CN105315722B - Salt-forming dye and colored curable resin composition - Google Patents

Abstract

A salt-forming dye is formed from a monovalent cationic dye, a dianionic compound, and a monovalent cationic compound having no chromophoric group.

Description

Salt-forming dye and colored curable resin composition

Technical Field

The present invention relates to a salt-forming dye and a colored curable resin composition.

Background

As a colorant for a color filter included in a liquid crystal display device or the like or a solid-state imaging element or the like, a dye can be used. As the dye, for example, WO2012/128318 describes a compound represented by formula (a-iii-1) (wherein Et represents an ethyl group).

Disclosure of Invention

The present invention includes the following inventions.

[1] A salt-forming dye is formed from a monovalent cationic dye, a dianionic compound, and a monovalent cationic compound having no chromophoric group.

[2] The salt-forming dye according to [1], which is composed of a monovalent anionic dye and a monovalent cationic compound having no chromophoric group, wherein the monovalent anionic dye is composed of a monovalent cationic dye and a divalent anionic compound.

[3] The salt-forming dye according to [1] or [2], wherein the divalent anionic compound is an aromatic compound having 2 identical monovalent anions or an aromatic heterocyclic compound having 2 identical monovalent anions.

[4] A salt-forming dye as described in [3], wherein the monovalent anion is a sulfonate anion.

[5] The salt-forming dye according to any one of [1] to [4], wherein the divalent anionic compound is a compound represented by the formula (1-b).

^-O₃S——R^1b——SO₃ ^-(1-b)

(in the formula, R^1bRepresents an optionally substituted aromatic hydrocarbon group having 6 to 18 carbon atoms. )

[6] The salt-forming dye according to any one of [1] to [5], wherein the monovalent cation dye is a compound represented by the formula (1-a).

[ in the formula (1-a), R^1A～R^8AEach independently represents a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group or an alkyl group having 1 to 20 carbon atoms, wherein-CH contained in the alkyl group having 1 to 20 carbon atoms₂-may be replaced by-O-.

R^9A～R^12AEach independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, wherein-CH contained in the alkyl group having 1 to 20 carbon atoms₂-may be replaced by-O-.

A represents an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms or an optionally substituted aromatic heterocyclic hydrocarbon group having 2 to 10 carbon atoms. ]

[7] The salt-forming dye according to any one of [1] to [6], wherein the monovalent cation compound having no chromophoric group is a compound having at least one substituent selected from the group consisting of a polymerizable group, a silicon atom and a phosphorus atom, and having no chromophoric group.

[8] A colorant comprising the salt-forming dye according to any one of [1] to [7 ].

[9] A colored curable resin composition comprising: the colorant, resin, polymerizable compound and polymerization initiator according to [8 ].

[10] A coating film comprising the colored curable resin composition according to [9 ].

[11] A color filter comprising the colored curable resin composition according to [9 ].

[12] A display device comprising the color filter according to [11 ].

Detailed Description

< salt-forming dye (I) >

The dye of the present invention is a salt-forming dye formed from a monovalent cation dye, a divalent anion compound, and a compound having a monovalent cation but no chromophoric group (hereinafter, referred to as a salt-forming dye (I) in some cases).

In the present invention, generally, the monoanionic dye is formed from a monoanionic dye and a dianionic compound. Hereinafter, the anionic dye may be referred to as "anionic dye (I-1)". The salt-forming dye (I) may be formed from an anionic dye (I-1) and a monovalent cationic compound having no chromophoric group.

The salt-forming dye of the present invention is formed by adding a monovalent cationic compound having no chromophoric group to the anionic dye (I-1), and therefore, the color is higher than that of the anionic dye (I-1).

Examples of the monovalent cationic dye include cationic dyes having 2 or more phenyl groups. Specific examples of the cationic dye include a compound represented by the formula (1-a) and a tautomer of the compound.

[ in the formula (1-a), R^1A～R^8AEach independently represents a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group or an alkyl group having 1 to 20 carbon atoms, wherein-CH contained in the alkyl group having 1 to 20 carbon atoms₂-may be replaced by-O-.

R^9A～R^12AEach independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, wherein-CH contained in the alkyl group having 1 to 20 carbon atoms₂-may be replaced by-O-.

A represents an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms or an optionally substituted aromatic heterocyclic hydrocarbon group having 2 to 10 carbon atoms. ]

As R^1A、R^2A、R^3A、R^4A、R^5A、R^6A、R^7AAnd R^8AExamples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom or a chlorine atom is preferable.

As R^1A、R^2A、R^3A、R^4A、R^5A、R^6A、R^7AAnd R^8AExamples of the alkyl group having 1 to 20 carbon atoms include straight-chain, branched-chain and cyclic alkyl groups, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, a 2-ethylhexyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cycloheptyl group, a cyclodecyl group, a decahydronaphthyl group, an adamantyl group, a 2-alkyladamantan-2-yl group, a1- (adamant-1-yl) alkan-1-yl group.

The alkyl group is preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably an alkyl group having 1 to 4 carbon atoms.

R^1A、R^2A、R^3A、R^4A、R^5A、R^6A、R^7AAnd R^8Aa-CH contained in the alkyl group having 1 to 20 carbon atoms₂-may be replaced by-O-. However, the-CH contained in the alkyl group having 1 to 20 carbon atoms₂When-is replaced with-O-, the number of carbon atoms does not include-O-.

As R^1A、R^2A、R^3A、R^4A、R^5A、R^6A、R^7AAnd R^8Aa-CH contained in the alkyl group having 1 to 20 carbon atoms₂Examples of the group substituted by-O-include the groups described below. In the formula, denotes a bond.

As R^9A、R^10A、R^11AAnd R^12AExamples of the alkyl group having 1 to 20 carbon atoms include the group represented by^1A、R^2A、R^3A、R^4A、R^5A、R^6A、R^7AAnd R^8AThe alkyl group having 1 to 20 carbon atoms is the same as the alkyl group.

R^9A、R^10A、R^11AAnd R^12Aa-CH contained in the alkyl group having 1 to 20 carbon atoms₂-may be replaced by-O-. However, the-CH contained in the alkyl group having 1 to 20 carbon atoms₂-when substituted with-O-, the carbon atom number does not contain-O-.

As R^9A、R^10A、R^11AAnd R^12Aa-CH contained in the alkyl group having 1 to 20 carbon atoms₂The group-substituted by-O-is exemplified by the group represented by^1A、R^2A、R^3A、R^4A、R^5A、R^6A、R^7AAnd R^8Aa-CH contained in the alkyl group having 1 to 20 carbon atoms₂-the same group substituted by-O-.

As R^9A、R^10A、R^11AAnd R^12AExamples of the substituent that the alkyl group having 1 to 20 carbon atoms may have include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; amino and dimethylamino groups or the like-NR¹¹¹R¹¹²(R¹¹¹And R¹¹²Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ).

As R^9A、R^10A、R^11AAnd R^12AExamples of the alkyl group having 1 to 20 carbon atoms which may have a substituent include those described below. Denotes a bond to a nitrogen atom.

As R^9A、R^10A、R^11AAnd R^12AExamples of the aromatic hydrocarbon group having 6 to 20 carbon atoms include a phenyl group, a naphthyl group and an anthryl group.

As R^9A、R^10A、R^11AAnd R^12AExamples of the substituent that may be contained in the aromatic hydrocarbon group having 6 to 20 carbon atoms include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; a halogenated alkyl group having 1 to 6 carbon atoms such as a chloromethyl group and a trifluoromethyl group; alkoxy groups having 1 to 6 carbon atoms such as methoxy and ethoxy; a hydroxyl group; a sulfamoyl group; an alkylsulfonyl group having 1 to 6 carbon atoms such as a methylsulfonyl group.

Examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms represented by A include a phenyl group and a naphthyl group, and an aromatic hydrocarbon group having 6 to 10 carbon atoms is preferable.

The aromatic heterocyclic hydrocarbon group having 2 to 10 carbon atoms represented by A may have at least one hetero atom as a constituent of the ring.

Examples of the hetero atom include a nitrogen atom, an oxygen atom and a sulfur atom.

Examples of the aromatic heterocyclic hydrocarbon group having 2 to 10 carbon atoms represented by A include a pyridyl group, an imidazolyl group, a pyrazolyl group, an oxazolyl group, an isoxazolyl group, a thiazolyl group, an isothiazolyl group, a benzothiazolyl group, a benzisothiazolyl group, a thienyl group and a benzothienyl group, an aromatic heterocyclic hydrocarbon group having 2 to 8 carbon atoms is preferable, an aromatic heterocyclic hydrocarbon group having 2 to 8 carbon atoms and having at least one nitrogen atom is more preferable, and an aromatic heterocyclic hydrocarbon group having 2 to 8 carbon atoms and having a nitrogen atom and a sulfur atom (for example, a thiazolyl group) is further preferable.

Examples of the substituent of the aromatic hydrocarbon group having 6 to 20 carbon atoms represented by A include a halogen atom, an amino group which may have a substituent, and an alkyl group having 1 to 6 carbon atoms.

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

Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a neopentyl group and a hexyl group.

Examples of the substituent in the amino group include an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 6 carbon atoms, and an aromatic hydrocarbon group which may have a substituent.

In A, the alkyl group having 1 to 20 carbon atoms includes straight-chain, branched-chain and cyclic alkyl groups, and specific examples thereof include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, 2-ethylhexyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, methylcyclohexyl group, dimethylcyclohexyl group, cycloheptyl group, cyclooctyl group, cycloheptyl group, cyclodecyl group, decahydronaphthyl group, adamantyl group, 2-alkyladamantan-2-yl group, 1- (adamant-1-yl) alkan-1-yl group, norbornyl group, methylnorbornyl group and isobornyl group.

Among the aromatic hydrocarbon groups having 6 to 20 carbon atoms represented by A, examples of the aromatic hydrocarbon group having a substituent include a phenyl group and a naphthyl group.

Examples of the substituent in the aromatic hydrocarbon group include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; alkoxy groups having 1 to 4 carbon atoms such as methoxy and ethoxy; and alkyl groups having 1 to 4 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, and tert-butyl groups.

Examples of the substituted amino group include alkylamino groups such as methylamino and ethylamino; phenylamino groups such as phenylamino group, 2-fluorophenylamino group, 2-chlorophenylamino group, (p-methoxyphenyl) amino group and (o-methylphenyl) amino group; dialkylamino groups such as dimethylamino and diethylamino; alkylphenylamino groups such as N-phenyl-N-methylamino, N- (o-methylphenyl) -N-ethyl and N-phenyl-N-isopropylamino.

Examples of the substituent that the aromatic heterocyclic hydrocarbon group having 2 to 10 carbon atoms represented by A may have include a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms that may have a substituent, and an amino group that may have a substituent.

Specific examples of the halogen atom, the alkyl group having 1 to 20 carbon atoms, the aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, and the amino group which may have a substituent include those exemplified as the substituents which may be contained in the above aromatic hydrocarbon group.

Examples of the group represented by A include a group represented by the formula (A1-1) to a group represented by the formula (A1-13), preferably a group represented by the formula (A1-2), a group represented by the formula (A1-7), a group represented by the formula (A1-8) and a group represented by the formula (A1-9), and more preferably a group represented by the formula (A1-8) and a group represented by the formula (A1-9).

As the monovalent cation dye represented by the formula (1-a), compounds represented by the formula (1-a-1) and tautomers thereof are preferable.

[ in the formula (1-a-1), X represents an oxygen atom or a sulfur atom.

R⁴⁵And R⁴⁶Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, the-CH contained in the alkyl group having 1 to 20 carbon atoms which may have a substituent₂-may be replaced by-O-.

R⁵⁵Represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.

R^1A～R^12AEach means the same as described above.]

As R⁴⁵And R⁴⁶The alkyl group having 1 to 20 carbon atoms includes straight-chain, branched-chain and cyclic alkyl groups, and specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, 2-ethylhexyl, octyl, nonyl and decylAlkyl, undecyl, dodecyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, cycloheptyl, cyclooctyl, cycloheptyl, cyclodecyl, decahydronaphthyl, adamantyl, 2-alkyladamantan-2-yl, 1- (adamant-1-yl) alk-1-yl, norbornyl, methylnorbornyl and isobornyl.

As R⁴⁵And R⁴⁶Examples of the substituent that the alkyl group having 1 to 20 carbon atoms may have include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; amino and dimethylamino groups or the like-NR¹¹¹R¹¹²(R¹¹¹And R¹¹²Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ).

As R⁴⁵And R⁴⁶Examples of the optionally substituted alkyl group having 1 to 20 carbon atoms include^9A、R^10A、R^11AAnd R^12AThe alkyl groups having 1 to 20 carbon atoms which may have a substituent are the same.

As R⁴⁵And R⁴⁶Examples of the aromatic hydrocarbon group include a phenyl group, a tolyl group and a naphthyl group.

As R⁴⁵And R⁴⁶Examples of the substituent that may be contained in the aromatic hydrocarbon group include an alkyl group having 1 to 4 carbon atoms such as a methyl group and an ethyl group; halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkoxy groups having 1 to 6 carbon atoms such as methoxy and ethoxy; halogenated alkyl groups having 1 to 6 carbon atoms such as chloromethyl group and trifluoromethyl group; a hydroxyl group; a sulfamoyl group; an alkylsulfonyl group having 1 to 6 carbon atoms such as a methylsulfonyl group.

As R⁴⁵And R⁴⁶The aromatic hydrocarbon group which may have a substituent(s) is exemplified by the groups described below. Denotes a bond to a nitrogen atom.

As R⁵⁵Examples of the alkyl group having 1 to 20 carbon atoms include the group represented by^1A、R^2A、R^3A、R^4A、R^5A、R^6A、R^7AAnd R^8AThe alkyl groups having 1 to 20 carbon atoms are the same.

As R⁵⁵The aromatic hydrocarbon group which may have a substituent(s) as shown may be exemplified by⁴⁵And R⁴⁶The aromatic hydrocarbon groups which may have substituents are the same.

R^1A、R^2A、R^3A、R^4A、R^5A、R^6A、R^7AAnd R^8AEach independently preferably a hydrogen atom, a halogen atom or an alkyl group having 1 to 8 carbon atoms, and each independently more preferably a hydrogen atom, a methyl group, a fluorine atom or a chlorine atom.

R^9A、R^10A、R^11AAnd R^12AEach independently preferably represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, and each independently more preferably represents a halogen atom, a halogenated alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a hydroxyl group, or an alkyl group having 1 to 8 carbon atoms.

R⁴⁵And R⁴⁶Each independently preferably an alkyl group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, and each independently more preferably a halogen atom, a halogenated alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a hydroxyl group, or an alkyl group having 1 to 8 carbon atoms.

R⁵⁵Preferably an alkyl group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, more preferably a halogen atom, a halogenated alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a hydroxyl group, or an alkyl group having 1 to 8 carbon atoms.

Examples of the monovalent cationic dye include compounds represented by the formula (1-a-2) to (1-a-14), and preferred are compounds represented by the formula (1-a-2), compounds represented by the formula (1-a-3), compounds represented by the formula (1-a-5), and compounds represented by the formula (1-a-6).

By a dianionic compound is meant a compound in which the number of valences of the anion in the compound totals divalent, preferably a compound having 2 monovalent anions, more preferably a compound having 2 identical monovalent anions.

As the monovalent anion, there may be mentioned a sulfonate anion [ -SO₃ ^-]Or carboxylate anion [ -COO^-]Sulfonate anions are preferred.

As the divalent anion compound, an aromatic compound having two monovalent anions or an aromatic heterocyclic compound having two monovalent anions is preferable, an aromatic compound having two monovalent anions is more preferable, an aromatic compound having at least one sulfonate anion is further preferable, and a compound represented by the formula (1-b) is particularly preferable.

O₃S——R^1b——SO₃ ^-(1-b)

(in the formula, R^1bRepresents an optionally substituted aromatic hydrocarbon group having 6 to 18 carbon atoms. )

As R^1bThe aromatic hydrocarbon group having 6 to 18 carbon atoms includes a phenyl group, a naphthyl group and an anthryl group, and a phenyl group or a naphthyl group is preferable.

As R^1bExamples of the substituent that may be contained in the aromatic hydrocarbon group having 6 to 18 carbon atoms include a halogen atom such as a fluorine atom, a chlorine atom, and a bromine atom; a nitro group; a hydroxyl group; an amino group; an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, and a tert-butyl group; or an alkoxy group having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a sec-butoxy group, and a tert-butoxy group, and is preferably a hydroxyl group or an amino group.

When R is^1bWhen the aromatic hydrocarbon group having 6 to 18 carbon atoms is a phenyl group, the number of the aromatic hydrocarbon groups is oneThe monovalent anion, the other monovalent anion is preferably in the meta or ortho position.

When R is^1bWhen the aromatic hydrocarbon group having 6 to 18 carbon atoms is a naphthyl group, one monovalent anion is preferably bonded to a carbon atom which is not adjacent to a carbon atom to which the other anion is bonded.

Examples of the divalent anion compound include compounds represented by the formula (1-b-1) to compounds represented by the formula (1-b-13).

As the divalent anion compound, a compound represented by the formula (1-b-1), a compound represented by the formula (1-b-2), a compound represented by the formula (1-b-3), a compound represented by the formula (1-b-9) and a compound represented by the formula (1-b-10) are preferable.

Examples of the anionic dye (I-1) include anionic dyes represented by the formula (I-1a) to (I-9a), and anionic dyes represented by the formula (I-4a) to (I-6a) are preferred.

As the monovalent cationic compound having no chromophoric group (hereinafter, this compound may be referred to as "monovalent cationic compound"), a monovalent cationic compound having at least one substituent selected from the group consisting of a polymerizable group, a silicon atom and a phosphorus atom and having no chromophoric group is preferable.

Examples of the polymerizable group include groups having an ethylenically unsaturated bond, and specific examples thereof include an alkenyl group, an acryloyl group, and a methacryloyl group.

Preferably, the monovalent cation has an ammonium ion [ -NH ]₄ ⁺]。

Examples of the monovalent cationic compound having a polymerizable group include compounds represented by the formula (Z-1).

[ in the formula (Z-1), R¹Represents an alkylene group having 1 to 10 carbon atoms, the alkylene group containing-CH₂May be substituted by-O-, -CO-, -NR¹¹-, -OCO-, -COO-, -OCONH-, -CONH-or-NHCO-.

R¹¹Represents an alkylene group having 1 to 10 carbon atoms.]

As R¹And R¹¹The alkylene group having 1 to 10 carbon atoms includes a linear, branched and cyclic alkylene group, and specific examples thereof include a methylene group, a1, 2-ethylene group, a1, 3-propylene group, a1, 4-butylene group, a1, 5-pentylene group, a1, 6-hexylene group, a1, 7-heptylene group, a1, 8-octylene group, a1, 1-ethylene group, a1, 1-propylene group, a1, 2-propylene group, a2, 4-pentylene group, a 2-methyl-1, 3-propylene group, a 2-methyl-1, 2-propylene group, a1, 4-pentylene group, a 2-methyl-1, 4-butylene group, a1, 3-cyclobutylene group, a1, 3-cyclopentylene group and a1, 4-cyclohexylidene, norbornane-1, 4-diyl, norbornane-2, 5-diyl, adamantane-1, 5-diyl, and adamantane-2, 6-diyl, and preferably an alkylene group having 1 to 8 carbon atoms.

As R¹-CH contained in alkylene group having 1 to 10 carbon atoms₂Examples of the group substituted by-O-include the groups described below (` denotes a bond).

As R¹-CH contained in alkylene group having 1 to 10 carbon atoms₂Examples of the group substituted by-CO-include the groups described below (` denotes a bond).

As R¹-CH contained in alkylene group having 1 to 10 carbon atoms₂-by-NR¹¹Examples of the "substituent" include the groups described below (— represents a bond).

As R¹-CH contained in alkylene group having 1 to 10 carbon atoms₂Examples of the group substituted with-OCO-include the groups described below (. times.represents a bond).

As R¹-CH contained in alkylene group having 1 to 10 carbon atoms₂Examples of the group substituted by-COO-include the groups described below (— represents a bond).

As R¹-CH contained in alkylene group having 1 to 10 carbon atoms₂Examples of the group substituted by-OCONH-include the groups described below (` denotes a bond).

As R¹-CH contained in alkylene group having 1 to 10 carbon atoms₂Examples of the group substituted by-CONH-include the groups described below (` denotes a bond).

As R¹-CH contained in alkylene group having 1 to 10 carbon atoms₂Examples of the group substituted with-NHCO-include the groups described below (. times.represents a bond).

Examples of the cationic compound having a polymerizable group include compounds represented by the formulae (Z-1-1) to (Z1-1-3), and compounds represented by the formula (Z-1-1) are preferred.

As the cationic compound having a silicon atom, a compound represented by the formula (Z-2) can be mentioned.

[ in the formula (Z-2), R²Represents an alkylene group having 1 to 10 carbon atoms, the alkylene group containing-CH₂May be substituted by-O-, -CO-, -NR²¹-, -OCO-, -COO-, -OCONH-, -CONH-or-NHCO-.

R⁴⁰、R⁴¹And R⁴²Each independently represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.

q represents an integer of 1 to 10. ]

As R²And R²¹The alkylene group having 1 to 10 carbon atoms includes the group represented by¹And R¹¹The alkylene group having 1 to 10 carbon atoms.

For R²-CH contained in alkylene group having 1 to 10 carbon atoms₂by-O-, -CO-, -NR²¹Examples of the group substituted by-OCO-, -COO-, -OCONH-, -CONH-or-NHCO-include a group substituted by R¹-CH contained in alkylene group having 1 to 10 carbon atoms₂by-O-, -CO-, -NR¹¹-, -OCO-, -COO-, -OCONH-, -CONH-or-NHCO-are the same groups.

As R⁴⁰、R⁴¹And R⁴²The alkyl group having 1 to 4 carbon atoms may beMethyl, ethyl, propyl, isopropyl, butyl, sec-butyl and tert-butyl are mentioned, preferably methyl or ethyl.

As R⁴⁰、R⁴¹And R⁴²Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a sec-butoxy group and a tert-butoxy group, and a methoxy group or an ethoxy group is preferable.

R⁴⁰、R⁴¹And R⁴²Preferably the same groups.

R⁴⁰、R⁴¹And R⁴²Each independently is preferably a hydroxyl group or an alkoxy group having 1 to 4 carbon atoms, and more preferably a methoxy group or an ethoxy group.

q is preferably an integer of 1 to 8, more preferably an integer of 1 to 3.

Examples of the cationic compound having a silicon atom include the compounds represented by the formula (Z-2-1) to the compounds represented by the formula (Z-2-12), and the compounds represented by the formula (Z-2-1) to the compounds represented by the formula (Z-2-6) are preferable.

As the cationic compound having a phosphorus atom, a compound represented by the formula (Z-3) can be mentioned.

[ formula (Z-3) wherein R⁵⁰、R⁵¹、R⁵²And R⁵³Each independently represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a phenyl group which may have a substituent.]

As R⁵⁰、R⁵¹、R⁵²And R⁵³Examples of the alkyl group having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 1-methylbutyl, 1,3, 3-tetramethylbutyl, 1, 5-dimethylhexyl and 2-ethylhexyl, and methyl, ethyl and the like are preferableOr 2-ethylhexyl.

As R⁵⁰、R⁵¹、R⁵²And R⁵³Examples of the alkenyl group having 2 to 10 carbon atoms include a vinyl group, an isopropenyl group, a pentenyl group, a hexenyl group and the like, and a vinyl group is preferable.

As R⁵⁰、R⁵¹、R⁵²And R⁵³Examples of the substituent of the phenyl group include an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, and a tert-butyl group; methoxy group, ethoxy group, propoxy group, alkoxy group having 1 to 4 carbon atoms.

Examples of the cationic compound having a phosphorus atom include compounds represented by the formulae (Z-3-1) to (Z-3-6). The cation having a phosphorus atom is preferably a compound represented by the formula (Z-3-1) or a compound represented by the formula (Z-3-2).

Examples of the salt-forming dye (I) include dyes represented by the formulae (I-1) to (I-47). The salt-forming dye (I) is preferably a dye represented by the formula (I-16) to a dye represented by the formula (I-27) or a dye represented by the formula (I-33) to a dye represented by the formula (I-47), and more preferably a dye represented by the formula (I-16), a dye represented by the formula (I-19), a dye represented by the formula (I-27) or a dye represented by the formula (I-33) to a dye represented by the formula (I-35).

Next, a method for producing the salt-forming dye (I) will be described.

The salt-forming dye (I) can be obtained by reacting the anionic dye (I-1) with a monovalent cationic compound in water. The procedure of this reaction is described later.

The anionic dye (I-1) can be obtained by reacting a monovalent cationic dye with a divalent anionic compound in water.

The reaction temperature of the monovalent cationic dye with the divalent anionic compound is preferably from 0 ℃ to 120 ℃, more preferably from 10 ℃ to 100 ℃. The reaction time is preferably 1 to 24 hours, more preferably 3 to 8 hours.

As a method for obtaining the anionic dye (I-1) from the reaction mixture, various known methods can be used. For example, the following methods can be mentioned: after the reaction was completed, the resulting precipitate was collected by filtration and washed with water. If necessary, the extract may be further purified by a known method such as recrystallization.

When the monovalent cationic dye is a substance represented by the formula (I-a), it can be produced, for example, by reacting a compound represented by the formula (C-II) with a compound represented by the formula (C-III). The relevant reaction can be carried out in the presence of an organic solvent or in the absence of a solvent.

[ in the formula, R^1A～R^12AAnd A are each as defined above.]

The amount of the compound represented by the formula (C-III) in the reaction is preferably 1 to 8 mol, more preferably 1 to 3 mol, based on 1mol of the compound represented by the formula (C-II).

The reaction temperature is preferably from 30 ℃ to 180 ℃, more preferably from 80 ℃ to 130 ℃. The reaction time is preferably 1 to 12 hours, more preferably 3 to 8 hours.

In the reaction of the compound represented by the formula (C-III) with the compound represented by the formula (C-II), it is preferable to carry out the reaction in the presence of an organic solvent from the viewpoint of yield. Examples of the organic solvent include hydrocarbon solvents such as toluene and xylene; halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, and chloroform; alcohol solvents such as methanol, ethanol, isopropanol, and butanol; nitrohydrocarbon solvents such as nitrobenzene; ketone solvents such as methyl isobutyl ketone; amide solvents such as 1-methyl-2-pyrrolidone, and the like.

The amount of the organic solvent used is preferably 1 to 300 parts by mass, more preferably 2 to 200 parts by mass, based on 1 part by mass of the compound represented by the formula (C-II).

From the viewpoint of yield, the reaction of the compound represented by the formula (C-III) with the compound represented by the formula (C-II) is preferably carried out in the presence of a condensing agent. Examples of the condensing agent include phosphoric acid, polyphosphoric acid, phosphorus oxychloride, sulfuric acid, and thionyl chloride.

The amount of the condensing agent to be used is preferably 1 to 20 parts by mass, more preferably 1 to 5 parts by mass, based on 1 part by mass of the compound represented by the formula (C-II).

As a method for obtaining a monovalent anionic dye from the reaction mixture, various known methods can be used. For example, the following methods can be mentioned: the precipitated crystals were collected by mixing the reaction mixture with an alcohol (methanol, etc.) and filtering.

The method for obtaining the monovalent anionic dye is preferably a method in which the reaction mixture is added to an alcohol. The temperature at which the reaction mixture is added is preferably-100 to 50 ℃, more preferably-80 to 0 ℃. After that, the mixture is preferably stirred at the same temperature for about 0.5 to 2 hours. For the crystals collected by filtration, it is preferable to wash with water or the like and then dry. Further, if necessary, the extract may be further purified by a known method such as recrystallization.

As the salt-forming dye (I), as described above, it can be obtained by reacting the anionic dye (I-1) with a monovalent cationic compound.

The reaction temperature of the anionic dye (I-1) and the monovalent cation compound is preferably 0 to 120 ℃, more preferably 10 to 100 ℃. The reaction time is preferably 1 to 24 hours, more preferably 3 to 8 hours.

The salt-forming dye (I) can be obtained from the reaction mixture by a known method. For example, the following methods can be mentioned: after the reaction was completed, the resulting precipitate was collected by filtration and washed with water. If necessary, the extract may be further purified by a known method such as recrystallization.

The colored curable resin composition of the present invention comprises: a colorant (A) containing a salt-forming dye (I), a resin (B), a polymerizable compound (C), and a polymerization initiator (D). Further, a solvent (E) may be contained.

< colorant (A) >

The colorant (a) may comprise two or more salt-forming dyes (I).

For toning, i.e. for adjusting the spectral properties, the colorant (a) may comprise, in addition to the salt-forming dye (I), a further dye (a2), a pigment (P) or a mixture thereof.

Examples of The dye (a2) include oil-soluble dyes, acid dyes, amine salts of acid dyes, and sulfonamide derivatives of acid dyes, and known dyes described in The Color Index (published by The Society of Dyers and colourists) or dyeing notes (dyeing notes). In addition, according to the chemical structure, coumarin dyes; a metal-containing azo dye; a pyridone azo dye; barbiturate azo dyes; a quinophthalone dye; methine-type dyes; a cyanine dye; anthraquinone dyes; a triphenylmethane dye; a xanthene dye; a porphyrazine dye; a phthalocyanine dye; and mixtures thereof.

The content of the salt-forming dye (I) is preferably 3 to 99.9% by mass, more preferably 4 to 80% by mass, and still more preferably 5 to 30% by mass, based on the total amount of the colorant (a). When the content of the salt-forming dye (I) is within the above range, the luminance when used as a color filter is high, and therefore, it is preferable.

As The pigment (P), known pigments can be used, and there can be mentioned pigments classified as pigments in The color index (published by The Society of dyers and Colourists).

Examples thereof include yellow pigments such as 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, 194, 214; 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 green 7, 36, 58, etc.

As the pigment (P), preferred are yellow pigments such as 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, 194, 214 and the like; and green pigments such as c.i. pigment green 7, 36, 58; more preferred are c.i. pigment yellow 150, 185 and c.i. pigment green 58. By including the pigment, optimization of a light transmission spectrum is facilitated, and light resistance and chemical resistance of the color filter are improved.

The content of the colorant (a) is preferably 5 to 60% by mass, more preferably 8 to 55% by mass, and still more preferably 10 to 50% by mass, based on the total amount of solid components. When the content of the colorant (a) is within the above range, the color density is sufficient when the composition is used as a color filter, and a pattern having sufficient mechanical strength can be formed because the resin (B) and the polymerizable compound (C) can be contained in necessary amounts in the composition.

The total amount of the solid components is an amount obtained by removing the solvent content from the total amount of the colored curable resin composition. The total amount of the solid components and the contents of the respective components relative to the total amount can be measured by a known analytical method such as liquid chromatography or gas chromatography.

< resin (B) >

The resin (B) is preferably an alkali-soluble resin. Examples of the resin (B) include the following resins [ K1] to [ K6 ].

Resin [ K1 ]: a copolymer of at least one (Ba) (hereinafter, sometimes referred to as "(Ba)") selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides and a monomer (Bb) (hereinafter, sometimes referred to as "(Bb)"); wherein the monomer (Bb) has a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond;

resin [ K2 ]: (Ba), (Bb) and a monomer (Bc) copolymerizable with (Ba) (but different from (Ba) and (Bb)) (hereinafter, sometimes referred to as "(Bc)");

resin [ K3 ]: copolymers of (Ba) and (Bc);

resin [ K4 ]: a resin obtained by reacting (Bb) with a copolymer of (Ba) and (Bc);

resin [ K5 ]: a resin obtained by reacting (Bb) with a copolymer of (Bc) and (Ba);

resin [ K6 ]: a resin obtained by reacting (Bb) with (Bc) and (Ba) and further reacting with a carboxylic acid anhydride.

Examples of (Ba) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-vinylbenzoic acid, m-vinylbenzoic acid and p-vinylbenzoic acid, 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-cyclohexenedicarboxylic acid, methyl-5-norbornene-2, 3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] -2-heptene, 5, 6-dicarboxybicyclo [2.2.1] -2-heptene, 5-carboxy-5-methylbicyclo [2.2.1] -2-heptene, 5-carboxy-6-ethylbicyclo [ 2.1] -2-heptene, 5-carboxy-ethylbicyclo [ 2.1] -2-heptene, 5-2-1-2-tetrahydrophthalic anhydride, 5-epoxyphthalic anhydride, 5-epoxydicarboxylic anhydride, maleic anhydride, 5-epoxysuccinic anhydride, maleic anhydride.

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

(Bb) is a polymerizable compound having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring) and an ethylenically unsaturated bond. The (Bb) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth) acryloyloxy group.

In the present specification, "(meth) acrylic acid" means at least one selected from the group consisting of acrylic acid and methacrylic acid. The expressions "(meth) acryloyl group" and "(meth) acrylate" and the like also have the same meaning.

Examples of (Bb) include monomers having an ethylene oxide group and an ethylenically unsaturated bond; a monomer having an oxetanyl group and an ethylenically unsaturated bond; monomers having a tetrahydrofuranyl group and an ethylenically unsaturated bond, and the like.

As (Bb), monomers having an ethylene oxide group and an ethylenically unsaturated bond are preferable in terms of further improving reliability such as heat resistance and chemical resistance of the obtained color filter.

Examples of (Bc) 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, and (meth) acrylic acidLauryl ester, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, and tricyclo [5.2.1.0 (meth) acrylate^2,6]Decane-8-yl ester (in the art, referred to as "dicyclopentyl (meth) acrylate" as a common name, and in some cases "tricyclodecanyl (meth) acrylate"), and tricyclo (meth) acrylate [5.2.1.0^2,6](meth) acrylates such as decen-8-yl ester (which is conventionally referred to in the art as "dicyclopentenyl (meth) acrylate"), (meth) acrylic acid esters such as dicyclopentenyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propynyl (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]-2-heptene, 5-methylbicyclo [2.2.1]-2-heptene, 5-ethylbicyclo [2.2.1]-2-heptene, 5-hydroxybicyclo [2.2.1]-2-heptene, 5-hydroxymethylbicyclo [2.2.1]-2-heptene, 5- (2' -hydroxyethyl) bicyclo [2.2.1]-2-heptene, 5-methoxybicyclo [2.2.1]-2-heptene, 5-ethoxybicyclo [2.2.1]2-heptene, 5, 6-dihydroxybicyclo [2.2.1]-2-heptene, 5, 6-bis (hydroxymethyl) bicyclo [2.2.1]-2-heptene, 5, 6-bis (2' -hydroxyethyl) bicyclo [2.2.1]-2-heptene, 5, 6-dimethoxybicyclo [2.2.1]-2-heptene, 5, 6-diethoxydicyclo [2.2.1]-2-heptene, 5-hydroxy 5-methylbicyclo [2.2.1]-2-heptene, 5-hydroxy-5-ethylbicyclo [2.2.1]-2-heptene, 5-hydroxymethyl-5-methylbicyclo [2.2.1]-2-heptene, 5-tert-butoxycarbonylbicyclo [2.2.1]-2-heptene, 5-cyclohexyloxycarbonylbicyclo [2.2.1]-2-heptene, 5-phenoxycarbonylbicyclo [2.2.1]-2-heptene, 5, 6-bis (tert-butoxycarbonyl) bicyclo [2.2.1]-2-heptene and 5, 6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1]Bicyclic unsaturated compounds such as-2-heptene; n-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidoDicarbonylimide derivatives such as iminohexanoate, N-succinimidyl-3-maleimidopropionate and N- (9-acridinyl) maleimide, and styrene, α -methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1, 3-butadiene, isoprene and 2, 3-dimethyl-1, 3-butadiene.

Of these, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] -2-heptene and the like are preferable from the viewpoints of copolymerization reactivity and heat resistance.

Examples of the resin (B) include a 3, 4-epoxycyclohexylmethyl (meth) acrylate/(meth) acrylic acid copolymer, and an acrylic acid 3, 4-epoxytricyclo [5.2.1.0 ]^2,6]Resins [ K1] such as decyl ester/(meth) acrylic acid copolymers](ii) a Glycidyl (meth) acrylate/(benzyl (meth) acrylate/(meth) acrylic acid copolymer, glycidyl (meth) acrylate/styrene/(meth) acrylic acid copolymer, acrylic acid 3, 4-epoxy tricyclo [5.2.1.0 ]^2,6]Resins such as decyl ester/(meth) acrylic acid/N-cyclohexylmaleimide copolymer, 3-methyl-3- (meth) acryloyloxymethyloxetane/(meth) acrylic acid/styrene copolymer [ K2](ii) a Resins [ K3] such as benzyl (meth) acrylate/(meth) acrylic acid copolymer and styrene/(meth) acrylic acid copolymer]；

Resins obtained by adding benzyl (meth) acrylate/(meth) acrylic acid copolymer and glycidyl (meth) acrylate, resins obtained by adding tricyclodecyl (meth) acrylate/styrene/(meth) acrylic acid copolymer and glycidyl (meth) acrylate, and resins obtained by adding tricyclodecyl (meth) acrylate/(benzyl (meth) acrylate/(meth) acrylic acid copolymer and glycidyl (meth) acrylate [ K4 ];

resins obtained by reacting a tricyclodecyl (meth) acrylate/(glycidyl (meth) acrylate) copolymer with (meth) acrylic acid, and resins obtained by reacting a tricyclodecyl (meth) acrylate/styrene/(glycidyl (meth) acrylate) copolymer with (meth) acrylic acid [ K5 ]; and resins obtained by reacting a copolymer of tricyclodecyl (meth) acrylate/(glycidyl (meth) acrylate) with (meth) acrylic acid, and further reacting the resulting resin with tetrahydrophthalic anhydride [ K6 ].

As the resin (B), the resin [ K1] and the resin [ K2] are preferable.

The resin (B) can be produced by a method described in "Experimental method for Polymer Synthesis" (published by Otsuka corporation, Ltd.; first edition first printing, published 3/1/1972) and a cited reference described in the above document.

The obtained copolymer may be used as it is, as a solution after the reaction, as a concentrated or diluted solution, or as a solid (powder) taken out by a method such as reprecipitation. In particular, by using the solvent contained in the colored curable resin composition of the present invention as a solvent in the polymerization, the solution after the reaction can be used as it is for the preparation of the colored curable resin composition of the present invention, and therefore, the production process of the colored curable resin composition of the present invention can be simplified.

The mass average molecular weight of the resin (B) in terms of polystyrene is preferably 3000 to 100000, more preferably 5000 to 50000, and still more preferably 5000 to 30000. When the molecular weight is within the above range, the following tendency is exhibited: the color filter has increased hardness, high residual film ratio, good solubility of unexposed part in developer, and increased resolution of colored pattern.

The molecular weight distribution [ mass 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) is preferably 50 to 170mg-KOH/g, more preferably 60 to 150mg-KOH/g, and still more preferably 70 to 135 mg-KOH/g. The acid value is a value measured by neutralizing the amount (mg) of potassium hydroxide required for 1g of the resin (B), and can be determined, for example, by titration with an aqueous solution of potassium hydroxide.

The content of the resin (B) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and further preferably 17 to 55% by mass, based on the total amount of solid components. When the content of the resin (B) is within the above range, there is a tendency that a colored pattern can be formed and the resolution and the residual film ratio of the colored pattern are improved.

< polymerizable Compound (C) >

The polymerizable compound (C) is a compound which is polymerized by an active radical and/or an acid generated by the polymerization initiator (D), and examples thereof include compounds having a polymerizable ethylenically unsaturated bond, and a (meth) acrylate compound is preferable.

The polymerizable compound (C) is preferably a polymerizable compound having 3 or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, pentaerythritol deca (meth) acrylate, pentaerythritol nona (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, ethylene glycol-modified pentaerythritol tetra (meth) acrylate, ethylene glycol-modified dipentaerythritol hexa (meth) acrylate, propylene glycol-modified pentaerythritol tetra (meth) acrylate, propylene glycol-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified pentaerythritol tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, propylene glycol-modified dipentaerythritol hexa (meth) acrylate, and caprolactone-modified pentaerythritol tetra, Caprolactone-modified dipentaerythritol hexa (meth) acrylate, and the like.

As the polymerizable compound having 3 or more ethylenically unsaturated bonds, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferable.

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

The content of the polymerizable compound (C) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and still more preferably 17 to 55% by mass, based on the total amount of the solid content. When the content of the polymerizable compound (C) is within the above range, the residual film ratio at the time of forming a colored pattern and the chemical resistance of the color filter tend to be improved.

< polymerization initiator (D) >

When the polymerization initiator (D) is a compound which generates an active radical, an acid, or the like by the action of light or heat and starts polymerization, a known polymerization initiator can be used. As the polymerization initiator generating active radicals, there may be mentioned O-acyloxime compounds, alkylphenone compounds, triazine compounds, acylphosphine oxide compounds and bisimidazole compounds.

Examples of the O-acyloxime compound include N-benzoyloxy-1- (4-phenylmercaptophenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylmercaptophenyl) octan-1-one-2-imine, N-benzoyloxy-1- (4-phenylmercaptophenyl) -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-dioxopentylmethyloxy) benzoyl } -9H-carbazol-3-yl ] ethane-1-imine, N-acetoxy-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -3-cyclopentylpropane-1-imine and N-benzoyloxy-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -3-cyclopentylpropane-1-one-2-imine, etc. Commercially available products such as イルガキュア (registered trademark), OXE01, OXE02 (manufactured by BASF corporation, supra) and N-1919 (manufactured by ADEKA corporation) may also be used. Among them, the O-acyloxime compound is preferably at least one member selected from the group consisting of N-benzoyloxy-1- (4-phenylmercaptophenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylmercaptophenyl) octan-1-one-2-imine, and N-benzoyloxy-1- (4-phenylmercaptophenyl) -3-cyclopentylpropane-1-one-2-imine, and more preferably N-benzoyloxy-1- (4-phenylmercaptophenyl) octan-1-one-2-imine. When these O-acyloxime compounds are used, there is a tendency to obtain a color filter with high luminance.

Examples of the phenylalkyl ketone compound include 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one, 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholino) phenyl ] butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] propan-1-one, 1-hydroxycyclohexylphenyl ketone, oligomers of 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one, α -diethoxyacetophenone and benzyldimethyl ketal, and commercially available products such as イルガキュア (registered trademark) 369, 907 and 379 (mentioned above, manufactured by BASF corporation) can also be used.

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 and 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. A commercially available product such as イルガキュア (registered trademark) 819 (manufactured by BASF) may 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, e.g., Japanese patent application laid-open publication No. 6-75372 and Japanese patent application laid-open publication No. 6-75373), 2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenylbiimidazole, 2' -bis (2-chlorophenyl) -4,4',5,5' -tetrakis (alkoxyphenyl) biimidazole, 2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetrakis (dialkoxyphenyl) biimidazole and 2,2' -bis (2-chlorophenyl) -4,4',5,5' -tetrakis (trialkoxyphenyl) biimidazole (see Japanese patent publication No. 48-38403, Japanese patent laid-open No. 62-174204, etc.), imidazole compounds in which the phenyl group at the 4,4',5,5' -position is substituted with a carboalkoxy group (see Japanese patent laid-open No. 7-10913, etc.), and the like.

Further, 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 ' -methyldiphenylsulfide, 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 phenylglyoxylate, titanocene compounds, and the like.

Examples of the polymerization initiator generating an acid include onium salts such as 4-hydroxyphenyl dimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyl dimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyl dimethylsulfonium p-toluenesulfonate, 4-acetoxyphenyl methylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodine p-toluenesulfonate and diphenyliodine hexafluoroantimonate, and nitrobenzyl toluenesulfonate and benzoin toluenesulfonate.

As the polymerization initiator (D), the following polymerization initiators are preferably contained: at least one selected from the group consisting of an O-acyloxime compound, a phenylalkylketone compound, a triazine compound, an acylphosphine oxide compound, and a bisimidazole compound; more preferred are polymerization initiators containing O-acyloxime compounds.

The content of the polymerization initiator (D) 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). When the content of the polymerization initiator (D) is within the above range, the sensitivity tends to be high and the exposure time tends to be short, and therefore, the productivity of the color filter tends to be improved.

< solvent (E) >

As the solvent (E), a solvent generally used in the art can be used. Examples thereof include ester solvents (solvents containing-COO-but not-O-in the molecule), ether solvents (solvents containing-O-but not-COO-in the molecule), ether ester solvents (solvents containing-COO-and-O-in the molecule), ketone solvents (solvents containing-CO-but not-COO-in the molecule), alcohol solvents (solvents containing-OH but not-O-, -CO-, and-COO-, aromatic hydrocarbon solvents, amide solvents, 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-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methylethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole and methyl anisole.

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, and the like, Ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate and diethylene glycol monobutyl ether acetate.

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, and glycerin.

As the aromatic hydrocarbon solvent, benzene, toluene, xylene, and mesitylene may be mentioned.

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

The solvent (E) is preferably an organic solvent having a boiling point of 120 to 210 ℃ at 1atm, from the viewpoint of coatability and drying property.

As the solvent, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone, and N, N-dimethylformamide are preferable, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, N-dimethylformamide, N-methylpyrrolidone, and ethyl 3-ethoxypropionate are more preferable.

The content of the solvent (E) is preferably 70 to 95% by mass, more preferably 75 to 92% by mass, based on the total amount of the colored curable resin composition of the present invention.

The total solid content of the colored curable resin composition is preferably 5 to 30% by mass, more preferably 8 to 25% by mass. When the content of the solvent (E) is within the above range, there is a tendency that: flatness at the time of coating becomes good; and since the color density is not insufficient when forming the color filter, the display characteristics are good.

< other ingredients >

The colored curable resin composition of the present invention may further contain additives known in the art, such as a polymerization initiation aid, a leveling agent, a filler, other polymer compounds, an adhesion promoter, an antioxidant, a light stabilizer, and a chain transfer agent, as required.

< method for producing colored curable resin composition >

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

When the colorant (a) contains the pigment (P), it is preferable that the pigment (P) and a part or the whole of the solvent (E) are mixed in advance and dispersed by a bead mill or the like until the average particle diameter of the pigment becomes about 0.2 μm or less. In this case, a part or all of the pigment dispersant and the resin (B) may be mixed as necessary. To the pigment dispersion liquid obtained in this manner, the remaining components are mixed to prepare a predetermined concentration, and the objective colored curable resin composition is prepared.

The dyes such as the salt-forming dyes may be dissolved in a part or the whole of the solvent (E) in advance to prepare a solution. The solution is preferably filtered through a filter having a pore size of about 0.01 to 1 μm.

The mixed colored curable resin composition is preferably filtered through a filter having a pore size of 0.1 to 10 μm.

< method for producing color Filter >

The color filter of the present invention is formed from the colored curable resin composition.

The method for producing a color filter 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.

Photolithography is one of the following methods: a colored curable resin composition is applied to a substrate, dried to form a colored composition layer, and the colored composition layer is exposed through a photomask to develop a colored pattern.

In the photolithography method, a colored coating film as a cured product of the colored composition layer can be formed without using a photomask and/or without developing at the time of exposure. The color filter of the present invention may be a coating film containing a colored pattern, or may be a colored coating film.

The film thickness of the color filter can be suitably adjusted according to the purpose, application, etc., and is usually 0.1 to 30 μm, preferably 0.1 to 20 μm, and more preferably 0.5 to 6 μm.

As the substrate, a glass plate such as quartz glass, borosilicate glass, aluminosilicate glass, or soda lime glass coated with silica on the surface, a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate, or silicon may be used, and a substrate such as an aluminum, silver/copper/palladium alloy film may be formed on the substrate. On these substrates, another color filter layer, a resin layer, a transistor, a circuit, and the like may be formed.

The formation of the colored pattern by the photolithography can be carried out under the conditions of a known or conventional apparatus. For example, the production can be performed as follows.

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

Examples of the coating method include a spin coating method, a slit and spin coating method, and the like.

The temperature for heating and drying is preferably 30 to 120 ℃, more preferably 50 to 110 ℃. The heating time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes.

When the drying is carried out under reduced pressure, it is preferably carried out under a pressure of 50 to 150Pa and at 20 to 25 ℃.

The film thickness of the colored composition layer can 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 a pattern corresponding to the intended use.

As the light source used for exposure, a light source generating light having a wavelength of 250 to 450nm is preferable. For example, for light less than 350nm, removal may be performed using a filter that removes this wavelength region; light in the vicinity of 436nm, 408nm, or 365nm can be appropriately extracted by using a band-pass filter for extracting these wavelength regions. Specifically, mercury lamps, light emitting diodes, metal halide lamps, halogen lamps, and the like can be cited.

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

The exposed colored composition layer is brought into contact with a developer to develop the layer, thereby forming a colored pattern on the substrate. By the development, the unexposed portion of the colored composition layer is dissolved in a developing solution to be removed. The developer is preferably an aqueous solution of an alkaline compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, or tetramethylammonium hydroxide.

The concentration of the aqueous solution of the basic compound is preferably 0.01 to 10 mass%, more preferably 0.03 to 5 mass%. Further, the developer may further include a surfactant.

The developing method may be any of a paddle method, a dipping method, a spraying method, and the like. Further, the substrate may be inclined at an arbitrary angle at the time of development.

After development, washing with water is preferred.

For the resulting colored pattern, post baking is preferably performed. The post-baking temperature is preferably 150-250 ℃, and more preferably 160-235 ℃. The post-baking time is preferably 1 to 120 minutes, and more preferably 10 to 60 minutes.

[ examples ] A method for producing a compound

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In the examples, the% and parts of the content or the amount used are by mass unless otherwise specified.

In the following synthesis examples, the structure of the compound was confirmed by MASS spectrometry (LC; model 1200 manufactured by Agilent, MASS; LC/MSD manufactured by Agilent).

Synthesis example 1

The following reaction was carried out under a nitrogen atmosphere.

36.3 parts of potassium thiocyanate and 160 parts of acetone were put into a flask equipped with a cooling tube and a stirrer, and then stirred at room temperature for 30 minutes. To the resulting mixture, 50 parts of benzoic acid chloride (manufactured by tokyo chemical corporation) was added dropwise over 10 minutes, and the mixture was stirred at room temperature for 2 hours. After the reaction mixture was ice-cooled, 45.7 parts of N-ethyl-o-toluidine (manufactured by tokyo chemical corporation) was added dropwise and stirred at room temperature for 30 minutes. The reaction mixture was ice-cooled, 34.2 parts of a 30% aqueous sodium hydroxide solution was added dropwise thereto, and the mixture was stirred at room temperature for 30 minutes. To the resulting reaction mixture was added dropwise 35.3 parts of chloroacetic acid at room temperature, followed by heating and refluxing for 7 hours. Then, after the reaction mixture was cooled to room temperature, the reaction solution was poured into 120 parts of water, 200 parts of toluene was added thereto, and the mixture was stirred for 30 minutes. The resulting mixture was allowed to stand for 30 minutes, separated into an organic layer and an aqueous layer, and subjected to a liquid separation operation to obtain an organic layer. The resulting organic layer was washed with 200 parts of 1N hydrochloric acid, 200 parts of water and 200 parts of saturated brine. And adding mirabilite into the organic layer, stirring for 30 minutes, and filtering to obtain a dried organic layer. The solvent was removed by distillation from the obtained organic layer to obtain a pale yellow liquid. The resulting pale yellow liquid was purified by column chromatography. The purified pale yellow liquid was dried under reduced pressure at 60 ℃ to obtain 52.0 parts of a compound represented by the formula (B-I-1).

The following reaction was carried out under a nitrogen atmosphere.

9.3 parts of a compound represented by the formula (B-I-1), 10 parts of 4,4' -bis (diethylamino) benzophenone (manufactured by Tokyo Kasei Co., Ltd.) and 20 parts of toluene were put into a flask equipped with a cooling tube and a stirrer, and 14.8 parts of phosphorus oxychloride was added thereto, followed by stirring at 95 to 100 ℃ for 3 hours. The resulting reaction mixture was cooled to room temperature and diluted with 170 parts of isopropanol. After the diluted reaction solution was poured into 300 parts of saturated saline solution, 100 parts of toluene was added thereto, and the mixture was stirred for 30 minutes. The resulting mixture was allowed to stand for 30 minutes, and separated into an organic layer and an aqueous layer. By performing a liquid separation operation, an organic layer was obtained. The resulting organic layer was washed with 300 parts of saturated brine. And adding mirabilite into the organic layer, stirring for 30 minutes, and filtering to obtain a dried organic layer. The organic layer was distilled to remove the solvent to give a bluish purple solid. The resulting bluish purple solid was dried under reduced pressure at 60 ℃ to obtain 19.8 parts of a compound represented by the formula (A-II-1).

Identification of Compound represented by formula (A-II-1)

(mass spectrometry) ionization mode ESI +: 601.3[ M-Cl ] M/z]⁺

Accurate quality: 636.3

Synthesis example 2

6.3 parts of the compound represented by the formula (A-II-1) was dissolved in 500 parts of ion-exchanged water. To the resulting mixture, 2.8 parts of 1, 5-dinaphthalenesulfonic acid (manufactured by tokyo chemical corporation) was added, and the mixture was stirred at 40 ℃ for 12 hours. The resulting reaction mixture was cooled to room temperature, and the formed crystals were collected by filtration, washed with ion-exchanged water, and then dried at 60 ℃ for 24 hours to obtain 8.8 parts of a solid containing the compound represented by the formula (A-II-2).

Example 1

8.8 parts of a solid containing the compound represented by the formula (A-II-2) was dissolved in 500 parts of ion-exchanged water.

To the aqueous solution obtained, 2.2 parts of 3-aminopropylethoxysilane (manufactured by Tokyo Kasei Co., Ltd.) was added, and the mixture was stirred at 30 ℃ for 12 hours. The resulting reaction mixture was cooled to room temperature, and the formed crystals were collected by filtration, washed with ion-exchanged water, and then dried at 60 ℃ for 24 hours to obtain 11.1 parts of a compound represented by the formula (A2-Z2-4).

Example 2

Synthesis was carried out in the same manner as in example 1 except that the salt of the formula (d-1) was used in place of 3-aminopropylethoxysilane in example 1 to give a compound represented by the formula (A2-Z1-1).

Example 3

Synthesis was carried out in the same manner as in example 1 except that the salt of the formula (d-2) was used in place of 3-aminopropylethoxysilane in example 1 to give a compound represented by the formula (A2-Z3-1).

Synthesis example 3

Mixing 19 parts of methacrylic acid and 3, 4-epoxy tricyclo [5.2.1.0 ] acrylic acid^2,6]Decan-8-yl ester and acrylic acid 3, 4-epoxytricyclo [5.2.1.0^2,6]171 parts of a mixture of decan-9-yl esters (containing a molar ratio of 50:50) (trade name "E-DCPA", manufactured by ダイセル Co., Ltd.) was dissolved in 40 parts of propylene glycol monomethyl ether acetate to obtain a solution (hereinafter, referred to as a solution (1)).

26 parts of 2,2' -azobis (2, 4-dimethylvaleronitrile) was dissolved in 120 parts of propylene glycol monomethyl ether acetate to obtain a solution (hereinafter, sometimes referred to as a solution (2)).

In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, 100 parts of propylene glycol monomethyl ether acetate was put under a nitrogen atmosphere and heated to 85 ℃ with stirring. Next, the resulting solution was added dropwise in a flask in such a manner that it took about 5 hours. Subsequently, the solution (2) was added dropwise in the flask in such a manner that it took about 5 hours.

After the completion of the dropwise addition of the solution (2), the mixture was kept at the same temperature for about 3 hours and then cooled to room temperature to obtain a copolymer (resin (B-1)) solution having a solid content of 43.5%. The mass-average molecular weight of the obtained resin (B-1) was 8000, the molecular weight distribution was 1.98, and the acid value in terms of solid content was 53 mg-KOH/g.

[ preparation of colored curable resin composition ]

Example 4

The colored curable resin composition (1) is obtained by mixing the following colorant (a), resin (B), polymerizable compound (C), polymerization initiator (D), solvent (E), and leveling agent (F).

Colorant (a): 20 parts of dye shown as a formula (A2-Z2-4);

resin (B): 53 parts of a resin (B-1) (in terms of solid content);

polymerizable compound (C): 16 parts of dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by japan chemical corporation);

polymerization initiator (D): 4 parts of N-benzoyloxy-1- (4-phenylmercaptophenyl) octane-1-one-2-imine (イルガキュア (registered trademark) OXE-01; manufactured by BASF Co., Ltd.; O-acyloxime compound);

solvent (E): 120 parts of propylene glycol monomethyl ether acetate; 480 parts of 4-hydroxy-4-methyl-2-pentanone; and

leveling agent (F): 0.15 part of polyether-modified silicone oil (トーレシリコーン SH 8400; manufactured by Torredo Corning Co., Ltd.)

Example 5

The colored curable resin composition (2) is obtained by mixing the following colorant (a), resin (B), polymerizable compound (C), polymerization initiator (D), solvent (E), and leveling agent (F).

Colorant (a): 21 parts of a dye shown as a formula (A2-Z1-1);

resin (B): 50 parts of a resin (B-1) (in terms of solid content);

polymerizable compound (C): 16 parts of dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by japan chemical corporation);

polymerization initiator (D): 4 parts of N-benzoyloxy-1- (4-phenylmercaptophenyl) octane-1-one-2-imine (イルガキュア (registered trademark) OXE-01; manufactured by BASF Co., Ltd.; O-acyloxime compound);

solvent (E): 120 parts of propylene glycol monomethyl ether acetate; 480 parts of 4-hydroxy-4-methyl-2-pentanone; and

leveling agent (F): 0.15 part of polyether-modified silicone oil (トーレシリコーン SH 8400; manufactured by Torredo Corning Co., Ltd.)

Example 6

The colored curable resin composition (3) is obtained by mixing the following colorant (a), resin (B), polymerizable compound (C), polymerization initiator (D), solvent (E), and leveling agent (F).

Colorant (a): 26 parts of a dye shown as a formula (A2-Z3-1);

resin (B): 50 parts of a resin (B-1) (in terms of solid content);

polymerizable compound (C): 20 parts of dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kagaku Co., Ltd.);

polymerization initiator (D): 4 parts of N-benzoyloxy-1- (4-phenylmercaptophenyl) octane-1-one-2-imine (イルガキュア (registered trademark) OXE-01; manufactured by BASF Co., Ltd.; O-acyloxime compound);

solvent (E): 120 parts of propylene glycol monomethyl ether acetate; 480 parts of 4-hydroxy-4-methyl-2-pentanone; and

leveling agent (F): 0.15 part of polyether-modified silicone oil (トーレシリコーン SH 8400; manufactured by Torredo Corning Co., Ltd.)

Comparative example 1

The following colorant (a), resin (B), polymerizable compound (C), polymerization initiator (D), solvent (E), and leveling agent (F) were mixed to obtain a colored curable resin composition (1').

Colorant (a): 26 parts of a dye shown as a formula (A-III-1);

resin (B): 53 parts of a resin (B-1) (in terms of solid content);

polymerizable compound (C): 16 parts of dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by japan chemical corporation);

polymerization initiator (D): 4 parts of N-benzoyloxy-1- (4-phenylmercaptophenyl) octane-1-one-2-imine (イルガキュア (registered trademark) OXE-01; manufactured by BASF Co., Ltd.; O-acyloxime compound);

solvent (E): 120 parts of propylene glycol monomethyl ether acetate; 480 parts of 4-hydroxy-4-methyl-2-pentanone; and

leveling agent (F): 0.15 part of polyether-modified silicone oil (トーレシリコーン SH 8400; manufactured by Torredo Corning Co., Ltd.)

Test examples

[ preparation of color Filter ]

The colored curable resin composition was applied to a 2-inch square glass substrate (# 1737; manufactured by コーニング Co.) 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 150mJ/cm in an air atmosphere using an exposure apparatus (TME-150 RSK; manufactured by トプコン Co., Ltd.)²Exposure was performed with the exposure amount (reference 365 nm). In addition, no photomask is used. The color filter (film thickness: 2.8 μm) was produced by post-baking the exposed colored composition layer in an oven at 180 ℃ for 20 minutes.

[ evaluation of Heat resistance ]

The color filter was heated at 30 ℃ for 20 minutes, and the color difference (. DELTA.Eab.) before and after heating the color filter was measured using a color measuring machine (OSP-SP-200; manufactured by OLYMPUS).

The color difference (Δ Eab) was determined for the coating films obtained from the colored photosensitive resin compositions of examples 4,5,6 and comparative example 1. The results are shown in Table 1.

The color difference (Δ Eab) indicates that the smaller the value, the more heat-resistant the material is.

TABLE 1

	△Eab*
		Example 4	5.1
Example 5	6.3
		Example 6	4.3
Comparative example 1	12.1

Industrial applicability of the invention

The colored curable resin composition containing a salt-forming dye of the present invention can provide a color filter exhibiting good heat resistance. The color filter can be used for display devices (liquid crystal display devices, organic EL devices, electronic paper, and the like) and solid-state imaging elements.

Claims (10)

1. A salt-forming dye is formed by a monovalent cation dye, a divalent anion compound and a monovalent cation compound without chromophoric groups,

wherein the monovalent cation dye is a compound shown as a formula (1-a-1),

wherein the monovalent cationic compound having no chromophoric group is selected from any one of the formulae (Z-1) and (Z-2),

in the formula (1-a-1), X represents an oxygen atom or a sulfur atom,

R^1A～R^8Aeach independently represents a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group or an alkyl group having 1 to 20 carbon atoms, wherein-CH contained in the alkyl group having 1 to 20 carbon atoms₂-can be replaced by-O-,

R^9A～R^12Aeach independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, wherein-CH contained in the alkyl group having 1 to 20 carbon atoms₂-can be replaced by-O-,

R⁴⁵and R⁴⁶Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or a substituentThe C6-20 aromatic hydrocarbon group, the said C1-20 alkyl group which may have a substituent group contains-CH₂-can be replaced by-O-,

R⁵⁵represents an alkyl group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent,

in the formula (Z-1), R¹Represents an alkylene group having 1 to 10 carbon atoms, and-CH contained in the alkylene group₂May be substituted by-O-, -CO-, -NR¹¹-, -OCO-, -COO-, -OCONH-, -CONH-or-NHCO-,

R¹¹represents an alkylene group having 1 to 10 carbon atoms,

in the formula (Z-2), R²Represents an alkylene group having 1 to 10 carbon atoms, and-CH contained in the alkylene group₂May be substituted by-O-, -CO-, -NR²¹-, -OCO-, -COO-, -OCONH-, -CONH-or-NHCO-,

R²¹represents an alkylene group having 1 to 10 carbon atoms,

R⁴⁰～R⁴²each independently represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms,

q represents an integer of 1 to 10.

2. Salt-forming dye according to claim 1, formed from a monovalent anionic dye and a monovalent cationic compound having no chromophoric group, wherein the monovalent anionic dye is formed from a monovalent cationic dye and a divalent anionic compound.

3. Salt-forming dye according to claim 1 or 2, wherein the dianionic compound is an aromatic compound having 2 monovalent anions or an heteroaromatic compound having 2 monovalent anions.

4. Salt-forming dye according to claim 3, wherein the monovalent anion is a sulfonate anion.

5. Salt-forming dye according to claim 1 or 2, wherein the dianionic compound is a compound of formula (1-b);

^-O₃S-R^1b-SO₃ ^-(1-b)

wherein, in the formula (1-b), R^1bRepresents an optionally substituted aromatic hydrocarbon group having 6 to 18 carbon atoms.

6. A colorant comprising the salt-forming dye of claim 1 or 2.

7. A colored curable resin composition comprising: the colorant, resin, polymerizable compound and polymerization initiator according to claim 6.

8. A coating film formed from the colored curable resin composition according to claim 7.

9. A color filter comprising the colored curable resin composition according to claim 7.

10. A display device comprising the color filter of claim 9.