CN105929636A

CN105929636A - Coloring Curable Resin Composition, Color Filter, And Display

Info

Publication number: CN105929636A
Application number: CN201610108507.8A
Authority: CN
Inventors: 藤田拓麻; 铃木智也; 权宁竖
Original assignee: Dongwoo Fine Chem Co Ltd
Current assignee: Dongwoo Fine Chem Co Ltd
Priority date: 2015-02-26
Filing date: 2016-02-26
Publication date: 2016-09-07

Abstract

The subject of the present invention is to provide a coloring curable resin composition, a color filter and a display. The coloring curable resin composition can obtain a coating film with improved heat resistance, and is characterized by containing a compound (Aa), a dye (Ab), a resin (B), a polymerized compound (C) and a polymerization initiator (D) which are represented by specified formulas, wherein a composition formed by mixing a coloring dispersion liquid prepared by the compound (Aa) and a solvent with the residual components, is not contained.

Description

Colored curable resin composition, color filter and display device

Technical field

The present invention relates to and use into salt coloring agent and the colored curable resin composition of dyestuff, color filter and display dress Put.

Background technology

In colored curable resin composition used in color filter, display device, disclose and use following change Compound (patent documentation 1,2).

[chemical formula 4]

In patent documentation 1, in terms of storage stability raising, disclose and make above-claimed cpd and pigment be dispersed in regulation Technology in organic solvent.In patent documentation 2, in terms of the brightness raising making color filter, disclose and make above-claimed cpd divide It is dispersed in the technology in the dispersant of the amine number with regulation.But, arbitrary patent documentation is not all instructed and is being used above-claimed cpd Deng dyestuff, become salt coloring agent time can make the colored curable resin composition that thermostability improves.

Prior art literature

Patent documentation

Patent documentation 1: Japanese Unexamined Patent Publication 2013-234319 publication

Patent documentation 2: Japanese Unexamined Patent Publication 2013-235257 publication

Summary of the invention

Invent problem to be solved

As it has been described above, existing known colored curable resin composition cannot fully meet needs in terms of thermostability.

For solving the means of problem

That is, the purport of the present invention is as described below.

[1] colored curable resin composition, it is characterised in that containing the compound (Aa) shown in formula (A-I), dyestuff (Ab), resin (B), polymerizable compound (C) and polymerization initiator (D), wherein, be not included in described compound (Aa) and The compositions that solvent mixes with remaining composition after preparing color dispersion liquid.

[chemical formula 5]

[in formula (A-I),

R⁴¹～R⁴⁴Separately represent the alkyl of the carbon number 1～20 can with substituent group, for the alkane of carbon number 2～20 Base and constitute insert aerobic atom between the methylene of this alkyl group, can have the aromatic hydrocarbyl of substituent group, permissible There is aralkyl or the hydrogen atom of substituent group.R⁴¹And R⁴²Ring, R is formed together with the nitrogen-atoms can being bonded and be bonded with them⁴³With R⁴⁴Ring is formed together with the nitrogen-atoms can being bonded and be bonded with them.

R⁴⁷～R⁵⁴Separately represent hydrogen atom, oxygen atom, nitrogen-atoms, sulphur atom, halogen atom, nitro, sulphonyl Base, hydroxyl or the alkyl of carbon number 1～8, can insert oxygen atom constituting between the methylene of this alkyl.R⁴⁸And R⁵²Can be mutual It is bonded and forms-NH-,-S-or-SO₂-。

Ring T¹Expression can have the heteroaromatic of substituent group.

[Y]^m-Represent that at least 1 element in the group containing the free tungsten of choosing, molybdenum, silicon and phosphorus composition and oxygen are as indispensable element The anion of arbitrary m valency.

M represents arbitrary natural number.

It addition, containing in the case of the cation shown in multiple following formula in 1 molecule, they can be identical knot Structure, it is also possible to for different structures.

[chemical formula 6]

[in formula, ring T¹、R⁴¹～R⁴⁴And R⁴⁷～R⁵⁴Respectively with above-mentioned same meaning.]]

[2] according to the colored curable resin composition described in [1], wherein, [Y] in formula (A-I)^m-For containing tungsten conduct The heteropoly acid of indispensable element or the anion of isopolyacid.

[3] according to the colored curable resin composition described in [2], wherein, [Y] in formula (A-I)^m-The moon for phosphotungstic acid Ion, the anion of silico-tungstic acid or the anion of tungsten system isopolyacid.

[4] according to the colored curable resin composition according to any one of [1]～[3], wherein, dyestuff (Ab) is for being selected from In the group being made up of ton dyestuff, triarylmethane dye, anthraquinone dye and tetraazatetradecane porphyrin dyestuff a kind.

[5] according to the colored curable resin composition according to any one of [1]～[4], wherein, dyestuff (Ab) is ton Dyestuff.

[6] according to the colored curable resin composition described in [4] or [5], wherein, ton dyestuff is by below formula (a1- 1) represent.

[chemical formula 7]

[in formula (a1-1), R¹～R⁴Represent hydrogen atom independently of each other, can have 1 valency of the carbon number 1～20 of substituent group Saturated hydrocarbyl, maybe can have the aromatic hydrocarbyl of 1 valency of the carbon number 6～10 of substituent group, Asia contained in this saturated hydrocarbyl Methyl (-CH₂-) can be by-O-,-CO-or-NR¹¹-substitute.R¹And R²The ring containing nitrogen-atoms, R can be formed together³And R⁴Can To form the ring containing nitrogen-atoms together.

R⁵Represent-OH ,-SO₃ ^-、-SO₃H、-SO₃ ^-Z⁺、-CO₂H、-CO₂ ^-Z⁺、-CO₂R⁸、-SO₃R⁸Or-SO₂NR⁹R¹⁰。

R⁶And R⁷Represent hydrogen atom or the alkyl of carbon number 1～6 independently of each other.

M represents the integer of 0～5.When m is more than 2, multiple R⁵Can be identical, it is also possible to different.

A represents the integer of 0 or 1.

X represents halogen atom.

Z⁺Represent⁺N(R¹¹)₄、Na⁺Or K⁺, 4 R¹¹Can be identical, it is also possible to different.

R⁸Representing the saturated hydrocarbyl of 1 valency of carbon number 1～20, hydrogen atom contained in this saturated hydrocarbyl can be by halogen atom Replace.

R⁹And R¹⁰Represent that hydrogen atom maybe can have the saturated hydrocarbyl of 1 valency of the carbon number 1～20 of substituent group independently of each other, -CH contained in this saturated hydrocarbyl₂-can be by-O-,-CO-,-NH-or-NR⁸-substitute, R⁹And R¹⁰Can be bonded mutually and be formed The heterocycle of 3～10 rings containing nitrogen-atoms.

R¹¹Represent saturated hydrocarbyl or the aralkyl of carbon number 7～10 of 1 valency of hydrogen atom, carbon number 1～20.]

[7] according to the colored curable resin composition according to any one of [1]～[6], wherein, the weight average of resin (B) Molecular weight is more than 9000.

[8] according to the colored curable resin composition according to any one of [1]～[7], wherein, the acid number of resin (B) For more than 60mg-KOH/g.

[9] according to the colored curable resin composition according to any one of [1]～[8], wherein, the content of dyestuff (Ab) Solid constituent 100 mass % of colored curable resin composition is 0.01～5 mass %.

[10] according to the colored curable resin composition according to any one of [1]～[9], wherein, dyestuff (Ab)/chemical combination The mass ratio of thing (Aa) is 0.001～0.5.

[11] color filter, it is formed by the colored curable resin composition according to any one of [1]～[10].

[12] display device, it comprises the color filter described in [11].

The effect of invention

According to the present invention it is possible to provide colored curable resin composition, color filter and display device, described color solidification Property resin combination can provide the film that thermostability improves.

Detailed description of the invention

The colored curable resin composition of the present invention contains the compound shown in formula (A-I) and (below, is sometimes referred to as into salt Coloring agent or compound (Aa).), dyestuff (Ab), resin (B), polymerizable compound (C) and polymerization initiator (D).Wherein, no It is included in the compositions mixed after preparing color dispersion liquid with described compound (Aa) and solvent with remaining composition.

Compound (Aa)

[chemical formula 8]

[in formula (A-I), R⁴¹～R⁴⁴Separately represent the alkyl of the carbon number 1～20 can with substituent group, for carbon The alkyl of several 2～20 and insert the group of aerobic atom between the methylene of this alkyl constituting, can have the fragrance of substituent group Race's alkyl, the aralkyl can with substituent group or hydrogen atom.R⁴¹And R⁴²Together with the nitrogen-atoms can being bonded and be bonded with them Form ring, R⁴³And R⁴⁴Ring is formed together with the nitrogen-atoms can being bonded and be bonded with them.

Ring T¹Expression can have the heteroaromatic of substituent group.

M represents arbitrary natural number.

[chemical formula 9]

Ring T¹Heteroaromatic can be monocycle, it is also possible to for condensed ring.It addition, heteroaromatic is preferably 5～10 yuan Ring, more preferably 5～9 rings.

As the heteroaromatic of monocycle, can enumerate: pyrrole ring, azoles ring, pyrazole ring, imidazole ring, thiazole ring etc. contain There are 5 rings of nitrogen-atoms；5 rings of the not nitrogen atom such as furan nucleus, thiphene ring；Pyridine ring, pyrimidine ring, pyridazine ring, pyrazine ring Deng 6 rings etc. containing nitrogen-atoms, as the heteroaromatic of condensed ring, can enumerate: indole ring, benzimidazole ring, benzo thiophene The condensed ring containing nitrogen-atoms such as azoles ring, quinoline ring；The ring etc. of the not nitrogen atom such as benzofuran ring.

As ring T¹The substituent group that can have of heteroaromatic, can enumerate: halogen atom, cyano group, can be by halogen The alkyl of the substituted carbon number of atom 1～20, the aromatic hydrocarbyl of the carbon number 6～20 that can be substituted with halogen atoms, can be replaced Amino etc..

As halogen atom, can enumerate: fluorine atom, chlorine atom and bromine atoms.

As the amino that can be replaced, can enumerate: amino；N-methylamino, N-ethylamino, N-phenyl amino etc. can The amino replaced by the alkyl of 1 carbon number 1～10: N, N-dimethylamino, N, N-diethylamino etc. can by 2 carbon numbers 1～ The substituted amino of alkyl of 10.

Wherein, ring T¹Heteroaromatic preferably comprise the heteroaromatic of nitrogen-atoms, more preferably contain 5 yuan of nitrogen-atoms The heteroaromatic of ring.

It addition, ring T¹The further preferably ring shown in formula (Ab2-x1), the ring shown in particularly preferred formula (Ab2-y1).

[chemical formula 10]

[ring T²Represent heteroaromatic.

R⁴⁵And R⁴⁶Separately represent the alkyl of the carbon number 1～20 can with substituent group, for the alkane of carbon number 2～20 Base and constitute insert aerobic atom between the methylene of this alkyl group, can have the aromatic hydrocarbyl of substituent group, permissible There is aralkyl or the hydrogen atom of substituent group.R⁴⁵And R⁴⁶Ring is formed together with the nitrogen-atoms can being bonded and be bonded with them.

R⁵⁵Represent the alkyl of carbon number 1～20, maybe can have the aromatic hydrocarbyl of substituent group.

K1 represents 0 or 1.

* the bonding end with carbocation is represented.]

[chemical formula 11]

[R⁵⁶Represent hydrogen atom, the alkyl of carbon number 1～20, maybe can have the aromatic hydrocarbyl of substituent group.

X2 represents oxygen atom ,-NR⁵⁷-or sulphur atom.

R⁵⁷Represent hydrogen atom or the alkyl of carbon number 1～10.

R⁴⁵And R⁴⁶With above-mentioned same meaning.

* the bonding end with carbocation is represented.]

Ring T²Heteroaromatic can enumerate and ring T¹The ring that the heteroaromatic of middle illustration is same.

It addition, ring T¹The preferably also ring shown in formula (Ab2-x2),

[chemical formula 12]

[ring T³Represent the heteroaromatic with nitrogen-atoms.

R⁵⁸The alkyl representing carbon number 1～20, the aromatic hydrocarbyl maybe can being replaced.

R⁵⁹The alkyl of the carbon number 1～20 that represent hydrogen atom, can be replaced, the aromatic hydrocarbyl that can be replaced maybe can be replaced Aralkyl.

K2 represents 0 or 1.

* the bonding end with carbocation is represented.]

Ring T¹Further preferably for the ring shown in formula (Ab2-y2).

[chemical formula 13]

[R⁶⁰Represent hydrogen, the alkyl of carbon number 1～20, the aromatic hydrocarbyl that maybe can be replaced.

R⁵⁹With above-mentioned same meaning.

* the bonding end with carbocation is represented.]

As R⁴¹And R⁴²The ring that formed together with bonding the nitrogen-atoms that is bonded with them, R⁴³And R⁴⁴Bonding and with they keys The ring that formed together of nitrogen-atoms closed and R⁴⁵And R⁴⁶The ring formed together with the nitrogen-atoms being bonded and be bonded with them, such as may be used To enumerate following ring.

[chemical formula 14]

As R⁴¹～R⁴⁶、R⁵⁵、R⁵⁶And R⁵⁸～R⁶⁰The alkyl of shown carbon number 1～20, can enumerate: methyl, ethyl, third The straight-chain alkyl such as base, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, dodecyl, cetyl, eicosyl； The branched-chain alkyls such as isopropyl, isobutyl group, isopentyl, neopentyl, 2-ethylhexyl；Cyclopropyl, cyclopenta, cyclohexyl, cycloheptyl The cyclic alkyl of the carbon numbers 3～20 such as base, ring octyl group, tricyclodecyl.

The carbon number of the alkyl of straight-chain or branched is preferably 1～8, more preferably 1～6, and more preferably 1～4.Separately Outward, the carbon number of cyclic alkyl is preferably 3～10, more preferably 6～10.It addition, constituting R⁴¹～R⁴⁶Alkyl methylene between It is inserted with in the group of oxygen atom, the carbon number between oxygen atom further preferably 1～4, more preferably 2～3.

As R⁴¹～R⁴⁶The substituent group that shown alkyl can have, can enumerate: amino；N-methylamino, N-ethyl The amino that amino, N-phenyl amino, N, N-dimethylamino, N, N-diethylamino etc. can be replaced；Fluorine atom, chlorine atom, The halogen atoms such as bromine atoms.

As R⁵⁹The substituent group that can have of alkyl, can enumerate: the halogen atoms such as fluorine atom, chlorine atom, bromine atoms； Cyano group etc..

It addition, as R⁴¹～R⁴⁶、R⁵⁵、R⁵⁶、R⁵⁸～R⁶⁰Shown aromatic hydrocarbyl, can enumerate: phenyl, tolyl, The aromatic hydrocarbyl of the carbon numbers 6～20 such as xylyl, naphthyl, anthryl, phenanthryl, xenyl, terphenyl, preferably carbon number 6～ The aromatic hydrocarbyl of 15, the more preferably aromatic hydrocarbyl of carbon number 6～12.

This aromatic hydrocarbyl can also have substituent group, as this substituent group, can enumerate: fluorine atom, chlorine atom, iodine are former The halogen atoms such as son, bromine atoms；The alkoxyl of the carbon number such as methoxyl group, ethyoxyl 1～6；Hydroxyl；Sulfamoyl；Methyl sulphonyl Alkyl sulphonyl Deng carbon number 1～6；The alkoxy carbonyl etc. of the carbon number such as methoxycarbonyl, ethoxy carbonyl 1～6.

As R⁴¹～R⁴⁶、R⁵⁹The shown aralkyl can with substituent group, can enumerate as above-mentioned aromatic hydrocarbon Group (benzyl and the benzene second of the alkane 2 basis of the carbon numbers 1～5 such as methylene, ethylidene, propylidene it is bonded with on the group of base explanation Base) etc..

R⁴⁷～R⁵⁴The alkyl of shown carbon number 1～8 can be straight-chain, branched and ring-type in any one, be preferably Chain.R can be enumerated⁴¹～R⁴⁶、R⁵⁵、R⁵⁶And R⁵⁸～R⁶⁰Carbon number 1～8 in the straight-chain of middle illustration, branched and cyclic alkyl Group etc..

R⁴¹～R⁴⁴、R⁵⁵、R⁵⁸And R⁵⁹Separately preferably carbon number 1～20 alkyl, can have the fragrance of substituent group The alkyl of race's alkyl, more preferably carbon number 1～6, can have the phenyl of substituent group.

R⁴⁵And R⁴⁶The most preferably can have the alkyl of the carbon number 1～20 of substituent group, for the alkane of carbon number 2～20 Base and constitute insert aerobic atom between the methylene of this alkyl group, can have the aromatic hydrocarbyl of substituent group, more excellent Select methyl, ethyl, propyl group, butyl, amyl group, methoxy, methoxy ethyl, ethoxyl methyl, ethoxyethyl group, propoxyl group Methyl, Among, propoxypropyl, phenyl, o-tolyl, a tolyl, p-methylphenyl.

R⁴⁷～R⁵⁴Separately represent hydrogen atom, halogen atom or the alkyl of carbon number 1～8, the most excellent Select hydrogen atom, methyl, fluorine atom or chlorine atom.

R⁵⁶Preferably carbon number 1～10 alkyl, maybe can have an aromatic hydrocarbyl of substituent group, more preferably carbon number 1～8 Alkyl or can by halogen atom, the haloalkyl of carbon number 1～4, the alkoxyl of carbon number 1～4, hydroxyl, the alkyl of carbon number 1～4, Or the substituted aromatic hydrocarbyl of methyl sulphonyl, more preferably phenyl, o-tolyl, a tolyl, p-methylphenyl, relatively In bonding end at ortho position, para-position, arbitrary place of meta be bonded with fluorine atom, chlorine atom, bromine atoms, trifluoromethyl or first The phenyl of alkane sulfonyl.

As R⁵⁷, preferably hydrogen atom or the alkyl of carbon number 1～8.

As the cationic moiety of formula (Ab2), as shown in table 1 below, the sun shown in formula (Ab2-1) can be enumerated Ion 1～cation 12 etc..In table, * represents bonding end.

[chemical formula 15]

[table 1]

In table 1, Ph1～Ph9 refers to the group shown in following formula.In formula, * represents bonding end.

[chemical formula 16]

It addition, as the cationic moiety of formula (Ab2), as shown in table 2 below, it is also possible to enumerate formula (Ab2-2) Shown cation 13～cation 16 etc..In table, * represents bonding end.

[chemical formula 17]

[table 2]

R⁴¹

R⁴²

R⁴³

R⁴⁴

R⁵⁹

R⁶⁰

Cation 13

CH₂CH₃

CH₃

Ph1

Cation 14

CH₂CH₃

(CH₂)₅CH₃

Ph10

Cation 15

CH₂CH(CH₃)CH₃

CH₃

Ph1

Cation 16

CH₂CH₃

Ph1

CH₂CH₃

Ph1

(CH₂)₅CH₃

Ph11

In table 2, Ph1, Ph10, Ph11 refer to the group shown in following formula.In formula, * represents bonding end.

[chemical formula 18]

Wherein, as the cationic moiety of formula (Ab2), preferred cationic 1～cation 6, cation 11 or cation 12, particularly preferred cation 1, cation 2 or cation 12, most preferably cation 12.

As [Y] that be equivalent to anion^m-, use containing at least 1 unit in the group selecting free tungsten, molybdenum, silicon, phosphorus to constitute Element and oxygen are as the anion of indispensable element.Such anion can improve thermostability, solvent resistance.

Anion [Y]^m-Preferably comprise the tungsten heteropoly acid as indispensable element or the anion of isopolyacid, particularly preferred phosphorus tungsten Acid, silico-tungstic acid and the anion of tungsten system isopolyacid.

As containing the tungsten heteropoly acid as indispensable element or the anion of isopolyacid, can enumerate: Keggin-type phosphorus tungsten Acid ion α-[PW₁₂O₄₀]^3-, Dawson type phosphotungstic acid ion α-[P₂W₁₈O₆₂]^6-、β-[P₂W₁₈O₆₂]^6-, Keggin-type silico-tungstic acid from Sub-α-[SiW₁₂O₄₀]^4-、β-[SiW₁₂O₄₀]^4-、γ-[SiW₁₂O₄₀]^4-、[P₂W₁₇O₆₁]^10-、[P₂W₁₅O₅₆]^12-、[H₂P₂W₁₂O₄₈ ]^12-、[NaP₅W₃₀O₁₁₀]^14-、α-[SiW₉O₃₄]^10-、γ-[SiW₁₀O₃₆]^8-、α-[SiW₁₁O₃₉]^8-、β-[SiW₁₁O₃₉]^8-、[W₆O₁₉ ]^2-、[W₁₀O₃₂]^4-、WO₄ ^2-And their mixture.

[Y]^m-It is also preferred that the anion being made up of at least 1 element in the group selecting free silicon and phosphorus to constitute and oxygen.

As the anion being made up of at least 1 element in the group selecting free silicon and phosphorus to constitute and oxygen, can enumerate SiO₃ ^2-、PO₄ ^3-。

From the standpoint of the easiness of synthesis and post processing, preferably Keggin-type phosphotungstic acid ion, Dawson type phosphotungstic acid The phosphotungstic anions such as ion；Silico-tungstic acid the anion, [W such as Keggin-type silico-tungstic acid ion₁₀O₃₂]^4-Deng tungsten system isopolyacid cloudy from Son.Wherein, particularly preferred phosphotungstic anion, tungsten system isopolyacid anion.

Compound shown in formula (A-I) can close according to the synthetic method described in Japanese Unexamined Patent Publication 2015-28121 publication Become.

As compound (Aa), the compound shown in following formula can be enumerated.

[chemical formula 19]

[chemical formula 20]

[chemical formula 21]

[chemical formula 22]

[chemical formula 23]

[chemical formula 24]

[chemical formula 25]

[chemical formula 26]

[chemical formula 27]

[chemical formula 28]

[chemical formula 29]

[chemical formula 30]

[chemical formula 31]

[chemical formula 32]

Compound shown in formula (A-I) can combine two or more.Wherein, compound (Aa) is preferably formula (Aa2-53) institute The compound shown.

Relative to the total amount of solid constituent, the containing ratio of compound (Aa) be usually more than 1 mass % and 70 mass % with Under, more than preferably 10 mass % and below 60 mass %, more than more preferably 20 mass % and below 60 mass %, the most excellent Elect below more than 30 mass % and 50 mass % as.If the containing ratio of above-claimed cpd (Aa) is in above-mentioned scope, it is easier to Obtain desired light splitting, colour saturation.It addition, in this manual, " total amount of solid constituent " refers to from the coloring of the present invention solid The property changed resin combination eliminates the total amount of the composition of solvent.The total amount of solid constituent and relative to its containing of each composition Amount such as can be measured by the known analytical equipment such as liquid chromatograph, gas chromatogram.

Above-mentioned dyestuff (Ab) is preferably selected from by ton dyestuff, triarylmethane dye, anthraquinone dye and tetraazatetradecane porphyrin In the group that dyestuff is constituted a kind, more preferably ton dyestuff.

Compound shown in ton dyestuff more preferably below formula (a1-1) is (hereinafter also referred to as compound (a1- 1)).Compound (a1-1) can also be its tautomer.

[chemical formula 33]

[in formula (a1-1), R¹～R⁴Represent hydrogen atom independently of each other, can have 1 valency of the carbon number 1～20 of substituent group Saturated hydrocarbyl, maybe can have the aromatic hydrocarbyl of 1 valency of the carbon number 6～10 of substituent group, Asia contained in this saturated hydrocarbyl Methyl (-CH₂-) can be by-O-,-CO-or-NR¹¹-replace.R¹And R²The ring containing nitrogen-atoms, R can be formed together³And R⁴Can To form the ring containing nitrogen-atoms together.

M represents the integer of 0～5.When m is more than 2, multiple R⁵Can be identical, it is also possible to different.A represents the integer of 0 or 1.

X represents halogen atom.

In formula (a1-1), there is-SO₃ ^-In the case of, its number is 1.

As R¹～R⁴In the aromatic hydrocarbyl of 1 valency of carbon number 6～10, such as can enumerate: phenyl, tolyl, diformazan Phenyl, sym-trimethylbenzene. base, propyl group phenyl and butyl phenyl etc..Wherein, R¹、R⁴It is preferably phenyl, tolyl, xylyl.

The substituent group can having as this aromatic hydrocarbyl, can enumerate: halogen atom ,-R⁸、-OH、-OR⁸、- SO₃ ^-、-SO₃H、-SO₃ ^-Z⁺、-CO₂H、-CO₂R⁸、-SR⁸、-SO₂R⁸、-SO₃R⁸Or-SO₂NR⁹R¹⁰, these substituent groups preferably replace virtue Hydrogen atom contained in fragrant race alkyl.In these, alternatively base, preferably-SO₃ ^-、-SO₃H、-SO₃ ^-Z⁺And-SO₂NR⁹R¹⁰, more Preferably-SO₃ ^-Z⁺And-SO₂NR⁹R¹⁰.As-SO now₃ ^-Z⁺, preferably-SO₃ ^-+N(R¹¹)₄.If R¹～R⁴For these groups, then may be used Less and thermostability is excellent to form the generation of foreign body with the colored curable resin composition by the present invention containing compound (a1-1) Different color filter.

As R¹～R⁴And R⁸～R¹¹In the saturated hydrocarbyl of 1 valency of carbon number 1～20, such as can enumerate: methyl, ethyl, The straight-chain alkane such as propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, dodecyl, cetyl, eicosyl Base；The branched-chain alkyls such as isopropyl, isobutyl group, isopentyl, neopentyl, 2-ethylhexyl；Cyclopropyl, cyclopenta, cyclohexyl, ring The ester ring type saturated hydrocarbyl of the carbon numbers 3～20 such as heptyl, ring octyl group, tricyclodecyl.Wherein, R²、R³It is preferably methyl, ethyl, isopropyl Base, propyl group.

R¹～R⁴In this saturated hydrocarbyl in contained hydrogen atom such as can be by the virtue of the carbon number 6～10 of alternatively base Fragrant race's alkyl or halogen atom replace.As replacing R¹～R⁴The aromatic series of carbon number 6～10 of hydrogen atom of saturated hydrocarbyl Alkyl, can enumerate and as R¹～R⁴In the same group of group that illustrates of the aromatic hydrocarbyl of carbon number 6～10.

R⁹And R¹⁰In this saturated hydrocarbyl in contained hydrogen atom such as can be former by the hydroxyl of alternatively base or halogen Son replaces.

As R¹And R²The ring formed together and R³And R⁴The ring formed together, such as, can enumerate following ring.

[chemical formula 34]

As-OR⁸, such as, can enumerate: methoxyl group, ethyoxyl, propoxyl group, butoxy, amoxy, hexyloxy, oxygen in heptan The alkoxyls etc. such as base, octyloxy, 2-ethyl hexyl oxy and eicosane epoxide.

As-CO₂R⁸, such as can enumerate: methoxycarbonyl, ethoxy carbonyl, propoxycarbonyl, tert-butoxycarbonyl, The alkoxy carbonyls etc. such as hexyloxy carbonyl and eicosane epoxide carbonyl.

As-SR⁸, such as, can enumerate: methylsulfanyl, Ethylsulfanyl, butyl sulfanyl, hexyl sulfanyl, the last of the ten Heavenly stems The alkyl alkylthio bases etc. such as base sulfanyl and eicosyl sulfanyl.

As-SO₂R⁸, such as, can enumerate: methyl sulphonyl, ethylsulfonyl, butyl sulfonyl, hexyl sulfonyl, the last of the ten Heavenly stems The alkyl sulphonyls etc. such as base sulfonyl and eicosyl sulfonyl.

As-SO₃R⁸, such as, can enumerate: methoxysulfonyl, ethoxysulfonyl, propoxysulfonyl, tertiary fourth oxygen The alkyloxysulfonyl etc. such as base sulfonyl, hexyloxy sulfonyl and eicosane epoxide sulfonyl.

As-SO₂NR⁹R¹⁰, such as, can enumerate: sulfamoyl；

N-Methylsulfamoyl, N-ethylsulfamovl, N-propylsulfamov, N-isopropylsulfamoyl base, N-butyl Sulfamoyl, N-isobutyl group sulfamoyl, N-sec-butyl sulfamoyl, N-tert-butyl group sulfamoyl, N-amyl group sulfamoyl, N- (1-ethyl propyl) sulfamoyl, N-(1,1-dimethyl propyl) sulfamoyl, N-(1,2-dimethyl propyl) sulfamoyl, N- (2,2-dimethyl propyl) sulfamoyl, N-(1-methyl butyl) sulfamoyl, N-(2-methyl butyl) sulfamoyl, N-(3- Methyl butyl) sulfamoyl, N-Cyclopentylsulfamoyl base, N-hexyl sulfamoyl, N-(1,3-dimethylbutyl) sulfamoyl, N-(3,3-dimethylbutyl) sulfamoyl, N-heptyl sulfamoyl, N-(1-methylhexyl) sulfamoyl, N-(1,4-diformazan Base amyl group) sulfamoyl, N-octyl group sulfamoyl, N-(2-ethylhexyl) sulfamoyl, N-(1,5-dimethylhexanyl) ammonia sulphur The N-1 such as acyl group, N-(1,1,2,2-tetramethyl butyl) sulfamoyl replace sulfamoyl；

N, N-DimethylsuIfamoyl, N, N-ethyl-methyl sulfamoyl, N, N-diethyl amino sulfonyl, N, N-propyl group first Base sulfamoyl, N, N-isopropyl methyl sulfamoyl, N, N-tertbutyl methyl sulfamoyl, N, N-butyl ethyl sulfonamides Base, N, the N, N-2 such as N-double (1-methyl-propyl) sulfamoyl, N, N-hept-ylmethyl sulfamoyls replace sulfamoyl etc..

As R⁵, preferably-CO₂H、-CO₂ ^-Z⁺、-CO₂R⁸、-SO₃ ^-、-SO₃ ^-Z⁺、-SO₃H or-SO₂NHR⁹, more preferably-SO₃ ^-、- SO₃ ^-Z⁺、-SO₃H or-SO₂NHR⁹, further preferably-SO₃ ^-。

M preferably 1～4, more preferably 1 or 2, further preferred 1.

As R⁶And R⁷In the alkyl of carbon number 1～6, the alkyl of carbon number 1～6 in the above-mentioned alkyl enumerated can be enumerated.Its In, as R⁶、R⁷, preferably hydrogen atom.

As R¹¹In the aralkyl of carbon number 7～10, can enumerate: benzyl, phenylethyl, phenyl butyl etc..

Z⁺For⁺N(R¹¹)₄、Na⁺Or K⁺, it is preferably⁺N(R¹¹)₄。

As above-mentioned⁺N(R¹¹)₄, preferably 4 R¹¹In at least 2 be the saturated hydrocarbyl of 1 valency of carbon number 5～20.It addition, 4 R¹¹Total carbon number preferably 20～80, more preferably 20～60.Compound (a1-1) exists⁺N(R¹¹)₄In the case of, if R¹¹ For these groups, then can be formed few foreign by the colored curable resin composition of the present invention containing compound (a1-1) Color filter.

It addition, as ton dyestuff, it is also preferred that the compound (hereinafter sometimes referred to " compound (a1-shown in formula (a1-2) 2)”).Compound (a1-2) can also be its tautomer.

[chemical formula 35]

[in formula (a1-2), R²¹And R²²Represent the saturated hydrocarbyl of 1 valency of carbon number 1～10, this R independently of each other²¹、R²²Full Can be replaced by the aromatic hydrocarbyl of carbon number 6～10 or halogen atom, in this aromatic hydrocarbyl with hydrogen atom contained in alkyl Contained hydrogen atom can be replaced by the alkoxyl of carbon number 1～3, above-mentioned R²¹、R²²Saturated hydrocarbyl in contained-CH₂-permissible By-O-,-CO-or-NR¹¹-substitute.

R²³And R²⁴Represent the alkyl of carbon number 1～4, the alkyl alkylthio base of carbon number 1～4 or carbon number 1～4 independently of each other Alkyl sulphonyl.

R²¹And R²³The ring containing nitrogen-atoms, R can be formed together²²And R²⁴The ring containing nitrogen-atoms can be formed together.

P and q represents the integer of 0～5 independently of each other.When p is more than 2, multiple R²³Can be identical, it is also possible to different, q is When more than 2, multiple R²⁴Can be identical, it is also possible to different.

R¹¹Represent and above-mentioned R¹¹Identical implication.]

As R²¹And R²²In the saturated hydrocarbyl of 1 valency of carbon number 1～10, R can be enumerated⁸In group in carbon number 1～10 Group.

The aromatic hydrocarbyl of the carbon number 6～10 that alternatively base can have, can enumerate and R¹In group identical Group.

As the alkoxyl of carbon number 1～3, such as, can enumerate: methoxyl group, ethyoxyl, propoxyl group etc..

R²¹And R²²It is the saturated hydrocarbyl of 1 valency of carbon number 1～3 the most independently of each other.

As R²³And R²⁴In the alkyl of carbon number 1～4, can enumerate: methyl, ethyl, propyl group, butyl, isopropyl, different Butyl, sec-butyl, the tert-butyl group etc..

As R²³And R²⁴In the alkyl alkylthio base of carbon number 1～4, can enumerate: methylsulfanyl, Ethylsulfanyl, third Base sulfanyl, butyl sulfanyl and isopropyl sulfanyl etc..

As R²³And R²⁴In the alkyl sulphonyl of carbon number 1～4, can enumerate: methyl sulphonyl, ethylsulfonyl, third Base sulfonyl, butyl sulfonyl and isopropelsulfonyl etc..

R²³And R²⁴The preferably alkyl of carbon number 1～4, more preferably methyl, ethyl, further preferred methyl.

The integer of p and q preferably 0～2, preferably 1 or 2.

As ton dyestuff, such as, can enumerate the compound shown in formula (1-1)～formula (1-43).It addition, in formula, R⁴⁰Table Show the saturated hydrocarbyl of 1 valency of carbon number 1～20, the preferably branched-chain alkyl of carbon number 6～12, more preferably 2-ethyl hexyl Base.

[chemical formula 36]

[chemical formula 37]

[chemical formula 38]

[chemical formula 39]

[chemical formula 40]

[chemical formula 41]

[chemical formula 42]

[chemical formula 43]

In above-claimed cpd, any one shown compound of formula (1-24)～formula (1-36) is equivalent to compound (a1- 2)。

In these, the sulfonamide compound of preferably C.I. Xylene Red 289, the quaternary ammonium salt of C.I. Xylene Red 289, C.I. acid violet The sulfonamide compound of 102 or the quaternary ammonium salt of C.I. acid violet 102.As such compound, such as, can enumerate: formula (1-1) ～formula (1-8), formula (1-11) or the compound etc. shown in formula (1-12).

It addition, from the standpoint of dissolubility in organic solvent is excellent, it is also preferred that formula (1-24)～formula (1-33) Any one shown compound, the particularly preferably compound shown in formula (1-32).

Ton dyestuff can use commercially available ton dyestuff (" the Chugai Aminol that in such as, tank formation (strain) manufactures Fast Pink R-H/C ", ridge, field chemical industry (strain) " the Rhodamin 6G " that manufacture).Alternatively, it is also possible to commercially available ton Dyestuff, as initiation material, synthesizes with reference to Japanese Unexamined Patent Publication 2010-32999 publication.

Triarylmethane dye preferably comprises the chemical combination with the structure that 3 aromatic hydrocarbyls are bonded to a carbon atom The dyestuff of thing.As triarylmethane dye, such as, can enumerate: C.I. solvent blue 2,4,5,43,124；C.I. alkaline purple 3, 14、25；C.I. alkali blue 1,5,7,11,26 and the triarylmethane dye etc. described in No. 4492760 publications of Japanese Patent No..

As anthraquinone dye, can enumerate: C.I. solvent violet 11 (below, is omitted the record of C.I. solvent violet, is only and compiles Number.)、13、14、26、31、36、37、38、45、47、48、51、59、60、

C.I. solvent blue 19 4,18,35,36,45,58,59,59:1,63,68,69,78,79,83,94,97,98,100, 101、102、104、105、111、112、122、128、132、136、139、

C.I. solvent green 3,28,29,32,33,

C.I. ACID GREEN 25,27,28,41,

C.I. acid violet 34,

C.I. acid blue 25,27,40,45,78,80,112

C.I. disperse violet 26,27,

C.I. disperse blue 1,14,56,60,

C.I. sun blue 40,

C.I. mordant dyeing indigo plant 8 etc..

Tetraazatetradecane porphyrin dyestuff is the compound that intramolecular has tetraazatetradecane porphyrin skeleton.It addition, contaminate at tetraazatetradecane porphyrin In the case of material is for acid stain or basic stain, salt can be formed with arbitrary cation or anion.

Dyestuff as other, it is possible to use azo dye, piperazine dyestuff, phthalocyanine dye etc., can use known respectively Dyestuff.

As azo dye, can enumerate: C.I. sun blue 51 (below, omits the record of C.I. sun blue, only records volume Number.)、57、71、81、84、85、90、93、94、95、98、100、101、113、149、150、153、160、162、163、164、 166、167、170、172、188、192、193、194、196、198、200、207、209、210、212、213、214、222、228、 229、237、238、242、243、244、245、247、248、250、251、252、256、257、259、260、268、274、275；

C.I. direct green 27,34,37,65,67,68,69,72,77,79,82 etc.；

C.I. acid violet 11,56,58；

C.I. acid blue 92,102,113,117 etc.；C.I. alkali blue 41,54,64,66,67,129 etc..

As piperazine dyestuff, can enumerate: C.I. sun blue 97,99,106,107,108,109,190,293 etc..

As phthalocyanine dye, can enumerate: C.I. sun blue 86,87,189,199, C.I. acid blue 249, C.I. alkalescence Blue 3 etc..

The content of dyestuff (Ab), in solid constituent 100 mass % of colored curable resin composition, for example, 0.01 ～5 mass %, preferably 0.05～4 mass %, more preferably 0.1～3 mass %, particularly preferably 0.2～2 mass %.

Dyestuff preferably comprises the above-mentioned ton dyestuff (the preferably compound shown in formula (1-32)) of more than 50 mass %, more Preferably comprise more than 60 mass %, further preferably containing more than 70 mass %, further preferably containing more than 80 mass %, special Do not preferably comprise more than 90 mass %, most preferably 100 mass %.

In dyestuff in addition to ton dyestuff, it is also possible to be applied in combination more than a kind other dyestuff.

The mass ratio of dyestuff (Ab) (solid constituent conversion)/compound (Aa) (solid constituent conversion) be preferably 0.001～ 0.5, more preferably 0.005～0.4, more preferably 0.007～0.3, it is even more preferably 0.009～0.2.Discontented In the case of the numerical range that foot is above-mentioned, sometimes cannot be improved the effect of thermostability.

Resin (B) contained in the colored curable resin composition of the present invention is preferably alkali soluble resin, more preferably The addition with the construction unit of at least one being derived from the group selecting free unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides to constitute gathers Compound.As such resin, can enumerate: following resin [K1]～[K6].

Resin [K1]: select at least one (a) in the group of free unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides composition (to have below Time be referred to as " (a) ") and there is the monomer (b) of the cyclic ether structure of carbon number 2～4 and ethylenic unsaturated bond (hereinafter sometimes referred to " (b) ") copolymer

Resin [K2]: (a), (b) and can be (wherein, different from (a) and (b) with the monomer (c) of (a) copolymerization.) (the most sometimes Copolymer referred to as " (c) ")

Resin [K3]: the copolymer of (a) and (c)

Resin [K4]: the resin obtained by making the copolymer of (a) and (c) react with (b)

Resin [K5]: the resin obtained by making the copolymer of (b) and (c) react with (a)

Resin [K6]: by making the copolymer of (b) and (c) react with (a), then make carboxylic acid anhydrides reaction and the resin that obtains.

As (a), can enumerate: acrylic acid, methacrylic acid .beta.-methylacrylic acid, o-, m-, p-vinyl benzoic acid etc. are no Saturated monocarboxylic acid；

The unsaturated dicarboxylics such as maleic acid；

Methyl-5-norborene-2,3-dicarboxylic acids, 5-carboxyl dicyclo [2.2.1] hept-2-ene", 5,6-dicarboxyl dicyclo The dicyclo unsaturated compound containing carboxyl such as [2.2.1] hept-2-ene"；

The unsaturated dicarboxylic acid anhydrides such as maleic anhydride；

α-(hydroxymethyl) acrylic acid is equal in a part containing hydroxyl and the unsaturated acrylate of carboxyl.

Wherein, from the viewpoint of copolyreaction, the resin that the obtains dissolubility aqueous alkali, preferably propylene Acid, methacrylic acid and maleic anhydride.

B () refers to that the cyclic ether structure with carbon number 2～4 (is selected from by oxirane ring, oxetanes ring and four At least one in the group that hydrogen furan nucleus is constituted) and the polymerizable compound of ethylenic unsaturated bond.(b) preferably have carbon number 2～ The cyclic ether structure of 4 and the monomer of (methyl) acryloxy.It addition, in this manual, " (methyl) acrylic acid " represents choosing At least one in the group that free acrylic acid and methacrylic acid are constituted, " (methyl) acryloyl group " and " (methyl) acrylate " Record also illustrate that same implication.

As (b), can enumerate: there is the monomer (b1) of epoxy ethyl and ethylenic unsaturated bond (hereinafter sometimes referred to " (b1) "), there is the monomer (b2) (hereinafter sometimes referred to " (b2) ") of oxetanylmethoxy and ethylenic unsaturated bond and there is tetrahydrochysene The monomer (b3) (hereinafter sometimes referred to " (b3) ") of furyl and ethylenic unsaturated bond.

As (b1), can enumerate: there is the structure that the unsaturated aliphatic hydrocarbon of straight-chain or branched is at least partially epoxidized Monomer (b1-1) (hereinafter sometimes referred to " (b1-1) ") and there is the monomer (b1-of the structure that ester ring type unsaturated hydrocarbons is at least partially epoxidized 2) (hereinafter sometimes referred to " (b1-2) ").

As (b1-1), preferably there is the monomer of glycidyl and ethylenic unsaturated bond.As (b1-1), concrete and Speech, can enumerate: (methyl) glycidyl acrylate, (methyl) propenoic acid beta-methylglycidyl esters, (methyl) acrylic acid β-ethyl glycidyl ester, glycidyl vinyl ether, adjacent vinylbenzyl glycidyl base ether, a vinyl benzyl shrink Glyceryl ether, to vinylbenzyl glycidyl base ether, Alpha-Methyl-neighbour's vinylbenzyl glycidyl base ether, an Alpha-Methyl-second Thiazolinyl benzyl glycidyl ether, Alpha-Methyl-to vinylbenzyl glycidyl base ether, 2,3-pair (glycidoxypropyl methyl) Double (glycidoxypropyl methyl) styrene of styrene, 2,4-, double (glycidoxypropyl methyl) styrene of 2,5-, 2,6-are double (glycidoxypropyl methyl) styrene, 2,3,4-tri-(glycidoxypropyl methyl) styrene, 2,3,5-tri-((+)-2,3-Epoxy-1-propanol oxygen Ylmethyl) styrene, 2,3,6-tri-(glycidoxypropyl methyl) styrene, 3,4,5-tri-(glycidoxypropyl methyl) benzene second Alkene and 2,4,6-tri-(glycidoxypropyl methyl) styrene.

As (b1-2), can enumerate: vinylcyclohexene monoxide, 1,2-epoxy-4-vinyl cyclohexane (example As, Celloxide (registered trade mark) 2000；(strain) Diacel manufacture), 3,4-epoxycyclohexyl-methyl (methyl) acrylate (such as, Cyclomer (registered trade mark) A400；(strain) Diacel manufacture), 3,4-epoxycyclohexyl-methyl (methyl) acrylate (such as, Cyclomer M100；(strain) Diacel manufactures), the compound shown in formula (1) and the compound shown in formula (2).

[chemical formula 44]

(in formula, R^aAnd R^bSeparately represent hydrogen atom or the alkyl of carbon number 1～4, hydrogen atom contained in this alkyl Can be optionally substituted by a hydroxyl group.X^aAnd X^bSeparately represent singly-bound, *-R^c-、*-R^c-O-、*-R^c-S-or *-R^c-NH-。R^cRepresent The alkane 2 basis of carbon number 1～6.* the bonding end with O is represented.)

As the compound shown in formula (1), can enumerate: the compound shown in formula (1-1)～formula (1-15), wherein, excellent Select the compound shown in formula (1-1), formula (1-3), formula (1-5), formula (1-7), formula (1-9) and formula (1-11)～formula (1-15), more Preferred formula (1-1), formula (1-7), formula (1-9) and the compound shown in formula (1-15).

[chemical formula 45]

As the compound shown in formula (2), can enumerate: the compound shown in formula (2-1)～formula (2-15), wherein, excellent Select the compound shown in formula (2-1), formula (2-3), formula (2-5), formula (2-7), formula (2-9) and formula (2-11)～formula (2-15), more Preferred formula (2-1), formula (2-7), formula (2-9) and the compound shown in formula (2-15).

[chemical formula 46]

Compound shown in formula (1) and the compound shown in formula (2) can individually use, it is also possible to and with formula (1) Compound shown in shown compound and formula (2).And with these in the case of, the compound shown in formula (1) and formula (2) institute The ratio (compound shown in formula (1): the compound shown in formula (2)) of the compound shown with molar basis be preferably 5:95～ 95:5, more preferably 10:90～90:10, more preferably 20:80～80:20.

As (b2), more preferably there is the monomer of oxetanylmethoxy and (methyl) acryloxy.

As (b3), more preferably there is the monomer of tetrahydrofuran base and (methyl) acryloxy.

From the standpoint of can further improve the reliabilities such as the thermostability of the color filter obtained, chemical-resistant, (b) is excellent Electing (b1) as, from the standpoint of the excellent storage stability of colored curable resin composition, (b1) is preferably (b1-2).

As (c), can enumerate: (methyl) acrylic acid methyl ester., (methyl) ethyl acrylate, the positive fourth of (methyl) acrylic acid Ester, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) 2-EHA, (methyl) acrylic acid Dodecyl ester, (methyl) lauryl acrylate, (methyl) stearyl acrylate ester, (methyl) acrylic acid ring pentyl ester, (methyl) third Olefin(e) acid cyclohexyl, (methyl) acrylic acid 2-methyl cyclohexyl, three ring [5.2.1.0^2,6] decane-8-base (methyl) acrylate ( In this technical field, as trivial name, it is referred to as " (methyl) acrylic acid bicyclo-pentyl ester ".It addition, be sometimes referred to as " (methyl) acrylic acid Tricyclodecyl ".), three ring [5.2.1.0^2,6] decene-8-base (methyl) acrylate (in this technical field, as trivial name, It is referred to as " (methyl) acrylic acid dicyclopentenyl ester ".), (methyl) acrylic acid two cyclopentyloxy ethyl ester, (methyl) isobomyl acrylate Ester, (methyl) acrylic acid adamantane esters, (methyl) allyl acrylate, (methyl) propargylacrylate, (methyl) acrylic acid (methyl) acrylate such as phenyl ester, (methyl) acrylic acid naphthalene ester, (methyl) benzyl acrylate；(methyl) acrylic acid 2-hydroxyl second Hydroxyl (methyl) acrylate such as ester, (methyl) acrylic acid 2-hydroxy propyl ester；

The dicarboxylic diesters such as ethyl maleate., DEF, diethyl itaconate；

Dicyclo [2.2.1] hept-2-ene", 5-methyl bicycle [2.2.1] hept-2-ene", 5-ethyl dicyclo [2.2.1] hept-2-ene", 5-hydroxyl dicyclo [2.2.1] hept-2-ene", 5-hydroxymethyl dicyclo [2.2.1] hept-2-ene", 5-(2 '-hydroxyethyl) dicyclo [2.2.1] hept-2-ene", 5-methoxyl group dicyclo [2.2.1] hept-2-ene", 5-ethyoxyl dicyclo [2.2.1] hept-2-ene", 5,6-dihydroxy Base dicyclo [2.2.1] hept-2-ene", 5,6-bis-(hydroxymethyl) dicyclo [2.2.1] hept-2-ene", 5,6-bis-(2 '-hydroxyethyl) are double Ring [2.2.1] hept-2-ene", 5,6-dimethoxy dicyclo [2.2.1] hept-2-ene", 5,6-diethoxy dicyclo [2.2.1] hept-2- Alkene, 5-hydroxy-5-methyl base dicyclo [2.2.1] hept-2-ene", 5-hydroxyl-5-ethyl dicyclo [2.2.1] hept-2-ene", 5-hydroxyl first Base-5-methyl bicycle [2.2.1] hept-2-ene", 5-tert-butoxycarbonyl dicyclo [2.2.1] hept-2-ene", 5-cyclohexyloxy carbonyl are double Double (tert-butoxycarbonyl) dicyclo of ring [2.2.1] hept-2-ene", 5-phenyloxycarbonyl dicyclo [2.2.1] hept-2-ene", 5,6- The dicyclo unsaturated compounds such as double (cyclohexyloxy carbonyl) dicyclo [2.2.1] hept-2-ene"s of [2.2.1] hept-2-ene", 5,6-；

N-phenylmaleimide, N-N-cyclohexylmaleimide, N-benzyl maleimide, N-succinimido- 3-maleimidobenzoyl salt, N-succinimido-4-maleimidobutyrate salt, N-succinimido-6-Malaysia The dicarbapentaborane such as acid imide caproate, N-succinimido-3-maleimidopropionic acid salt, N-(9-acridinyl) maleimide Imide compound；

Styrene, α-methyl styrene, a methyl styrene, p-methylstyrene, vinyltoluene, to methoxybenzene second Alkene etc. are containing vinyl aromatic compounds；Acrylonitrile, methacrylonitrile etc. are containing vinyl nitrile；The halogen such as vinyl chloride, vinylidene chloride For hydrocarbon；Acrylamide, Methacrylamide etc. are containing vinylamide；The esters such as vinyl acetate；1,3-butadiene, isoprene and The diene etc. of 2,3-dimethyl-1,3-butadiene.

In these, from the viewpoint of copolyreaction and thermostability, preferably containing vinyl aromatic compounds, dicarbapentaborane Imide compound, dicyclo unsaturated compound.Specifically, optimization styrene, vinyltoluene, (methyl) acrylic acid benzyl Ester, three ring [5.2.1.0^2,6] decane-8-base (methyl) acrylate, N-phenylmaleimide, N-cyclohexyl maleimide Amine, N-benzyl maleimide and dicyclo [2.2.1] hept-2-ene".

As carboxylic acid anhydrides, can enumerate: maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic acid acid anhydride, 4-vinylphthalic acid acid anhydride, 3,4,5,6-tetrabydrophthalic anhydride, 1,2,3,6-tetrabydrophthalic anhydride, dimethyl Tetrabydrophthalic anhydride and 5,6-dicarboxyl dicyclo [2.2.1] hept-2-ene" anhydride.The usage amount of carboxylic acid anhydrides preferably with respect to A the usage amount of () 1 mole is 0.5～1 mole.

As resin (B), can enumerate: (methyl) acrylic acid 3,4-epoxycyclohexanecarboxylate/(methyl) acrylic acid copolymer Thing, 3,4-epoxy three ring [5.2.1.0^2,6] resin [K1] such as decyl (methyl) acrylate/(methyl) acrylic copolymer；(first Base) glycidyl acrylate/(methyl) benzyl acrylate/(methyl) acrylic copolymer, (methyl) glycidyl Ester/styrene/(methyl) acrylic copolymer, 3,4-epoxy three ring [5.2.1.0^2,6] decyl (methyl) acrylate/(methyl) Acrylic acid/N-N-cyclohexylmaleimide copolymer, 3,4-epoxy three ring [5.2.1.0^2,6] decyl (methyl) acrylate/(first Base) acrylic acid/vinyl toluene copolymer, 3-methyl-3-(methyl) acryloyloxymethyl oxetanes/(methyl) propylene The resins [K2] such as acid/styrol copolymer；(methyl) benzyl acrylate/(methyl) acrylic copolymer, styrene/(methyl) third The resins such as olefin(e) acid copolymer, (methyl) benzyl acrylate/(methyl) acrylic acid tricyclodecyl/(methyl) acrylic copolymer [K3]；Make (methyl) glycidyl acrylate and (methyl) benzyl acrylate/(methyl) acrylic copolymer addition Resin, make (methyl) glycidyl acrylate and (methyl) acrylic acid tricyclodecyl/styrene/(methyl) acrylic copolymer The resin of addition, make (methyl) glycidyl acrylate and (methyl) acrylic acid tricyclodecyl/(methyl) acrylic acid benzyl The resins [K4] such as the resin of ester/(methyl) acrylic copolymer addition；Make (methyl) acrylic acid and (methyl) acrylic acid three The resin of the copolymer reaction of ring ester in the last of the ten Heavenly stems/(methyl) glycidyl acrylate, make (methyl) acrylic acid and (methyl) third The resins [K5] such as the resin of the copolymer reaction of olefin(e) acid tricyclodecyl/styrene/(methyl) glycidyl acrylate；Make (methyl) acrylic acid and the copolymer reaction of (methyl) acrylic acid tricyclodecyl/(methyl) glycidyl acrylate, then make four The resins [K6] such as the resin of hydrogen phthalic anhydride and the resin reaction obtained.

The weight average molecular weight of the polystyrene conversion of resin (B) is usually 3,000～100,000, preferably 5,000～ 50,000, more preferably 5,000～35,000, more preferably 5,000～30,000, particularly preferably 6,000～30, 000, most preferably 9000～30,000.If molecular weight is in above-mentioned scope, then exist hardness of film improve, residual film ratio the highest, The tendency that unexposed portion improves relative to the favorable solubility of developer solution, the resolution of colored pattern.

The molecular weight distribution [weight average molecular weight (Mw)/number-average molecular weight (Mn)] of resin (B) preferably 1.1～6, more preferably It is 1.2～4, more preferably 1.3～3.

The acid number (solid constituent conversion) of resin (B) is preferably 20～170mg-KOH/g, more preferably 30～170mg- KOH/g, wherein, preferably 40～170mg-KOH/g, wherein, preferably 50～170mg-KOH/g, more preferably more than 60mg-KOH/g, Below 150mg-KOH/g, further preferred below 135mg-KOH/g.

Here, the value that acid number is the amount (mg) as the potassium hydroxide needed for neutralizing resin (B) 1g to be recorded, such as, can pass through Potassium hydroxide aqueous solution is used to titrate and obtain.

The content of resin (B) is 7～65 mass %, wherein, preferably 10～60 preferably with respect to the total amount of solid constituent Quality %, wherein, preferably 13～60 mass %, wherein, preferably 17～55 mass %.If the content of resin (B) is above-mentioned Scope, then there is the tendency that colored pattern is formed easily, the resolution of colored pattern and residual film ratio improve.

Polymerizable compound (C) is the available living radical produced by polymerization initiator and/or acid carries out being polymerized Compound, such as, can enumerate the compound with ethylenic unsaturated bond, preferably have the chemical combination of (methyl) acrylate structural Thing.Polymerizable compound (C) preferably has the polymerizable compound of more than 3 ethylenic unsaturated bonds, more preferably has 5 ～the polymerizable compound of 6 ethylenic unsaturated bonds.

As having the polymerizable compound of 1 ethylenic unsaturated bond, can enumerate: nonyl phenyl carbitol acrylic acid Ester, acrylic acid 2-hydroxyl-3-phenoxy-propyl, 2-ethylhexyl carbitol acrylate, acrylic acid 2-hydroxy methacrylate, N-ethylene Base ketopyrrolidine, above-mentioned (a), (b) and (c).As having the polymerizable compound of 2 ethylenic unsaturated bonds, can enumerate: 1,6-HD two (methyl) acrylate, ethylene glycol bisthioglycolate (methyl) acrylate, neopentyl glycol two (methyl) acrylate, three Glycol two (methyl) acrylate, double (acryloyl-oxyethyl) ethers of bisphenol-A and 3-methyl pentanediol two (methyl) acrylic acid Ester.As having the polymerizable compound of more than 3 ethylenic unsaturated bonds, can enumerate: trimethylolpropane tris (methyl) third Olefin(e) acid ester, tetramethylolmethane three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, dipentaerythritol five (methyl) third Olefin(e) acid ester, dipentaerythritol six (methyl) acrylate, tripentaerythritol eight (methyl) acrylate, tripentaerythritol seven (first Base) acrylate, tetrapentaerythritol ten (methyl) acrylate, tetrapentaerythritol nine (methyl) acrylate, three (2-(methyl) Acryloyl-oxyethyl) isocyanuric acid ester, glycol-modified tetramethylolmethane four (methyl) acrylate, glycol-modified two seasons penta Tetrol six (methyl) acrylate, propylene glycol modified tetramethylolmethane four (methyl) acrylate, propylene glycol modified dipentaerythritol Six (methyl) acrylate, caprolactone modification tetramethylolmethane four (methyl) acrylate and caprolactone modification dipentaerythritol six (methyl) acrylate.

In these, preferably dipentaerythritol five (methyl) acrylate and dipentaerythritol six (methyl) acrylate.

The weight average molecular weight of polymerizable compound (C) be preferably more than 150 and 2, less than 900, more preferably more than 250 and Less than 1,500.

Relative to the total amount of solid constituent, the polymerizable compound in the colored curable resin composition thing of the present invention (C) content is usually 1～60 mass %, preferably 5～50 mass %, more preferably 10～40 mass %, further preferably It is 12～30 mass %.The content ratio (resin (B): polymerizable compound (C)) of resin (B) and polymerizable compound (C) is with matter Amount benchmark meter is usually 20:80～80:20, preferably 35:65～80:20.If the amount of polymerizable compound (C) is above-mentioned In the range of, then there is the tendency that the chemical-resistant of residual film ratio when colored pattern is formed and color filter improves.

Polymerization initiator (D) if for can pass through light, heat effect generation living radical, acid etc. thus cause polymerization Just there is no particular limitation for compound, can use known polymerization initiator.

Polymerization initiator (D) is preferably containing choosing free alkyl phenyl ketonic compound, triaizine compounds, acylphosphine oxide The polymerization initiator of at least one in the group that compound, O-acyl group oxime compound and united imidazole are constituted, more preferably contains There is the polymerization initiator of O-acyl group oxime compound.

As O-acyl group oxime compound, can enumerate: N-benzoyloxy-1-(4-Phenylsulfanyl phenyl) butane-1- Ketone-2-imines, N-benzoyloxy-1-(4-Phenylsulfanyl phenyl) octane-1-ketone-2-imines, N-benzoyloxy-1- (4-Phenylsulfanyl phenyl)-3-cyclopenta propane-1-ketone-2-imines, N-acetoxyl group-1-[9-ethyl-6-(2-methylbenzene Formoxyl)-9H-carbazole-3-base] ethane-1-imines, N-acetoxyl group-1-[9-ethyl-6-{2-methyl-4-(3,3-diformazan Base-2,4-dioxolyl methoxyl group) benzoyl-9H-carbazole-3-base] ethane-1-imines, N-acetoxyl group-1-[9- Ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base]-3-cyclopenta propane-1-imines and N-benzoyloxy-1-[9- Ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base]-3-cyclopenta propane-1-ketone-2-imines.Can also use Irgacure (registered trade mark) OXE01, OXE02 (manufacturing for BASF AG above), N-1919 (manufacture of ADEKA company) etc. are commercially available Product.Wherein, it is preferably selected from by N-benzoyloxy-1-(4-Phenylsulfanyl phenyl) butane-1-ketone-2-imines, N-benzoyl Oxy-1-(4-Phenylsulfanyl phenyl) octane-1-ketone-2-imines and N-benzoyloxy-1-(4-Phenylsulfanyl phenyl)- At least one in the group that 3-cyclopenta propane-1-ketone-2-imines is constituted, more preferably N-benzoyloxy-1-(4-phenyl sulfane Base phenyl) octane-1-ketone-2-imines.

Alkyl phenyl ketonic compound can be enumerated: 2-methyl-2-morpholino-1-(4-methylsulfanyl phenyl) propane-1- Ketone, 2-dimethylamino-1-(4-morphlinophenyl)-2-benzyl butane-1-ketone and 2-(dimethylamino)-2-[(4-methylbenzene Base) methyl]-1-[4-(4-morpholinyl) phenyl] butane-1-ketone.The Irgacure 369,907,379 can also be used (to be above BASF AG manufacture) etc. commercially available product.

Alkyl phenyl ketonic compound can also be 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 2-hydroxy-2-methyl- 1-[4-(2-hydroxyl-oxethyl) phenyl] propane-1-ketone, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-(4-isopropyl Thiazolinyl phenyl) oligomer of propane-1-ketone, α, α-diethoxy acetophenone and benzil dimethyl ketal.

As triaizine compounds, can enumerate: 2,4-double (trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazines, Double (trichloromethyl)-6-(4-methoxyl group the naphthyl)-1,3,5-triazine of 2,4-, double (the trichloromethyl)-6-piperonyl-1,3,5-of 2,4- Double (trichloromethyl)-6-(4-the methoxyl-styrene)-1,3,5-triazine of triazine, 2,4-, double (trichloromethyl)-6-[2-of 2,4- (5-methylfuran-2-base) vinyl]-1,3,5-triazine, double (the trichloromethyl)-6-[2-(furan-2-base) vinyl] of 2,4-- Double (trichloromethyl)-6-[2-(4-diethylamino-2-aminomethyl phenyl) the vinyl]-1,3,5-triazine of 1,3,5-triazine, 2,4- And double (trichloromethyl)-6-[2-(3,4-Dimethoxyphenyl) the vinyl]-1,3,5-triazine of 2,4-.

As acylphosphine oxide compound, can enumerate: TMDPO.Can also Use the commercially available products such as Irgacure (registered trade mark) 819 (BASF AG's manufacture).

As united imidazole, specifically, can enumerate: 2,2 '-bis-(2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl Bisglyoxaline, 2,2 '-bis-(2,3-Dichlorobenzene base)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline is (for example, referring to Japanese Unexamined Patent Publication 6- No. 75372 publications, Japanese Unexamined Patent Publication 6-75373 publications etc..), 2,2 '-bis-(2-chlorphenyls)-4,4 ', 5,5 '-tetraphenyl join Imidazoles, 2,2 '-bis-(2-chlorphenyls)-4,4 ', 5,5 '-four (alkoxyl phenyl) bisglyoxaline, 2,2 '-bis-(2-chlorphenyls)-4,4 ', 5,5 '-four (dialkoxy phenyl) bisglyoxaline, 2,2 '-bis-(2-chlorphenyls)-4,4 ', 5,5 '-four (tri-alkoxy phenyl) connection miaow Azoles is (for example, referring to Japanese Patent Publication 48-38403 publication, Japanese Laid-Open Patent Publication 62-174204 publication etc..) and 4,4 ', 5, The imidazolium compounds (for example, referring to Japanese Unexamined Patent Publication 07-010913 publication etc.) that the phenyl of 5 '-position is replaced by alkoxy carbonyl group. Wherein, the preferably compound shown in following formula and their mixture.

[chemical formula 47]

As other polymerization initiator, can enumerate: benzoin, benzoin methylether, benzoin ethyl ether, benzoin isopropyl The benzoin compound such as ether, benzoin isobutyl ether；Benzophenone, o-benzoyl yl benzoic acid methyl ester, 4-phenyl benzophenone, 4- Benzoyl-4 '-dimethyl diphenyl sulfide, 3,3 ', 4,4 '-four (t-butyl peroxy carbonyl) benzophenone, 2,4,6-trimethyl The benzophenone cpds such as benzophenone；The naphtoquinone compounds such as 9,10-phenanthrenequione, 2-ethyl-anthraquinone, camphorquinone；10-butyl-2-chlorine a word used for translation Pyridine ketone, benzil, phenylglyoxalates methyl ester, titanocenes compound etc..These are preferably polymerized initiation auxiliary agent (particularly with described later The polymerization of amine system causes auxiliary agent) it is applied in combination.

Relative to total amount 100 mass parts of resin (B) and polymerizable compound (C), the content of polymerization initiator (D) leads to It is often 0.1～40 mass parts, preferably 0.1～30 mass parts, more preferably 1～30 mass parts, particularly preferably 1～20 mass Part.

Polymerization causes auxiliary agent to be the polymerization for promoting to be caused the polymerizable compound (C) of polymerization by polymerization initiator (D) Compound or sensitizer.In the case of the colored curable resin composition of the present invention contains polymerization initiation auxiliary agent, generally It is applied in combination with polymerization initiator (D).

Cause auxiliary agent as polymerization, can enumerate: the polymerization of amine system causes auxiliary agent, the polymerization of alkoxy anthracene system to cause auxiliary agent, thiophene The polymerization of ton ketone system causes auxiliary agent and carboxylic serials polymerization to cause auxiliary agent etc..

Cause auxiliary agent as the polymerization of amine system, can enumerate: the alkanes such as triethanolamine, methyl diethanolamine, triisopropanolamine Hydramine；4-dimethylaminobenzoic acid methyl ester, EDMAB, 4-dimethylaminobenzoic acid isopentyl ester, The Aminobenzoates such as benzoic acid 2-dimethylamino ethyl ester, 4-dimethylaminobenzoic acid 2-Octyl Nitrite；N, N-dimethyl Para-totuidine, 4,4 '-bis-(dimethylamino) benzophenone (common name Michler's keton), 4,4 '-bis-(diethylamino) benzophenone And 4,4 '-bis-(ethylmethylamino) benzophenone, wherein, the alkyl ammonia such as preferably 4,4 '-bis-(diethylamino) benzophenone Base benzophenone.Wherein, preferably alkyl amino benzophenone, preferably 4,4 '-bis-(diethylamino) benzophenone.Can also make By commercially available products such as EAB-F (hodogaya chemical industry (strain) manufactures).

Cause auxiliary agent as the polymerization of alkoxy anthracene system, can enumerate: 9,10-dimethoxy anthracenes, 2-ethyl-9,10-diformazan Epoxide anthracene, 9,10-diethoxy anthracene, 2-ethyl-9,10-diethoxy anthracene, 9,10-dibutoxy anthracene and 2-ethyl-9,10-two Butoxy anthracene.

As thiaxanthone system polymerization cause auxiliary agent, can enumerate: ITX, ITX, 2,4- Diethyl thioxanthone, 2,4-bis-clopenthixal ketone and 1-chloro-4-propoxythioxanthone.

Cause auxiliary agent as carboxylic serials polymerization, can enumerate: Phenylsulfanyl acetic acid, methyl phefzylsulfanyl acetic acid, second Base Phenylsulfanyl acetic acid, Methylethyl phenyl sulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, methoxyphenyl sulfanyl Acetic acid, Dimethoxyphenyl sulfanyl acetic acid, chlorophenylsulfanyl acetic acid, Dichlorobenzene base sulfanyl acetic acid, N-phenylglycine, Phenoxyacetic acid, naphthylthio acetic acid, N-naphthyl glycine and naphthoxy acetic acid.

In the case of using polymerization to cause auxiliary agent, its content is relative to resin (B) and the total of polymerizable compound (C) Measure 100 mass parts, preferably 0.1～30 mass parts, more preferably 1～20 mass parts.If polymerization causes the content of auxiliary agent at this In the range of, then there is the tendency of the productivity ratio raising that can form colored pattern, color filter further with high sensitivity.

Solvent (E) does not limit, and may be used alone or in combination commonly used solvent in two or more this field of use. Specifically, can enumerate: ester solvent (intramolecular contains-COO-and without the solvent of-O-), (intramolecular contains-O-to ether solvents And without the solvent of-COO-), the ether-ether solvent solvent of-COO-and-O-(intramolecular contain), (intramolecular contains-CO-to ketone solvent And without the solvent of-COO-), alcoholic solvent (intramolecular contains OH and without-O-,-CO-and the solvent of-COO-), aromatic hydrocarbon molten Agent, amide solvent and dimethyl sulfoxide.

As ester solvent, can enumerate: methyl lactate, ethyl lactate, butyl lactate, 2-hydroxy-methyl isobutyl acid, acetic acid Ethyl ester, butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl isobutyrate, ethyl n-butyrate., fourth Acid butyl ester, methyl pyruvate, ethyl pyruvate, Propyl 2-oxopropionate, methyl acetoacetate, ethyl acetoacetate, Hexacyclonic Acid Ester and gamma-butyrolacton.

As ether solvents, can enumerate: ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monopropyl ether, second two Alcohol single-butyl ether, diethylene glycol monomethyl ether, carbiphene, diethylene glycol monobutyl ehter, propylene glycol monomethyl ether, propylene glycol Single ethylether, propylene glycol monopropyl ether, glycol monobutyl ether, 3-methoxyl group-n-butyl alcohol, 3-methoxyl group-3-methyl butanol, four Hydrogen furan, Pentamethylene oxide., 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, two Glycol dipropyl ether, diethylene glycol dibutyl ether, methoxybenzene, ethyl phenyl ether and methyl anisole.

As ether-ether solvent, can enumerate: methoxy menthyl acetate, ethyl methoxyacetate, 2-Methoxyacetic acid butyl ester, second Ethoxyacetic acid methyl ester, ethoxy ethyl acetate, 3-methoxy methyl propionate, 3-methoxypropionate, 3-ethoxy-propionic acid first Ester, 3-ethoxyl ethyl propionate, 2-methoxy methyl propionate, 2-methoxypropionate, 2-methoxy propyl propyl propionate, 2-ethoxy Base methyl propionate, 2-ethoxyl ethyl propionate, 2-methoxyl group-2 Methylpropionic acid methyl ester, 2-ethyoxyl-2 Methylpropionic acid ethyl ester, 3-methoxybutyl acetas, 3-methyl-3-methoxybutyl acetas, propylene glycol monomethyl ether, propylene glycol list second Base ether acetic acid ester, propylene glycol monopropyl ether acetas, ethylene glycol monomethyl ether acetic acid ester, ethylene glycol monomethyl ether acetate, two Glycol list monoethyl ether acetate, diethylene glycol monobutyl ehter acetas and dipropylene glycol methyl ether acetas.

As ketone solvent, can enumerate: 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4- Heptanone, 4-methyl-2 pentanone, Ketocyclopentane, Ketohexamethylene and isophorone.

As alcoholic solvent, can enumerate: methanol, ethanol, propanol, butanol, hexanol, Hexalin, ethylene glycol, propylene glycol and sweet Oil.

As aromatic hydrocarbon solvents, can enumerate: benzene,toluene,xylene and sym-trimethylbenzene..

As amide solvent, can enumerate: DMF, N,N-dimethylacetamide and N-crassitude Ketone.

These solvents can also be by two kinds of combination of the above.

In above-mentioned solvent, from the standpoint of coating, drying property, the boiling point under preferably 1atm is more than 120 DEG C and 210 Organic solvent below DEG C.Wherein, preferably propylene glycol monomethyl ether, ethyl lactate, propylene glycol monomethyl ether, 3-ethoxy Base ethyl propionate, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, carbiphene, 3-methoxy Base butylacetic acid ester, 3-methoxyl group-n-butyl alcohol, 4-hydroxy-4-methyl-2-pentanone, N,N-dimethylformamide and N-methyl pyrrole Pyrrolidone, more preferably propylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monobutyl ether, dipropylene glycol methyl Ether acetic acid ester, ethyl lactate, 3-methoxybutyl acetas, 3-methoxyl group-n-butyl alcohol, 3-ethoxyl ethyl propionate, N, N-bis- Methylformamide and N-Methyl pyrrolidone.

Relative to the total amount of colored curable resin composition, the content of solvent (E) is usually 70～95 mass %, preferably It is 75～92 mass %, more preferably 75～90 mass %.If the content of solvent (E) is in above-mentioned scope, then when there is coating Flatness become good, it addition, colour saturation will not be not enough when forming color filter, therefore, display characteristic becomes good inclining To.

As levelling agent, can enumerate: silicone based surfactants, fluorine system surfactant and there is having of fluorine atom Machine silicon system surfactant.These surfactants can also have polymerizable group at side chain.

As silicone based surfactants, intramolecular can be enumerated there is the surfactant of siloxane bond.Concrete and Speech, can enumerate: Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA、Toray Silicone SH28PA、Toray Silicone SH29PA、Toray Silicone SH30PA, Toray Silicone SH8400 (manufacture of eastern beautiful DOW CORNING (strain)), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (SHIN-ETSU HANTOTAI's chemical industry (strain) manufacture), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452 and TSF4460 (Momentive Performance Materials Japan contract commercial firm manufactures).

As fluorine system surfactant, intramolecular can be enumerated there is the surfactant of fluorocarbon chain.Specifically, permissible Enumerate: Fluorad (registered trade mark) FC430, Fluorad FC431 (Sumitomo 3M (strain) manufacture), Megafac (registered trade mark) F142D、Megafac F171、Megafac F172、Megafac F173、Megafac F177、Megafac F183、 Megafac F554, Megafac R30, Megafac RS-718-K (DIC (strain) manufacture), EFTOP (registered trade mark) EF301, EFTOP EF303, EFTOP EF351, EFTOP EF352 (Mitsubishi Materials electronics chemical conversion (strain) manufactures), Surflon (registrar Mark) S381, Surflon S382, Surflon SC101, Surflon SC105 (Asahi Glass (strain) manufacture) and E5844 ((strain) Daikin Fine Chemical institute manufactures).

As having the silicone based surfactants of fluorine atom, intramolecular can be enumerated there is siloxane bond and fluorocarbon chain Surfactant.Specifically, can enumerate: Megafac (registered trade mark) R08, Megafac BL20, Megafac F475, Megafac F477 and Megafac F443 (DIC (strain) manufacture).

Relative to the total amount of colored curable resin composition, the content of levelling agent be usually more than 0.0005 mass % and Below 0.6 mass %, more than preferably 0.001 mass % and below 0.5 mass %, more than more preferably 0.001 mass % and Below 0.2 mass %, more preferably more than 0.002 mass % and below 0.1 mass %, particularly preferably 0.005 matter Below amount more than % and 0.07 mass %.If the content of levelling agent is in above-mentioned scope, then can make the flatness of color filter Well.

Relative to the solid constituent total amount of colored curable resin composition, the content of levelling agent is usually 0.001 matter Below amount more than % and 2.0 mass %, more than preferably 0.002 mass % and below 1.5 mass %, more preferably 0.004 matter Below amount more than % and 1.0 mass %, more preferably more than 0.008 mass % and below 0.5 mass %, particularly preferably More than 0.01 mass % and below 0.3 mass %.

The colored curable resin composition of the present invention can contain filler, other macromolecule chemical combination as required Known additive in these technical fields such as thing, closely sealed accelerator, antioxidant, light stabilizer, chain-transferring agent.

The colored curable resin composition of the present invention such as can pass through mixing cpd (Aa), dyestuff (Ab), resin (B), polymerizable compound (C), polymerization initiator (D), solvent (E) and levelling agent as required, polymerization cause auxiliary agent and Prepared by its composition.In addition to compound (Aa), it is also possible to the coloring agent such as further hybrid pigment.Pigment preferably with in advance with It is below 0.2 μm left and right that part or all of solvent (E) mixes and use the mean diameter that ball mill etc. is dispersed to pigment The state of dispersible pigment dispersion uses.At this time it is also possible to coordinate as required above-mentioned pigment dispersing agent, a part for resin (B) or All.

Preferably the filter about the μm of mixed colored curable resin composition aperture 0.01～10 is filtered.

As the method being manufactured colored pattern by the colored curable resin composition of the present invention, can enumerate: photoetching process, Ink-jet method, print process etc..Wherein, preferred photoetching process.Photoetching process for coating substrate by colored curable resin composition so that it is It is dried and forms coloring compositions nitride layer, via photomask, this coloring compositions nitride layer is exposed, the method carrying out developing.In photoetching process In, by not using photomask when exposure and/or do not develop, can be formed solidfied material as above-mentioned coloring compositions nitride layer Color film.Colored pattern, coloring film as formed above are the color filter of the present invention.

The thickness of the color filter made suitably can adjust according to purpose, purposes etc., usually 0.1～30 μm, is preferably 0.1～20 μm, more preferably 0.5～6 μm.

As substrate, glass plate, resin plate, silicon can be used, on aforesaid substrate, define aluminum, silver, silver/copper/palldium alloy The substrate of thin film etc..Other color-filter layer, resin bed, transistor, circuit etc. can also be formed on these substrates.

The formation utilizing photolithographic each color pixel can be carried out by known or usual device, condition.Such as can be such as Under described making.

First, colored curable resin composition is coated on substrate, is thermally dried (prebake) and/or decompression It is dried, thus removes the volatile ingredients such as solvent and make it be dried, obtain the coloring compositions nitride layer smoothed.As coating process, can To enumerate: spin-coating method, slot coated method and slit and spin-coating method.

Then, coloring compositions nitride layer is exposed via the photomask being used for being formed target coloration pattern.In order to can be right Plane of exposure is overall to be irradiated parallel rays equably and maybe can carry out photomask and be formed with substrate correct of coloring compositions nitride layer Para-position, the exposure device such as mask aligner and stepper is preferably used.By making the coloring compositions nitride layer after exposure and development Liquid contacts and develops, and forms colored pattern on substrate.By development, the unexposed portion of coloring compositions nitride layer is dissolved in aobvious Shadow liquid and be removed.As developer solution, the preferably alkalescence such as potassium hydroxide, sodium bicarbonate, sodium carbonate, tetramethyl ammonium hydroxide chemical combination The aqueous solution of thing.Developing method can be any one in paddle (puddle) method, infusion process and nebulization.And then, in development Time, substrate can be made along arbitrarily angled inclination.After development, preferably wash.

Bakee after preferably the colored pattern obtained being carried out further.There is colored pattern, the coloring film as above obtained Color filter in order to give various characteristic, it is also possible to further for surface coated treatment.

The color filter formed by the colored curable resin composition of the present invention is as display device (such as, liquid crystal display Device, organic el device, Electronic Paper etc.) and solid-state imager used in color filter useful.

[embodiment]

Hereinafter, enumerate embodiment and the present invention is more specifically illustrated, but the present invention is not limited by following embodiment certainly System, naturally it is also possible to the scope of objective described later is suitably changed and implements before can being suitable for, they are both contained in this The technical scope of invention.It addition, below, unless otherwise specified, " part " refers to " mass parts ", and " % " refers to " quality % ".

Following reaction is carried out under nitrogen atmosphere.Throw-in type (A-II-in possessing the flask of cooling tube and agitating device 18), after the compound shown in 8 parts, methanol 396 parts, it is stirred at room temperature 30 minutes and prepares blue solution.Then, molten in blueness After liquid puts into 396 parts of water, then it is stirred at room temperature 30 minutes and obtains reaction solution.

[chemical formula 48]

53 parts of water is put in beaker, and then by Keggin-type phosphotungstic acid (Aldrich manufacture) 11.8 parts and methanol Put in this water, in air atmosphere, at room temperature mix and prepare Salkowski's solution for 53 parts.

The Salkowski's solution obtained was dripped in the reaction solution prepared before with 1 hour.It is stirred at room temperature 30 again After minute, carry out filtering and obtaining blue solid.The blue solid obtained is put in methanol 200 parts, after disperseing 1 hour, It is repeated 2 times the operation carrying out filtering.The blue solid obtained by this operation is put in 200 parts of water, after disperseing 1 hour, It is repeated 2 times the operation carrying out filtering.The blue solid obtained by this operation is under reduced pressure dried at 60 DEG C, obtains 17.1 The compound (Aa2-53) shown in formula (A-I-18) of part.

[chemical formula 49]

Resins synthesis example 1

In the flask possessing reflux condenser, Dropping funnel and blender, flow through nitrogen with 0.02L/ minute and form nitrogen Atmosphere, puts into 3-methoxyl group-n-butyl alcohol 200 parts and 3-methoxybutyl acetas 105 parts, stirs and be heated to 70 ℃.Then, by methacrylic acid 60 parts, 3,4-epoxy three ring [5.2.1.0^2.6] (the change shown in formula (1-1) of decyl acrylate The mixture that mol ratio is 50:50 of the compound shown in compound and formula (2-1).) 240 parts be dissolved in 3-methoxybutyl acetic acid Ester 140 parts and prepare solution, this lysate uses Dropping funnel be incubated in the flask of 70 DEG C with within 4 hours, being added drop-wise to.Another Aspect, uses another Dropping funnel 4 hours dropping dissolving polymerization initiators 2 in flask, double (2, the 4-dimethyl of 2 '-azo Valeronitrile) 30 parts in the solution of 3-methoxybutyl acetas 225 parts.After the completion of dropwise addition of the solution of polymerization initiator, protect Hold 70 DEG C 4 hours, be then cooled to room temperature, obtain solid constituent be 32.6%, acid number be 110mg-KOH/g (solid constituent Conversion) resin B-1b solution.Weight average molecular weight Mw of the resin B-1b obtained is 13,400, molecular weight distribution is 2.50.

Embodiment 1:<colored curable resin composition>

By coloring agent (A): the compound shown in formula (A-I-18) 41.6 parts；

Compound shown in formula (*) 0.4 part

[chemical formula 50]

Alkali soluble resin (B): resin B-1b (solid constituent conversion) 29 parts；

Polymerizable compound (C): dipentaerythritol acrylate (KAYARAD (registered trade mark) DPHA；Japan's chemical medicine (strain) manufactures) 11 parts；

Polymerization initiator (D): N-benzoyloxy-1-(4-Phenylsulfanyl phenyl) octane-1-ketone-2-imines (Irgacure (registered trade mark) OXE-01；BASF AG manufactures；O-acyl group oxime compound) 4 parts；

Solvent (E): propylene glycol monomethyl ether 413 parts；And

Levelling agent (F): polyether modified silicon oil (Toray Silicone SH8400；The beautiful DOW CORNING in east (strain) manufactures) 0.15 Part

Mixing, obtains colored curable resin composition.

Comparative example 1:<colored curable resin composition>

By coloring agent (A): the compound shown in formula (A-I-18) 26 parts；

Alkali soluble resin (B): resin B-1b (solid constituent conversion) 44 parts；

Polymerizable compound (C): dipentaerythritol acrylate (KAYARAD (registered trade mark) DPHA: Japan's chemical medicine (strain) manufactures) 11 parts；

Solvent (E): propylene glycol monomethyl ether 68 parts；

Solvent (E): 4-hydroxy-4-methyl-2-pentanone 561 parts；And

Mixing, obtains colored curable resin composition.

Glass substrate (Eagle XG at 2 inch square；Corning company manufacture) on be coated with above-mentioned reality by spin-coating method After executing the colored curable resin composition obtained in example 1 and comparative example 1, prebake 3 minutes at 100 DEG C and form colour cell Compound layer.After cooling, use exposure machine (TME-150RSK；Topcon (strain) manufactures), with 150mJ/cm under air atmosphere²'s Light exposure (365nm benchmark) is exposed.It addition, do not use photomask.Will exposure after coloring compositions nitride layer in an oven with 180 DEG C carry out 20 minutes after bakee, thus make color filter (thickness 2.0 μm).

The color filter obtained is heated 20 minutes at 230 DEG C, uses colour examining machine (OSP-SP-200；OLYMPUS company system Make) measure the aberration (Δ Eab*) before and after heating.The colour filter made by the colored curable resin composition obtained in embodiment 1 The aberration (Δ Eab*) of device is 3.8, the colored curable resin composition obtained in comparative example 1 aberration of the color filter made (Δ Eab*) is 8.5.

Industrial utilizability

Claims

1. colored curable resin composition, it is characterised in that containing the compound (Aa) shown in formula (A-I), dyestuff (Ab), tree Fat (B), polymerizable compound (C) and polymerization initiator (D), wherein, be not included in preparing with described compound (Aa) and solvent The compositions mixed with remaining composition after color dispersion liquid,

[chemical formula 1]

In formula (A-I), R⁴¹～R⁴⁴Separately represent the alkyl of the carbon number 1～20 can with substituent group, for carbon number 2～20 Alkyl and constitute this alkyl methylene between insert aerobic atom group, can have substituent group aromatic hydrocarbyl, Can have aralkyl or the hydrogen atom of substituent group, R⁴¹And R⁴²Ring is formed together with the nitrogen-atoms can being bonded and be bonded with them, R⁴³And R⁴⁴Ring is formed together with the nitrogen-atoms can being bonded and be bonded with them,

R⁴⁷～R⁵⁴Separately represent hydrogen atom, oxygen atom, nitrogen-atoms, sulphur atom, halogen atom, nitro, sulfonyl, hydroxyl Base or the alkyl of carbon number 1～8, can insert oxygen atom, R constituting between the methylene of this alkyl⁴⁸And R⁵²Can be bonded mutually And form-NH-,-S-or-SO₂-,

Ring T¹Expression can have the heteroaromatic of substituent group,

[Y]^m-Represent the appointing as indispensable element containing at least 1 element in the group selecting free tungsten, molybdenum, silicon and phosphorus to constitute and oxygen The anion of the m valency of meaning,

M represents arbitrary natural number,

It addition, containing in the case of the cation shown in multiple following formula in 1 molecule, they can be identical structure, also Can be different structures,

[chemical formula 2]

In formula, ring T¹、R⁴¹～R⁴⁴And R⁴⁷～R⁵⁴Respectively with above-mentioned same meaning.

Colored curable resin composition the most according to claim 1, wherein, [Y]^m-For containing tungsten as indispensable element Heteropoly acid or the anion of isopolyacid.

Colored curable resin composition the most according to claim 2, wherein, [Y]^m-Anion, silicon tungsten for phosphotungstic acid The anion of acid or the anion of tungsten system isopolyacid.

4. according to the colored curable resin composition according to any one of claims 1 to 3, wherein, dyestuff (Ab) is for being selected from In the group being made up of ton dyestuff, triarylmethane dye, anthraquinone dye and tetraazatetradecane porphyrin dyestuff a kind.

5. according to the colored curable resin composition according to any one of Claims 1 to 4, wherein, dyestuff (Ab) is ton Dyestuff.

6. according to the colored curable resin composition described in claim 4 or 5, wherein, ton dyestuff is shown in formula (a1-1) Compound,

[chemical formula 3]

In formula (a1-1), R¹～R⁴Represent hydrogen atom independently of each other, can have 1 valency saturated of the carbon number 1～20 of substituent group Alkyl, maybe can have the aromatic hydrocarbyl of 1 valency of the carbon number 6～10 of substituent group, methylene contained in this saturated hydrocarbyl (- CH₂-) can be by-O-,-CO-or-NR¹¹-substitute, R¹And R²The ring containing nitrogen-atoms, R can be formed together³And R⁴Can be together Form the ring containing nitrogen-atoms,

R⁵Represent-OH ,-SO₃ ^-、-SO₃H、-SO₃ ^-Z⁺、-CO₂H、-CO₂ ^-Z⁺、-CO₂R⁸、-SO₃R⁸Or-SO₂NR⁹R¹⁰,

R⁶And R⁷Represent hydrogen atom or the alkyl of carbon number 1～6 independently of each other,

M represents the integer of 0～5, when m is more than 2, and multiple R⁵Can be identical, it is also possible to different,

A represents the integer of 0 or 1,

X represents halogen atom,

Z⁺Represent⁺N(R¹¹)₄、Na⁺Or K⁺, 4 R¹¹Can be identical, it is also possible to different,

R⁸Representing the saturated hydrocarbyl of 1 valency of carbon number 1～20, hydrogen atom contained in this saturated hydrocarbyl can be substituted with halogen atoms,

R⁹And R¹⁰Representing that hydrogen atom maybe can have the saturated hydrocarbyl of 1 valency of the carbon number 1～20 of substituent group independently of each other, this is satisfied With-CH contained in alkyl₂-can be by-O-,-CO-,-NH-or-NR⁸-substitute, R⁹And R¹⁰Can be bonded mutually and formed containing The heterocycle of 3～10 rings of nitrogen-atoms,

R¹¹Represent saturated hydrocarbyl or the aralkyl of carbon number 7～10 of 1 valency of hydrogen atom, carbon number 1～20.

7. according to the colored curable resin composition according to any one of claim 1～6, wherein, the weight average of resin (B) divides Son amount is more than 9000.

8. according to the colored curable resin composition according to any one of claim 1～7, wherein, the acid number of resin (B) is More than 60mg-KOH/g.

9. according to the colored curable resin composition according to any one of claim 1～8, wherein, the content of dyestuff (Ab) Solid constituent 100 mass % of colored curable resin composition is 0.01～5 mass %.

10. according to the colored curable resin composition according to any one of claim 1～9, wherein, dyestuff (Ab)/chemical combination The mass ratio of thing (Aa) is 0.001～0.5.

11. color filters, it is formed by according to the colored curable resin composition according to any one of claim 1～10.

12. display devices, it comprises color filter according to claim 11.