JP2016164246A - Coloring curable resin composition, color filter and display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coloring curable resin composition capable of providing a coated film having enhanced heat resistance, a color filter and a display device.SOLUTION: There is provided a coloring curable resin composition containing a compound (Aa) represented by a predetermined formula, a dye (Ab), a resin (B), a polymerizable compound (C) and a polymerization initiator (D), excluding one obtained by preparing a coloring dispersion by using the compound (Aa) and a solvent and thereafter mixing with remaining components.SELECTED DRAWING: None

Description

  The present invention relates to a colored curable resin composition, a color filter, and a display device that use a salt-forming colorant and a dye in combination.

  It is disclosed that the following compounds are used in a colored curable resin composition used for a color filter or a display device (Patent Documents 1 and 2).

  Patent Document 1 discloses a technique for dispersing the above-described compound and pigment in a predetermined organic solvent in terms of improving storage stability. Patent Document 2 discloses a technique for dispersing the above compound in a dispersant having a predetermined amine value in terms of improving the brightness of a color filter. However, none of the patent documents teaches a colored curable resin composition capable of improving heat resistance when a dye such as the above compound or a salt-forming colorant is used.

JP 2013-234319 A JP 2013-235257 A

  Thus, the conventionally known colored curable resin compositions have not been sufficiently satisfactory in terms of heat resistance.

That is, the gist of the present invention is as follows.
[1] Coloring comprising a compound (Aa) represented by the formula (AI), a dye (Ab), a resin (B), a polymerizable compound (C), and a polymerization initiator (D) Curable resin composition (however, it does not include what is mixed with the remaining components after preparing a colored dispersion with the compound (Aa) and a solvent).

[In the formula (AI),
R ^{41 to} R ⁴⁴ are each independently a C 1-20 alkyl group which may have a substituent, a C 2-20 alkyl group, and a methylene group constituting the alkyl group. It represents a group having an oxygen atom inserted between them, an aromatic hydrocarbon group which may have a substituent, an aralkyl group which may have a substituent, or a hydrogen atom. 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 be bonded to form a ring with the nitrogen atom to which they are bonded.
R ^{47 to} R ⁵⁴ each independently represents a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a halogen atom, a nitro group, a sulfonyl group, a hydroxy group, or an alkyl group having 1 to 8 carbon atoms. An oxygen atom may be inserted between the methylene groups constituting the group. R ⁴⁸ and R ⁵² may be bonded to each other to form —NH—, —S— or —SO ₂ —.
Ring T ¹ represents an aromatic heterocyclic ring which may have a substituent.
[Y] ^m− represents an arbitrary m-valent anion containing at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus and oxygen as essential elements.
m represents an arbitrary natural number.
When a plurality of cations represented by the following formula are contained in one molecule, they may have the same structure or different structures.

[Wherein, rings T ¹ , R ^{41 to} R ⁴⁴ and R ^{47 to} R ⁵⁴ have the same meanings as described above, respectively. ]]
[2] The colored curable resin composition according to [1], wherein [Y] ^m− in the formula (AI) is an anion of a heteropolyacid or an isopolyacid containing tungsten as an essential element.
[3] The colored curable resin composition according to [2], wherein [Y] ^m− in the formula (AI) is an anion of phosphotungstic acid, an anion of silicotungstic acid, or an anion of tungsten-based isopolyacid. .
[4] The coloring according to any one of [1] to [3], wherein the dye (Ab) is one selected from the group consisting of a xanthene dye, a triarylmethane dye, an anthraquinone dye, and a tetraazaporphyrin dye. Curable resin composition.
[5] The colored curable resin composition according to any one of [1] to [4], wherein the dye (Ab) is a xanthene dye.
[6] The colored curable resin composition according to [4] or [5], wherein the xanthene dye is represented by the following formula (a1-1).

[In formula (a1-1), R ^{1 to} R ⁴ are each independently a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a substituent. Represents a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a methylene group (—CH ₂ —) contained in the saturated hydrocarbon group, —O—, —CO— or It may be replaced by —NR ¹¹ —. R ¹ and R ² may be combined to form a ring containing a nitrogen atom, and R ³ and R ⁴ may be combined 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 represents NR ⁹ R ¹⁰
R ⁶ and R ⁷ each 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 2 or more, the plurality of R ⁵ may be the same or different.
a represents an integer of 0 or 1.
X represents a halogen atom.
Z ⁺ represents ⁺ N (R ¹¹ ) ₄ , Na ⁺ or K ⁺ , and four R ¹¹ may be the same or different.
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.
R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and —CH ₂ contained in the saturated hydrocarbon group — May be replaced by —O—, —CO—, —NH— or —NR ⁸ —, wherein R ⁹ and R ¹⁰ are bonded to each other and are a 3- to 10-membered heterocyclic ring containing a nitrogen atom. May be formed.
R ¹¹ represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms. ]
[7] The colored curable resin composition according to any one of [1] to [6], wherein the resin (B) has a weight average molecular weight of 9000 or more.
[8] The colored curable resin composition according to any one of [1] to [7], wherein the acid value of the resin (B) is 60 mg-KOH / g or more.
[9] The colored curing according to any one of [1] to [8], wherein the content of the dye (Ab) is 0.01 to 5% by mass in 100% by mass of the solid content of the colored curable resin composition. Resin composition.
[10] The colored curable resin composition according to any one of [1] to [9], wherein the mass ratio of the dye (Ab) / the compound (Aa) is 0.001 to 0.5.
[11] A color filter formed from the colored curable resin composition according to any one of [1] to [10].
[12] A display device including the color filter according to [11].

  According to the present invention, it is possible to provide a colored curable resin composition, a color filter, and a display device that can provide a coating film with improved heat resistance.

<Colored curable resin composition>
The colored curable resin composition of the present invention comprises a compound represented by the formula (AI) (hereinafter sometimes referred to as a salt-forming colorant or compound (Aa)), a dye (Ab), and a resin (B). , A polymerizable compound (C), and a polymerization initiator (D). However, it does not include those prepared by preparing a colored dispersion with the compound (Aa) and a solvent and then mixing with the remaining components.

Compound (Aa)

[In the formula (AI), R ^{41 to} R ⁴⁴ each independently represents an optionally substituted alkyl group having 1 to 20 carbon atoms or an alkyl group having 2 to 20 carbon atoms. A group in which an oxygen atom is inserted between methylene groups constituting the alkyl group, an aromatic hydrocarbon group which may have a substituent, an aralkyl group or a hydrogen atom which may have a substituent, Represent. 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 be bonded to form a ring with the nitrogen atom to which they are bonded.
R ^{47 to} R ⁵⁴ each independently represents a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a halogen atom, a nitro group, a sulfonyl group, a hydroxy group, or an alkyl group having 1 to 8 carbon atoms. An oxygen atom may be inserted between the methylene groups constituting the group. R ⁴⁸ and R ⁵² may be bonded to each other to form —NH—, —S— or —SO ₂ —.
Ring T ¹ represents an aromatic heterocyclic ring which may have a substituent.
[Y] ^m− represents an arbitrary m-valent anion containing at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus and oxygen as essential elements.
m represents an arbitrary natural number.
When a plurality of cations represented by the following formula are contained in one molecule, they may have the same structure or different structures.

[Wherein, rings T ¹ , R ^{41 to} R ⁴⁴ and R ^{47 to} R ⁵⁴ have the same meanings as described above, respectively. ]]
The aromatic heterocyclic ring of ring T ¹ may be a single ring or a condensed ring. The aromatic heterocycle is preferably a 5- to 10-membered ring, and more preferably a 5- to 9-membered ring.
As the monocyclic aromatic heterocycle, a 5-membered ring containing a nitrogen atom such as a pyrrole ring, an oxazole ring, a pyrazole ring, an imidazole ring or a thiazole ring; a 5-membered ring containing no nitrogen atom such as a furan ring or a thiophene ring; 6-membered ring containing nitrogen atom such as pyridine ring, pyrimidine ring, pyridazine ring, pyrazine ring, etc., and examples of the condensed aromatic heterocycle include indole ring, benzimidazole ring, benzothiazole ring, quinoline ring, etc. A condensed ring containing a nitrogen atom, a ring not containing a nitrogen atom such as a benzofuran ring, and the like.

Examples of the substituent that the aromatic heterocyclic ring of ring T ¹ may have include a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms that may be substituted with a halogen atom, and a halogen atom. Examples thereof may include an aromatic hydrocarbon group having 6 to 20 carbon atoms and an optionally substituted amino group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.
The amino group which may be substituted includes an amino group; an amino substituted with one hydrocarbon group having 1 to 10 carbon atoms such as an N-methylamino group, an N-ethylamino group, and an N-phenylamino group. Group: An amino group substituted with two hydrocarbon groups having 1 to 10 carbon atoms such as N, N-dimethylamino group and N, N-diethylamino group.
Among them, the aromatic heterocycle of the ring T ¹ is preferably an aromatic heterocycle containing a nitrogen atom, and more preferably a 5-membered aromatic heterocycle containing a nitrogen atom.

The ring T ¹ is more preferably a ring represented by the formula (Ab2-x1), and particularly preferably a ring represented by the formula (Ab2-y1).

[Ring T ² represents an aromatic heterocyclic ring.
R ⁴⁵ and R ⁴⁶ are each independently an alkyl group having 1 to 20 carbon atoms and an alkyl group having 2 to 20 carbon atoms which may have a substituent, and a methylene group constituting the alkyl group It represents a group having an oxygen atom inserted between them, an aromatic hydrocarbon group which may have a substituent, an aralkyl group which may have a substituent, or a hydrogen atom. R ⁴⁵ and R ⁴⁶ may be bonded to form a ring together with the nitrogen atom to which they are bonded.
R ⁵⁵ represents an alkyl group, or optionally substituted aromatic hydrocarbon group having 1 to 20 carbon atoms.
k1 represents 0 or 1.
* Represents a bond with a carbocation. ]

[R ⁵⁶ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group which may have a substituent.
X2 represents an oxygen atom, -NR ⁵⁷ - represents a or sulfur atom.
R ⁵⁷ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
R ⁴⁵ and R ⁴⁶ are as defined above.
* Represents a bond with a carbocation. ]

Examples of the aromatic heterocycle of the ring T ² include the same rings as the aromatic heterocycle exemplified in the ring T ¹ .

Ring T ¹ is also preferably a ring represented by the formula (Ab2-x2),

[Ring T ³ represents an aromatic heterocyclic ring having a nitrogen atom.
R ⁵⁸ represents an alkyl group having 1 to 20 carbon atoms or an optionally substituted aromatic hydrocarbon group.
R ⁵⁹ represents a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group or an optionally substituted aralkyl group.
k2 represents 0 or 1.
* Represents a bond with a carbocation. ]

Ring T ¹ is more preferably a ring represented by the formula (Ab2-y2).

[R ⁶⁰ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an optionally substituted aromatic hydrocarbon group.
R ⁵⁹ has the same meaning as described above.
* Represents a bond with a carbocation. ]

A ring formed by combining R ⁴¹ and R ⁴² with a nitrogen atom to which they are bonded, a ring formed by combining R ⁴³ and R ⁴⁴ with a nitrogen atom to which they are bonded, and R ⁴⁵ and R ⁴⁶ Examples of the ring formed together with the nitrogen atom to which they are bonded include the following.

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ^{41 to} R ⁴⁶ , R ⁵⁵ , R ⁵⁶ and R ^{58 to} R ⁶⁰ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, Linear alkyl groups such as heptyl, octyl, nonyl, decyl, dodecyl, hexadecyl and icosyl; branched alkyl such as isopropyl, isobutyl, isopentyl, neopentyl and 2-ethylhexyl Group; C3-C20 cyclic alkyl groups, such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a tricyclodecyl group, are mentioned.
Carbon number of a linear or branched alkyl group becomes like this. Preferably it is 1-8, More preferably, it is 1-6, More preferably, it is 1-4. Moreover, carbon number of a cyclic alkyl group becomes like this. Preferably it is 3-10, More preferably, it is 6-10. In the group in which an oxygen atom is inserted between the methylene groups constituting the alkyl group of R ^{41 to} R ^46, the number of carbon atoms between the oxygen atoms is preferably 1 to 4, and more preferably 2 to 3. .
Examples of the substituent that the alkyl group represented by R ^{41 to} R ⁴⁶ may have include an amino group; N-methylamino group, N-ethylamino group, N-phenylamino group, N, N-dimethylamino. Group, an amino group which may be substituted such as N, N-diethylamino group; and halogen atoms such as fluorine atom, chlorine atom and bromine atom.
Examples of the substituent that the alkyl group of R ⁵⁹ may have include a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom; a cyano group, and the like.
The aromatic hydrocarbon groups represented by R ^{41 to} R ⁴⁶ , R ⁵⁵ , R ⁵⁶ , R ^{58 to} R ⁶⁰ include phenyl group, tolyl group, xylyl group, naphthyl group, anthryl group, phenanthryl group, biphenyl. And aromatic hydrocarbon groups having 6 to 20 carbon atoms such as terphenyl groups, preferably aromatic hydrocarbon groups having 6 to 15 carbon atoms, more preferably aromatic carbon groups having 6 to 12 carbon atoms. It is a hydrogen group.
The aromatic hydrocarbon group may have a substituent, and examples of the substituent include halogen atoms such as a fluorine atom, a chlorine atom, an iodine atom and a bromine atom; carbon atoms of 1 to 6 such as a methoxy group and an ethoxy group. Hydroxy group; sulfamoyl group; alkylsulfonyl group having 1 to 6 carbon atoms such as methylsulfonyl group; alkoxycarbonyl group having 1 to 6 carbon atoms such as methoxycarbonyl group and ethoxycarbonyl group; and the like.
Examples of the aralkyl group which may have a substituent represented by R ^{41 to} R ⁴⁶ and R ⁵⁹ include carbon atoms of 1 such as a methylene group, an ethylene group, and a propylene group in addition to the groups described as the aromatic hydrocarbon group. Group (benzyl group and phenethyl group) to which 5 to 5 alkanediyl groups are bonded.

The alkyl group having 1 to 8 carbon atoms represented by R ^{47 to} R ⁵⁴ may be linear, branched or cyclic, and is preferably linear. Examples of the linear, branched and cyclic alkyl groups exemplified for R ^{41 to} R ⁴⁶ , R ⁵⁵ , R ⁵⁶ and R ^{58 to} R ⁶⁰ include groups having 1 to 8 carbon atoms.

R ^{41 to} R ⁴⁴ , R ⁵⁵ , R ⁵⁸ and R ⁵⁹ are each independently preferably an alkyl group having 1 to 20 carbon atoms or an aromatic hydrocarbon group which may have a substituent. The alkyl group of -6 and the phenyl group which may have a substituent are more preferable.
R ⁴⁵ and R ⁴⁶ are each independently an alkyl group having 1 to 20 carbon atoms and an alkyl group having 2 to 20 carbon atoms which may have a substituent, and a methylene group constituting the alkyl group A group in which an oxygen atom is inserted, or an aromatic hydrocarbon group which may have a substituent is preferable, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a methoxymethyl group, a methoxyethyl group , Ethoxymethyl group, ethoxyethyl group, propoxymethyl group, propoxyethyl group, propoxypropyl group, phenyl group, o-tolyl group, m-tolyl group, and p-tolyl group are more preferable.
R ^{47 to} R ⁵⁴ are each independently preferably a hydrogen atom, a halogen atom or an alkyl group having 1 to 8 carbon atoms, and each independently preferably a hydrogen atom, a methyl group, a fluorine atom or a chlorine atom.
R ⁵⁶ is preferably an alkyl group having 1 to 10 carbon atoms or an aromatic hydrocarbon group which may have a substituent, more preferably an alkyl group having 1 to 8 carbon atoms, a halogen atom, or a carbon number. An aromatic hydrocarbon group that may be substituted with a 1-4 haloalkyl group, an alkoxy group with 1 to 4 carbon atoms, a hydroxy group, an alkyl group with 1 to 4 carbon atoms, or a methylsulfonyl group, more preferably A phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a fluorine atom, a chlorine atom, a bromine atom, a trifluoromethyl group in at least one of an ortho position, a para position and a meta position with respect to a bond; Or it is the phenyl group which the methanesulfonyl group couple | bonded.
R ⁵⁷ is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

  Examples of the cation moiety of formula (Ab2) include cation 1 to cation 12 represented by formula (Ab2-1) as shown in Table 1 below. In the table, * represents a bond.

  In Table 1, Ph1 to Ph9 mean groups represented by the following formulae. In the formula, * represents a bond.

  Examples of the cation moiety of the formula (Ab2) include cations 13 to 16 represented by the formula (Ab2-2) as shown in Table 2 below. In the table, * represents a bond.

  In Table 2, Ph1, Ph10, and Ph11 mean groups represented by the following formulae. In the formula, * represents a bond.

  Among them, as the cation moiety of the formula (Ab2), cation 1 to cation 6, cation 11 or cation 12 is preferable, cation 1, cation 2 or cation 12 is particularly preferable, and cation 12 is most preferable.

<Anion part>
As [Y] ^m− corresponding to the anion, an anion containing at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus and oxygen as essential elements is used. Such an anion can improve heat resistance and solvent resistance.
The anion [Y] ^m- is preferably an anion of a heteropolyacid or isopolyacid containing tungsten as an essential element, particularly an anion of phosphotungstic acid, silicotungstic acid and tungsten-based isopolyacid.

As anions of heteropolyacid or isopolyacid containing tungsten as an essential element, Keggin type phosphotungstate ion α- [PW ₁₂ O ₄₀ ] ³⁻ , Dawson type phosphotungstate ion α- [P ₂ W ₁₈ O ₆₂ ] ^6- , β- [P ₂ W ₁₈ O ₆₂ ] ^6- , Keggin type silicotungstate ion α- [SiW ₁₂ O ₄₀ ] ^4- , β- [SiW ₁₂ O ₄₀ ] ^4- , γ- [SiW ₁₂ O ₄₀ ] ^4- , [P ₂ W ₁₇ O ₆₁ ] ^10- , [P ₂ W ₁₅ O ₅₆ ] ^12- , [H ₂ P ₂ W ₁₂ O ₄₈ ] ^12- , [NaP ₅ W ₃₀ O ₁₁₀ ] ^14- , Α- [SiW ₉ O ₃₄ ] ^10- , γ- [SiW ₁₀ O ₃₆ ] ^8- , α- [SiW ₁₁ O ₃₉ ] ^8- , β- [SiW ₁₁ O ₃₉ ] ^8- , [W ₆ O ₁₉ ] ^2- , [W ₁₀ O ₃₂ ] ^4- , WO ₄ ^2- and mixtures thereof.

[Y] ^m− is also preferably an anion composed of oxygen and at least one element selected from the group consisting of silicon and phosphorus.
Examples of the anion consisting of oxygen and at least one element selected from the group consisting of silicon and phosphorus include SiO ₃ ²⁻ and PO ₄ ³⁻ .

Because of the ease of synthesis and post-treatment, phosphotungstic anions such as Keggin-type phosphotungstate ions and Dawson-type phosphotungstate ions; silicotungstate anions such as Keggin-type phosphotungstate ions, [W ₁₀ O ₃₂ ] ^4- A tungsten isopolyacid anion such as Of these, phosphotungstate anions and tungsten isopolyacid anions are particularly preferred.

  The compound represented by the formula (AI) can be synthesized according to the synthesis method described in JP-A-2015-28121.

  Examples of the compound (Aa) include compounds represented by the following formula.

  Two or more compounds represented by the formula (AI) may be combined. Among them, the compound (Aa) is preferably a compound represented by the formula (Aa2-53).

  The content of the compound (Aa) is usually 1% by mass or more and 70% by mass or less, preferably 10% by mass or more and 60% by mass or less, more preferably 20% by mass or more and 60% by mass or less with respect to the total amount of solids. It is not more than mass%, and particularly preferably not less than 30 mass% and not more than 50 mass%. When the content of the compound (Aa) is within the above range, a desired spectrum and color density can be easily obtained. In addition, in this specification, "the total amount of solid content" means the total amount of the component remove | excluding the solvent from the colored curable resin composition of this invention. The total amount of solids and the content of each component relative thereto can be measured by known analytical means such as liquid chromatography and gas chromatography, for example.

<Dye (Ab)>
The dye (Ab) is preferably one selected from the group consisting of a xanthene dye, a triarylmethane dye, an anthraquinone dye, and a tetraazaporphyrin dye, and more preferably a xanthene dye.

<Xanthene dye>
The xanthene dye is more preferably a compound represented by the following formula (a1-1) (hereinafter also referred to as compound (a1-1)). The compound (a1-1) may be a tautomer thereof.

[In formula (a1-1), R ^{1 to} R ⁴ are each independently a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a substituent. Represents a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a methylene group (—CH ₂ —) contained in the saturated hydrocarbon group, —O—, —CO— or It may be replaced by —NR ¹¹ —. R ¹ and R ² may be combined to form a ring containing a nitrogen atom, and R ³ and R ⁴ may be combined 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 represents NR ⁹ R ¹⁰
R ⁶ and R ⁷ each 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 2 or more, the plurality of R ⁵ may be the same or different.
a represents an integer of 0 or 1.
X represents a halogen atom.
Z ⁺ represents ⁺ N (R ¹¹ ) ₄ , Na ⁺ or K ⁺ , and four R ¹¹ may be the same or different.
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.
R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and —CH ₂ contained in the saturated hydrocarbon group — May be replaced by —O—, —CO—, —NH— or —NR ⁸ —, wherein R ⁹ and R ¹⁰ are bonded to each other and are a 3- to 10-membered heterocyclic ring containing a nitrogen atom. May be formed.
R ¹¹ represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms. ]

In the formula (a1-1), when —SO ₃ ^— is present, the number is one.

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ^{1 to} R ⁴ include a phenyl group, a toluyl group, a xylyl group, a mesityl group, a propylphenyl group, and a butylphenyl group. Among these, R ¹ and R ⁴ are preferably a phenyl group, a toluyl group, or a xylyl group.

The aromatic hydrocarbon group substituent 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, or —SO ₂ NR ⁹ R ¹⁰ are included, and these substituents are included in the aromatic hydrocarbon group. It is preferable to substitute a hydrogen atom. Among them, as the _{^{substituent, -SO 3 -, -SO 3 H}} , -SO 3 - Z + and preferably _{^{-SO 2 NR 9 R 10, -SO}} 3 - Z + and -SO ₂ NR ⁹ R ¹⁰ Is more preferable. In this case, —SO ₃ ^{− +} N (R ¹¹ ) ₄ is preferable as —SO ₃ ⁻ Z ⁺ . When R ^{1 to} R ⁴ are these groups, the colored curable resin composition of the present invention containing the compound (a1-1) can form a color filter with less generation of foreign matters and excellent heat resistance.

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ^{1 to} R ⁴ and R ^{8 to} R ¹¹ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl group. Linear alkyl groups such as octyl group, nonyl group, decyl group, dodecyl group, hexadecyl group, icosyl group; branched alkyl groups such as isopropyl group, isobutyl group, isopentyl group, neopentyl group, 2-ethylhexyl group; C3-C20 alicyclic saturated hydrocarbon groups, such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a tricyclodecyl group, are mentioned. Among these, R ² and R ³ are preferably a methyl group, an ethyl group, an isopropyl group, or a propyl group.
The hydrogen atom contained in the saturated hydrocarbon group in R ^{1 to} R ⁴ may be substituted with, for example, an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom as a substituent. Examples of the aromatic hydrocarbon group of R ¹ to R ⁴ saturated hydrocarbon carbon atoms which may be substituted with hydrogen atoms of the groups 6 to 10, having 6 to 10 carbon atoms in R ¹ to R ⁴ aromatic hydrocarbons Examples thereof include the same groups as those exemplified as the group.
The hydrogen atom contained in the saturated hydrocarbon group in R ⁹ and R ¹⁰ may be substituted with, for example, a hydroxy group or a halogen atom as a substituent.

Examples of the ring formed by R ¹ and R ² together and the ring formed by R ³ and R ⁴ together include the following.

Examples of —OR ⁸ include alkyloxy groups such as methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group and icosyloxy group. Is mentioned.

Examples of —CO ₂ R ⁸ include alkyloxycarbonyl such as methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, tert-butoxycarbonyl group, hexyloxycarbonyl group and icosyloxycarbonyl group.

Examples of —SR ⁸ include alkylsulfanyl groups such as 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 alkylsulfonyl groups such as 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 alkyloxysulfonyl groups such as a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a tert-butoxysulfonyl group, a hexyloxysulfonyl group, and an icosyloxysulfonyl group.

—SO ₂ NR ⁹ R ¹⁰ includes, for example, a sulfamoyl group;
N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group, N-isobutylsulfamoyl group, N- sec-butylsulfamoyl group, N-tert-butylsulfamoyl group, N-pentylsulfamoyl group, N- (1-ethylpropyl) sulfamoyl group, N- (1,1-dimethylpropyl) sulfamoyl group, N- (1,2-dimethylpropyl) sulfamoyl group, N- (2,2-dimethylpropyl) sulfamoyl group, N- (1-methylbutyl) sulfamoyl group, N- (2-methylbutyl) sulfamoyl group, N- (3 -Methylbutyl) sulfamoyl group, N-cyclopentylsulfamoyl group, N-hexylsulfamoyl N- (1,3-dimethylbutyl) sulfamoyl group, N- (3,3-dimethylbutyl) sulfamoyl group, N-heptylsulfamoyl group, N- (1-methylhexyl) sulfamoyl group, N- (1 , 4-Dimethylpentyl) sulfamoyl group, N-octylsulfamoyl group, N- (2-ethylhexyl) sulfamoyl group, N- (1,5-dimethylhexyl) sulfamoyl group, N- (1,1,2,2 -N-substituted sulfamoyl groups such as -tetramethylbutyl) sulfamoyl group;
N, N-dimethylsulfamoyl group, N, N-ethylmethylsulfamoyl group, N, N-diethylsulfamoyl group, N, N-propylmethylsulfamoyl group, N, N-isopropylmethylsulfa Moyl group, N, N-tert-butylmethylsulfamoyl group, N, N-butylethylsulfamoyl group, N, N-bis (1-methylpropyl) sulfamoyl group, N, N-heptylmethylsulfamoyl And N, N-2-substituted sulfamoyl groups such as a group.

The _{^{R 5, -CO 2 H, -CO}} 2 - Z +, -CO 2 R 8, -SO 3 -, -SO 3 - Z +, -SO 3 H or -SO ₂ NHR ⁹ are preferred, -SO ^{_{3 -, -SO 3 - Z +}} , more preferably -SO ₃ H or -SO ₂ NHR ^9, -SO ₃ ^- is more preferable.
m is preferably 1 to 4, more preferably 1 or 2, and even more preferably 1.

The alkyl group having 1 to 6 carbon atoms in R ⁶ and R ^7, among the alkyl groups listed above, include those having 1 to 6 carbon atoms. Among these, as R ⁶ and R ⁷ , a hydrogen atom is preferable.

Examples of the aralkyl group having 7 to 10 carbon atoms in 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 , at least two of the four R ¹¹ are preferably monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. The total number of carbon atoms of the four R ¹¹ is preferably 20 to 80, 20 to 60 is more preferable. When ⁺ N (R ¹¹ ) ₄ is present in the compound (a1-1), when R ¹¹ is any of these groups, the colored curable resin composition of the present invention containing the compound (a1-1) can be used as a foreign substance. A color filter with less can be formed.

  Moreover, as a xanthene dye, the compound (henceforth a "compound (a1-2)") represented by a formula (a1-2) is also preferable. The compound (a1-2) may be a tautomer thereof.

[In Formula (a1-2), R ²¹ and R ²² each independently represent a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, and are included in the saturated hydrocarbon group of R ²¹ and R ^22. The hydrogen atom 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 is substituted with an alkoxy group having 1 to 3 carbon atoms. And —CH ₂ — contained in the saturated hydrocarbon group of R ²¹ and R ²² may be replaced by —O—, —CO— or —NR ¹¹ —.
R ²³ and R ²⁴ each 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 ²¹ and R ²³ may together form a ring containing a nitrogen atom, and R ²² and R ²⁴ may together form a ring containing a nitrogen atom.
p and q represent the integer of 0-5 mutually independently. When p is 2 or more, the plurality of R ²³ may be the same or different, and when q is 2 or more, the plurality of R ²⁴ may be the same or different.
R ¹¹ represents the same meaning as described above. ]

Examples of the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms in R ²¹ and R ²² include those having 1 to 10 carbon atoms among those in R ⁸ .
Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms which may be present as a substituent include the same groups as those in R ¹ .
As a C1-C3 alkoxy group, a methoxy group, an ethoxy group, a propoxy group etc. are mentioned, for example.
R ²¹ and R ²² are preferably each independently a monovalent saturated hydrocarbon group having 1 to 3 carbon atoms.

Examples of the alkyl group having 1 to 4 carbon atoms in R ²³ and R ²⁴ include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.
Examples of the alkylsulfanyl group having 1 to 4 carbon atoms in R ²³ and R ²⁴ 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 ²³ and R ²⁴ include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, a butylsulfonyl group, and an isopropylsulfonyl group.
R ²³ and R ²⁴ are preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and even more preferably a methyl group.

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

As a xanthene dye, the compound represented by Formula (1-1)-Formula (1-43) is mentioned, for example. In the formula, R ⁴⁰ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, preferably a branched alkyl group having 6 to 12 carbon atoms, and more preferably a 2-ethylhexyl group.

Among the above compounds, the compound represented by any one of formula (1-24) to formula (1-36) corresponds to compound (a1-2).
Among these, C.I. I. Acid red 289 sulfonamidation product, C.I. I. Quaternary ammonium salt of Acid Red 289, C.I. I. Acid violet 102 sulfonamidate or C.I. I. The quaternary ammonium salt of Acid Violet 102 is preferred. Examples of such a compound include compounds represented by formula (1-1) to formula (1-8), formula (1-11), or formula (1-12).
In addition, a compound represented by any one of the formulas (1-24) to (1-33) is also preferable, and particularly preferably, the compound is represented by the formula (1-32) in terms of excellent solubility in an organic solvent. A compound.

  As the xanthene dye, a commercially available xanthene dye (for example, “Chugai Aminol Fast Pink R-H / C” manufactured by Chugai Kasei Co., Ltd., “Rhodamin 6G” manufactured by Taoka Chemical Industry Co., Ltd.) can be used. Moreover, it can also synthesize | combine with reference to Unexamined-Japanese-Patent No. 2010-32999 using the commercially available xanthene dye as a starting material.

<Triarylmethane dye>
The triarylmethane dye is preferably a dye containing a compound having a structure in which three aromatic hydrocarbon groups are bonded to one carbon atom. Examples of the triarylmethane dye include C.I. I. Solvent Blue 2, 4, 5, 43, 124; I. Basic Violet 3, 14, 25; C.I. I. And triarylmethane dyes described in Basic Blue 1, 5, 7, 11, 26 and Japanese Patent No. 4492760.

<Anthraquinone dye>
As an anthraquinone dye, C.I. I. Solvent Violet 11 (hereinafter, the description of CI Solvent Violet is omitted, and only numbers are given), 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60 ,
C. I. Solvent Blue 14, 18, 35, 36, 45, 58, 59, 59: 1, 63, 68, 69, 78, 79, 83, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139,
C. I. Solvent Green 3, 28, 29, 32, 33,
C. I. Acid Green 25, 27, 28, 41,
C. I. Acid Violet 34,
C. I. Acid Blue 25, 27, 40, 45, 78, 80, 112
C. I. Disperse violet 26, 27,
C. I. Disperse Blue 1, 14, 56, 60,
C. I. Direct Blue 40,
C. I. Modern Blue 8
Etc.

<Tetraazaporphyrin dye>
The tetraazaporphyrin dye is a compound having a tetraazaporphyrin skeleton in the molecule. Further, when the tetraazaporphyrin dye is an acid dye or a basic dye, it may form a salt with any cation or anion.

As other dyes, azo dyes, oxazine dyes, phthalocyanine dyes and the like may be used, and known dyes are used.
As the azo dye, C.I. I. Direct Blue 51 (hereinafter, the description of CI Direct Blue is omitted and only the number is described), 57, 71, 81, 84, 85, 90, 93, 94, 95, 98, 100, 101 113, 149, 150, 153, 160, 162, 163, 164, 166, 167, 170, 172, 188, 192, 193, 194, 196, 198, 200, 207, 209, 210, 212, 213, 214 222, 228, 229, 237, 238, 242, 243, 244, 245, 247, 248, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275;
C. I. Direct green 27, 34, 37, 65, 67, 68, 69, 72, 77, 79, 82, etc .;
C. I. Acid Violet 11, 56, 58;
C. I. Acid Blue 92, 102, 113, 117, etc .; C.I. I. Basic blue 41, 54, 64, 66, 67, 129 etc. are mentioned.

Examples of the oxazine dye include C.I. I. Direct Blue 97, 99, 106, 107, 108, 109, 190, 293 and the like can be mentioned.
Examples of the phthalocyanine dye include C.I. I. Direct Blue 86, 87, 189, 199, C.I. I. Acid Blue 249, C.I. I. Basic blue 3 etc. are mentioned.

The content of the dye (Ab) is, for example, 0.01 to 5% by mass, preferably 0.05 to 4% by mass, and more preferably 0 in 100% by mass of the solid content of the colored curable resin composition. It is 0.1-3 mass%, Most preferably, it is 0.2-2 mass%.
The dye preferably contains 50% by mass or more of the xanthene dye (preferably a compound represented by the formula (1-32)), more preferably 60% by mass or more, still more preferably 70% by mass or more, and still more preferably. Is 80 mass% or more, particularly preferably 90 mass% or more, and most preferably 100 mass%.
In addition to the xanthene dye, one or more other dyes may be used in combination.

  The mass ratio of dye (Ab) (in terms of solid content) / compound (Aa) (in terms of solid content) is preferably 0.001 to 0.5, more preferably 0.005 to 0.4, and still more preferably 0.00. It is 007-0.3, More preferably, it is 0.009-0.2. If the above numerical range is not satisfied, the effect of improving heat resistance may not be obtained.

<Resin (B)>
The resin (B) contained in the colored curable resin composition of the present invention is preferably an alkali-soluble resin and has a structure derived from at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides. More preferred are addition polymers having units. Examples of such a resin include the following resins [K1] to [K6].
Resin [K1]: at least one (a) selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic acid anhydride (hereinafter sometimes referred to as “(a)”), and a cyclic ether structure having 2 to 4 carbon atoms And a monomer (b) having an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b)”) Resin [K2]: (a), (b), (a) A copolymer with a monomer (c) copolymerizable with (but different from (a) and (b)) (hereinafter sometimes referred to as “(c)”) Resin [K3]: (a ) And (c) Copolymer Resin [K4]: Resin obtained by reacting (b) with copolymer of (a) and (c) Resin [K5]: (b) and (c Resin [K6]: a resin obtained by reacting a copolymer with (a) with a copolymer with (a) The reacted resin obtained by further reacting a carboxylic acid anhydride.

As (a), unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid;
Unsaturated dicarboxylic acids such as maleic acid;
Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, etc. A bicyclounsaturated compound containing a carboxy group of
Unsaturated dicarboxylic anhydrides such as maleic anhydride;
Examples thereof include unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule such as α- (hydroxymethyl) acrylic acid.
Of these, acrylic acid, methacrylic acid and maleic anhydride are preferred from the viewpoint of copolymerization reactivity and solubility of the resulting resin in an aqueous alkali solution.

  (B) refers to a polymerizable compound having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and an ethylenically unsaturated bond. . (B) is preferably a monomer having a C2-C4 cyclic ether structure and a (meth) acryloyloxy group. In the present specification, “(meth) acrylic acid” represents at least one selected from the group consisting of acrylic acid and methacrylic acid, and the notation of “(meth) acryloyl” and “(meth) acrylate” is also used. Indicate the same meaning.

  (B) includes a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b1)”), and a monomer having an oxetanyl group and an ethylenically unsaturated bond. (B2) (hereinafter sometimes referred to as “(b2)”) and a monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b3)”).

  (B1) may be a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter referred to as “(b1-1)”) ) And a monomer (b1-2) having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as “(b1-2)”).

  (B1-1) is preferably a monomer having a glycidyl group and an ethylenically unsaturated bond. Specific examples of (b1-1) include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinyl. Benzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis ( Glycidyloxymethyl) styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxymethyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris ( Glycidyl oxime Chill) styrene, 2,3,5-tris (glycidyloxymethyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene and 2,4,4 Examples include 6-tris (glycidyloxymethyl) styrene.

  Examples of (b1-2) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celoxide (registered trademark) 2000; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth) Acrylate (for example, Cyclomer (registered trademark) A400; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer M100; manufactured by Daicel Corporation), represented by Formula (1) And a compound represented by the formula (2).

(Wherein, R ^a and R ^b each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a hydroxy group. X each ^a and X ^b are independently a single ^{bond, * - R c -, *} - R c -O -, * - R c -S- or * .R ^c representing a -R ^c -NH- is carbon Represents an alkanediyl group of formulas 1 to 6. * represents a bond to O.)

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

  Examples of the compound represented by the formula (2) include compounds represented by the formula (2-1) to the formula (2-15). Among them, the formula (2-1) and the formula (2-3) And compounds represented by formula (2-5), formula (2-7), formula (2-9) and formula (2-11) to formula (2-15) are preferred, and formula (2-1), The compounds represented by formula (2-7), formula (2-9) and formula (2-15) are more preferred.

  The compound represented by the formula (1) and the compound represented by the formula (2) may be used alone, or the compound represented by the formula (1) and the compound represented by the formula (2) May be used in combination. When these are used in combination, the ratio of the compound represented by formula (1) and the compound represented by formula (2) (compound represented by formula (1): compound represented by formula (2)) is mol. The standard is preferably 5:95 to 95: 5, more preferably 10:90 to 90:10, and still more preferably 20:80 to 80:20.

  (B2) is more preferably a monomer having an oxetanyl group and a (meth) acryloyloxy group.

  (B3) is more preferably a monomer having a tetrahydrofuryl group and a (meth) acryloyloxy group.

  (B) is preferably (b1), and the storage stability of the colored curable resin composition is excellent in that the reliability of the obtained color filter such as heat resistance and chemical resistance can be further increased. In this respect, (b1) is preferably (b1-2).

As (c), methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, Dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^{2, 6} ] Decan-8-yl (meth) acrylate (in this technical field, it is said to be “dicyclopentanyl (meth) acrylate” as a common name. It may also be referred to as “tricyclodecyl (meth) acrylate”) ), Tricyclo [ .2.1.0 ^2,6] (in the art, it is said that "dicyclopentenyl (meth) acrylate" as trivial name.) Decene-8-yl (meth) acrylate, dicyclopentenyl oxyethyl (Meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, benzyl (meth) acrylate, etc. ) Acrylic acid ester;
Hydroxy group-containing (meth) acrylic acid esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;
Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, diethyl itaconate;
Bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5- Hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2′-hydroxyethyl) bicyclo [2.2.1] Hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2 .1] Hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (2′-hydroxyethyl) bicyclo [2.2. 1] hept-2-ene, 5,6-dimethoxybicyclo [2.2 1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5 -Hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, 5-tert-butoxycarbonylbicyclo [ 2.2.1] Hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5 , 6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene, etc. Bicyclo unsaturated compounds;
N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3 -Dicarbonylimide compounds such as maleimide propionate, N- (9-acridinyl) maleimide;
Vinyl group-containing aromatic compounds such as styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene and p-methoxystyrene; vinyl group-containing nitriles such as acrylonitrile and methacrylonitrile; vinyl chloride and vinylidene chloride Halogenated hydrocarbons such as: vinyl group-containing amides such as acrylamide and methacrylamide; esters such as vinyl acetate; 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene dienes; .

Among these, a vinyl group-containing aromatic compound, a dicarbonylimide compound, and a bicyclounsaturated compound are preferable from the viewpoints of copolymerization reactivity and heat resistance. Specifically, styrene, vinyl toluene, 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.
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. As for the usage-amount of carboxylic acid anhydride, 0.5-1 mol is preferable with respect to 1 mol of usage-amount of (a).

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 (meta ) Resin such as acrylate / (meth) acrylic acid copolymer [K1]; glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / styrene / (meth) Acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate / (meth) acrylic acid / N-cyclohexylmaleimide copolymer, 3,4-epoxy tricyclo [5.2.1.0 ^{2, 6]} decyl (meth) acrylate / (meth) acrylic acid / vinyl toluene copolymer, 3-methyl-3- (meth) acrylate Resin [K2] such as luroyloxymethyloxetane / (meth) acrylic acid / styrene copolymer; benzyl (meth) acrylate / (meth) acrylic acid copolymer, styrene / (meth) acrylic acid copolymer, benzyl Resin [K3] such as (meth) acrylate / tricyclodecyl (meth) acrylate / (meth) acrylic acid copolymer; glycidyl (meth) acrylate is added to benzyl (meth) acrylate / (meth) acrylic acid copolymer Added resin, resin obtained by adding glycidyl (meth) acrylate to tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer, tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / ( Glycidyl (meth) acrylate was added to a (meth) acrylic acid copolymer Resins such as fat [K4]; resin obtained by reacting a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate with (meth) acrylic acid, tricyclodecyl (meth) acrylate / styrene / glycidyl (meta ) Resin such as resin obtained by reacting (meth) acrylic acid with acrylate copolymer [K5]; (meth) acrylic acid reacted with tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate copolymer Resin [K6] such as a resin obtained by further reacting tetrahydrophthalic anhydride with the resin.

The weight average molecular weight in terms of polystyrene of the resin (B) is usually from 3,000 to 100,000, preferably from 5,000 to 50,000, more preferably from 5,000 to 35,000, Preferably it is 5,000-30,000, Most preferably, it is 6,000-30,000, Most preferably, it is 9000-30,000. When the molecular weight is in the above range, the coating film hardness is improved, the residual film ratio is high, the solubility of the unexposed area in the developer is good, and the resolution of the colored pattern tends to be improved.
The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B) is preferably 1.1 to 6, more preferably 1.2 to 4, and still more preferably 1. 3 to 3.

The acid value (in terms of solid content) of the resin (B) is preferably 20 to 170 mg-KOH / g, more preferably 30 to 170 mg-KOH / g, and most preferably 40 to 170 mg-KOH / g. Among these, 50 to 170 mg-KOH / g is preferable, 60 mg-KOH / g or more and 150 mg-KOH / g or less is more preferable, and 135 mg-KOH / g or less is more preferable.
Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g of the resin (B), and can be determined by titration with an aqueous potassium hydroxide solution, for example.

  The content of the resin (B) is preferably 7 to 65% by mass, preferably 10 to 60% by mass, and more preferably 13 to 60% by mass, based on the total amount of solids. Of these, the content is preferably 17 to 55% by mass. When the content of the resin (B) is in the above range, a colored pattern can be easily formed, and the resolution of the colored pattern and the remaining film rate tend to be improved.

<Polymerizable compound (C)>
The polymerizable compound (C) is a compound that can be polymerized by an active radical and / or an acid generated from a polymerization initiator, and examples thereof include a polymerizable compound having an ethylenically unsaturated bond, and a (meth) acrylic acid ester. Compounds having a structure are preferred. The polymerizable compound (C) is preferably a polymerizable compound having 3 or more ethylenically unsaturated bonds, and more preferably a polymerizable compound having 5 to 6 ethylenically unsaturated bonds.

Examples of the polymerizable compound having one ethylenically unsaturated bond include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, (A), (b) and (c). Examples of the polymerizable compound having two ethylenically unsaturated bonds include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and triethylene glycol di (meta). ) Acrylate, bis (acryloyloxyethyl) ether of bisphenol A and 3-methylpentanediol di (meth) acrylate. Examples of the polymerizable compound having three or more ethylenically unsaturated bonds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tris (2- ( (Meth) acryloyloxyethyl) isocyanurate, ethylene glycol modified pentaerythritol tetra (meth) acrylate, ethylene glycol modified di Intererythritol hexa (meth) acrylate, propylene glycol modified pentaerythritol tetra (meth) acrylate, propylene glycol modified dipentaerythritol hexa (meth) acrylate, caprolactone modified pentaerythritol tetra (meth) acrylate and caprolactone modified dipentaerythritol hexa (meth) An acrylate is mentioned.
Among these, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferable.

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

  Content of the polymeric compound (C) in the colored curable resin composition of this invention is 1-60 mass% normally with respect to the total amount of solid content, Preferably it is 5-50 mass%, More Preferably it is 10-40 mass%, More preferably, it is 12-30 mass%. The content ratio of the resin (B) and the polymerizable compound (C) (resin (B): polymerizable compound (C)) is usually 20:80 to 80:20, preferably 35:65, based on mass. ~ 80: 20. When the content of the polymerizable compound (C) is within the above range, the remaining film ratio at the time of forming the colored pattern and the chemical resistance of the color filter tend to be improved.

<Polymerization initiator (D)>
The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating an active radical, an acid or the like by the action of light or heat and initiating polymerization, and a known polymerization initiator can be used.
The polymerization initiator (D) is preferably a polymerization initiator containing at least one selected from the group consisting of alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, O-acyloxime compounds and biimidazole compounds, and more preferably. Is a polymerization initiator containing an O-acyloxime compound.

  Examples of O-acyloxime compounds include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1- On-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1- [9-ethyl-6- (2- Methylbenzoyl) -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4-di) Oxacyclopentanylmethyloxy) benzoyl} -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl 6- (2-Methylbenzoyl) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-imine and N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H- Carbazol-3-yl] -3-cyclopentylpropan-1-one-2-imine. Commercial products such as Irgacure (registered trademark) OXE01, OXE02 (above, manufactured by BASF), N-1919 (manufactured by ADEKA) may be used. Among them, N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine And at least one selected from the group consisting of N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan-1-one-2-imine, and N-benzoyloxy-1- (4- More preferred is phenylsulfanylphenyl) octane-1-one-2-imine.

  Alkylphenone compounds include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one And 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butan-1-one. Commercial products such as Irgacure 369, 907, 379 (above, manufactured by BASF) may be used.

  Alkylphenone compounds include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, It may be -hydroxycyclohexyl phenyl ketone, oligomer of 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one, α, α-diethoxyacetophenone and benzyldimethyl ketal.

  As triazine compounds, 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl)- 1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis ( Trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methyl) Phenyl) ethenyl -1,3,5-triazine and 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

  Examples of the acyl phosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Commercial products such as Irgacure (registered trademark) 819 (manufactured by BASF) may be used.

  Specific examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and 2,2′-bis (2,3-dichlorophenyl). ) -4,4 ′, 5,5′-tetraphenylbiimidazole (for example, see JP-A-6-75372 and JP-A-6-75373), 2,2′-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) biimidazole, 2,2 ' -Bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (dialkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (Trial Xylphenyl) biimidazole (for example, see JP-B-48-38403, JP-A-62-174204, etc.) and the phenyl group at the 4,4′5,5′-position is substituted with a carboalkoxy group. Examples thereof include imidazole compounds (for example, see JP-A-07-010913). Of these, compounds represented by the following formula and mixtures thereof are preferred.

  Other polymerization initiators include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4 ′. -Benzophenone compounds such as methyldiphenyl sulfide, 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, 2- Examples include quinone compounds such as ethyl anthraquinone and camphor quinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds. These are preferably used in combination with a polymerization initiation assistant described below (particularly an amine polymerization initiation assistant).

  Content of a polymerization initiator (D) is 0.1-40 mass parts normally with respect to 100 mass parts of total amounts of resin (B) and polymeric compound (C), Preferably it is 0.1-30. It is a mass part, More preferably, it is 1-30 mass parts, Most preferably, it is 1-20 mass parts.

<Polymerization initiation aid>
The polymerization initiation assistant is a compound or a sensitizer used for accelerating the polymerization of the polymerizable compound (C) whose polymerization has been initiated by the polymerization initiator (D). When the colored curable resin composition of the present invention contains a polymerization initiation assistant, it is usually used in combination with a polymerization initiator (D).
Examples of the polymerization initiation assistant include amine polymerization initiation assistants, alkoxyanthracene polymerization initiation assistants, thioxanthone polymerization initiation assistants, and carboxylic acid polymerization initiation assistants.

  Examples of the amine polymerization initiation aid include alkanolamines such as triethanolamine, methyldiethanolamine, and triisopropanolamine; methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, benzoic acid Aminobenzoic acid esters such as 2-dimethylaminoethyl and 2-dimethylhexyl 4-dimethylaminobenzoate; N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4 ′ -Bis (diethylamino) benzophenone and 4,4'-bis (ethylmethylamino) benzophenone are mentioned, and alkylaminobenzophenone such as 4,4'-bis (diethylamino) benzophenone is preferred. Among these, alkylaminobenzophenone is preferable, and 4,4′-bis (diethylamino) benzophenone is preferable. Commercial products such as EAB-F (Hodogaya Chemical Co., Ltd.) may be used.

  As an alkoxyanthracene polymerization initiation assistant, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9, Examples include 10-dibutoxyanthracene and 2-ethyl-9,10-dibutoxyanthracene.

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

  Carboxylic acid polymerization initiators include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chlorophenylsulfanylacetic acid, dichlorophenyl And sulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine and naphthoxyacetic acid.

  When using a polymerization initiation aid, the content thereof is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts per 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). Part by mass. When the content of the polymerization initiation assistant is within this range, a colored pattern can be formed with higher sensitivity, and the productivity of the color filter tends to be improved.

<Solvent (E)>
A solvent (E) is not limited, The solvent normally used in the said field | area can be used individually or in combination of 2 or more types. Specifically, an ester solvent (a solvent containing —COO— in the molecule and not containing —O—), an ether solvent (a solvent containing —O— in the molecule and not containing —COO—), an ether ester solvent (Solvent containing -COO- and -O- in the molecule), ketone solvent (solvent containing -CO- in the molecule and not containing -COO-), alcohol solvent (containing OH in the molecule, -O -, -CO- and -COO- free solvents), aromatic hydrocarbon solvents, amide solvents and dimethyl sulfoxide.

  Examples of ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, pyruvin Examples include methyl acid, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate and γ-butyrolactone.

  Ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether , Propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethyl Glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, include phenetol and methyl anisole.

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

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

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

  Aromatic hydrocarbon solvents include benzene, toluene, xylene and mesitylene.

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

  Two or more of these solvents may be combined.

  Among the above solvents, an organic solvent having a boiling point of 120 ° C. or more and 210 ° C. or less at 1 atm is preferable from the viewpoints of coating properties and drying properties. Among them, propylene glycol monomethyl 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-dimethylformamide and N-methylpyrrolidone are preferred, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethylene glycol monobutyl ether, di- Propylene glycol methyl ether acetate, ethyl lactate, 3-metho Shi butyl acetate, 3-methoxy-1-butanol, ethyl 3-ethoxypropionate, N, N- dimethylformamide and N- methylpyrrolidone is more preferred.

  Content of a solvent (E) is 70-95 mass% normally with respect to the total amount of colored curable resin composition, Preferably it is 75-92 mass%, More preferably, it is 75-90 mass%. . When the content of the solvent (E) is in the above range, the flatness at the time of coating is good, and when the color filter is formed, the color density does not become insufficient and the display characteristics tend to be good. .

<Leveling agent>
Examples of the leveling agent include silicone surfactants, fluorine surfactants, and silicone surfactants having a fluorine atom. These may have a polymerizable group in the side chain.

  Examples of the silicone-based surfactant include surfactants having a siloxane bond in the molecule. Specifically, Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH29PA, SH30PA, 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, TSF-4446, TSF4452 and TSF4460 (made by Momentive Performance Materials Japan GK) are listed.

  Examples of the fluorosurfactant include surfactants having a fluorocarbon chain in the molecule. Specifically, Florard (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), MegaFac (registered trademark) F142D, F171, F172, F173, F177, F183, F183, F554, R30, RS-718-K (manufactured by DIC Corporation), Ftop (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals), Surflon (registered trademark) S381, S382, SC101, SC105 (Asahi Glass Co., Ltd.) and E5844 (Daikin Fine Chemical Laboratory Co., Ltd.).

  Examples of the silicone-based surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain in the molecule. Specifically, Megafac (registered trademark) R08, BL20, F475, F477, and F443 (manufactured by DIC Corporation) can be mentioned.

The content of the leveling agent is usually 0.0005% by mass or more and 0.6% by mass or less, preferably 0.001% by mass or more and 0.5% by mass or less, based on the total amount of the colored curable resin composition. More preferably 0.001% by mass to 0.2% by mass, still more preferably 0.002% by mass to 0.1% by mass, and particularly preferably 0.005% by mass to 0.07% by mass. It is below mass%. When the leveling agent content is within the above range, the flatness of the color filter can be improved.
The content of the leveling agent is usually from 0.001% by mass to 2.0% by mass, preferably from 0.002% by mass to 1.5% by mass, based on the total solid content of the colored curable resin composition. Or less, more preferably 0.004% by mass or more and 1.0% by mass or less, further preferably 0.008% by mass or more and 0.5% by mass or less, and particularly preferably 0.01% by mass or more and 0% by mass or less. .3% by mass or less.

<Other ingredients>
The colored curable resin composition of the present invention includes additives known in the art, such as fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, chain transfer agents, etc., if necessary. May be included.

<Method for producing colored curable resin composition>
The colored curable resin composition of the present invention includes, for example, compound (Aa), dye (Ab), resin (B), polymerizable compound (C), polymerization initiator (D), solvent (E), and necessary Depending on the case, it can be prepared by mixing a leveling agent, a polymerization initiation aid and other components. In addition to the compound (Aa), a colorant such as a pigment may be further mixed. The pigment is preferably mixed in advance with a part or all of the solvent (E) and used in the state of a pigment dispersion dispersed using a bead mill or the like until the average particle size of the pigment is about 0.2 μm or less. . Under the present circumstances, you may mix | blend a part or all of the said pigment dispersant and resin (B) as needed.
The colored curable resin composition after mixing is preferably filtered with a filter having a pore size of about 0.01 to 10 μm.

<Color filter manufacturing method>
Examples of the method for producing a colored pattern from the colored curable resin composition of the present invention include a photolithographic method, an inkjet method, and a printing method. Of these, the photolithographic method is preferable. The photolithographic method is a method in which a colored curable resin composition is applied to a substrate, dried to form a colored composition layer, and the colored composition layer is exposed and developed through a photomask. In the photolithography method, a colored coating film that is a cured product of the colored composition layer can be formed by not using a photomask and / or not developing during exposure. The colored pattern and the colored coating film thus formed are the color filter of the present invention.

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

  As the substrate, a glass plate, a resin plate, silicon, or an aluminum, silver, silver / copper / palladium alloy thin film formed on the substrate is used. On these substrates, another color filter layer, a resin layer, a transistor, a circuit, and the like may be formed.

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

  First, a colored curable resin composition is applied on a substrate, dried by heating (prebaking) and / or drying under reduced pressure to remove volatile components such as a solvent, and a smooth colored composition layer is obtained. Examples of the coating method include a spin coating method, a slit coating method, and a slit and spin coating method.

  Next, the coloring composition layer is exposed through a photomask for forming a target coloring pattern. Use an exposure device such as a mask aligner or stepper because it can irradiate parallel light uniformly over the entire exposure surface and perform precise alignment between the photomask and the substrate on which the colored composition layer is formed. Is preferred. A colored pattern is formed on the substrate by developing the exposed colored composition layer in contact with a developer. By the development, the unexposed portion of the colored composition layer is dissolved in the developer and removed. The developer is preferably an aqueous solution of an alkaline compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, tetramethylammonium hydroxide. The development method may be any of paddle method, dipping method and spray method. Further, the substrate may be tilted at an arbitrary angle during development. After development, it is preferable to wash with water.

  It is preferable to further post-bake the resulting colored pattern. The color filter having a colored pattern or a colored coating film thus obtained may be further subjected to surface coating treatment in order to impart various characteristics.

  The color filter formed from the colored curable resin composition of the present invention is useful as a color filter used for display devices (for example, liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state imaging devices.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by the following examples, but may be appropriately modified within a range that can meet the purpose described above and below. Of course, it is possible to implement them, and they are all included in the technical scope of the present invention. In the following, “part” means “part by mass” and “%” means “mass%” unless otherwise specified.

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

A beaker is charged with 53 parts of water, and 11.8 parts of Keggin-type phosphotungstic acid (manufactured by Aldrich) and 53 parts of methanol are poured into the water and mixed at room temperature in an air atmosphere to prepare a phosphotungstic acid solution. Prepared.
The obtained phosphotungstic acid solution was dropped into the previously prepared reaction solution over 1 hour. The mixture was further stirred at room temperature for 30 minutes and then filtered to obtain a blue solid. The obtained blue solid was put into 200 parts of methanol and dispersed for 1 hour, followed by filtration twice. The operation of filtering the blue solid obtained by this operation in 200 parts of water and dispersing for 1 hour was repeated twice. The blue solid obtained by this operation was dried at 60 ° C. under reduced pressure to obtain 17.1 parts of the compound (Aa2-53) represented by the formula (AI-18).

Resin synthesis example 1
In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was allowed to flow at 0.02 L / min to form a nitrogen atmosphere, and 200 parts of 3-methoxy-1-butanol and 105 parts of 3-methoxybutyl acetate were added and stirred. While heating to 70 ° C. Next, 60 parts of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (compound represented by formula (1-1) and compound represented by formula (2-1)) (Mix ratio of 50:50) 240 parts are dissolved in 140 parts of 3-methoxybutyl acetate to prepare a solution, and the solution is heated to 70 ° C. over 4 hours using a dropping funnel. It was dripped in the flask kept warm. On the other hand, a solution obtained by dissolving 30 parts of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 225 parts of 3-methoxybutyl acetate was placed in a flask using another dropping funnel over 4 hours. It was dripped. After completion of dropping of the polymerization initiator solution, the solution was kept at 70 ° C. for 4 hours, and then cooled to room temperature. Resin B having a solid content of 32.6% and an acid value of 110 mg-KOH / g (solid content conversion) A -1b solution was obtained. The obtained resin B-1b had a weight average molecular weight Mw of 13,400 and a molecular weight distribution of 2.50.

Example 1: <Colored curable resin composition>
Colorant (A): 41.6 parts of a compound represented by formula (AI-18);
Compound represented by formula (*) 0.4 part

Alkali-soluble resin (B): Resin B-1b (in terms of solid content) 29 parts;
Polymerizable compound (C): 11 parts of dipentaerystol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.);
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 4 parts;
Solvent (E): 413 parts of propylene glycol monomethyl ether acetate;
In addition, 0.15 part of leveling agent (F): polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) was mixed to obtain a colored curable resin composition.

Comparative Example 1: <Colored curable resin composition>
Colorant (A): 26 parts of a compound represented by formula (AI-18);
Alkali-soluble resin (B): 44 parts of resin B-1b (in terms of solid content);
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA: manufactured by Nippon Kayaku Co., Ltd.) 11 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 4 parts;
Solvent (E): 68 parts of propylene glycol monomethyl ether acetate;
Solvent (E): 561 parts of 4-hydroxy-4-methyl-2-pentanone;
In addition, 0.15 part of leveling agent (F): polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) was mixed to obtain a colored curable resin composition.

<Production of color filter>
The colored curable resin composition obtained in Example 1 and Comparative Example 1 was applied on a 2-inch square glass substrate (Eagle XG; manufactured by Corning) by spin coating, and then pre-baked at 100 ° C. for 3 minutes. Thus, a colored composition layer was formed. After cooling, using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.), exposure was performed at an exposure amount (based on 365 nm) of 150 mJ / cm ^{2 in} an air atmosphere. A photomask was not used. The colored composition layer after exposure was post-baked in an oven at 180 ° C. for 20 minutes to produce a color filter (film thickness: 2.0 μm).

<Evaluation of heat resistance>
The obtained color filter was heated at 230 ° C. for 20 minutes, and the color difference (ΔEab *) before and after heating was measured using a colorimeter (OSP-SP-200; manufactured by OLYMPUS). The color difference (ΔEab *) of the color filter produced from the colored curable resin composition obtained in Example 1 is 3.8, and the color filter produced from the colored curable resin composition obtained in Comparative Example 1 The color difference (ΔEab *) was 8.5.

  The color filter formed from the colored curable resin composition of the present invention is useful as a color filter used for display devices (for example, liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state imaging devices.

Claims (12)

A colored curable resin comprising a compound (Aa) represented by the formula (AI), a dye (Ab), a resin (B), a polymerizable compound (C), and a polymerization initiator (D) Composition (however, it does not include those prepared by preparing a colored dispersion with the compound (Aa) and a solvent and then mixing with the remaining components).
[In the formula (AI), R ^{41 to} R ⁴⁴ each independently represents an optionally substituted alkyl group having 1 to 20 carbon atoms or an alkyl group having 2 to 20 carbon atoms. A group in which an oxygen atom is inserted between methylene groups constituting the alkyl group, an aromatic hydrocarbon group which may have a substituent, an aralkyl group or a hydrogen atom which may have a substituent, Represent. 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 be bonded to form a ring with the nitrogen atom to which they are bonded.
R ^{47 to} R ⁵⁴ each independently represents a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a halogen atom, a nitro group, a sulfonyl group, a hydroxy group, or an alkyl group having 1 to 8 carbon atoms. An oxygen atom may be inserted between the methylene groups constituting the group. R ⁴⁸ and R ⁵² may be bonded to each other to form —NH—, —S— or —SO ₂ —.
Ring T ¹ represents an aromatic heterocyclic ring which may have a substituent.
[Y] ^m− represents an arbitrary m-valent anion containing at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus and oxygen as essential elements.
m represents an arbitrary natural number.
When a plurality of cations represented by the following formula are contained in one molecule, they may have the same structure or different structures.
[Wherein, rings T ¹ , R ^{41 to} R ⁴⁴ and R ^{47 to} R ⁵⁴ have the same meanings as described above, respectively. ]] The colored curable resin composition according to claim 1, wherein [Y] ^m- is an anion of a heteropolyacid or isopolyacid containing tungsten as an essential element. The colored curable resin composition according to claim 2, wherein [Y] ^m- is an anion of phosphotungstic acid, an anion of silicotungstic acid, or an anion of tungsten-based isopolyacid.   The colored curable resin composition according to any one of claims 1 to 3, wherein the dye (Ab) is one selected from the group consisting of a xanthene dye, a triarylmethane dye, an anthraquinone dye, and a tetraazaporphyrin dye. .   The colored curable resin composition according to any one of claims 1 to 4, wherein the dye (Ab) is a xanthene dye. The colored curable resin composition according to claim 4 or 5, wherein the xanthene dye is a compound represented by the formula (a1-1).
[In formula (a1-1), R ^{1 to} R ⁴ are each independently a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a substituent. Represents a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a methylene group (—CH ₂ —) contained in the saturated hydrocarbon group, —O—, —CO— or It may be replaced by —NR ¹¹ —. R ¹ and R ² may be combined to form a ring containing a nitrogen atom, and R ³ and R ⁴ may be combined 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 represents NR ⁹ R ¹⁰
R ⁶ and R ⁷ each 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 2 or more, the plurality of R ⁵ may be the same or different.
a represents an integer of 0 or 1.
X represents a halogen atom.
Z ⁺ represents ⁺ N (R ¹¹ ) ₄ , Na ⁺ or K ⁺ , and four R ¹¹ may be the same or different.
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.
R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and —CH ₂ contained in the saturated hydrocarbon group — May be replaced by —O—, —CO—, —NH— or —NR ⁸ —, wherein R ⁹ and R ¹⁰ are bonded to each other and are a 3- to 10-membered heterocyclic ring containing a nitrogen atom. May be formed.
R ¹¹ represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms. ]   The colored curable resin composition according to any one of claims 1 to 6, wherein the resin (B) has a weight average molecular weight of 9000 or more.   The colored curable resin composition according to any one of claims 1 to 7, wherein the acid value of the resin (B) is 60 mg-KOH / g or more.   The colored curable resin composition according to any one of claims 1 to 8, wherein the content of the dye (Ab) is 0.01 to 5% by mass in 100% by mass of the solid content of the colored curable resin composition.   The colored curable resin composition according to any one of claims 1 to 9, wherein a mass ratio of the dye (Ab) / the compound (Aa) is 0.001 to 0.5.   The color filter formed from the colored curable resin composition in any one of Claims 1-10.   A display device comprising the color filter according to claim 11.