a dipping method, and a spray method. Moreover, you may incline a board|substrate at an arbitrary angle at the time of image development. It is preferable to wash with water after image development.

[0191] In the colored curable resin composition of the present invention, on a substrate, the unexposed portion of the coloring composition layer is dissolved in the developer and there is little residue of the removed portion.

[0192] Furthermore, it is preferable to post-bake the obtained colored pattern. As post-baking temperature, 150 degreeC or more and 250 degrees C or less are preferable, and 160 degreeC or more and 235 degrees C or less are more preferable. As post-baking time, 1 to 120 minutes are preferable, and 10 to 60 minutes are more preferable.

[0193] The colored curable resin composition of the present invention has the thickness of the colored composition layer after exposure, development and post-baking with respect to the thickness of the colored composition layer before exposure (after heat drying (pre-baking) and/or drying under reduced pressure) The ratio of is high, for example, may be 50% or more.

[0194] Since the film thickness of the colored coating film or the colored pattern formed from the colored curable resin composition affects adjacent pixels, it is preferably as thin as possible. In the case of a particularly thick film, when a liquid crystal panel is manufactured, the light from the light source may leak through pixels of two or more colors, and when the panel is viewed from an angle, the vividness of the color may be lost. Generally, it is preferable that it is 3 micrometers or less, and, as for the film thickness of the colored coating film or coloring pattern after a post-baking, it is more preferable that it is 2.8 micrometers or less. Although the lower limit of the film thickness of a colored coating film or a coloring pattern is not specifically limited, Usually, it is 1 micrometer or more, and 1.5 micrometers or more may be sufficient. Since the said colored coating film or a colored pattern can exhibit the outstanding developability, it is excellent as a color filter.

[0195] In general, when the film thickness retention rate in the colored coating film or coloring pattern before and after post-baking is low, in order to secure a predetermined film thickness in the colored coating film or coloring pattern after post-baking, the colored coating film before post-baking or It is necessary to enlarge the film thickness of a coloring pattern, and a large amount of curable resin composition will be used. On the other hand, since the colored curable resin composition of this invention has a high film-thickness retention of the colored coating film before and behind a post-baking, or a colored pattern, even a comparatively small amount of curable resin composition can obtain a predetermined|prescribed film thickness. As for the colored curable resin composition of this invention, film thickness retention is high compared with the film thickness retention of the conventional colored curable resin composition, The difference between the film thickness retention of the colored curable resin composition of this invention, and the conventional colored curable resin composition ) may be, for example, 2% or more. When the film thickness retention is increased by 2% or more, the amount of the colored curable resin composition used for the production of the colored coating film or the colored pattern can be remarkably reduced.

[0196] The color filter according to the present invention is useful as a color filter used in a display device (a liquid crystal display device, an organic EL device, an electronic paper, etc.) and a solid-state image sensor.

Example

[0197] Hereinafter, the colored curable resin composition of the present invention will be described with reference to specific examples, but the present invention is not limited to the following examples unless departing from the gist thereof. Unless otherwise specified, "part" means "part by mass" and "%" means "mass %", respectively. In addition, unless otherwise specified, the reaction was carried out under a nitrogen atmosphere.

[0198] In the following, the structure of the compound was confirmed by mass spectrometry (LC; 1200 manufactured by Agilent Technologies, Inc., MASS; LC/MSD manufactured by Agilent Technologies, Inc.).

[0199] The polystyrene equivalent weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin were measured by GPC method under the following conditions.

Device ; HLC-8120GPC (manufactured by TOSOH CORPORATION)

column ; TSK-GELG2000HXL

column temperature; 40℃

solvent; THF

flow rate ; 1.0mL/min

test solution solids concentration; 0.001 to 0.01 mass %

injection volume ; 50 μL

detector ; RI

standard for calibration; TSK STANDARD POLYSTYRENE

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

(manufactured by TOSOH CORPORATION)

Ratio (Mw/Mn) of the polystyrene conversion weight average molecular weight and number average molecular weight obtained above was made into dispersion degree.

[0200] The acid value in terms of the solid content of the resin was obtained by titrating the solution containing the resin using an aqueous potassium hydroxide solution to obtain the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin.

[0201] (Synthesis Example 1)

Sodium tert-amyl alcoholate was synthesized by reacting 17.4 parts of tert-amyl alcohol with 2.22 parts of metallic sodium at 130° C. under a nitrogen atmosphere. This is heated to 60° C., 9.1 parts of 4-bromobenzonitrile, 7.105 parts of di-tert-amyl succinate, and 10.89 parts of tert-amyl alcohol are added, and stirred for 2 hours so that the liquid temperature is 85° C. or less. did. This suspension was further stirred for 18 hours or more, 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, the mixture was stirred at 0° C. for 5 hours, and after the reaction was completed, the solid was filtered. The solid content was washed with methanol and water alternately until the coloration of the filtrate disappeared and salt precipitation disappeared. Thereafter, the solid content was dried in a vacuum dryer at 80°C for 18 hours to obtain 10.7 parts of the desired red pigment 1.

[0202] (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 the formula (1-34) was obtained.

[0203]

[0204] Identification of the compound represented by formula (1-34)

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

Exact Mass: 598.1

[0205] (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 the formula (1-87) was obtained.

[0206]

[0207] Identification of the compound represented by formula (1-199)

(mass spectrometry) ionization mode=ESI+: m/z=[M+H] ⁺ 747.5

Exact Mass: 746.3

[0208] (Synthesis Example 4)

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

[0209]

[0210] Identification of the compound represented by formula (1-32)

(mass spectrometry) ionization mode=ESI+: m/z=[M+H] ⁺ 659.9

Exact Mass: 658.9

[0211] (Synthesis Example 5)

The following reaction was performed in nitrogen atmosphere. In a flask equipped with a cooling tube and a stirring device, 26.4 parts of potassium thiocyanate and 156 parts of acetonitrile were added, followed by stirring at room temperature for 30 minutes. 40.0 parts of 2,6-difluorobenzoic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise to the flask over 30 minutes, followed by stirring at room temperature for 1 hour. 30.6 parts of N-ethyl-o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise to the flask over 30 minutes, followed by stirring at room temperature for 1 hour. An aqueous solution in which 79.2 parts of sodium monochloroacetate was dissolved in 120 parts of ion-exchanged water was added to the flask, and 60.4 parts of a 30% aqueous sodium hydroxide solution was added thereto, followed by stirring at room temperature for 18 hours. After adding 600 parts of ion-exchanged water to the flask, the mixture was stirred for 1 hour, and the precipitated yellowish-white solid was obtained by filtration. The obtained off-white solid was washed with 120 parts of acetonitrile and then washed with 560 parts of ion-exchanged water. The washed off-white solid, 156 parts of ion-exchanged water, 35.0 parts of 99% acetic acid (manufactured by Wako Pure Chemical Industries, 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. After 80.8 parts of 30% sodium hydroxide aqueous solution was dripped here over 10 minutes, it stirred for 5 minutes, and the water layer was removed by liquid separation operation. After adding 156 parts of ion-exchanged water to the obtained organic layer for liquid-separation washing, 156 parts of ion-exchanged water and 0.1 part of 35% hydrochloric acid were added and liquid-separation washing|cleaning was carried out. The obtained organic layer was concentrated with an evaporator and dried under reduced pressure at 35°C to obtain the compound represented by the formula (t-1) as a white solid. The yield (收量) was 43.4 parts, and the yield was 58.0%.

[0212]

[0213] The following reaction was carried out in a nitrogen atmosphere. 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 thrown into the flask provided with the cooling tube and the stirring device, Then, phosphorus oxychloride 9.2 parts 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 methylethylketone. Then, a mixed solution of 114 parts of ion-exchanged water and 10 parts of a 35% aqueous hydrochloric acid solution was poured into the diluted reaction mixture, and the water layer was removed by a liquid separation operation. After removing the solvent from the obtained organic layer with an evaporator, the compound represented by Formula (t-3) was obtained as a bluish purple solid by drying at 60 degreeC under reduced pressure. The yield (得量) of the blue-violet solid was 39.4 parts.

[0214]

[0215]

[0216] The following reaction was performed in a nitrogen atmosphere. 38.4 parts of the compound represented by Formula (t-3) and 112 parts of methylene chloride were added to a flask equipped with a cooling tube and a stirring device, and stirred for 30 minutes. After cooling the reaction solution on ice and maintaining the internal temperature at 10°C, 31.6 parts of chlorosulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and then the temperature of the reaction solution was raised to room temperature for 9 hours stirred for a while. Subsequently, the reaction solution was cooled on ice and diluted with a mixed solution of 64 parts of N,N-dimethylformamide and 4.9 parts of ion-exchanged water while maintaining the internal temperature at 10°C. The diluted reaction solution was poured into 1120 parts of toluene and stirred for 30 minutes to precipitate a viscous solid. After discharging the oil layer by decantation, 320 parts of toluene was added to the obtained viscous solid and stirred for 30 minutes. The oil layer was discharged by decantation, and 832 parts of 20% saline was added to the obtained viscous solid and stirred for 1 hour, followed by filtration to obtain a blue solid. The obtained blue solid was washed with 576 parts of 20% brine, and dried under reduced pressure at 35°C. Into a flask equipped with a stirring device, the obtained solid and 128 parts of methanol were added, stirred for 30 minutes, and filtered to separate the solid and the filtrate. This filtrate is called filtrate A. The solid obtained by filtration was washed with 192 parts of methanol, and the solid and the filtrate were separated by filtration. This filtrate is called filtrate B. The filtrate A and the filtrate B were mixed, the solvent was removed with an evaporator, and then dried under reduced pressure at 40°C to obtain the compound represented by the formula (t-4) as a blue-violet solid. The yield of the blue-violet solid was 38.3 parts.

[0217]

[0218] 28.0 parts of the compound represented by Formula (t-4), 43.2 parts of barium chloride dihydrate, and 356 parts of ion-exchanged water were added to a flask equipped with a cooling tube and a stirring device, followed by stirring at 40° C. for 2 hours , the reaction suspension was filtered. The solid obtained by filtration and 350 parts of ion-exchanged water were added to a flask equipped with a stirring device and stirred for 30 minutes, and then the suspension was filtered. The obtained solid was washed with 280 parts of ion-exchanged water, and then dried under reduced pressure at 60°C to obtain the compound represented by the formula (t-5) as a blue-violet solid. The yield was 24.5 parts and the yield was 81.7%.

[0219]

[0220] Identification of the compound represented by the formula (t-5)

(Mass spectrometry) Ionization mode = ESI-: m/z = 949.5 [M-Ba+2H] ^-

Exact Mass [M-Ba]: 947.28

[0221] (Synthesis Example 6)

In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, an appropriate amount of nitrogen was flowed into the flask, replaced with a nitrogen atmosphere, 151 parts of ethyl lactate and 178 parts of propylene glycol monomethyl ether acetate were placed, and the mixture was heated to 85° C. while stirring. Then, 38 parts of acrylic acid, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decan-8-ylacrylate and 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decan-9-ylacrylic A mixed solution of 25 parts (content ratio of 1:1), 137 parts of N-cyclohexylmaleimide, 50 parts of 2-hydroxyethyl methacrylate, and 338 parts of propylene glycol monomethyl ether acetate was added in 5 hours. It was dripped over. On the other hand, the solution which melt|dissolved 5 parts of 2, 2- azobisisobutyronitrile in 88 parts of propylene glycol monomethyl ether acetate was dripped over 6 hours. After completion of the dropwise addition, the temperature was maintained 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 resulting copolymer had a weight average molecular weight (Mw) of 8.0×10 ³ , a dispersion degree of 2.1, and an acid value in terms of solid content of 109 mg-KOH/g. Resin B1 has the following structural units.

[0222]

[0223] Among the examples below, in the preparation of the colored curable resin composition, any one shown below was used as each component, respectively.

Resin (B): Resin B1 obtained in (Synthesis Example 6) above

Polymeric compound (C): dipentaerythritol hexaacrylate (manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD.)

Polymerization initiator (D): N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; oxime compound)

Thiol compound (E): pentaerythritol trispropanethiol (PEPT)

Leveling agent (G): polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Dow Corning Toray Co., Ltd.), described as “SH8400” in Examples

[0224] [Example 1]

[Preparation of colored curable resin composition]

The components shown below were mixed, and the pigment dispersion liquid 1 in which the pigment was fully disperse|distributed using the bead mill was prepared. Using this, each component shown below was mixed, and colored curable resin composition was obtained.

<Pigment Dispersion 1>

Red pigment 1 obtained in (Synthesis Example 1) Part 66.22

Acrylic pigment dispersant Part 14.17

Resin B1 (in terms of solid content) obtained in (Synthesis Example 6) 28.38 parts

Propylene glycol monomethyl ether acetate 361.87 parts

<Colored Curable Resin Composition>

Colorant (A): Pigment Dispersion 1 471 copies

Xanthene dye obtained in (Synthesis Example 2) 10 copies

Resin (B): Resin B1 (in terms of solid content) Part 37

Polymeric compound (C): dipentaerythritol hexaacrylate 35 copies

Polymerization initiator (D): Irgacure (registered trademark) OXE-01 10 copies

Thiol compound (E): PEPT Part 3

Solvent (F): lactic acid part 22

diacetone alcohol 348 copies

Propylene glycol monomethyl ether acetate 262 copies

Leveling agent (G): SH8400 (in terms of solid content) 0.2 copies

[0225] The obtained colored curable resin composition was evaluated by the following method.

[0226] <Formation of color filter>

On a 2-inch square glass substrate (Eagle 2000; manufactured by Corning Incorporated), a colored curable resin composition was applied by spin coating, and then prebaked at 100° C. for 3 minutes to form a colored composition layer. After cooling, using an exposure machine (TME-150RSK; manufactured by TOPCON CORPORATION), in an atmospheric atmosphere, using a ^{photomask (line width 100 μm) at an exposure dose of 60 mJ/cm 2} (based on 365 nm), the gap between the glass substrate and the photomask It was set as 250 micrometers, and it light-irradiated to the coloring composition layer. After light irradiation, a 0.04% solution of potassium hydroxide was developed with a spray pressure of 0.1 Pa for 60 seconds, washed with water, and dried with an air knife, and then the film thickness of the color filter was measured with a film thickness measuring device (DEKTAK3; Japan Vacuum) Engineering Co., Ltd. manufacture) was used and it measured (film thickness before post-baking). In oven, the color filter was obtained by performing post-baking at 230 degreeC for 20 minutes. After standing to cool, the film thickness of the obtained color filter was measured using a film thickness measuring apparatus (DEKTAK3; manufactured by Japan Vacuum Engineering Co., Ltd.) (film thickness after post-baking).

The film thickness retention was calculated|required by the following formula. A result is shown in Table 1.

Film thickness retention [%] = (film thickness after post-baking [μm]/film thickness before post-baking [μm]) x 100

[0227] <Line width>

The obtained color filter measured the patterned line|wire width using the scanning electron microscope (S-4000: made by Hitachi, Ltd.), and confirmed the shape (cross-section). Table 1 shows the pattern line width [μm] of the color filter with respect to the photomask line width 100 μm.

[0228] [Comparative Example 1]

A colored curable resin composition and a color in the same manner as in Example 1 except that trimethylolpropanetris(3-mercaptopropionate) (TMMP) was used instead of the thiol compound (E) pentaerythritol trispropanethiol (PEPT); A filter was produced and evaluated. A result is shown in Table 1.

[0229] [Comparative Example 2]

A colored curable resin composition in the same manner as in Example 1 except that pentaerythritol tetrakis (3-mercaptopropionate) (PEMP) was used instead of the thiol compound (E) pentaerythritol trispropanethiol (PEPT), and A color filter was produced and evaluated. A result is shown in Table 1.

[0230] [Table 1]

[0231] [Example 2]

Except having mixed each component shown below, it carried out similarly to Example 1, the pigment dispersion liquid 2, colored curable resin composition, and a color filter were produced, and it evaluated. A result is shown in Table 2.

<Pigment Dispersion 2>

C.I. Pigment Blue 15:6 Part 22.12

Acrylic pigment dispersant 7.76 parts

Resin B1 (in terms of solid content) obtained in (Synthesis Example 6) 8.87 parts

Propylene glycol monomethyl ether acetate 182.91 copies

<Colored Curable Resin Composition>

Colorant (A): Pigment Dispersion 2 222 copies

Xanthene dye obtained in (Synthesis Example 3) Part 3

Resin (B): Resin B1 (in terms of solid content) 56 copies

Polymeric compound (C): dipentaerythritol hexaacrylate 35 copies

Polymerization initiator (D): Irgacure (registered trademark) OXE-01 10 copies

Thiol compound (E): PEPT Part 3

Solvent (F): ethyl lactate Part 33

diacetone alcohol 71 copies

Propylene glycol monomethyl ether acetate 424 copies

Leveling agent (G): SH8400 (in terms of solid content) 0.1 copies

[0232] [Comparative Example 3]

A colored curable resin composition and color in the same manner as in Example 2 except that trimethylolpropanetris(3-mercaptopropionate) (TMMP) was used instead of the thiol compound (E) pentaerythritol trispropanethiol (PEPT); A filter was produced and evaluated. A result is shown in Table 2.

[0233] [Table 2]

[0234] [Example 3]

Each component shown below was mixed and the color filter was produced similarly to Example 1 except having obtained the colored curable resin composition, and it evaluated. A result is shown in Table 3.

Colorant (A): Pigment Dispersion 2 222 copies

Xanthene dye obtained in (Synthesis Example 4) Part 3

Resin (B): Resin B1 (in terms of solid content) 56 copies

Polymeric compound (C): dipentaerythritol hexaacrylate 35 copies

Polymerization initiator (D): Irgacure (registered trademark) OXE-01 10 copies

Thiol compound (E): PEPT Part 3

Solvent (F): ethyl lactate Part 33

diacetone alcohol Part 11

Propylene glycol monomethyl ether acetate 485 copies

Leveling agent (G): SH8400 (in terms of solid content) 0.1 copies

[0235] [Example 4]

Except having changed 218 parts for the pigment dispersion liquid 2, 0.5 parts for the thiol compound (E), and 473 parts for propylene glycol monomethyl ether acetate, it carried out similarly to Example 3, and obtained the colored curable resin composition. Using this, a color filter was produced in the same manner as in Example 1, and evaluation was performed. A result is shown in Table 3.

[0236] [Comparative Example 4]

A colored curable resin composition and a color in the same manner as in Example 3 except that trimethylolpropanetris(3-mercaptopropionate) (TMMP) was used instead of the thiol compound (E) pentaerythritol trispropanethiol (PEPT); A filter was produced and evaluated. A result is shown in Table 3.

[0237] [Comparative Example 5]

A colored curable resin composition in the same manner as in Example 3 except that pentaerythritol tetrakis (3-mercaptopropionate) (PEMP) was used instead of thiol compound (E) pentaerythritol trispropanethiol (PEPT); A color filter was produced and evaluated. A result is shown in Table 3.

[0238] [Table 3]

[0239] [Example 5]

Except having mixed each component shown below, it evaluated by carrying out similarly to Example 1, producing the colored curable resin composition and a color filter. A result is shown in Table 4.

<Dispersion 3>

The components shown below were mixed, and the dispersion liquid 3 was prepared.

Compound represented by formula (t-5) obtained in (Synthesis Example 5) 10 copies

Acrylic pigment dispersant Part 8

Resin B1 (in terms of solid content) obtained in (Synthesis Example 6) Part 3

diacetone alcohol part 12

Propylene glycol monomethyl ether acetate 91 copies

<Colored Curable Resin Composition>

Colorant (A): Dispersion 3 119 copies

Pigment Dispersion 2 134 copies

Xanthene dye obtained in (Synthesis Example 4) Part 3

Resin (B): Resin B1 (in terms of solid content) 57 copies

Polymeric compound (C): dipentaerythritol hexaacrylate 35 copies

Polymerization initiator (D): Irgacure (registered trademark) OXE-01 10 copies

Thiol compound (E): PEPT Part 3

Solvent (F): ethyl lactate part 34

diacetone alcohol Part 11

Propylene glycol monomethyl ether acetate 481 copies

Leveling agent (G): SH8400 (in terms of solid content) 0.1 copies

[0240] [Comparative Example 6]

A colored curable resin composition and color in the same manner as in Example 5 except that trimethylolpropanetris(3-mercaptopropionate) (TMMP) was used in place of the thiol compound (E) pentaerythritol trispropanethiol (PEPT); A filter was produced and evaluated. A result is shown in Table 4.

[0241] [Table 4]

[0242] [Example 6]

Except having mixed each component shown below, it evaluated by carrying out similarly to Example 1, producing the colored curable resin composition and a color filter. A result is shown in Table 5.

Colorant (A): xanthene dye obtained in (Synthesis Example 4) Part 23

Resin (B): Resin B1 (in terms of solid content) 65 copies

Polymeric compound (C): dipentaerythritol hexaacrylate 35 copies

Polymerization initiator (D): Irgacure (registered trademark) OXE-01 10 copies

Thiol compound (E): PEPT Part 3

Solvent (F): ethyl lactate 38 copies

diacetone alcohol 93 copies

Propylene glycol monomethyl ether acetate 534 copies

Leveling agent (G): SH8400 (in terms of solid content) 0.1 copies

[0243] [Comparative Example 7]

A colored curable resin composition and color in the same manner as in Example 6 except that trimethylolpropanetris(3-mercaptopropionate) (TMMP) was used instead of the thiol compound (E) pentaerythritol trispropanethiol (PEPT); A filter was produced and evaluated. A result is shown in Table 5.

[0244] [Comparative Example 8]

A colored curable resin composition in the same manner as in Example 6 except that pentaerythritol tetrakis (3-mercaptopropionate) (PEMP) was used instead of thiol compound (E) pentaerythritol trispropanethiol (PEPT); A color filter was produced and evaluated. A result is shown in Table 5.

[0245] [Table 5]

[0246] [Example 7]

Except having mixed each component shown below, it evaluated by carrying out similarly to Example 1, producing the colored curable resin composition and a color filter. A result is shown in Table 6.

Colorant (A): Dispersion 3 Part 227.1

Xanthene dye obtained in (Synthesis Example 3) part 2.8

Resin (B): Resin B1 (in terms of solid content) 50.4 parts

Polymeric compound (C): dipentaerythritol hexaacrylate 45.0 copies

Polymerization initiator (D): Irgacure (registered trademark) OXE-01 5.0 copies

Thiol compound (E): PEPT 1.0 copies

Solvent (F): diacetone alcohol Part 137.1

ethyl lactate 29.5 copies

Propylene glycol monomethyl ether acetate 442.2 parts

Leveling agent (G): SH8400 (in terms of solid content) 0.1 copies

[0247] [Comparative Example 9]

A colored curable resin composition and color in the same manner as in Example 7 except that trimethylolpropanetris(3-mercaptopropionate) (TMMP) was used instead of the thiol compound (E) pentaerythritol trispropanethiol (PEPT); A filter was produced and evaluated. A result is shown in Table 6.

[0248] [Comparative Example 10]

A colored curable resin composition in the same manner as in Example 7 except that pentaerythritol tetrakis (3-mercaptopropionate) (PEMP) was used instead of thiol compound (E) pentaerythritol trispropanethiol (PEPT), and A color filter was produced and evaluated. A result is shown in Table 6.

[0249] [Table 6]

[0250] As shown in Tables 1 to 6, when a color filter was manufactured using the colored curable resin composition according to the present invention, when a color filter was manufactured using a colored curable resin composition not according to the present invention In comparison with , it was confirmed that a high film thickness retention rate was obtained and the line width could be maintained.

Industrial Applicability

[0251] According to the colored curable resin composition of the present invention, the obtained color filter has a high film thickness retention and can maintain a line width, so it is very useful industrially.

Claims (8)

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) is xanthene A colored curable resin composition containing a dye, wherein the thiol compound (E) contains an ether bond-containing thiol compound. According to claim 1,
The colored curable resin composition in which the said ether bond containing thiol compound is a compound represented by Formula (I).
A-(R^One-SH)_n (I)
[Wherein, A represents a residue of a polyhydric alcohol having m hydroxyl groups,
A plurality of R bonded to an oxygen atom derived from the m hydroxyl groups^Onerepresents, each independently, an alkylene group having 1 to 10 carbon atoms,
m is an integer of 2 or more, n is an integer of 2 or more, and m≥n.] 3. The method of claim 2,
m is 2-10, colored curable resin composition. 4. The method of claim 2 or 3,
The said polyhydric alcohol is pentaerythritol or trimethylol propane, Colored curable resin composition. 5. The method according to any one of claims 1 to 4,
The said xanthene dye contains the compound represented by Formula (1a), Colored curable resin composition.

[In formula (1a), R ^1a to R ^4a are each independently a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or 6 to 10 carbon atoms which may have a substituent Phosphorus represents a monovalent aromatic hydrocarbon group, and -CH ₂ - contained in the saturated hydrocarbon group may be substituted with -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 is 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 ^7a each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
m represents the integer of 0-5. When m is 2 or more, a plurality of R ^5a may be the same or different.
a represents the integer of 0 or 1.
Xa ⁻ represents a counter ion.
Za ⁺ represents ⁺ N(R ^11a ) ₄ , Na ⁺ or K ⁺ , and four R ^11a 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 with 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, -CH ₂ - contained in the saturated hydrocarbon group is -O-, -CO- , -NH- or -NR ^8a - may be substituted, and R ^9a and R ^10a may be bonded 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 hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms.] 6. The method of claim 5,
The colored curable resin composition whose compound represented by the said Formula (1a) is a compound represented by Formula (2a).

[In formula (2a), R ^21a to R ^24a are each independently a hydrogen atom, -R ^26a , a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or 6 to carbon atoms which may have a substituent 10 represents a monovalent aromatic hydrocarbon group. 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 the integer of 0-5. When m1 is 2 or more, a plurality of R ^25a may be the same or different.
a1 represents the integer of 0 or 1.
Xa1 ^- represents a counter ion.
R ^28a and R ^29a each independently represent 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 is -O- or -CO It may be substituted with -, 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 halogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a carboxy group.
Za1 ⁺ represents ⁺ N(R ^27a ) ₄ , Na ⁺ or K ⁺ , and 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.] The color filter formed from the colored curable resin composition in any one of Claims 1-6. A display device comprising the color filter according to claim 7 .