阅读说明：本技术 着色固化性树脂组合物、滤色器和显示装置 (Colored curable resin composition, color filter, and display device ) 是由 冈本信之 辻内翔 于 2020-02-13 设计创作，主要内容包括：本公开涉及一种着色固化性树脂组合物,其后烘前后的滤色器的膜厚保持率高、后烘后得到的滤色器的线宽不会变粗,该着色固化性树脂组合物包含着色剂(A)、树脂(B)、聚合性化合物(C)、聚合引发剂(D)和硫醇化合物(E),上述着色剂(A)包含呫吨染料,上述硫醇化合物(E)包含含有醚键的硫醇化合物。(The present disclosure relates to a colored curable resin composition having a high film thickness retention ratio of a color filter before and after post-baking and a line width of the color filter obtained after post-baking, the colored curable resin composition comprising a colorant (a), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a thiol compound (E), the colorant (a) comprising a xanthene dye, and the thiol compound (E) comprising a thiol compound containing an ether bond.)

1. A colored curable resin composition comprising a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a thiol compound (E), wherein the colorant (A) comprises a xanthene dye, and the thiol compound (E) comprises a thiol compound having an ether bond.

2. The colored curable resin composition according to claim 1, wherein the thiol compound having an ether bond is a compound represented by formula (I),

A－(R¹－SH)_n (I)

wherein A represents a residue of a polyol having m hydroxyl groups,

a plurality of R bonded to oxygen atoms from the m hydroxyl groups¹Each 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 is not less than n.

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

4. The colored curable resin composition according to claim 2 or 3, wherein the polyol is pentaerythritol or trimethylolpropane.

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

in the formula (1a), R^1a～R^4aEach independently represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent, wherein-CH is contained in the saturated hydrocarbon group₂May be substituted by-O-, -CO-or-NR^11a-substituted, R^1aAnd R^2aMay together form a ring containing a nitrogen atom, R^3aAnd R^4aMay together form a ring containing a nitrogen atom,

R^5arepresents a halogen atom, -OH, -SO₃ ^－、－SO₃H、－SO₃ ^－Za⁺、－CO₂H、－CO₂ ^－Za⁺、－CO₂R^8a、－SO₃R^8a、－NR^9aR^10aor-SO₂NR^9aR^10a，

R^6aAnd R^7aEach independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,

m represents an integer of 0 to 5, and when m is 2 or more, a plurality of R^5aWhich may be the same or different from each other,

a represents an integer of 0 or 1,

Xa^－represents a counter-ion, and is represented by,

Za⁺to represent⁺N(R^11a)₄、Na⁺Or K⁺4 of R^11aWhich may be the same or different from each other,

R^8arepresents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, wherein hydrogen atoms contained in the saturated hydrocarbon group may be substituted with halogen atoms,

R^9aand R^10aEach independently represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and-CH is contained in the saturated hydrocarbon group₂May be substituted by-O-, -CO-, -NH-or-NR^8a-substituted, R^9aAnd R^10aCan be bonded to each other to form a heterocyclic ring having 3 to 10 membered rings containing a nitrogen atom,

R^11arepresents 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 claim 5, wherein the compound represented by formula (1a) is a compound represented by formula (2a),

in the formula (2a), R^21a～R^24aEach independently represents a hydrogen atom, -R^26aA monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent, R^21aAnd R^22aMay together form a ring containing a nitrogen atom, R^23aAnd R^24aMay together form a ring containing a nitrogen atom,

R^25arepresents a halogen atom, -SO₃ ^－、－SO₃H、－SO₃ ^－Za1⁺、－NR^28aR^29aor-SO₂NHR^26a，

m1 represents an integer of 0 to 5, and when m1 is 2 or more, a plurality of R^25aCan be used forThe same or different, and the same or different,

a1 represents an integer of 0 or 1,

Xa1^－represents a counter-ion, and is represented by,

R^28aand R^29aEach independently represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and-CH is contained in the saturated hydrocarbon group₂-may be substituted by-O-or-CO-, R^28aAnd R^29aCan be bonded to each other to form a heterocyclic ring having 3 to 10 membered rings containing a nitrogen atom,

R^26arepresents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a halogen atom or a carboxyl group,

Za1⁺to represent⁺N(R^27a)₄、Na⁺Or K⁺4 of R^27aWhich may be the same or different from each other,

R^27arepresents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a benzyl group.

7. A color filter comprising the colored curable resin composition according to any one of claims 1 to 6.

8. A display device comprising the color filter of claim 7.

Technical Field

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

Background

Jp 2018 a-101015 a (patent document 1) describes a colored resin composition for a color filter containing a coloring material represented by the following formula, a binder component, and a solvent.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2018-101015

Disclosure of Invention

In the colored curable resin composition used for the production of a color filter, if the film thickness retention ratio before and after post-baking of the obtained color filter is to be increased, the line width of the pattern of the color filter obtained after post-baking tends to be wider.

The present invention aims to provide a colored curable resin composition which has a high film thickness retention ratio (hereinafter, may be simply referred to as "film thickness retention ratio") of a color filter before and after post-baking and does not cause line width thickening of the color filter obtained after post-baking.

[1] A colored curable resin composition comprising a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a thiol compound (E), wherein the colorant (A) comprises a xanthene dye, and the thiol compound (E) comprises a thiol compound having an ether bond.

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

A-(R¹－SH)_n (I)

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

a plurality of R bonded to oxygen atoms derived from the m hydroxyl groups¹Each 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 is not less than 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 polyol is pentaerythritol or trimethylolpropane.

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

[ in the formula (1a), R^1a～R^4aEach independently represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent, wherein-CH is contained in the saturated hydrocarbon group₂May be substituted by-O-, -CO-or-NR^11a-substitution. R^1aAnd R^2aMay together form a ring containing a nitrogen atom, R^3aAnd R^4aMay together form a ring containing a nitrogen atom.

R^5aRepresents a halogen atom, -OH, -SO₃ ^－、－SO₃H、－SO₃ ^－Za⁺、-CO₂H、－CO₂ ^－Za⁺、－CO₂R^8a、－SO₃R^8a、-NR^9aR^10aor-SO₂NR^9aR^10a。

R^6aAnd R^7aEach independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

m represents an integer of 0 to 5. When m is 2 or more, plural R^5aMay be the same or different.

a represents an integer of 0 or 1.

Xa^－Represents a counter ion.

Za⁺To represent⁺N(R^11a)₄、Na⁺Or K⁺4 of R^11aMay be the same or different.

R^8aRepresents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, wherein hydrogen atoms contained in the saturated hydrocarbon group may be substituted with halogen atoms.

R^9aAnd R^10aEach independently represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and-CH is contained in the saturated hydrocarbon group₂May be substituted by-O-, -CO-, -NH-or-NR^8a-substituted, R^9aAnd R^10aCan be bonded to each other to form a heterocyclic ring having 3 to 10 membered rings containing a nitrogen atom.

R^11aRepresents 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 (2 a).

[ in the formula (2a), R^21a～R^24aEach independently represents a hydrogen atom, -R^26aA monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent. R^21aAnd R^22aMay together form a ring containing a nitrogen atom, R^23aAnd R^24aMay together form a ring containing a nitrogen atom.

R^25aRepresents a halogen atom, -SO₃ ^－、－SO₃H、－SO₃ ^－Za1⁺，－NR^28aR^29aor-SO₂NHR^26a。

m1 represents an integer of 0 to 5. When m1 is 2 or more, plural R' s^25aMay be the same or different.

a1 represents an integer of 0 or 1.

Xa1^－Represents a counter ion.

R^28aAnd R^29aEach independently represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and-CH is contained in the saturated hydrocarbon group₂-may be substituted by-O-or-CO-, R^28aAnd R^29aCan be bonded to each other to form a heterocyclic ring having 3 to 10 membered rings containing a nitrogen atom.

R^26aRepresents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a halogen atom or a carboxyl group.

Za1⁺To represent⁺N(R^27a)₄、Na⁺Or K⁺4 of R^27aMay be the same or different.

R^27aRepresents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a benzyl group]

[7] A color filter comprising the colored curable resin composition according to any one of [1] to [6 ].

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

According to the present invention, a colored curable resin composition can be provided which has a high film thickness retention ratio of a color filter before and after post-baking and does not cause a wide line width of the color filter obtained after post-baking.

Detailed Description

< colored curable resin composition >

[ xanthene dye ]

The xanthene dye is a dye comprising a compound having a xanthene skeleton in the molecule. Examples of the xanthene dye include c.i. acid red 51 (hereinafter, the description of c.i. acid red is omitted, and only the number is described, and the same applies to the others), 52, 87, 92, 94, 289, 388, c.i. acid violet 9, 30, 102, c.i. basic red 1 (rhodamine 6G), 2,3,4, 8, c.i. basic red 10, 11, c.i. basic violet 10 (rhodamine B), 11, c.i. solvent red 218, c.i. intermediate red 27, c.i. active red 36 (rose bengal B), sulforhodamine G, a xanthene dye described in jp 2010-a 32999, and a xanthene dye described in jp 4492760 a. Xanthene dyes dissolved in organic solvents are preferred.

Among these, the xanthene dye is preferably a dye containing a compound represented by the formula (1a) (hereinafter, may be referred to as "compound (1 a)"). The compound (1a) may also be a tautomer thereof. When the compound (1a) is used, the content of the compound (1a) in the xanthene dye is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more. The xanthene dye is particularly preferably used only as the compound (1 a). The compound represented by formula (1a) also includes tautomers thereof.

[ in the formula (1a), R^1a～R^4aEach independently represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent, wherein-CH is contained in the saturated hydrocarbon group₂May be substituted by-O-, -CO-or-NR^11a-substitution. R^1aAnd R^2aMay together form a ring containing a nitrogen atom, R^3aAnd R^4aMay together form a ring containing a nitrogen atom.

R^5aRepresents a halogen atom, -OH, -SO₃ ^－、－SO₃H、－SO₃ ^－Za⁺、－CO₂H、－CO₂ ^－Za⁺、－CO₂R^8a、－SO₃R^8a、－NR^9aR^10aor-SO₂NR^9aR^10a。

R^6aAnd R^7aEach independently represents a hydrogen atom or a carbon atom number of 1 to6 alkyl group.

m represents an integer of 0 to 5. When m is 2 or more, plural R^5aMay be the same or different.

a represents an integer of 0 or 1.

Xa^－Represents a counter ion.

Za⁺To represent⁺N(R^11a)₄、Na⁺Or K⁺4 of R^11aMay be the same or different.

R^8aRepresents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, wherein hydrogen atoms contained in the saturated hydrocarbon group may be substituted with halogen atoms.

R^9aAnd R^10aEach independently represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and-CH is contained in the saturated hydrocarbon group₂May be substituted by-O-, -CO-, -NH-or-NR^8a-substituted, R^9aAnd R^10aMay be bonded to form a 3-to 10-membered heterocyclic ring containing a nitrogen atom.

R^11aRepresents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or an aralkyl group having 7 to 10 carbon atoms]

As R^1a～R^4aExamples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in (b) include a phenyl group, a tolyl group, a xylyl group, a mesityl group, a propylphenyl group, and a butylphenyl group.

Examples of the substituent which may be contained in the aromatic hydrocarbon group include a halogen atom, a carboxyl group, a silicon atom-containing group, -R^8a、－OH、－OR^8a、－SO₃ ^－、－SO₃H、－SO₃ ^－Za⁺、－CO₂H、－CO₂R^8a、－SR^8a、－SO₂R^8a、－SO₃R^8aand-SO₂NR^9aR^10a. Among these, the substituent is preferably a silicon atom-containing group, -SO₃ ^－、－SO₃H、－SO₃ ^－Za⁺、－SO₂NR^9aR^10aMore preferably a silicon atom-containing group, -SO₃ ^－Za⁺and-SO₂NR^9aR^10a. as-SO at this time₃ ^－Za⁺Is preferably-SO₃ ^－+N(R^11a)₄. If R is^1a～R^4aThese groups enable formation of a color filter which generates little foreign matter and has excellent heat resistance from the colored curable resin composition of the present invention containing the compound (1 a). The silicon atom-containing group means a group containing a silicon atom, and may be, for example, a group represented by the formula (ii).

－Si(R^50a)₃ (ii)

[ in the formula, R^50aRepresents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. Plural R^50aMay be the same or different]

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

As R^1a～R^4aAnd R^8a～R^11aThe monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in (b) includes, for example, a linear alkyl group such as 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, a decyl group, a dodecyl group, a hexadecyl group, or an eicosyl group; branched alkyl groups such as isopropyl, isobutyl, isopentyl, neopentyl, and 2-ethylhexyl groups; and (c) 3-20 alicyclic saturated hydrocarbon groups such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and cyclodecyl.

As R^1a～R^4aExamples of the substituent that the saturated hydrocarbon group may have include a carboxyl group, an aromatic hydrocarbon group having 6 to 10 carbon atoms, a silicon atom-containing group, and a halogen atom. Examples of the C6-10 aromatic hydrocarbon group and R^1a～R^4aThe aromatic hydrocarbon groups in (A) are the same. Exemplary and preferred ranges for silicon atom containing groups and as R^1a～R^4aThe aromatic hydrocarbon group in (b) may have the same substituents as those described in the substituents.

As R^1a～R^4aThe saturated hydrocarbon group in (1) is preferably a carboxyl group or a silicon atom-containing group.

As R^9aAnd R^10aExamples of the substituent that the saturated hydrocarbon group may have 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 those described above. Examples and preferred ranges of the silicon atom-containing group are the same as described above.

As R^1aAnd R^2aTogether form a ring and R^3aAnd R^4aExamples of the ring to be formed together include the following rings.

as-OR^8aExamples thereof include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, and eicosyloxy group.

as-CO₂R^8aExamples thereof include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, tert-butoxycarbonyl, hexyloxycarbonyl, and eicosyloxycarbonyl.

As a-SR^8aExamples thereof include methylsulfanyl, ethylsulfanyl, butylsulfanyl, hexylsulfanyl, decylthioyl and eicosylsulfanyl groups.

as-SO₂R^8aExamples thereof include methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, hexylsulfonyl group, decylsulfonyl group and eicosylsulfonyl group.

as-SO₃R^8aExamples thereof include methoxysulfonyl, ethoxysulfonyl, propoxysulfonyl, tert-butoxysulfonyl, hexyloxysulfonyl and eicosyloxysulfonyl.

as-SO₂NR^9aR^10aFor example, a sulfamoyl group; n-1 substituted sulfamoyl groups such as N-methylsulfamoyl, N-ethylsulfamoyl, N-propylsulfamoyl, N-isopropylsulfamoyl, N-butylsulfamoyl, N-t-butylsulfamoyl, N-pentylsulfamoyl, N- (1, 1-dimethylpropyl) sulfamoyl, N- (2, 2-dimethylpropyl) sulfamoyl, N- (2-methylbutyl) sulfamoyl, N-cyclopentylsulfamoyl, N-hexylsulfamoyl, N- (1, 3-dimethylbutyl) sulfamoyl, N-heptylsulfamoyl, N- (1-methylhexyl) sulfamoyl, N- (2-ethylhexyl) sulfamoyl, and N- (1,1,2, 2-tetramethylbutyl) sulfamoyl; n, N-2-substituted sulfamoyl groups such as N, N-dimethylsulfamoyl, N-ethylsulfamoyl, N-diethylsulfamoyl, N-propylmethylsulfamoyl, N-isopropylmethylsulfamoyl, N-tert-butylmethylsulfamoyl, N-butylethylsulfamoyl, N-bis (1-methylpropyl) sulfamoyl, and N, N-heptylmethylsulfamoyl.

R^5aPreferably halogen atoms, -CO₂H、－CO₂ ^－Za⁺、－CO₂R^8a、－SO₃ ^－、－SO₃ ^－Za⁺、－SO₃H or SO₂NHR^9aMore preferably SO₃ ^－、－SO₃ ^－Za⁺、－SO₃H、－NR^9aR^10aOr SO₂NHR^9a。

R^9aAnd R^10aEach independently preferably represents a saturated hydrocarbon group having 1 to 6 carbon atoms which may have a substituent.

As R^6aAnd R^7aExamples of the alkyl group having 1 to 6 carbon atoms in the above-mentioned group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group and a heptyl group.

As R^11aExamples of the aralkyl group having 7 to 10 carbon atoms in (A) include benzyl, phenylethyl and phenylbutyl.

Za⁺Is composed of⁺N(R^11a)₄、Na⁺Or K⁺Preferably, it is⁺N(R^11a)₄。

As mentioned above⁺N(R^11a)₄Preferably 4R^11aAt least 2 of them are monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. In addition, 4R^11aThe total number of carbon atoms of (1) is preferably 20 to 80, more preferably 20 to 60. Present in Compound (1a)⁺N(R^11a)₄When R is equal to^11aThese groups enable the color filter with less foreign matters to be formed from the colored curable resin composition of the present invention containing the compound (1 a).

Xa^－Examples of the counter ion include a halogen ion and counter ions represented by the formulae (y1) and (y 2).

[ in the formula (y1), R^B1Represents a fluorinated alkyl group having 1 to 12 carbon atoms.

In the formula (y2), R^B2And R^B3Each independently represents a halogen atom or a fluorinated alkyl group having 1 to 12 carbon atoms]

Examples of the halogen ion include a fluorine ion, a chlorine ion, a bromine ion, and an iodine ion.

As R^B1Specific examples of the fluorinated alkyl group having 1 to 12 carbon atoms include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a1, 1,2,2, 2-pentafluoroethyl group, a 2,2, 2-trifluoroethyl group, a 3- (trifluoromethyl) -3, 4,4, 4-pentafluorobutyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, a perfluorotert-butyl group, a perfluoropentyl group and a perfluorohexyl group, preferred examples thereof include a group in which all hydrogen atoms are substituted by fluorine atoms (that is, a perfluoroalkyl group), and more preferred examples thereof include a perfluoroalkyl group having 1 to 4 carbon atoms.

As R^B2And R^B3Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable.

As R^B2And R^B3A fluorinated alkyl group having 1 to 12 carbon atoms represented byAre mentioned with R^B1The fluorinated alkyl group represented by the above formula is the same as the fluorinated alkyl group, and preferable examples thereof include a perfluoroalkyl group having 1 to 4 carbon atoms.

R^B2And R^B3Can be bonded to each other to form a structure containing-SO₂－N^－－SO₂-a ring of (a).

The compound (1a) is preferably a compound represented by the formula (2a) (hereinafter, may be referred to as "compound (2 a)"). The compound (2a) may also be a tautomer thereof.

[ in the formula (2a), R^21a～R^24aEach independently represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent. R^21aAnd R^22aMay together form a ring containing a nitrogen atom, R^23aAnd R^24aMay together form a ring containing a nitrogen atom.

R^25aRepresents a halogen atom, -SO₃ ^－、－SO₃H、－SO₃ ^－Za1⁺、－NR^28aR^29aor-SO₂NHR^26a。

m1 represents an integer of 0 to 5. When m1 is 2 or more, plural R' s^25aMay be the same or different.

a1 represents an integer of 0 or 1.

Xa1^－Represents a counter ion.

R^28aAnd R^29aEach independently represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and-CH is contained in the saturated hydrocarbon group₂-may be substituted by-O-or-CO-, R^28aAnd R^29aCan be bonded to each other to form a heterocyclic ring having 3 to 10 membered rings containing a nitrogen atom.

R^26aRepresents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms and optionally having a halogen atom or a carboxyl group。

Za1⁺To represent⁺N(R^27a)₄、Na⁺Or K⁺4 of R^27aMay be the same or different.

R^27aRepresents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a benzyl group]

As R^21a～R^24aIn the above formula, the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms includes the group represented by R^1a～R^4aThe same applies to the aromatic hydrocarbon group as mentioned above. The hydrogen atom contained in the aromatic hydrocarbon group may be substituted by carboxyl, a silicon atom-containing group, -SO₃ ^－、-SO₃H、－SO₃ ^-Za1⁺、-SO₃R^26aor-SO₂NHR^26aAnd (4) substitution.

As R^21a～R^24aIn a combination of (1), preferably R^21aAnd R^23aEach independently represents 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 carboxyl group), and R^22aAnd R^24aEach independently a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms (the hydrogen atom in the aromatic hydrocarbon group may be a carboxyl group, a silicon atom-containing group, -SO₃ ^-、-SO₃H、－SO₃ ^-Za1⁺、-SO₃R^26aor-SO₂NHR^26aSubstitution). A more preferred combination is R^21aAnd R^23aEach independently represents 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 carboxyl group), and R^22aAnd R^24aA monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms (the hydrogen atom in the aromatic hydrocarbon group may be a carboxyl group, a silicon atom-containing group, -SO₃ ^-Za1⁺or-SO₂NHR^26aSubstitution). If R is^21a～R^24aThese groups enable the colored curable resin composition of the present invention containing the compound (2a) to form a color filter having excellent heat resistance. Exemplary and preferred ranges of silicon atom-containing groups are as described above for formula (1a)The preferred ranges and illustrations in the specification are the same.

As R^21a～R^24aIn the above (1), the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent(s) is represented by the formula^1a～R^4aThe same applies to the aromatic hydrocarbon group as mentioned above. The hydrogen atom contained in the aromatic hydrocarbon group may be substituted by a silicon atom-containing group, -SO₃ ^-、－SO₃H、-SO₃ ^-Za1⁺、－SO₃R^26aor-SO₂NHR^26aAnd (4) substitution. Examples and preferred ranges of the silicon atom-containing group are the same as those in the description of the above formula (1 a).

R^28aAnd R^29aExamples thereof include the compounds represented by the formula (1a) and R^9aAnd R^10aThe same groups.

As R^21aAnd R^22aTogether forming a ring containing a nitrogen atom and R^23aAnd R^24aExamples of the ring containing a nitrogen atom formed together with R^1aAnd R^2aThe rings formed together are identical rings. Among them, aliphatic heterocyclic rings are preferable. Examples of the aliphatic heterocyclic ring include the following aliphatic heterocyclic rings.

As R^26aAnd R^27aIn the above (A), the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms is represented by^8a～R^11aThe same groups as those mentioned for the saturated hydrocarbon group in (1).

R^21a～R^24aWhen the alkyl group is a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent(s), R^21a～R^24aEach independently is preferably methyl or ethyl. In addition, as-SO₃R^26aand-SO₂NHR^26aR in (1)^26aA branched alkyl group having 3 to 20 carbon atoms is preferable, a branched alkyl group having 6 to 12 carbon atoms is more preferable, and a 2-ethylhexyl group is further preferable. If R is^26aThese groups enable the color filter to be formed from the colored curable resin composition of the present invention containing the compound (2a) with less generation of foreign substances.

Za1⁺Is composed of⁺N(R^27a)₄、Na⁺Or K⁺Preferably, it is⁺N(R^27a)₄。

As mentioned above⁺N(R^27a)₄Preferably 4R^27aAt least 2 of them are monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. In addition, 4R^27aThe total number of carbon atoms of (1) is preferably 20 to 80, more preferably 20 to 60. Present in Compound (2a)⁺N(R^27a)₄When R is equal to^27aThese groups enable the color filter to be formed from the colored curable resin composition of the present invention containing the compound (2a) with less generation of foreign substances.

Xa1^－The counter ion of (A) and Xa^－The preferred ranges and examples in the description are the same.

Further, as the compound (1a), a compound represented by the formula (3a) (hereinafter, may be referred to as "compound (3 a)") is also preferable. The compound (3a) may also be a tautomer thereof.

[ in the formula (3a), R^31aAnd R^32aEach independently represents a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, the hydrogen atom contained in the saturated hydrocarbon group may be substituted with an aromatic hydrocarbon group having 6 to 10 carbon atoms, a carboxyl group, a silicon atom-containing group or a halogen atom, 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, or-CH contained in the saturated hydrocarbon group₂May be substituted by-O-, -CO-or-NR^11a-substitution.

R^33aAnd R^34aEach independently represents a silicon atom-containing group, a C1-4 alkyl group, a C1-4 alkylsulfanyl group, or a C1-4 alkyl groupA sulfonyl group.

R^31aAnd R^33aMay together form a ring containing a nitrogen atom, R^32aAnd R^34aMay together form a ring containing a nitrogen atom.

p and q each independently represent an integer of 0 to 5. When p is 2 or more, plural R^33aMay be the same or different, and when q is 2 or more, plural R' s^34aMay be the same or different.

R^11aMeans the same as above]

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

Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms which may be a substituent include a phenyl group, a tolyl group, a xylyl group, a mesityl group, a propylphenyl group, a butylphenyl group and the like.

Examples of the alkoxy group having 1 to 3 carbon atoms include a methoxy group, an ethoxy group, and a propoxy group.

R^31aAnd R^32aEach independently preferably a monovalent saturated hydrocarbon group having 1 to 3 carbon atoms (the saturated hydrocarbon group may have a halogen atom or a carboxyl group).

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

As R^33aAnd R^34aExamples of the alkyl group having 1 to 4 carbon atoms in (A) 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.

As R^33aAnd R^34aExamples of the alkylsulfanyl group having 1 to 4 carbon atoms in (A) include methylsulfanyl, ethylsulfanyl, propylsulfanyl, butylsulfanyl, and isopropylsulfanyl.

As R^33aAnd R^34aExamples of the alkylsulfonyl group having 1 to 4 carbon atoms in (A) include methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, butylsulfonyl group and isopropylsulfonyl group.

R^33aAnd R^34aEach independently is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group.

R^33aAnd R^34aThe exemplary and preferred ranges of the silicon atom-containing group in (1) are the same as those described above for the formula (1 a).

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

Examples of the compound (1a) include compounds represented by the formulae (1-1) to (1-97). In the formula, R^40aRepresents 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^26aHaving the formula (2a) with R^26aThe same meaning is used.

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

As the xanthene dye, commercially available xanthene dyes (for example, "Chugai amino Fast Pink R-H/C" manufactured by Zhongzhou Kabushiki Kaisha and "Rhodamin 6G" manufactured by Tiangang chemical Co., Ltd.) can be used. Alternatively, a commercially available xanthene dye may be synthesized as a starting material with reference to Japanese patent application laid-open No. 2010-32999.

The content of the xanthene dye in the colorant (a) may be, for example, 0.1 to 100% by mass, more preferably 0.1 to 99.0% by mass, still more preferably 0.5 to 90.0% by mass, particularly preferably 1.0 to 50.0% by mass, and particularly preferably 1.5 to 30.0% by mass, based on the total amount of solid components in the colorant (a).

In the present specification, the "total amount of solid components in the colorant (a)" means the total amount of components obtained by removing the solvent (F) from the colorant (a). In the present invention, the total amount of solid components and the content of each component relative to the total amount can be measured by a known analysis method such as liquid chromatography or gas chromatography.

[1] coloring agent (A)

The content of the colorant (a) in the colored curable resin composition is preferably 5 to 80% by mass, more preferably 5 to 70% by mass, and still more preferably 5 to 60% by mass, based on the total amount of solid components in the colored curable resin composition. When the content of the colorant (a) is within the above range, a desired spectrum and color density can be obtained.

In the present specification, the "total amount of solid components in the colored curable resin composition" refers to the total amount of components obtained by removing the solvent (F) from the colored curable resin composition.

When the colored curable resin composition contains a solvent (hereinafter, also referred to as solvent (F)), a colorant-containing liquid containing the colorant (a) and the solvent (F) may be prepared in advance, and then the colorant-containing liquid may be used to prepare the colored curable resin composition. When the colorant (a) is insoluble in the solvent (F), the liquid containing the colorant can be prepared as a dispersion by dispersing the colorant (a) and mixing the dispersion with the solvent (F). The colorant-containing liquid may contain a part or all of the solvent (F) contained in the colored curable resin composition.

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

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

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

The colorant (a) can be dispersed by a dispersing agent to form a state in which the colorant (a) is uniformly dispersed in a liquid containing the colorant.

Examples of the dispersant include surfactants, and the dispersant may be any of cationic, anionic, nonionic and amphoteric surfactants. Specifically, there may be mentioned polyester, polyamide, acrylic and other surfactants. These dispersants may be used alone or in combination of 2 or more. Examples of the dispersant include KP (manufactured by shin-Etsu chemical Co., Ltd.), FLOWLEN (manufactured by Kyoho chemical Co., Ltd.), Solsperse (registered trademark) (manufactured by Zeneca corporation), EFKA (registered trademark) (manufactured by BASF corporation), AJISPER (registered trademark) (manufactured by Naiyu Fine chemical Co., Ltd.), Disperbyk (registered trademark) (manufactured by BYK-Chemie Co., Ltd.), BYK (registered trademark) (manufactured by BYK-Chemie Co., Ltd.), and the like.

When a dispersant is used for the preparation of the colorant-containing liquid, the amount of the dispersant (solid content) to be used is preferably 5 to 100 parts by mass, more preferably 5 to 50 parts by mass, based on 100 parts by mass of the colorant (a). If the amount of the dispersant used is within the above range, there is a tendency that a more uniformly dispersed state of the liquid containing the colorant is obtained.

The colorant (a) may further contain a colorant other than the above-described xanthene dye [ hereinafter, also referred to as a colorant (a1) ].

The colorant (a1) may contain at least 1 selected from dyes and pigments other than the above-mentioned xanthene dyes.

As The dye contained in The colorant (a1), known dyes can be used, including solvent dyes, acid dyes, direct dyes, mordant dyes, and The like, and for example, compounds classified as dyes such as solvent, acid, basic, reactive, direct, disperse, mediator, or reducing dyes in The color index (published by The Society of Dyers and Colourists), and known dyes described in dyeing guidelines (chromo corporation) can be used. The dye may be appropriately selected according to the spectral spectrum of the desired color filter. These dyes may be used alone, or 2 or more of them may be used in combination. The dye is preferably an organic solvent soluble dye.

Specific examples of the dye include c.i. solvent yellow 4 (hereinafter, c.i. solvent yellow is omitted, and only the number is 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: 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 dyes such as c.i. solvent green 1,3,4, 5, 7, 28, 29, 32, 33, 34, 35,

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, 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: 1. 91, 92, 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: 1. 58, 63, 65, 80, 104, 105, 106, 109 and the like,

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, 244, 246, 247, 245, 250, 251, 252, 257, 275, 268, 293, 268, 248;

c.i. direct dyes such as c.i. direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82,

c.i. disperse yellow 51, 54, 76;

c.i. disperse violet 26, 27;

c.i. disperse dyes such as c.i. disperse blue 1, 14, 56, 60, etc.,

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 dyes such as c.i. basic green 1,

c.i. reactive yellow 2, 76, 116;

c.i. reactive orange 16;

C.I. reactive dyes such as C.I. reactive red 36,

c.i. media yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;

c.i. medium 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. intermediate 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. intermediate 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. medium 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 dyes such as c.i. mordant green 1,3,4, 5, 10, 13, 15, 19, 21, 23, 26, 29, 31, 33, 34, 35, 41, 43, 53,

c.i. vat dyes such as c.i. vat green 1, and the like.

Further, the dye includes triarylmethane dyes, azo dyes, cyanine dyes, triphenylmethane dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, and squaric acid depending on the chemical structureDyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, nitro dyes, porphyrazine dyes, and the like.

The colored curable resin composition of the present invention preferably contains a triarylmethane dye as the colorant (a). It is preferable that the colorant (A) contains a triarylmethane dye because the brightness of the obtained color filter tends to be improved.

Examples of The pigment contained in The colorant (a1) include organic pigments and inorganic pigments, and examples thereof include compounds classified as pigments (pigments) in The color index (published by The Society of Dyers and Colourists). The pigment may be used alone or in combination of 2 or more.

Examples of the pigment include c.i. pigment red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 179, 180, 192, 202, 208, 209, 215, 216, 224, 242, 254, 255, 264, 265, 266, 268, 269, 273, 291;

c.i. pigment yellow 1,3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 180, 185, 194, 214, 231, and the like;

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

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

c.i. pigment violet 1, 14, 19, 23, 29, 32, 33, 36, 37, 38 and other violet pigments;

green pigments such as c.i. pigment green 7, 10, 15, 25, 36, 47, 58, 59;

brown pigments such as c.i. pigment brown 23, 25, 28;

and black pigments such as c.i. pigment black 1 and 7.

The pigment may be subjected to rosin treatment, surface treatment using a pigment derivative or the like into which an acidic group or a basic group has been introduced, grafting treatment of the pigment surface with a polymer compound or the like, micronization treatment by a sulfuric acid micronization method or the like, cleaning treatment by an organic solvent, water or the like for removing impurities, removal treatment by an ion exchange method or the like for removing ionic impurities, or the like, as necessary. The particle diameters of the pigments are preferably uniform.

The pigment can be dispersed by including a pigment dispersant to prepare a pigment dispersion liquid in a state of being uniformly dispersed in the pigment dispersant solution. The pigment may be dispersed individually or in combination of two or more.

Examples of the pigment dispersant include surfactants such as cationic, anionic, nonionic, amphoteric, polyester, polyamide, and acrylic surfactants. These pigment dispersants may be used alone, or 2 or more kinds may be used in combination. Examples of the pigment dispersant include KP (manufactured by shin-Etsu chemical Co., Ltd.), FLOWLEN (manufactured by Kyoho chemical Co., Ltd.), Solsperse (manufactured by Lubrizol Co., Ltd.), EFKA (manufactured by BASF Co., Ltd.), AJISPER (manufactured by Najinggu Fine chemical Co., Ltd.), Disperbyk (manufactured by BYK-Chemie Co., Ltd.), and the like.

When the pigment dispersant is used, the amount thereof is preferably 100 parts by mass or less, and more preferably 5 to 50 parts by mass, per 100 parts by mass of the pigment. If the amount of the pigment dispersant used is within the above range, there is a tendency that a pigment dispersion liquid in a uniformly dispersed state is obtained.

When the colorant (a) includes the colorant (a1), the content of the colorant (a1) in the colorant (a) may be, for example, 0.1 to 99.9% by mass, more preferably 0.1 to 99% by mass, and still more preferably 0.5 to 97% by mass, based on the total solid content of the colorant (a).

When the colorant (a) contains a triarylmethane dye, the content of the triarylmethane dye in the colorant (a) may be in the range of the content of the colorant (a1), and is more preferably 98% by mass or less, still more preferably 95% by mass or less, yet more preferably 10% by mass or more, and still more preferably 20% by mass or more, based on the total amount of solid components of the colorant (a). When the colorant (a) contains a triarylmethane-based dye, the colorant (a) may contain only a xanthene dye and a triarylmethane-based dye, or may contain another colorant (a1) in addition to these dyes.

[2] resin (B)

The colored curable resin composition of the present invention contains 1 or 2 or more kinds of resins (B). The resin (B) is preferably an alkali-soluble resin. The alkali solubility refers to a property of dissolving in a developer solution which is an aqueous solution of an alkali compound. Examples of the resin (B) include the following resins [ K1] to [ K6 ].

Resin [ K1 ]: a copolymer of at least 1 (a) (hereinafter, sometimes referred to as "(a)") selected from unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides and a monomer (b) (hereinafter, sometimes referred to as "(b)") having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond.

Resin [ K2 ]: (a) and (b) and a monomer (c) copolymerizable with (a) (wherein, unlike (a) and (b) [ hereinafter, sometimes referred to as "(c)"). A copolymer of (a).

Resin [ K3 ]: (a) copolymers with (c).

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

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

Resin [ K6 ]: a resin obtained by reacting the copolymer of (b) and (c) with (a) and further with a carboxylic acid anhydride.

Specific examples of (a) include unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, o-, m-and p-vinylbenzoic acid, and the like;

unsaturated dicarboxylic acids such as 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, dimethyltetrahydrophthalic acid, and 1, 4-cyclohexene dicarboxylic acid;

carboxyl group-containing bicyclic unsaturated compounds such as methyl-5-norbornene-2, 3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5, 6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] hept-2-ene and 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;

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

unsaturated mono [ (meth) acryloyloxyalkyl ] esters of 2 or more valent polycarboxylic acids such as mono [ 2- (meth) acryloyloxyethyl ] succinate and mono [ 2- (meth) acryloyloxyethyl ] phthalate;

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

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

In the present specification, "(meth) acrylic acid" means at least 1 selected from acrylic acid and methacrylic acid. The same applies to "(meth) acryloyl group" and "(meth) acrylate" and the like.

(b) The polymerizable compound has a cyclic ether structure having 2 to 4 carbon atoms (for example, at least 1 selected from an oxirane ring, a cyclobutane ring and a tetrahydrofuran ring (oxolane)) and an ethylenically unsaturated bond. (b) Preferably, the monomer has a cyclic ether structure having 2 to 4 carbon atoms and a (meth) acryloyloxy group.

Examples of (b) include a monomer (b1) (hereinafter sometimes referred to as "(b 1)") having an oxirane group and an ethylenically unsaturated bond, a monomer (b2) (hereinafter sometimes referred to as "(b 2)") having an oxetanyl group and an ethylenically unsaturated bond, and a monomer (b3) (hereinafter sometimes referred to as "(b 3)") having a tetrahydrofuranyl group and an ethylenically unsaturated bond.

Examples of (b1) include a monomer (b 1-1) [ hereinafter sometimes referred to as "(b 1-1)" ] having a structure in which an unsaturated aliphatic hydrocarbon is epoxidized, and a monomer (b 1-2) [ hereinafter sometimes referred to as "(b 1-2)" ] having a structure in which an unsaturated alicyclic hydrocarbon is epoxidized.

Examples of (b 1-1) include glycidyl (meth) acrylate,. beta. -methylglycidyl (meth) acrylate,. beta. -ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether,. alpha. -methyl-o-vinylbenzyl glycidyl ether,. alpha. -methyl-m-vinylbenzyl glycidyl ether,. alpha. -methyl-p-vinylbenzyl glycidyl ether, 2, 3-bis (glycidoxymethyl) styrene, 2, 4-bis (glycidoxymethyl) styrene, 2, 5-bis (glycidoxymethyl) styrene, 2, 6-bis (glycidoxymethyl) styrene, 2,3, 4-tris (glycidoxymethyl) styrene, 2,3, 5-tris (glycidoxymethyl) styrene, 2,3, 6-tris (glycidoxymethyl) styrene, 3,4, 5-tris (glycidoxymethyl) styrene, 2,4, 6-tris (glycidoxymethyl) styrene and the like.

Examples of (B1-2) include vinylcyclohexene monooxide, 1, 2-epoxy-4-vinylcyclohexane (for example, Celloxide 2000; manufactured by Daicel Co., Ltd.), 3, 4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer A400; manufactured by Daicel Co., Ltd.), 3, 4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer M100; manufactured by Daicel Co., Ltd.), a compound represented by the formula (B-I), a compound represented by the formula (B-II), and the like.

[ formula (B-I) and formula (B-II) wherein R^aAnd R^bEach independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group. X¹And X²Each independently represents a single bond, [ R ]^c－、*－R^c－O－、*－R^c-S-or R^c－NH－。R^cRepresents a C1-6 alkaneAnd (2) a second group. Denotes a bonding site to 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 a hydroxyl group include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, a 1-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^aAnd R^bPreferably 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.

As a constituent R^cExamples of the alkanediyl group include a methylene group, an ethylene group, a propane-1, 2-diyl group, a propane-1, 3-diyl group, a butane-1, 4-diyl group, a pentane-1, 5-diyl group, and a hexane-1, 6-diyl group.

X¹And X²Preferably a single bond, methylene, ethylene, — CH₂-O- ('represents a bonding site to O)' -CH₂CH₂-O-radical, more preferably single bond, -CH₂CH₂-O-group.

Specific examples of the compounds represented by the formula (B-I) include compounds represented by the formulae (B-I-1) to (B-I-15), preferable examples include compounds represented by the formulae (B-I-1), (B-I-3), (B-I-5), (B-I-7), (B-I-9), and (B-I-11) to (B-I-15), and more preferable examples include compounds represented by the formulae (B-I-1), (B-I-7), (B-I-9), and (B-I-15).

Specific examples of the compounds represented by the formula (B-II) include compounds represented by the formulae (B-II-1) to (B-II-15), preferable examples include compounds represented by the formulae (B-II-1), (B-II-3), (B-II-5), (B-II-7), (B-II-9), and (B-II-11) to (B-II-15), and more preferable examples include compounds represented by the formulae (B-II-1), (B-II-7), (B-II-9), and (B-II-15).

The compound represented by the formula (B-I) and the compound represented by the formula (B-II) may be used alone, respectively. They may be mixed in any ratio. When mixed, the mixing ratio is represented by the formula (B-I): the molar ratio of the formula (B-II) is preferably 5: 95-95: 5, more preferably 10: 90-90: 10, more preferably 20: 80-80: 20.

the monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond is preferably a monomer having an oxetanyl group and a (meth) acryloyloxy group.

Preferable examples of (b2) include 3-methyl-3- (meth) acryloyloxymethyloxetane, 3-ethyl-3- (meth) acryloyloxymethyloxetane, 3-methyl-3- (meth) acryloyloxyethyloxyoxetane and 3-ethyl-3- (meth) acryloyloxyethyloxyethyloxetane.

The monomer having a tetrahydrofuranyl group and an ethylenically unsaturated bond (b3) is preferably a monomer having a tetrahydrofuranyl group and a (meth) acryloyloxy group.

Preferable examples of (b3) include tetrahydrofurfuryl acrylate (for example, Viscoat V #150, manufactured by Osaka organic chemical industries, Ltd.), tetrahydrofurfuryl methacrylate, and the like.

As a specific example of (c),

examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, and (meth) acrylate2-methylcyclohexyl (meth) acrylate tricyclo [5.2.1.0^2,6]Decan-8-yl ester (which is known as "dicyclopentyl (meth) acrylate" as a common name in the art, and may be referred to as "tricyclodecyl (meth) acrylate" in some cases), and tricyclo (meth) acrylate [5.2.1.0^2,6](meth) acrylates such as decen-8-yl ester (commonly known in the art as "dicyclopentenyl (meth) acrylate"), (meth) acrylates such as dicyclopentenyl ethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, and benzyl (meth) acrylate;

hydroxyl group-containing (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;

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

bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2 '-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5, 6-dihydroxybicyclo [2.2.1] hept-2-ene, 5, 6-bis (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5, 6-bis (2' -hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5, 6-dimethoxybicyclo [ 2.1] hept-2-ene, 5, 6-bis (2.1) hept-2-ene, 5-hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxyhept-2-ene, 5-hydroxybicyclo [2.2.1] hept-2-ene, 5-2.1 ] hept-2-ene, 5-hydroxy-2-hydroxy-2-hydroxy-1-2-hydroxy-2-1-hydroxy-2-hydroxy-2-1-2-ethyl-2-ene, 5-hydroxy-2-hydroxy-2, 5, 6-2-hydroxy-2-one, 5-2-one, 5, 6-one, 2-one, 2-one, 5, Bicyclic unsaturated compounds such as 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonybicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5, 6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene and 5, 6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene;

dicarbonylimide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate and N- (9-acridinyl) maleimide;

styrene, α -methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluenes, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1, 3-butadiene, isoprene, 2, 3-dimethyl-1, 3-butadiene and the like.

Among them, benzyl (meth) acrylate, tricyclodecyl (meth) acrylate, styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hept-2-ene and the like are preferable as (c) from the viewpoint of copolymerization reactivity and heat resistance. In addition, benzyl (meth) acrylate and tricyclodecanyl (meth) acrylate are more preferable as (c) in terms of excellent developability during pattern formation.

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

Structural unit from (a): 2 to 50 mol% (more preferably 10 to 45 mol%),

structural element from (b), in particular structural element from (b 1): 50 to 98 mol% (more preferably 55 to 90 mol%).

When the ratio of the structural units in the resin [ K1] is in the above range, the storage stability, the developability, and the solvent resistance of the obtained pattern tend to be excellent.

The resin [ K1] can be produced by a method described in "Experimental method for Polymer Synthesis" (published by Otsuka corporation, 1 st edition, 1972, 3/1) and a literature cited therein.

Specifically, the following methods are mentioned: predetermined amounts of (a) and (b) (particularly (b1)), a polymerization initiator, a solvent and the like are charged into a reaction vessel, and stirring, heating and heat-maintaining are carried out in a deoxygenated atmosphere. The polymerization initiator and the solvent used herein are not particularly limited, and any polymerization initiator and solvent generally used in the art may be used. Examples of the polymerization initiator include azo compounds (e.g., 2 '-azobisisobutyronitrile, 2' -azobis (2, 4-dimethylvaleronitrile), and organic peroxides (e.g., benzoyl peroxide). The solvent may be any solvent that dissolves the monomers, and the solvent (F) described below as a solvent for the colored curable resin composition may be used.

The copolymer obtained may be used as it is as a solution after the reaction, may be used as a concentrated or diluted solution, or may be used as a substance taken out as a solid (powder) by a method such as reprecipitation. In particular, by using the solvent (F) described later as a solvent in the polymerization, the solution after the reaction can be used as it is, and thus the production process can be simplified.

In the resin [ K2], the ratio of the structural units derived from the respective monomers is preferably in the following range among all the structural units constituting the resin [ K2 ].

Structural unit from (a): 4 to 45 mol%, more preferably 10 to 40 mol%, still more preferably 15 to 35 mol%,

structural element from (b), in particular structural element from (b 1): 2 to 95 mol%, more preferably 3 to 70 mol%, still more preferably 5 to 45 mol%,

structural units from (c): 1 to 94 mol%, more preferably 20 to 85 mol%, and still more preferably 40 to 80 mol%.

When the ratio of the structural units in the resin [ K2] is in the above range, the storage stability, developability, solvent resistance of the resulting pattern, and heat resistance and mechanical strength tend to be excellent.

The resin [ K2] can be produced in the same manner as described for the production method of the resin [ K1 ]. Specifically, the following methods are mentioned: the reaction vessel is charged with predetermined amounts of (a), (b) (particularly (b1)) and (c), a polymerization initiator and a solvent, and the mixture is stirred, heated and kept at a temperature under a deoxygenated atmosphere. The copolymer obtained may be used as it is as a solution after the reaction, may be used as a concentrated or diluted solution, or may be used as a substance taken out as a solid (powder) by a method such as reprecipitation.

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

Structural unit 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%,

structural units from (c): 45 to 98 mol%, more preferably 50 to 90 mol%, still more preferably 50 to 85 mol%, and particularly preferably 50 to 75 mol%.

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

The resin [ K4] can be produced by obtaining a copolymer of (a) and (c), and cycloaddition of a cyclic ether structure having 2 to 4 carbon atoms of (b), particularly ethylene oxide of (b1), to a carboxylic acid and/or carboxylic acid anhydride of (a). Specifically, first, a copolymer of (a) and (c) was produced in the same manner as the method described for producing the resin [ K1 ]. In this case, the ratio of the structural units derived from the respective monomers is preferably in the following range among all the structural units constituting the copolymer of (a) and (c).

Structural unit from (a): 5 to 50 mol% (more preferably 10 to 45 mol%),

structural units from (c): 50 to 95 mol% (more preferably 55 to 90 mol%).

Then, a cyclic ether structure having 2 to 4 carbon atoms of (b), particularly an oxirane ring of (b1), is reacted with a part of the carboxylic acid and/or carboxylic acid anhydride derived from (a) in the copolymer. Specifically, after the production of the copolymer of (a) and (c), the atmosphere in the flask is replaced with air from nitrogen, and (b) (particularly (b1)), a reaction catalyst of a carboxylic acid or a carboxylic anhydride and a cyclic ether structure (for example, tris (dimethylaminomethyl) phenol) and a polymerization inhibitor (for example, hydroquinone) are charged into the flask and reacted at 60 to 130 ℃ for 1 to 10 hours, whereby a resin [ K4] can be obtained.

(b) The amount of (b1) used is preferably 5 to 80 moles, more preferably 10 to 75 moles, based on 100 moles of (a). When the content is in this range, the balance among storage stability, developability, solvent resistance, heat resistance, mechanical strength, and sensitivity tends to be good. From the viewpoint of high reactivity of the cyclic ether structure and difficulty in leaving unreacted (b), the (b) used for the resin [ K4] is preferably (b1), and more preferably (b 1-1).

The amount of the reaction catalyst used is preferably 0.001 to 5% by mass based on the total amount of (a), (b) (particularly (b1)) and (c). The amount of the polymerization inhibitor used is preferably 0.001 to 5% by mass based on the total amount of (a), (b) and (c).

The reaction conditions such as the charging method, the reaction temperature and time can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by polymerization, and the like. Similarly to the polymerization conditions, the charging method and the reaction temperature may be appropriately adjusted in consideration of the production facilities, the amount of heat generated by polymerization, and the like.

As the first stage, the resin [ K5] was subjected to the same process as the process for producing the resin [ K1] to obtain a copolymer of (b) (particularly (b1)) and (c). The copolymer obtained may be used as it is as a solution after the reaction, may be used as a concentrated or diluted solution, or may be used as a substance taken out as a solid (powder) by a method such as reprecipitation.

The ratio of the structural units derived from (b) (particularly (b1)) and (c) is preferably in the following range relative to the total mole number of all the structural units constituting the copolymer.

Structural element from (b), in particular structural element from (b 1): 5 to 95 mol% (more preferably 10 to 90 mol%),

structural units from (c): 5 to 95 mol% (more preferably 10 to 90 mol%).

Further, the resin [ K5] can be obtained by reacting (a) the carboxylic acid or carboxylic anhydride and (b) (particularly (b1)) with the cyclic ether structure derived from (b) which is contained in the copolymer of (c) under the same conditions as the process for producing the resin [ K4 ]. The amount of (a) to be used in the reaction with the copolymer is preferably 5 to 80 mol based on 100 mol of (b) (particularly (b 1)). From the viewpoint of high reactivity of the cyclic ether structure and difficulty in remaining unreacted (b), the (b) used in the resin [ K5] is preferably (b1), and more preferably (b 1-1).

The resin [ K6] is a resin obtained by further reacting a carboxylic acid anhydride with the resin [ K5 ]. Reacting a carboxylic anhydride with a hydroxyl group generated by the reaction of the cyclic ether structure with the carboxylic acid or carboxylic anhydride.

Examples of the carboxylic anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5, 6-tetrahydrophthalic anhydride, 1,2,3, 6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5, 6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride (nadic anhydride).

Among the resins [ K1] to [ K6], the resin [ K1] or [ K2] is preferable as the resin (B). The resin (B) may be composed of 1 resin, or may contain 2 or more resins.

The weight average molecular weight (Mw) of the resin (B) in terms of polystyrene is preferably 3000 to 100000, more preferably 5000 to 50000, still more preferably 5000 to 30000, and particularly preferably 10000 to 30000. When the weight average molecular weight (Mw) is in the above range, the unexposed portion tends to have high solubility in a developer, and the obtained colored pattern tends to have high film thickness retention and high hardness. The molecular weight distribution [ weight average molecular weight (Mw)/number average molecular weight (Mn) ] of the resin (B) is preferably 1.1 to 6, more preferably 1.2 to 4.

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

The content of the resin (B) is preferably 1 to 50% by mass, and 5 to 45% by mass, based on 100% by mass of the solid content of the colored curable resin composition. If the content of the resin (B) is within the above range, the solubility of the unexposed portion in the developer tends to be high.

[3] polymerizable Compound (C)

The polymerizable compound (C) is not particularly limited as long as it can be polymerized by an active radical or the like generated from the polymerization initiator (D) by light irradiation or the like, and examples thereof include compounds having a polymerizable ethylenically unsaturated bond. The weight average molecular weight of the polymerizable compound (C) is preferably 3000 or less.

Among these, as the polymerizable compound (C), preferable are photopolymerizable compounds having 3 or more ethylenically unsaturated bonds, and examples thereof include trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol poly (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, ethylene glycol-modified pentaerythritol tetra (meth) acrylate, ethylene glycol-modified dipentaerythritol hexa (meth) acrylate, propylene glycol-modified pentaerythritol tetra (meth) acrylate, and the like, Propylene glycol-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified pentaerythritol tetra (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, and the like. Among them, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like are preferable.

The colored curable resin composition of the present invention may contain 1 or 2 or more polymerizable compounds (C). The content of the polymerizable compound (C) is preferably 20 to 150 parts by mass, and more preferably 40 to 110 parts by mass, based on 100 parts by mass of the resin (B) in the colored curable resin composition.

The content of the polymerizable compound (C) is preferably 7 to 65% by mass, more preferably 10 to 60% by mass, and still more preferably 10 to 50% by mass, based on the total amount of solid components in the colored curable resin composition. If the content of the polymerizable compound (C) is within the above range, the film thickness retention rate at the time of forming a colored pattern and the chemical resistance of the color filter tend to be improved.

[4] polymerization initiator (D)

The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating an active radical, an acid, or the like by the action of light or heat to initiate polymerization, and a known polymerization initiator can be used. Examples of the polymerization initiator generating active radicals include an O-acyloxime compound, an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, and a bisimidazole compound.

The O-acyloxime compound is a compound having a partial structure represented by formula (d 1). Hereinafter, the bonding site is denoted.

Examples of the O-acyloxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butane-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-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-dioxocyclopentylmethyloxy) benzoyl } -9H-carbazol-3-yl ] ethane-1-imine, and N-acetoxy-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -3-cycloimine Pentylpropane-1-imine, N-benzoyloxy-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -3-cyclopentylpropane-1-one-2-imine, and the like. Commercially available products such as Irgacure OXE01, OXE02 (both of which are available from BASF corporation), N-1919 (available from ADEKA corporation) and the like can also be used. Among them, the O-acyloxime compound is preferably at least 1 selected from the group consisting of N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine, and more preferably N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine. These O-acyloxime compounds tend to give color filters with high luminance.

The above-mentioned alkylphenone compound has a partial structure represented by the formula (d2) or a partial structure represented by the formula (d 3). In these partial structures, the benzene ring may have a substituent.

Examples of the compound having a partial structure represented by the formula (d2) include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one, and 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [ 4- (4-morpholinyl) phenyl ] butan-1-one. Commercially available products such as Irgacure 369, 907, and 379 (all of which are manufactured by BASF corporation) may be used.

Examples of the compound having a partial structure represented by the formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1- [ 4- (2-hydroxyethoxy) phenyl ] propan-1-one, 1-hydroxycyclohexylphenyl ketone, oligomers of 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one, α -diethoxyacetophenone, benzildimethylketal, and the like.

From the viewpoint of sensitivity, the alkylphenone compound is preferably a compound having a partial structure represented by the formula (d 2).

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

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

Examples of the biimidazole compound include 2,2 '-bis (2-chlorophenyl) -4, 4', 5,5 '-tetraphenylbiimidazole, 2' -bis (2, 3-dichlorophenyl) -4, 4 ', 5, 5' -tetraphenylbiimidazole (see, for example, japanese unexamined patent publication No. 6-75372, japanese unexamined patent publication No. 6-75373, etc.), 2 '-bis (2-chlorophenyl) -4, 4', 5,5 '-tetraphenylimidazole, 2' -bis (2-chlorophenyl) -4, 4 ', 5, 5' -tetrakis (alkoxyphenyl) biimidazole, 2 '-bis (2-chlorophenyl) -4, 4', 5,5 '-tetrakis (dialkoxyphenyl) biimidazole, 2' -bis (2-chlorophenyl) -4, 4 ', 5, 5' -tetrakis (trialkoxyphenyl) biimidazole (see, for example, japanese unexamined patent publication No. sho 48-38403, Japanese patent application laid-open No. 62-174204, etc.), bisimidazole compounds in which the phenyl group at the 4,4 ', 5, 5' -position is substituted with a carboalkoxy group (see, for example, Japanese patent application laid-open No. 7-10913, etc.), and the like.

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 compounds such as benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4 ' -methyldiphenyl sulfide, 3 ', 4,4 ' -tetrakis (t-butylperoxycarbonyl) benzophenone, and 2,4, 6-trimethylbenzophenone; quinone compounds such as 9, 10-phenanthrenequinone, 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzil, methyl benzoylformate, titanocene compounds, and the like. These are preferably used in combination with a polymerization initiation aid (D1) (particularly amines) described later.

Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, and diphenyliodoniumP-toluenesulfonate and diphenyliodineHexafluoroantimonate and the likeSalts, nitrobenzyl tosylates, benzoin tosylates, and the like.

As the polymerization initiator (D), a polymerization initiator containing at least 1 selected from the group consisting of an O-acyloxime compound, an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, and a bisimidazole compound is preferable, and a polymerization initiator containing an O-acyloxime compound is more preferable.

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

[5] polymerization initiation aid (D1)

The polymerization initiation aid (D1) is a compound or sensitizer for promoting the polymerization of the polymerizable compound whose polymerization is initiated by the polymerization initiator (D). When the polymerization initiator (D1) is contained, it is used in combination with the polymerization initiator (D).

Examples of the polymerization initiation aid (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds. Among them, a thioxanthone compound is preferable. It is also possible to use 2 or more polymerization initiation aids (D1) in combination.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N-dimethyl-p-toluidine, 4 '-bis (dimethylamino) benzophenone (commonly known as michelson), 4' -bis (diethylamino) benzophenone, and 4,4 '-bis (ethylmethylamino) benzophenone, and among them, 4' -bis (diethylamino) benzophenone is preferable. Commercially available products such as EAB-F (manufactured by Baotu chemical industries, Ltd.) can be used.

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

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2, 4-diethylthioxanthone, 2, 4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.

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

The content of the polymerization initiation aid (D1) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). If the content of the polymerization initiation aid (D1) is within the above range, a pattern can be further formed with high sensitivity, and the productivity of the color filter tends to be improved.

[6] thiol Compound (E)

The thiol compound (E) includes a thiol compound having an ether bond. When the colored curable resin composition contains a thiol compound containing an ether bond, the film thickness retention tends to be high. The colored curable resin composition of the present invention may contain 1 or 2 or more kinds of thiol compounds containing an ether bond.

The thiol compound having an ether bond may contain, for example, 2 to 6 sulfanyl groups (-SH), preferably 3 to 5.

The thiol compound having an ether bond may have, for example, 2 to 6 ether bonds, and preferably 3 to 5 ether bonds.

The thiol compound having an ether bond is preferably a compound represented by the formula (I).

A－(R¹－SH)_n(I)

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

a plurality of R bonded to oxygen atoms derived from the m hydroxyl groups¹Each 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 is not less than n ]

A represents a residue of a polyol having m hydroxyl groups. The residue of the polyol refers to a structure obtained by removing a hydrogen atom (H) constituting at least one hydroxyl group (OH) from the polyol. In the formula (I), the oxygen atom (O) bonded to the removed hydrogen atom, that is, the oxygen atom derived from the hydroxyl group and n R¹And (4) bonding. The oxygen atoms from the hydroxyl groups in the polyol may all be bonded to R¹Bonded, or partially bonded, to R¹And (4) bonding.

The polyol is not particularly limited as long as it is a compound having 2 or more hydroxyl groups in 1 molecule. Examples thereof include aliphatic polyols, alicyclic polyols, aromatic ring-containing polyols, saccharides and derivatives thereof. Among them, aliphatic polyols, alicyclic polyols, and/or aromatic ring-containing polyols are preferable. More preferably an aliphatic polyol.

The aliphatic polyol is preferably an aliphatic polyol having 2 to 30 carbon atoms. Specific examples thereof include alkylene glycols such as ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 6-hexanediol, and 1, 12-dodecamethylene glycol; polyalkylene glycols such as diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, and polypropylene glycol; and 3-or more-membered polyols such as (poly) glycerol, trimethylolpropane, pentaerythritol, dipentaerythritol, sorbitol, and sorbitan, and alkylene oxide adducts thereof (for example, the number of addition mols is 1 to 50).

As the alicyclic polyol, for example, an alicyclic polyol having 3 to 30 carbon atoms is preferable. Specific examples thereof include alicyclic diols such as 1, 4-cyclohexanedimethanol and hydrogenated bisphenol A.

The aromatic ring-containing polyol is preferably an aromatic ring-containing polyol having 6 to 30 carbon atoms. Specifically, for example, alkylene oxide adducts of bisphenols such as bisphenol A, bisphenol F and bisphenol S (for example, the number of moles added is 2 to 30) and the like can be cited.

m is not less than 2, preferably 2 to 10, more preferably 2 to 8, further preferably 2 to 6, and particularly preferably 3 to 6.

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

R¹The same or different alkylene groups each having 1 to 10 carbon atoms. The alkylene group may be linear or branched.

R¹In the alkylene group represented, the carbon atom bonded to the mercapto group may be a primary carbon atom, a secondary carbon atom, or a tertiary carbon atom, from the viewpoint of reactivityPreferably, the carbon atom is a primary carbon atom or a secondary carbon atom.

R¹May have 1 or 2 or more substituents, preferably R¹Contains no substituent. As R¹Examples of the substituent which may be present include a halogen atom, a hydroxyl group, a carboxyl group, a sulfonic acid group, an amino group, a phosphoric acid group and the like.

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

Examples of the thiol compound having an ether bond include pentaerythritol tripropylene thiol, trimethylolpropane dipropyl thiol and the like.

The thiol compound having an ether bond can be produced by a known production method. For example, the compound can be produced by the method described in WO 2016/171072.

The thiol compound (E) may contain 1 or 2 or more kinds of thiol compounds (E1) other than the above-mentioned ether bond-containing thiol compound. The thiol compound (E1) is particularly preferably used when the polymerization initiator (D) is an oxime compound such as an O-acyloxime compound and/or a biimidazole compound. The thiol compound (E1) is a compound having at least 1 sulfanyl group (-SH) in the molecule. The thiol compound (E1) is preferably a compound having 1 sulfanyl group in the molecule.

Examples of the compound having 1 sulfanyl group in the molecule include a 2 sulfanyl groupAzoles, 2-sulfanyl thiazoles, 2-sulfanyl benzimidazoles, 2-sulfanyl benzothiazoles, 2-sulfanyl benzolsAzoles, 2-sulfanylnicotinic acid, 2-sulfanylpyridine, 2-sulfanylpyridin-3-ol, 2-sulfanylpyridine N-oxide, 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-sulfanylpyrimidine, 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-thiadiazole-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-sulfanyl-5-nitrobenzimidazole, 6-amino-2-sulfanyl benzothiazole, 5-chloro-2-sulfanyl benzothiazole, 6-ethoxy-2-sulfanyl benzothiazole, 6-nitro-2-sulfanyl benzothiazole, 2-sulfanylnaphthoimidazole, 3-sulfanyl-1, 2, 4-triazole, 4-amino-6-sulfanylpyrazolo [2,4-d ]]Pyridine, 2-amino-6-purine thiol, 6-sulfanylpurine and 4-sulfanyl-1H-pyrazolo [2,4-d ]]Pyrimidines, and the like.

Examples of the compound having 2 or more sulfanyl groups in the molecule include hexanedithiol, decanedithiol, 1, 4-bis (methylsulfanyl) benzene, butanediolbis (3-sulfanyl propionate), butanediolbis (3-sulfanyl acetate), ethanedioldis (3-sulfanyl acetate), trimethylolpropane tris (3-sulfanyl acetate), butanedioldis (3-sulfanyl propionate), trimethylolpropane tris (3-sulfanyl acetate), pentaerythritol tetrakis (3-sulfanyl propionate), pentaerythritol tetrakis (3-sulfanyl acetate), trihydroxyethyltris (3-sulfanyl propionate), pentaerythritol tetrakis (3-sulfanyl butyrate), and 1, 4-bis (3-sulfanylbutyloxy) butane.

The content of the thiol compound (E) is preferably 0.5 to 50 parts by mass, more preferably 1 to 45 parts by mass, and still more preferably 5 to 40 parts by mass, based on 100 parts by mass of the polymerization initiator (D). If the content of the thiol compound (E) is within the above range, the sensitivity tends to be high and the developability tends to be good.

[7] solvent (F)

The colored curable resin composition of the present invention preferably contains 1 or 2 or more solvents (F). Examples of the solvent (F) include an ester solvent (a solvent containing-COO-, an ether solvent (a solvent containing-O-) other than the ester solvent, an ether ester solvent (a solvent containing-COO-and-O-), a ketone solvent (a solvent containing-CO-) other than the ester solvent, an alcohol solvent, an aromatic hydrocarbon solvent, an amide solvent, and dimethyl sulfoxide.

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

Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, 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-di-nAlkane, diethylene glycol dimethyl etherAlcohol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, methyl anisole, and the like.

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

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

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

The solvent (F) preferably contains an organic solvent having a boiling point of 120 to 180 ℃ at 1atm, from the viewpoint of coatability and drying property. Among them, the solvent (F) preferably contains at least 1 selected from propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, and N, N-dimethylformamide, and more preferably contains at least 1 selected from propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol, and ethyl 3-ethoxypropionate.

The content of the solvent (F) in the colored curable resin composition is preferably 70 to 95% by mass, and more preferably 75 to 92% by mass. In other words, the solid content of the colored curable resin composition is preferably 5 to 30% by mass, and more preferably 8 to 25% by mass. If the content of the solvent (F) is in the above range, flatness at the time of coating becomes good, and color density is not insufficient at the time of forming a color filter, so that there is a tendency that display characteristics become good.

[8] leveling agent (G)

Examples of the leveling agent (G) include a silicone surfactant (having no fluorine atom), a fluorine surfactant, and a silicone surfactant having a fluorine atom. These may have a polymerizable group in a side chain.

Examples of the silicone 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 (product name: Toray Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (product name: manufactured by shin-Etsu chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, and TSF4460 (product name: Moive Performance Materials Japan Co., Ltd.) can be cited.

Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain in the molecule. Specifically, the examples include FLUORAD (registered trademark) FC430, FLUORAD FC431 (manufactured by Sumitomo 3M Co., Ltd.), MEGAFAC (registered trademark) F142D, MEGAFAC F171, MEGAFAC F172, MEGAFAC F173, MEGAFAC F177, MEGAFAC F183, MEGAFAC F554, MEGAFAC R30, MEGAFAC RS-718-K (manufactured by DIC Co., Ltd.), F-top (registered trademark) EF301, F-top EF303, F-top EF351, F-top EF352 (manufactured by Mitsubishi electro chemical Co., Ltd.), Surflon (registered trademark) S381, Surflon S382, Surflon SC101, Surflon SC105 (manufactured by Asahi Nippon Kabushiki Kaisha) and E5844 (manufactured by Mitsui chemical Co., Ltd.).

Examples of the silicone surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain in the molecule. Specifically, there may be mentioned MEGAFAC (registered trademark) R08, MEGAFAC BL20, MEGAFAC F475, MEGAFAC F477, and MEGAFAC F443 (available from DIC Co., Ltd.).

The content of the leveling agent (G) in the colored curable resin composition is usually 0.0001 to 0.6% by mass, preferably 0.0001 to 0.4% by mass, and more preferably 0.0001 to 0.2% by mass. The content does not include the content of the pigment dispersant.

[ 9] other Components

The colored curable resin composition of the present invention may contain 1 or 2 or more kinds of fillers, polymer compounds other than the resin (B), adhesion promoters, ultraviolet absorbers, anti-coagulation agents, organic acids, curing agents, and other additives, as necessary.

< method for producing colored curable resin composition >

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

< color filter and method for manufacturing the same, and display device >

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

The method for producing a colored pattern from the colored curable resin composition of the present invention includes a photolithography method, an ink jet method, a printing method, and the like, and a photolithography method is preferable. The photolithography method is a method in which the colored curable resin composition is applied to a substrate and dried to form a colored composition layer, and the colored composition layer is exposed to light through a photomask and developed. In the photolithography method, a colored coating film which is a cured product of the colored composition layer can be formed without using a photomask and/or without performing development at the time of exposure. The colored pattern and the colored coating film formed from the colored curable resin composition of the present invention are the color filter of the present invention. The color filter of the present invention can be typically used as a colored pixel.

As the substrate, a glass plate such as quartz glass, borosilicate glass, aluminosilicate glass, soda-lime glass having a silica-coated surface, a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate, a substrate made of silicon, or a substrate made of aluminum, silver, or a silver/copper/palladium alloy thin film formed on the substrate can be used. Other color filter layers, resin layers, transistors, circuits, transparent electrodes, and the like may be formed on these substrates.

The formation of each color pixel by photolithography can be performed by using a known or conventional apparatus and conditions. For example, the following can be used. First, a colored curable resin composition is applied onto a substrate, and is dried by heating (prebaking) and/or drying under reduced pressure to remove volatile components such as a solvent and to obtain a smooth colored composition layer. Examples of the coating method include spin coating, slit and spin coating.

The temperature for the heat drying is preferably 30 to 120 ℃, more preferably 50 to 110 ℃. The heating time is preferably 10 seconds to 5 minutes, and more preferably 30 seconds to 3 minutes. When drying under reduced pressure is carried out, the drying is preferably carried out at a pressure of 50Pa to 150Pa and at a temperature of 20 ℃ to 25 ℃. The film thickness of the colored composition layer is not particularly limited, and may be appropriately selected according to the film thickness of the target color filter.

Next, the colored composition layer is exposed through a photomask for forming a target colored pattern. The pattern on the photomask is not particularly limited, and a pattern corresponding to the intended use may be used. The light source used for exposure is preferably a light source that generates light having a wavelength of 250 to 450 nm. For example, light less than 350nm may be cut off using a filter that cuts off the wavelength region, or light near 436nm, near 408nm, or near 365nm may be selectively extracted using a band-pass filter that extracts these wavelength regions. Specifically, the light source includes a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp, and the like.

In the exposure, it is preferable to use an exposure device such as a mask aligner or a stepper in order to uniformly irradiate the entire exposure surface with parallel light beams and to precisely align the photomask with the substrate on which the colored composition layer is formed.

The exposed colored composition layer is brought into contact with a developer to develop the colored composition layer, thereby forming a colored pattern on the substrate. The unexposed portion of the colored composition layer is dissolved in a developer and removed by development.

As the developer, for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, or tetramethylammonium hydroxide is preferable. The concentration of these basic compounds in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. In addition, the developer may also contain a surfactant.

The developing method may be any of a slurry method, a dipping method, a spraying method, and the like. Further, the substrate can be inclined at an arbitrary angle during development. After development, washing with water is preferred.

The colored curable resin composition of the present invention has less residue on a substrate in a portion of the colored composition layer which is removed by dissolving an unexposed portion in a developer.

It is further preferable to post-bake the obtained colored pattern. The post-baking temperature is preferably 150 to 250 ℃ and more preferably 160 to 235 ℃. The post-baking time is preferably 1 to 120 minutes, and more preferably 10 to 60 minutes.

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

The thickness of the colored coating film or the colored pattern formed from the colored curable resin composition is preferably as thin as possible because it affects adjacent pixels. In particular, when the thickness is thick, light from the light source may leak through 2 or more pixels when the liquid crystal panel is manufactured, and when the panel is viewed obliquely, the vividness of the color may be lost. The film thickness of the colored coating film or colored pattern after postbaking is preferably 3 μm or less, more preferably 2.8 μm or less. The lower limit of the film thickness of the colored coating film or the colored pattern is not particularly limited, and is usually 1 μm or more, and may be 1.5 μm or more. The colored coating film or the colored pattern can exhibit excellent developability and is therefore excellent as a color filter.

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

The color filter of the present invention is useful as a color filter used in a display device (a liquid crystal display device, an organic EL device, electronic paper, or the like) or a solid-state imaging element.

Examples

The colored curable resin composition of the present invention will be described below by way of specific examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. Unless otherwise specified, "part" means "part by mass" and "%" means "% by mass". In addition, unless otherwise specified, the reaction was carried out under a nitrogen atmosphere.

The structure of the compound was confirmed by MASS analysis (LC; model 1200 by Agilent, MASS; LC/MSD by Agilent).

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin in terms of polystyrene were measured by GPC under the following conditions.

A device; HLC-8120 GPC (manufactured by Tosoh corporation)

A column; TSK-GELG 2000HXL

Column temperature; 40 deg.C

A solvent; THF (tetrahydrofuran)

A flow rate; 1.0mL/min

The concentration of the solid component of the test liquid; 0.001 to 0.01% by mass

Sample size; 50 μ L

A detector; RI (Ri)

A calibration standard substance; TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corp.)

The ratio (Mw/Mn) of the weight average molecular weight to the number average molecular weight in terms of polystyrene obtained above was defined as the degree of dispersion.

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

(Synthesis example 1)

Sodium tert-amylate was synthesized by reacting 17.4 parts of tert-amylalcohol with 2.22 parts of metallic sodium under nitrogen at 130 ℃. The mixture was heated to 60 ℃ and then 9.1 parts of 4-bromobenzonitrile, 7.105 parts of di-tert-amyl succinate and 10.89 parts of tert-amyl alcohol were added thereto, followed by stirring at a liquid temperature of 85 ℃ or lower for 2 hours. The suspension was further stirred for 18 hours or more, and then added to a mixture of 20 parts of methanol, 100 parts of water and 4.921 parts of sulfuric acid cooled to-10 ℃. After the addition of the suspension was completed, the reaction was stirred at 0 ℃ for 5 hours to complete the reaction, and then the solid content was filtered. The solid component was washed with methanol and water alternately and repeatedly until the coloration of the filtrate disappeared and no salt was precipitated. Then, the solid content was dried with a vacuum drier at 80 ℃ for 18 hours, to obtain 10.7 parts of the objective red pigment 1.

(Synthesis example 2)

52 parts of the compound represented by the formula (1-34) was obtained in accordance with the method described in example 1 of Japanese patent application laid-open No. 2016-277075.

Identification of Compounds represented by formulas (1-34)

(mass analysis) ionization mode ═ ESI +: m/z ═ M + H]⁺599.2

Accurate quality: 598.1

(Synthesis example 3)

1.0 part of a compound represented by the formula (1-87) was obtained in accordance with the method described in example 2 of Japanese patent laid-open publication No. 2017-226814.

Identification of Compound represented by formula (1-199)

(mass analysis) ionization mode ═ ESI +: m/z ═ M + H]⁺747.5

Accurate quality: 746.3

(Synthesis example 4)

24 parts of a compound represented by the formula (1-22) was obtained in accordance with the method described in Synthesis example 2 of Japanese patent application laid-open No. 2016-176075. The yield thereof was found to be 80%.

Identification of Compounds represented by formulas (1-32)

(mass analysis) ionization mode ═ ESI +: m/z ═ M + H]⁺659.9

Accurate quality: 658.9

(Synthesis example 5)

The following reaction was carried out under nitrogen atmosphere. 26.4 parts of potassium thiocyanate and 156 parts of acetonitrile were put into a flask equipped with a cooling tube and a stirrer, and then stirred at room temperature for 30 minutes. 40.0 parts of 2, 6-difluorobenzoyl chloride (manufactured by Tokyo Kasei 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 (Tokyo chemical Co., Ltd.) was added dropwise to the flask over 30 minutes, and the mixture was stirred at room temperature for 1 hour. Into the flask were charged an aqueous solution of 79.2 parts of sodium monochloroacetate dissolved in 120 parts of ion-exchanged water, and 60.4 parts of a 30% aqueous sodium hydroxide solution, followed by stirring at room temperature for 18 hours. 600 parts of ion-exchanged water was further added to the flask, followed by stirring for 1 hour, and the precipitated yellowish white solid was collected by filtration. The obtained yellowish white solid was washed with 120 parts of acetonitrile and then 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 put into a flask equipped with a stirrer, and stirred at room temperature for 2 hours. 80.8 parts of a 30% aqueous sodium hydroxide solution was added dropwise thereto over 10 minutes, followed by stirring for 5 minutes, and the aqueous layer was removed by a liquid separation operation. To the obtained organic layer, 156 parts of ion-exchanged water was added for liquid-separation washing, and then 156 parts of ion-exchanged water and 0.1 part of 35% hydrochloric acid were added for liquid-separation washing. The obtained organic layer was concentrated by an evaporator and then dried at 35 ℃ under reduced pressure to obtain a compound represented by the formula (t-1) as a white solid. The yield was 43.4 parts, and the yield was 58.0%.

The following reaction was carried out under nitrogen atmosphere. 13.2 parts of the compound represented by the formula (t-1), 19.0 parts of the compound represented by the formula (t-2) and 38 parts of toluene were charged into a flask equipped with a cooling tube and a stirrer, and then 9.2 parts of phosphorus oxychloride was added thereto and the mixture was stirred at 100 ℃ for 7 hours. Subsequently, the reaction mixture was cooled to room temperature and then diluted with 29 parts of methyl ethyl ketone. Next, a mixed solution of 114 parts of ion-exchanged water and 10 parts of 35% aqueous hydrochloric acid was poured into the diluted reaction mixture, and the aqueous layer was removed by a liquid separation operation. The obtained organic layer was subjected to solvent removal with an evaporator and then dried at 60 ℃ under reduced pressure, whereby the compound represented by the formula (t-3) was obtained as a bluish violet solid.

The obtained amount of a bluish-violet solid was 39.4 parts.

The following reaction was carried out under nitrogen atmosphere. A flask equipped with a cooling tube and a stirrer was charged with 38.4 parts of the compound represented by the formula (t-3) and 112 parts of methylene chloride, and stirred for 30 minutes. The reaction solution was cooled with ice, 31.6 parts of chlorosulfonic acid (manufactured by Tokyo Kasei Co., Ltd.) was added while maintaining the internal temperature at 10 ℃ and then the reaction solution was warmed to room temperature and stirred for 9 hours. Subsequently, the reaction solution was cooled in 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 ℃. After the diluted reaction solution was poured into 1120 parts of toluene, a viscous solid precipitated when stirred for 30 minutes. After the oil layer was drained by decantation, 320 parts of toluene was added to the obtained viscous solid and stirred for 30 minutes. 832 parts of 20% saline solution was added to the viscous solid obtained by removing the oil layer by decantation, and after stirring for 1 hour, the blue solid was filtered off by filtration. The obtained blue solid was washed with 576 parts of 20% saline solution and dried at 35 ℃ under reduced pressure. The obtained solid and 128 parts of methanol were put into a flask equipped with a stirrer, stirred for 30 minutes, and then filtered to separate the solid and the filtrate. The filtrate was used as filtrate A. The filtered solid was washed with 192 parts of methanol, and separated into a solid and a filtrate by filtration. This filtrate was used as filtrate B. The filtrate A and the filtrate B were mixed, and the solvent was removed by an evaporator, followed by drying under reduced pressure at 40 ℃ to obtain a compound represented by the formula (t-4) as a bluish violet solid. The obtained amount of a bluish-violet solid was 38.3 parts.

28.0 parts of the compound represented by the 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 stirrer, and the mixture was stirred at 40 ℃ for 2 hours, followed by filtration of the reaction suspension. The filtered solid and 350 parts of ion-exchanged water were put into a flask equipped with a stirrer, and after stirring for 30 minutes, the suspension was filtered. The obtained solid was washed with 280 parts of ion-exchanged water and then dried at 60 ℃ under reduced pressure to obtain a compound represented by the formula (t-5) as a bluish violet solid. The yield was 81.7% with 24.5 parts.

Identification of Compound represented by formula (t-5)

(mass analysis) ionization mode-ESI-: m/z 949.5[ M-Ba +2H]^-

Accurate mass [ M-Ba ]: 947.28

(Synthesis example 6)

An appropriate amount of nitrogen was introduced into a flask equipped with a reflux condenser, a dropping funnel and a stirrer, and the atmosphere was changed to nitrogen, and 151 parts of ethyl lactate and 178 parts of propylene glycol monomethyl ether acetate were placed therein and heated to 85 ℃ while stirring. Then, 38 parts of acrylic acid and 3, 4-epoxytricyclo [5.2.1.0 ] were added dropwise over 5 hours^2，6]Decane-8-yl acrylate with 3, 4-epoxytricyclo [5.2.1.0^2，6]25 parts of a mixture of decane-9-yl acrylate (containing 1: 1 in terms of molar ratio), 137 parts of N-cyclohexylmaleimide, and methyl methacrylate50 parts of 2-hydroxyethyl methacrylate and 338 parts of propylene glycol monomethyl ether acetate. On the other hand, a solution in which 5 parts of 2, 2-azobisisobutyronitrile was dissolved in 88 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After completion of the dropwise addition, the mixture was held at 85 ℃ for 4 hours and then cooled to room temperature to obtain a copolymer (resin B1) solution having a viscosity of 23mPas as measured by a type B viscometer (23 ℃) and a solid content of 25.4%. The weight-average molecular weight Mw of the resulting copolymer was 8.0X 10³The dispersion degree was 2.1, and the acid value in terms of solid content was 109 mg-KOH/g. The resin B1 has the following structural units.

In the following examples, any one of the following components was used as each component in the preparation of the colored curable resin composition.

Resin (B): resin B1 obtained in the above (Synthesis example 6)

Polymerizable compound (C): dipentaerythritol hexaacrylate (New Zhongcun chemical industry Co., Ltd.)

Polymerization initiator (D): n-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01, manufactured by BASF Corp.; oxime compound)

Thiol compound (E): pentaerythritol Tripropylmercaptan (PEPT)

Leveling agent (G): polyether-modified Silicone oil (Toray Silicone SH 8400; manufactured by Dow Corning Toray Co., Ltd.), described as "SH 8400" in examples "

[ example 1]

[ preparation of colored curable resin composition ]

The following components were mixed to prepare a pigment dispersion liquid 1 in which a pigment was sufficiently dispersed by a bead mill. Using this pigment dispersion liquid 1, the following components were mixed to obtain a colored curable resin composition.

< pigment Dispersion 1 >

< colored curable resin composition >

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

< formation of color Filter >

The colored curable resin composition was applied onto a 2-inch square glass substrate (EAGLE 2000; manufactured by CORNING corporation) by a spin coating method, and then prebaked at 100 ℃ for 3 minutes to form a colored composition layer. After cooling, the resultant was exposed to 60mJ/cm in an air atmosphere using an exposure machine (TME-150 RSK; manufactured by TOPCON K.K.)²The exposure amount (365nm standard) was measured by irradiating the colored composition layer with light using a photomask (line width 100 μm) so that the gap between the glass substrate and the photomask was 250 μm. After the light irradiation, the film was developed with a 0.04% potassium hydroxide solution at a discharge pressure of 0.1Pa for 60 seconds, washed with water, and then dehydrated with an air knife, and the film thickness of the color filter was measured (film thickness before post-baking) using a film thickness measuring apparatus (DEKTAK 3; manufactured by Japan vacuum technology Co., Ltd.). In an oven, post-baking was performed at 230 ℃ for 20 minutes, thereby obtaining a color filter. After cooling, the film thickness of the obtained color filter was measured (film thickness after post-baking) using a film thickness measuring apparatus (DEKTAK 3; manufactured by Nippon vacuum technology Co., Ltd.).

The film thickness retention rate was determined from the following equation. The results are shown in Table 1.

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

< line width >

The line width of the obtained color filter after patterning was measured with a scanning electron microscope (S-4000, manufactured by Hitachi, Ltd.) to confirm the shape (cross section). Table 1 shows the pattern line width [ μm ] of the color filter of 100 μm with respect to the photomask line width.

Comparative example 1

A colored curable resin composition and a color filter were produced and evaluated in the same manner as in example 1, except that trimethylolpropane tris (3-mercaptopropionate) (tmpp) was used instead of the thiol compound (E) pentaerythritol tripropylalkanethiol (PEPT). The results are shown in Table 1.

Comparative example 2

A colored curable resin composition and a color filter were produced and evaluated in the same manner as in example 1, except that pentaerythritol tetrakis (3-mercaptopropionate) (PEMP) was used instead of the thiol compound (E) pentaerythritol tripropylene thiol (PEPT). The results are shown in Table 1.

[ Table 1]

	Example 1	Comparative example 1	Comparative example 2
				Film thickness retention ratio (%)	87	84	84
Line width (mum)	102	101	102

[ example 2]

A pigment dispersion 2, a colored curable resin composition, and a color filter were produced and evaluated in the same manner as in example 1, except that the following components were mixed. The results are shown in Table 2.

< pigment Dispersion 2>

< colored curable resin composition >

Comparative example 3

A colored curable resin composition and a color filter were produced and evaluated in the same manner as in example 2, except that trimethylolpropane tris (3-mercaptopropionate) (tmpp) was used instead of the thiol compound (E) pentaerythritol tripropylalkanethiol (PEPT). The results are shown in Table 2.

[ Table 2]

	Example 2	Comparative example 3
			Film thickness retention ratio (%)	88	84
Line width (mum)	92	93

[ example 3]

A color filter was produced and evaluated in the same manner as in example 1, except that the following components were mixed to obtain a colored curable resin composition. The results are shown in Table 3.

[ example 4]

A colored curable resin composition was obtained in the same manner as in example 3, except that the pigment dispersion liquid 2 was changed to 218 parts, the thiol compound (E) was changed to 0.5 part, and the propylene glycol monomethyl ether acetate was changed to 473 parts. Using this colored curable resin composition, a color filter was produced and evaluated in the same manner as in example 1. The results are shown in Table 3.

Comparative example 4

A colored curable resin composition and a color filter were produced and evaluated in the same manner as in example 3, except that trimethylolpropane tris (3-mercaptopropionate) (tmpp) was used instead of the thiol compound (E) pentaerythritol tripropylalkanethiol (PEPT). The results are shown in Table 3.

Comparative example 5

A colored curable resin composition and a color filter were produced and evaluated in the same manner as in example 3, except that pentaerythritol tetrakis (3-mercaptopropionate) (PEMP) was used instead of the thiol compound (E) pentaerythritol tripropylene thiol (PEPT). The results are shown in Table 3.

[ Table 3]

	Example 3	Example 4	Comparative example 4	Comparative example 5
					Film thickness retention ratio (%)	88	86	82	84
Line width (mum)	94	94	94	95

[ example 5]

A colored curable resin composition and a color filter were produced and evaluated in the same manner as in example 1, except that the following components were mixed. The results are shown in Table 4.

< Dispersion 3>

The following components were mixed to prepare a dispersion 3.

< colored curable resin composition >

Comparative example 6

A colored curable resin composition and a color filter were produced and evaluated in the same manner as in example 5, except that trimethylolpropane tris (3-mercaptopropionate) (tmpp) was used instead of the thiol compound (E) pentaerythritol tripropylalkanethiol (PEPT). The results are shown in Table 4.

[ Table 4]

	Example 5	Comparative example 6
			Film thickness retention ratio (%)	86	84
Line width (mum)	106	105

[ example 6]

A colored curable resin composition and a color filter were produced and evaluated in the same manner as in example 1, except that the following components were mixed. The results are shown in Table 5.

Comparative example 7

A colored curable resin composition and a color filter were produced and evaluated in the same manner as in example 6, except that trimethylolpropane tris (3-mercaptopropionate) (tmpp) was used instead of the thiol compound (E) pentaerythritol tripropylalkanethiol (PEPT). The results are shown in Table 5.

Comparative example 8

A colored curable resin composition and a color filter were produced and evaluated in the same manner as in example 6, except that pentaerythritol tetrakis (3-mercaptopropionate) (PEMP) was used instead of the thiol compound (E) pentaerythritol tripropylene thiol (PEPT). The results are shown in Table 5.

[ Table 5]

	Example 6	Comparative example 7	Comparative example 8
				Film thickness retention ratio (%)	86	83	84
Line width (mum)	97	97	98

[ example 7]

A colored curable resin composition and a color filter were produced and evaluated in the same manner as in example 1, except that the following components were mixed. The results are shown in Table 6.

Comparative example 9

A colored curable resin composition and a color filter were produced and evaluated in the same manner as in example 7, except that trimethylolpropane tris (3-mercaptopropionate) (tmpp) was used in place of the thiol compound (E) pentaerythritol tripropylalkanethiol (PEPT). The results are shown in Table 6.

Comparative example 10

A colored curable resin composition and a color filter were produced and evaluated in the same manner as in example 7, except that pentaerythritol tetrakis (3-mercaptopropionate) (PEMP) was used instead of the thiol compound (E) pentaerythritol tripropylene thiol (PEPT). The results are shown in Table 6.

[ Table 6]

	Example 7	Comparative example 9	Comparative example 10
				Film thickness retention ratio (%)	84	82	82
Line width (mum)	116	118	117

As shown in tables 1 to 6, it was confirmed that when a color filter was produced using the colored curable resin composition of the present invention, a high film thickness retention rate was obtained and a line width was maintained, as compared with a case where a color filter was produced using a color filter not based on the colored curable resin composition of the present invention.

Industrial applicability

According to the colored curable resin composition of the present invention, the obtained color filter can have a high film thickness retention rate and can maintain the line width, and therefore, the colored curable resin composition is extremely useful industrially.