KR20180038391A - Colored curable resin composition - Google Patents

Abstract

The present invention relates to a colored curable resin composition for forming a color filter which is included in a liquid crystal display device or a solid imaging device. The colored curable resin composition comprises a colorant, a resin, a polymerizable compound and a polymerization initiator. The colorant includes a triarylmethane colorant, a xanthene dye, and a tetraazaporphyrin dye.

Description

COLORED CURABLE RESIN COMPOSITION [0002]

The present invention relates to a colored curable resin composition.

Japanese Patent Application Laid-Open No. 2015-199912 discloses a colored curable resin composition for forming a color filter contained in a liquid crystal display device or the like or a solid-state image pickup element, A curable resin composition is disclosed.

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

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

Wherein the colorant comprises a triarylmethane colorant, a xanthene dye, and a tetraazaporphyrin dye.

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

[3] The colored curable resin composition according to [2], wherein the content of the tetraazaporphyrin dye is 1.0 to 9.0 parts by mass relative to 100 parts by mass of the triarylmethane colorant.

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

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

According to the colored curable resin composition of the present invention, a color filter of high contrast can be obtained.

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) includes a triarylmethane colorant (Aa1), a xanthene dye (Aa2) and a tetraazaporphyrin dye (Aa3). According to the present invention, a high contrast color filter can be manufactured.

≪ Colorant (A) >

The colorant (A) includes triarylmethane colorant (Aa1), xanthene dye (Aa2) and tetraazaporphyrin dye (Aa3). It may also contain a dye different from the triarylmethane colorant (Aa1), the xanthene dye (Aa2) and the tetraazaporphyrin dye (Aa3) (hereinafter sometimes referred to as "dye (Aa4)").

(Triarylmethane colorant (Aa1))

The triarylmethane colorant (Aa1) is a colorant containing a compound having a triarylmethane skeleton in its molecule. As the triarylmethane colorant (Aa1), a compound represented by the formula (A-I) and a tautomer thereof (hereinafter sometimes referred to as "compound (A-I)" collectively) Are preferred.

When the compound (A-I) is used, the content of the compound (A-I) in the triarylmethane colorant (Aal) is preferably 50 mass% or more, more preferably 70 mass% Is not less than 90% by mass. Particularly, it is preferable to use only the compound (A-I) as the triarylmethane colorant (Aa1).

[In the formula (A-I), [Y ² ] ^m- represents an anion of m.

R ⁴¹ to R ⁴⁴ independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may be substituted, a group having an oxygen atom inserted between carbon atoms constituting the alkyl group having 2 to 20 carbon atoms, An aralkyl group which may be substituted, or an aralkyl group which may be substituted. R ⁴¹ and R ⁴² may be bonded to form a ring with the nitrogen atom to which they are bonded, or R ⁴³ and R ⁴⁴ may bond to form a ring together with the nitrogen atom to which they are bonded.

R ⁴⁵ to R ⁵² independently represent an oxygen atom inserted between carbon atoms constituting a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, a saturated hydrocarbon group having 1 to 8 carbon atoms, or an alkyl group having 2 to 8 carbon atoms Or R ⁴⁶ and R ⁵⁰ may combine with each other to form -O-, -NH-, -S- or -SO ₂ -.

Y ¹ represents an optionally substituted aryl group or an optionally substituted heteroaryl group.

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.

m represents an arbitrary natural number.]

[Y ² ] ^m- represents anion of m. The anion represented by [Y ² ] ^m- is not particularly limited as long as it is an anion capable of forming a counter cation with the dye cation, and preferably an anion such as boron anion, Halogen anion such as fluorine, chlorine and anion, and anion having at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and an oxygen atom.

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

[Wherein W ¹ and W ² are independently of each other a group formed by releasing a proton from a compound having two monovalent proton donating substituents. And M represents boron or aluminum.

Examples of the compound having two monovalent proton donating substituents include compounds having two monovalent proton donating substituents (hydroxy group, carboxyl group, etc.), and examples thereof include dihydroxynaphthalene, 2 , 2'-biphenol, 3-hydroxy-2-naphthoic acid which may have a substituent, 2-hydroxy-1-naphthoic acid which may have a substituent, 1-hydroxy Naphthoic acid, 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.

The group in which a proton is released from the compound means a group in which all protons are released from a plurality of proton donating substituents in the compound, and has a group having O ^- or COO ^- .

Examples of the substituent in each of the above compounds include a saturated hydrocarbon group (such as an alkyl group and 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 salicylic acid, 3-methylsalicylic acid, 3-tert-butylsalicylic acid, 3-methoxysalicylic acid, 3-nitrosalicylic acid, 4-trifluoromethylsalicylic acid, Monoaminosalicylic acids such as salicylic acid, 3-amino salicylic acid, 4-amino salicylic acid, 5-amino salicylic acid and 6-amino salicylic acid; (2,4-dihydroxybenzoic acid), 5-hydroxysalicylic acid (2,5-dihydroxybenzoic acid), and 6-hydroxysalicylic acid Monohydroxysalicylic acid such as hydroxysalicylic acid (2,6-dihydroxybenzoic acid); Dihydroxysalicylic acid such as 4,5-dihydroxysalicylic acid and 6-dihydroxysalicylic acid; Monohalosilicic acid such as 3-chlorosalicylic acid, 4-chlorosalicylic acid, 5-chlorosalicylic acid, 6-chlorosalicylic acid, 3-bromosalicylic acid, 4-bromosalicylic acid, 5-bromosalicylic acid and 6-bromosalicylic acid; Dihalosalicylic acids such as 3,5-dichlorosalicylic acid, 3,5-dibromosalicylic acid and 3,5-diiodo salicylic acid; Trihalosalicylic acid such as 3,5,6-trichlorosalicylic acid; And the like.

Examples of the benzylic acid which may have a substituent include the following compounds.

Examples of the mandelic acid which may have a substituent include the following compounds.

Preferred anions represented by the formula (4) include anions (BC-1) to anion (BC-24) having a substituent described in Table 1 and anions Anion (BC-25) to anion (BC-28) represented by the formula (BC-25), formula (BC-26), formula (BC- .

[M represents boron or aluminum]

[In the formulas (BC-25) to (BC-28), M represents boron or aluminum.]

Anion (BC-1), anion (BC-2), anion (BC-3), anion (BC-25), anion (BC- Anion (BC-1), anion (BC-2) and anion (BC-25) BC-2) is more preferable. The compound represented by the formula (A-I) having any of these anions tends to have an excellent solubility in an organic solvent.

Examples of fluorine atoms include groups represented by the formulas (6) to (9).

[In the formula (6), W ³ and W ⁴ independently represent a fluorine atom or an alkyl fluoride group having 1 to 4 carbon atoms, or W ³ and W ⁴ together form a fluorinated alkyl group having 1 to 4 carbon atoms Indicates candidiasis.]

[In the formula (7), W ⁵ , W ⁶ and W ⁷ independently represent a fluorine atom or an alkyl fluoride group having 1 to 4 carbon atoms.]

[In the formula (8), Y ^a represents a fluorinated alkanediyl group having 1 to 4 carbon atoms.]

[In the formula (9), Y ^b represents an alkyl fluoride group having 1 to 4 carbon atoms.]

In the formulas (6), (7) and (9), the fluorinated alkyl group having 1 to 4 carbon atoms is preferably a perfluoroalkyl group having 1 to 4 carbon atoms. Examples of the perfluoroalkyl group having 1 to 4 carbon atoms include -CF ₃ , -CF ₂ CF ₃ , -CF ₂ CF ₂ CF ₃ , -CF (CF ₃ ) ₂ , -CF ₂ CF ₂ CF ₂ CF ₃ , -CF ₂ CF (CF _{3) 2} or -C (CF ₃₎ indicate the _three.

In the formulas (6) and (8), the fluorinated alkanediyl group having 1 to 4 carbon atoms is preferably a perfluoroalkanediyl group, more preferably a -CF ₂ -, -CF ₂ CF ₂ - , -CF ₂ CF ₂ CF ₂ -, -C (CF ₃ ) ₂ - and -CF ₂ CF ₂ CF ₂ CF ₂ -.

Anion represented by the formula (6) (hereinafter sometimes referred to as "anion (6)") includes anions represented by the formulas (6-1) to (6-6) (6-1) "to" anion (6-6) ").

Anion represented by the formula (7-1) (hereinafter sometimes referred to as "anion (7)") is anion represented by the formula (7-1) And the like).

Anion represented by the formula (8) (hereinafter also referred to as anion (8)) may be anion represented by the formula (8-1) to formula (8-4) 8-1) " to " anon (8-4) ".

Anion represented by the formula (9) (hereinafter sometimes referred to as "anion (9)") is anion represented by the formulas (9-1) to (9-4) 9-1) " to " Anion (9-4) ").

[Y ² ] ^m- is preferably a fluorine anion and a polyanion, and is preferably an anion represented by the formula (6), [PW ₁₂ O ₄₀ ] ^3- , [P ₂ W ₁₈ O ₆₂ ] ^6- , [SiW ₁₂ O ₄₀ ] ^4- and [W ₁₀ O ₃₂ ] ^4- are more preferable, and anion represented by formulas (6-1) to (6-5), [PW ₁₂ O ₄₀ ] ^3- , [P ₂ W ₁₈ O ₆₂ ] ^6- is more preferable, and anion represented by the formula (6-2), [PW ₁₂ O ₄₀ ] ^3- is particularly preferable.

m represents an arbitrary natural number and is equivalent to the negative charge of anion [Y ² ] ^m- . The m on the cation side is determined such that the charge of anion [Y ² ] ^m- and cation is equal. m is preferably a natural number of 1 to 10.

The saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ⁴¹ to R ⁴⁴ may be any of linear, branched and cyclic. The number of carbon atoms in the saturated hydrocarbon group is preferably 1 to 10, more preferably 1 to 8, still more preferably 1 to 6, and particularly preferably 1 to 4.

Examples of the straight chain or branched chain saturated hydrocarbon group include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl and decyl groups; An isopropyl group, an isobutyl group, and a 2-ethylhexyl group. The number of carbon atoms of the straight chain or branched chain saturated hydrocarbon 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 a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and an adamantyl group. The number of carbon atoms of the cyclic saturated hydrocarbon group is preferably from 3 to 10, and more preferably from 6 to 10. [

The hydrogen atom of the saturated hydrocarbon group in R ⁴¹ to R ⁴⁴ 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 a dialkylamino group such as a dimethylamino group and the like, 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 by a substituted or unsubstituted amino group or a halogen atom include groups represented by the following formulas. In the following formulas, * represents a bonding bond with a nitrogen atom.

Examples of the group in which an oxygen atom is inserted between the methylene groups (carbon atoms) constituting the alkyl group having 2 to 20 carbon atoms in R ⁴¹ to R ⁴⁴ include groups represented by the following formulas. In the following formulas, * represents a bonding bond with a nitrogen atom. Among them, the group having an oxygen atom inserted between the methylene groups constituting the alkyl group is preferably a group having 2 to 10 carbon atoms, more preferably a group having 2 to 6 carbon atoms. The alkyl group into which the oxygen atom is inserted is preferably a straight chain alkyl group. The number of carbon atoms between oxygen atoms is preferably 1 to 4, and more preferably 2 to 3.

In R ⁴¹ to R ⁴⁴ , the number of carbon atoms of the aryl group is preferably from 6 to 20, more preferably from 6 to 10, and the carbon number of the aralkyl group is preferably from 7 to 20, to be.

Examples of the aryl group represented by R ⁴¹ to R ⁴⁴ include a phenyl group, a naphthyl group and a toluyl group.

Examples of the aryl group in the aralkyl group represented by R ⁴¹ to R ⁴⁴ include a phenyl group and a naphthyl group, and examples of the aralkyl group include groups in which the bond of the aryl group and the alkanediyl group are bonded. The number of carbon atoms of the alkanediyl group is preferably from 1 to 10, more preferably from 1 to 5, and is preferably a linear alkanediyl group. Specific examples of the alkanediyl group include a methylene group, an ethylene group, a propylene group, a butane diyl group and a pentanediyl group. Examples of the aralkyl group include a benzyl group, a phenylethyl group, a naphthylmethyl group and a naphthylethyl group. .

Examples of the substituent which the aryl group and the aralkyl group in R ⁴¹ to R ⁴⁴ may have include a halogen atom such as a fluorine atom, a chlorine atom and an iodine atom; An alkoxy group having 1 to 6 carbon atoms such as methoxy group and ethoxy group; A hydroxy group; An alkylsulfonyl group having 1 to 6 carbon atoms such as a methylsulfonyl group; An alkoxycarbonyl group having 2 to 6 carbon atoms such as a methoxycarbonyl group and an ethoxycarbonyl group; And the like.

Specific examples of the aryl group which may be substituted include, for example, groups represented by the following formulas. In the following formulas, * represents a bonding bond with a nitrogen atom.

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

A ring formed by R ⁴¹ and R ⁴² together with a nitrogen atom to which they are bonded and a ring formed by R ⁴³ and R ⁴⁴ together with a nitrogen atom to which they are bonded include a 5-membered ring such as a pyrrolidine ring; A 6-membered ring such as a morpholine ring, a piperidine ring and a piperazine ring; And the like.

R ⁴¹ to R ⁴⁴ are preferably independently a substituted hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aryl group, or an optionally substituted aralkyl group, in view of ease of synthesis, Independently of each other, a saturated hydrocarbon group having 1 to 8 carbon atoms or a group represented by the following formula. In the following formulas, * represents a bonding bond with a nitrogen atom.

The saturated hydrocarbon group represented by R ⁴⁵ to R ⁵² may be any of straight chain, branched chain and cyclic, and is preferably chain. Examples of the saturated hydrocarbon group represented by R ⁴⁵ to R ⁵² include groups having 1 to 8 carbon atoms among the groups exemplified as the saturated hydrocarbon groups in R ⁴¹ to R ⁴⁴ . The group in which an oxygen atom is inserted between the methylene group (carbon atom) constituting the alkyl group is more preferably an alkyl group having 2 to 8 carbon atoms. As the alkyl group into which the oxygen atom is inserted, a straight chain alkyl group is preferable, and the number of carbon atoms between the oxygen atoms is preferably 1 to 4, and more preferably 2 to 3. For example, a group represented by the following formula can be mentioned. In the following formulas, * represents a bonding bond with a carbon atom.

R ⁴⁵ to R ⁵² are preferably a hydrogen atom, a halogen atom or a saturated hydrocarbon group having 1 to 8 carbon atoms, and independently of each other, a hydrogen atom, a methyl group, a fluorine atom or a chlorine atom Is more preferable.

R ⁴⁶ and R ⁵⁰ may combine with each other to form -O-, -NH-, -S- or -SO ₂ -.

Y ¹ represents an optionally substituted aryl group or an optionally substituted heteroaryl group.

The aryl group may be either a monocyclic or condensed ring, and an aromatic hydrocarbon group 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, .

The heteroaryl group is a substituent derived from an aromatic heterocycle. The aromatic heterocycle may be either a monocyclic or condensed ring, 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 having a nitrogen atom such as a pyrrole ring, oxazole ring, pyrazole ring, imidazole ring and thiazole ring;

A 5-membered ring having an oxygen atom or a sulfur atom such as a furan ring and a thiophene ring;

A 6-membered ring having a nitrogen atom such as a pyridine ring, a pyrimidine ring, a pyridazine ring and a pyrazine ring; And the like. Examples of the aromatic heterocycle of the condensed ring include a condensed ring having a nitrogen atom such as an indole ring, a benzoimidazole ring, a benzothiazole ring and a quinoline ring;

A ring having an oxygen atom or sulfur atom such as benzofuran ring; And the like. As the heteroaryl group which may be substituted, a group represented by the formula (Ab2-x1) is more preferable.

[Ring T ² represents an aromatic heterocycle.

R ⁵³ and R ⁵⁴ independently represent a saturated hydrocarbon group having 1 to 20 carbon atoms which may be substituted, a group having an oxygen atom interposed between carbon atoms constituting the alkyl group having 2 to 20 carbon atoms, an optionally substituted aryl group , An aralkyl group which may be substituted, or a hydrogen atom.

R ⁵⁵ represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an optionally substituted aryl group.

k1 represents 0 or 1;

* Represents the bond with carbocatein.]

Ring T ² represents an aromatic heterocycle, preferably an aromatic heterocycle having 2 to 9 carbon atoms.

Details of R ⁵³ to R ⁵⁵ will be described later.

As the compound (A-I), a compound represented by the formula (A-II) is more preferable.

[In the formula (A-II), [Y ² ] ^m- , R ⁴¹ to R ⁵² and m have the same meanings as defined above.

R ⁵³ and R ⁵⁴ independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may be substituted, a group having an oxygen atom interposed between carbon atoms constituting the alkyl group having 2 to 20 carbon atoms, An aralkyl group which may be substituted, or an aralkyl group which may be substituted.

R ⁵⁵ represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an optionally substituted aryl group.

X represents an oxygen atom, -NR < ⁵⁷ > - or a sulfur atom.

R ⁵⁷ represents 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.

Examples of R ⁵³ and R ⁵⁴ include the same groups as those exemplified for R ⁴¹ to R ⁴⁴ .

Examples of the saturated hydrocarbon group having 1 to 20 carbon atoms in R ⁵⁵ include groups similar to those exemplified as the saturated hydrocarbon groups represented by R ⁴¹ to R ⁴⁴ , preferably an alkyl group having 1 to 10 carbon atoms, May be an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms.

Examples of the group in R ⁵⁵ in which an oxygen atom is inserted between the carbon atoms constituting the alkyl group include groups similar to those exemplified for R ⁴¹ to R ⁴⁴ . As the alkyl group into which the oxygen atom is inserted, a straight-chain alkyl group is preferable. The number of carbon atoms between oxygen atoms is preferably 1 to 4, and more preferably 2 to 3.

In R ⁵⁵ , the carbon number of the aryl group is preferably 6 to 20, more preferably 6 to 10.

As the aryl group, the same groups as those exemplified for R ⁴¹ to R ⁴⁴ are exemplified, and a phenyl group is preferable.

In R ⁵⁵ , examples of the substituent of the aryl group include a halogen atom such as a fluorine atom, a chlorine atom and an iodine atom; An alkoxy group having 1 to 6 carbon atoms such as methoxy group and ethoxy group; A hydroxy group; Sulfamoyl group; An alkylsulfonyl group having 1 to 6 carbon atoms such as a methylsulfonyl group; An alkoxycarbonyl group having 2 to 6 carbon atoms such as a methoxycarbonyl group and an ethoxycarbonyl group; And the like.

R ⁵⁵ is preferably a saturated hydrocarbon group having 1 to 10 carbon atoms or an aryl group which may be substituted, more preferably an alkyl group having 1 to 8 carbon atoms or a halogen atom, An aryl group which may be substituted with an alkoxy group, a hydroxy group or a methylsulfonyl group of 1 to 4 carbon atoms, more preferably a group represented by the following formula: In the following formulas, * represents a bonding bond with a carbon atom.

R ⁵⁷ is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group.

X represents an oxygen atom, -NR < ⁵⁷ > - or a sulfur atom. As the cyclic structure containing X, there may be mentioned, for example, groups represented by the following formulas. In the formulas, R ⁵³ to R ⁵⁵ each have the same meaning as above, and * represents a bonding bond with a carbocatechine. Among them, X is preferably an oxygen atom or a sulfur atom, more preferably a sulfur atom.

Examples of the cation of the formula (A-I) include a cation represented by the formula (A-I-1), and cationic groups 1 through 27 having substituents shown in Table 2 below.

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

As the cation in the formula (A-I), the cation 1 to cation 6, the cation 11 and the cation 12 are preferable, and the cation 1, the cation 2 and the cation 12 are more preferable.

When the compound represented by the formula (A-II) includes a plurality of cations, the plurality of cations may be the same structure or different structures.

(Xanthene dye (Aa2))

The xanthene dye (Aa2) is a dye containing a compound having a xanthene skeleton in the molecule. As the xanthene dye (Aa2), 52, 87, 92, 94, 289, 388, CI (hereinafter, referred to as CI acid red) Acid Violet 9, 30, 102, CI Basic Red 1 (Rhodamine 6G), 2,3,4,8, CI Basic Red 10 (Rhodamine B), 11, CI Basic Violet 10,11,25, CI Solvent Red 218, CI Modernt Red 27, CI Reactive Red 36 (Rose Bengol B), Sulfolodamine G, the xanthene dyes disclosed in Japanese Patent Application Laid-Open No. 2010-32999, and the xanthene dyes described in Japanese Patent No. 4492760 And the like. It is preferable that it is dissolved in an organic solvent.

Among them, as the xanthene dye (Aa2), a dye containing a compound represented by the formula (1a) and a tautomer thereof (hereinafter collectively referred to as "compound (1a)") is preferable. 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 even more preferably 90% by mass or more. In particular, as the xanthene dye (A2), it is preferable to use only the compound (1a).

[In the formula (1a), R ¹ to R ⁴ independently represent 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 and the hydrogen atom contained in the aromatic hydrocarbon group may be substituted with an alkoxy group having 1 to 3 carbon atoms, -CH ₂ - included in the hydrocarbon group may be substituted with -O-, -CO- or -NR ¹¹ -. R ¹ and R ² may be taken together to form a ring containing a nitrogen atom, and R ³ and R ⁴ may be taken together to form a ring containing a nitrogen atom.

R ^{5 _{is, -OH, -SO 3 -, -SO}} 3 H, -SO 3 - Z +, -CO 2 H, -CO 2 - Z +, -CO 2 R 8, -SO 3 R 8 or -SO ₂ NR ⁹ R ¹⁰ .

R ⁶ and R ⁷ independently represent 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, a plurality of R ^{5 s} may be the same or different.

a represents an integer of 0 or 1;

X0 represents a halogen atom.

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

Z ⁺ represents ⁺ N (R < ¹¹ >) ₄ , Na ⁺ or K ⁺ .

R ⁹ and R ¹⁰ independently represent a hydrogen atom or a monovalent saturated hydrocarbon group of 1 to 20 carbon atoms which may have a substituent, and -CH ₂ - included in the saturated hydrocarbon group may be -O-, -CO- , -NH- or -NR ⁸ -, and R ⁹ and R ¹⁰ may be bonded to each other to form a 3- to 10-membered heterocyclic ring containing a nitrogen atom.

⁺ N (R ¹¹⁾ _{4 4} of R ¹¹ are, independently, represent an aralkyl group of a hydrogen atom, a monovalent saturated hydrocarbon group of 1 to 20 carbon atoms or 7 to 10 carbon atoms with each other in the.;

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

The substituent group is the art aromatic hydrocarbon which may have a halogen ^{atom, -R 8, -OH, -OR 8} , -SO 3 -, -SO 3 H, -SO 3 - Z +, -CO 2 H, -CO 2 R _{^{8, -SR 8, -SO 2 R}} 8, -SO 3 R 8 and -SO there may be mentioned ₂ NR ⁹ R ^10, preferably from _{^{-SO 3 -, -SO 3 H,}} -SO 3 - Z + and -SO there may be mentioned ₂ NR ⁹ R ^10, more preferably -SO ₃ ^- Z ⁺ may be mentioned, and -SO ₂ NR ⁹ R ^10. In this case, -SO ₃ ^- Z ⁺ is preferably -SO ₃ ^{- +} N (R ¹¹ ) ₄ . When R ¹ to R ⁴ are these groups, a color filter having less occurrence of foreign matter and excellent in heat resistance can be formed from the colored curable resin composition of the present invention containing the compound (1a).

Examples of the ring formed by R ¹ and R ² together and the ring formed by R ³ and R ⁴ together are, for example, the following.

Examples of the monovalent saturated hydrocarbon group represented by R ⁸ to R ¹¹ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, A straight chain alkyl group of 1 to 20 carbon atoms such as an eicosyl group; A branched chain alkyl group having 3 to 20 carbon atoms such as an isopropyl group, an isobutyl group, an isopentyl group, a neopentyl group and a 2-ethylhexyl group; And alicyclic saturated hydrocarbon groups having 3 to 20 carbon atoms such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and tricyclodecyl group.

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

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

Examples of -SR ⁸ include a methylsulfanyl group, an ethylsulfanyl group, a butylsulfanyl group, a hexylsulfanyl group, a decylsulfanyl group and an icosylsulfanyl group.

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

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

Examples of -SO ₂ NR ⁹ R ^10, a sulfamoyl group;

N-isopropylsulfamoyl group, N-methylsulfamoyl group, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, (1, 1-dimethylpropyl) sulfamoyl group, N- (1, 2-dimethylpropyl) sulfamoyl group, N-methylpyrrolyl group, N- (2-dimethylpropyl) sulfamoyl group, N- (2,2-dimethylpropyl) sulfamoyl group, N- (1-methylbutyl) sulfamoyl group, N- (3-methylbutyl) sulfamoyl group, an N-cyclopentylsulfamoyl group, an N-hexylsulfamoyl group, N- (1,3-dimethylbutyl) sulfamoyl group, N- (1-methylhexyl) sulfamoyl group, N- (1,4-dimethylpentyl) sulfamoyl group, N-octylsulfamoyl group, N- (2-ethylhexyl) An N-1 substituted sulfamoyl group such as a sulfamoyl group, N- (1,5-dimethyl) hexylsulfamoyl group and N- (1,1,2,2-tetramethylbutyl) sulfamoyl group;

N, N-dimethylsulfamoyl group, N, N-ethylmethylsulfamoyl group, N, N-diethylsulfamoyl group, N, N-propylmethylsulfamoyl group, N, N-diethylamino groups such as N, N-tert-butylmethylsulfamoyl group, N, N-butylethylsulfamoyl group, N, N-bis (1-methylpropyl) sulfamoyl group, N-2-substituted sulfamoyl group, and the like.

Examples of the substituent which the monovalent saturated hydrocarbon group in R ⁹ and R ¹⁰ may have include a hydroxyl group and a halogen atom.

Examples of R ^{5 _{-CO 2 H, -CO 2 - Z}} +, -CO 2 R 8, -SO 3 -, -SO 3 - Z +, -SO 3 H and SO ₂ NHR ⁹ are preferred, SO ₃ ^{-, _{-SO 3 - Z +, -SO 3}} H and SO ₂ NHR ⁹ is more preferable.

m is preferably 1 to 4, and more preferably 1 or 2.

The alkyl group in R ⁶ and R ⁷ may be either straight chain or branched chain, and examples thereof include methyl, ethyl, propyl, butyl, pentyl and hexyl.

Examples of the aralkyl group for R ¹¹ include a benzyl group, a phenylethyl group, and a phenylbutyl group.

Z ⁺ is ⁺ N (R ¹¹ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N (R ¹¹ ) ₄ .

As the ⁺ N (R ¹¹ ) ₄ , it is preferable that at least two of the four R ^{11 s} are monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. The total carbon number of four R < ¹¹ > is preferably 20 to 80, more preferably 20 to 60. [ When the ⁺ N (R ¹¹⁾ ₄ present in the compound (1a), R ¹¹ is When these groups, from the colored curable resin composition of the present invention containing compound (1a), it is possible to form a small foreign body color filter .

As a preferable example of the compound (1a), a compound represented by the formula (2a) and a tautomer thereof (hereinafter collectively referred to as "compound (2a)"). When the compound (2a) is used, the content of the compound (2a) in the xanthene dye (A2) is preferably 50 mass% or more, more preferably 70 mass% or more, and even more preferably 90 mass% or more.

[In the formula (2a), R ²¹ to R ²⁴ independently represent a hydrogen atom, -R ^26, or an aromatic hydrocarbon group which may have a substituent and may have a monovalent substituent having 6 to 10 carbon atoms. R ²¹ and R ²² may be taken together to form a ring containing a nitrogen atom, and R ²³ and R ²⁴ may be taken together to form a ring containing a nitrogen atom.

R ²⁵ is -SO ₃ ^- shows the Z1 ⁺ or _{^{-SO 2 NHR 26 -, -SO 3}} H, -SO 3.

m1 represents an integer of 0 to 5; If m1 is an integer of 2 or more, plural R ²⁵ it may be the same and different.

a1 represents an integer of 0 or 1;

X1 represents a halogen atom.

And R < ²⁶ > represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.

Z 1 ⁺ represents ⁺ N (R ²⁷ ) ₄ , Na ⁺ or K ⁺ .

A plurality of R ²⁷ in ⁺ N (R ²⁷ ) ₄ independently represent a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a benzyl group;

Examples of the monovalent aromatic hydrocarbon group represented by R ²¹ to R ²⁴ include the same groups as those described above as the aromatic hydrocarbon group in R ¹ to R ⁴ . The art of hydrogen atoms included aromatic hydrocarbon _{^{groups, -SO 3 -, -SO 3 H}} , -SO 3 - or may Z1 ^+, substituted by -SO ₃ R ²⁶ or -SO ₂ NHR ^26.

As the combination of R ²¹ ~R ^24, R ²¹ and R ²³ is a hydrogen atom, R ²² and R ²⁴ is a monovalent aromatic hydrocarbon group having a carbon number of 6 to 10 valency, hydrogen atoms contained art aromatic hydrocarbon groups, -SO ₃ ^{- _{, -SO 3 H, -SO 3 -}} Z1 +, is preferably substituted by -SO ₃ R ²⁶ or -SO ₂ NHR ^26. More preferable combination is, R ²¹ and R ²³ is a hydrogen atom, R ²² and R ²⁴ is a group 1-valent aromatic hydrocarbon group of a carbon number of 6 to 10, the hydrogen atoms contained art aromatic hydrocarbon groups, -SO ₃ ^- Z1 ⁺ or - SO ₂ NHR ²⁶ . When R ²¹ to R ²⁴ are these groups, a color filter excellent in heat resistance can be formed from the colored curable resin composition of the present invention containing the compound (2a).

As the ring containing the nitrogen atom formed by R ²¹ and R ²² together and the nitrogen atom formed by R ²³ and R ²⁴ together, it is preferable that R ¹ and R ² are formed together And the same ring as the ring. Of these, aliphatic heterocyclic rings are preferred. Examples of the aliphatic heterocycle include the following rings.

Examples of the monovalent saturated hydrocarbon group for R ²⁶ and R ²⁷ include the same groups as those for the saturated hydrocarbon group for R ⁸ to R ¹¹ .

When R ²¹ to R ²⁴ are -R ²⁶ , it is preferable that the plurality of -R ²⁶ independently represent a methyl group or an ethyl group. In addition, as -SO ₃ R ^26, and -SO ₂ NHR ²⁶ R ²⁶ in, a branched chain alkyl group of 3 to 20 carbon atoms are preferable and, a branched chain alkyl group having a carbon number of 6 to 12 and more preferably a 2-ethylhexyl group Is more preferable. When R < ²⁶ > is one of these groups, it is possible to form a color filter which generates less foreign matter from the colored curable resin composition of the present invention containing the compound (2a).

Z 1 ⁺ is ⁺ N (R ²⁷ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N (R ²⁷ ) ₄ .

As the ⁺ N (R ²⁷ ) ₄ , it is preferable that at least two of the four R ^{27 s} are monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. The total carbon number of the four R < ²⁷ > s is preferably 20 to 80, more preferably 20 to 60. [ When the compound (2a) has ⁺ N (R ²⁷ ) ₄ , it is possible to form a color filter which generates less foreign matter from the colored curable resin composition of the present invention containing the compound (2a) wherein R ²⁷ is these groups.

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

As preferred examples of the compound (1a), a compound represented by the formula (3a) and a tautomer thereof (hereinafter collectively referred to as "compound (3a)"). 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 even more preferably 90% by mass or more.

[Wherein, in formula (3a), R ³¹ and R ³² independently represent a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group is an aromatic hydrocarbon group having 6 to 10 carbon atoms or halogen And the hydrogen atom contained in the aromatic hydrocarbon group may be substituted by an alkoxy group having 1 to 3 carbon atoms, and -CH ₂ - included in the saturated hydrocarbon group may be replaced by -O-, -CO- Or -NR < ¹¹ > -.

R ³³ and R ³⁴ independently represent an alkyl group having 1 to 4 carbon atoms, an alkylsulfanyl group having 1 to 4 carbon atoms, or an alkylsulfonyl group having 1 to 4 carbon atoms.

R ³¹ and R ³³ may be taken together to form a ring containing a nitrogen atom, and R ³² and R ³⁴ may be taken together to form a ring containing a nitrogen atom.

p and q independently represent an integer of 0 to 5; When p is 2 or more, a plurality of R ^{33 s} may be the same or different, and when q is 2 or more, a plurality of R ^{34 s} may be the same or different.

R < ¹¹ > has the same meaning as defined above.

Examples of the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms in R ³¹ and R ³² include a monovalent saturated hydrocarbon group 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 straight chain alkyl group having 1 to 10 carbon atoms; A branched chain alkyl group having 3 to 10 carbon atoms such as an isopropyl group, an isobutyl group, an isopentyl group, a neopentyl group and a 2-ethylhexyl group; An alicyclic saturated hydrocarbon group having 3 to 10 carbon atoms such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and tricyclodecyl group.

The aromatic hydrocarbon group which may be contained as a substituent includes the same group as the aromatic hydrocarbon group in R ¹ .

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

R ³¹ and R ³² each independently represent a monovalent saturated hydrocarbon group having 1 to 3 carbon atoms.

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

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

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

R ³³ and R ³⁴ are preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group.

As p and q, an integer of 0 to 2 is preferable, and 0 or 1 is more preferable.

Examples of the compound (1a) include compounds represented by the formulas (1-1) to (1-42) and (1-21 '). In the formulas, R ²⁶ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, preferably a branched alkyl group having 6 to 12 carbon atoms, more preferably a 2-ethylhexyl group. The compounds represented by formulas (1-1) to (1-29) and (1-21 ') correspond to compound (2a), and the compounds represented by formulas (1-30) to The compound corresponds to compound (3a).

Among these, preferred are sulfonamides of C. I. Acid Red 289, quaternary ammonium salts of C. I. Acid Red 289, sulfonamides of C. I. Acid Violet 102 or quaternary ammonium salts of C. I. Acid Violet 102. Examples of such a compound include compounds represented by formulas (1-1) to (1-8), (1-11) and (1-12).

From the viewpoint of excellent solubility in an organic solvent, compounds represented by formulas (1-30) to (1-39) are preferable.

(For example, " Chugai Aminol Fast Pink RH / C ", manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., " Rhodamin 6G " Can be used. It is also possible to synthesize a commercially available xanthene dye as a starting material by referring to Japanese Patent Application Laid-Open No. 2010-32999.

(Tetraazaporphyrin dye (Aa3))

The tetraazaporphyrin dye (Aa3) is a compound having a tetraaza porphyrin skeleton in its molecule. When the tetraazaporphyrin dye is an acidic dye or a basic dye, it may form a salt with any cation or anion.

Among them, as the tetraazaporphyrin dye (Aa3), a dye containing a compound represented by the formula (1c) (hereinafter sometimes referred to as a compound (1c)) is preferable.

[In the formula (1c), R ⁷¹ to R ⁷⁸ independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group which may be substituted, an alkoxy group which may be substituted, An optionally substituted aryloxy group, an optionally substituted aralkyloxy group, or an optionally substituted amino group.

x represents 1 or 2;

When x represents 1, M1 represents a divalent metal atom, a trivalent substituted metal atom, or a metal oxide metal.

When x represents 2, M1 represents a hydrogen atom or a monovalent metal atom.

Examples of the monovalent metal atom include alkali metal atoms such as Na, K and Li.

Examples of the divalent metal atom include Cu, Zn, Fe, Co, Ni, Ru, Rh, Pd, Pt, Mn, Mg Ti, Be, Ca, Ba, Cd, Hg, Pb and Sn.

Trivalent substituted as the metal atom Al-Cl, Ga-Br, Ga-I, In-Cl, Al-C 6 H 5, In-C 6 H 5, Mn (OH), Mn [OSi (CH 3) 3] And Fe-Cl.

Examples of the metal oxide atom include V (= O), Mn (= O), and Ti (= O).

M 1 is preferably a divalent metal atom or a metal oxide metal, more preferably Cu, Zn, Fe, Co, Ni, Pd, Mn, Mg, V (= O) Ni, Pd or V (= O) is more preferable, and Cu, Pd or V (= O) is particularly preferable.

In the compound (1c), a compound wherein x is 1, M 1 is a divalent metal atom or a metal oxide atom, or x is 2 and M 1 is a hydrogen atom are preferable, x is 1, M 1 is a divalent More preferably a compound which is a metal atom or a metal oxide atom.

R ⁷¹ to R ⁷⁸ independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, an optionally substituted alkyl group having 1 to 24 carbon atoms, an optionally substituted alkoxy group having 1 to 24 carbon atoms, An optionally substituted aryl group having 6 to 30 carbon atoms, an optionally substituted aryloxy group having 7 to 30 carbon atoms, an optionally substituted aralkyloxy group having 6 to 30 carbon atoms, or a substituted amino group having 1 to 30 carbon atoms, , A halogen atom, a bromine atom, a cyano group, an optionally substituted alkyl group having 1 to 16 carbon atoms, an optionally substituted alkoxy group having 1 to 16 carbon atoms, an optionally substituted aryl group having 6 to 24 carbon atoms An optionally substituted aryloxy group having 6 to 24 carbon atoms, an optionally substituted aralkyloxy group having 7 to 24 carbon atoms, or a substituted amino group having 1 to 16 carbon atoms, , A fluorine atom, a bromine atom, a cyano group, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted alkoxy group having 1 to 10 carbon atoms, a substituted or unsubstituted C6- An optionally substituted aryl group, an optionally substituted aryloxy group having 6 to 16 carbon atoms, an optionally substituted aralkyloxy group having 7 to 16 carbon atoms, or a substituted amino group having 1 to 12 carbon atoms.

Specific examples of R ⁷¹ to R ^{78 in} the formula (1c) are shown below.

Examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom. Examples of the alkyl group include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, Butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, n-hexyl group, 1-methylpentyl group, Methylhexyl group, 2-ethylhexyl group, 2-propylpentyl group, n-nonyl group, 2,2-dimethylheptyl group, 2-methylheptyl group, N-decyl group, n-dodecyl group, n-dodecyl group, n-heptyl group, n-octyl group, N-hexadecyl group, n-heptadecyl group, 1-octyldonyl group, n-octadecyl group, n-hexadecyl group, N-octyl group, n-tetradecyl group, 1-adamantyl group, cyclopentyl group, and cyclo Branched or cyclic alkyl group composed of only carbon atoms and hydrogen atoms such as hexyl group and norbornyl group.

Examples of the substituent in the alkyl group include an alkyloxy group having 1 to 16 carbon atoms, an alkyloxyalkyloxy group having 2 to 16 carbon atoms, an aralkyloxy group having 7 to 16 carbon atoms, an aryloxy group having 6 to 16 carbon atoms, An alkylthio group, a halogen atom, a halogenoalkyloxy group having 1 to 16 carbon atoms, and an aryloxy group having 6 to 16 carbon atoms.

Specific examples of the alkyl group having a substituent include methoxymethyl, ethoxymethyl, n-butoxymethyl, n-hexyloxymethyl, (2-ethylbutyloxy) methyl, 2-n-butoxyethyl group, 2-n-pentyloxyethyl group, 2-n-hexyloxyethyl group, 2-n-pentyloxyethyl group, (2'-ethylhexyloxy) ethyl group, 2-n-decyloxyethyl group, 2-n-octyloxyethyl group, 2- a 3-methoxypropyl group, a 3-ethoxypropyl group, a 3-n-propyl group, a 2-n-propyloxyethyl group, Propyl group, 3- (n-pentyloxy) propyl group, 3- (n-hexyloxy) propyl group, 3- 3- (n-octyloxy) propyl group, 3- (2'-ethylhexyloxy) propyl group, 3- 3- (n-dodecyloxy) propyl group, 3-cyclohexyloxypropyl group, 4-methoxybutyl group, 4- 4-n-butoxybutyl group, 4-n-hexyloxybutyl group, 4-n-octyloxybutyl group, 4-n-propyloxybutyl group, 4-n-propyloxybutyl group, ethoxyphenyl group, a 5-n-propoxypentyl group, a 6-ethoxyhexyl group, a 6-methoxyphenyl group, a 6- Hexyloxyhexyl group, 6-n-decyloxyhexyl group, 4-methoxycyclohexyl group, 7-ethoxyheptyl group, 7-n-hexyloxyhexyl group, Isopropyldodecyl group, a 12-isopropoxydodecyl group, a tetrahydrofurfuryl group and the like, and the like can be given, for example, An alkyl group having an alkyloxy group;

(2-methoxyethoxy) methyl group, (2-ethoxyethoxy) methyl group, (2-n-butyloxyethoxy) (3-n-butyloxypropyloxy) methyl, (4-methoxybutyloxy) methyl, (3-n-butyloxypropyloxy) Ethoxyethoxy) ethyl group, 2- (2-methoxyethoxy) ethyl group, 2- (2-methoxyethoxy) ethoxyethoxy) propyl group, 3- (2'-methoxypropoxy) propyl group, 3- (2'-isopropyloxypropoxy) An alkyl group having an alkyloxyalkyloxy group such as a propyl group, a 3- (3'-methoxypropyloxy) propyl group and a 3- (3'-ethoxypropyloxy) propyl group; For example, a benzyloxymethyl group, a 2-benzyloxyethyl group, a 2-phenethyloxyethyl group, a 2- (4'-methylbenzyloxy) (4'-methoxybenzyloxy) ethyl group, 2- (4'-chlorobenzyloxy) ethyl group, 3- An alkyl group having an aralkyloxy group such as a (benzyloxymethoxy) ethyl group and a 2- (4'-methylbenzyloxymethoxy) ethyl group;

A 2-methylphenyloxymethyl group, a 4-methoxyphenyloxymethyl group, a 4-fluorophenyloxymethyl group, a 4-chlorophenyloxymethyl group, a 2-chlorophenyloxy group, Methylphenyloxy) ethyl group, 2- (4'-methoxyphenyloxy) ethyl group, 2- (4'- (2'-naphthyloxy) ethyl group, a 3-phenyloxypropyl group, a 2- (2'-naphthyloxy) Butylphenyloxy group, a 3- (2'-naphthyloxy) propyl group, a 4-phenyloxybutyl group, a 4- (2'-chlorophenyloxy) hexyl group, 8-phenyloxyoctyl group, 10-phenyloxydecyl group, 10- (3'-chlorophenyloxy) , A 3- (2'-phenyloxyethoxy) propyl group, and a 4- (2'-phenyloxyethoxy) butyl group;

butylthioethyl group, 2-n-hexylthioethyl group, 2-n-octylthioethyl group, 2-n-butylthiomethyl group, 2-methylthioethyl group, n-butylthioethyl group, 4-n-propylthiobutyl group, 4-n-butylthio group, An alkyl group having an alkylthio group such as a thiobutyl group, a 5-ethylthiopentyl group, a 6-methylthiohexyl group, a 6-ethylthiohexyl group, a 6-n-butylthiohexyl group and an 8-methylthiooctyl group;

Fluorohexyl group, 8-fluorooctyl group, trifluoromethyl group, 1,1-dihydro-perfluoroethyl group, 1,1-dihydro-purple Perfluoro-n-propyl group, 1,1-dihydro-perfluoro-n-propyl group, n-butyl group, 1,1-dihydro-perfluoro-n-pentyl group, 1,1-dihydroperfluoro-n-hexyl group, 6-fluorohexyl group, 4-fluorocyclohexyl Perfluoro-n-decyl group, 1,1-dihydro-perfluoro-n-decyl group, 1,1-dihydro- N-hexadecyl group, perfluoroethyl group, perfluoro-n-propyl group, perfluoro-n-pentadecyl group, perfluoro-n- N-hexyl group, 2,2-bis (trifluoromethyl) propyl group, dichloromethyl group, 2-chloroethyl group, 3- chloropropyl group, An alkyl group having a halogen atom such as a 4-chlorocyclohexyl group, a 7-chloroheptyl group, an 8-chlorooctyl group and a 2,2,2-trichloroethyl group;

Fluoro-n-hexyloxymethyl group, trifluoromethyloxymethyl group, 1,1-dihydro-perfluoroethyloxymethyl group, 1-fluoro-n-propyloxymethyl group, Perfluoro-n-propyloxymethyl group, 2-hydro-perfluoro-2-propyloxymethyl group, 1,1-dihydroperfluoro-n-butyloxymethyl group, 1,1-dihydro- Perfluoro-n-pentyloxymethyl group, 1,1-dihydro-perfluoro-n-hexyloxymethyl group, 1,1-dihydro- perfluoro- (Trifluoromethyl) propyloxymethyl group, a 3-methyl-3-methyl-3-pentyloxy group, (1,1-dihydro-perfluoroethyloxy) ethyl group, 2- (1,1,3-tetrahydro-naphthyloxy) ethyl group, Trihydro-perfluoro-n-propyloxy) ethyl group, 2- (1,1-dihydro-perfluoro-n (Pentyloxy) ethyl group, 2- (6-fluoro-n-hexyloxy) Perfluoro-n-dodecyloxy) propyl group, 3- (1,1-dihydro-perfluoroethyloxy) Perfluoroethyloxy) butyl group, 6- (2-chloroethyloxy) hexyl group and 6- (2-chloroethyloxy) An alkyl group having a halogenoalkyloxy group such as a 1,1-dihydro-perfluoroethyloxy) hexyl group;

4-tert-butylphenyloxymethyl group, 4-n-butylphenyloxymethyl group, 4-tert-butylphenyloxymethyl group, 4-methylphenyloxymethyl group, 4-n-hexylphenyloxymethyl group, 4-n-octylphenyloxymethyl group, 4-n-decylphenyloxymethyl group, 4-methoxyphenyloxymethyl group, 4-ethoxyphenyloxymethyl group, 4 -Butoxyphenyloxymethyl, 4-n-pentyloxyphenyloxymethyl, 4-fluorophenyloxymethyl, 3-fluorophenyloxymethyl, 2-fluorophenyloxymethyl, 3,4-difluorophenyloxy 2-naphthyloxymethyl group, 2-furyloxymethyl group, 1-phenyloxyethyl group, 2-naphthyloxymethyl group, 2-naphthyloxymethyl group, (4'-n-hexylphenyloxy) ethyl group, 2- (4'-methoxyphenyloxy) ethyl group, 2- (4'-fluorophenyloxy) ethyl group, 2- (4'-chlorophenyloxy) ethyl group, 2- (4'- (2'-naphthyloxy) ethyl group, 2-phenyloxypropyl group, 3-phenyloxypropyl group, 3- (4'-naphthyloxy) (2'-ethylphenyloxy) propyl group, a 3- (2'-naphthyloxy) propyl group, a 4-phenyloxybutyl group, (2'-chlorophenyloxy) hexyl group, 8-phenyloxyoctyl group, 10-phenylphenyloxyphenyl group, And an alkyl group having an aryloxy group such as an oxydecyl group and a 10- (3'-methylphenyloxy) decyl group.

As the substituent in the alkoxy group, there may be mentioned the same substituent as the above-mentioned substituent in the alkyl group, and examples of the alkoxy group having a substituent include groups derived from groups described as specific examples of the alkyl group having the above substituent.

Examples of the aryl group include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 2-anthracenyl group, a 1-phenanthryl group, a 2-phenanthryl group, a 3-phenanthryl group, A 2-perylenyl group, a 3-perylenyl group, a 2-fluoranthenyl group, a 3-fluoranthenyl group, a 7-fluoranthenyl group and an 8-fluoranthenyl group.

Examples of the substituent in the aryl group include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms and a halogen atom.

Specific examples of the aryl group having a substituent include a 1-methyl-2-pyrenyl group, a 2- methylphenyl group, a 4-ethylphenyl group, a 4- (4'-tert-butylcyclohexyl) An aryl group having an alkyl group such as a cyclohexylphenyl group, a 4-ethyl-1-naphthyl group, a 6-n-butyl-2-naphthyl group and a 2,4-dimethylphenyl group;

Propoxyphenyl group, a 4-isopropoxyphenyl group, a 3-isopropoxyphenyl group, a 2-ethoxyphenyl group, a 3-n-propoxyphenyl group, An alkoxy group such as an isopropoxyphenyl group, a 2-sec-butoxyphenyl group, a 4-n-pentyloxyphenyl group, a 4-isopentyloxyphenyl group, a 2-methyl-5-methoxyphenyl group, An aryl group having an oxy group;

Phenyl-1-naphthyl group, 1-phenyl-2-naphthyl group, 2-phenyl-2-naphthyl group, An aryl group having an aryl such as a t-butyl group and a 7-phenyl-1-pyrenyl group;

Bromophenyl group, 2-chloro-5-methylphenyl group, 2-chloro-6-methylphenyl group, 2-methylphenyl group, 2-chlorophenyl group, An aryl group having a halogen atom such as a 3-chlorophenyl group, a 2-methoxy-4-fluorophenyl group and a 2-fluoro-4-methoxyphenyl group;

2-trifluoromethylphenyl group, 3-trifluoromethylphenyl group, 4-trifluoromethylphenyl group, 3,5-bistrifluoromethylphenyl group, 4-perfluoroethylphenyl group, 4-methylthiophenyl group, 4 -Ethylthiophenyl group, 4-cyanophenyl group and 3-cyanophenyl group.

As the substituent in the aryloxy group, the same substituent as the substituent in the above-mentioned aryl group can be exemplified. As the aryloxy group having a substituent, the group derived from the group described as a specific example of the aryl group having the above- have.

Examples of the optionally substituted aralkyloxy group include a benzyloxy group, an? -Methylbenzyloxy group, a phenethyloxy group,? -Methylphenethyloxy group,?,? - dimethylbenzyloxy group,?,? - dimethylphenethyloxy group, An aralkyloxy group having an unsubstituted or alkyl group such as a methylphenethyloxy group, a 4-methylbenzyloxy group and a 4-isopropylbenzyloxy group;

An aralkyloxy group having an aryl group or an aralkyl group such as a 4-benzylbenzyloxy group, a 4-phenethylbenzyloxy group or a 4-phenylbenzyloxy group; 4-methoxycarbonyloxy group, 4-methoxybenzyloxy group, 4-n-tetradecyloxybenzyloxy group, 4-n-heptadecyloxybenzyloxy group, An aralkyloxy group having a substituted oxy group such as a vinyloxymethylbenzyloxy group, a 4-benzyloxybenzyloxy group and a 4-phenethyloxybenzyloxy group;

An aralkyloxy group having a hydroxyl group such as a 4-hydroxybenzyloxy group and a 4-hydroxy-3-methoxybenzyloxy group; An aralkyloxy group having a halogen atom such as a 4-fluorobenzyloxy group, a 3-chlorobenzyloxy group and a 3,4-dichlorobenzyloxy group;

2-furfuryloxy group, diphenylmethyloxy group, 1-naphthylmethyloxy group and 2-naphthylmethyloxy group.

Specific examples of the amino group having a substituent include an amino group having an alkyl group such as N-methylamino group, N-ethylamino group, N-n-butylamino group, N-cyclohexylamino group, Nn-octylamino group and N-n-decylamino group;

(4-methylphenyl) amino group, N- (4-n-butylphenyl) amino group, N- (4-methoxyphenyl) amino group, , An amino group having an aralkyl group or an aryl group such as N- (3-fluorophenyl) amino group, N- (4-chlorophenyl) amino group, N- (1-naphthyl) ;

N, N-di-n-hexylamino group, N, N-di-n-octylamino group, N, N-diethylamino group, N-methyl-N-ethylamino group, N-ethyl-N-butylamino group, N-methyl-N-phenylamino group, N- Ethyl-N-phenylamino group and Nn-butyl-N-phenylamino group, or an aralkyl group disubstituted amino group;

(4-methylphenyl) amino group, N, N-di (4-ethylphenyl) amino group, N, N-di (4-tert-butylphenyl) amino group, an N, N-di (4-n-hexylphenyl) amino group, (1-naphthyl) amino group, N, N-di (4-n-butoxyphenyl) amino group, (4-methylphenyl) amino group, N-phenyl-N- (4-octylphenyl) amino group, (4-methoxyphenyl) amino group, an N-phenyl-N- (4-methoxyphenyl) amino group, (1-naphthyl) amino group, N-phenyl-N- (2-naphthyl) amino group, N-phenyl- Phenylphenyl) amino group, and an N-phenyl-N- (4-phenylphenyl) amino group.

Specific examples of the compound (1c) include compounds represented by the formulas (2-1) to (2-38).

As the tetraazaporphyrin dyes, compounds represented by the formula (1c) wherein x is 1, M 1 is a divalent metal atom, R ⁷¹ to R ⁷⁸ are each independently a substituted or unsubstituted alkyl group having 1 to 24 carbon atoms, An optionally substituted aryl group having 6 to 30 carbon atoms, x is 1, M 1 is Cu, R ⁷¹ to R ⁷⁸ are each independently a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, Is more preferably a compound represented by formula (2-29). When the composition contains the tetraazaporphyrin dye, a high-contrast coating film or pattern can be formed, and the generation of foreign matter is also small.

(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 tetraazaporphyrin dye (Aa3), and the dye (Aa4) , Dyes such as basic dyes, direct dyes, mordant dyes, amine salts of acid dyes and sulfonamide derivatives of acid dyes. For example, in the color index (The Society of Dyers and Colourists) , That is, compounds classified into other than pigments, and known dyes described in dyeing notes (Shika Sensha). According to the chemical structure, the azo dyes, cyanine dyes, phthalocyanine dyes, naphthoquinone dyes, quinone imine dyes, methine dyes, azomethine dyes, squarylium dyes, acridine dyes, styryl dyes, coumarin dyes, Nitro dyes and the like. Of these, organic solvent-soluble dyes are preferred.

Specific examples include 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, 56;

C. I. Solvent Blue 37, 67, 70, 90;

C. I. Solvent Green 5, 7, 34, 35 C. I. Solvent Dyes,

CI 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;

CI 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, 418 , 422, 426;

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

C. I. Acid Violet 6, 7;

CI Acid Blue 18, 29, 59, 60, 70, 72, 74, 82, 87, 92, 102, 113, 117, 120, 126, 130, 131, 142, 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,

CI 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;

CI Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211 , 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;

C. I. Direct Orange 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;

CI 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, , 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 242, 243, 244, 245, 246, 247, 248, 249, 250, 251, 252, 256, 257, , 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,

C. I. Basic Blue 3, 9, 19, 24, 25, 28, 29, 40, 41, 54, 58, 59, 64, 65, 66, 67, 68;

C. I. Moderate Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;

CI Modern Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95;

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

C. I. Modern Violet 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;

CI modern blue 2, 7, 9, 12, 13, 15, 16, 19, 20, 21, 22, 26, 30, 31, 39, 40, 41, 43, 44, 49, 53, 77, 83, 84;

C. I. Modern dyes such as C. I. Modern Green 1, 4, 5, 10, 15, 26, 29, 33, 34, 35, 41, 43,

(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. For example, pigments classified in pigments in the color index (The Society of Dyers and Colourists) are cited.

As the pigment (Ab), CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, , 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194 and 214;

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

CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, Pigments;

Blue pigments such as C. I. Pigment Blue 15, 15: 3, 15: 4, 15: 6, and 60; C. I. violet pigments such as Pigment Violet 1, 19, 23, 29, 32, 36, 38;

Green pigments such as C.I. Pigment Green 7, 36, 58;

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

And C. I. Pigment Black 1, 7 black pigments.

The pigment (Ab) is preferably a blue pigment, more preferably a phthalocyanine pigment and a dioxazine pigment, and more preferably at least one selected from the group consisting of CI Pigment Blue 15: 6 and Pigment Violet 23 to be.

The pigment (Ab) may be subjected to a surface treatment using a rosin treatment, a pigment derivative into which an acidic group or a basic group has been introduced, a graft treatment on a pigment surface with a polymer compound or the like, an atomization treatment with a sulfuric acid atomization method, A cleaning treatment with an organic solvent or water for removing the ionic impurities, a removal treatment with an ion exchange method of ionic impurities, or the like may be performed. The particle diameters of the pigments are preferably uniform.

The pigment may be a pigment dispersion in a state of being uniformly dispersed in a pigment dispersant solution by containing a pigment dispersant and carrying out a dispersion treatment. Each of the pigments may be dispersed singly or plural kinds may be mixed and dispersed.

Examples of the pigment dispersant include pigment dispersants such as cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic pigments. These pigment dispersants may be used singly or in combination of two or more. Examples of the pigment dispersant include trade name KP (manufactured by Shin-Etsu Chemical Co., Ltd.), fluorene (manufactured by Kyoeisha Chemical Co., Ltd.), SOLSPERSE (manufactured by Zeneca), EFKA AJISPER (manufactured by Ajinomoto Fine Techno Co., Ltd.) and Disperbyk (manufactured by BYK Chemicals).

When a 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 based on 100 parts by mass of the pigment. When the amount of the pigment dispersant is in the above range, there is a tendency to obtain a pigment dispersion liquid in a uniformly dispersed state.

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

The content of the colorant (A) in the color-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 relative to the total amount of solid matter, Is 5 mass% or more and 50 mass% or less. If the content of the colorant (A) is within the above range, desired spectral or color density can be obtained.

In the present specification, the "total amount of solid content" refers to the total amount of components from which the solvent (E) is removed from the colored curable resin composition of the present invention. The total amount of the solid content and the content of each component in the above can be measured by a known analytical means such as liquid chromatography or gas chromatography.

In the colorant (A), the content of each dye can be appropriately selected in accordance with the desired spectroscopy, but from the viewpoint of forming a high-contrast coating film or pattern, the following range is preferable. The content of the triarylmethane colorant (Aal) in the colorant (A) is preferably 0.5% by mass or more and 98% by mass or less, more preferably 61% by mass or more and 97% by mass or less, Mass% to 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, % Or more and 20 mass% or less.

The content of the tetraazaporphyrin dye (Aa3) in the colorant (A) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, further preferably 1.0 to 9.0% by mass, More preferably 1.2 to 8.8 parts by mass. The content of the tetraazaporphyrin dye (Aa3) in the colorant (A) is preferably 50% by mass or less, more preferably 30% by mass or less, and further preferably 10% by mass or less.

In the colorant (A), the content of the tetraazaporphyrin dye (Aa3) is preferably 0.5 to 50 parts by mass, more preferably 1.0 to 20 parts by mass, per 100 parts by mass of the triarylmethane colorant (Aa1) More preferably 1.2 to 8.8 parts by mass. When the content of the tetraazaporphyrin dye (Aa3) is within the above-mentioned range, a coating film or pattern of higher contrast can be formed.

≪ Resin (B) >

The resin (B) is not particularly limited, but is preferably an alkali-soluble resin (B). The alkali-soluble resin (B) (hereinafter sometimes referred to as " resin (B) ") contains 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 ≪ / RTI >

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

At least one kind of monomer (a) (hereinafter also referred to as "(a)") selected from the group consisting of a resin [K1] unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, a cyclic ether structure having a carbon number of 2 to 4 A monomer (b) having an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b)");

(Hereinafter sometimes referred to as "(c)") which is copolymerizable with the resin (K2) (a), (b) and (a) ≪ / RTI >

Resin [K3] Copolymer of (a) and (c);

Resin [K4] Resin (b) is reacted with the copolymer of (a) and (c);

Resin [K5] Resin (a) is reacted with the copolymer of (b) and (c);

Resin [K6] Resin (a) is reacted with the copolymer of (b) and (c) and further reacted with carboxylic acid anhydride.

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

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

Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept- 5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] hept- [2.2.1] hept-2-ene, and 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;

Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride , Unsaturated dicarboxylic anhydrides such as dimethyl tetrahydrophthalic anhydride and 5,6-dicarboxybicyclo [2.2.1] hept-2-eno anhydride;

(Meth) acryloyloxyalkyl] unsaturated monocarboxylic acid mono [2- (meth) acryloyloxyethyl] phthalic acid mono [2- (meth) acryloyloxyethyl] ester;

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

Of these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferable in view of copolymerization reactivity and solubility of the obtained resin in an aqueous alkali solution.

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

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

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

(b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter may be referred to as "(b1)"), a monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond, (Hereinafter sometimes referred to as "(b2)"), a monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b3)") and the like.

(b1-1) having a structure in which a straight chain or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter may be referred to as "(b1-1)"), alicyclic unsaturated And a monomer (b1-2) having a structure in which a hydrocarbon is epoxidized (hereinafter occasionally referred to as "(b1-2)").

(meth) acrylate,? -methyl glycidyl (meth) acrylate,? -ethyl glycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl Vinylbenzyl glycidyl ether,? -Methyl-o-vinylbenzyl glycidyl ether,? -Methyl-o-vinylbenzyl glycidyl ether,? Methyl-p-vinylbenzyl glycidyl ether, 2,3-bis (glycidyloxymethyl) styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5- Styrenes such as 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene, 2,3,5-tris (glycidyloxymethyl) styrene, (Glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4,6-tris (glycidyloxymethyl) .

(b1-2) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celloxide 2000 manufactured by Daicel Chemical Industries Ltd.), 3,4-epoxycyclohexylmethyl Acrylate (for example, cyclomer A400 manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl (meth) acrylate (e.g., , A compound represented by the formula (II) and a compound represented by the formula (III).

[In the formulas (II) and (III), R ^a and R ^b represent 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 by a hydroxy group. X ^a and X ^b independently represent a single bond, -R ^c -, -R ^c -O- *, -R ^c -S- or * -R ^c -NH-. R ^c represents an alkanediyl group having 1 to 6 carbon atoms.

* Stands for a binding hand with O.]

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

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

Preferable examples of R ^a and R ^b are a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group and a 2-hydroxyethyl group, more preferably 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- Dihexyl group, hexane-1, 6-diyl group and the like.

X ^a and X ^b each independently preferably represent a single bond, a methylene group, an ethylene group, * -CH ₂ -O- and * -CH ₂ CH ₂ -O-, more preferably, , * -CH ₂ CH ₂ -O- (* represents a bond with O).

Examples of the compound represented by the formula (II) include compounds represented by any one of the formulas (II-1) to (II-15), preferably the compounds represented by the formulas (II- ), Formula (II-5), Formula (II-7), Formula (II-9) and Formula (II-11) to Formula (II-15) (II-1), (II-7), (II-9) and (II-15).

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

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

(b2) is more preferably a monomer having an oxetanyl group and a (meth) acryloyloxy group. methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3-methacryloyloxymethyloxetane, 3-methyl- Ethyl-3-acryloyloxymethyloxetane, 3-methyl-3-methacryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyl oxetane, 3- 3-ethyl-3-acryloyloxyethyl oxetane, and the like.

As the monomer (b3), a monomer having a tetrahydrofuryl group and a (meth) acryloyloxy group is more preferable. Specific examples of the compound (b3) include tetrahydrofurfuryl acrylate (for example, Viscot V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.) and tetrahydrofurfuryl methacrylate.

(b) is preferably (b1) in that the reliability of the obtained color filter can be further improved, such as heat resistance and chemical resistance. Further, (b1-2) is more preferable because the storage stability of the colored curable resin composition is excellent.

(meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert- (Meth) acrylate, cyclohexyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclohexyl (meth) acrylate, Dicyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate (referred to in the art as "dicyclopentanyl (Also referred to as "tricyclodecyl (meth) acrylate"), tricyclo [5.2.1.0 ^2,6 ] decen-8-yl (meth) acrylate (Hereinafter referred to as " dicyclopentenyl (meth) acrylate "), di (Meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (Meth) acrylate such as naphthyl (meth) acrylate and benzyl (meth) acrylate;

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

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

2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept- 2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] hept- 2.2.1] hept-2-ene, 5-methoxybicyclo [2.2.1] (2'-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept- Ene, 5,6-dimethoxybicyclo [2.2.1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept- 2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept- 2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept- Cyclohexyl [2.2.1] hept-2-ene, 5,6-bis (Tertiary butoxycarbonyl) bicyclo [2.2.1] hept-2-ene and 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept- Cyclounsaturated compounds;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N- Dicarbonylimide derivatives such as N-succinimidyl-3-maleimidepropionate and N- (9-acridinyl) maleimide;

And examples thereof include styrene,? -Methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, Vinyl, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like.

Of these, styrene, vinyltoluene, benzyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide and bicyclo [2.2.1] hept-2-ene are preferred.

In the resin [K1], the ratio of the structural units derived from each other is preferably within a range of from 0.1%

(a); 2 to 60 mol%

(b); 40 to 98 mol%

, ≪ / RTI >

(a); 10 to 50 mol%

(b); 50 to 90 mol%

Is more preferable.

When the ratio of the structural unit of the resin [K1] is within the above range, there is a tendency that storage stability of the colored curable resin composition, developability in forming a colored pattern, and solvent resistance of the resulting color filter are excellent.

The resin [K1] can be synthesized by a method described in, for example, "Experimental Method of Polymer Synthesis" (published by Otsu Takayuki Co., Ltd., published by Kagaku Dojin, 1st Edition, 1st Edition, March 1, 1972) Can be produced by referring to the cited document.

Specifically, a predetermined amount of (a) and (b), a polymerization initiator and a solvent are placed in a reaction vessel, and oxygen is replaced by, for example, nitrogen to prepare a deoxygen atmosphere, Heating and keeping warm. The polymerization initiator, the solvent and the like are not particularly limited, and those conventionally used in the art can be used. Examples of the polymerization initiator include azo compounds (2,2'-azobisisobutylonitrile, 2,2'-azobis (2,4-dimethylvaleronitrile) and the like) and organic peroxides such as benzoyl peroxide ). The solvent may be any one that dissolves the respective monomers. Examples of the solvent (E) of the colored curable resin composition of the present invention include solvents described later.

As the obtained copolymer, the solution after the reaction may be used as it is, or a concentrated or diluted solution may be used, or it may be taken out as a solid (powder) by re-precipitation or the like. In particular, by using the solvent contained in the colored curable resin composition of the present invention as a solvent during the polymerization, the solution after the reaction can be used as it is for preparing the colored curable resin composition of the present invention, The manufacturing process of the composition can be simplified.

In the resin [K2], the ratio of the structural units derived from each other is preferably from 1 to 100,

(a); 2 to 45 mol%

(b); 2 to 95 mol%

(c); 1 to 65 mol%

, ≪ / RTI >

(a); 5 to 40 mol%

(b); 5 to 80 mol%

(c); 5 to 60 mol%

Is more preferable.

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

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 respective structural units derived from the respective resins is, among the total structural units constituting the resin [K3]

(a); 2 to 60 mol%

(c); 40 to 98 mol%

, ≪ / RTI >

(a); 10 to 50 mol%

(c); 50 to 90 mol%

Is more preferable.

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

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 carboxylic anhydride of (a) .

First, the copolymer of (a) and (c) is prepared in the same manner as described for the method of producing the resin [K1]. In this case, the proportion of the structural units derived from each of them is preferably the same as that of the resin [K3].

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

(a) and (c), the atmosphere in the flask is replaced with air from nitrogen, and (b) a reaction catalyst of a carboxylic acid or a carboxylic anhydride with a cyclic ether (tris (dimethylaminomethyl) Phenol, etc.) and a polymerization inhibitor (hydroquinone or the like) are placed in a flask and reacted at, for example, 60 to 130 ° C for 1 to 10 hours to prepare resin [K4].

(b) is preferably 5 to 80 moles, more preferably 10 to 75 moles, per 100 moles of (a). By setting the content within this range, there is a tendency that the balance between the storage stability of the colored curable resin composition, the developability in forming the pattern, and the solvent resistance, heat resistance, mechanical strength and sensitivity of the resulting pattern tends to be good. (B1) is more preferable, and (b1-1) is more preferable for the resin (K4) because the reactivity of the cyclic ether is high and unreacted (b)

The amount of the reaction catalyst to be used is preferably 0.001 to 5 parts by mass per 100 parts by mass of the total amount of (a), (b) and (c). The amount of the polymerization inhibitor to be used is preferably 0.001 to 5 parts by mass per 100 parts by mass of the total amount of (a), (b) and (c).

The reaction conditions such as the feeding method, the reaction temperature and the time can be appropriately adjusted in consideration of the production equipment or the amount of heat generated by polymerization. Also, in the same manner as in the polymerization conditions, the method of charging and the reaction temperature can be appropriately adjusted in consideration of the production facility or the amount of heat generated by polymerization.

Resin [K5] is a first step, and a copolymer of (b) and (c) is obtained in the same manner as in the above-mentioned production method of resin [K1]. In the same manner as described above, the solution obtained after the reaction may be used as it is, or a concentrated or diluted solution may be used, or it may be taken out as a solid (powder) by a method such as re-precipitation.

the proportion of the structural units derived from (b) and (c) is preferably such that the total number of moles of the total structural units constituting the copolymer is

(b); 5 to 95 mol%

(c); 5 to 95 mol%

, ≪ / RTI >

(b); 10 to 90 mol%

(c); 10 to 90 mol%

Is more preferable.

In addition, by reacting a cyclic ether derived from (b) having a copolymer of (b) and (c) with a carboxylic acid or carboxylic anhydride of (a) in the same manner as in the production of resin [K4] , And resin [K5] can be obtained.

The amount of (a) to be reacted with the above copolymer is preferably 5 to 80 moles per 100 moles of (b). (B1) is more preferable, and (b1-1) is more preferable for the resin (K5) because the reactivity of the cyclic ether is high and unreacted (b)

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

Examples of the carboxylic anhydrides include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6- Tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride. The amount of the carboxylic acid anhydride to be used is preferably 0.5 to 1 mole based on 1 mole of the amount of (a).

Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl (meth) A resin [K1] such as a (meth) acrylic acid copolymer; (Meth) acrylate / styrene / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2 (meth) acrylate / glycidyl .1.0 ^2.6] decyl (meth) acrylate / (meth) acrylic acid / N- cyclohexyl maleimide copolymer, the resin composition comprising 3,4-tricyclo [5.2.1.0 ^2.6] decyl (meth) acrylate / (meth) acrylic acid / Vinyltoluene copolymer, and a resin [K2] such as 3-methyl-3- (meth) acryloyloxymethyloxetane / (meth) acrylic acid / styrene copolymer; (Meth) acrylate / (meth) acrylic acid copolymer, styrene / (meth) acrylic acid copolymer, benzyl (meth) acrylate / tricyclodecyl K3]; A resin obtained by adding glycidyl (meth) acrylate to a benzyl (meth) acrylate / (meth) acrylic acid copolymer, a resin obtained by adding glycidyl (meth) acrylate to a tricyclodecyl (meth) acrylate / styrene / (K4) such as a resin obtained by adding glycidyl (meth) acrylate to a tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer; A resin obtained by reacting a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate with (meth) acrylic acid, a resin obtained by reacting tricyclodecyl (meth) acrylate / styrene / glycidyl (meth) A resin [K5] such as a resin obtained by reacting (meth) acrylic acid with a copolymer; A resin such as a resin obtained by reacting a (meth) acrylic acid with a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate and tetrahydrophthalic anhydride in addition to the resin [K6] have.

The resin (B) is preferably at least one kind selected from the group consisting of the resin [K1], the resin [K2] and the resin [K3], more preferably the resin [K2] ≪ / RTI > If these resins are used, the colored curable resin composition is excellent in developing property. From the viewpoint of adhesion between the colored pattern and the substrate, the 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 molecular weight is in the above range, the hardness of the coating film is improved, the residual film ratio is high, the solubility in the developing solution of the unexposed portion is good, and the resolution of the coloring pattern tends to be improved.

The dispersion degree (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the resin (B) is preferably 1.1 to 6, and more preferably 1.2 to 4.

The acid value of the resin (B) is preferably 50 to 170 mg-KOH / g, more preferably 60 to 150 mg-KOH / g, and even more preferably 70 to 135 mg-KOH / g. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary for neutralizing 1 g of the resin (B) and can be determined by titration using, for example, 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 in the above range, a coloring pattern can be formed, and the resolution and residual film ratio of the coloring pattern tend to be improved.

≪ Polymerizable compound (C) >

The polymerizable compound (C) is a compound which can be polymerized by an active radical and / or an acid generated from the polymerization initiator (D). As the polymerizable compound (C), a compound having a polymerizable ethylenically unsaturated bond and the like are exemplified, and a (meth) acrylic acid ester compound is preferable.

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

Examples of polymerizable compounds having two ethylenically unsaturated bonds include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (Acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, and the like.

The polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenic unsaturated bonds. Examples of such a polymerizable compound include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (Meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hexa (metha) acrylate, tripentaerythritol hepta (Meth) acryloyloxyethyl) isocyanurate, ethylene glycol-modified pentaerythritol tetra (meth) acrylate, ethylene glycol-modified dipentaerythritol hexa (metha) acrylate, propylene glycol-modified pentaerythritol tetra Propylene glycol-modified dipentaerythritol hexa (meth) acrylate, (Meth) acrylate modified with prolactone, pentaerythritol tetra (meth) acrylate modified with caprolactone and dipentaerythritol hexa (meth) acrylate modified with caprolactone, and more preferably dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa ) Acrylate.

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

The content of the polymerizable compound (C) is preferably from 7 to 65% by mass, more preferably from 13 to 60% by mass, and still more preferably from 17 to 55% by mass, based on the total solid content.

The content ratio of the resin (B) to the polymerizable compound (C) (resin (B): polymerizable compound (C)) is preferably 20:80 to 80:20, more preferably 35: 65 to 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 color 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 far as it is a compound capable of generating an active radical or an acid by the action of light or heat and capable of initiating polymerization, and a known polymerization initiator can be used.

Examples of the polymerization initiator (D) include O-acyloxime compounds, alkylphenone compounds, imidazole compounds, triazine compounds and acylphosphine oxide compounds.

The O-acyloxime compound is a compound having a structure represented by formula (d1). Herein, * denotes a combined hand.

Examples of the O-acyloxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy- 1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3- cyclopentylpropan- Yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3- Dimethyl-2,4-dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazol-3-yl] ethan- 1-imine, N- acetoxy- 1- [ ) -9H-carbazol-3-yl] -3-cyclopentylpropan-l-imine and N-benzoyloxy- Yl] -3-cyclopentylpropan-1-one-2-imine and the like. Commercially available products such as Irgacure OXE01 and OXE02 (manufactured by BASF Corporation) and N-1919 (manufactured by ADEKA Corporation) may also be used. Among them, the O-acyloxime compound is preferably an N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan- 1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan- N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine is more preferable. When these O-acyloxime compounds are used, a color filter of high brightness tends to be obtained.

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

Examples of the compound having a structure represented by the formula (d2) include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan- 2- (4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butane- 1- And the like. IRGACURE 369, 907, 379 (manufactured by BASF Co., Ltd.) and the like may be used.

Examples of the compound having a structure represented by the formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2- Propan-1-one, 1-hydroxycyclohexyl phenyl ketone, oligomers of 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan- -Diethoxyacetophenone, benzyldimethylketal, and the like.

From the viewpoint of sensitivity, the alkylphenone compound is preferably a compound having a structure represented by formula (d2).

The non-imidazole compound is, for example, a compound represented by the formula (d5).

[In the formula (d5), R ¹³ to R ¹⁸ independently represent 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 and a naphthyl group, and preferably a phenyl group.

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

Examples of the imidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3- , 4 ', 5,5'-tetraphenylbiimidazole (see JP-A 6-75372 and JP-A 6-75373), 2,2'-bis (2- Chlorophenyl) -4,4 ', 5,5'-tetra (alkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) Phenyl) imidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole (Japanese Examined Patent Publication No. 48-38403, Japanese Unexamined Patent Publication (Kokai) No. 62-174204), and an imidazole compound in which the phenyl group at the 4,4 ', 5,5'-position is substituted by a carboalkoxy group (JP-A No. 7-10913 And the like). Among them, compounds represented by the following formulas 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- (Methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4- Methyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (Trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2, Bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine and 2,4- - [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

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, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra (tert- butylperoxycarbonyl) benzophenone, Benzophenone compounds such as 2,4,6-trimethylbenzophenone; Quinone compounds such as 9,10-phenanthrenequinone, 2-ethyl anthraquinone, camphorquinone, etc .; Butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate and titanocene compounds.

These are preferably used in combination with a polymerization initiator (D1) (particularly, an amine compound) to be described later.

The polymerization initiator (D) is preferably a polymerization initiator comprising at least one member selected from the group consisting of an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, an O-acyloxime compound and a nonimidazole compound, More preferred is a polymerization initiator comprising an O-acyloxime compound.

The content of the polymerization initiator (D) is preferably 0.1 to 40 parts by mass, and 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 initiator (D1) >

The polymerization initiator (D1) is a compound or a sensitizer used for promoting the polymerization of the polymerizable compound initiated by the polymerization initiator. When the polymerization initiator (D1) is included, the polymerization initiator (D1) is usually used in combination with the polymerization initiator (D).

Examples of the polymerization initiator (D1) include an amine compound, an alkoxyanthracene compound, a thioxanthone compound, and a carboxylic acid compound.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethylbenzoate, N, N-dimethyl paratoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'-bis (diethylamino) benzophenone and 4,4 ' -Bis (ethylmethylamino) benzophenone, and the like, preferably 4,4'-bis (diethylamino) benzophenone. And commercially available products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) may be used.

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

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

Examples of the carboxylic acid compound include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, Diphenylacetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine and naphthoxyacetic acid.

When these polymerization initiator (D1) is used, its content is preferably 0.1 to 30 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) 20 parts by mass. When the amount of the polymerization initiator (D1) is within this range, it is possible to form a colored pattern with higher sensitivity, and the productivity of the color filter tends to be improved.

≪ Solvent (E) >

The solvent (E) is not particularly limited, and solvents commonly used in the art can be used. Examples of the solvent (E) include an ester solvent (a solvent containing -COO- in the molecule and not containing -O-), an ether solvent (a solvent containing -O- and -COO- in the molecule) An ester solvent (a solvent containing -COO- and -O- in the molecule), a ketone solvent (a solvent containing -CO- in the molecule and containing no -COO-), an alcohol solvent (containing OH in the molecule, -O-, -CO- and -COO-), aromatic hydrocarbon solvents, amide solvents, and dimethylsulfoxide.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, Butyl, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetone and? -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 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, Methoxypropionate, ethyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, Methyl propionate, ethyl propionate, ethyl propionate, ethyl propionate, ethyl propionate, ethyl propionate, ethyl propionate, ethyl propionate, ethyl propionate, ethyl propionate, ethyl propionate, propyleneglycol monomethyl ether acetate, Ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether And the like Le acetate, diethylene glycol monobutyl ether acetate and dipropylene glycol methyl ether acetate.

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

Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol and glycerin.

Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, and mesitylene.

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

These solvents may be used alone or in combination of two or more.

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, N- Propyleneglycol 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 are more preferable.

The content of the solvent (E) is preferably 70 to 95% by mass, and 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 color-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 at the time of application of the colored curable resin composition becomes good, and the color characteristic tends not to become insufficient when the color filter is formed.

≪ Leveling agent (F) >

Examples of the leveling agent (F) include a silicone surfactant, a fluorine surfactant, and a silicon surfactant having a fluorine atom. These may have a polymerizable group in the side chain.

Examples of the silicone surfactant include a surfactant having a siloxane bond in the molecule. Specific examples thereof include Toray silicon DC3PA, copper SH7PA, copper DC11PA, copper SH21PA, copper SH28PA, copper SH29PA, copper SH30PA, copper SH8400 (manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460 (produced by Momentive Performance Materials Japan Joint-Industrial Company).

Examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain in the molecule. Specific examples thereof include Fluorad (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Corporation), Megapack (registered trademark) F142D, copper F171, copper F172, copper F173, copper F177, copper F183, copper F554 (Manufactured by Mitsubishi Materials Electronics Co., Ltd.), RS-718-K (manufactured by DIC Corporation), FTOP (registered trademark) EF301, EF303, EF351, Surflon (registered trademark) S381, S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemical Research Co., Ltd.).

Examples of the silicon-containing surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain in the molecule. Specific examples thereof include Megapac (registered trademark) R08, Copolymer BL20, Copolymer F475, Copolymer F477 and Copolymer 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 based on the total amount of the colored curable resin composition, More preferably, it is 0.005 mass% or more and 0.07 mass% or less. 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 standpoint of improving the heat resistance and light resistance of the colorant, it is preferable to use the antioxidant alone or in combination of two or more thereof. The antioxidant is not particularly limited as long as it is an antioxidant generally used industrially, and phenol antioxidants, phosphorus antioxidants and sulfur antioxidants can be used.

Examples of the phenolic antioxidant include Irganox 1010 (pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], BASF Co., (Irganox 1076: octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, manufactured by BASF), Irganox 1330: 3 , 3 ", 3", 5,5 ', 5 "-hexa-tert-butyl-a, a', a" - (mesitylene-2,4,6-triyl) (Irganox 3114: 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine- , 6 (1H, 3H, 5H) -tione from BASF, Irganox 3790: 1,3,5-tris ((4-tert- (1H, 3H, 5H) -triene, manufactured by BASF Corporation), Irganox 1035 (manufactured by BASF Corporation), thiadiene (Irganox 1135: benzenepropanoic acid, 3,5-di-tert-butyl-4-hydroxyphenyl) propionate, manufactured by BASF Co., ratio (1,1-dimethylethyl) -4-hydroxy, C7-C9 branched alkyl ester, manufactured by BASF), Irganox 1520L (4,6-bis (octylthiomethyl) , Irganox 3125 (manufactured by BASF), Irganox 565: 2,4-bis (n-octylthio) -6- (4-hydroxyphenyl) (3'5'-di-tert-butyl anilino) -1,3,5-triazine, manufactured by BASF), adekastab AO-80 (adekastab AO- Bis (2- (3- (tert -butyl-4-hydroxy-5-methylphenyl) propionyloxy) -1,1- dimethylethyl) -2,4,8,10-tetraoxaspiro (Sumilizer GA-80, manufactured by Sumitomo Chemical Co., Ltd.) and Smilizer GS (manufactured by Sumitomo Chemical Co., Ltd.) Sumilizer GS, manufactured by Sumitomo Chemical Co., Ltd.), Cyanox 1790 (manufactured by Cytec Co., Ltd.) and vitamin E (manufactured by Eizo K.K.).

As the phosphorus antioxidant, Irgafos 168 (tris (2,4-di-tert-butylphenyl) phosphite, manufactured by BASF), Irgafos 12 (tris [2- [ Butyldibenzo [d, f] [1,3,2] dioxaphosphin-6-yl] oxy] ethyl] amine, produced by BASF Co., (Manufactured by BASF), Adekastab 329K (manufactured by ADEKA Corporation), and the like, Adekastab PEP36 (ADEKA), Adekastab PEP-8 (ADEKA), Sandstab P-EPQ (Clariant), Weston 618 (GE) (Manufactured by GE), Ultronox 626 (manufactured by GE) and Sumilizer GP: 6- [3- (3-tert-butyl-4-hydroxy-5 -Methylphenyl) propoxy] -2,4,8,10-tetra-tert-butyldibenz [d, f] [1.3.2] dioxaphosphepin) (manufactured by Sumitomo Chemical Co., Ltd.) .

Examples of the sulfur-based antioxidant include a dialkyl thiodipropionate compound such as dilauryl thiodipropionate, dimyristyl or distearyl, and a polyol such as tetrakis [methylene (3-dodecylthio) propionate] methane ? -alkylmercaptopropionic acid ester compounds, and the like.

≪ Other components >

The colored curable resin composition of the present invention may contain additives known in the art such as fillers, other polymer compounds, adhesion promoters, light stabilizers, chain transfer agents and the like, if necessary.

≪ Process for producing colored curable resin composition >

The colored curable resin composition of the present invention is a colored curable resin composition comprising a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D) and a solvent (E) (D1), an antioxidant (H), and other components.

The pigment in the case of containing the pigment (Ab) is preferably mixed with part or all of the solvent (E) in advance and dispersed with a bead mill or the like until the average particle diameter of the pigment becomes about 0.2 탆 or less . At this time, if necessary, a part or all of the pigment dispersant and the resin (B) may be blended. The desired colored curable resin composition can be prepared by mixing the remaining components in the thus obtained pigment dispersion to a predetermined concentration.

With respect to the colorant (A), it is preferable that the dye is dissolved in a part or all of the solvent (E) in advance to prepare a solution. It is preferable to filter the solution with a filter having a pore diameter of about 0.01 to 1 mu m.

The colored curable resin composition after mixing is preferably filtered with a filter having a pore size of about 0.01 to 10 mu m.

<Manufacturing Method of Color Filter>

A colored pattern can be formed from the colored curable resin composition of the present invention. Examples of the production method of the coloring pattern include a photolithographic method, an ink-jet method, a printing method and the like, and a photolithographic method is preferable. The photolithography method is a method in which the above-mentioned colored curable resin composition is applied to a substrate, followed by drying to form a colored composition layer, and then the colored composition layer is exposed through a photomask to perform development. In the photolithographic method, a colored coating film which is a cured product of the colored composition layer can be formed by not using a photomask at the time of exposure and / or by not developing it. The coloring pattern or colored coating film thus formed is 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 in accordance with the purpose and application, and is, for example, from 0.1 to 30 탆, preferably from 0.1 to 20 탆, more preferably from 0.5 to 6 탆 .

Examples of the substrate include glass plates such as quartz glass, borosilicate glass, alumina silicate glass and soda lime glass whose surface is coated with a silica, resin plates such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate and the like, silicon, A silver / copper / palladium alloy thin film, or the like is formed. Other color filter layers, resin layers, transistors, circuits, and the like may be formed on these substrates.

The formation of each color pixel by the photolithographic method can be performed by a known apparatus or condition. For example, it can be produced as follows.

First, a colored curable resin composition is coated on a substrate, and then heated and dried (pre-baked) and / or reduced-pressure dried to remove volatile components such as a solvent and dried to obtain a smooth colored composition layer.

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

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

In the case of performing the reduced-pressure drying, it is preferably carried out at a temperature of 20 to 25 캜 under a pressure of 50 to 150 Pa.

The film thickness of the coloring composition layer is not particularly limited and may be suitably selected in accordance with the intended thickness of the color filter.

Next, the coloring composition layer is exposed through a photomask for forming a desired coloring pattern. The pattern on the photomask is not particularly limited, and a pattern according to the intended use is used.

As a light source used for exposure, a light source that generates light having a wavelength of 250 to 450 nm is preferable. For example, light having a wavelength of less than 350 nm is cut using a filter that cuts the wavelength region, or light having a wavelength in the vicinity of 436 nm, around 408 nm, and around 365 nm is extracted using a bandpass filter Or may be selectively taken out. Specifically, examples of the light source include a mercury lamp, a light emitting diode, a metal halide lamp, and a halogen lamp.

It is preferable to use an exposure apparatus such as a mask aligner and a stepper so as to uniformly irradiate the entire surface of the exposure surface with parallel rays or to accurately align the photomask with the substrate on which the coloring composition layer is formed.

The colored composition layer after exposure is brought into contact with a developing solution to develop a colored pattern on the substrate. By the development, the unexposed portion of the colored composition layer is dissolved and removed in the developer. As the developing solution, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogen chloride, sodium carbonate, tetramethylammonium hydroxide or the like is preferable. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01 to 10% by mass, and more preferably 0.03 to 5% by mass. In addition, the developer may contain a surfactant. The developing method may be any of paddle method, dipping method and spray method. Further, the substrate may be inclined at an arbitrary angle during development. After development, it is preferable to rinse with water.

Further, post-baking is preferably performed on the obtained coloring pattern. The post bake temperature is preferably 150 to 250 占 폚, more preferably 160 to 235 占 폚. The post baking time is preferably 1 to 120 minutes, more preferably 10 to 60 minutes.

With the colored curable resin composition of the present invention, a color filter of high contrast can be produced. Such a color filter is useful as a color filter used in display devices (liquid crystal display device, organic EL device, electronic paper, etc.) and solid-state image pickup devices.

[Example]

Hereinafter, the colored curable resin composition of the present invention will be described in more detail by way of examples. In the examples, &quot;% &quot; and &quot; part (s) &quot;

[Synthesis Example 1: Synthesis of triarylmethane colorant (A-I-18)]

The following reaction was carried out in a nitrogen atmosphere. 15.3 parts of N-methylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) and 60 parts of N, N-dimethylformamide were added to a flask equipped with a condenser and a stirrer, and the mixed solution was frozen. 5.7 parts of 60% sodium hydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added little by little over 30 minutes under ice-cooling, followed by stirring for 1 hour while raising the temperature to room temperature. 10.4 parts of 4,4'-difluorobenzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) was added little by little to the reaction solution, which was stirred for 24 hours at room temperature. The reaction solution was added little by little to 200 parts of ice water, and the mixture was allowed to stand at room temperature for 15 hours. When water was removed by decantation, a viscous solid was obtained as a residue. After adding 60 parts of methanol to the resulting solid, the mixture was stirred at room temperature for 15 hours. The precipitated solid was separated by filtration and then purified by column chromatography. The purified light yellow solid was dried at 60 캜 under reduced pressure to obtain 9.8 parts of a compound represented by the formula (C-I-18).

The following reaction was carried out in a nitrogen atmosphere. 8.2 parts of the compound represented by the formula (B-I-7), 10 parts of the compound represented by the formula (C-I-18) and 20 parts of toluene were added to a flask equipped with a stirrer, And the mixture was stirred at 95 to 100 占 폚 for 3 hours. Next, the reaction mixture was cooled to room temperature and then diluted with 170 parts of isopropanol. Next, the diluted reaction solution was poured into 300 parts of saturated saline, 100 parts of toluene was added, and the mixture was stirred for 30 minutes. Then, the stirring was stopped, and the mixture was allowed to stand for 30 minutes. Then, the organic layer and the water layer were separated. After the water layer was discarded by separating operation, the organic layer was washed with 300 parts of saturated saline. An appropriate amount of sodium sulfate was added to the organic layer, followed by stirring for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was subjected to solvent removal with a diverter to obtain a blue-violet solid. Further, the violet solid was dried under reduced pressure at 60 캜 to obtain 18.4 parts of a compound represented by the formula (A-II-18).

The following reaction was carried out in a nitrogen atmosphere. 8 parts of the compound represented by the formula (A-II-18) and 396 parts of methanol were added to a flask equipped with a cooling tube and a stirrer, and the mixture was stirred at room temperature for 30 minutes to prepare a blue solution. 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 added to the beaker, and further 11.8 parts of tungstic acid (manufactured by Aldrich), which is a keel type, and 53 parts of methanol were added to the water and mixed at room temperature to prepare a tungstic acid solution.

The resulting tungstic acid solution was added dropwise to the previously prepared reaction solution for 1 hour. The mixture was further stirred at room temperature for 30 minutes, and then filtered to obtain a blue solid. The resulting blue solid was added to 200 parts of methanol, dispersed for 1 hour, and then filtered twice. The blue solid obtained by the above operation was added to 200 parts of water, dispersed for 1 hour, and filtered, and the operation of filtration was repeated twice. The blue solid obtained by this operation was dried at 60 캜 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 (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed under light shielding conditions and the resulting solution was stirred at 110 ° C for 6 hours. The resulting reaction solution was cooled to room temperature, added to a mixed solution of 800 parts of water and 50 parts of 35 mass% hydrochloric acid, and stirred at room temperature for 1 hour, and crystals were precipitated. The precipitated crystals were collected as a residue of suction filtration and dried to obtain a xanthene dye (1-38) represented by the formula (1-38).

[Synthesis Example 3: Synthesis of tetraazaporphyrin dye (Aa3-1)]

(2-29), formula (2-39), formula (2-40) and formula (2-41) by a synthesis method described in Japanese Patent No. 3961078. The tetraazaporphyrin dye Lt; / RTI &gt; compound).

[Synthesis Example 4: Synthesis of Resin B1]

In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, an appropriate amount of nitrogen was allowed to flow to make a nitrogen atmosphere, 305 parts of ethyl lactate was added, and the mixture was heated to 70 deg. Next, 46 parts of acrylic acid, and 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl acrylate (compound represented by formula (I-1) and compound represented by formula (II-1) : 50) was dissolved in 185 parts of ethyl lactate, and the resulting solution was added dropwise to a flask kept at 70 캜 for 4 hours using a dropping funnel.

On the other hand, a solution prepared by dissolving 30 parts of polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) in 225 parts of ethyl lactate was added dropwise to the flask over 4 hours using another dropping funnel. After the dropwise addition of the polymerization initiator solution was completed, the solution was maintained at 70 占 폚 for 4 hours and then cooled to room temperature to obtain a copolymer having a weight average molecular weight (Mw) of 9.1 占⁰³ , a dispersion degree of 2.1, a solid content of 26% A resin B1 solution having a solid acid value of 120 mg-KOH / g was obtained. Resin B1 has a structural unit shown below.

[Synthesis Example 5: Synthesis of Resin B2]

A flask equipped with a reflux condenser, a dropping funnel and a stirrer was charged with an appropriate amount of nitrogen, replacing the flask with a nitrogen atmosphere, adding 371 parts of propylene glycol monomethyl ether acetate, and heating to 85 DEG C with stirring. Next, 54 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl acrylate (the compound represented by formula (I-1) and the compound represented by formula (II-1) ), 81 parts of vinyltoluene (isomer mixture) and 80 parts of propylene glycol monomethyl ether acetate was added dropwise over 4 hours.

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 the completion of the dropwise addition, the mixture was kept at the same temperature for 4 hours and then cooled to room temperature to obtain a copolymer (resin B2) having a B-type (23 ° C) viscosity of 246 mPas, a solid content of 37.5% and a solution acid value of 43 mg- . The resin B2 had a weight average molecular weight (Mw) of 1.1 x 10 ⁴ and a degree of dispersion of 2.01. Resin B2 has the following structural units.

The weight average molecular weight (Mw) and number average molecular weight (Mn) of the resins obtained in Synthesis Examples 4 and 5 were measured by the GPC method under the following conditions.

Device; K2479 (manufactured by Shimadzu Corporation)

column; SHIMADZU Shim-pack GPC-80M

Column temperature; 40 ℃

menstruum; THF (tetrahydrofuran)

Flow rate; 1.0 mL / min

Detector; RI

Calibration standards; 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 as described above was dispersed.

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) -LPN 6919 (manufactured by Big Chem Japan Co., Ltd.)) and the resin B2 obtained in Synthesis Example 5 ) And propylene glycol monomethyl ether acetate (84 parts) were mixed and the triarylmethane colorant (A-I-18) was thoroughly dispersed using a bead mill to obtain a dispersion (1).

[Preparation Example 2: Preparation of Dispersion (2)]

12 parts of a pigment (CI Pigment Blue 15: 6), 2 parts of an acrylic pigment dispersant and 80.5 parts of propylene glycol monomethyl ether acetate were thoroughly dispersed using a bead mill to obtain a dispersion (2) .

[Examples 1 to 7 and Comparative Examples 1 to 3]

(Preparation of colored curable resin composition)

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

Xanthene dyes (1-38),

· Tetraazaporphyrin dye (Aa3-1),

Dispersions (2),

(B) Resin: Resin B1,

(C) Polymerizable compound: dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Yakuza Co., Ltd.)

(D) Polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXE01, manufactured by BASF)

(F) Leveling agent: polyether-modified silicone oil (TORAYI Silicone SH8400, manufactured by Toray Dow Corning Co., Ltd.)

(E) Solvent: Ethyl lactate (EL),

(E) Solvent: propylene glycol monomethyl ether acetate (PGMEA)

Were mixed with the additives shown in Table 3 to obtain a colored curable resin composition.

&Lt; Preparation of colored pattern >

A colored curable resin composition was coated on a glass substrate (Eagle 2000; Corning) having a size of 5 cm on both sides by spin coating, and then prebaked at 100 ° C for 3 minutes to obtain a colored composition layer. After cooling, the distance between the substrate on which the coloring composition layer was formed and the quartz glass photomask was set to 100 mu m and an exposure amount of 150 mJ / cm &lt; 2 &gt; was measured using an exposure machine (TME- 365 nm). As the photomask, a 100 μm line and space pattern was formed. After the light irradiation, the coloring composition layer was immersed in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 24 DEG C for 60 seconds, and after washing with water, post-baking was performed in an oven at 230 DEG C for 30 minutes , And a coloring pattern was obtained.

&Lt; Measurement of film thickness &

With respect to the obtained coloring pattern, the film thickness was measured using a film thickness measuring device (DEKTAK3; manufactured by Japan Vacuum Technology Co., Ltd.)). The results are shown in Table 4. Table 4 shows the content of each component calculated so that the total amount of the coloring agent (A) becomes 100 with respect to the coloring agent (A) contained in the colored curable resin composition obtained by mixing the additives shown in Table 3.

&Lt; Evaluation of color &

Spectroscopy was measured using a colorimeter (OSP-SP-200, manufactured by Olympus Corporation), and the xy chromaticity coordinates (x, y) in the XYZ color system of CIE were measured using the characteristic function of the C light source ) And three stimulus values Y were measured. The larger the value of Y, the higher the brightness. The results are shown in Table 4.

<Evaluation of contrast>

Except that the photomask was not used at the time of exposure, the same operation as that of the production of the colored pattern was carried out to prepare a colored coating film. The coloring coating film thus obtained was applied to the obtained colored coating film by using a contrast system (CT-1; Tsubosaka Kikai Co., Ltd., color chromaticity meter BM-5A; Topcon, light source: F-10, polarizing film; Tsubosaka Denki Co., , And the blank value was set to 30000, and the contrast was measured. If the contrast in the colored coating film is high, the coloring pattern can be said to have high contrast as well. The results are shown in Table 4.

In the colored curable resin compositions of Examples 1 and 2 and Comparative Example 2, a chromaticity coordinate of y was 0.095, a chromaticity coordinate of x was 0.135 to 0.138, and a coloring pattern with a close chromaticity was obtained. In Examples 1 and 2, a colored pattern with high brightness was obtained as compared with Comparative Example 2, and a colored coating film showing high contrast was obtained.

In the colored curable resin compositions of Examples 3 to 7 and Comparative Examples 1 and 3, a chromaticity coordinate of y was 0.095, a chromaticity coordinate of x was 0.150 to 0.151, and a coloring pattern with a close chromaticity was obtained. In Examples 3 to 7, a colored pattern with high brightness was obtained as compared with Comparative Examples 1 and 3, and a colored coating film showing high contrast was obtained.

Thus, it can be seen that 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 (5)

A colorant, a resin, a polymerizable compound and a polymerization initiator,
Wherein the colorant comprises a triarylmethane colorant, a xanthene dye, and a tetraazaporphyrin dye. The method according to claim 1,
Wherein the content of the tetraazaporphyrin dye is 0.5 to 50 parts by mass relative to 100 parts by mass of the triarylmethane colorant. The method according to claim 1,
Wherein the content of the tetraazaporphyrin dye is 1.0 to 9.0 parts by mass with respect to 100 parts by mass of the triarylmethane colorant. A color filter formed from the colored curable resin composition according to claim 1. A display device comprising the color filter according to claim 4.