JP2017133008A - Colored curable resin composition, color filter and display device comprising the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored curable resin composition which can form a color filter which can show excellent brightness and has excellent heat resistance, a color filter formed from the colored curable resin composition, and a display device comprising the color filter.SOLUTION: The present invention provides a colored curable resin composition which comprises a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D), the composition comprising as the colorant (A) a dye having a xanthene skeleton, and comprising as the polymerizable compound (C) a polymerizable compound with a hydroxyl value of 100 mgKOH/g or more, and a color filter and a display device prepared therewith.SELECTED DRAWING: None

Description

  The present invention relates to a colored curable resin composition suitable for forming a colored image constituting a color filter used in a liquid crystal display device or a solid-state imaging device, and a color filter and a display device using the same.

In recent years, development of colored curable resin compositions containing dyes as colorants has been actively promoted. However, the heat resistance of the dye itself is not sufficient, and it is necessary to supplement the heat resistance with a transparent component other than the colorant.
JP 2009-237151 A (Patent Document 1) includes (A) a colorant, (B) a binder resin, (C) a photopolymerizable compound having an ethylenically unsaturated bond, and (D) photopolymerization. The photopolymerizable compound containing an initiator and (E) a solvent and having (C) an ethylenically unsaturated bond has a hydroxyl group, and the hydroxyl value of the photopolymerizable compound is 90 mgKOH / g to 140 mgKOH / The coloring curable composition for color filters which is g is disclosed. This numerical value range of the hydroxyl value is recognized in view of the development removability of the colored curable composition.

JP 2009-237151 A

  The present invention provides a colored curable resin composition capable of forming a color filter having excellent lightness and excellent heat resistance, a color filter formed from the colored curable resin composition, and the An object is to provide a display device including a color filter.

  The present invention provides the following colored curable resin composition, color filter, and display device.

[1] Including a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D),
As a colorant (A), including a dye having a xanthene skeleton,
A colored curable resin composition comprising a polymerizable compound having a hydroxyl value of 100 mgKOH / g or more as the polymerizable compound (C).
[2] The colored curable resin composition according to [1], wherein the polymerizable compound having a hydroxyl value of 100 mgKOH / g or more contains pentaerythritol triacrylate.
[3] The ratio of the content of the polymerizable compound (C) to the content of the resin (B) (the content of the polymerizable compound (C) / the content of the resin (B)) is 0.6 to The colored curable resin composition according to [1] or [2], which is 5.
[4] The ratio of the content of the polymerizable compound (C) to the content of the resin (B) (the content of the polymerizable compound (C) / the content of the resin (B)) is 0.75 to 5 by mass ratio. The colored curable resin composition according to any one of [1] to [3], which is 5, [5] The colorant (A) is C.I. I. The colored curable resin composition according to any one of [1] to [4], further including CI Pigment Blue 15: 6.
[6] The colored curable resin composition according to any one of [1] to [5], wherein the content of the dye having a xanthene skeleton is 1 to 50% by mass in 100% by mass of the colorant (A). .
[7] The colored curable resin composition according to any one of [1] to [6], wherein the polymerization initiator (D) includes an oxime compound.
[8] A color filter formed from the colored curable resin composition according to any one of [1] to [7].
[9] A display device including the color filter according to [8].

  According to the colored curable resin composition according to the present invention, it is possible to provide a color filter excellent in heat resistance and a display device including the color filter, which can exhibit good brightness.

<Colored curable resin composition>
The colored curable resin composition according to the present invention includes a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), and has a xanthene skeleton as the colorant (A). Contains dye. Moreover, in this invention, the polymeric compound whose hydroxyl value is 100 mgKOH / g or more is included as a polymeric compound (C).
According to such a colored curable resin composition, it is possible to form a color filter that exhibits good lightness and excellent heat resistance despite containing a dye.
In addition, unless otherwise indicated, the compound illustrated as each component in this specification can be used individually or in combination of multiple types.

[1] Colorant (A)
The colorant (A) contains a dye.
The colored curable resin composition of the present invention contains a dye having a xanthene skeleton (hereinafter, the dye is referred to as a xanthene dye) as the dye. Since the colored curable resin composition of this invention contains the below-mentioned polymeric compound (C) and a xanthene dye, it can obtain favorable brightness. As the xanthene dye, C.I. I. Acid Red 51, 52, 87, 92, 289, 388, C.I. I. Acid Violet 9, 30, C.I. I. Basic Red 8, C.I. I. Modern Red 27, Rose Bengal B, Sulforhodamine G, Rhodamine 6G, xanthene dye described in JP 2010-32999 A, xanthene dye described in Japanese Patent No. 4492760, and the like. The colorant (A) can contain one or more xanthene dyes.
Especially, it is preferable that a xanthene dye contains the compound (henceforth "compound (1)") represented by Formula (1) as a main component.

In Expression ^(1), R 1 to R ⁴ are each independently hydrogen atom, or a monovalent aromatic hydrocarbon group -R ⁸ or 6 to 10 carbon atoms, or, ^{R 1} and ^{R 2} R ³ and R ⁴ together form a ring containing a nitrogen atom. Hydrogen atoms contained in the aromatic hydrocarbon group, a halogen _{^{atom, -R 8, -OH, -OR 8}} , -SO 3 -, -SO 3 H, -SO 3 - M +, -CO 2 H, - It may be substituted with CO ₂ R ⁸ , —SO ₃ R ⁸ or —SO ₂ NR ⁹ R ¹⁰ . Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
R ^{5 _{is, -OH, -SO 3 -, -SO}} 3 H, -SO 3 - M +, -CO 2 H, -CO 2 - M +, -CO 2 R 8, -SO 3 R 8 or -SO ₂ represents NR ⁹ R ¹⁰
m represents an integer of 0 to 5. When m is an integer of 2 or more, the plurality of R ⁵ may be the same or different from each other.
R ⁶ and R ⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
M ⁺ represents ⁺ N (R ¹¹ ) ₄ , Na ⁺ or K ⁺ . X represents a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
a represents 0 or 1.
R ⁸ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group is substituted with an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom. The —CH ₂ — contained in the saturated hydrocarbon group may be replaced by —S—, —O—, —CO— or —NR ¹¹ —. 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. When a plurality of R ¹¹ are present, all or part of them may be the same.
R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group is substituted with —OH or a halogen atom. And —CH ₂ — contained in the saturated aliphatic hydrocarbon group may be replaced by —S—, —O—, —CO—, —NH— or —NR ⁸ —. , R ⁹ and R ¹⁰ may be bonded to each other to form a 3- to 10-membered heterocyclic ring containing a nitrogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. ]

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.
Monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ¹ to R ⁴ are, as a _{^{substituent, -SO 3 -, -SO 3 H}} , -SO 3 - M + and _-SO 2 ^NR 9 ^{R 10} it is preferable to have at least one member selected from the group consisting of, _-SO ³ - to have at least one member selected from the group consisting of ^{M +} and _-SO 2 ^NR 9 ^{R 10} More preferred. _-SO ³ in this case - ^{M + _{Examples, -SO 3 - + N (R}} 11) 4 are preferred. When R ^{1 to} R ⁴ are these groups, it is advantageous for forming a color filter having excellent heat resistance.
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 rings. In the following rings, * represents a bond.

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ^{8 to} R ¹¹ include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, isopentyl group, neopentyl group, and hexyl. Group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, dodecyl group, hexadecyl group, icosyl group, etc. alkyl group having 1 to 20 carbon atoms; cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl C3-C20 cycloalkyl groups, such as a group, a cyclooctyl group, and a tricyclodecyl group.

Regarding R ⁸ , the aromatic hydrocarbon group having 6 to 10 carbon atoms in which the hydrogen atom contained in the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms may be substituted includes phenyl group, toluyl group, xylyl Group, mesityl group, propylphenyl group, butylphenyl group and the like. Examples of the group in which —CH ₂ — contained in R ⁸ is replaced by —S—, —O—, —CO—, or —NR ¹¹ — include the following groups. In the following groups, * represents a bond.

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.

Examples of the group represented by —SO ₂ NR ⁹ R ¹⁰ include groups represented by the following formulae. In the following groups, * represents a bond.

In the above formula, X ⁰ and X ² each independently represent a halogen atom. Examples of the halogen atom in X ⁰ and X ² include a fluorine atom, a chlorine atom and a bromine atom.

Examples of the aralkyl group having 7 to 10 carbon atoms in R ¹¹ in the formula (1) include a benzyl group, a phenylethyl group, and a phenylbutyl group.

M ⁺ is ⁺ N (R ¹¹ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N (R ¹¹ ) ₄ . ⁺ N (R ¹¹ ) ₄ is preferably a monovalent saturated hydrocarbon group having 5 to 20 carbon atoms, at least two of the four R ¹¹ . The total number of carbon atoms of the four ^{R 11} is preferably 20 to 80, 20 to 60 is more preferable.

  More preferably, the xanthene dye contains a compound represented by the formula (2) as a main component.

[In the formula (2), R ^{21 to} R ²⁴ each independently represents a hydrogen atom, —R ²⁶ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and is included in the aromatic hydrocarbon group. hydrogen atoms _{^{are, -SO 3 -, -SO 3 -}} M a +, -SO 3 H, optionally substituted by -SO ^{3 R 26} or _-SO 2 ^{NHR 26.} X represents a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
a1 represents 0 or 1. m1 represents the integer of 0-5. When m1 is an integer of 2 or more, the plurality of R ²⁵ may be the same or different. M ^{a +} represents ⁺ N (R ²⁷ ) ₄ , Na ⁺ or K ⁺ .
R ²⁵ _is, ^-SO 3 _- represents a M a +, -SO ₃ H or _{^{SO 2 NHR 26 -, -SO 3}} .
R ²⁶ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms. Four R < ²⁷ > represents a C1-C20 monovalent | monohydric saturated hydrocarbon group or benzyl group mutually independently. ]

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ^{21 to} R ²⁴ in the formula (2) include the same groups as those exemplified as the aromatic hydrocarbon group in R ^{1 to} R ⁴ . It is done. Among them, R ²¹ and R ²³ are hydrogen atoms, R ²² and R ²⁴ are monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms, and the hydrogen atoms contained in the aromatic hydrocarbon groups are substituted. when a group is _{^{substituted, -SO 3 -, -SO 3 -}} M +, -SO 3 H, is preferably -SO ^{3 R 26} or _-SO 2 ^{NHR 26.} Furthermore, R ²¹ and R ²³ are hydrogen atoms, R ²² and R ²⁴ are monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms, and the hydrogen atoms contained in the aromatic hydrocarbon groups are: more preferably M ⁺ or those which may be substituted with _-SO 2 ^{NHR 26 -} _{-SO 3.} When R ^{21 to} R ²⁴ are these groups, it is advantageous for forming a color filter having excellent heat resistance.
Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ²⁶ and R ²⁷ include the same groups as those exemplified as the saturated hydrocarbon group in R ^{8 to} R ¹¹ . ^{-R 26} in ^R 21 ^{to R 24} in the formula (2) each independently represent a hydrogen atom, a methyl group or an ethyl group.
The ^{R 26} in -SO ₃ R ²⁶ and _-SO 2 ^{NHR 26,} preferably branched alkyl group having 3 to 20 carbon atoms, more preferably a branched alkyl group having 6 to 12 carbon atoms, 2- More preferred is an ethylhexyl group.
M ^{a +} is ⁺ N (R ²⁷ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N (R ²⁷ ) ₄ . ⁺ N (R ²⁷ ) ₄ is preferably a monovalent saturated hydrocarbon group having 5 to 20 carbon atoms, at least two of the four R ²⁷ . The total number of carbon atoms of the four ^{R 27} is preferably 20 to 80, 20 to 60 is more preferable.
The xanthene dye preferably contains one or more compounds represented by formulas (1-1) to (1-16) as a main component. In formulas (1-1) to (1-16), Ra represents a 2-ethylhexyl group.

  Among these compounds, C.I. I. Acid Red 289 sulfonamidated product or C.I. I. A quaternary ammonium salt of Acid Red 289 is more preferable. Examples of such a compound include compounds represented by formula (1-1) to formula (1-8), formula (1-11), and formula (1-12), respectively.

The compound represented by formula (1-1) to formula (1-16) is, for example, a dye having —SO ₂ Cl obtained by chlorinating a dye or dye intermediate having —SO ₃ H by a conventional method. Alternatively, it can be produced by reacting a dye intermediate with an amine represented by R ⁸ —NH ₂ .
Moreover, it can manufacture also by the method with which the pigment | dye manufactured by the method of the upper right column-lower left column of Unexamined-Japanese-Patent No. 3-78702 3 is made to react with an amine after chlorination like the above.

  Another preferable xanthene dye contains any one or more of the compounds represented by the formulas (1-17) to (1-31) as a main component.

The compounds represented by the formula (1-17) to the formula (1-31) can be produced according to the methods described in the upper right column to the lower left column of the third page of JP-A-3-78702. Examples of such a method include a method of reacting the compound represented by the formula (1a) with the compound represented by the formula (1b) and the compound represented by the formula (1c). In formula (1b) and formula (1c), R ^{1 to} R ⁴ each represent the same meaning as described above.

The colorant (A) can further contain a pigment in addition to a dye such as a xanthene dye.
Examples of the pigment include organic pigments such as C.I. I. Blue pigments such as CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60; I. And violet color pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, and 38. Among these, pigments are C.I. from the viewpoint of obtaining good brightness. I. Pigment red violet 23, C.I. I. Preferably at least one pigment selected from CI Pigment Blue 15: 3 and 15: 6; I. More preferably, it contains CI Pigment Blue 15: 6. The colorant (A) can contain one kind or two or more kinds of pigments (A-2).
If necessary, the pigment can be atomized by rosin treatment, surface treatment using a pigment derivative having an acidic group or basic group introduced, graft treatment on the pigment surface with a polymer compound, sulfuric acid atomization method, etc. Treatment or cleaning treatment with an organic solvent or water for removing impurities, removal treatment by ion exchange method of ionic impurities, or the like may be performed.
The pigment preferably has a uniform particle size. By carrying out a dispersion treatment by containing a pigment dispersant, a pigment dispersion in which the pigment is uniformly dispersed in the solution can be obtained.
Examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic surfactants. These pigment dispersants may be used alone or in combination of two or more.
When a pigment dispersant is used, the amount used is preferably 100 parts by mass or less, more preferably 5 to 50 parts by mass per 100 parts by mass of the pigment. When the amount of the pigment dispersant used is within this range, there is a tendency that a pigment dispersion in a uniform dispersion state is obtained.

  Content of a coloring agent (A) is 1-70 mass% normally in 100 mass% of solid content of a colored curable resin composition, Preferably it is 5-60 mass%, More preferably, it is 8-50 mass. %. When the content of the colorant (A) is within the above range, sufficient color density and mechanical strength are easily obtained when a color filter is formed. The “solid content of the colored curable resin composition” refers to the total of the components excluding the solvent (E) in the colored curable resin composition.

The content of xanthene dye and the like in the colorant (A) is usually 1% by mass or more, preferably 3% by mass or more, more preferably 5% by mass or more in 100% by mass of the colorant (A). More preferably, it is 10% by mass or more. The content of the dye may be 100% by mass in 100% by mass of the colorant (A).
The colorant (A) can contain a pigment. In this case, the content of the dye may be 90% by mass or less and 100% by mass or less in 100% by mass of the colorant (A). 70 mass% or less may be sufficient, but 50 mass% or less may be sufficient.
When the colorant (A) contains a pigment, the mass ratio of the dye content to the pigment content (dye content / pigment content) is usually 1/99 to 99/1, preferably 3 / 97 to 99/1, more preferably 3/97 to 70/30, and even more preferably 3/97 to 50/50.
C. which is a preferred pigment. I. Pigment Blue 15: 6, the dye content and C.I. I. The mass ratio to the content of Pigment Blue 15: 6 (the content of dye / the content of CI Pigment Blue 15: 6) is preferably 3/97 to 70/30, more preferably 3 / 97-50 / 50. When the mass ratio is within this range, it is advantageous for obtaining high brightness and high contrast.
The colorant (A) can contain a pigment, and the pigment is C.I. I. Pigment violet 23, C.I. I. Preferably at least one pigment selected from CI Pigment Blue 15: 3 and 15: 6; I. More preferably, it contains CI Pigment Blue 15: 6. From the viewpoint of obtaining good brightness, C.I. I. The content of CI Pigment Blue 15: 6 is preferably 50% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and still more preferably 95% in 100% by mass of the pigment. It is at least mass%, most preferably 100 mass%.

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

Resin [K1]: At least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (hereinafter referred to as “(a)”). ] And a monomer (b) having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond [hereinafter sometimes referred to as “(b)”. ] And a copolymer.
Resin [K2]: (a) and (b), monomer (c) copolymerizable with (a) (however, different from (a) and (b)) [hereinafter referred to as “(c)” There is. ) And a copolymer.
Resin [K3]: Copolymer of (a) and (c).
Resin [K4]: A resin obtained by reacting (b) with a copolymer of (a) and (c).
Resin [K5]: A resin obtained by reacting (a) with a copolymer of (b) and (c).
Resin [K6]: A resin obtained by reacting (a) with a copolymer of (b) and (c) and further reacting with a carboxylic acid anhydride.

Specifically, as (a),
Unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, o-, m-, 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, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid, 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-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] bicyclounsaturated compounds containing a carboxy group such as hept-2-ene, 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- Unsaturated dicarboxylic acid anhydrides such as tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride (hymic acid anhydride);
Unsaturated mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl]. ;
Examples thereof include unsaturated (meth) acrylic acid containing a hydroxy group and a carboxy group in the same molecule, such as α- (hydroxymethyl) (meth) acrylic acid.
Especially, it is preferable that (a) is (meth) acrylic acid, maleic anhydride, etc. from a viewpoint of copolymerization reactivity or a solubility viewpoint to aqueous alkali solution.

  In the present specification, “(meth) acryl” represents at least one selected from the group consisting of acryl and methacryl. The same applies to notations such as “(meth) acryloyl” and “(meth) acrylate”.

(B) is a polymerization 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 (oxolane ring)) and an ethylenically unsaturated bond. Refers to a chemical compound. (B) is preferably a monomer having a cyclic ether structure having 2 to 4 carbon atoms and a (meth) acryloyloxy group.
(B) is a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond [hereinafter, 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)”. ] Etc. are mentioned.

(B1) is a monomer (b1-1) having a structure obtained by epoxidizing an unsaturated aliphatic hydrocarbon [hereinafter referred to as “(b1-1)”. ] Monomer (b1-2) having a structure obtained by epoxidizing unsaturated alicyclic hydrocarbon [hereinafter, referred to as “(b1-2)”. ].
As (b1-1), glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl 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 (glycidyloxymethyl) styrene 2,3,5-tris (glycidyloxymethyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4,6- Examples include tris (glycidyloxymethyl) styrene.

  Examples of (b1-2) include vinylcyclohexene monooxide, 1,2-epoxy 4-vinylcyclohexane (for example, Celoxide 2000; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, , Cyclomer A400; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer M100; manufactured by Daicel Chemical Industries, Ltd.), a compound represented by the formula (I) And compounds represented by the formula (II).

[In Formula (I) and Formula (II), R ^a and R ^b each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is a hydroxy group May be substituted. X ¹ and X ² are each independently a single ^{bond, * - R c -, *} - R c -O -, * - R c -S-, or * represents a -R ^c -NH-. R ^c represents an alkanediyl group having 1 to 6 carbon atoms. * Represents a bond with O. ]

Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group.
Examples of the alkyl group in which a hydrogen atom is substituted with hydroxy include hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxy Examples include a -1-methylethyl group, a 2-hydroxy-1-methylethyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group, and a 4-hydroxybutyl group.
R ^a and R ^b are preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, or a 2-hydroxyethyl group, and more preferably a hydrogen atom or a methyl group.
Examples of the alkanediyl group constituting R ^c include methylene group, ethylene group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5- Examples thereof include a diyl group and a hexane-1,6-diyl group.

X ¹ and X ² are preferably a single bond, a methylene group, an ethylene group, * —CH ₂ —O— (* represents a bond to O) group, or * —CH ₂ CH ₂ —O— group. More preferably, it is a single bond or a * —CH ₂ CH ₂ —O— group.
Specific examples of the compound represented by the formula (I) include compounds represented by the formula (I-1) to the formula (I-15), preferably the formula (I-1) and the formula (I-3). ), Formula (I-5), formula (I-7), formula (I-9), and compounds represented by formula (I-11) to formula (I-15), and more preferably Examples thereof include compounds represented by I-1), formula (I-7), formula (I-9), and formula (I-15).

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

The compound represented by the formula (I) and the compound represented by the formula (II) can be used alone. They can be mixed in any ratio. In the case of mixing, the mixing ratio is the formula (I): formula (II) [molar ratio], preferably 5:95 to 95: 5, more preferably 10:90 to 90:10, still more preferably 20: 80-80: 20.
The monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond is preferably a monomer having an oxetanyl group and a (meth) acryloyloxy group.
Preferred examples of (b2) include 3-methyl-3- (meth) acryloyloxymethyl oxetane, 3-ethyl-3- (meth) acryloyloxymethyl oxetane, 3-methyl-3- (meth) acryloyloxyethyl oxetane, 3-ethyl-3- (meth) acryloyloxyethyl oxetane is mentioned.
The monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond is preferably a monomer having a tetrahydrofuryl group and a (meth) acryloyloxy group. Preferred examples of (b3) include tetrahydrofurfuryl acrylate (for example, Biscoat V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

As a specific example of (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 ] decane-8- Ile (meth) acrylate [in this technical field, it is called "dicyclopentanyl (meth) acrylate" as a common name. It may also be called “tricyclodecyl (meth) acrylate”. ], Tricyclo [5.2.1.0 ^2,6 ] decen-8-yl (meth) acrylate [in this technical field, it is called "dicyclopentenyl (meth) acrylate" as a common name. ], Dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, benzyl (Meth) acrylic acid esters such as (meth) acrylates;
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 derivatives such as maleimide propionate, N- (9-acridinyl) maleimide;
Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyl toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene , Isoprene, 2,3-dimethyl-1,3-butadiene and the like.
Among these, from the viewpoint of copolymerization reactivity and heat resistance, (c) includes benzyl (meth) acrylate, tricyclodecyl (meth) acrylate, styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, Bicyclo [2.2.1] hept-2-ene and the like are preferable. Moreover, since it is excellent in the developability at the time of pattern formation, benzyl (meth) acrylate and tricyclodecyl (meth) acrylate are more preferable as (c).

In the resin [K1], the ratio of the structural units derived from each is preferably in the following range among all the structural units constituting the resin [K1].
A structural unit derived from (a); 2-50 mol% (more preferably 10-45 mol%),
A structural unit derived from (b), particularly a structural unit derived from (b1); 50 to 98 mol% (more preferably 55 to 90 mol%).
When the ratio of the structural unit of the resin [K1] is in the above range, the storage stability, developability, and solvent resistance of the resulting pattern tend to be excellent.
Resin [K1] is described in the document “Experimental Method for Polymer Synthesis” (Takayuki Otsu, published by Kagaku Dojin Co., Ltd., 1st edition, 1st edition, published on March 1, 1972) and the document. It can be produced with reference to the cited references.
Specifically, there is a method in which a predetermined amount of (a) and (b) (particularly (b1)), a polymerization initiator, a solvent, and the like are charged into a reaction vessel and stirred, heated, and kept warm in a deoxygenated atmosphere. Can be mentioned. In addition, the polymerization initiator, the solvent, and the like used here are not particularly limited, and any of those usually used in the field can be used. Examples of the polymerization initiator include azo compounds (such as 2,2′-azobisisobutyronitrile and 2,2′-azobis (2,4-dimethylvaleronitrile)) and organic peroxides (such as benzoyl peroxide). It is done. The solvent is not particularly limited as long as it dissolves each monomer, and a solvent (E) described later can be used as a solvent for the colored curable resin composition.
As the obtained copolymer, the solution after the reaction may be used as it is, a concentrated or diluted solution may be used, or a solid (powder) taken out by a method such as reprecipitation. May be used. In particular, by using a solvent (E) described later as a solvent in the polymerization, the solution after the reaction can be used as it is, and the manufacturing process can be simplified.

In the resin [K2], the ratio of the structural units derived from each is preferably within the following range among all the structural units constituting the resin [K2].
A structural unit derived from (a); 4-45 mol% (more preferably 10-30 mol%),
A structural unit derived from (b), in particular a structural unit derived from (b1); 2-95 mol% (more preferably 5-80 mol%),
Structural unit derived from (c); 1 to 65 mol% (more preferably 5 to 60 mol%).
When the ratio of the structural unit of the resin [K2] is in the above range, the storage stability, developability, solvent resistance of the resulting pattern, heat resistance and mechanical strength tend to be excellent.
Resin [K2] can be produced in the same manner as described for the production method of resin [K1]. Specifically, a predetermined amount of (a), (b) (particularly (b1)) and (c), a polymerization initiator and a solvent are charged into a reaction vessel, and the mixture is stirred, heated and kept warm in a deoxygenated atmosphere. The method of doing is mentioned. As the obtained copolymer, the solution after the reaction may be used as it is, a concentrated or diluted solution may be used, or a solid (powder) taken out by a method such as reprecipitation. May be used.

In the resin [K3], the ratio of the structural unit derived from each is preferably in the following range among all the structural units constituting the resin [K3].
A structural unit derived from (a); 2-55 mol% (more preferably 10-50 mol%),
Structural unit derived from (c); 45 to 98 mol% (more preferably 50 to 90 mol%).
Resin [K3] can be produced in the same manner as described for the production method of resin [K1].

Resin [K4] obtains a copolymer of (a) and (c), and (b) has an oxirane ring of (b1) having a C2-C4 cyclic ether structure (b). It can manufacture by adding to the carboxylic acid and / or carboxylic anhydride which it has. Specifically, first, a copolymer of (a) and (c) is produced in the same manner as the method described as the production method of the resin [K1]. In this case, the ratio of the structural units derived from each is preferably in the following range among all the structural units constituting the copolymer of (a) and (c).
A structural unit derived from (a); 5-50 mol% (more preferably 10-45 mol%),
Structural unit derived from (c); 50 to 95 mol% (more preferably 55 to 90 mol%).

Next, a part of the carboxylic acid and / or carboxylic anhydride derived from (a) in the copolymer has a C2-C4 cyclic ether structure (b1), particularly (b1). React the oxirane ring. Specifically, following the production of the copolymer of (a) and (c), the atmosphere in the flask is replaced with nitrogen to air, and (b) (particularly (b1)), carboxylic acid or carboxylic anhydride A reaction catalyst (such as tris (dimethylaminomethyl) phenol) and a polymerization inhibitor (such as hydroquinone) in a flask and reaction at 60 to 130 ° C. for 1 to 10 hours. Resin [K4] can be obtained.
The amount of (b) used, in particular (b1), is preferably 5 to 80 mol, more preferably 10 to 75 mol, per 100 mol of (a). By setting it as this range, there exists a tendency for the balance of storage stability, developability, solvent resistance, heat resistance, mechanical strength, and sensitivity to become favorable. Since the reactivity of the cyclic ether structure is high and unreacted (b) hardly remains, (b1) is preferable as (b) used in the resin [K4], and (b1-1) is more preferable.
It is preferable that the usage-amount of the said reaction catalyst is 0.001-5 mass% with respect to the total amount of (a), (b) (especially (b1)) and (c). It is preferable that the usage-amount of the said polymerization inhibitor is 0.001-5 mass% with respect to the total amount of (a), (b) and (c).
The reaction conditions such as the charging method, reaction temperature, and time can be appropriately adjusted in consideration of the production equipment and the amount of heat generated by polymerization. In addition, like the polymerization conditions, the charging method and the reaction temperature can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, and the like.

Resin [K5] obtains a copolymer of (b) (particularly (b1)) and (c) in the same manner as in the method for producing resin [K1] described above. Similarly to the above, the obtained copolymer may be used as it is after the reaction, or may be a concentrated or diluted solution, or may be solid (powder) by a method such as reprecipitation. You may use what was taken out as.
The ratio of the structural units derived from (b) (particularly (b1)) and (c) is preferably in the following range with respect to the total number of moles of all structural units constituting the copolymer.
A structural unit derived from (b), in particular a structural unit derived from (b1); 5-95 mol% (more preferably 10-90 mol%),
Structural unit derived from (c); 5-95 mol% (more preferably 10-90 mol%).

  Furthermore, under the same conditions as in the production method of the resin [K4], the cyclic ether structure derived from (b) of the copolymer of (b) (particularly (b1)) and (c), The resin [K5] can be obtained by reacting the carboxylic acid or carboxylic anhydride having the resin. The amount of (a) to be reacted with the copolymer is preferably 5 to 80 mol with respect to 100 mol of (b) (particularly (b1)). Since the reactivity of the cyclic ether structure is high and unreacted (b) hardly remains, (b1) is preferable as (b) used in the resin [K5], and (b1-1) is more preferable.

Resin [K6] is a resin obtained by further reacting carboxylic anhydride with resin [K5]. Carboxylic anhydride is reacted with the hydroxy group generated by the reaction of the cyclic ether structure with carboxylic acid or carboxylic anhydride.
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, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride (highmic acid anhydride) and the like. It is done.

  Of the resins [K1] to [K6], a preferable resin as the resin (B) is [K1] or [K2]. Resin (B) may consist of 1 type of resin, and may contain 2 or more types of resin.

The polystyrene equivalent weight average molecular weight (Mw) of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and still more preferably 5,000 to 30,000. 000. When the weight average molecular weight (Mw) is in the above range, the solubility of the unexposed area in the developer is high, and the residual film ratio and hardness of the resulting pattern tend to be high. The molecular weight distribution [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 solution acid value of the resin (B) is preferably 5 to 180 mg-KOH / g, more preferably 10 to 100 mg-KOH / g, and further preferably 12 to 50 mg-KOH / g. The acid value is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g of the resin, and can be determined, for example, by titrating with an aqueous potassium hydroxide solution.
The content of the resin (B) is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and further preferably 15 to 30% in the solid content of 100% by mass of the colored curable resin composition. % By mass. When content of resin (B) exists in the said range, there exists a tendency for the solubility with respect to the developing solution of an unexposed part to be high.

[3] Polymerizable compound (C)
The polymerizable compound (C) is a compound that can be polymerized by an active radical generated from the polymerization initiator (D) by light irradiation or the like. The colored curable resin composition of the present invention contains a polymerizable compound having a hydroxyl value of 100 mgKOH / g or more as the polymerizable compound (C). According to the colored curable resin composition of the present invention containing such a polymerizable compound (C), it is possible to form a color filter excellent in heat resistance despite containing a dye as the colorant (A). Become.
The polymerizable compound (C) may be composed of one kind of polymerizable compound having a hydroxyl value of 100 mgKOH / g or more, and contains two or more kinds of polymerizable compounds having a hydroxyl value of 100 mgKOH / g or more. Also good. The polymerizable compound (C) includes one or more polymerizable compounds having a hydroxyl value of 100 mgKOH / g or more, and one or more polymerizable compounds having a hydroxyl value of less than 100 mgKOH / g. It may be a mixture of In the case of the mixture, from the viewpoint of heat resistance, the polymerizable compound (C) preferably has a hydroxyl value of 100 mgKOH / g or more as the mixture. From the viewpoint of heat resistance, the hydroxyl value of the polymerizable compound (C) is preferably 110 mgKOH / g or more. The hydroxyl value of the polymerizable compound (C) is usually 170 mgKOH / g or less. A hydroxyl value is measured according to description of the Example mentioned later.

Examples of the polymerizable compound (C) include compounds having a polymerizable ethylenically unsaturated bond and a hydroxyl group. The polymerizable compound (C) preferably has 2 or more ethylenically unsaturated bonds in the molecule, and more preferably 3 or more. Specific examples of the polymerizable compound having a hydroxyl value of 100 mgKOH / g or more include pentaerythritol triacrylate, pentaerythritol di (meth) acrylate, ethoxylated pentaerythritol tri (meth) acrylate, propoxylated pentaerythritol triacrylate, Trimethylolpropane di (meth) acrylate, ethoxylated trimethylolpropane di (meth) acrylate, ethoxylated glycerin di (meth) acrylate, propoxylated glycerin di (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, ethoxylated ditri Examples include methylolpropane tri (meth) acrylate and propoxylated ditrimethylolpropane triacrylate.
The content of the polymerizable compound (C) is a mass ratio (the content of the polymerizable compound (C) / the content of the resin (B)) to the content of the resin (B) in the colored curable resin composition. Usually, it is 0.2-10, Preferably it is 0.6-8, More preferably, it is 0.6-5, More preferably, it is 0.75-5. If the mass ratio is within the above range, a colored coating film having better heat resistance can be obtained.

[4] Polymerization initiator (D)
The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating an active radical, an acid or the like by the action of light or heat and starting polymerization, and a known polymerization initiator can be used.

Examples of the polymerization initiator (D) include oxime compounds such as O-acyl oxime compounds, alkylphenone compounds, biimidazole compounds, triazine compounds, and acyl phosphine oxide compounds.
Two or more polymerization initiators (D) may be used in consideration of sensitivity, formability of a precise pattern shape, and the like. The polymerization initiator (D) is advantageous for precisely creating a pattern shape having sensitivity and a desired line width, and therefore preferably contains an oxime compound such as an O-acyl oxime compound.

  The O-acyl oxime compound is a compound having a structure represented by the formula (d). Hereinafter, * represents a bond.

  The O-acyloxime compound is a compound represented by the formula (d1) (hereinafter sometimes referred to as “compound (d1)”), a compound represented by the formula (d2) (hereinafter referred to as “compound (d2)”). And at least one selected from the group consisting of compounds represented by formula (d3) (hereinafter sometimes referred to as “compound (d3)”).

[In the formulas (d1) to (d3),
R ^d1 has an optionally substituted aromatic hydrocarbon group having 6 to 18 carbon atoms, an optionally substituted heterocyclic group having 3 to 36 carbon atoms, and a substituent. Represents an optionally substituted alkyl group having 1 to 15 carbon atoms, or an aromatic hydrocarbon group and an alkanediyl group derived from the alkyl group, which may have a substituent. The contained methylene group (—CH ₂ —) may be replaced by —O—, —CO—, —S—, —SO ₂ — or —NR ^d5 —.
R ^d2 represents an aromatic hydrocarbon group having 6 to 18 carbon atoms, a heterocyclic group having 3 to 36 carbon atoms, or an alkyl group having 1 to 10 carbon atoms.
R ^d3 represents an optionally substituted aromatic hydrocarbon group having 6 to 18 carbon atoms or an optionally substituted heterocyclic group having 3 to 36 carbon atoms.
R ^d4 represents an optionally substituted aromatic hydrocarbon group having 6 to 18 carbon atoms or an optionally substituted aliphatic hydrocarbon group having 1 to 15 carbon atoms; The methylene group (—CH ₂ —) contained in the aromatic hydrocarbon group may be replaced by —O—, —CO— or —S—, and the methine group (—CH < ) May be replaced by —PO ₃ <, and a hydrogen atom contained in the aliphatic hydrocarbon group may be substituted with an OH group.
R ^d5 represents an alkyl group having 1 to 10 carbon atoms, and the methylene group (—CH ₂ —) contained in the alkyl group may be replaced with —O— or —CO—. ]

The carbon number of the aromatic hydrocarbon group represented by R ^d1 is preferably 6 to 15, more preferably 6 to 12, and still more preferably 6 to 10. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group, and a terphenyl group, preferably a phenyl group and a naphthyl group, and more preferably a phenyl group. It is done.
The aromatic hydrocarbon group represented by R ^d1 may have one or more substituents. The substituent is preferably substituted at the α-position or γ-position of the aromatic hydrocarbon group, and more preferably substituted at the γ-position.
Examples of the substituent include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group An alkyl group having 1 to 15 carbon atoms such as a halogen atom such as a fluorine atom, a chlorine atom, an iodine atom or a bromine atom;
The alkyl group as the substituent preferably has 1 to 10 carbon atoms, and more preferably 1 to 7 carbon atoms. The alkyl group as the substituent may be any of linear, branched, and cyclic, and may be a group in which a linear group and a cyclic group are combined. The methylene group (—CH ₂ —) contained in the alkyl group as the substituent may be replaced with —O— or —S—. The hydrogen atom contained in the alkyl group may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, an iodine atom or a bromine atom, and is preferably substituted with a fluorine atom.
In the aromatic hydrocarbon group represented by R ^d1 , examples of the alkyl group as a substituent include groups represented by the following formulas. In the formula, * represents a bond.

Examples of the aromatic hydrocarbon group which may have a substituent represented by R ^d1 include groups represented by the following formulas. In the formula, * represents a bond.

In R ^d1 , the aromatic hydrocarbon group which may have a substituent is preferably a group represented by the following formula.

[Wherein R ^d6 represents an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom, and a hydrogen atom contained in R ^d6 may be substituted with a halogen atom. m2 represents an integer of 1 to 5. * Represents a bond. ]

Examples of the alkyl group represented by R ^d6 include the same groups as the alkyl groups exemplified as the substituent for the aromatic hydrocarbon group represented by R ^d1 . R ^d6 has preferably 2 to 7 carbon atoms, more preferably 2 to 5 carbon atoms. The alkyl group represented by R ^d6 may be linear, branched, or cyclic, and is preferably linear.
Examples of the halogen atom for R ^d6 include a fluorine atom, a chlorine atom, an iodine atom, and a bromine atom, and a fluorine atom is particularly preferable. It is preferable that 2 or more and 10 or less of hydrogen atoms contained in R ^d6 are substituted with halogen atoms, and 3 or more and 6 or less are more preferably substituted with halogen atoms. The substitution position of the R ^d6 O— group is preferably the ortho position or the para position, and particularly preferably the para position. m2 is preferably 1 to 2, particularly preferably 1.
The number of carbon atoms in the heterocyclic group represented by R ^d1 is preferably 3-20, more preferably 3-10, and even more preferably 3-5. Examples of the heterocyclic group include a pyrrolyl group, a furyl group, a thienyl group, an indolyl group, a benzofuryl group, and a carbazolyl group.
The heterocyclic group represented by R ^d1 may have one or more substituents. Examples of the substituent include the same groups as those exemplified as the substituent that the aromatic hydrocarbon group represented by R ^d1 may have.
The number of carbon atoms of the alkyl group represented by R ^d1 is preferably 1-12. ^Examples of the alkyl group represented by R ^d1 include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, A tetradecyl group, a pentadecyl group, etc. are mentioned. These alkyl groups may be linear, branched, or cyclic, and may be a group in which a chain group and a cyclic group are combined. In the alkyl group represented by R ^d1 , the methylene group (—CH ₂ —) may be replaced by —O—, —CO—, —S—, —SO ₂ — or —NR ^d5 —, The hydrogen atom may be substituted with an OH group or an SH group.
R ^d5 represents an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 5 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms. The alkyl group may be linear (linear or branched) or cyclic, and may be linear, branched, or cyclic. And a group in which a cyclic group is combined. In the alkyl group for R ^d5 , the methylene group (—CH ₂ —) may be replaced by —O— or —CO—.
Specific examples of the alkyl group which may have a substituent in R ^d1 include groups represented by the following formulas. * Represents a bond.

Further, in R ^d1 , the number of carbon atoms of the group obtained by combining the aromatic hydrocarbon group and the alkanediyl group is preferably 7 to 33, more preferably 7 to 18, and still more preferably 7 to 12. is there. The combined group may have one or more substituents, and the substituents are the same as those exemplified as the substituents that the aromatic hydrocarbon group and the alkyl group may have. The group of is mentioned. Examples of the group that is a combination of the aromatic hydrocarbon group and the alkanediyl group represented by R ^d1 include an aralkyl group, and specifically include a group represented by the following formula. In the formula, * represents a bond.

Among them, R ^d1 is preferably an aromatic hydrocarbon group which may have a substituent or an alkyl group which may have a substituent, and an aromatic hydrocarbon group which may have a substituent. Is more preferable.
The carbon number of the aromatic hydrocarbon group represented by R ^d2 is preferably 6 to 15, more preferably 6 to 12, and still more preferably 6 to 10. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group, and a terphenyl group.
Carbon number of the heterocyclic group represented by R ^d2 is preferably 3 to 20, more preferably 3 to 10, and further preferably 3 to 5. Examples of the heterocyclic group include a pyrrolyl group, a furyl group, a thienyl group, an indolyl group, a benzofuryl group, and a carbazolyl group.
The carbon number of the alkyl group represented by R ^d2 is preferably 1 to 7, more preferably 1 to 5, and further preferably 1 to 3. Examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group and decyl group. The alkyl group may be linear, branched, or cyclic, or may be a group that combines a chain group and a cyclic group.
R ^d2 is preferably a chain alkyl group, more preferably a chain alkyl group having 1 to 5 carbon atoms, still more preferably a chain alkyl group having 1 to 3 carbon atoms, and particularly preferably methyl. It is a group.
The number of carbon atoms of the aromatic hydrocarbon group represented by R ^d3 is preferably 6 to 15, more preferably 6 to 12, and still more preferably 6 to 10. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group, and a terphenyl group, and a phenyl group and a naphthyl group are preferable.
The aromatic hydrocarbon group represented by R ^d3 may have one or more substituents. The substituent is preferably substituted at the α-position or γ-position of the aromatic hydrocarbon group. The substituent is preferably an aliphatic hydrocarbon group having 1 to 15 carbon atoms, specifically, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl. An alkyl group having 1 to 15 carbon atoms such as a group and a decyl group; an alkenyl group having 1 to 15 carbon atoms such as an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, a nonenyl group, and a decenyl group; Is mentioned.
The aromatic hydrocarbon group represented by R ^d3 may have an aliphatic hydrocarbon group. The aliphatic hydrocarbon group preferably has 1 to 7 carbon atoms, and the aliphatic hydrocarbon group may be linear, branched, or cyclic, and is a linear group. And a group in which a cyclic group is combined. The methylene group (—CH ₂ —) contained in the aliphatic hydrocarbon group may be replaced with —O—, —CO— or —S—, and the methine group (—CH <) is represented by —N— <May be replaced.
Examples of the aliphatic hydrocarbon group include groups represented by the following formulas. In the formula, * represents a bond.

In R ^d3 , examples of the aromatic hydrocarbon group which may have a substituent include groups represented by the following formulas. In the formula, * represents a bond.

The number of carbon atoms of the heterocyclic group represented by R ^d3 is preferably 3 to 20, more preferably 3 to 10, and still more preferably 3 to 5. Examples of the heterocyclic group include a pyrrolyl group, a furyl group, a thienyl group, an indolyl group, a benzofuryl group, and a carbazolyl group. The heterocyclic group represented by R ^d3 may have one or more substituents, and the substituent may have an aromatic hydrocarbon group represented by R ^d1. Examples thereof include the same groups as those exemplified as the substituent.
Among them, R ^d3 is preferably an aromatic hydrocarbon group having a substituent, and the substituent is preferably a chain alkyl group having 1 to 7 carbon atoms (more preferably 1 to 3 carbon atoms). The number of groups is preferably 2 or more and 5 or less.

The number of carbon atoms of the aromatic hydrocarbon group represented by R ^d4 is preferably 6 to 15, more preferably 6 to 12, and still more preferably 6 to 10. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group, and a terphenyl group. A phenyl group and a naphthyl group are more preferable, and a phenyl group is more preferable. Moreover, the aromatic hydrocarbon group represented by R ^d4 may have one or more substituents. Examples of the substituent include the same groups as the substituent that the aromatic hydrocarbon group represented by R ^d1 may have.
The carbon number of the aliphatic hydrocarbon group represented by R ^d4 is preferably 1 to 13, more preferably 2 to 10, and still more preferably 4 to 9. Examples of the aliphatic hydrocarbon group represented by R ^d4 include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, Alkyl groups such as tridecyl, tetradecyl and pentadecyl; ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, butadecenyl Groups, and alkenyl groups such as a pentadecenyl group. These aliphatic hydrocarbon groups may be chain (linear or branched), cyclic, or a combination of a chain group and a cyclic group. In the aliphatic hydrocarbon group for R ^d4 , the methylene group (—CH ₂ —) may be replaced by —O—, —CO— or —S—, and the methine group (—CH <) is represented by —PO ₃ The hydrogen atom contained in the aliphatic hydrocarbon group may be substituted with an OH group.
Examples of the aliphatic hydrocarbon group which may have a substituent represented by R ^d4 include groups represented by the following formulas. In the formula, * represents a bond.

R ^d4 is preferably a chain aliphatic hydrocarbon group which may have a substituent, more preferably a chain alkyl group having no substituent, and still more preferably a branched chain having no substituent. Alkyl group.

  Examples of the compound (d1) include compounds represented by the formula (d1), specifically, compounds (d1-1) to (d1-67) having each substituent described in Tables 1 to 7. In Tables 1 to 7, * represents a bond.

Among them, compounds represented by formula (d1-3) to formula (d1-6), compounds represented by formula (d1-18) to formula (d1-52), and formula (d1-55). A compound represented by formula (d1-56), a compound represented by formula (d1-60), and a compound represented by formula (d1-61) are preferred,
More preferred are compounds represented by formula (d1-3) to formula (d1-6), and compounds represented by formula (d1-18) to formula (d1-41),
More preferably, the compound represented by the formula (d1-24), the compound represented by the formula (d1-36) to the formula (d1-40),
The compound represented by the formula (d1-24) is particularly preferable.

Compound (d1) can be produced, for example, by the production method described in JP-T-2014-500852.
As the compound (d2),
R ^d1 may have a substituent, an alkyl group having 1 to 15 carbon atoms,
R ^d2 is an alkyl group having 1 to 10 carbon atoms,
An aromatic hydrocarbon group having 6 to 18 carbon atoms in which R ^d3 may have a substituent,
A compound in which R ^d4 is an ^optionally substituted aliphatic hydrocarbon group having 1 to 15 carbon atoms is preferred,
R ^d1 represents a methyl group, an ethyl group or a propyl group;
R ^d2 represents a methyl group, an ethyl group or a propyl group;
R ^d3 represents a phenyl group substituted with a methyl group;
More preferred are compounds wherein R ^d4 is a methyl group, an ethyl group or a propyl group,
More preferred are compounds wherein R ^d1 and R ^d2 are methyl groups, R ^d3 is an o-tolyl group and R ^d4 is an ethyl group.
As the compound (d3),
R ^d1 may have a substituent, an alkyl group having 1 to 15 carbon atoms,
A compound in which R ^d2 is an aromatic hydrocarbon group having 6 to 18 carbon atoms is preferred,
A compound in which R ^d1 is a hexyl group and R ^d2 is a phenyl group is more preferable.

  Examples of such O-acyloxime compounds include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane. -1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1- [9-ethyl-6- (2-Methylbenzoyl) -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2, 4-Dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [ -Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-imine, N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -3-cyclopentylpropan-1-one-2-imine and the like. Commercial products such as Irgacure OXE01, OXE02, OXE03 (above, manufactured by BASF Corporation), N-1919 (manufactured by ADEKA Corporation) may be used. When these O-acyloxime compounds are used, a color filter excellent in photolithography performance tends to be obtained.

  The alkylphenone compound is a compound having a structure represented by the formula (d4) or a structure represented by the formula (d5). * Represents a bond. In these structures, the benzene ring may have a substituent.

Examples of the compound having a structure represented by the formula (d4) include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) ) -2-benzylbutan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butan-1-one, and the like. It is done. Commercial products such as Irgacure 369, 907, 379 (above, manufactured by BASF Corporation) may be used.
Examples of the compound having a structure represented by the formula (d5) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy ) Phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, oligomer of 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one, α, α-diethoxyacetophenone, benzyl Examples thereof include dimethyl ketal.
In terms of sensitivity, the alkylphenone compound is preferably a compound having a structure represented by the formula (d4).

  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 (see, for example, 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 (trialkoxypheny ) Biimidazole (for example, see JP-B-48-38403, JP-A-62-174204, etc.), 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-7-10913). Among these, a compound represented by the following formula or a mixture thereof is preferable.

  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) etheni ] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
Furthermore, as the polymerization initiator (D), 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- Benzophenone compounds such as 4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, Examples include quinone compounds such as 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds. These are preferably used in combination with a polymerization initiation assistant (D1) (particularly an amine) described later.

  The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 5 to 25 parts per 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). It is a mass part, More preferably, it is 10-20 mass parts. When the content of the polymerization initiator (D) is within the above range, the sensitivity is increased and the exposure time tends to be shortened, so the productivity of the color filter tends to be improved.

[5] Polymerization initiation assistant (D1)
The polymerization initiation assistant (D1) is a compound or a sensitizer used for accelerating the polymerization of the polymerizable compound that has been polymerized by the polymerization initiator. When the polymerization initiation assistant (D1) is included, it is used in combination with the polymerization initiator (D).
Examples of the polymerization initiation aid (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds. Of these, thioxanthone compounds are preferred. Two or more polymerization initiation assistants (D1) may be used in combination.

  Examples of amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4- 2-ethylhexyl dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4′-bis (diethylamino) benzophenone, 4,4′-bis ( Ethylmethylamino) benzophenone and the like, among which 4,4′-bis (diethylamino) benzophenone is preferred. Commercial products such as EAB-F (Hodogaya Chemical 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, and 9,10-dibutoxy. Anthracene, 2-ethyl-9,10-dibutoxyanthracene, etc. are mentioned.

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

  Carboxylic acid compounds include phenylsulfanyl acetic acid, methylphenylsulfanyl acetic acid, ethylphenylsulfanyl acetic acid, methylethylphenylsulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, methoxyphenylsulfanyl acetic acid, dimethoxyphenylsulfanyl acetic acid, chlorophenylsulfanyl acetic acid, dichlorophenylsulfanyl acetic acid, N -Phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid and the like.

  The content of the polymerization initiation assistant (D1) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). Part. When the content of the polymerization initiation assistant (D1) is within the above range, a colored pattern can be formed with higher sensitivity and the productivity of the color filter tends to be improved.

[6] Thiol compound (T)
The colored curable resin composition of the present invention may contain a thiol compound (T), and the thiol compound (T) may contain one or more thiol compounds. The thiol compound (T) is particularly preferably used when the polymerization initiator (D) is an oxime compound such as an O-acyloxime compound and / or a biimidazole compound. The thiol compound (T) is a compound having at least one sulfanyl group (—SH) in the molecule. The thiol compound (T) is preferably a compound having one sulfanyl group in the molecule.

  The compounds having one sulfanyl group in the molecule include 2-sulfanyloxazole, 2-sulfanylthiazole, 2-sulfanylbenzimidazole, 2-sulfanylbenzothiazole, 2-sulfanylbenzoxazole, 2-sulfanylnicotinic acid, 2-sulfanyl. Pyridine, 2-sulfanylpyridin-3-ol, 2-sulfanylpyridine-N-oxide, 4-amino-6-hydroxy-2-sulfanylpyrimidine, 4-amino-6-hydroxy-2-sulfanylpyrimidine, 4-amino- 2-sulfanylpyrimidine, 6-amino-5-nitroso-2-thiouracil, 4,5-diamino-6-hydroxy-2-sulfanylpyrimidine, 4,6-diamino-2-sulfanylpyrimidine, 2,4-diamidine -6-sulfanylpyrimidine, 4,6-dihydroxy-2-sulfanylpyrimidine, 4,6-dimethyl-2-sulfanylpyrimidine, 4-hydroxy-2-sulfanyl-6-methylpyrimidine, 4-hydroxy-2-sulfanyl-6 -Propylpyrimidine, 2-sulfanyl-4-methylpyrimidine, 2-sulfanylpyrimidine, 2-thiouracil, 3,4,5,6-tetrahydropyrimidine-2-thiol, 4,5-diphenylimidazole-2-thiol, 2- Sulfanylimidazole, 2-sulfanyl-1-methylimidazole, 4-amino-3-hydrazino-5-sulfanyl-1,2,4-triazole, 3-amino-5-sulfanyl-1,2,4-triazole, 2- Methyl-4H-1,2,4-triazo Lu-3-thiol, 4-methyl-4H-1,2,4-triazole-3-thiol, 3-sulfanyl 1H-1,2,4-triazole-3-thiol, 2-amino-5-sulfanyl-1 , 3,4-thiadiazole, 5-amino-1,3,4-thiadiazole-2-thiol, 2,5-disulfanyl-1,3,4-thiadiazole, (furan-2-yl) methanethiol, 2- Sulfanyl-5-thiazolidone, 2-sulfanylthiazoline, 2-sulfanyl-4 (3H) -quinazolinone, 1-phenyl-1H-tetrazole-5-thiol, 2-quinolinethiol, 2-sulfanyl-5-methylbenzimidazole, 2 -Sulfanyl-5-nitrobenzimidazole, 6-amino-2-sulfanylbenzothiazole, 5-chloro Ro-2-sulfanylbenzothiazole, 6-ethoxy-2-sulfanylbenzothiazole, 6-nitro-2-sulfanylbenzothiazole, 2-sulfanylnaphthimidazole, 2-sulfanylnaphthoxazole, 3-sulfanyl-1,2,4- Triazole, 4-amino-6-sulfanylpyrazolo [2,4-d] pyridine, 2-amino-6-purinethiol, 6-sulfanylpurine, 4-sulfanyl-1H-pyrazolo [2,4-d] pyrimidine, etc. Is mentioned.

  Compounds having two or more sulfanyl groups in the molecule include hexanedithiol, decanedithiol, 1,4-bis (methylsulfanyl) benzene, butanediol bis (3-sulfanylpropionate), butanediol bis (3-sulfanyl) Acetate), ethylene glycol bis (3-sulfanyl acetate), trimethylolpropane tris (3-sulfanyl acetate), butanediol bis (3-sulfanylpropionate), trimethylolpropane tris (3-sulfanylpropionate), tri Methylolpropane tris (3-sulfanyl acetate), pentaerythritol tetrakis (3-sulfanylpropionate), pentaerythritol tetrakis (3-sulfanyl acetate), tris Mud carboxyethyl tris (3-sulfanyl propionate), pentaerythritol tetrakis (3-sulfanyl butyrate) and 1,4-bis (3-sulfanyl-butyloxy) include butane and the like.

  The content of the thiol compound (T) is preferably 0.5 to 50 parts by mass, more preferably 5 to 45 parts by mass, and still more preferably 10 to 40 parts by mass with respect to 100 parts by mass of the polymerization initiator (D). It is. When the content of the thiol compound (T) is within the above range, sensitivity tends to be high and developability tends to be good.

[7] Solvent (E)
The colored curable resin composition of the present invention preferably contains a solvent (E), and the solvent (E) preferably contains one or more solvents. As the solvent (E), ester solvents (solvents containing —COO—), ether solvents other than ester solvents (solvents containing —O—), ether ester solvents (solvents containing —COO— and —O—), Examples include ketone solvents (solvents containing —CO—) other than ester solvents, alcohol solvents, aromatic hydrocarbon solvents, amide solvents, and dimethyl sulfoxide.

As ester solvents, methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate Methyl pyruvate, 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 and the like.

  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 and the like.

  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. Etc.

  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.

  It is preferable that a solvent (E) contains the organic solvent whose boiling point in 1 atm is 120 degreeC or more and 180 degrees C or less from the point of applicability | paintability and drying property. Among them, the solvent (E) is propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3 It preferably contains at least one selected from the group consisting of -methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone and N, N-dimethylformamide, propylene glycol monomethyl ether acetate, propylene glycol monomethyl Ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1- More preferably contains at least one selected from methanol and the group consisting of ethyl 3-ethoxypropionate.

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

[8] Leveling agent (F)
The colored curable resin composition of the present invention can contain one or more leveling agents (F). Examples of the leveling agent (F) include silicone surfactants (having no fluorine atoms), fluorine surfactants, and silicone surfactants having fluorine atoms. 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. Specifically, Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (trade names: 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) Can be mentioned.

  Examples of the fluorosurfactant include a surfactant 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 a surfactant having a siloxane bond and a fluorocarbon chain in the molecule. Specifically, Megafac (registered trademark) R08, BL20, F475, F477, F443 (manufactured by DIC Corporation), and the like can be given.

  The content of the leveling agent (F) is usually 0.001% by mass or more and 0.2% by mass or less, preferably 0.002% by mass or more and 0.1% by mass or less in the colored curable resin composition. Preferably they are 0.005 mass% or more and 0.05 mass% or less. This content does not include the content of the pigment dispersant.

[9] Antioxidant (G)
From the viewpoint of improving the heat resistance and light resistance of the colorant (A), the colored curable resin composition preferably contains an antioxidant. The antioxidant is not particularly limited as long as it is an antioxidant generally used industrially, and a phenol-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, and the like can be used. Two or more antioxidants may be used.

  Examples of phenolic antioxidants include Irganox 1010 (Irganox 1010: Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], manufactured by BASF Corporation), Irganox 1076. (Irganox 1076: octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, manufactured by BASF Corp.), Irganox 1330 (Irganox 1330: 3, 3 ′, 3 ″, 5 , 5 ′, 5 ″ -hexa-tert-butyl-a, a ′, a ″-(mesitylene-2,4,6-triyl) tri-p-cresol, manufactured by BASF Corp.), Irganox 3114 (Irganox 3114: 1,3,5-tris (3,5-di-ter -Butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, manufactured by BASF Corporation), Irganox 3790 (Irganox 3790: 1,3) 5-tris ((4-tert-butyl-3-hydroxy-2,6-xylyl) methyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, BASF (strain ), Irganox 1035 (Irganox 1035: thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], manufactured by BASF Corp.), Irganox 1135 (Irganox 1135: Benzenepropanoic acid, 3,5-bis (1,1-dimethylethyl) -4-hydroxy, C7-C9 side chain alkyl ester , Manufactured by BASF), Irganox 1520L (Irganox 1520L: 4,6-bis (octylthiomethyl) -o-cresol, manufactured by BASF), Irganox 3125 (Irganox 3125, manufactured by BASF) ), Irganox 565: 2,4-bis (n-octylthio) -6- (4-hydroxy 3 ′, 5′-di-tert-butylanilino) -1,3,5-triazine, BASF (strain) ), Adekastab AO-80 (Adekastab AO-80: 3,9-bis (2- (3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy) -1,1-dimethyl Ethyl) -2,4,8,10-tetraoxaspiro (5,5) undecane, manufactured by ADEKA Corporation), Milliser BHT (Sumilizer BHT, manufactured by Sumitomo Chemical Co., Ltd.), Sumiser G-80 (Sumizer GA-80, manufactured by Sumitomo Chemical Co., Ltd.), Sumiser GS (Sumizer GS, manufactured by Sumitomo Chemical Co., Ltd.), Cyanox 1790 (Cyanox) 1790, manufactured by Cytec Co., Ltd.) and vitamin E (manufactured by Eisai Co., Ltd.).

  Examples of phosphorus antioxidants include Irgafos 168 (Irgafos 168: Tris (2,4-di-tert-butylphenyl) phosphite, manufactured by BASF Corp.), Irgafos 12 (Irgafos 12: Tris [2-[[2 , 4,8,10-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphin-6-yl] oxy] ethyl] amine (manufactured by BASF Corp.), Irgaphos 38 ( Irgafos 38: bis (2,4-bis (1,1-dimethylethyl) -6-methylphenyl) ethyl ester phosphorous acid, manufactured by BASF Corporation), Adeka Stub 329K (manufactured by ADEKA Corporation), Adeka Stub PEP36 ( (Manufactured by ADEKA), ADK STAB PEP-8 (manufactured by ADEKA), Sandstab PE Q (manufactured by Clariant), Weston 618 (Weston 618, manufactured by GE), Weston 619G (Weston 619G, manufactured by GE), Ultranox 626 (manufactured by Ultranox 626, manufactured by GE), and Sumitizer GP: 6- [ 3- (3-tert-Butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-tert-butyldibenz [d, f] [1.3.2] dioxaphosphine Pin) (manufactured by Sumitomo Chemical Co., Ltd.).

  Examples of sulfur-based antioxidants include dialkylthiodipropionate compounds such as dilauryl thiodipropionate, dimyristyl or distearyl, and β-alkyl mercaptopropionate compounds of polyols such as tetrakis [methylene (3-dodecylthio) propionate] methane. Is mentioned.

[10] Other components In the colored curable resin composition of the present invention, if necessary, a filler, a polymer compound other than the resin (B), an adhesion promoter, an ultraviolet absorber, an aggregation inhibitor, an organic acid In addition, one or more additives such as an organic amine compound and a curing agent can be contained.

  Examples of the filler include glass, silica, and alumina. Examples of the polymer compound other than the resin (B) include polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate.

  As adhesion promoters, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxy Examples include silane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane.

  Examples of ultraviolet absorbers include benzotriazole compounds such as 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole; benzophenone compounds such as 2-hydroxy-4-octyloxybenzophenone Compound; benzoate compounds such as 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate; 2- (4,6-diphenyl-1,3,5-triazine- 2-yl) -5-hexyloxyphenol and other triazine compounds; Examples of the aggregation inhibitor include sodium polyacrylate.

Organic acids are used to adjust developability. Specifically,
Aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid;
Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, Aliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, mesaconic acid;
Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, camphoric acid;
Aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, mesitylene acid;
Aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid;
And aromatic polycarboxylic acids such as trimellitic acid, trimesic acid, merophanic acid, and pyromellitic acid.

As an organic amine compound,
n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine Monoalkylamines such as n-undecylamine and n-dodecylamine;
Monocycloalkylamines such as cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine, 4-methylcyclohexylamine;
Methylethylamine, diethylamine, methyl n-propylamine, ethyl n-propylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine, di-tert-butylamine, di- dialkylamines such as n-pentylamine and di-n-hexylamine;
Monoalkylmonocycloalkylamines such as methylcyclohexylamine and ethylcyclohexylamine;
Dicycloalkylamines such as dicyclohexylamine;
Dimethylethylamine, methyldiethylamine, triethylamine, dimethyl-n-propylamine, diethyl-n-propylamine, methyldi-n-propylamine, ethyldi-n-propylamine, tri-n-propylamine, triisopropylamine, tri-n -Trialkylamines such as butylamine, triisobutylamine, tri-sec-butylamine, tri-tert-butylamine, tri-n-pentylamine, tri-n-hexylamine;
Dialkylmonocycloalkylamines such as dimethylcyclohexylamine and diethylcyclohexylamine;
Monoalkyldicycloalkylamines such as methyldicyclohexylamine, ethyldicyclohexylamine, tricyclohexylamine;
Monoalkanolamines such as 2-aminoethanol, 3-amino-1-propanol, 1-amino-2-propanol, 4-amino-1-butanol, 5-amino-1-pentanol, and 6-amino-1-hexanol ;
Monocycloalkanolamines such as 4-amino-1-cyclohexanol;
Dialkanolamines such as diethanolamine, di-n-propanolamine, diisopropanolamine, di-n-butanolamine, diisobutanolamine, di-n-pentanolamine, di-n-hexanolamine;
Dicycloalkanolamines such as di (4-cyclohexanol) amine;
Trialkanolamines such as triethanolamine, tri-n-propanolamine, triisopropanolamine, tri-n-butanolamine, triisobutanolamine, tri-n-pentanolamine, tri-n-hexanolamine;
Tricycloalkanolamines such as tri (4-cyclohexanol) amine;
3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol, 4-amino-1,3-butanediol, 3-dimethylamino-1 Aminoalkane diols such as 2, 2-propanediol, 3-diethylamino-1,2-propanediol, 2-dimethylamino-1,3-propanediol, 2-diethylamino-1,3-propanediol;
Aminocycloalkanediols such as 4-amino-1,2-cyclohexanediol, 4-amino-1,3-cyclohexanediol;
Amino group-containing cycloalkanone methanol such as 1-aminocyclopentanone methanol, 4-aminocyclopentanone methanol;
Amino group-containing cycloalkanemethanol such as 1-aminocyclohexanone methanol, 4-aminocyclohexanone methanol, 4-dimethylaminocyclopentanemethanol, 4-diethylaminocyclopentanemethanol, 4-dimethylaminocyclohexanemethanol, 4-diethylaminocyclohexanemethanol;
β-alanine, 2-aminobutyric acid, 3-aminobutyric acid, 4-aminobutyric acid, 2-aminoisobutyric acid, 3-aminoisobutyric acid, 2-aminovaleric acid, 5-aminovaleric acid, 6-aminocaproic acid, 1-aminocyclo Aminocarboxylic acids such as propanecarboxylic acid, 1-aminocyclohexanecarboxylic acid, 4-aminocyclohexanecarboxylic acid;
Aniline, o-methylaniline, m-methylaniline, p-methylaniline, p-ethylaniline, pn-propylaniline, p-isopropylaniline, pn-butylaniline, p-tert-butylaniline, 1- Aromatic amines such as naphthylamine, 2-naphthylamine, N, N-dimethylaniline, N, N-diethylaniline, p-methyl-N, N-dimethylaniline;
aminobenzyl alcohols such as o-aminobenzyl alcohol, m-aminobenzyl alcohol, p-aminobenzyl alcohol, p-dimethylaminobenzyl alcohol, p-diethylaminobenzyl alcohol;
aminophenols such as o-aminophenol, m-aminophenol, p-aminophenol, p-dimethylaminophenol, p-diethylaminophenol;
m-aminobenzoic acid, p-aminobenzoic acid, p-dimethylaminobenzoic acid, aminobenzoic acid such as p-diethylaminobenzoic acid; and the like.

  Examples of the curing agent include a compound that can react with the carboxy group in the resin (B) when heated to crosslink the resin (B), a compound that can be polymerized alone to cure the colored pattern, and the like. , Epoxy compounds, oxetane compounds and the like. Only 1 type may be used for a hardening | curing agent and it may use 2 or more types together.

  Epoxy compounds include bisphenol A epoxy resins, hydrogenated bisphenol A epoxy resins, bisphenol F epoxy resins, hydrogenated bisphenol F epoxy resins, novolac epoxy resins, other aromatic epoxy resins, and alicyclic compounds. Epoxy resins, heterocyclic epoxy resins, glycidyl ester resins, glycidyl amine resins, epoxy resins such as epoxidized oil, brominated derivatives of these epoxy resins, aliphatic resins other than epoxy resins and brominated derivatives thereof, fats Examples include cyclic or aromatic epoxy compounds, epoxidized products of butadiene (co) polymers, epoxidized products of isoprene (co) polymers, (co) polymers of glycidyl (meth) acrylate, triglycidyl isocyanurate, and the like. It is done. Examples of commercially available epoxy resins include orthocresol novolac type epoxy resins, “Sumiepoxy (registered trademark) ESCN-195XL-80” (manufactured by Sumitomo Chemical Co., Ltd.), and the like.

  Examples of the oxetane compound include carbonate bisoxetane, xylylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, and bisoxetane cyclohexanedicarboxylate.

  When the colored curable resin composition of the present invention contains an epoxy compound, an oxetane compound or the like as a curing agent, it may contain a compound capable of ring-opening polymerization of the epoxy group of the epoxy compound or the oxetane skeleton of the oxetane compound. Good. Examples of the compound include polyvalent carboxylic acids, polyvalent carboxylic acid anhydrides, and acid generators.

As polyvalent carboxylic acid,
Aromatic polyvalent carboxylic acids such as 3,4-dimethylphthalic acid, pyromellitic acid, trimellitic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid acid;
Aliphatic polycarboxylic acids such as 1,2,3,4-butanetetracarboxylic acid;
Hexahydrophthalic acid, 3,4-dimethyltetrahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, 1,2,4-cyclopentanetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, cyclopentanetetracarboxylic acid Alicyclic polycarboxylic acids such as 1,2,4,5-cyclohexanetetracarboxylic acid; and the like.

As polyvalent carboxylic acid anhydride,
Aromatic polycarboxylic anhydrides such as phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride;
Aliphatic polycarboxylic anhydrides such as itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarballylic anhydride, maleic anhydride, 1,2,3,4-butanetetracarboxylic dianhydride ;
Hexahydrophthalic anhydride, 3,4-dimethyltetrahydrophthalic anhydride, 1,2,4-cyclopentanetricarboxylic anhydride, 1,2,4-cyclohexanetricarboxylic anhydride, cyclopentanetetracarboxylic dianhydride Alicyclic polycarboxylic acid anhydrides such as 1,2,4,5-cyclohexanetetracarboxylic dianhydride, hymic anhydride and nadic anhydride;
And ester group-containing carboxylic acid anhydrides such as ethylene glycol bistrimellitic acid and glycerol tristrimellitic anhydride.

  As the carboxylic acid anhydride, a commercially available epoxy resin curing agent may be used. As the epoxy resin curing agent, trade name “Adeka Hardener (registered trademark) EH-700” (manufactured by ADEKA), trade name “Rikacid (registered trademark) HH” (manufactured by Shin Nippon Rika), trade name “MH-700” (manufactured by Shin Nippon Rika Co., Ltd.) and the like.

  Examples of acid generators include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenyl methyl benzylsulfonium. Onium salts such as hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, nitrobenzyl tosylate, benzoin tosylate Etc.

<Method for producing colored curable resin composition>
The colored curable resin composition of the present invention comprises a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D) and preferably a solvent (E), and other if necessary. It can be prepared by mixing the components.

<Color filter and manufacturing method thereof, color filter and display device>
The colored curable resin composition of the present invention is useful as a material for a color filter. A color filter formed from the colored curable resin composition of the present invention also falls within the scope of the present invention. The color filter may form a colored pattern.
Examples of the method for producing a colored pattern from the colored curable resin composition of the present invention include a photolithographic method, an ink jet method, a printing method, and the like, and preferably a photolithographic method. 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. A colored pattern or a colored coating film formed from the colored curable resin composition of the present invention is the color filter of the present invention.

  As a substrate, glass plate such as quartz glass, borosilicate glass, alumina silicate glass, soda lime glass coated with silica on the surface, resin plate such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, silicon, on the above substrate In addition, an aluminum, silver, silver / copper / palladium alloy thin film or the like 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 photolithography method can be performed by a known or commonly used apparatus or conditions, and can be manufactured as follows, for example. First, a colored curable resin composition is applied on a substrate, dried by heating (pre-baking) 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 spin coating, slit coating, and slit and spin coating.
As temperature in performing heat drying, 30-120 degreeC is preferable and 50-110 degreeC is more preferable. Further, the heating time is preferably 10 seconds to 5 minutes, more preferably 30 seconds to 3 minutes. When performing vacuum drying, it is preferable to carry out in the temperature range of 20-25 degreeC under the pressure of 50-150 Pa. The film thickness of the coloring composition layer is not particularly limited, and may be appropriately selected according to the film thickness of the target color filter.
Next, the coloring composition layer is exposed through a photomask for forming a target coloring pattern. The pattern on the photomask is not particularly limited, and a pattern according to the intended use is used. The light source used for exposure is preferably a light source that generates light having a wavelength of 250 to 450 nm. For example, light less than 350 nm can be cut using a filter that cuts this wavelength range, or light near 436 nm, 408 nm, and 365 nm can be selectively extracted using a bandpass filter that extracts these wavelength ranges. Or you may. Specifically, examples of the light source include a mercury lamp, a light emitting diode, a metal halide lamp, and a halogen lamp.
The exposure can be performed by irradiating the entire exposed surface with parallel light rays or by accurately aligning the photomask with the substrate on which the colored composition layer is formed. It is preferred to use an apparatus.
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 hydrogen carbonate, sodium carbonate, or tetramethylammonium hydroxide. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. Further, the developer may contain a surfactant.
The developing method may be any of paddle method, dipping method, spray method and the like. Further, the substrate may be tilted at an arbitrary angle during development. After development, it is preferable to wash with water.
Furthermore, it is preferable to post-bake the obtained colored pattern. As post-baking temperature, 150-250 degreeC is preferable and 160-235 degreeC is more preferable. As post-baking time, 1-120 minutes are preferable and 10-60 minutes are more preferable.
Since the thickness of the obtained color filter affects adjacent pixels, it is preferably as thin as possible. In particular, when the film is thick, the light from the light source may leak through the pixels of two or more colors when the liquid crystal panel is manufactured. May be lost. The coating film after post-baking is generally preferably 3 μm or less, and more preferably 2.8 μm or less. Although the minimum of a coating film is not specifically limited, Usually, 1 micrometer or more may be 1.5 micrometers or more.
The color filter according to the present invention is useful as a color filter used in display devices (liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state image sensors.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated further more concretely, this invention is not limited by these examples. In the examples, “%” and “part” representing the content or amount used are based on mass unless otherwise specified.

<Synthesis Example 1: Preparation of xanthene dye (A-1)>
40.5 parts of the compound represented by the above formula (1a) and 60.5 parts of 2,6-xylidine (manufactured by Tokyo Chemical Industry Co., Ltd.) are mixed under light-shielding conditions, and 150 ° C. in 200 parts of N-methylpyridone. For 8 hours.
The obtained reaction solution was cooled to room temperature, then added to a mixed solution of 1200 parts of water and 75 parts of 35% hydrochloric acid, and stirred at room temperature for 1 hour, whereby crystals were deposited. The precipitated crystals were obtained as a residue of suction filtration, washed with 100 parts of methanol, and dried overnight at 60 ° C. under reduced pressure to obtain 49 parts of a compound represented by the formula (1-2). The yield was 85%.

Next, 28.8 parts of the compound represented by the formula (1-2), 21.6 parts of 1-bromopropane and 24.2 parts of potassium carbonate are added to 144 parts of N-methylpyridone, and the mixture is stirred at 90 ° C. for 4 hours. Stir. The obtained reaction solution was cooled to room temperature, concentrated, added to 560 parts of water, and stirred at 10 to 15 ° C. for 1 hour to precipitate crystals. The resulting crystals were obtained as a residue of suction filtration and then dried, washed with 1000 parts of ion-exchanged water, and dried overnight at 60 ° C. under reduced pressure to obtain 30.0 parts of a compound represented by the above formula (1-24). . The yield was 91%.
[Identification of Compound Represented by Formula (1-24)]
(Mass spectrometry) ionization mode = ESI +: m / z = [M + H] +659.3
Exact Mass: 658.3

<Synthesis Example 2: Preparation of resin (B)>
An appropriate amount of nitrogen was passed through a flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace the nitrogen atmosphere, and 371 parts of propylene glycol monomethyl ether acetate was added and heated to 85 ° C. with stirring. Then 54 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate and 3,4-epoxytricyclo [5.2.1.0 ^{2, 6} ] A mixed solution prepared by dissolving 225 parts of a mixture of decan-9-yl acrylate (content ratio is 50:50 in molar ratio) and 81 parts of vinyltoluene (isomer mixture) in 80 parts of propylene glycol monomethyl ether acetate. Was dropped into the flask over 4 hours.
On the other hand, a solution prepared by dissolving 30 parts of a polymerization initiator 2,2-azobis (2,4-dimethylvaleronitrile) in 160 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. After completion of the dropwise addition of the solution, the solution was kept at 85 ° C. for 4 hours and then cooled to room temperature to obtain a resin (B) solution. The solid content of the resin (B) solution was 37.5%, and the viscosity measured with a B-type viscometer (23 ° C.) was 246 mPa · s. The weight average molecular weight (Mw) of the resin (B) was 1.06 × 10 ⁴ , the acid value in terms of solid content was 115 mg-KOH / g, and the molecular weight distribution was 2.01.
The weight average molecular weight (Mw) and number average molecular weight (Mn) of the obtained resin (B) were measured using the GPC method under the following conditions. The ratio (Mw / Mn) between the weight average molecular weight (Mw) in terms of polystyrene and the number average molecular weight (Mn) obtained under the following conditions was defined as the molecular weight distribution.

Apparatus; HLC-8120GPC (manufactured by Tosoh Corporation),
Column; TSK-GELG2000HXL,
Column temperature; 40 ° C
Solvent; THF,
Flow rate: 1.0 mL / min,
Test liquid solid content concentration; 0.001 to 0.01% by mass,
Injection volume: 50 μL,
Detector; RI,
Reference material for calibration; TSK STANDARD POLYSTYRENE
F-40, F-4, F-288, A-2500, A-500
(Manufactured by Tosoh Corporation).

The components used in this example are as follows, and may be omitted below.
Colorant (A-1): Compound (dye) represented by Formula (1-24) obtained in Synthesis Example 1
Coloring agent (A-2): C.I. I. Pigment Blue 15: 6 (pigment)
Colorant (A-3): Compound represented by the following formula (A) (thiazole dye)

Coloring agent (A-4): C.I. I. Solvent Blue 45; Savinyl Blue RS (manufactured by Clariant) (anthraquinone dye)
Resin (B): Resin (B) contained in the resin solution obtained in Synthesis Example 2
Polymerizable compound (C-1): Pentaerythritol triacrylate (trade name “A-TMM-3LM-N” manufactured by Shin-Nakamura Chemical Co., Ltd., hydroxyl value: 110 mgKOH / g)
Polymerizable compound (C-2): Dipentaerythritol polyacrylate (trade name “A-9550” manufactured by Shin-Nakamura Chemical Co., Ltd., hydroxyl value: 50 mgKOH / g)
Polymerizable compound (C-3): a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (trade name “A-9530” manufactured by Shin-Nakamura Chemical Co., Ltd., hydroxyl value: 40 mgKOH / g)
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (trade name “Irgacure OXE 01” manufactured by BASF Corporation)
Polymerization initiation aid: 2,4-diethylthioxanthone (trade name “KAYACURE DETX-S” manufactured by Nippon Kayaku Co., Ltd.)
Solvent (E): Propylene glycol monomethyl ether acetate Leveling agent (F): Polyether-modified silicone oil (trade name “Toray Silicone SH8400” manufactured by Toray Dow Corning Co., Ltd.)

(1) Preparation of colored curable resin composition <Examples 1-4 and Comparative Examples 1-4>
Each component was mixed by the compounding ratio of Table 8 and Table 9, and the colored curable resin composition was obtained. The unit of the amount of each component in Table 8 and Table 9 is “part by mass”, and the amount is in terms of solid content.

<Example 5>
(Preparation of colored curable resin composition)
Colorant (A-2) 23.5 parts by mass Acrylic pigment dispersant 8.2 parts by mass, and solvent (E) 194 parts by mass are mixed, and the pigment is sufficiently dispersed using a bead mill.
Resin (B) 50 parts by mass (solid content conversion)
Polymerizable compound (C-1) 50 parts by weight Polymerization initiator (D) 16 parts by weight Polymerization initiation aid 11 parts by weight Solvent (E) 465 parts by weight, and leveling agent (F) 0.1 parts by weight A colored curable resin composition 2 was obtained.

<Comparative Examples 5-6>
Colored curable resin compositions 5 to 6 were prepared in the same manner as in Example 5 except that the blending composition was changed as shown in Table 9.

(2) Measurement of hydroxyl value of polymerizable compound In accordance with JIS K 0070-1992, an acetylating reagent is added to a sample, heated in a glycerin bath, allowed to cool, then added with a phenolphthalein solution as an indicator, and water Titrated with potassium oxide ethanol solution and measured. The measurement results are as described above.

(3) Preparation of pattern A colored curable resin composition was applied by spin coating on a 2-inch square glass substrate ("Eagle XG" manufactured by Corning), and then pre-baked at 100 ° C for 3 minutes to give a colored composition. A physical layer was formed. After cooling, the distance between the substrate on which the colored composition layer is formed and the photomask made of quartz glass is set to 150 μm, and an exposure machine (“TME-150RSK” manufactured by Topcon Co., Ltd.) is used in an air atmosphere at 50 mJ / Light was irradiated with an exposure amount of cm ² (reference to 365 nm). As the photomask, a photomask in which a 100 μm line and space pattern was formed was used. The colored composition layer after the light irradiation is developed by immersion in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 24 ° C. for 60 seconds, washed with water, After baking at 20 ° C. for 20 minutes, a colored pattern was obtained.

(4) Film thickness measurement About the obtained colored pattern, the film thickness was measured using the film thickness measuring apparatus ("DEKTAK3" by Nippon Vacuum Technology Co., Ltd.). The results of Examples 1 to 4 and Comparative Examples 1 to 4 are shown in Table 10, and the results of Example 5 and Comparative Examples 5 to 6 are shown in Table 11.

(5) Chromaticity Evaluation The obtained coloring pattern was measured for spectrum using a colorimeter ("OSP-SP-200" manufactured by Olympus Corporation), and CIE XYZ was measured using the characteristic function of the C light source. The xy chromaticity coordinates (x, y) and the tristimulus value Y in the color system were measured. The larger the value of Y, the higher the brightness. The results of Examples 1 to 4 and Comparative Examples 1 to 4 are shown in Table 10, and the results of Example 5 and Comparative Examples 5 to 6 are shown in Table 11.

(6) Heat resistance evaluation The obtained colored pattern was heated in an oven at 230 ° C for 3 hours. The xy chromaticity coordinates (x, y) and Y were measured before and after heating, and the color difference ΔEab * was calculated from the measured values by the method described in JIS Z 8730: 2009 (7. Color difference calculation method). The results of Examples 1 to 4 and Comparative Examples 1 to 4 are shown in Table 10, and the results of Example 5 and Comparative Examples 5 to 6 are shown in Table 11. ΔEab * means that the smaller the color change, the smaller the color change. Moreover, if the heat resistance of a colored coating film is favorable, it can be said that the heat resistance of the coloring pattern produced from the same colored curable resin composition is also favorable.

  According to the colored curable resin composition of this invention, while being able to show favorable brightness, the color filter excellent in heat resistance, and a display apparatus containing the same can be provided.

Claims (9)

A colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D);
As a colorant (A), including a dye having a xanthene skeleton,
A colored curable resin composition comprising a polymerizable compound having a hydroxyl value of 100 mgKOH / g or more as the polymerizable compound (C).   The colored curable resin composition according to claim 1, wherein the polymerizable compound having a hydroxyl value of 100 mgKOH / g or more contains pentaerythritol triacrylate.   The ratio of the content of the polymerizable compound (C) to the content of the resin (B) (the content of the polymerizable compound (C) / the content of the resin (B)) is 0.6 to 5 by mass ratio. The colored curable resin composition according to claim 1 or 2.   The ratio of the content of the polymerizable compound (C) to the content of the resin (B) (the content of the polymerizable compound (C) / the content of the resin (B)) is 0.75 to 5 by mass ratio. The colored curable resin composition according to any one of claims 1 to 3.   The colorant (A) is C.I. I. The colored curable resin composition according to any one of claims 1 to 4, further comprising CI Pigment Blue 15: 6.   The colored curable resin composition according to any one of claims 1 to 5, wherein the content of the dye having a xanthene skeleton is 1 to 50% by mass in 100% by mass of the colorant (A).   The colored curable resin composition according to any one of claims 1 to 6, wherein the polymerization initiator (D) comprises an oxime compound.   The color filter formed from the colored curable resin composition of any one of Claims 1-7.   A display device comprising the color filter according to claim 8.