CN107918246B

CN107918246B - Colored curable resin composition

Info

Publication number: CN107918246B
Application number: CN201710920192.1A
Authority: CN
Inventors: 市冈贤二
Original assignee: Sumitomo Chemical Co Ltd
Current assignee: Sumitomo Chemical Co Ltd
Priority date: 2016-10-06
Filing date: 2017-09-30
Publication date: 2022-02-25
Anticipated expiration: 2037-09-30
Also published as: TW201823374A; JP2018059097A; TWI770067B; JP6957298B2; KR102509937B1; KR20180038387A; CN107918246A

Abstract

The present invention relates to a colored curable resin composition. The colored curable resin composition contains a colorant, a resin, a polymerizable compound, and a polymerization initiator, wherein the colorant contains a triarylmethane colorant, a xanthene dye, and an anthraquinone dye.

Description

Colored curable resin composition

Technical Field

The present invention relates to a colored curable resin composition.

Background

As a colored curable resin composition for forming a color filter included in a liquid crystal display device or the like or a solid-state imaging device or the like, a colored curable resin composition including a triarylmethane dye and a xanthene dye as colorants is described in japanese patent application laid-open No. 2015-199912.

Disclosure of Invention

The present invention provides the following [1] to [5 ].

[1] A colored curable resin composition comprising a colorant, a resin, a polymerizable compound and a polymerization initiator,

the colorant comprises a triarylmethane colorant, a xanthene dye, and an anthraquinone dye.

[2] The colored curable resin composition according to [1], wherein the content of the anthraquinone dye is 0.5 to 50 parts by mass per 100 parts by mass of the triarylmethane colorant.

[3] The colored curable resin composition according to [2], wherein the content of the anthraquinone dye is 1.0 to 13.5 parts by mass per 100 parts by mass of the triarylmethane colorant.

[4] A color filter comprising the colored curable resin composition according to any one of [1] to [3 ].

[5] A display device comprising the color filter of [4 ].

Detailed Description

The colored curable resin composition of the present invention comprises a colorant (a), a resin (B), a polymerizable compound (C), and a polymerization initiator (D). The colored curable resin composition of the present invention preferably contains a solvent (E) and/or a leveling agent (F), and may further contain an antioxidant (H) and other components. The colorant (a) contains a triarylmethane colorant (Aa1), a xanthene dye (Aa2), and an anthraquinone dye (Aa 3). The colored curable resin composition of the present invention has the above-described configuration, and therefore, a color filter with high contrast (contrast) can be manufactured.

< colorant (A) >)

The colorant (a) contains a triarylmethane colorant (Aa1), a xanthene dye (Aa2), and an anthraquinone dye (Aa 3). A dye different from the triarylmethane dye (Aa1), the xanthene dye (Aa2), and the anthraquinone dye (Aa3) (hereinafter sometimes referred to as "dye (Aa 4)") may also be contained.

(triarylmethane colorant (Aa1))

The triarylmethane colorant (Aa1) is a colorant containing a compound having a triarylmethane skeleton in the molecule. The colorant may be a dye or a pigment, or a laked pigment. As the triarylmethane colorant (Aa1), a dye containing a compound represented by the formula (a-I) and a tautomer thereof (hereinafter, these may be collectively referred to as "compound (a-I)") is preferable.

When the compound (a-I) is used, the content of the compound (a-I) in the triarylmethane colorant (Aa1) is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more. Among them, as the triarylmethane colorant (Aa1), it is preferable to use only the compound (A-I).

[ formula (A-I) [ Y ]²]^m-Represents an m-valent anion.

R⁴¹～R⁴⁴Each independently represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may be substituted, a group in which an oxygen atom is inserted between carbon atoms constituting an alkyl group having 2 to 20 carbon atoms, an aryl group which may be substituted, or an aralkyl group which may be substituted. R⁴¹And R⁴²May be bonded and form a ring together with the nitrogen atom to which they are bonded, R⁴³And R⁴⁴May be bonded and form a ring together with the nitrogen atom to which they are bonded.

R⁴⁵～R⁵²Each independently represents a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, a saturated hydrocarbon group having 1 to 8 carbon atoms, or a group having an oxygen atom inserted between carbon atoms constituting an alkyl group having 2 to 8 carbon atoms, or R⁴⁶And R⁵⁰Can be bonded to each other to form-O-, -NH-,-S-or-SO₂-。

Y¹Represents an aryl group which may be substituted, or a heteroaryl group which may be substituted.

When the compound represented by the formula (A-I) contains a plurality of cations, the plurality of cations may have the same structure or different structures from each other.

m represents an arbitrary natural number. ]

[Y²]^m-Represents an m-valent anion. As a group [ Y²]^m-The anion represented is not particularly limited as long as it is an anion capable of forming a counter ion with the dye cation, and is preferably a halogen anion such as a boron-containing anion, an aluminum-containing anion, a fluorine-containing anion, or a chlorine anion, or an anion containing at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus, and an oxygen atom.

Examples of the boron-containing anion and the aluminum-containing anion include anions represented by the formula (4).

[ in the formula (4), W¹And W²Each independently represents a group formed by liberating a proton from a compound having 2 monovalent proton-donating substituents. M represents boron or aluminum.]

In the formula (4), examples of the compound having 2 monovalent proton-donating substituents include compounds having 2 monovalent proton-donating substituents (for example, a hydroxyl group, a carboxyl group, and the like), and examples thereof include dihydroxynaphthalene, optionally substituted 2, 2' -biphenol, optionally substituted 3-hydroxy-2-naphthoic acid, optionally substituted 2-hydroxy-1-naphthoic acid, optionally substituted 1-hydroxy-2-naphthoic acid, optionally substituted binaphthol, optionally substituted salicylic acid, optionally substituted benzilic acid, or optionally substituted mandelic acid.

The group formed by releasing a proton from the compound means that all protons are dissociated from a plurality of proton-donating substituents in the compoundFormed of a compound having O^-And/or COO^-A group of (1).

The above-mentioned compound is preferably catechol which may have a substituent, 2, 3-dihydroxynaphthalene which may have a substituent, 2' -biphenol which may have a substituent, 3-hydroxy-2-naphthoic acid which may have a substituent, 2-hydroxy-1-naphthoic acid which may have a substituent, 1-hydroxy-2-naphthoic acid which may have a substituent, binaphthol which may have a substituent, salicylic acid which may have a substituent, benzilic acid which may have a substituent, or mandelic acid which may have a substituent.

In each of the above compounds, examples of the substituent include a saturated hydrocarbon group (e.g., an alkyl group or a cycloalkyl group), a halogen atom, a hydroxyl group, an amino group, a nitro group, and an alkoxy group.

Examples of the salicylic acid which may have a substituent include: monoaminosalicylic acids such as salicylic acid, 3-methylsalicylic acid, 3-tert-butylsalicylic acid, 3-methoxysalicylic acid, 3-nitrosalicylic acid, 4-trifluoromethylsalicylic acid, 3, 5-di-tert-butylsalicylic acid, 3-aminosalicylic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, and 6-aminosalicylic acid; monohydroxysalicylic acids such as 3-hydroxysalicylic acid (2, 3-dihydroxybenzoic acid), 4-hydroxysalicylic acid (2, 4-dihydroxybenzoic acid), 5-hydroxysalicylic acid (2, 5-dihydroxybenzoic acid), and 6-hydroxysalicylic acid (2, 6-dihydroxybenzoic acid); dihydroxysalicylic acids such as 4, 5-dihydroxysalicylic acid and 4, 6-dihydroxysalicylic acid; monohalogenated salicylic acids such as 3-chlorosalicylic acid, 4-chlorosalicylic acid, 5-chlorosalicylic acid, 6-chlorosalicylic acid, 3-bromosalicylic acid, 4-bromosalicylic acid, 5-bromosalicylic acid, 6-bromosalicylic acid, etc.; dihalogenated salicylic acids such as 3, 5-dichlorosalicylic acid, 3, 5-dibromosalicylic acid, 3, 5-diiodosalicylic acid, etc.; trihalosalicylic acids such as 3,5, 6-trichlorosalicylic acid; and so on.

Examples of benzilic acid which may have a substituent include compounds represented by the following structural formula.

As mandelic acid which may have a substituent, a compound represented by the following structural formula and the like can be given.

Preferred examples of the anion represented by formula (4) include anions (BC-1) to (BC-24) having substituents shown in Table 1, which are represented by the following formulae, and anions (BC-25) to (BC-28) represented by formulae (BC-25), (BC-26), (BC-27) and (BC-28), respectively.

[ in the formula, M represents boron or aluminum. ]

[ Table 1]

Anion(s)	R⁶¹	R⁶²	R⁶³	R⁶⁴
					Anion (BC-1)	H	H	H	H
Anion (BC-2)	OH	H	H	H
					Anion (BC-3)	H	OH	H	H
Anion (BC-4)	H	H	OH	H
					Anion (BC-5)	H	H	H	OH
Anion (BC-6)	Cl	H	H	H
					Anion (BC-7)	H	Cl	H	H
Anion (BC-8)	H	H	Cl	H
					Anion (BC-9)	H	H	H	Cl
Anion (BC-10)	Br	H	H	H
					Anion (BC-11)	H	Br	H	H
Anion (BC-12)	H	H	Br	H
					Anion (BC-13)	H	H	H	Br
Anion (BC-14)	NH₂	H	H	H
					Anion (BC-15)	H	NH₂	H	H
Anion (BC-16)	H	H	NH₂	H
					Anion (BC-17)	H	H	H	NH₂
Anion (BC-18)	H	tBu	H	tBu
					Anion (BC-19)	H	Cl	H	Cl
Anion (BC-20)	H	Br	H	Br
					Anion(s)(BC-21)	H	I	H	I
Anion (BC-22)	H	OH	OH	H
					Anion (BC-23)	OH	H	OH	H
Anion (BC-24)	Cl	Cl	H	Cl

[ in the formula (BC-25), M represents boron or aluminum. ]

[ in the formula (BC-26), M represents boron or aluminum. ]

[ in the formula (BC-27), M represents boron or aluminum. ]

[ in the formula (BC-28), M represents boron or aluminum. ]

The anion represented by formula (4) is preferably an anion (BC-1), an anion (BC-2), an anion (BC-3), an anion (BC-25), an anion (BC-26), or an anion (BC-27), more preferably an anion (BC-1), an anion (BC-2), or an anion (BC-25), and still more preferably an anion (BC-1) or an anion (BC-2). The compound represented by the formula (a-I) containing any of the above anions tends to have excellent solubility in an organic solvent.

Examples of the fluorine-containing anion include groups represented by the formulae (6), (7), (8), and (9).

In [ formula (6), W³And W⁴Each independently represents a fluorine atom or a fluoroalkyl group having 1 to 4 carbon atoms, or W³And W⁴The fluorinated alkanediyl (alkanediyl) group is a single-body of a fluorinated alkanediyl group having 1 to 4 carbon atoms.]

[ in the formula (7), W⁵、W⁶And W⁷Each independently represents a fluorine atom or a fluoroalkyl group having 1 to 4 carbon atoms.]

[ in the formula (8), Y^aRepresents a C1-4 fluoroalkanediyl group.]

[ in the formula (9), Y^bRepresents a C1-4 fluoroalkyl group.]

In the formulae (6), (7) and (9), the fluoroalkyl group having 1 to 4 carbon atoms is preferably a perfluoroalkyl group. The perfluoroalkyl group may be-CF₃、-CF₂CF₃、-CF₂CF₂CF₃、-CF(CF₃)₂、-CF₂CF₂CF₂CF₃、-CF₂CF(CF₃)₂、-C(CF₃)₃。

In the formulae (6) and (8), the fluoroalkanediyl group having 1 to 4 carbon atoms includes a perfluoroalkanediyl group, and preferably includes-CF₂-、-CF₂CF₂-、-CF₂CF₂CF₂-、-C(CF₃)₂-、-CF₂CF₂CF₂CF₂-and the like.

Examples of the anion represented by the formula (6) (hereinafter, may be referred to as "anion (6)") include anions represented by the formulae (6-1) to (6-6) (hereinafter, may be referred to as "anion (6-1)" to "anion (6-6)").

Examples of the anion represented by the formula (7) (hereinafter, may be referred to as "anion (7)") include an anion represented by the following formula (7-1).

Examples of the anion represented by the formula (8) (hereinafter, may be referred to as "anion (8)") include anions represented by the formulae (8-1) to (8-4) (hereinafter, may be referred to as "anion (8-1)" to "anion (8-4)").

Examples of the anion represented by the formula (9) (hereinafter, may be referred to as "anion (9)") include anions represented by the formulae (9-1) to (9-4) (hereinafter, may be referred to as "anion (9-1)" to "anion (9-4)").

As [ Y ]²]^m-Preferably a fluorine-containing anion or a polyacid anion, more preferably an anion represented by the formula (6) [ PW₁₂O₄₀]^3-、[P₂W₁₈O₆₂]^6-、[SiW₁₂O₄₀]^4-And [ W ]₁₀O₃₂]^4-More preferably, the anion represented by the formulae (6-1) to (6-5) [ PW₁₂O₄₀]^3-And [ P₂W₁₈O₆₂]^6-Particularly preferred are an anion represented by the formula (6-2) and [ PW₁₂O₄₀]^3-。

m represents an arbitrary natural number, and is bonded to an anion [ Y ]²]^m-Have equal negative charges. For m on the cationic side, an anion [ Y ]²]^m-Is determined in a manner equivalent to the charge of the cation. m is preferably a natural number of 1 to 10.

R⁴¹～R⁴⁴The saturated hydrocarbon group having 1 to 20 carbon atoms may be any of straight-chain, branched and cyclic. The saturated hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 4 carbon atoms.

Examples of the linear or branched saturated hydrocarbon group include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, and decyl groups; branched alkyl groups such as isopropyl, isobutyl and 2-ethylhexyl. The number of carbon atoms of the linear or branched saturated hydrocarbon group is preferably 1 to 8, more preferably 1 to 6, and still more preferably 1 to 4.

The cyclic saturated hydrocarbon group may be monocyclic or polycyclic. Examples of the cyclic saturated hydrocarbon group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and adamantyl. The number of carbon atoms of the cyclic saturated hydrocarbon group is preferably 3 to 10, more preferably 6 to 10.

R⁴¹～R⁴⁴The hydrogen atom of the saturated hydrocarbon group (2) may be substituted with a substituent. Examples of the substituent include a substituted or unsubstituted amino group and a halogen atom. Examples of the substituted amino group include dialkylamino groups such as dimethylamino group, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the saturated hydrocarbon group in which a hydrogen atom is substituted with a substituted or unsubstituted amino group or a halogen atom include a group represented by the following formula. In the following formula, the symbol "A" represents a bond to a nitrogen atom.

As R⁴¹～R⁴⁴Among the groups represented by the above formula, examples of the group having an oxygen atom inserted between methylene groups (carbon atoms) constituting an alkyl group having 2 to 20 carbon atoms include groups represented by the following formula. In the following formula, the symbol "A" represents a bond to a nitrogen atom. Among these, the group having an oxygen atom inserted between methylene groups constituting the alkyl group is preferably a group having 2 to 10 carbon atoms, and more preferably a group having 2 to 6 carbon atoms. The alkyl group inserted with an oxygen atom is preferably a straight-chain alkyl group. The number of carbon atoms between oxygen atoms is preferably 1 to 4, more preferably 2 to 3.

R⁴¹～R⁴⁴In the above formula, the aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms, the aralkyl group preferably has 7 to 20 carbon atoms, and more preferably has 7 to 20 carbon atoms7～10。

As R⁴¹～R⁴⁴Examples of the aryl group of (b) include phenyl, naphthyl and toluyl.

As R⁴¹～R⁴⁴Examples of the aryl group in the aralkyl group in (2) include a phenyl group and a naphthyl group, and examples of the aralkyl group include a group in which a connecting bond of the aryl group is bonded to an alkanediyl group. The aforementioned alkanediyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and is preferably a straight-chain alkanediyl group. Specific examples of the alkanediyl group include a methylene group, an ethylene group, a propylene group, a butanediyl group, and a pentanediyl group, and specific examples of the aralkyl group include a benzyl group, a phenethyl group, a naphthylmethyl group, and a naphthylethyl group.

At R⁴¹～R⁴⁴In the aryl group and the aralkyl group in the group represented by (a), examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom, an iodine atom and the like; alkoxy groups having 1 to 6 carbon atoms such as methoxy and ethoxy; a hydroxyl group; c1-6 alkylsulfonyl such as methylsulfonyl; alkoxycarbonyl groups having 2 to 6 carbon atoms such as methoxycarbonyl and ethoxycarbonyl; and so on.

Specific examples of the aryl group which may be substituted include those represented by the following formula. In the following formula, the symbol "A" represents a bond to a nitrogen atom.

Examples of the aralkyl group which may be substituted include those in which an alkylene group such as a methylene group or an ethylene group is bonded to the bond of the aryl group.

As R⁴¹And R⁴²A ring bonded to form together with the nitrogen atom to which they are bonded, and R⁴³And R⁴⁴A ring bonded to form a ring together with the nitrogen atom to which they are bonded, and examples thereof include a 5-membered ring such as a pyrrolidine ring; a 6-membered ring such as a morpholine ring, a piperidine ring, or a piperazine ring; and so on.

From the viewpoint of ease of synthesis, R⁴¹～R⁴⁴Preferably each independentlyThe alkyl group is a saturated hydrocarbon group having 1 to 20 carbon atoms which may be substituted, an aryl group which may be substituted, or an aralkyl group which may be substituted, and more preferably each independently a saturated hydrocarbon group having 1 to 8 carbon atoms or a group represented by the following formula. In the following formula, the symbol "A" represents a bond to a nitrogen atom.

R⁴⁵～R⁵²The saturated hydrocarbon group represented by (a) may be linear, branched or cyclic, and is preferably linear. As R⁴⁵～R⁵²Examples of the saturated hydrocarbon group represented by the formula (I) include R⁴¹～R⁴⁴Examples of the saturated hydrocarbon group include groups having 1 to 8 carbon atoms.

The group having an oxygen atom inserted between methylene groups (carbon atoms) constituting the alkyl group is more preferably an alkyl group having 2 to 8 carbon atoms. The alkyl group having an oxygen atom inserted therein is preferably a straight-chain alkyl group, and the number of carbon atoms between oxygen atoms is preferably 1 to 4, more preferably 2 to 3. For example, a group represented by the following formula may be mentioned. In the following formula, the symbol represents a bond to a carbon atom.

From the viewpoint of ease of synthesis, R⁴⁵～R⁵²Preferably, each independently represents a hydrogen atom, a halogen atom or a saturated hydrocarbon group having 1 to 8 carbon atoms, and more preferably each independently represents a hydrogen atom, a methyl group, a fluorine atom or a chlorine atom.

R⁴⁶And R⁵⁰Can be bonded to each other to form-O-, -NH-, -S-or-SO₂-。

The aryl group may be any of a monocyclic ring and a condensed ring, and examples thereof include aromatic hydrocarbon groups having 6 to 20 carbon atoms such as a phenyl group, a tolyl group, a xylyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group, and a terphenyl group.

Heteroaryl is a substituent derived from an aromatic heterocycle. The aromatic heterocyclic ring may be any of a monocyclic ring and a condensed ring, and is preferably a 5-to 10-membered ring, more preferably a 5-to 9-membered ring.

Examples of the monocyclic aromatic heterocycle include:

a 5-membered ring containing a nitrogen atom such as a pyrrole ring, an oxazole ring, a pyrazole ring, an imidazole ring, a thiazole ring and the like;

a 5-membered ring containing an oxygen atom and a sulfur atom, such as a furan ring and a thiophene ring;

a 6-membered ring containing a nitrogen atom such as a pyridine ring, a pyrimidine ring, a pyridazine ring, or a pyrazine ring; and so on.

As the aromatic heterocycle of the condensed ring, there may be mentioned:

condensed rings containing a nitrogen atom such as an indole ring, a benzimidazole ring, a benzothiazole ring, and a quinoline ring;

a ring containing an oxygen atom or a sulfur atom such as a benzofuran ring; and so on.

As the heteroaryl group which may be substituted, a group represented by the formula (Ab2-x1) is more preferable.

[ Ring T²Represents an aromatic heterocycle.

R⁵³And R⁵⁴Each independently represents a saturated hydrocarbon group having 1 to 20 carbon atoms which may be substituted, a group in which an oxygen atom is inserted between carbon atoms constituting an alkyl group having 2 to 20 carbon atoms, an aryl group which may be substituted, an aralkyl group which may be substituted, or a hydrogen atom.

R⁵⁵Represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aryl group which may be substituted.

k1 represents 0 or 1.

Represents a bond to a carbocation. ]

Ring T²The aromatic heterocyclic ring is preferably an aromatic heterocyclic ring having 2 to 9 carbon atoms.

In addition, R is⁵³～R⁵⁵The details of which are described later.

The compound (A-I) is more preferably a compound represented by the formula (A-II).

[ formula (A-II) [ Y ]²]^m-、R⁴¹～R⁵²And m has the same meaning as above.

R⁵³And R⁵⁴Each independently represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may be substituted, a group in which an oxygen atom is inserted between carbon atoms constituting an alkyl group having 2 to 20 carbon atoms, an aryl group which may be substituted, or an aralkyl group which may be substituted. R⁵⁵Represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aryl group which may be substituted.

X represents an oxygen atom, -NR⁵⁷-or a sulfur atom.

R⁵⁷Represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

When the compound represented by the formula (a-II) contains a plurality of cations, the plurality of cations may have the same structure or different structures from each other. ]

As R⁵³And R⁵⁴Examples thereof include the compounds with R⁴¹～R⁴⁴The same groups as those exemplified in (1) above.

As R⁵⁵The saturated hydrocarbon group having 1 to 20 carbon atoms is represented by R⁴¹～R⁴⁴The saturated hydrocarbon group of (3) is the same as the exemplified group. Among them, preferred is an alkyl group having 1 to 10 carbon atoms, more preferred is an alkyl group having 1 to 8 carbon atoms, still more preferred is an alkyl group having 1 to 6 carbon atoms, and particularly preferred is an alkyl group having 1 to 4 carbon atoms.

As R⁵⁵Examples of the group represented by the above-mentioned formula in which an oxygen atom is inserted between carbon atoms constituting the alkyl group include the group represented by the formula⁴¹～R⁴⁴The same groups as those exemplified in (1) above. The alkyl group inserted into the oxygen atom is preferablyA linear alkyl group. The number of carbon atoms between oxygen atoms is preferably 1 to 4, more preferably 2 to 3.

At R⁵⁵In the above formula, the number of carbon atoms in the aryl group is preferably 6 to 20, more preferably 6 to 10. Examples of the aryl group include those related to R⁴¹～R⁴⁴The same group as the aryl group exemplified above is preferably a phenyl group.

At R⁵⁵In (b), examples of the substituent group of the aryl group include a halogen atom such as a fluorine atom, a chlorine atom, and an iodine atom; alkoxy groups having 1 to 6 carbon atoms such as methoxy and ethoxy; a hydroxyl group; an aminosulfonyl group; c1-6 alkylsulfonyl such as methylsulfonyl; alkoxycarbonyl groups having 2 to 6 carbon atoms such as methoxycarbonyl and ethoxycarbonyl; and so on.

From the viewpoint of ease of synthesis, R⁵⁵Preferably a saturated hydrocarbon group or an optionally substituted aryl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, or an aryl group optionally substituted with a halogen atom, an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, or a methylsulfonyl group, and still more preferably a group represented by the following formula. In the following formula, the symbol represents a bond to a carbon atom.

R⁵⁷Preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group.

X represents an oxygen atom, -NR⁵⁷-or a sulfur atom. Examples of the cyclic structure containing X include a group represented by the following formula. In the formula, R⁵³～R⁵⁵The meanings of (A) and (B) are the same as above, respectively, and represent a bond to a carbocation. Among them, X is preferably an oxygen atom or a sulfur atom, and more preferably a sulfur atom.

Examples of the cation of formula (A-I) include cations 1 to 27 having substituents shown in Table 2 and represented by formula (A-I-1).

[ Table 2]

In Table 2, Ph1 to Ph12 represent groups represented by the following formulae.

The cation in the formula (a-I) is preferably a cation 1 to a cation 6, a cation 11, and a cation 12, and more preferably a cation 1, a cation 2, and a cation 12.

When the compound represented by the formula (a-II) contains a plurality of cations, the plurality of cations may have the same structure or different structures from each other.

(xanthene dye (Aa2))

The xanthene dye (Aa2) is a dye containing a compound having a xanthene skeleton in the molecule. Examples of the xanthene dye (Aa2) include c.i. acid red 51 (hereinafter, the description of c.i. acid red is omitted, and only the number is described, the same as the other), 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 (rhodamine B), 11, c.i. basic violet 10, 11, 25, c.i. solvent red 218, c.i. mordant red 27, c.i. active red 36 (rose red B (rose Bengal B)), sulforhodamine G, the xanthene dye described in jp 2010-a 32999, and the xanthene dye described in japanese patent No. 4492760. Among these, xanthene dyes that are soluble in organic solvents are preferable.

Among them, the xanthene dye (Aa2) is preferably a dye containing a compound represented by the formula (1a) and a tautomer thereof (hereinafter, these may be collectively referred to as "compound (1 a)"). When the compound (1a) is used, the content of the compound (1a) in the xanthene dye (a2) is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more. Among them, the xanthene dye (a2) is preferably used alone as the compound (1 a).

[ in the formula (1a), R¹～R⁴Each independently represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent, the hydrogen atom contained in the saturated hydrocarbon group may be substituted with an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom, the hydrogen atom contained in the aromatic hydrocarbon group may be substituted with an alkoxy group having 1 to 3 carbon atoms, or-CH contained in the saturated hydrocarbon group₂-may be replaced by-O-, -CO-or-NR¹¹-。R¹And R²May be integrated to form a ring containing a nitrogen atom, R³And R⁴May be integrated to form a ring containing a nitrogen atom.

R⁵represents-OH or-SO₃ ^-、-SO₃H、-SO₃ ^-Z⁺、-CO₂H、-CO₂ ^-Z⁺、-CO₂R⁸、-SO₃R⁸or-SO₂NR⁹R¹⁰。

R⁶And R⁷Each 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 an integer of 2 or more, plural R⁵May be the same or different.

a represents an integer of 0 or 1.

X0 represents a halogen atom.

R⁸Represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, wherein a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom.

Z⁺To represent⁺N(R¹¹)₄、Na⁺Or K⁺。

R⁹And R¹⁰Each independently represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms and a substituent, and-CH is contained in the saturated hydrocarbon group₂-may be replaced by-O-, -CO-, -NH-or-NR⁸-，R⁹And R¹⁰May be bonded to each other to form a heterocyclic ring having 3 to 10 membered rings including a nitrogen atom.

⁺N(R¹¹)₄4 of (2)¹¹Each independently represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms.]

As a representation of R¹～R⁴Examples of the monovalent aromatic hydrocarbon group include a phenyl group, a toluyl group, a xylyl group, a mesityl group, a propylphenyl group, and a butylphenyl group.

As the substituent that the aromatic hydrocarbon group may have, there may be mentioned a halogen atom, -R⁸、-OH、-OR⁸、-SO₃ ^-、-SO₃H、-SO₃ ^-Z⁺、-CO₂H、-CO₂R⁸、-SR⁸、-SO₂R⁸、-SO₃R⁸or-SO₂NR⁹R¹⁰. Among them, as the substituent, preferred is-SO₃ ^-、-SO₃H、-SO₃ ^-Z⁺and-SO₂NR⁹R¹⁰More preferably-SO₃ ^-Z⁺and-SO₂NR⁹R¹⁰. as-SO in this case₃ ^-Z⁺Is preferably-SO₃ ^-+N(R¹¹)₄. If R is¹～R⁴The above-mentioned groups enable the 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).

As R¹And R²A ring formed integrally with R³And R⁴Examples of the ring formed integrally include the following rings.

As a representation of R⁸～R¹¹Examples of the monovalent saturated hydrocarbon group include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, hexadecyl and eicosyl; branched alkyl groups such as isopropyl, isobutyl, isopentyl, neopentyl, and 2-ethylhexyl groups; and (c) 3-20 alicyclic saturated hydrocarbon groups such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, tricyclodecyl, and the like.

as-OR⁸Examples thereof include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy, and eicosyloxy groups.

as-CO₂R⁸Examples thereof include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, tert-butoxycarbonyl, hexyloxycarbonyl, and eicosyloxycarbonyl.

As a-SR⁸Examples thereof include methylthio (methyl sulfonyl), ethylthio, butylthio, hexylthio, decylthio and eicosylthio.

as-SO₂R⁸Examples thereof include methylsulfonyl, ethylsulfonyl, butylsulfonyl, hexylsulfonyl, decylsulfonyl and eicosylsulfonyl groups.

as-SO₃R⁸Examples thereof include methoxysulfonyl, ethoxysulfonyl, propoxysulfonyl, tert-butoxysulfonyl, hexyloxysulfonyl and eicosyloxysulfonyl.

as-SO₂NR⁹R¹⁰Examples thereof include:

an aminosulfonyl group;

n-methylaminosulfonyl, N-ethylaminosulfonyl, N-propylaminosulfonyl, N-isopropylaminosulfonyl, N-butylaminosulfonyl, N-isobutylaminosulfonyl, N-sec-butylaminosulfonyl, N-tert-butylaminosulfonyl, N-pentylaminosulfonyl, N- (1-ethylpropyl) aminosulfonyl, N- (1, 1-dimethylpropyl) aminosulfonyl, N- (1, 2-dimethylpropyl) aminosulfonyl, N- (2, 2-dimethylpropyl) aminosulfonyl, N- (1-methylbutyl) aminosulfonyl, N- (2-methylbutyl) aminosulfonyl, N- (3-methylbutyl) aminosulfonyl, N-isopropylaminosulfonyl, N-butylaminosulfonyl, N- (1, 1-dimethylpropyl) aminosulfonyl, N- (2-methylbutyl) aminosulfonyl, N- (3-methylbutyl) aminosulfonyl, N-butylaminosulfonyl, N-2-b-butylaminosulfonyl, N-methyl-butylaminosulfonyl, N-butylaminosulfonyl, or a salt, N-methyl-substituted or a salt thereof, N-monosubstituted aminosulfonyl groups such as N-cyclopentylaminosulfonyl group, N-hexylaminosulfonyl group, N- (1, 3-dimethylbutyl) aminosulfonyl group, N- (3, 3-dimethylbutyl) aminosulfonyl group, N-heptylaminosulfonyl group, N- (1-methylhexyl) aminosulfonyl group, N- (1, 4-dimethylpentyl) aminosulfonyl group, N-octylaminosulfonyl group, N- (2-ethylhexyl) aminosulfonyl group, N- (1, 5-dimethyl) hexylaminosulfonyl group, and N- (1,1,2, 2-tetramethylbutyl) aminosulfonyl group;

n, N-disubstituted aminosulfonyl groups such as N, N-dimethylaminosulfonyl group, N-ethylmethylaminosulfonyl group, N-diethylaminosulfonyl group, N-propylmethylaminosulfonyl group, N-isopropylmethylaminosulfonyl group, N-tert-butylmethylaminosulfonyl group, N-butylethylaminosulfonyl group, N-bis (1-methylpropyl) aminosulfonyl group, and N, N-heptylmethylaminosulfonyl group.

As a representation of R⁹、R¹⁰Examples of the substituent in the monovalent saturated hydrocarbon group include a hydroxyl group and a halogen atom.

As R⁵preferably-CO₂H、-CO₂ ^-Z⁺、-CO₂R⁸、-SO₃ ^-、-SO₃ ^-Z⁺、-SO₃H or SO₂NHR⁹More preferably SO₃ ^-、-SO₃ ^-Z⁺、-SO₃H or SO₂NHR⁹。

M is preferably 1 to 4, more preferably 1 or 2.

As a representation of R⁶And R⁷The alkyl group having 1 to 6 carbon atoms may be a straight chain or a branched chain, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and a hexyl group.

As a representationR¹¹Examples of the aralkyl group in (2) include benzyl, phenethyl and phenylbutyl.

Z⁺Is composed of⁺N(R¹¹)₄、Na⁺Or K⁺Preferably, it is⁺N(R¹¹)₄。

As mentioned above⁺N(R¹¹)₄Preferably 4R¹¹At least 2 of them are monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. 4R¹¹The total number of carbon atoms of (A) is preferably 20 to 80, more preferably 20 to 60. In the compound (1a)⁺N(R¹¹)₄In the case of (1), if R¹¹The above-mentioned groups enable the formation of a color filter containing less foreign matters from the colored curable resin composition of the present invention containing the compound (1 a).

Preferred examples of the compound (1a) include compounds represented by the formula (2a) and tautomers thereof (hereinafter, these may be collectively referred to as "compound (2 a)"). When the compound (2a) is used, the content of the compound (2a) in the xanthene dye (a2) is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more.

[ in the formula (2a), R²¹～R²⁴Each independently represents a hydrogen atom, -R²⁶Or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent. R²¹And R²²May be taken together to form a ring containing nitrogen atoms, R²³And R²⁴May be integrated to form a ring containing a nitrogen atom.

R²⁵represents-SO₃ ^-、-SO₃H、-SO₃ ^-Z1⁺or-SO₂NHR²⁶。

m1 represents an integer of 0 to 5. When m1 is an integer of 2 or more, plural R' s²⁵May be the same or different.

a1 represents an integer of 0 or 1.

X1 represents a halogen atom.

R²⁶Represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.

Z1⁺To represent⁺N(R²⁷)₄、Na⁺Or K⁺。

⁺N(R²⁷)₄4 of (2)²⁷Each independently represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a benzyl group.]

As a representation of R²¹～R²⁴The monovalent aromatic hydrocarbon group of (1) includes the group formed by the above-mentioned R¹～R⁴The same applies to the aromatic hydrocarbon group mentioned above. The hydrogen atom contained in the aromatic hydrocarbon group may be replaced by-SO₃ ^-、-SO₃H、-SO₃ ^-Z1⁺、-SO₃R²⁶or-SO₂NHR²⁶And (4) substitution.

As R²¹～R²⁴Preferably, R is²¹And R²³Is a hydrogen atom, R²²And R²⁴Is a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and hydrogen atoms contained in the aromatic hydrocarbon group are substituted with-SO₃ ^-、-SO₃H、-SO₃ ^-Z1⁺、-SO₃R²⁶or-SO₂NHR²⁶And (4) substitution. Further preferred combinations are as follows: r²¹And R²³Is a hydrogen atom, R²²And R²⁴Is a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and hydrogen atoms contained in the aromatic hydrocarbon group are substituted with-SO₃ ^-Z1⁺or-SO₂NHR²⁶And (4) substitution.

If R is²¹～R²⁴The above-mentioned groups enable the color filter having excellent heat resistance to be formed from the colored curable resin composition of the present invention containing the compound (2 a).

As R²¹And R²²A ring containing a nitrogen atom formed as one body, and R²³And R²⁴Examples of the ring containing a nitrogen atom formed integrally with R¹And R²Are integrated into one bodyThe formed ring is the same as the formed ring. Among them, aliphatic heterocyclic rings are preferable. Examples of the aliphatic heterocyclic ring include the following rings.

As a representation of R²⁶And R²⁷The monovalent saturated hydrocarbon group having 1 to 20 carbon atoms of (A) includes⁸～R¹¹The same groups as those mentioned for the saturated hydrocarbon group in (1).

When R is²¹～R²⁴is-R²⁶When is, -R²⁶Preferably each independently is methyl or ethyl. as-SO₃R²⁶and-SO₂NHR²⁶R in (1)²⁶The alkyl group is preferably a branched alkyl group having 3 to 20 carbon atoms, more preferably a branched alkyl group having 6 to 12 carbon atoms, and still more preferably a 2-ethylhexyl group. If R is²⁶The above-mentioned groups enable the formation of a color filter with less generation of foreign matter from the colored curable resin composition of the present invention containing the compound (2 a).

Z1⁺Is composed of⁺N(R²⁷)₄、Na⁺Or K⁺Preferably, it is⁺N(R²⁷)₄。

As mentioned above⁺N(R²⁷)₄Preferably 4R²⁷At least 2 of them are monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. In addition, 4R²⁷The total number of carbon atoms of (A) is preferably 20 to 80, more preferably 20 to 60. When the compound (2a) contains⁺N(R²⁷)₄Can be prepared from²⁷The colored curable resin composition of the present invention which is the compound (2a) having the above-mentioned group forms a color filter with less generation of foreign matter.

m1 is preferably 1 to 4, more preferably 1 or 2.

Preferred examples of the compound (1a) include a compound represented by the formula (3a) and tautomers thereof (hereinafter, these may be collectively referred to as "compound (3 a)"). When the compound (3a) is used, the content of the compound (3a) in the xanthene dye (Aa) is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more.

[ in the formula (3a), R³¹And R³²Each 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 or a halogen atom, the hydrogen atom contained in the aromatic hydrocarbon group may be substituted with an alkoxy group having 1 to 3 carbon atoms, or the-CH group contained in the saturated hydrocarbon group₂-may be replaced by-O-, -CO-or-NR¹¹-。

R³³And R³⁴Each independently represents an alkyl group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms or an alkylsulfonyl group having 1 to 4 carbon atoms.

R³¹And R³³May be taken together to form a ring containing nitrogen atoms, R³²And R³⁴May be integrated to 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 R³³May be the same or different, and when q is 2 or more, plural R' s³⁴May be the same or different. R¹¹The same meaning as above is indicated.]

As R³¹And R³²Examples of the monovalent saturated hydrocarbon group in (1) include linear alkyl groups 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, and a decyl group; branched alkyl groups such as isopropyl, isobutyl, isopentyl, neopentyl, and 2-ethylhexyl groups; and (c) 3-10 alicyclic saturated hydrocarbon groups such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, tricyclodecyl, and the like.

As the aromatic hydrocarbon group which may be substituted, there may be mentioned¹The aromatic hydrocarbon group in (1) is the same as that in (2).

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

R³¹And R³²Each of the monovalent saturated hydrocarbon groups is preferably a monovalent saturated hydrocarbon group having 1 to 3 carbon atoms.

As a representation of R³³And R³⁴Examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, propyl, butyl, isopropyl, isobutyl, sec-butyl, tert-butyl, and the like.

As R³³And R³⁴Examples of the alkylthio group having 1 to 4 carbon atoms in the group include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, and an isopropylthio group.

As R³³And R³⁴Examples of the alkylsulfonyl group having 1 to 4 carbon atoms in (A) include methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, butylsulfonyl group and isopropylsulfonyl group.

R³³And R³⁴Preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group.

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 (1-42) and (1-21'). In the formula, R²⁶Represents 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. The compounds represented by the formulae (1-1) to (1-29) and (1-21') correspond to the compound (2a), and the compounds represented by the formulae (1-30) to (1-42) correspond to the compound (3 a).

Among them, preferred is a sulfonamide of c.i. acid red 289, a quaternary ammonium salt of c.i. acid red 289, a sulfonamide of c.i. acid violet 102, or a quaternary ammonium salt of c.i. acid violet 102. Examples of such compounds include compounds represented by formulae (1-1) to (1-8), formulae (1-11), and formulae (1-12).

The compounds represented by the formulae (1-30) to (1-39) are preferable from the viewpoint of excellent solubility in organic solvents.

The xanthene dye (Aa2) may be a commercially available xanthene dye (for example, "Chugai amino Fast Pink R-H/C" manufactured by Mizhou chemical industry Co., Ltd. "Rhodamin 6G" manufactured by Takaga chemical industry Co., Ltd.). A commercially available xanthene dye may be used as a starting material and synthesized by referring to Japanese patent application laid-open No. 2010-32999.

(anthraquinone dye (Aa3))

The anthraquinone dye (Aa3) may be a known substance. Examples of the anthraquinone dye (Aa3) include:

c.i. solvent yellow 117 (hereinafter, the description of c.i. solvent yellow is omitted, and only the number is described), 163, 167, and 189,

c.i. solvent orange 77, 86,

c.i. solvent red 111, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 222, 227, 230, 245, 247,

c.i. solvent violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60,

c.i. solvent blue 14, 18, 35, 36, 45, 58, 59: 1. 63, 68, 69, 78, 79, 83, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139,

c.i. solvent green 3, 28, 29, 32, 33,

c.i. acid red 80, c.i.,

c.i. acid green 25, 27, 28, 41,

C.I. acid violet 34,

c.i. acid blue 25, 27, 40, 45, 78, 80, 112

C.i. disperse yellow 51,

C.I. disperse Violet 26, 27,

c.i. disperse blues 1, 14, 56, 60,

c.i. direct blue 40,

c.i. mordant reds 3, 11,

c.i. mordant blue 8, etc.

The anthraquinone dye is preferably a dye soluble in an organic solvent.

More preferably, the anthraquinone dye is blue, violet or red.

The anthraquinone dye (Aa3) is preferably a compound represented by formula (1b) (hereinafter, may be referred to as "compound (1 b)").

[ in the formula (1b), R⁹¹And R⁹²Each independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, an alicyclic hydrocarbon group having 3 to 10 carbon atoms which may have a substituent, or a group represented by the formula (1 b').]

[ formula (1 b'), R⁹³Represents an alkyl group having 1 to 6 carbon atoms, a halogen atom or-SO₃H、-CO₂H、-CO₂R⁹⁴、-NHCOR⁹⁴、-SO₃R⁹⁴or-SO₂NR⁹⁴R⁹⁵。

R⁹⁴Represents a saturated hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a halogen atom, a hydroxyl group or an amino group, or an alicyclic hydrocarbon group having 3 to 10 carbon atoms which may be substituted with a halogen atom, a hydroxyl group or an amino group.

R⁹⁵Represents a hydrogen atom or a saturated hydrocarbon group having 1 to 10 carbon atoms.

r represents an integer of 0 to 5. When R is 2 or more, plural R⁹³May be the same or different.

X⁹¹Represents a single bond or an alkanediyl group having 1 to 6 carbon atoms.]

When the compound (1b) contains-SO₃H and/or-CO₂H, they may form salts (e.g., sodium, potassium).

As R⁹¹And R⁹²Examples of the aliphatic hydrocarbon group include alkyl groups having 1 to 10 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, and 2-ethylhexyl groups.

Examples of the substituent that the aliphatic hydrocarbon group may contain include a hydroxyl group, a halogen atom and the like.

As R⁹¹、R⁹²And R⁹⁴Examples of the alicyclic hydrocarbon group include cycloalkyl groups having 3 to 10 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, tricyclodecyl, and the like.

Examples of the substituent that the alicyclic hydrocarbon group may contain include a hydroxyl group, a halogen atom and the like.

As R⁹³Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, and neopentyl.

As R⁹⁴And R⁹⁵Examples of the saturated hydrocarbon group include alkyl groups having 1 to 10 carbon atoms 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, and a decyl group.

as-CO₂R⁹⁴Examples thereof include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl and tert-butoxyCarbonyl, hexyloxycarbonyl, eicosyloxycarbonyl, and the like.

as-NHCOR⁹⁴Examples thereof include N-acetylamino, N-propionylamino, N-butyrylamino, N-isobutyrylamino, N-pivaloylamino and the like.

as-SO₃R⁹⁴Examples thereof include methoxysulfonyl, ethoxysulfonyl, propoxysulfonyl, tert-butoxysulfonyl, hexyloxysulfonyl and eicosyloxysulfonyl.

as-SO₂NR⁹⁴R⁹⁵Examples thereof include N-methylaminosulfonyl, N-ethylaminosulfonyl, N-propylaminosulfonyl, N-isopropylaminosulfonyl, N-butylaminosulfonyl, N-isobutylaminosulfonyl, N-sec-butylaminosulfonyl, N-tert-butylaminosulfonyl, N-pentylaminosulfonyl, N- (1-ethylpropyl) aminosulfonyl, N- (1, 1-dimethylpropyl) aminosulfonyl, N- (1, 2-dimethylpropyl) aminosulfonyl, N- (2, 2-dimethylpropyl) aminosulfonyl, N- (1-methylbutyl) aminosulfonyl, N- (2-methylbutyl) aminosulfonyl, N- (3-methylbutyl) aminosulfonyl, N-butylaminosulfonyl, and the like, N-monosubstituted aminosulfonyl groups such as N-cyclopentylaminosulfonyl group, N-cyclohexylaminosulfonyl group, N-hexylaminosulfonyl group, N- (1, 3-dimethylbutyl) aminosulfonyl group, N- (3, 3-dimethylbutyl) aminosulfonyl group, N-heptylaminosulfonyl group, N- (1-methylhexyl) aminosulfonyl group, N- (1, 4-dimethylpentyl) aminosulfonyl group, N-octylaminosulfonyl group, N- (2-ethylhexyl) aminosulfonyl group, N- (1, 5-dimethyl) hexylaminosulfonyl group, N- (1,1,2, 2-tetramethylbutyl) aminosulfonyl group, N- (5-aminopentyl) aminosulfonyl group and the like; n, N-disubstituted aminosulfonyl groups such as N, N-dimethylaminosulfonyl group, N-ethylmethylaminosulfonyl group, N-diethylaminosulfonyl group, N-propylmethylaminosulfonyl group, N-isopropylmethylaminosulfonyl group, N-tert-butylmethylaminosulfonyl group, N-butylethylaminosulfonyl group, N-bis (1-methylpropyl) aminosulfonyl group, and N, N-heptylmethylaminosulfonyl group.

As a representation of X⁹¹Examples of the alkanediyl group include a methylene group, an ethylene group, a propane-1, 3-diyl group and a propane-l-diyl groupAlkane-1, 2-diyl, butane-1, 4-diyl, pentane-1, 5-diyl, hexane-1, 6-diyl, ethane-1, 1-diyl, butane-1, 3-diyl, 2-methylpropane-1, 2-diyl, pentane-1, 4-diyl, 2-methylbutane-1, 4-diyl, and the like.

As the compound (1b), compounds represented by the formulae (3-1) to (3-11) can be mentioned.

As the anthraquinone dye (Aa3), c.i. solvent blue 45 is more preferable. The anthraquinone dye can form a coating film or pattern having a higher contrast, and can form a coating film or pattern having less generation of foreign matter and excellent light resistance.

(dye (Aa4))

The dye (Aa4) is not particularly limited as long as it is a dye different from the triarylmethane colorant (Aa1), the xanthene dye (Aa2), and the anthraquinone dye (Aa 3). Examples of the dye (Aa4) include oil-soluble dyes, acid dyes, basic dyes, direct dyes, mordant dyes, ammonium salts of acid dyes, sulfonamide derivatives of acid dyes, and the like. Specifically, there are mentioned compounds classified as dyes (i.e., other than pigments) in The color index (published by The Society of Dyers and Colourists), and known dyes described in dye Note (shikisnsha co., LTD.). Depending on the chemical structure, azo dyes, cyanine dyes, phthalocyanine dyes, naphthoquinone dyes, quinonimine dyes, methine dyes, azomethine dyes, squarylium (squarylium) dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, nitro dyes, and the like can be given. Among them, organic solvent-soluble dyes are preferable.

Specifically, there may be mentioned:

c.i. solvent yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162;

c.i. solvent red 125, 130;

c.i. solvent orange 2, 7, 11, 15, 26, 56;

c.i. solvent blue 37, 67, 70, 90;

c.i. solvent dyes such as c.i. solvent green 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, 34, 35, 37, 42, 44, 57, 66, 73, 80, 88, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 195, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 394, 401, 412, 417, 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 6, 7;

c.i. acid blue 18, 29, 59, 60, 70, 72, 74, 82, 87, 92, 102, 113, 117, 120, 126, 130, 131, 142, 147, 151, 154, 158, 161, 166, 167, 168, 170, 171, 184, 187, 192, 199, 210, 229, 234, 236, 242, 243, 256, 259, 267, 285, 296, 315, 335;

c.i. acid dyes such as c.i. acid green 58, 63, 65, 80, 104, 105, 106, and 109;

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 oranges 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, 6, 8, 15, 22, 25, 57, 71, 76, 78, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196, 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 242, 243, 244, 245, 246, 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293;

c.i. 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. basic blue 3,9, 19, 24, 25, 28, 29, 40, 41, 54, 58, 59, 64, 65, 66, 67, 68;

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

c.i. mordant red 2,3,4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95;

c.i. mordant oranges 3,4,5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;

c.i. mordant violet 1,2, 4,5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;

c.i. mordant blue 2, 7, 9, 12, 13, 15, 16, 19, 20, 21, 22, 26, 30, 31, 39, 40, 41, 43, 44, 49, 53, 61, 74, 77, 83, 84;

c.i. mordant dyes such as c.i. mordant green 1,4, 5, 10, 15, 26, 29, 33, 34, 35, 41, 43, 53; and so on.

(pigment (Ab))

The colored curable resin composition of the present invention may contain a pigment (Ab). The Pigment (Ab) is not particularly limited, and known pigments can be used, and examples thereof include pigments classified as pigments (pigments) in The dye index (published by The Society of Dyers and Colourists).

Examples of the pigment (Ab) include:

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;

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

red pigments such as c.i. pigment red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265;

c.i. pigment blue 15, 15: 3. 15: 4. 15: 6. 60, etc. blue pigments; c.i. pigment violet 1, 19, 23, 29, 32, 36, 38 and the like violet pigment;

green pigments such as c.i. pigment green 7, 36, 58;

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

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

The pigment (Ab) is preferably a blue pigment, more preferably a phthalocyanine pigment and a dioxazine pigment, and further preferably a pigment selected from the group consisting of c.i. pigment blue 15: 6 and pigment violet 23.

As for the pigment (Ab), the following treatments may be carried out as necessary: rosin treatment; surface treatment using a pigment derivative or the like having an acidic group or a basic group introduced thereto; grafting treatment of the pigment surface with a polymer compound or the like; micronization treatment by sulfuric acid micronization method; a washing treatment for removing impurities with an organic solvent, water, or the like; or a treatment for removing ionic impurities by an ion exchange method or the like. The pigment particles are preferably uniform in size.

By adding a pigment dispersant to the pigment and performing dispersion treatment, a pigment dispersion liquid in which the pigment is uniformly dispersed in the pigment dispersant solution can be prepared. The pigment may be dispersed separately or by mixing a plurality of pigments.

Examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, polyamine, acrylic, and other pigment dispersants. The pigment dispersant may be used alone or in combination of 2 or more. Examples of the pigment dispersant include KP (manufactured by shin-Etsu chemical Co., Ltd.), FLOREN (manufactured by Kyoho chemical Co., Ltd.), Solsperse (manufactured by ZENECA Co., Ltd.), EFKA (manufactured by BASF Co., Ltd.), AJISPER (Ajinomoto Fine-technique Co., Ltd., Inc.), Disperbyk (manufactured by Bikk chemical Co., Ltd.), and the like.

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

In the present specification, unless otherwise specified, the compounds exemplified as the respective components may be used alone or in combination of a plurality of them.

The content of the colorant (a) in the colored curable resin is preferably 5% by mass or more and 70% by mass or less, more preferably 5% by mass or more and 60% by mass or less, and further preferably 5% by mass or more and 50% by mass or less, based on the total amount of the solid components. When the content of the colorant (a) is within the above range, desired spectral and color density can be obtained.

In the present specification, the "total amount of solid components" refers to the total amount of components obtained by removing the solvent (E) from the colored curable resin composition of the present invention. The total amount of the solid components and the content of each component corresponding to the total amount of the solid components can be measured by a known analysis method such as liquid chromatography or gas chromatography.

The content of each dye in the colorant (a) may be appropriately selected depending on the desired spectral content, but is preferably in the following range from the viewpoint of forming a coating film or pattern having high contrast.

The content of the triarylmethane colorant (Aa1) in the colorant (a) is preferably 0.5 mass% or more and 98 mass% or less, more preferably 61 mass% or more and 97 mass% or less, and still more preferably 81 mass% or more and 96 mass% or less.

The content of the xanthene dye (Aa2) in the colorant (a) is preferably 0.1% by mass or more and 80% by mass or less, more preferably 0.5% by mass or more and 40% by mass or less, and still more preferably 1% by mass or more and 20% by mass or less.

The content of the anthraquinone dye (Aa3) in the colorant (a) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and still more preferably 1.0% by mass or more. The content of the anthraquinone dye (Aa3) is preferably 50% by mass or less, more preferably 30% by mass or less, and still more preferably 10% by mass or less.

In the colorant (a), the content of the anthraquinone dye (Aa3) is preferably 0.5 to 50 parts by mass, more preferably 1.0 to 35 parts by mass, even more preferably 1.0 to 13.5 parts by mass, and even more preferably 1.2 to 13.1 parts by mass, relative to 100 parts by mass of the triarylmethane colorant (Aa 1).

When the content of the anthraquinone dye (Aa3) is in the above range, a coating film or pattern with higher contrast can be formed.

< resin (B) >

The resin (B) is not particularly limited, and is preferably an alkali-soluble resin (B). The alkali-soluble resin (B) (hereinafter sometimes referred to as "resin (B)") is a copolymer comprising a structural unit derived from at least one monomer (a) selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride.

Examples of such a resin (B) include the following resins [ K1] to [ K6 ].

A resin [ K1] which is a copolymer of a monomer (a) (hereinafter sometimes referred to as "(a)") comprising at least one member selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides, and a monomer (b) (hereinafter sometimes referred to as "(b)") comprising a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond;

a copolymer of a resin [ K2] (a), (b) and a monomer (c) copolymerizable with (a) (which is different from (a) and (b)) (hereinafter, may be referred to as "(c)");

a copolymer of a resin [ K3] (a) and (c);

resin [ K4] a resin obtained by reacting a copolymer formed from (a) and (c) with (b);

resin [ K5] a resin obtained by reacting a copolymer formed from (b) and (c) with (a);

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

Specific examples of (a) include:

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

unsaturated carboxylic 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;

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, bicyclo [2.2.1] hept-2-ene-5, 6-dicarboxylic anhydride and the like;

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;

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

Among them, acrylic acid, methacrylic acid, maleic anhydride and the like are preferable from the viewpoint of copolymerization reactivity and solubility of the obtained resin in an alkaline aqueous solution.

(b) For example, the polymerizable compound is a polymerizable compound containing a cyclic ether structure having 2 to 4 carbon atoms (for example, at least 1 selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and an ethylenically unsaturated bond.

(b) Preferably a monomer containing a cyclic ether having 2 to 4 carbon atoms and a (meth) acryloyloxy group.

In the present specification, "(meth) acrylic acid" means at least 1 selected from the group consisting of acrylic acid and methacrylic acid. The expressions "(meth) acryloyl group" and "(meth) acrylate" and the like have the same meanings.

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 (b1-1) (hereinafter sometimes referred to as "(b 1-1)") having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized, and a monomer (b1-2) (hereinafter sometimes referred to as "(b 1-2)") having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized.

Examples of (b1-1) 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 (glycidyloxymethyl) styrene, 2, 4-bis (glycidyloxymethyl) styrene, 2, 5-bis (glycidyloxymethyl) styrene, 2, 6-bis (glycidyloxymethyl) styrene, poly (ethylene-co-propylene-butylene-co-butylene-co-butylene co-butylene co-butylene co-monomer, co-butylene co-butylene co-butylene co-butylene co-monomer, co-butylene co-monomer, co-butylene co-monomer, co-butylene co-butylene co-monomer, co-butylene co-monomer, and-monomer, co-butylene co-propylene co-monomer, co-butylene co-monomer, co-butylene co-propylene-butylene co-monomer, co-butylene co-monomer, and-butylene co-monomer, 2,3, 4-tris (glycidyloxymethyl) styrene, 2,3, 5-tris (glycidyloxymethyl) styrene, 2,3, 6-tris (glycidyloxymethyl) styrene, 3,4, 5-tris (glycidyloxymethyl) styrene, 2,4, 6-tris (glycidyloxymethyl) styrene and the like.

Examples of (b1-2) include vinylcyclohexene monooxide, 1, 2-epoxy-4-vinylcyclohexane (for example, CELLOXIDE 2000; manufactured by Daicel Corporation), 3, 4-epoxycyclohexylmethyl (meth) acrylate (for example, CYCLOMER A400; manufactured by Daicel Corporation), 3, 4-epoxycyclohexylmethyl (meth) acrylate (for example, CYCLOMER M100; manufactured by Daicel Corporation), the compound represented by formula (II), the compound represented by formula (III), and the like.

[ formula (II) and formula (III) wherein R^aAnd R^bRepresents 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. X^aAnd X^bRepresents a single bond, -R^c-、＊-R^c-O-、＊-R^c-S-or-R^c-NH-。R^cRepresents an alkanediyl group having 1 to 6 carbon atoms. Represents a bond with O.]

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

Examples of the alkyl group in which a hydrogen atom is substituted with 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.

As R^aAnd R^bPreferred examples thereof include a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group and a 2-hydroxyethyl group, and more preferred examples thereof include a hydrogen atom and a methyl group.

Examples of the alkanediyl group having 1 to 6 carbon atoms 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.

As X^aAnd X^bPreferred are a single bond, methylene, ethylene and perylene-CH₂-O-and-CH₂CH₂-O-and more preferably a single bond or O-CH₂CH₂-O- (. sup.p.represents a bond to O).

Examples of the compound represented by the formula (II) include compounds represented by any one of the formulae (II-1) to (II-15). Among them, preferred are compounds represented by the formula (II-1), the formula (II-3), the formula (II-5), the formula (II-7), the formula (II-9) or the formulae (II-11) to (II-15), and more preferred are compounds represented by the formula (II-1), the formula (II-7), the formula (II-9) or the formula (II-15).

Examples of the compound represented by the formula (III) include compounds represented by any one of the formulae (III-1) to (III-15). Among them, preferred are compounds represented by the formula (III-1), the formula (III-3), the formula (III-5), the formula (III-7), the formula (III-9) or the formulae (III-11) to (III-15), and more preferred are compounds represented by the formula (III-1), the formula (III-7), the formula (III-9) or the formula (III-15).

The compound represented by the formula (II) and the compound represented by the formula (III) may be used alone or in combination. When they are used in combination, the content ratio of the compound represented by the formula (II) and the compound represented by the formula (III) is preferably 5: 95-95: 5, more preferably 10: 90-90: 10, more preferably 20: 80-80: 20.

as (b2), a monomer containing an oxetanyl group and a (meth) acryloyloxy group is more preferable. Examples of (b2) include 3-methyl-3-methacryloxymethyloxetane, 3-methyl-3-acryloxymethyloxetane, 3-ethyl-3-methacryloxymethyloxetane, 3-ethyl-3-acryloxymethyloxetane, 3-methyl-3-methacryloxyethyloxetane, 3-methyl-3-acryloxyethyloxetane, 3-ethyl-3-methacryloxyethyloxetane, and 3-ethyl-3-acryloxyethyloxetane.

As (b3), monomers containing a tetrahydrofuranyl group and a (meth) acryloyloxy group are more preferable. Specific examples of (b3) include tetrahydrofurfuryl acrylate (e.g., VISCOAT V #150, manufactured by Osaka organic chemical industries, Ltd.), tetrahydrofurfuryl methacrylate, and the like.

The component (b) is preferably (b1) in view of further improving the reliability of the obtained color filter, such as heat resistance and chemical resistance. Further, (b1-2) is more preferable from the viewpoint of excellent storage stability of the colored curable resin composition.

Examples of (c) include:

methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 (meth) acrylate^2,6]Decan-8-yl esters (in the art)In (b), the term "is used as a common name, and is referred to as" dicyclopentyl (meth) acrylate ". Also, it is sometimes referred to as "tricyclodecanyl (meth) acrylate". ) And (meth) acrylic acid tricyclo [5.2.1.0^2,6]Decen-8-yl ester (commonly known in the art by the names "dicyclopentenyl" (meth) acrylate "), (meth) acrylic acid esters such as dicyclopentenyl oxyethyl (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 [2.2.1] hept-2-ene, 5, 6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, bicyclic unsaturated compounds such as 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, 3-maleimidobenzoic acid-N-succinimidyl ester, 4-maleimidobutyric acid-N-succinimidyl ester, 6-maleimidocaproic acid-N-succinimidyl ester, 3-maleimidopropionic acid-N-succinimidyl ester, 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, styrene, vinyltoluene, benzyl (meth) acrylate, tricyclo [5.2.1.0 ] meth (acrylic acid) are preferable from the viewpoint of copolymerization reactivity and heat resistance^2,6]Decan-8-yl esters, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1]Hept-2-ene.

In the resin [ K1], the ratio of the structural units derived from the respective components among all the structural units constituting the resin [ K1] is preferably,

2 to 60 mol% of a structural unit derived from (a),

40 to 98 mol% of a structural unit derived from (b),

it is more preferable that the content of the organic compound,

10 to 50 mol% of a structural unit derived from (a),

the structural unit derived from (b) is 50 to 90 mol%.

When the ratio of the structural units of the resin [ K1] is within the above range, the colored curable resin composition tends to have excellent storage stability, developability in forming a colored pattern, and solvent resistance of the resulting color filter.

The resin [ K1] can be produced, for example, by referring to the method described in "Experimental method for Polymer Synthesis" (published by Otsuka-shochu Kabushiki Kaisha 1 st edition, 1972, 3 and 1 days), and the citation described in the document.

Specifically, the following methods are mentioned: the reaction vessel is charged with predetermined amounts of (a) and (b), a polymerization initiator, a solvent, etc., and oxygen is replaced with nitrogen, for example, to form a deoxygenated atmosphere, and heating and heat-holding are performed while stirring. The polymerization initiator and the solvent are not particularly limited, and those generally used in the art can be used. Examples of the polymerization initiator include azo compounds (e.g., 2,2 '-azobisisobutyronitrile, 2, 2' -azobis (2, 4-dimethylvaleronitrile), and organic peroxides (e.g., benzoyl peroxide), and examples of the solvent include solvents that can dissolve the monomers, and those described later as the solvent (E) of the colored curable resin composition of the present invention.

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

In the resin [ K2], the ratio of the structural units derived from the respective components among all the structural units constituting the resin [ K2] is preferably,

2 to 45 mol% of a structural unit derived from (a),

2 to 95 mol% of a structural unit derived from (b),

1 to 65 mol% of a structural unit derived from (c),

it is more preferable that the content of the organic compound,

5 to 40 mol% of a structural unit derived from (a),

5 to 80 mol% of a structural unit derived from (b),

the structural unit derived from (c) is 5 to 60 mol%.

When the ratio of the structural units of the resin [ K2] is within the above range, the colored curable resin composition tends to have excellent storage stability, developability in forming a colored pattern, and solvent resistance, heat resistance, and mechanical strength of the obtained color filter.

The resin [ K2] can be produced, for example, in the same manner as the method described as the method for producing the resin [ K1 ].

In the resin [ K3], the ratio of the structural units derived from the respective components among all the structural units constituting the resin [ K3] is preferably,

2 to 60 mol% of a structural unit derived from (a),

40 to 98 mol% of a structural unit derived from (c),

it is more preferable that the content of the organic compound,

10 to 50 mol% of a structural unit derived from (a),

the structural unit derived from (c) is 50 to 90 mol%.

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

The resin [ K4] can be produced by: obtaining a copolymer of (a) and (c), and adding a cyclic ether having 2 to 4 carbon atoms of (b) to a carboxylic acid and/or a carboxylic acid anhydride of (a).

First, a copolymer of (a) and (c) was produced in the same manner as the method described as the method for producing the resin [ K1 ]. In this case, the ratio of the structural units derived from each component is preferably the same as the ratio recited in resin [ K3 ].

Then, a part of the carboxylic acid and/or carboxylic acid anhydride derived from (a) in the copolymer is reacted with the cyclic ether having 2 to 4 carbon atoms of (b).

After the production of the copolymer of (a) and (c), the atmosphere in the flask is replaced with air from nitrogen, and (b), a catalyst (tris (dimethylaminomethyl) phenol or the like) for catalyzing the reaction of a carboxylic acid or a carboxylic anhydride with a cyclic ether, a polymerization inhibitor (hydroquinone or the like) and the like are added to the flask, and the mixture is reacted at 60 to 130 ℃ for 1 to 10 hours, whereby a resin [ K4] can be produced.

The amount of (b) used is preferably 5 to 80 moles, more preferably 10 to 75 moles, based on 100 moles of (a). When the content is within this range, the storage stability of the colored curable resin composition, the developability in forming a pattern, and the balance among solvent resistance, heat resistance, mechanical strength, and sensitivity of the obtained pattern tend to be good. Since the cyclic ether has high reactivity and unreacted (b) hardly remains, 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 parts by mass based on 100 parts by mass of the total amount of (a), (b) and (c). The amount of the polymerization inhibitor used is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total amount of (a), (b) and (c).

The reaction conditions such as the method of feeding, the reaction temperature and time may 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 feeding 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.

The resin [ K5] was subjected to the same procedure as the above-mentioned process for producing the resin [ K1] to obtain a copolymer of (b) and (c) as a first step. As described above, 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 product taken out as a solid (powder) by a method such as reprecipitation.

The ratio of the structural units derived from (b) and (c) is preferably such that, with respect to the total molar number of all the structural units constituting the copolymer,

5 to 95 mol% of a structural unit derived from (b),

5 to 95 mol% of a structural unit derived from (c),

it is more preferable that the content of the organic compound,

10 to 90 mol% of a structural unit derived from (b),

the structural unit derived from (c) is 10 to 90 mol%.

Further, the resin [ K5] can be obtained by reacting the cyclic ether derived from (b) and contained in the copolymer of (b) and (c) with the carboxylic acid or carboxylic acid anhydride contained in (a) under the same conditions as in the process for producing the resin [ K4 ].

The amount of (a) to be reacted with the copolymer is preferably 5 to 80 moles per 100 moles of (b). Since the cyclic ether has high reactivity and unreacted (b) hardly remains, the (b) used for the resin [ K5] is preferably (b1), and more preferably (b 1-1).

The resin [ K6] was obtained by further reacting the resin [ K5] with a carboxylic acid anhydride.

The hydroxyl group produced by the reaction of the cyclic ether with the carboxylic acid or carboxylic anhydride is reacted with the 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, bicyclo [2.2.1] hept-2-ene-5, 6-dicarboxylic anhydride, and the like. The amount of the carboxylic anhydride used is preferably 0.5 to 1 mole per 1 mole of the amount of (a).

Specific examples of the resin (B) include a3, 4-epoxycyclohexylmethyl (meth) acrylate/(meth) acrylic acid copolymer, and a3, 4-epoxytricyclo [5.2.1.0 ] meth (acrylic acid)^2.6]Resins such as decyl ester/(meth) acrylic acid copolymers [ K1]](ii) a Glycidyl (meth) acrylate/(benzyl (meth) acrylate/(meth) acrylic acid copolymer, glycidyl (meth) acrylate/styrene/(meth) acrylic acid copolymer, 3, 4-epoxy tricyclo [5.2.1.0 ] meth) acrylate^2.6]Decyl ester/(meth) acrylic acid/N-cyclohexylmaleimide copolymer, 3, 4-epoxytricyclo [5.2.1.0 ] meth (acrylic acid)^2.6]Resins such as decyl ester/(meth) acrylic acid/vinyltoluene copolymer, 3-methyl-3- (meth) acryloyloxymethyl oxetane/(meth) acrylic acid/styrene copolymer [ K2](ii) a Resins [ K3] such as benzyl (meth) acrylate/(meth) acrylic acid copolymer, styrene/(meth) acrylic acid copolymer, benzyl (meth) acrylate/(tricyclodecanyl (meth) acrylate/(meth) acrylic acid copolymer](ii) a A resin obtained by adding benzyl (meth) acrylate/(meth) acrylic acid copolymer and glycidyl (meth) acrylate, and a resin obtained by adding tricyclodecyl (meth) acrylate/styrene/(meth) acrylate) Resins obtained by adding an acrylic copolymer to glycidyl (meth) acrylate, and resins obtained by adding tricyclodecyl (meth) acrylate/(benzyl (meth) acrylate/(meth) acrylic copolymer to glycidyl (meth) acrylate [ K4]](ii) a Resins such as 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](ii) a A resin obtained by reacting a copolymer of tricyclodecyl (meth) acrylate/(glycidyl (meth) acrylate) with (meth) acrylic acid, and a resin obtained by further reacting with tetrahydrophthalic anhydride [ K6]]And the like.

The resin (B) is preferably one selected from the group consisting of resin [ K1], resin [ K2] and resin [ K3], and more preferably one selected from the group consisting of resin [ K2] and resin [ K3 ]. The colored curable resin composition is excellent in developability with the above resin. From the viewpoint of adhesion between the colored pattern and the substrate, a resin [ K2] is more preferable.

The weight average molecular weight (Mw) of the resin (B) in terms of polystyrene is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and still more preferably 5,000 to 30,000. When the weight average molecular weight (Mw) is within the above range, the following tendency is present: the coating film formed from the colored curable resin composition containing the resin (B) has improved hardness, high residual film ratio, good solubility of unexposed parts in a developing solution, and improved resolution of a colored pattern.

The dispersity [ 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) 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 as the amount (mg) of potassium hydroxide required for neutralizing 1g of the resin (B), and can be determined, for example, by titration using an aqueous potassium hydroxide solution.

The content of the resin (B) is preferably 7 to 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 components. When the content of the resin (B) is within the above range, a colored pattern can be formed, and the resolution and the residual film ratio of the colored pattern tend to be improved.

< polymerizable Compound (C) >)

The polymerizable compound (C) is a compound polymerizable by an active radical and/or an acid generated by the polymerization initiator (D). The polymerizable compound (C) includes a compound having a polymerizable ethylenically unsaturated bond, and is preferably a (meth) acrylate compound.

Examples of the polymerizable compound having 1 ethylenically unsaturated bond include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, and the above-mentioned (a), (b), and (c).

Examples of the polymerizable compound having 2 ethylenically unsaturated bonds include 1, 6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, bis (acryloyloxyethyl) ether of bisphenol a, 3-methylpentanediol di (meth) acrylate, and the like.

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, 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, propylene glycol-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified pentaerythritol tetra (meth) acrylate, and (meth) acrylate, and (meth) acrylate, and (meth) acrylate) and (meth) acrylate, and (meth) acrylate, and (meth) acrylate, and (meth) acrylate, and (meth) acrylate, and (meth) and, Caprolactone-modified dipentaerythritol hexa (meth) acrylate, etc., and among them, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferable.

The weight average molecular weight of the polymerizable compound (C) is preferably 150 to 2,900, more preferably 250 to 1,500.

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 components.

Content ratio of the resin (B) to the polymerizable compound (C) [ resin (B): polymerizable compound (C) ] is preferably 20: 80-80: 20, more preferably 35: 65-80: 20.

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) >)

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 (D) include an O-acyloxime compound, an alkylphenone compound, a bisimidazole compound, a triazine compound, and an acylphosphine oxide compound.

The O-acyloxime compound is a compound having a structure represented by formula (d 1). Hereinafter, the symbol denotes a bond.

Examples of the O-acyloxime compound include N-benzoyloxy-1- (4-phenylthiophenyl) butane-1-one-2-imine, N-benzoyloxy-1- (4-phenylthiophenyl) octane-1-one-2-imine, N-benzoyloxy-1- (4-phenylthiophenyl) -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, 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 (manufactured by BASF corporation), N-1919 (manufactured by 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-thiophenylphenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-thiophenylphenyl) octan-1-one-2-imine, and N-benzoyloxy-1- (4-thiophenylphenyl) -3-cyclopentylpropan-1-one-2-imine, and more preferably N-benzoyloxy-1- (4-thiophenylphenyl) octan-1-one-2-imine. In the case of the O-acyloxime compound, a color filter having high brightness tends to be obtained.

The above-mentioned alkylphenone compound is, for example, a compound having a structure represented by the formula (d2) or a structure represented by the formula (d 3). In the above structure, the benzene ring may have a substituent.

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

Examples of the compound having a structure represented by formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, oligomers of 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one, α -diethoxy acetophenone, benzyl dimethyl ketal, and the like.

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

The biimidazole compound is, for example, a compound represented by the formula (d 5).

[ in the formula (d5), R¹³～R¹⁸Represents an aryl group having 6 to 10 carbon atoms which may have a substituent.]

Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, a toluyl group, a xylyl group, an ethylphenyl group, a naphthyl group and the like, and a phenyl group is preferable.

Examples of the substituent include a halogen atom, an alkoxy group having 1 to 4 carbon atoms, and the like. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and preferably include a chlorine atom. Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group and the like, and a methoxy group is preferable.

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 japanese unexamined patent publication No. 6-75372, japanese unexamined patent publication No. 6-75373, etc.), 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 japanese unexamined patent publication No. 48-38403, a, Japanese patent laid-open publication No. 62-174204 and the like. ) And imidazole compounds in which the phenyl group at the 4,4 ', 5, 5' -position is substituted with a carbonylalkoxy group (see, for example, Japanese patent laid-open publication No. 7-10913). Among them, compounds represented by the following formula and mixtures thereof are preferable.

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 ] -triazine -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.

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, camphorquinone, etc.; 10-butyl-2-chloroacridone, benzil, methyl phenylglyoxylate, titanocene compounds, and the like.

These are preferably used in combination with a polymerization initiation aid (D1) (particularly an amine compound) described later.

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

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

< polymerization initiation assistant (D1) >)

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

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 Micheller ketone), 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 also be used.

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

Examples of the 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 phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthyloxyacetic acid, and the like.

When the polymerization initiator aid (D1) is used, the content thereof 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 amount of the polymerization initiator aid (D1) is within this range, a colored pattern can be formed with higher sensitivity, and the productivity of the color filter tends to be improved.

< solvent (E) >

The solvent (E) is not particularly limited, and a solvent generally used in this field can be used. Examples of the solvent (E) include an ester solvent (a solvent containing-COO-but not-O-in the molecule), an ether solvent (a solvent containing-O-but not-COO-in the molecule), an ether ester solvent (a solvent containing-COO-and-O-in the molecule), a ketone solvent (a solvent containing-CO-but not-COO-in the molecule), an alcohol solvent (a solvent containing OH but not-O-, -CO-, and-COO-, a 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-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl 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 monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 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, and glycerol.

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 above solvents may be used alone, or 2 or more of them may be used in combination.

Among them, propylene glycol monomethyl ether acetate, dipropylene glycol methyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, N-dimethylformamide, N-methylpyrrolidone, and the like are preferable, more preferred are propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethylene glycol monobutyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol, ethyl 3-ethoxypropionate and N-methylpyrrolidone.

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. 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. When the content of the solvent (E) is within the above range, the flatness when the colored curable resin composition is applied becomes good, and the color density does not become insufficient when the color filter is formed, so that the display characteristics tend to become good.

< leveling agent (F) >

Examples of the leveling agent (F) include a silicone surfactant, a fluorine surfactant, and a silicone surfactant containing a fluorine atom. They 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 (manufactured by Toray Dow Corning Corporation), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by shin-Etsu chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, F4440, TSF4445, TSF4446, TSF4452, and TSF4460 (manufactured by Moviive Performance Materials Inc.) can be mentioned.

Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain in the molecule. Specifically, examples thereof include Fluorad (registered trademark) FC430, Fluorad FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megaface F142D, Megaface F171, Megaface F172, Megaface F173, Megaface F177, Megaface F183, Megaface F554, Megaface R30, Megaface RS-718-K (manufactured by DIC Co., Ltd.), EFTOP (registered trademark) EF301, EFTOP EF303, EFTOP EF351, EFTOP EF352(Mitsubishi Material Electronic Chemicals Co., manufactured by Ltd.), Surflon (registered trademark) S381, Surflon S382, Surflon SC101, Surflon SC105 (manufactured by Asahi Katsuki Co., Ltd.) and E5844 (manufactured by Datik fire Chemical Co., Ltd.).

Examples of the above-mentioned silicone surfactant containing a fluorine atom include surfactants containing a siloxane bond and a fluorocarbon chain in the molecule. Specifically, examples thereof include Megaface (registered trademark) R08, Megaface BL20, Megaface F475, Megaface F477, and Megaface F443 (manufactured by DIC corporation).

When the leveling agent (F) is contained, the content thereof is preferably 0.001 mass% or more and 0.2 mass% or less, more preferably 0.002 mass% or more and 0.1 mass% or less, and further preferably 0.005 mass% or more and 0.07 mass% or less, with respect to the total amount of the colored curable resin composition. When the content of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.

< antioxidant (H) >

From the viewpoint of improving the heat resistance and light resistance of the colorant, it is preferable to use the antioxidant singly or in combination of 2 or more. The antioxidant is not particularly limited as long as it is an industrially commonly used antioxidant, and a phenol-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, and the like can be used.

Examples of the phenolic antioxidant include Irganox 1010(イルガノックス 1010: pentaerythrityl tetrakis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ], manufactured by BASF corporation, Irganox 1076(イルガノックス 1076: octadecyl 3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate), manufactured by BASF corporation, Irganox 1330(イルガノックス 1330: 3,3 ', 5,5 ' -hexa-t-butyl-a, a ' - (mesitylene-2, 4, 6-triyl) tri-p-cresol, manufactured by BASF corporation), Irganox 3114(イルガノックス 3114: 1,3, 5-tris (3, 5-di-t-butyl-4-hydroxybenzyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione, manufactured by BASF corporation), Irganox 3790(イルガノックス 3790: 1,3, 5-tris ((4-tert-butyl-3-hydroxy-2, 6-xylyl) methyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione, manufactured by BASF (ltd.), Irganox 1035(イルガノックス 1035: thiodiethylene bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], manufactured by BASF corporation), Irganox 1135(イルガノックス 1135: C7-C9 side chain alkyl ester of 3, 5-bis (1, 1-dimethylethyl) -4-hydroxypropionic acid, manufactured by BASF (ltd.), Irganox 1520L (イルガノックス 1520L: 4, 6-bis (octylthiomethyl) -o-cresol, manufactured by BASF corporation), Irganox 3125(イルガノックス 3125, manufactured by BASF corporation), Irganox 565(イルガノックス 565: 2, 4-bis (n-octylthio) -6- (4-hydroxy-3 ', 5' -di-tert-butylanilino) -1,3, 5-triazine manufactured by BASF (ltd)), Adekastab AO-80(アデカスタブ AO-80: 3, 9-bis (2- (3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy) -1, 1-dimethylethyl) -2,4,8, 10-tetraoxaspiro (5,5) undecane (manufactured by ADEKA), Sumilizer BHT (スミライザー BHT, manufactured by Sumitomo chemical Co., Ltd.), Sumilizer GA-80(スミライザー GA-80, manufactured by Sumitomo chemical Co., Ltd.), Sumilizer GS (スミライザー GS, manufactured by Sumitomo chemical Co., Ltd.), Cyanox 1790(シアノックス 1790, manufactured by Cytec Corporation), vitamin E (Eisai Co., Ltd.), and the like.

Examples of the phosphorus-based antioxidant include IRGAFOS 168(イルガフォス 168: tris (2, 4-di-t-butylphenyl) phosphite, manufactured by BASF corporation), IRGAFOS 12(イルガフォス 12: tris [2- [ [2,4,8, 10-tetra-t-butyldibenzo [ d, f ] [1,3,2] dioxaphosphorin-6-yl ] oxy ] ethyl ] amine, manufactured by BASF corporation), IRGAFOS 38(イルガフォス 38: bis (2, 4-bis (1, 1-dimethylethyl) -6-methylphenyl) ethyl phosphite, manufactured by BASF corporation), Adekab 329K (manufactured by ADEKA), Adekab PEP36 (manufactured by ADEKA), Adekab PEP-8 ((manufactured by SAEKA)), dstab P-EPQ (manufactured by Clariant), Weston 618 (618, manufactured by Weston 618, manufactured by ウェストン 618), Weston 619G (ウェストン 619G, GE Co., Ltd.), Ultranox 626(ウルトラノックス 626, GE Co., Ltd.), Sumilizer GP (スミライザー GP: 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy ] -2,4,8, 10-tetra-tert-butyldibenzo [ d, f ] [1.3.2] dioxaphosphepin (dioxiphospin)) (manufactured by Sumitomo chemical Co., Ltd.), and the like.

Examples of the sulfur-based antioxidant include dialkyl thiodipropionate compounds such as dilauryl thiodipropionate, dimyristyl thiodipropionate and distearyl thiodipropionate, and β -alkylmercaptopropionate compounds of polyhydric alcohols such as tetrakis [ methylene (3-dodecylthio) propionate ] methane.

< other ingredients >

The colored curable resin composition of the present invention may contain additives known in the art, such as a filler, another polymer compound, an adhesion promoter, a light stabilizer, and a chain transfer agent, 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), the solvent (E), the leveling agent (F) used as needed, the polymerization initiation aid (D1), the antioxidant (H), and other components.

Preferably, the pigment (Ab) is contained in the pigment dispersion liquid, and the pigment is dispersed in advance with a part or all of the solvent (E) by using 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 blended as necessary. The residual components are mixed with the pigment dispersion liquid obtained as described above so as to have a predetermined concentration, whereby the target colored curable resin composition can be prepared.

As for the colorant (a), it is preferable that the dye is 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 colored curable resin composition is preferably obtained by filtering and mixing the resin composition with a filter having a pore size of about 0.01 to 10 μm.

< method for manufacturing color filter >

A colored pattern can be produced from the colored curable resin composition of the present invention. The method for producing the colored pattern includes photolithography, ink jet printing, printing and the like, and preferably photolithography.

The photolithography method is as follows: the colored curable resin composition is applied onto a substrate, dried to form a colored composition layer, and the colored composition layer is exposed to light through a photomask and then developed. 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 performing development at the time of exposure. The colored pattern and the colored coating film formed as described above are the color filter of the present invention.

The film thickness of the color filter to be produced is not particularly limited, and can be suitably adjusted according to the purpose, application, and the like, and is, for example, 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, soda lime glass coated with silica on the surface, a resin plate such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, or the like, silicon, a substrate in which an aluminum, silver/copper/palladium alloy thin film, or the like is formed on the substrate, and the like can be used. Other color filter layers, resin layers, transistors, circuits, and the like may be formed on the substrate.

The formation of each color pixel by photolithography can be performed by a known or conventional apparatus and conditions. For example, the following method can be used.

First, a colored curable resin composition is applied onto a substrate, and is dried by removing volatile components such as a solvent by heat drying (prebaking) and/or drying under reduced pressure, thereby obtaining a smooth colored composition layer.

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

The temperature for the heat drying is preferably 30 to 120 ℃, and 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, the drying is preferably carried out under a pressure of 50 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 coloring composition layer is exposed through a photomask for forming a target coloring pattern. The pattern on the photomask is not particularly limited, and a pattern suitable for the intended use may be used.

The light source for exposure is preferably a light source emitting light having a wavelength of 250 to 450 nm. For example, light of less than 350nm may be cut by a filter for cutting the wavelength region, or light of around 436nm, around 408nm, or around 365nm may be selectively extracted by a band pass filter for extracting the wavelength region. Specifically, the light source may be a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp, or the like.

Since parallel light beams can be uniformly irradiated on the entire exposure surface and accurate alignment between the photomask and the substrate on which the colored composition layer is formed can be performed, an exposure apparatus such as a mask aligner or a stepper is preferably used.

The color pattern can be formed on the substrate by bringing the exposed color composition layer into contact with a developer to develop the layer. By performing the development, the unexposed portion of the colored composition layer is dissolved in the developer and 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 basic compound in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. Further, the developer may contain a surfactant. The developing method may be any of a spin-on immersion (dip) 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.

Further, the obtained colored pattern is preferably subjected to post-baking. 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.

The colored curable resin composition of the present invention can produce a color filter having a high contrast. The color filter is useful as a color filter used for a display device (a liquid crystal display device, an organic EL device, electronic paper, or the like) and a solid-state imaging device.

Examples

Hereinafter, the colored curable resin composition of the present invention will be described in more detail by way of examples.

Unless otherwise specified, "%" and "parts" in the examples are mass% and parts by mass.

[ Synthesis example 1: synthesis of triarylmethane colorant (A-I-18)

The following reaction was carried out under nitrogen atmosphere. 15.3 parts of N-methylaniline (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and 60 parts of N, N-dimethylformamide were added to a flask equipped with a condenser and a stirrer, and the mixture was cooled in ice. 5.7 parts of 60% sodium hydride (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added little by little over 30 minutes under ice-cooling, and the mixture was stirred for 1 hour while being warmed to room temperature. 10.4 parts of 4, 4' -difluorobenzophenone (manufactured by Tokyo chemical Co., Ltd.) was added little by little to the reaction mixture, and the mixture was stirred at room temperature for 24 hours. The reaction solution was added little by little to 200 parts of ice water, and then allowed to stand at room temperature for 15 hours, followed by decantation to remove water, thereby obtaining a viscous solid as a residue. To the viscous solid, 60 parts of methanol was added, and the mixture was stirred at room temperature for 15 hours. The precipitated solid was collected by filtration and purified by column chromatography. The purified pale yellow solid was dried under reduced pressure at 60 ℃ to obtain 9.8 parts of a compound represented by the formula (C-I-18).

The following reaction was carried out under nitrogen atmosphere. 8.2 parts of a compound represented by the formula (B-I-7), 10 parts of a compound represented by the formula (C-I-18) and 20 parts of toluene were charged into a flask equipped with a condenser and a stirrer, and then 12.2 parts of phosphorus oxychloride was added thereto, followed by stirring at 95 to 100 ℃ for 3 hours. Next, the reaction mixture was cooled to room temperature, and then diluted with 170 parts of isopropyl alcohol. Next, the diluted reaction solution was poured into 300 parts of saturated brine, and then 100 parts of toluene was added thereto and stirred for 30 minutes. Next, the stirring was stopped, and the mixture was allowed to stand for 30 minutes, thereby separating into an organic layer and an aqueous layer. After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed with 300 parts of saturated brine. After adding an appropriate amount of mirabilite to the organic layer and stirring for 30 minutes, filtration was performed and it was dried to obtain an organic layer. The solvent in the obtained organic layer was distilled off by an evaporator to obtain a bluish violet solid. The bluish violet solid was further dried at 60 ℃ under reduced pressure to obtain 18.4 parts of a compound represented by the formula (A-II-18).

The following reaction was carried out under nitrogen atmosphere. A blue solution was prepared by adding 8 parts of the compound represented by the formula (A-II-18) and 396 parts of methanol to a flask equipped with a condenser and a stirrer and stirring at room temperature for 30 minutes. Next, 396 parts of water was added to the blue solution, and the mixture was further stirred at room temperature for 30 minutes to obtain a reaction solution.

53 parts of water was poured into a beaker, and 11.8 parts of Keggin-type phosphotungstic acid (manufactured by Aldrich) and 53 parts of methanol were further poured into the water and mixed at room temperature to prepare a phosphotungstic acid solution.

The obtained phosphotungstic acid solution was added dropwise to the previously prepared reaction solution over 1 hour. After further stirring at room temperature for 30 minutes, filtration was carried out to obtain a blue solid. After the obtained blue solid was added to 200 parts of methanol and dispersed for 1 hour, the filtration operation was repeated 2 times. The blue solid obtained in this operation was poured into 200 parts of water and dispersed for 1 hour, and then the filtration operation was repeated 2 times. The blue solid obtained in this operation was dried at 60 ℃ under reduced pressure to obtain 17.1 parts of a triarylmethane colorant (A-I-18) represented by the formula (A-I-18).

[ Synthesis example 2: synthesis of xanthene dye (1-38)

20 parts of the compound represented by the formula (1x) and 200 parts of N-propyl-2, 6-dimethylaniline (Wako pure chemical industries, Ltd.) were mixed under dark conditions, and the resulting solution was stirred at 110 ℃ for 6 hours. The obtained reaction solution was cooled to room temperature, and then added to a mixture of 800 parts of water and 50 parts of 35% by weight hydrochloric acid, and stirred at room temperature for 1 hour, whereby crystals were precipitated. The precipitated crystals were collected as a residue after suction filtration and dried to obtain the xanthene dye (1-38) represented by the formula (1-38).

[ Synthesis example 3: synthesis of resin B1 ]

An appropriate amount of nitrogen gas was introduced into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to form a nitrogen atmosphere, 305 parts of ethyl lactate was added thereto, and the mixture was heated to 70 ℃ while stirring and heat-preserved. Then, 46 parts of acrylic acid and 3, 4-epoxytricyclo [5.2.1.0 ] acrylic acid were added^2.6]A solution was prepared by dissolving 240 parts of decyl ester (the compound represented by formula (I-1) and the compound represented by formula (II-1) in 185 parts of ethyl lactate at a molar ratio of 50: 50) and the solution was added dropwise to a flask kept at 70 ℃ over 4 hours using a dropping funnel.

On the other hand, a solution in which 30 parts of 2, 2' -azobis (2, 4-dimethylvaleronitrile), a polymerization initiator, was dissolved in 225 parts of ethyl lactate, was added dropwise to the flask over 4 hours using another dropping funnel. After completion of dropping of the polymerization initiator solution, the solution was held at 70 ℃ for 4 hours, and then cooled to room temperature to obtain a weight average molecular weight (Mw) of 9.1X 10³A resin B1 solution having a dispersity of 2.1, a solid content of 26% by mass, and a solid content acid value of 120 mg-KOH/g. The resin B1 has the following structural units.

[ Synthesis example 4: synthesis of resin B2 ]

An appropriate amount of nitrogen gas was introduced into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace the atmosphere with nitrogen, 371 parts of propylene glycol monomethyl ether acetate was added thereto, and the mixture was heated to 85 ℃ while stirring. Then, 54 parts of acrylic acid and 3, 4-epoxytricyclo [5.2.1.0 ] acrylic acid were added dropwise over 4 hours^2,6]A mixed solution of 225 parts of decyl ester (obtained by mixing the compound represented by the formula (I-1) and the compound represented by the formula (II-1) at a molar ratio of 50: 50), 81 parts of vinyltoluene (isomer mixture), and 80 parts of propylene glycol monomethyl ether acetate.

On the other hand, a mixed solution obtained by dissolving 30 parts of 2, 2-azobis (2, 4-dimethylvaleronitrile) in 160 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. After completion of the dropwise addition, the mixture was held at the same temperature for 4 hours and then cooled to room temperature to obtain a B-type copolymer (resin B2) having a viscosity (23 ℃ C.) of 246mPas, a solid content of 37.5% by mass and a solution acid value of 43 mg-KOH/g. The weight average molecular weight (Mw) of the resin B2 was 1.1X 10⁴The dispersity was 2.01. The resin B2 has the following structural units.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resins obtained in synthesis examples 3 and 4 were measured by GPC under the following conditions.

The device comprises the following steps: k2479 ((manufactured by Kabushizu Shimadzu corporation))

Column: shimadzu Shim GPC-80M

Column temperature: 40 deg.C

Solvent: THF (tetrahydrofuran)

Flow rate: 1.0mL/min

A detector: RI (Ri)

Calibration standard substance: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)

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

[ preparation example 1: preparation of Dispersion (1)

10 parts of the triarylmethane colorant (A-I-18) obtained in Synthesis example 1,2 parts of a dispersant (BYK (registered trademark) -LPN6919 (manufactured by BYK Japan KK)), 4 parts of the resin B2 (converted to solid content) obtained in Synthesis example 4, and 84 parts of propylene glycol monomethyl ether acetate were mixed, and the triarylmethane colorant (A-I-18) was sufficiently dispersed by a bead mill to obtain a dispersion (1).

[ preparation example 2: preparation of Dispersion (2)

12 parts of a pigment (c.i. pigment blue 15: 6), 2 parts of an acrylic pigment dispersant, and 80.5 parts of propylene glycol monomethyl ether acetate were mixed, and the pigment was sufficiently dispersed using a bead mill, thereby obtaining a dispersion (2).

[ examples 1 to 8, comparative examples 1 to 3]

(preparation of colored curable resin composition)

The following were mixed in the parts shown in table 3 to obtain a colored curable resin composition:

dispersion (1) (containing 10 mass% of triarylmethane colorant (A-I-18)),

xanthene dyes (1-38),

anthraquinone dye (C.I. solvent Blue 45; Savinyl Blue RS; manufactured by Clariant Co.),

the dispersion (2),

resin (B): the resin (B) was a resin (1),

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

polymerization initiator (D): n-benzoyloxy-1- (4-phenylthiophenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE 01; manufactured by BASF corporation)

Leveling agent (F): polyether-modified Silicone oil (Toray Silicone SH8400 manufactured by Toray Dow Corning Corporation),

solvent (E): ethyl Lactate (EL) was added to the reaction mixture,

solvent (E): propylene Glycol Monomethyl Ether Acetate (PGMEA).

[ Table 3]

< making of colored patterns >

A colored curable resin composition was applied to a 5cm square glass substrate (EAGLE 2000; manufactured by Corning Inc.) by spin coating, and then prebaked at 100 ℃ for 3 minutes to obtain a colored composition layer. After leaving and cooling, the substrate on which the colored composition layer was formed and a quartz glass photomask were placed at an interval of 100 μm and exposed to an exposure apparatus (TME-150 RSK; manufactured by TOPCON CORPORATION) at 150mJ/cm in an atmospheric air atmosphere²The exposure amount (based on 365 nm) of (A) was irradiated with light. As the photomask, a photomask in which a line-and-space pattern (line-and-space pattern) of 100 μm was formed was used. The colored composition layer after the light irradiation was subjected to immersion development at 24 ℃ for 60 seconds in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide, washed with water, and then baked in an oven at 230 ℃ for 30 minutes to obtain a colored pattern.

< measurement of film thickness >

The film thickness of the obtained colored pattern was measured by using a film thickness measuring apparatus (DEKTAK 3; manufactured by Japan vacuum technology, Ltd.). The results are shown in Table 4. The contents of the respective components in the coloring curable resin compositions obtained by mixing the colorants (a) in the amounts of parts shown in table 3, which were converted so that the total amount of the colorants (a) was 100, are shown in table 4.

< evaluation of color >

The resulting colored pattern was measured for spectral components using a colorimeter (OSP-SP-200; manufactured by Olympus), and xy chromaticity coordinates (x, Y) and tristimulus value Y in the XYZ color system of CIE were measured using a characteristic function of a C illuminant. The larger the value of Y, the higher the lightness. The results are shown in Table 4.

< evaluation of contrast >

A colored coating film was produced in the same manner as in the production of a colored pattern, except that a photomask was not used in the exposure. The obtained colored coating film was measured for contrast with a contrast value of 30000 using a contrast meter (CT-1; color difference meter BM-5A manufactured by Zhaban electric Co., Ltd., manufactured by Topcon, light source; F-10, polarizing film; manufactured by Zhaban electric Co., Ltd.). When the contrast of the colored coating film is high, it is considered that the colored pattern has a high contrast as well. The results are shown in Table 4.

[ Table 4]

According to the colored curable resin compositions of examples 1 to 3 and comparative example 2, colored patterns having a chromaticity coordinate y of 0.095 and a chromaticity coordinate x of 0.136 to 0.139 and similar chromaticities were obtained. In examples 1 to 3, a colored pattern with a higher brightness and a colored coating film with a higher contrast were obtained as compared with comparative example 2.

According to the colored curable resin compositions of examples 4 to 8 and comparative examples 1 and 3, colored patterns having a chromaticity coordinate y of 0.095 and a chromaticity coordinate x of 0.150 to 0.153 and similar chromaticities were obtained. In examples 4 to 8, a colored pattern with high brightness and a colored coating film with high contrast were obtained as compared with comparative examples 1 and 3.

As can be seen from the above, a colored pattern with high contrast can be produced by the colored curable resin composition of the present invention. The color filter obtained from the colored curable resin composition of the present invention has excellent display characteristics and is useful as a material for a liquid crystal display device.

Claims

1. A colored curable resin composition comprising a colorant, a resin, a polymerizable compound and a polymerization initiator,

the colorant comprises a triarylmethane colorant, a xanthene dye, and an anthraquinone dye,

the content of the xanthene dye in the colorant is 1 to 13.5 mass%,

the content of the anthraquinone dye is 0.5-50 parts by mass relative to 100 parts by mass of the triarylmethane colorant.

2. The colored curable resin composition according to claim 1, wherein the content of the anthraquinone dye is 1.0 to 13.5 parts by mass relative to 100 parts by mass of the triarylmethane colorant.

3. A color filter comprising the colored curable resin composition according to claim 1 or 2.

4. A display device comprising the color filter of claim 3.