CN104865796A

CN104865796A - Colored Curable Resin Composition

Info

Publication number: CN104865796A
Application number: CN201510085340.3A
Authority: CN
Inventors: 城内由子; 藤田拓麻; 织田胜成
Original assignee: Dongwoo Fine Chem Co Ltd
Current assignee: Sumitomo Chemical Co Ltd; Dongwoo Fine Chem Co Ltd
Priority date: 2014-02-20
Filing date: 2015-02-17
Publication date: 2015-08-26
Anticipated expiration: 2035-02-17
Also published as: TW201542703A; CN104865796B; JP6530924B2; JP2015172189A; KR102001709B1; KR20150098579A; TWI682002B

Abstract

A colored curable resin composition comprises a colorant, a resin, a polymerized compound and a polymerization initiator. The colorant contains at least one of a yellow dye and a yellow pigment, a blue dye and a green pigment.

Description

Colored curable resin composition

Technical field

The present invention relates to colored curable resin composition.

Background technology

Colored curable resin composition is used for the manufacture of the color filter used in the display device such as liquid crystal indicator, el display and plasma scope.In order to reduce the power consumption of display device, seek that transmissivity is high, the color filter of high brightness.As the colored curable resin composition for the manufacture of color filter, recite in Japanese Unexamined Patent Publication 2013-231165 publication containing halogenated phthalo-cyanine pigment and the coumarine dye colored curable resin composition as colorant.

Summary of the invention

The present invention includes following invention.

[1] colored curable resin composition, it contains colorant, resin, polymerizable compound and polymerization initiator,

Colorant is the colorant containing at least one be selected from weld and yellow uitramarine and blue dyes and viridine green.

[2] colored curable resin composition Gen Ju [1], wherein, the containing ratio of blue dyes is more than 0.1 quality % and below 20 quality % relative to the total content of colorant.

[3] according to [1] or the colored curable resin composition described in [2], wherein, blue dyes for being selected from the compound represented by formula (Ab1), at least a kind of dyestuff in methine dye well azomethine dyes,

(in formula, R ^1A~ R ^8Aseparately represent the alkyl (oxygen atom can be inserted between the carbon atom forming this alkyl) of hydrogen atom, halogen atom, nitro, hydroxyl, carbon number 1 ~ 20.R ^4Acan with R ^5Amutual bonding and form-NH-,-S-or-SO ₂-.

R ^9A~ R ^12Aseparately represent hydrogen atom; (oxygen atom can be inserted between the carbon atom forming this alkyl by the alkyl of carbon number 1 ~ 20 that is amino or that can be replaced by halogen atom; The aralkyl that can be substituted; The aryl that maybe can be substituted.R ^9Acan with R ^10Abonding and form ring together with the nitrogen-atoms of their institute's bonding, R ^11Acan with R ^12Abonding and form ring together with the nitrogen-atoms of their institute's bonding.

A represents the aromatic heterocycle that the aromatic hydrocarbyl that can be substituted maybe can be substituted.

G ^g-represent counter anion.

G represents 0 or arbitrary natural number.When g is 0, represent not there is counter anion.)

[4] according to the colored curable resin composition according to any one of [1] ~ [3], wherein, polymerization initiator is the polymerization initiator containing O-acyl group oxime compound.

[5] color filter, its colored curable resin composition any one of [1] ~ [4] described in any one is formed.

[6] display device, the color filter that it comprises described in [5].

According to colored curable resin composition of the present invention, the color filter that brightness (lightness) is excellent can be formed.

Embodiment

Colored curable resin composition of the present invention contains colorant (A), resin (B), polymerizable compound (C) and polymerization initiator (D), and colorant (A) is containing at least one be selected from weld and yellow uitramarine and blue dyes and viridine green.

Colored curable resin composition of the present invention is also preferably containing solvent (E) and/or levelling agent (F).

Colored curable resin composition of the present invention can cause auxiliary agent (D1) and/or mercaptan compound (T) containing polymerization.

In this manual, if illustrative compound does not have special provision as each composition, can use separately or by multiple combination.

< colorant (A) >

Colorant (A) is containing blue dyes (A1), viridine green (A2) and at least one (hereinafter sometimes referred to " yellow colorants (A3) ") that is selected from weld and yellow uitramarine.

In the present invention, blue dyes (A1) refers at more than 580nm and the scope of below 650nm, preferably have maximum absorption wavelength in the scope of below 645nm and a pigment to solvent-soluble at more than 600nm.

As blue dyes (A1), phthalocyanine dye, compound, triarylmethane colouring matters, anthraquinone dye, methine dyestuff, azomethine dyes etc. represented by formula (Ab1) can be enumerated.Wherein, preferred phthalocyanine dye, compound, methine dyestuff and azomethine dyes represented by formula (Ab1), the compound more preferably represented by formula (Ab1), methine dyestuff and azomethine dyes.

Phthalocyanine dye (Aa) is the dyestuff containing the compound in molecule with phthalocyanine frame.As phthalocyanine dye (Aa), the C.I. solvent blue 67,70 recorded in カラーイ Application デッ Network ス (color index) (The Societyof Dyers and Colourists publishes) can be enumerated; C.I. direct indigo plant 86,87,189,199; C.I. acid blue 249; C.I. medium indigo plant 77; The dyestuff etc. recorded in Japanese Unexamined Patent Publication 5-333207 publication, Japanese Unexamined Patent Publication 6-51115 publication, Japanese Unexamined Patent Publication 6-194828 publication.

(below, be sometimes referred to as " compound (Ab1) " as the compound represented by formula (Ab1).), also comprise color index (カラーイ Application デッ Network ス) (The Society of Dyers andColourists publishes) middle C.I. solvent blue 2,4,5,43,124 recorded; C.I. alkali blue 1,5,7,26; C.I. Blue VRS, 3,5,7,9,11,13,15,17,22,24,26,34,48,75,83,86,88,90,91,99,100,103,104,108,109,110,119,123,147,213,269 and Jap.P. No. 4492760 publication in the dyestuff etc. recorded.

In formula (Ab1), R ^1A~ R ^8Aseparately represent the alkyl (oxygen atom can be inserted between the carbon atom forming this alkyl) of hydrogen atom, halogen atom, nitro, hydroxyl, carbon number 1 ~ 20.R ^4Acan with R ^5Amutual bonding and form-NH-,-S-or-SO ₂-.

R ^9A~ R ^12Aseparately represent the alkyl (oxygen atom can be inserted between the carbon atom forming this alkyl) of the carbon number 1 ~ 20 that can be replaced by amino or halogen atom, the aralkyl that can be substituted, the aryl that maybe can be substituted or hydrogen atom, alkyl (oxygen atom can be inserted between the carbon atom forming this alkyl), the aryl that maybe can be substituted of carbon number 1 ~ 20 that preferably separately represent hydrogen atom, can be replaced by amino or halogen atom.R ^9Acan with R ^10Abonding and form ring together with the nitrogen-atoms of their institute's bondings, R ^11Acan with R ^12Abonding and form ring together with the nitrogen-atoms of their institute's bondings.

G ^g-represent counter anion.

G represents 0 or arbitrary natural number.When g is 0, represent not there is counter anion.

In the compound represented by formula (Ab1), also comprise its dynamic isomer.

R ^1A~ R ^8Athe separately alkyl of preferred hydrogen atom and carbon number 1 ~ 20.At R ^1A~ R ^8Ain, as the alkyl of carbon number 1 ~ 20, the alkyl of the carbon numbers 1 ~ 4 such as preferable methyl, ethyl, propyl group, butyl.

R ^9A~ R ^12Ain, as the alkyl of carbon number 1 ~ 20, the alkyl of the carbon numbers 1 ~ 4 such as preferable methyl, ethyl, propyl group, butyl.As the aryl that can be substituted, the phenyl that can be replaced by halogen atom, nitro, hydroxyl can be enumerated.R ^9A~ R ^12Ain, as aralkyl, can benzyl, phenylethyl etc. be enumerated.As the aralkyl that can be substituted, can enumerate and can have-SO ₃ ^-,-SO ₃the aralkyl of J (J represents kation) alternatively base.

R ^9A~ R ^12Athe separately preferably alkyl of hydrogen atom, carbon number 1 ~ 20 and the benzyl that can be substituted.

In A, as aromatic hydrocarbyl, the aromatic hydrocarbyl of the carbon numbers 6 ~ 10 such as phenyl, naphthyl, toluyl groups, xylyl can be enumerated.As aromatic heterocycle, the aromatic heterocycle that pyrrole radicals, oxazolyl, imidazole radicals, thiazolyl, indyl etc. comprise the heterocycle of 5 rings containing aerobic, nitrogen, sulphur can be enumerated.

In A, as the substituting group that aromatic hydrocarbyl and aromatic heterocycle can have, halogen atom, the amino that can be substituted, hydroxyl, sulfo group ,-SO can be enumerated ₃ ^-,-SO ₃j (J represents kation) etc.

As the substituting group in above-mentioned amino, the alkyl of carbon number 1 ~ 4 can be enumerated; The aryl of the alternatively base of the alkoxy can with carbon number 1 ~ 4;-SO can be had ₃ ^-,-SO ₃the benzyl of J alternatively base; Deng.

As J, inorganic cation or organic cation can be enumerated.As inorganic cation, alkali metal cation, ammonium cation can be enumerated.As organic cation, the glyoxaline cations such as the kation of such as organoammonium cations, following formula can be enumerated.

As G ^g-, can enumerative (y1), formula (y2) or the negative ion represented by formula (y3).

In formula, R ^b1represent the organic group of 1 valency.As this organic group, the aliphatic alkyl of the carbon numbers 1 ~ 20 such as methyl, ethyl, propyl group, butyl can be enumerated; The aromatic hydrocarbyl of the carbon numbers 6 ~ 20 such as phenyl, naphthyl, toluyl groups, the hydrogen atom comprised in this aliphatic alkyl and this aromatic hydrocarbyl can by replacements such as halogen atoms.

R ^b2and R ^b3represent halogen atom or halo alkyl, R ^b2and R ^b3can bonding and formed and comprise-SO mutually ₂-N ^--SO ₂-ring.Above-mentioned halo alkyl is preferably fluoro alkyl, is more preferably the fluoro-alkyl of carbon number 1 ~ 4, more preferably perfluoroalkyl.

R ^b4and R ^b5represent the organic group of divalent.This organic group is preferably the aromatic series base of divalent.As this aromatic series base, can enumerate the aromatic hydrocarbyl of the carbon number 6 ~ 10 of the divalent such as phenylene, naphthylene, the hydrogen atom comprised in this aromatic hydrocarbyl can by replacements such as hydroxyls.

M represents aluminium atom or boron atom.

As the negative ion represented by formula (y1), methane sulfonate anions, toluenesulfonate anion, dodecylbenzene sulfonic acid negative ion, trifluoromethayl sulfonic acid negative ion, perfluorobutane negative ion etc. can be enumerated.

As the negative ion represented by formula (y2), the negative ion etc. of following formula can be enumerated.

As the negative ion represented by formula (y3), the negative ion etc. of following formula can be enumerated.

Further, as G ^g-, the resin, three perfluoroalkyl group sulfonyl methide acid anions (トリスペ Le Off Le オロア Le キ Le ス Le ホニ Le メチ De acid アニオ Application) etc. with halide ion, silico-tungstic acid negative ion, sulfonic acid anion can be enumerated.

G ^g-be preferably halide ion or formula (y2) or the negative ion represented by formula (y3), be more preferably halide ion and the negative ion represented by formula (y2).

When A is aromatic hydrocarbyl in formula (Ab1), as compound (Ab1), the compound of such as following formula can be enumerated.J and above-mentioned synonym in following formula.

The compound that compound (Ab1) is preferably represented by formula (Ab2) (below, is sometimes referred to as " compound (Ab2) ".)。Also its dynamic isomer is comprised in compound represented by formula (Ab2).

In formula (Ab2), m represents arbitrary natural number.

X represents oxygen atom ,-NR ⁵⁶-or sulphur atom.

[Y] ^m-represent the negative ion of m valency.

R ⁵⁶represent the alkyl of hydrogen atom or carbon number 1 ~ 10.

R ⁴¹~ R ⁴⁶separately represent the alkyl (oxygen atom can be inserted between the carbon atom forming this alkyl) of the carbon number 1 ~ 20 that can be replaced by amino or halogen atom, the aralkyl that can be substituted, the aryl that can be substituted or hydrogen atom, preferably represent the alkyl (oxygen atom can be inserted between the carbon atom forming this alkyl) of the carbon number 1 ~ 20 that can be replaced by amino or halogen atom, the aryl that can be substituted or hydrogen atom.R ⁴¹can with R ⁴²bonding and form ring together with the nitrogen-atoms of their institute's bondings, R ⁴³can with R ⁴⁴bonding and form ring together with the nitrogen-atoms of their institute's bondings, R ⁴⁵can with R ⁴⁶bonding and form ring together with the nitrogen-atoms of their institute's bondings.

R ⁴⁷~ R ⁵⁴separately represent the alkyl (oxygen atom can be inserted between the carbon atom forming this alkyl) of hydrogen atom, halogen atom, nitro, hydroxyl, carbon number 1 ~ 8.R ⁴⁸can with R ⁵²mutual bonding and form-NH-,-S-or-SO ₂-.

R ⁵⁵the alkyl representing hydrogen atom, carbon number 1 ~ 20, the aryl that maybe can be substituted.

It should be noted that, containing multiple in 1 molecule

Time, they can be that identical structure also can for different structures.

R ⁴¹~ R ⁴⁶preferably separately for can be substituted benzyl, carbon number 1 ~ 20 the alkyl aryl that maybe can be substituted, or be the ring formed together with above-mentioned nitrogen-atoms, the aryl that the alkyl being more preferably carbon number 1 ~ 20 maybe can be substituted, or the ring for being formed together with above-mentioned nitrogen-atoms.

R ^41A~ R ^46Ain, as the alkyl of carbon number 1 ~ 20, the alkyl of the carbon numbers 1 ~ 4 such as preferable methyl, ethyl, propyl group, butyl.

R ^41A~ R ^46Ain, as aryl, the aryl of the carbon numbers 6 ~ 10 such as preferred phenyl, toluyl groups.

R ^41A~ R ^46Ain, as the benzyl that can be substituted, can enumerate and can have-SO ₃-,-SO ₃the benzyl of J (J represents kation) alternatively base.

R ⁴⁷~ R ⁵⁴the separately alkyl of preferred hydrogen atom and carbon number 1 ~ 4.

R ⁵⁵be preferably hydrogen atom, the alkyl of carbon number 1 ~ 4, the phenyl that maybe can be substituted.As the substituting group in this phenyl, the alkyl sulphonyl, trifluoromethyl etc. of halogen atom, methyl, carbon number 1 ~ 4 can be enumerated.

As the cationic moiety of formula (Ab2), the kation 1 ~ kation 12 etc. represented by formula (Ab2-0) shown in table 1 can be set forth in.In table, * represents bonding end.

[table 1]

Wherein, as the cationic moiety of formula (Ab2), preferred cationic 1 ~ kation 6, kation 8, kation 11 or kation 12, particularly preferably kation 1, kation 2, kation 8 or kation 12.

As [Y] ^m-known negative ion can be enumerated.From the viewpoint of thermotolerance, preferred [Y] ^m-for containing boron anion, containing aluminium negative ion, fluo anion and containing at least a kind of element be selected from tungsten, molybdenum, silicon and phosphorus and oxygen as must the negative ion of element.

As compound (Ab2), the compound such as represented by following formula can be enumerated.

Compound (Ab2) can be manufactured by making the compound represented by the compound represented by formula (B-I) and formula (C-I) react.This reaction can be carried out in presence of organic solvent, also can carry out in the absence of a solvent.

[in formula (B-I) and formula (C-I), each symbol represents the meaning same as described above respectively.]

Also compound (Ab2) can be manufactured by making the compound reaction represented by the compound represented by the compound represented by formula (B-II), formula (C-II) and formula (C-II ').This reaction can be carried out in presence of organic solvent, also can carry out in the absence of a solvent.

[in formula (B-II), formula (C-II) and formula (C-II '), each symbol represents the meaning same as described above respectively.]

As the manufacture method of compound (B-I) and compound (B-II), known various method can be enumerated, such as, the method recorded in No. P3928243.0, western German patent application.

Can manufacture compound (C-I) and compound (C-II) by known various method, they also can be the compounds obtained with the form of commercially available product.

For arbitrary compound (Ab2), desired compound (Ab2) can be manufactured further by anion exchange.Anion exchange such as can by will the compound (Ab2) that manufacture in above-mentioned method and desired [Y] ^m-alkali metal salt mix in a solvent to carry out.

As alkaline metal, lithium, sodium and potassium can be enumerated.

As [Y] ^m-alkali metal salt, No. 4097704th, Jap.P., No. 4341251st, Jap.P. and Journal of The Electrochemical Society can be enumerated, 148th volume the 1st phase, calendar year 2001., the alkali metal salt that No. 2008/075672, International Publication, Japanese Unexamined Patent Publication 2010-280586 publication are recorded.

Methine dyestuff is the dyestuff containing the compound with the structure that two groups are connected by odd number methine chain, and at least one of these two groups is heterocycle or aromatic rings (being sometimes also called by this methine dyestuff " poly-methine dyestuff (Port リメチ Application dyestuff) ").

As above-claimed cpd, specifically, can enumerate there is Xa-CH (=CH-CH) _x(Xa and Xb represents arbitrary group to=Xb respectively.The integer that x is more than 0) shown in the compound of structure.

Azomethine dyes refers to that the methine of in above-mentioned methine chain more than 1 or 2 is replaced into the dyestuff of nitrogen-atoms.

Methine dye well azomethine dyes is (following, sometimes be referred to as " methine dyestuff (Ac) ") preferably there is the compound of the structure that above-mentioned two groups are connected by 1 methine or 1 imino group, more there is the compound represented by the formula of electing as (Ac1).

[in formula (Ac1), X ⁶¹represent nitrogen-atoms or CH.

R ⁶¹represent the alkyl of hydrogen atom or carbon number 1 ~ 4.

R ⁶²represent the alkoxy carbonyl of hydrogen atom, cyano group, carbamyl, carboxyl or carbon number 1 ~ 4.

R ⁶³represent oxygen atom, C (CN) ₂, C (CN) CO ₂l ¹or C (CO ₂l ¹) ₂.L ¹represent the alkyl of carbon number 1 ~ 8, can be replaced by oxygen atom for 1 or 2 that forms the MU (methylene unit) of this alkyl.

R ⁶⁴~ R ⁶⁶separately represent the alkyl of the carbon number 1 ~ 20 that can be replaced by amino or halogen atom, the amino that can be substituted, the aryl that can be substituted, hydrogen atom or hydroxyl, oxygen atom can be inserted between the carbon atom forming this alkyl.]

X ⁶¹be preferably nitrogen-atoms.

R ⁶¹be preferably the alkyl of carbon number 1 ~ 3, be more preferably methyl.

R ⁶²be preferably cyano group.

R ⁶³be preferably oxygen atom.

R ⁶⁴be preferably methyl, ethyl or-CH (L ²) (L ³).-CH (L ²) (L ³) in, L ²and L ³separately represent alkyl, L ²and L ³total carbon number be 2 ~ 19, be more preferably 2 ~ 9.In addition, L ²and L ³be preferably straight-chain alkyl.

R ⁶⁵the amino that preferably be instead of by the alkyl of 2 carbon numbers 1 ~ 10 (being more preferably the alkyl of carbon number 3 ~ 6), be more preferably N, N-diisopropylaminoethyl, N, N-di-n-butyl amino, N, N-bis-n-pentyl is amino, N, N-di-n-hexyl is amino.

R ⁶⁶be preferably the alkyl of carbon number 1 ~ 8 of hydrogen atom, straight-chain or branched, naphthyl, phenyl or there is the phenyl of halogen atom (being preferably fluorine atom, chlorine atom) of more than 1, be more preferably hydrogen atom, the branched-chain alkyl (preferably isopropyl, isopentyl, the tert-butyl group) of carbon number 3 ~ 5, phenyl or chlorphenyl.

As the compound represented by formula (Ac1), such as following compound can be enumerated.The compound represented by formula (Ac1) can be manufactured by the method that such as Japanese Unexamined Patent Publication 3-166268 publication is recorded.

In the present invention, viridine green (A2) refers at more than 650nm and has maximum absorption wavelength in the scope of below 700nm and pigment that is insoluble to water, organic solvent equal solvent or indissoluble.The pigment being such as classified as pigment in color index (The Society of Dyers and Colourists publishes) can be enumerated.

As viridine green, can enumerate C.I. pigment Green 7,36,58,59, the halogenated phthalo-cyanine pigment such as viridine green recorded of Japanese Unexamined Patent Publication 2004-70342 publication, Japanese Unexamined Patent Publication 2008-19383 publication, Japanese Unexamined Patent Publication 2007-320986 publication.Be preferably C.I. pigment Green 7,36,58,59.

Yellow colorants (A3) is for being selected from least one in weld and yellow uitramarine.In the present invention, yellow colorants (A3) refers at more than 400nm and has the pigment of maximum absorption wavelength in the scope of below 470nm in the scope of below 470nm, preferably at more than 430nm.

As weld, azo dyes, metal complex dyes, methine dyestuff, coumarine dye, styryl color can be enumerated.Wherein, preferred coumarine dye.

Coumarine dye is the dyestuff containing the compound in molecule with coumarin skeleton.As coumarine dye, can be set forth in record in color index (The Society of Dyers and Colourists publishes) C.I. Indian yellow 227,250, C.I. disperse yellow 82,184, C.I. solvent orange 112, C.I. solvent yellow 16 0,172, the coumarine dye etc. recorded in Jap.P. No. 1299948 publication.This coumarine dye is preferably dissolved in organic solvent.

In them, as coumarine dye, preferred formula (Ad1) or the compound represented by formula (Ad2) (being sometimes called " compound (Ad1) ", " compound (Ad2) " below).

[in formula (Ad1), Q ^1Band Q ^2Bseparately represent hydrogen atom or-CO ₂m ^1B, but Q ^1Band Q ^2Bin any one expression-CO ₂m ^1B.

R ^1B~ R ^4Bseparately represent the alkyl of 1 valency of hydrogen atom or carbon number 1 ~ 20, or R ^1Band R ^3Bring is formed, R together with carbon atom in the lump on adjacent phenyl ring and adjacent nitrogen-atoms ^2Band R ^4Bring is formed together with carbon atom in the lump on adjacent phenyl ring and adjacent nitrogen-atoms, or R ^1Band R ^2Bbonding and form ring together with adjacent nitrogen-atoms.The methylene forming the alkyl of this 1 valency can be replaced into oxygen atom, sulphur atom ,-N (R ^5B)-, sulfonyl or carbonyl, the hydrogen atom comprised in the alkyl of this 1 valency can be substituted by halogen atom, cyano group, nitro, carbamyl, amino-sulfonyl ,-SO ₃m ^1B,-CO ₂m ^1B, hydroxyl or amino.

R ^5Brepresent the alkyl of 1 valency of hydrogen atom or carbon number 1 ~ 20.There is multiple R ^5Btime, they are mutually identical or different.

M ^1Brepresent hydrogen atom or alkali metal atom.]

R ^1Band R ^2Bseparately be preferably the aliphatic alkyl of 1 valency of carbon number 1 ~ 10, be more preferably ethyl, butyl, hexyl, 2-ethylhexyl or octyl group, more preferably ethyl, butyl, hexyl and 2-ethylhexyl.

R ^3Band R ^4Bbe preferably hydrogen atom.

R ^1Band R ^3Bwhen forming the ring comprising the nitrogen-atoms of their institute's bondings and carbon atom in the lump or R ^2Band R ^4Bwhen forming the ring of nitrogen-atoms and the carbon atom comprising their institute's bondings in the lump, as-R ^1B-R ^3B-and-R ^2B-R ^4B-, can-CH be enumerated ₂-CH ₂-,-CF ₂-CF ₂-or-CH ₂-C (CH ₃) ₂-etc., be preferably-CH ₂-CH ₂-or-CH ₂-C (CH ₃) ₂-, be more preferably-CH ₂-C (CH ₃) ₂-.

As R ^1Band R ^2Bbonding and form ring together with adjacent nitrogen-atoms time-R ^1B-R ^2B-,-(CH can be enumerated ₂) ₂-,-(CH ₂) ₃-,-(CH ₂) ₄-,-(CH ₂) ₅-,-(CH ₂) ₆-,-(CH ₂) ₇-,-(CF ₂) ₂-,-(CF ₂) ₃-,-(CF ₂) ₄-,-(CF ₂) ₅-,-(CF ₂) ₆-,-(CF ₂) ₇-etc., be preferably-(CH ₂) ₄-,-(CH ₂) ₅-,-(CH ₂) ₆-,-(CF ₂) ₄-,-(CF ₂) ₅-or-(CF ₂) ₆-, be more preferably-(CH ₂) ₄-,-(CH ₂) ₅-or-(CH ₂) ₆-, more preferably-(CH ₂) ₄-or-(CH ₂) ₅-.

M ^1Bbe preferably hydrogen atom, sodium atom or potassium atom, be more preferably hydrogen atom.

As compound (Ad1), the compound of such as following formula and the compound of Japanese Unexamined Patent Publication 2013-231165 publication record can be enumerated.

In formula (Ad2), L ^crepresent alkyl or the sulfonyl of the divalent of carbon number 1 ~ 20, the hydrogen atom comprised in this alkyl can be replaced by fluorine atoms.

X ^crepresent oxygen atom or sulphur atom.

R ^1Cand R ^2Cseparately represent the alkyl can with substituent phenyl or carbon number 1 ~ 20, oxygen atom can be inserted between the carbon atom forming this alkyl.

R ^7C~ R ^13Cseparately represent hydrogen atom, halogen atom, cyano group, nitro, carbamyl, amino-sulfonyl ,-SO ₃m ^c,-CO ₂m ^c, hydroxyl, formoxyl, amino, carbon number 1 ~ 20 the alkyl of 1 valency, oxygen atom, sulphur atom ,-N (R can be inserted between the carbon atom forming this alkyl ^14C)-, sulfonyl or carbonyl, the hydrogen atom comprised in this alkyl can by halogen atom, cyano group, nitro, carbamyl, amino-sulfonyl ,-SO ₃m ^c,-CO ₂m ^c, hydroxyl, formoxyl or amino to replace.

R ^14Crepresent the alkyl of 1 valency of hydrogen atom or carbon number 1 ~ 20, there is multiple R ^14Ctime, they can be identical, also can be different.

M ^crepresent hydrogen atom or alkali metal atom.

As R ^1Cand R ^2Cthe phenyl substituting group that can have, halogen atom, cyano group, nitro, carbamyl, amino-sulfonyl ,-SO can be enumerated ₃m ^c,-CO ₂m ^c, hydroxyl, formoxyl, amino, carbon number 1 ~ 20 the alkyl etc. of 1 valency.

L ^cthe alkyl of the divalent of the carbon number 1 ~ 5 that preferably can be replaced by fluorine atoms or sulfonyl, be more preferably propane-2,2-bis-base, HFC-236fa-2,2-bis-base or sulfonyl.

X ^cbe preferably oxygen atom.

As compound (Ad2), the compound such as represented by following formula can be enumerated.

As yellow uitramarine, the C.I. pigment yellow 1,3,12,13,14,15,16,17,20,24,31,53,83,86,93,94,109,110,117,125,128,129,137,138,139,147,148,150,153,154,166,173,180,185,194,214 etc. recorded in color index (The Society of Dyers and Colourists publishes) can be enumerated.Wherein, preferred C.I. pigment Yellow 12 9,138,139,150.

Yellow colorants (A3) is preferably weld.If yellow colorants (A3) is weld, then there is the tendency that can reduce the content of yellow colorants (A3), therefore can increase the content of the resin (B) in colored curable resin composition, polymerizable compound (C), the permanance such as the thermotolerance of the color filter obtained, chemical-resistant can be made to improve.

Colorant (A) can also contain other dyestuffs and/or pigment in the degree of performance not damaging the application's colored curable resin composition.As other dyestuffs, the dyestuff beyond blue dyes (A1) and yellow colorants (A3) in the compound being classified as the dyestuff beyond pigment with tone in color index (TheSociety of Dyers and Colourists publishes), the known dyestuff recorded in dyeing notes (Se Ran society) can be set forth in.According to chemical constitution, azo dyes, phthalocyanine dye, anthraquinone dye, cyanine dye, naphthoquinone dyestuff, quinoneimine dye, methine dyestuff, squaraine dye, acridine dye, styryl dye, quinoline dye and nitro dye etc. can be enumerated.

As other pigment, if the pigment beyond the yellow uitramarine of viridine green (A2), yellow colorants (A3), known pigment can be used with regard to being not particularly limited, the pigment being such as categorized as pigment in color index (The Society of Dyers and Colourists publishes) can be enumerated.

As pigment, can enumerate C.I. pigment orange 13,31,36,38,40,42,43,51,55,59,61,64,65,71, the orange pigment such as 73;

C.I. Pigment Red 9,97,105,122,123,144,149,166,168,176,177,180,192,209,215,216,224,242,254,255,264, the red pigments such as 265;

C.I. pigment blue 15,15:3,15:4,15:6, the blue pigments such as 60; C.I. pigment violet 1,19,23,29,32,36, the violet pigments etc. such as 38.

In colorant (A), the containing ratio of blue dyes (A1), viridine green (A2) and yellow colorants (A3) is preferably respectively in following scope.

Blue dyes (A1): more than 0.1 quality % and below 20 quality % (being more preferably more than 0.5 quality % and below 15 quality %, more preferably more than 1 quality % and below 10 quality %)

Viridine green (A2): more than 30 quality % and below 85 quality % (being more preferably more than 45 quality % and below 75 quality %, more preferably more than 50 quality % and below 70 quality %)

Yellow colorants (A3): more than 5 quality % and below 60 quality % (being more preferably more than 10 quality % and below 50 quality %, more preferably more than 15 quality % and below 45 quality %)

The content of blue dyes (A1) is preferably more than 0.2 mass parts relative to content 100 mass parts of viridine green (A2) and below 100 mass parts, be more preferably more than 0.4 mass parts and below 50 mass parts, more preferably more than 0.6 mass parts and below 20 mass parts.

The content of yellow colorants (A3) is preferably more than 10 mass parts relative to content 100 mass parts of viridine green (A2) and below 200 mass parts, be more preferably more than 20 mass parts and below 150 mass parts, more preferably more than 30 mass parts and below 120 mass parts.

If the containing ratio of blue dyes (A1) is in above-mentioned scope, then the further tendency improved of brightness existence due to the color filter obtained is therefore preferred.

In colorant (A), blue dyes (A1), the combination of viridine green (A2) and yellow colorants (A3) is preferably phthalocyanine dye (Aa)/C.I. pigment Green 7/coumarine dye, phthalocyanine dye (Aa)/C.I. naphthol green 58/ coumarine dye, phthalocyanine dye (Aa)/C.I. pigment Green 7/azo dyes, phthalocyanine dye (Aa)/C.I. naphthol green 58/ azo dyes, compound represented by formula (Ab1)/C.I. pigment Green 7/coumarine dye, compound represented by formula (Ab1)/C.I. pigment green 36/coumarine dye, compound represented by formula (Ab1)/C.I. naphthol green 58/ coumarine dye, compound represented by formula (Ab1)/C.I. pigment Green 7/azo dyes, compound represented by formula (Ab1)/C.I. pigment Green 7/C.I. pigment Yellow 12 9, compound represented by formula (Ab1)/C.I. pigment Green 7/C.I. pigment yellow 13 8, compound represented by formula (Ab1)/C.I. naphthol green 58/C.I. pigment Yellow 12 9, compound represented by formula (Ab1)/C.I. naphthol green 58/C.I. pigment yellow 13 8, compound represented by formula (Ab1)/C.I. naphthol green 58/ azo dyes, methine dyestuff (Ac)/C.I. pigment Green 7/coumarine dye, methine dyestuff (Ac)/C.I. pigment green 36/coumarine dye, methine dyestuff (Ac)/C.I. naphthol green 58/ coumarine dye, methine dyestuff (Ac)/C.I. pigment Green 7/azo dyes, methine dyestuff (Ac)/C.I. naphthol green 58/ azo dyes, methine dyestuff (Ac)/C.I. pigment Green 7/C.I. pigment Yellow 12 9, methine dyestuff (Ac)/C.I. pigment Green 7/C.I. pigment yellow 13 8, methine dyestuff (Ac)/C.I. naphthol green 58/C.I. pigment Yellow 12 9, methine dyestuff (Ac)/C.I. naphthol green 58/C.I. pigment yellow 13 8, the compound more preferably represented by formula (Ab1)/C.I. pigment Green 7/coumarine dye, compound represented by formula (Ab1)/C.I. naphthol green 58/ coumarine dye, methine dyestuff (Ac)/C.I. pigment Green 7/coumarine dye, methine dyestuff (Ac)/C.I. naphthol green 58/ coumarine dye.

The pigment such as viridine green (A2) can implement rosin process as required, use imported the pigment derivative of acidic groups or basic group etc. surface treatment, the grafting process to surface of pigments based on macromolecular compound etc., the micronize process based on sulfuric acid particles method etc. or the carrying out washing treatment based on the organic solvent for removing impurity, water etc., the ion exchange process based on ionic impurity etc. removing process etc.

Pigment preferable particle size is even.By carrying out dispersion treatment containing pigment dispersing agent, can obtain pigment dispersed in the solution after the dispersible pigment dispersion of state.

As above-mentioned pigment dispersing agent, the surfactants etc. such as such as kation system, negative ion system, nonionic system, both sexes, polyesters, polyamines class, acrylic acid series can be enumerated.These pigment dispersing agents may be used singly or in combination of two or more.As pigment dispersing agent, trade name KP (SHIN-ETSU HANTOTAI's chemical industry (strain) system), FLOWLEN (common prosperity society chemistry (strain) system), SOLSPERSE (Jie Likang (strain) system), EFKA (BASF AG's system), AJISPER (aginomoto fine chemistry (strain) system), Disperbyk (Bi Ke chemistry Inc.) etc. can be enumerated.

When using pigment dispersing agent, its use amount is preferably more than 1 quality % and below 100 quality % relative to the total amount of pigment, is more preferably more than 5 quality % and below 50 quality %.If the use amount of pigment dispersing agent is in above-mentioned scope, then there is the tendency that can obtain the dispersible pigment dispersion of uniform disperse state.

The content of colorant (A) is preferably 5 ~ 65 quality % relative to the total amount of solid constituent, is more preferably 8 ~ 60 quality %, more preferably 10 ~ 55 quality %.If the content of colorant (A) is in above-mentioned scope, then color density when making color filter is abundant, and can contain resin, the polymerizable compound of necessary amount in the composition, therefore can form the sufficient pattern of physical strength.

Herein, in this instructions, " total amount of solid constituent " refers to from the total amount of colored curable resin composition except the amount after the content of desolventizing.The total amount of solid constituent and can being measured by known analytical approach such as such as liquid phase chromatography or vapor-phase chromatography etc. relative to the content of its each composition.

< resin (B) >

Resin (B) is preferably alkali soluble resin.As resin (B), following resin [K1] ~ [K6] etc. can be enumerated.

Resin [K1]: be selected from least a kind (a) (hereinafter sometimes referred to " (a) ") in unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides and there is the multipolymer of the cyclic ether structure of carbon number 2 ~ 4 and the monomer (b) (hereinafter sometimes referred to " (b) ") of ethylenic unsaturated bond;

Resin [K2]: (a), (b) and can from the multipolymer of the monomer (c) of (a) copolymerization (but different with (a) and (b)) (hereinafter sometimes referred to " (c) ");

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

Resin [K4]: make the copolymer reaction of (b) and (a) and (c) and the resin that obtains;

Resin [K5]: make the copolymer reaction of (a) and (b) and (c) and the resin that obtains;

Resin [K6]: make (a) and (b) copolymer reaction with (c), then the resin reacting with carboxylic acid anhydrides and obtain.

As (a), specifically can enumerate: the unsaturated monocarboxylic acid class such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, p-vinyl benzoic 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, the unsaturated dicarboxylic acids such as 3,6-tetrahydrophthalic acid, dimethyl tetrahydro phthalic acid, Isosorbide-5-Nitrae-cyclohexene dioctyl phthalate;

Methyl-5-norborene-2, the carboxylic dicyclo unsaturated compound such as 3-dioctyl phthalate, 5-carboxyl dicyclo [2.2.1] hept-2-ene", 5,6-dicarboxyl dicyclo [2.2.1] hept-2-ene"s, 5-carboxyl-5-methyl bicycle [2.2.1] hept-2-ene", 5-carboxyl-5-ethyl dicyclo [2.2.1] hept-2-ene", 5-carboxyl-6-methyl bicycle [2.2.1] hept-2-ene", 5-carboxyl-6-ethyl dicyclo [2.2.1] hept-2-ene";

Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic acid acid anhydride, 4-vinylphthalic acid acid anhydride, 3,4,5,6-tetrabydrophthalic anhydride, 1,2, the unsaturated dicarboxylic acid acid anhydrides such as 3,6-tetrabydrophthalic anhydride, dimethyl tetrahydro phthalic anhydride, 5,6-dicarboxyl dicyclo [2.2.1] hept-2-ene" acid anhydrides;

Unsaturated list [(methyl) acryloxyalkyl] ester of the polybasic carboxylic acid of mono succinate [2-(methyl) acryloyloxyethyl ester], phthalic acid list [2-(methyl) acryloyloxyethyl ester] etc. more than 2 yuan;

The unsaturated acrylate etc. of hydroxyl and carboxyl is contained in same a part as α-(hydroxymethyl) acrylic acid.

In them, from viewpoint, the deliquescent viewpoint of gained resin in aqueous alkali of copolyreaction, preferred acrylic acid, methacrylic acid, maleic anhydride etc.

B () refers to the monomer of cyclic ether structure (such as, being selected from least a kind in oxirane ring, oxetanes ring and tetrahydrofuran ring) and the ethylenic unsaturated bond such as with carbon number 2 ~ 4.B () preferably has the cyclic ether structure of carbon number 2 ~ 4 and the monomer of (methyl) acryloxy.

It should be noted that, in this instructions, " (methyl) acrylic acid " represents at least a kind that is selected from acrylic acid and methacrylic acid.The statement such as " (methyl) acryloyl group " and " (methyl) acrylate " also has same implication.

As (b), can enumerate: the monomer (b1) (hereinafter sometimes referred to " (b1) ") with Oxyranyle and ethylenic unsaturated bond, the monomer (b2) (hereinafter sometimes referred to " (b2) ") with oxetanyl and ethylenic unsaturated bond, there is the monomer (b3) (hereinafter sometimes referred to " (b3) ") etc. of tetrahydrofuran base and ethylenic unsaturated bond.

As (b1), can enumerate the unsaturated aliphatic hydrocarbon with straight-chain or branched be at least partially epoxidized after structure monomer (b1-1) (hereinafter sometimes referred to " (b1-1) "), have ester ring type unsaturated hydrocarbon be at least partially epoxidized after the monomer (b1-2) (hereinafter sometimes referred to " (b1-2) ") of structure.

As (b1-1), (methyl) glycidyl acrylate can be enumerated, (methyl) propenoic acid beta-methylglycidyl esters, (methyl) propenoic acid beta-ethyl glycidyl ester, glycidyl vinyl ether, adjacent vinylbenzyl glycidyl base ether, between vinylbenzyl glycidyl base ether, to vinylbenzyl glycidyl base ether, Alpha-Methyl adjacent vinylbenzyl glycidyl base ether, vinylbenzyl glycidyl base ether between Alpha-Methyl, Alpha-Methyl is to vinylbenzyl glycidyl base ether, two (glycidoxypropyl methyl) styrene of 2,3-, two (glycidoxypropyl methyl) styrene of 2,4-, two (glycidoxypropyl methyl) styrene of 2,5-, two (glycidoxypropyl methyl) styrene of 2,6-, 2,3,4-tri-(glycidoxypropyl methyl) styrene, 2,3,5-tri-(glycidoxypropyl methyl) styrene, 2,3,6-tri-(glycidoxypropyl methyl) styrene, 3,4,5-tri-(glycidoxypropyl methyl) styrene, 2,4,6-tri-(glycidoxypropyl methyl) styrene etc.

As (b1-2), vinylcyclohexene monoxide, 1,2-epoxy-4-vinyl cyclohexane (such as, celloxide (registered trademark) 2000 can be enumerated; (strain) Daicel system), (methyl) acrylic acid 3,4-epoxycyclohexanecarboxylate (such as, cyclomer (registered trademark) A400; (strain) Daicel system), (methyl) acrylic acid 3,4-epoxycyclohexanecarboxylate (such as, cyclomer (registered trademark) M100; (strain) Daicel system), the compound represented by formula (I) and the compound etc. represented by formula (II).

[in formula (I) and formula (II), R ^aand R ^brepresent the alkyl of hydrogen atom or carbon number 1 ~ 4, the hydrogen atom comprised in this alkyl can be optionally substituted by a hydroxyl group.

X ^aand X ^brepresent singly-bound ,-R ^c-, *-R ^c-O-, *-R ^c-S-or *-R ^c-NH-.

R ^crepresent the alkylidene of carbon number 1 ~ 6.

* the bonding end with O is represented.]

As the alkyl of carbon number 1 ~ 4, methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group etc. can be enumerated.

Alkyl after being optionally substituted by a hydroxyl group as hydrogen atom, can enumerate hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxyl-1-Methylethyl, 2-hydroxyl-1-Methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl etc.

As R ^aand R ^b, preferably can enumerate hydrogen atom, methyl, hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, can more preferably enumerate hydrogen atom, methyl.

As alkylidene, methylene, ethylidene, propane-1,2-bis-base, propane-1,3-bis-base, butane-Isosorbide-5-Nitrae-two base, pentane-1,5-bis-base, hexane-1,6-bis-base etc. can be enumerated.

As X ^aand X ^b, preferably can enumerate singly-bound, methylene, ethylidene, *-CH ₂-O-and *-CH ₂cH ₂-O-, more preferably can enumerate singly-bound, *-CH ₂cH ₂-O-(* represents the bonding end with O).

As the compound represented by formula (I), can compound etc. in enumerative (I-1) ~ formula (I-15) represented by any one.Wherein, compound represented by preferred formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9) or formula (I-11) ~ formula (I-15), more preferably formula (I-1), formula (I-7), formula (I-9) or the compound represented by formula (I-15).

As the compound represented by formula (II), can compound etc. in enumerative (II-1) ~ formula (II-15) represented by any one.Wherein, compound represented by preferred formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9) or formula (II-11) ~ formula (II-15), more preferably formula (II-1), formula (II-7), formula (II-9) or the compound represented by formula (II-15).

Compound represented by formula (I) and the compound represented by formula (II) can individually use, and also two or more kinds may be used.By the compound represented by formula (I) and the compound represented by formula (II) and the used time, their ratio (compound represented by formula (I): the compound represented by formula (II)) that contains is preferably 5:95 ~ 95:5 with molar basis, is more preferably 20:80 ~ 80:20.

As (b2), more preferably there is the monomer of oxetanylmethoxy and (methyl) acryloxy.As (b2), 3-methyl-3-methacryloxymethyl oxetanes, 3-methyl-3-acryloyloxymethyl oxetanes, 3-ethyl-3-methacryloxymethyl oxetanes, 3-ethyl-3-acryloyloxymethyl oxetanes, 3-methyl-3-methylacryoyloxyethyl oxetanes, 3-methyl-3-acrylyl oxy-ethyl oxetanes, 3-ethyl-3-methylacryoyloxyethyl oxetanes, 3-ethyl-3-acrylyl oxy-ethyl oxetanes etc. can be enumerated.

As (b3), more preferably there is the monomer of tetrahydrofuran base and (methyl) acryloxy.As (b3), specifically, tetrahydrofurfuryl acrylate (such as, biscoat V#150, Osaka Organic Chemical Industry (strain) system), tetrahydrofurfuryl methacrylate etc. can be enumerated.

As (b), can improve further the color filter obtained thermotolerance, chemical-resistant etc. reliability in, be preferably (b1).Further, in the excellent storage stability of colored curable resin composition, more preferably (b1-2).

As (c), can enumerate: (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-butyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) 2-EHA, (methyl) dodecylacrylate, (methyl) lauryl acrylate, (methyl) stearyl acrylate ester, (methyl) acrylic acid ring pentyl ester, (methyl) cyclohexyl acrylate, (methyl) acrylic acid 2-methyl cyclohexyl, (methyl) acrylic acid three ring [5.2.1.0 ^2,6] decane-8-base ester (in the art, as popular name, is called " (methyl) acrylic acid Bicvclopentyl ester ".In addition, be sometimes referred to as " (methyl) acrylic acid three ring decyl ester "), (methyl) acrylic acid three ring [5.2.1.0 ^2,6] decene-8-base ester (in the art, as popular name, be called " (methyl) acrylic acid double cyclopentenyl ester "), (methyl) acrylate such as (methyl) acrylic acid dicyclo amoxy ethyl ester, (methyl) isobornyl acrylate, (methyl) acrylic acid adamantane esters, (methyl) allyl acrylate, (methyl) acrylic acid propargyl ester, (methyl) phenyl acrylate, (methyl) acrylic acid naphthalene ester, (methyl) benzyl acrylate;

(methyl) acrylate of the hydroxyls such as (methyl) acrylic acid 2-hydroxyethyl ester, (methyl) acrylic acid 2-hydroxy-propyl ester;

The dicarboxylic diesters such as diethyl 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 dicyclo [2.2.1] hept-2-ene", 5-ethoxy dicyclo [2.2.1] hept-2-ene", 5,6-dihydroxy dicyclo [2.2.1] hept-2-ene", 5,6-bis-(hydroxymethyl) dicyclo [2.2.1] hept-2-ene", 5,6-bis-(2 '-hydroxyethyl) dicyclo [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-ene", 5-hydroxy-5-methyl base dicyclo [2.2.1] hept-2-ene", 5-hydroxyl-5-ethyl dicyclo [2.2.1] hept-2-ene", 5-hydroxymethyl-5-methyl bicycle [2.2.1] hept-2-ene", 5-tert-butoxycarbonyl dicyclo [2.2.1] hept-2-ene", 5-cyclohexyl oxygen base carbonyl dicyclo [2.2.1] hept-2-ene", 5-phenyloxycarbonyl dicyclo [2.2.1] hept-2-ene", 5,6-bis-(tert-butoxycarbonyl) dicyclo [2.2.1] hept-2-ene", the dicyclo unsaturated compounds such as 5,6-bis-(cyclohexyl oxygen base carbonyl) dicyclo [2.2.1] hept-2-ene",

The dicarbonyl imides derivants such as N-phenylmaleimide, N-N-cyclohexylmaleimide, N-benzyl maleimide, N-succinimido-3-maleimidobenzoyl ester, N-succinimido-4-malimidobutanoate, N-succinimido-6-maleimidohexanoic acid ester, N-succinimido-3-maleimidopropionic acid ester, N-(9-acridinyl) maleimide;

Styrene, α-methyl styrene, a methyl styrene, p-methylstyrene, vinyltoluene, to methoxy styrene, vinyl cyanide, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, Methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene etc.

In them, from the view point of copolyreaction and thermotolerance, optimization styrene, vinyltoluene, N-phenylmaleimide, N-N-cyclohexylmaleimide, N-benzyl maleimide, dicyclo [2.2.1] hept-2-ene" etc.

In resin [K1], for the ratio from respective structural unit, in the entire infrastructure unit forming resin [K1], preferably:

Structural unit from (a): 2 ~ 60 % by mole

Structural unit from (b): 40 ~ 98 % by mole,

More preferably:

From the structural unit of (a); 10 ~ 50 % by mole

From the structural unit of (b); 50 ~ 90 % by mole.

If the ratio of the structural unit of resin [K1] is in above-mentioned scope, then there is the storage stability of colored curable resin composition, developability when forming colored pattern and the tendency of the excellent solvent resistance of color filter that obtains.

Can by reference to the method such as recorded in document " experimental method of Polymer Synthesizing " (the grand row in large Tianjin work sale room (strain) chemistry is with people's the 1st edition the 1st printing distribution on March 1st, 1972) and the citing document recorded in the publication to manufacture resin [K1].

Specifically, can enumerate and the ormal weight of (a) and (b), polymerization initiator and solvent etc. are added in reaction vessel, such as, replace oxygen with nitrogen, be arranged to deoxidizing atmosphere thus, the method heating while stirring and be incubated.It should be noted that, polymerization initiator used herein and solvent etc. are not particularly limited, and can use normally used polymerization initiator and solvent in this field.Such as, as polymerization initiator, azo-compound (2 can be enumerated, 2 '-azoisobutyronitrile, 2,2 '-azo two (2,4-methyl pentane nitrile) etc.), organic peroxide (benzoyl peroxide etc.), as solvent, as long as dissolve the solvent of each monomer, the solvent (E) as colored curable resin composition of the present invention can enumerate solvent described later etc.

It should be noted that, the multipolymer obtained can directly use reacted solution, also can use the solution after concentrated or dilution, can also use the material taken out with the form of solid (powder) by the method such as precipitating again.Particularly by using the solvent comprised in colored curable resin composition of the present invention as solvent when this polymerization, reacted solution directly can be used in the preparation of colored curable resin composition of the present invention, therefore can simplify the manufacturing process of colored curable resin composition of the present invention.

In resin [K2], for the ratio from respective structural unit, in the entire infrastructure unit forming resin [K2], preferably:

Structural unit from (a): 2 ~ 45 % by mole

Structural unit from (b): 2 ~ 95 % by mole

Structural unit from (c): 1 ~ 65 % by mole,

More preferably:

Structural unit from (a): 5 ~ 40 % by mole

Structural unit from (b): 5 ~ 80 % by mole

Structural unit from (c): 5 ~ 60 % by mole.

If the ratio of the structural unit of resin [K2] is in above-mentioned scope, then there is the storage stability of colored curable resin composition, the tendency of the solvent resistance of developability when forming colored pattern and the color filter that obtains, thermotolerance and mechanical strength.

Such as, manufacture resin [K2] in the same manner as the method can recorded with the manufacture method as resin [K1].

In resin [K3], for the ratio from respective structural unit, in the entire infrastructure unit forming resin [K3], preferably:

Structural unit from (a): 2 ~ 60 % by mole

Structural unit from (c): 40 ~ 98 % by mole,

More preferably:

Structural unit from (a): 10 ~ 50 % by mole

Structural unit from (c): 50 ~ 90 % by mole.

Such as, manufacture resin [K3] in the same manner as the method can recorded with the manufacture method as resin [K1].

Can by obtaining the multipolymer of (a) and (c), the cyclic ether of the carbon number 2 ~ 4 that (b) is had adds and is formed in carboxylic acid and/or carboxylic acid anhydrides that (a) have to manufacture resin [K4].

First the multipolymer of (a) and (c) is manufactured in the same manner as the method recorded with the manufacture method as resin [K1].Now, for the ratio from respective structural unit, be preferably the ratio identical with the ratio enumerated in resin [K3].

Then, the carboxylic acid from (a) in the cyclic ether of the carbon number 2 ~ 4 (b) being had and above-mentioned multipolymer and/or a part for carboxylic acid anhydrides are reacted.

And then the manufacture of the multipolymer of (a) and (c), atmosphere in flask is replaced into air by nitrogen, the catalysts (such as three (dimethylaminomethyl) phenol etc.) and polymerization inhibitor (such as quinhydrones etc.) etc. of (b), carboxylic acid or carboxylic acid anhydrides and cyclic ether are dropped in flask, 60 ~ 130 DEG C of reactions 1 ~ 10 hour, resin [K4] can be manufactured thus.

B the use amount of () is preferably 5 ~ 80 moles relative to (a) 100 moles, be more preferably 10 ~ 75 moles.By being set to this scope, there is the storage stability of colored curable resin composition, the balance of the solvent resistance of developability when forming pattern and the pattern that obtains, thermotolerance, physical strength and sensitivity becomes good tendency.Because the reactivity of cyclic ether is high, be difficult to (b) of remained unreacted, therefore as (b) that use in resin [K4] preferably (b1), further preferably (b1-1).

The use amount of above-mentioned catalysts is preferably 0.001 ~ 5 mass parts relative to total amount 100 mass parts of (a), (b) and (c).The use amount of above-mentioned polymerization inhibitor is preferably 0.001 ~ 5 mass parts relative to total amount 100 mass parts of (a), (b) and (c).

Can consider manufacturing equipment, polymerization caused by thermal value etc. suitably regulate the reaction conditionss such as feeding method, temperature of reaction and time.It should be noted that, in the same manner as polymerizing condition, can consider manufacturing equipment, polymerization caused by thermal value etc. suitably regulate feeding method, temperature of reaction.

For resin [K5], as the first step, obtain the multipolymer of (b) and (c) in the same manner as the manufacture method of above-mentioned resin [K1].As described above, the multipolymer obtained can directly use reacted solution, also can use the solution after concentrated or dilution, can also use by the material after the method such as precipitating again and taking out with the form of solid (powder).

From the ratio of the structural unit of (b) and (c) relative to the total molal quantity of entire infrastructure unit forming above-mentioned multipolymer, respectively preferably:

Structural unit from (b): 5 ~ 95 % by mole

Structural unit from (c): 5 ~ 95 % by mole,

More preferably:

Structural unit from (b): 10 ~ 90 % by mole

Structural unit from (c): 10 ~ 90 % by mole.

Further, under the condition same with the manufacture method of resin [K4], the cyclic ether from (b) that the multipolymer of the carboxylic acid had by making (a) or carboxylic acid anhydrides and (b) and (c) has reacts, and can obtain resin [K5].

5 ~ 80 moles are preferably relative to (b) 100 moles with the use amount of (a) of above-mentioned copolymer reaction.Because the reactivity of cyclic ether is high, be difficult to (b) of remained unreacted, therefore as (b) that use in resin [K5] preferably (b1), further preferably (b1-1).

Resin [K6] is the resin making carboxylic acid anhydrides and resin [K5] react further.Make carboxylic acid anhydrides and the reaction by cyclic ether and carboxylic acid or carboxylic acid anhydrides and the hydroxyl reaction that produces.

As carboxylic acid anhydrides, maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic acid acid anhydride, 4-vinylphthalic acid acid anhydride, 3 can be enumerated, 4,5,6-tetrabydrophthalic anhydride, 1,2,3,6-tetrabydrophthalic anhydride, dimethyl tetrahydro phthalic anhydride, 5,6-dicarboxyl dicyclo [2.2.1] hept-2-ene" acid anhydrides etc.The use amount of carboxylic acid anhydrides is preferably 0.5 ~ 1 mole relative to the use amount 1 mole of (a).

As resin (B), specifically, (methyl) acrylic acid 3,4-epoxycyclohexanecarboxylate/(methyl) acrylic copolymer, 3,4-epoxy three ring [5.2.1.0 can be enumerated ^2.6] resin [K1] such as decyl acrylate/(methyl) acrylic copolymer, (methyl) glycidyl acrylate/(methyl) benzyl acrylate/(methyl) acrylic copolymer, (methyl) glycidyl acrylate/styrene/(methyl) acrylic copolymer, 3,4-epoxy three ring [5.2.1.0 ^2.6] resin [K2] such as decyl acrylate/(methyl) acrylic acid/N-N-cyclohexylmaleimide multipolymer, 3-methyl-3-(methyl) acryloyloxymethyl oxetanes/(methyl) acrylic acid/styrol copolymer, the resins [K3] such as (methyl) benzyl acrylate/(methyl) acrylic copolymer, styrene/(methyl) acrylic copolymer, make (methyl) glycidyl acrylate and (methyl) benzyl acrylate/(methyl) acrylic copolymer addition and the resin that obtains, make (methyl) glycidyl acrylate and ester/styrene in the last of the ten Heavenly stems/(methyl) the acrylic copolymer addition of (methyl) acrylic acid three ring and the resin that obtains, make (methyl) glycidyl acrylate and ester in the last of the ten Heavenly stems/(methyl) benzyl acrylate/(methyl) the acrylic copolymer addition of (methyl) acrylic acid three ring and the resins [K4] such as the resin that obtains, make the resin of the copolymer reaction of (methyl) acrylic acid and (methyl) acrylic acid three ring ester in the last of the ten Heavenly stems/(methyl) glycidyl acrylate, make the resins [K5] such as the resin of the copolymer reaction of (methyl) acrylic acid and (methyl) acrylic acid three ring ester/styrene in the last of the ten Heavenly stems/(methyl) glycidyl acrylate, the resins [K6] etc. such as the resin that (methyl) acrylic acid is reacted with tetrabydrophthalic anhydride further with the resin of the copolymer reaction of (methyl) acrylic acid three ring ester in the last of the ten Heavenly stems/(methyl) glycidyl acrylate.

Wherein, as resin (B), preferred resin [K1], resin [K2] and resin [K3], more preferably resin [K1] and resin [K2].

The weight-average molecular weight of the polystyrene conversion of resin (B) is preferably 3,000 ~ 100,000, is more preferably 5,000 ~ 50,000, and more preferably 5,000 ~ 30,000.If molecular weight is in described scope, then the hardness that there is color filter improves, and residual film ratio is high, unexposed portion to the favorable solubility of developer solution, the tendency that the resolution of colored pattern improves.

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

The acid number of resin (B) is preferably 50 ~ 170mg-KOH/g, is more preferably 60 ~ 150mg-KOH/g, more preferably 70 ~ 135mg-KOH/g.Herein acid number be as in order in and the amount (mg) of potassium hydroxide needed for resin (B) 1g and the value that measures, such as can carry out titration to obtain by use potassium hydroxide aqueous solution.

The content of resin (B) is preferably 7 ~ 65 quality % relative to the total amount of solid constituent, is more preferably 13 ~ 60 quality %, more preferably 17 ~ 55 quality %.If the content of resin (B) is in described scope, then exists and can form colored pattern, in addition the resolution of colored pattern and the tendency of residual film ratio raising.

< polymerizable compound (C) >

The compound that polymerizable compound (C) is living radical by being produced by polymerization initiator (D) and/or acid and can be polymerized, the compound etc. of the ethylenic unsaturated bond such as with polymerism can be enumerated, be preferably (methyl) acrylate compounds.

Wherein, polymerizable compound (C) preferably has the polymerizable compound of more than 3 ethylenic unsaturated bonds.As such polymerizable compound, such as trimethylolpropane tris (methyl) acrylate can be enumerated, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, tripentaerythritol eight (methyl) acrylate, tripentaerythritol seven (methyl) acrylate, tetrapentaerythritol ten (methyl) acrylate, tetrapentaerythritol nine (methyl) acrylate, three (2-(methyl) acrylyl oxy-ethyl) isocyanuric acid ester, glycol-modified pentaerythrite four (methyl) acrylate, glycol-modified dipentaerythritol six (methyl) acrylate, propylene glycol modified pentaerythrite four (methyl) acrylate, propylene glycol modified dipentaerythritol six (methyl) acrylate, caprolactone modification pentaerythrite four (methyl) acrylate, caprolactone modification dipentaerythritol six (methyl) acrylate etc.

Wherein, preferred dipentaerythritol five (methyl) acrylate and dipentaerythritol six (methyl) acrylate.

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

The content of polymerizable compound (C) is preferably 7 ~ 65 quality % relative to the total amount of solid constituent, is more preferably 13 ~ 60 quality %, more preferably 17 ~ 55 quality %.If the content of polymerizable compound (C) is in described scope, then also exist colored pattern formed time residual film ratio and color filter chemical-resistant improve tendency.

< polymerization initiator (D) >

Polymerization initiator (D), as long as just can be not particularly limited by the compound of the dissociation produces active free radical, acid etc. of light, heat also initiated polymerization, can use known polymerization initiator.As the polymerization initiator producing living radical, such as O-acyl group oxime compound, alkyl phenones compound, triaizine compounds, acylphosphine oxide compound and united imidazole can be enumerated.

Above-mentioned O-acyl group oxime compound is for having the compound of the partial structurtes represented by formula (d1).Below, * represents bonding end.

As O-acyl group oxime compound, such as N-benzoyloxy-1-(4-Phenylsulfanylphenyl) butane-1-ketone-2-imines can be enumerated, N-benzoyloxy-1-(4-Phenylsulfanylphenyl) octane-1-ketone-2-imines, N-benzoyloxy-1-(4-Phenylsulfanylphenyl)-3-cyclopentyl propane-1-ketone-2-imines, N-acetoxyl group-1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base] ethane-1-imines, N-acetoxyl group-1-[9-ethyl-6-{2-methyl-4-(3, 3-dimethyl-2, 4-dioxolyl methyl oxygen base) benzoyl }-9H-carbazole-3-base] ethane-1-imines, N-acetoxyl group-1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base]-3-cyclopentyl propane-1-imines, N-benzoyloxy-1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base]-3-cyclopentyl propane-1-ketone-2-imines etc.The commercially available product such as irgacure (registered trademark) OXE01, OXE02 (more than, BASF AG's system), N-1919 (ADEKA Inc.) can be used.Wherein, O-acyl group oxime compound is preferably selected from least a kind in N-benzoyloxy-1-(4-Phenylsulfanylphenyl) butane-1-ketone-2-imines, N-benzoyloxy-1-(4-Phenylsulfanylphenyl) octane-1-ketone-2-imines and N-benzoyloxy-1-(4-Phenylsulfanylphenyl)-3-cyclopentyl propane-1-ketone-2-imines, is more preferably N-benzoyloxy-1-(4-Phenylsulfanylphenyl) octane-1-ketone-2-imines.If these O-acyl group oxime compounds, be then in the tendency of the color filter that can obtain high brightness.

Abovementioned alkyl benzophenone compound is the compound with the partial structurtes represented by formula (d2) or the partial structurtes represented by formula (d3).In these partial structurtes, phenyl ring can have substituting group.

As the compound of the partial structurtes had represented by formula (d2), 2-methyl-2-morpholino-1-(4-methyl mercapto phenyl) propane-1-ketone, 2-dimethylamino-1-(4-morphlinophenyl)-2-benzyl butane-1-ketone, 2-(dimethylamino)-2-[(4-aminomethyl phenyl) methyl]-1-[4-(4-morpholinyl) phenyl] butane-1-ketone, irgacure (registered trademark) 369,907,379 (more than, BASF AG's system) can be enumerated.

As the compound of the partial structurtes had represented by formula (d3), such as 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 2-hydroxy-2-methyl-1-(oligomer, α, α-diethoxy acetophenone, the benzil dimethyl ketal etc. of 4-(2-hydroxyl-oxethyl) phenyl propane-1-ketone, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-(4-isopropyl phenyl) propane-1-ketone can be enumerated.

As above-mentioned triaizine compounds, such as 2 can be enumerated, two (the trichloromethyl)-6-(4-methoxyphenyl)-1 of 4-, 3, 5-triazine, 2, two (the trichloromethyl)-6-(4-methoxyl naphthyl)-1 of 4-, 3, 5-triazine, 2, two (the trichloromethyl)-6-piperonyl-1 of 4-, 3, 5-triazine, 2, two (the trichloromethyl)-6-(4-methoxyl-styrene)-1 of 4-, 3, 5-triazine, 2, two (the trichloromethyl)-6-(2-(5-methylfuran-2-base) vinyl)-1 of 4-, 3, 5-triazine, 2, two (the trichloromethyl)-6-(2-(furans-2-base) vinyl)-1 of 4-, 3, 5-triazine, 2, two (the trichloromethyl)-6-(2-(4-diethylamino-2-aminomethyl phenyl) vinyl)-1 of 4-, 3, 5-triazine, 2, two (trichloromethyl)-6-(2-(3 of 4-, 4-Dimethoxyphenyl) vinyl)-1, 3, 5-triazine etc.

As acylphosphine oxide compound, 2,4,6-trimethylbenzoyldiphenyl oxide etc. can be enumerated.The commercially available products such as irgacure (registered trademark) 819 (BASF AG's system) can be used.

As united imidazole, can 2 be enumerated, 2 '-bis-(2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-bis-(2,3-dichlorophenyl)-4,4 ' 5,5 '-tetraphenyl bisglyoxaline is (for example, referring to Japanese Unexamined Patent Publication 6-75372 publication, Japanese Unexamined Patent Publication 6-75373 publication etc.), 2,2 '-bis-(2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-bis-(2-chlorphenyl)-4,4 ', 5,5 '-four (alkoxyl phenyl) bisglyoxaline, 2,2 '-bis-(2-chlorphenyl)-4,4 ', 5,5 '-four (dialkoxy phenyl) bisglyoxaline, 2,2 '-bis-(2-chlorphenyl)-4,4 ', 5,5 '-four (tri-alkoxy phenyl) bisglyoxaline is (for example, referring to Japanese Patent Publication 48-38403 publication, Japanese Laid-Open Patent Publication 62-174204 publication etc.), 4,4 ', 5, the imidazolium compounds that the phenyl of 5 '-position be instead of by carbonylic alkoxy is (for example, referring to Japanese Unexamined Patent Publication 7-10913 publication etc.) etc.

Be further used as polymerization initiator (D), the benzoin compounds such as benzoin, benzoin methylether, benzoin ethyl ether, benzoin iso-propylether, benzoin isobutyl ether can be enumerated; Benzophenone, o-benzoyl yl benzoic acid methyl esters, 4-phenyl benzophenone, 4-benzoyl-4 '-methyldiphenyl sulfide, 3,3 ', 4,4 '-four (t-butyl peroxy carbonyl) benzophenone, 2, the benzophenone cpds such as 4,6-tri-methyl benzophenone; The naphtoquinone compounds such as 9,10-phenanthrenequione, 2-EAQ, camphorquinone; 10-butyl-2-chloro-acridine, dibenzoyl, phenylglyoxalates methyl esters, two cyclopentadiene titanium compounds etc.Preferably they are caused auxiliary agent (D1) (particularly amine) combinationally use with described later polymerization.

As acid agent, can enumerate: salt or nitrobenzyl tosylat, the benzoin tosylate etc. such as 4-hydroxy phenyl dimethyl sulfonium tosilate, 4-hydroxy phenyl dimethyl sulfonium hexafluoro antimonate, 4-acetoxyl group phenyl dimethyl sulfonium tosilate, 4-acetoxyl group phenyl methyl benzyl sulfonium hexafluoro antimonate, triphenylsulfonium tosilate, triphenylsulfonium hexafluoro antimonate, diphenyl iodine tosilate, diphenyl iodine hexafluoro antimonate.

Polymerization initiator (D) is preferably the polymerization initiator containing at least one be selected from O-acyl group oxime compound, alkyl phenones compound, triaizine compounds, acylphosphine oxide compound and united imidazole, is more preferably the polymerization initiator containing O-acyl group oxime compound.

The content of polymerization initiator (D) is preferably 0.1 ~ 30 mass parts relative to total amount 100 mass parts of resin (B) and polymerizable compound (C), is more preferably 1 ~ 20 mass parts.If the content of polymerization initiator (D) is in above-mentioned scope, then the tendency that the time shutter shortens owing to there is high-sensitivity, therefore the throughput rate of color filter improves.

< polymerization causes auxiliary agent (D1) >

Polymerization initiation auxiliary agent (D1) is compound or sensitizer for promoting to have been caused by polymerization initiator the polymerization of the polymerizable compound of polymerization.When causing auxiliary agent (D1) containing polymerization, usual and polymerization initiator (D) combinationally uses.

Cause auxiliary agent as polymerization, amines, alkoxy anthracene compound, thioxanthone compound and carboxylic acid compound etc. can be enumerated.

As above-mentioned amines, triethanolamine can be enumerated, methyldiethanolamine, triisopropanolamine, 4-dimethylaminobenzoic acid methyl esters, EDMAB, 4-dimethylaminobenzoic acid isopentyl ester, benzoic acid 2-dimethylamino ethyl ester, 4-dimethylaminobenzoic acid 2-Octyl Nitrite, N, N-dimethyl-p-toluidine, 4, 4 '-bis-(dimethylamino) benzophenone (common name Michler's keton), 4, 4 '-bis-(diethylamino) benzophenone, 4, 4 '-bis-(ethylmethylamino) benzophenone etc., wherein preferably 4, 4 '-bis-(diethylamino) benzophenone.The commercially available products such as EAB-F (hodogaya chemical industry (strain) system) can be used.

As above-mentioned alkoxy anthracene compound, 9,10-dimethoxy anthracene, EDMO, 9,10-diethoxy anthracenes, 2-ethyl-9,10-diethoxy anthracene, 9,10-dibutoxy anthracenes, 2-ethyl-9,10-dibutoxy anthracene etc. can be enumerated.

As above-mentioned thioxanthone compound, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthones, 2,4-bis-chlorothiaxanthenones, 1-chloro-4-propoxyl group thioxanthone etc. can be enumerated.

As above-mentioned carboxylic acid compound, thiophenyl acetic acid, methylphenyl-sulfanyl acetic acid, ethylthiophenyl acetic acid, ethyl methyl benzene ethyl thioglycollic acid, dimethyl benzene ethyl thioglycollic acid, Methoxv-phenylsulfanvl acetic acid, dimethoxyphenylthio acetic acid, chlorophenylsulfanyl acetic acid, dichloro-benzenes ethyl thioglycollic acid, N-phenylglycine, phenoxyacetic acid, naphthalene ethyl thioglycollic acid, N-naphthyl glycocoll, naphthoxy acetic acid etc. can be enumerated.

When using these polymerizations to cause auxiliary agent (D1), its content is preferably 0.1 ~ 30 mass parts relative to total amount 100 mass parts of resin (B) and polymerizable compound (C), is more preferably 1 ~ 20 mass parts.If polymerization causes the amount of auxiliary agent (D1) within the scope of this, being then in can with the tendency that sensitivity high further forms colored pattern, the throughput rate of color filter improves.

< mercaptan compound (T) >

Mercaptan compound (T) is the compound in molecule with sulfydryl (-SH).

As the compound in molecule with 1 sulfydryl, such as 2-Qiu Ji oxazole can be enumerated, 2-thyroidan, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptonicotinic acid, 2-mercaptopyridine, 2-mercaptopyridine-3-alcohol, pyrithione, 4-Amide-6-hydroxy-2--mercaptopyrimidine, 4-Amide-6-hydroxy-2--mercaptopyrimidine, 4-amino-2-mercapto phenyl formic pyrimidine, 6-amino-5-nitroso--2-deracil, 4,5-diamido-6-hydroxyl-2-mercaptopyrimidine, 4,6-diamido-2-mercaptopyrimidine, 2,4-diamido-6-mercaptopyrimidine, 4,6-dihydroxy-2-mercaptopyrimidine, 4,6-dimethyl-2-mercaptopyrimidine, 4-hydroxyl-2-sulfydryl-6-methylpyrimidine, 4-hydroxyl-2-sulfydryl-6-propyl group pyrimidine, 2-sulfydryl-4-methylpyrimidine, 2-mercaptopyrimidine, 2-deracil, 3,4,5,6-tetrahydropyrimidine-2-mercaptan, 4,5-diphenyl-imidazole-2-mercaptan, 2-mercaptoimidazole, 2-sulfydryl-1-methylimidazole, 4-amino-3-diazanyl-5-sulfydryl-1,2,4-triazole, 3-amino-5-sulfydryl-1,2,4-triazole, 2-methyl-4H-1,2,4-triazole-3-mercaptan, 4-methyl-4H-1,2,4-triazole-3-mercaptan, 3-sulfydryl-1H-1,2,4-triazole-3-mercaptan, 2-amino-5-sulfydryl-1,3,4-thiadiazoles, 5-amido-1,3,4-thiadiazoles-2-mercaptan, 2,5-dimercapto-1,3,4-thiadiazole, (furans-2-base) methyl mercaptan, 2-sulfydryl-5-thiazolidone, 2-sulfydryl thiazoline, 2-sulfydryl-4 (3H)-quinazolinone, 1-phenyl-1H-TETRAZOLE-5-mercaptan, 2-quinoline thiol, 2-sulfydryl-5-tolimidazole, 2-sulfydryl-5-nitrobenzimidazole, 6-amino-2-mercapto phenyl formic benzothiazole, the chloro-2-mercaptobenzothiazole of 5-, 6-ethoxy-2-mercaptobenzothiazole, nitrocaptax, 2-sulfydryl naphtho-imidazoles, 2-sulfydryl naphtho-oxazole, 3-sulfydryl-1,2,4-triazole, 4-amino-6-sulfydryl pyrazolo [2,4-d] pyridine, 2-amino-6-purine mercaptan, Ismipur, 4-sulfydryl-1H-pyrazolo [2,4-d] pyrimidine etc.

As the compound of sulfydryl in molecule with more than 2, ethanthiol can be enumerated, the last of the ten Heavenly stems two mercaptan, 1, two (methyl mercapto) benzene of 4-, butylene glycol two (3-mercaptopropionic acid ester), butylene glycol two (3-mercaptoacetate), ethylene glycol bis (3-mercaptoacetate), trimethylolpropane tris (3-mercaptoacetate), butylene glycol two (3-mercaptopropionic acid ester), trimethylolpropane tris (3-mercaptopropionic acid ester), trimethylolpropane tris (3-mercaptoacetate), pentaerythrite four (3-mercaptopropionic acid ester), pentaerythrite four (3-mercaptoacetate), trihydroxy ethyl three (3-mercaptopropionic acid ester), pentaerythrite four (3-mercaptobutylate), 1, two (3-sulfydryl butoxy) butane of 4-etc.

The content of mercaptan compound (T) is preferably 0.5 ~ 20 mass parts relative to polymerization initiator (D) 100 mass parts, is more preferably 1 ~ 15 mass parts.If the content of mercaptan compound (T) is within the scope of this, then there is sensitivity and to uprise and developability becomes good tendency.

< solvent (E) >

Solvent (E) is not particularly limited, and can use solvent usually used in this field.As this solvent, ester solvent can be enumerated (containing-COO-in molecule, containing the solvent of-O-), ether solvents is (containing-O-in molecule, containing the solvent of-COO-), ether-ether solvent (solvent containing-COO-and-O-in molecule), ketone solvent be (containing-CO-in molecule, containing the solvent of-COO-), alcoholic solvent (containing OH in molecule, not containing the solvent of-O-,-CO-and-COO-), aromatic hydrocarbon solvents, amide solvent, dimethyl sulfoxide (DMSO) etc.

As ester solvent, methyl lactate, ethyl lactate, butyl lactate, 2-hydroxy-methyl isobutyl acid, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl isobutyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, Propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl cyclohexyl alcohol ester, gamma-butyrolacton etc. can be enumerated.

As ether solvents, glycol monoethyl ether can be enumerated, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxyl-n-butyl alcohol, 3-methoxyl-3-methyl butanol, tetrahydrofuran, oxinane, 1, 4-diox, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethylmethyl ether, diethylene glycol dipropyl ether, dibutyl ethylene glycol ether, methyl phenyl ethers anisole, phenetol, methylanisole etc.

As ether-ether solvent, methoxy menthyl acetate can be enumerated, ethyl methoxyacetate, methoxyacetic acid butyl ester, ethoxy acetate, ethoxy ethyl acetate, 3-methoxy methyl propionate, 3-methoxypropionate, 3-ethoxypropanoate, 3-ethoxyl ethyl propionate, 2-methoxy methyl propionate, 2-methoxypropionate, 2-methoxy propyl propyl propionate, 2-ethoxypropanoate, 2-ethoxyl ethyl propionate, 2-methoxyl-2 Methylpropionic acid methyl esters, 2-ethoxy-2 Methylpropionic acid ethyl ester, 3-methoxybutyl acetic acid esters, 3-methyl-3-methoxybutyl acetic acid esters, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetic acid esters, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetic acid esters and butyl carbitol acetate etc.

As ketone solvent, 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-HEPTANONE, 3-heptanone, 4-heptanone, 4-methyl-2 pentanone, cyclopentanone, cyclohexanone, isophorone etc. can be enumerated.

As alcoholic solvent, methyl alcohol, ethanol, propyl alcohol, butanols, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerine etc. can be enumerated.

As aromatic hydrocarbon solvents, benzene,toluene,xylene and sym-trimethyl benzene etc. can be enumerated.

As amide solvent, DMF, DMA and 1-METHYLPYRROLIDONE etc. can be enumerated.

In above-mentioned solvent, from the viewpoint of coating, drying property, the boiling point preferably under 1atm is more than 120 DEG C and the organic solvent of less than 180 DEG C.As solvent, preferred propylene glycol methyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, 3-ethoxyl ethyl propionate, glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone and N, dinethylformamide, more preferably propylene glycol methyl ether acetate, propylene glycol monomethyl ether, ethyl lactate and 4-hydroxy-4-methyl-2-pentanone.

The content of solvent (E) is preferably 70 ~ 95 quality % relative to the total amount of colored curable resin composition of the present invention, is more preferably 75 ~ 92 quality %.In other words, the total amount of the solid constituent of colored curable resin composition is preferably 5 ~ 30 quality %, is more preferably 8 ~ 25 quality %.If the content of solvent (E) is in above-mentioned scope, then flatness when being coated with becomes good, and during formation color filter, color density can not be not enough in addition, therefore there is the tendency that display characteristic becomes good.

< levelling agent (F) >

As levelling agent (F), silicone-based surfactant, fluorine system surfactant can be enumerated and there is the silicone-based surfactant etc. of fluorine atom.They can have polymerizable group at side chain.

As silicone-based surfactant, the surfactant etc. with siloxane bond can be set forth in molecule.Specifically, Toray silicone DC3PA can be enumerated, Toray silicone SH7PA, Toraysilicone DC11PA, Toray silicone SH21PA, Toray silicone SH28PA, Toraysilicone SH29PA, Toray silicone SH30PA, Toray silicone SH8400 (trade name: eastern beautiful DOW CORNING (strain) system), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (SHIN-ETSU HANTOTAI's chemical industry (strain) system), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460 (stepping contract commercial firm of figure new high-tech material Japan system) etc.

As above-mentioned fluorine system surfactant, the surfactant etc. with fluorocarbon chain can be set forth in molecule.Specifically, fluorad (registered trademark) FC430 can be enumerated, fluorad FC431 (Sumitomo 3M (strain) system), megafac (registered trademark) F142D, megafac F171, megafacF172, megafac F173, megafac F177, megafac F183, megafac F554, megafacR30, megafac RS-718-K (DIC (strain) system), eftop (registered trademark) EF301, eftopEF303, eftop EF351, eftop EF352 (Mitsubishi Materials electronics changes into (strain) system), surflon (registered trademark) S381, surflon S382, surflon SC101, surflon SC105 (Asahi Glass (strain) system) and E5844 (research of (strain) great Jin fine chemistry industry is made) etc.

As the above-mentioned silicone-based surfactant with fluorine atom, the surfactant etc. with siloxane bond and fluorocarbon chain can be set forth in molecule.Specifically, megafac (registered trademark) R08, megafac BL20, megafac F475, megafac F477 and megafac F443 (DIC (strain) system) etc. can be enumerated.

The content of levelling agent (F) is preferably more than 0.001 quality % and below 0.2 quality % relative to the total amount of colored curable resin composition, be preferably more than 0.002 quality % and below 0.1 quality %, be more preferably more than 0.01 quality % and below 0.05 quality %.It should be noted that, in this content, do not comprise the content of above-mentioned pigment dispersing agent.If the content of levelling agent (F) is in above-mentioned scope, then the flatness of color filter can be made good.

Other compositions of < >

Colored curable resin composition of the present invention can contain the adjuvants well-known in the art such as filling agent, other macromolecular compounds, closely sealed promoter, antioxidant, light stabilizer, chain-transferring agent as required.

The manufacture method > of < colored curable resin composition

Colored curable resin composition of the present invention can be prepared by mixing such as colorant (A), resin (B), polymerizable compound (C), polymerization initiator (D) and the solvent (E) used as required, levelling agent (F), polymerization initiation auxiliary agent (D1), mercaptan compound (T) and other compositions.

The pigment such as viridine green (A2) preferably mixs with part or all of solvent (E) in advance, and the mean grain size that use ball mill etc. is dispersed to pigment is the degree of less than 0.2 μm.Now, part or all of above-mentioned pigment dispersing agent, resin (B) can be coordinated as required.By mixing all the other compositions in the mode of the concentration reaching regulation in the dispersible pigment dispersion obtained like this, target coloration hardening resin composition can be prepared.

The dyestuffs such as blue dyes (A1) can be made to be dissolved in part or all and previously prepared solution of solvent (E) respectively.Preferably use this solution of metre filter in about 0.01 ~ 1 μm, aperture.

Preferably use the mixed colored curable resin composition of metre filter in about 0.01 ~ 10 μm, aperture.

The manufacture method > of < color filter

Color filter of the present invention is formed by colored curable resin composition of the present invention.This color filter can be formed by making this colored curable resin composition solidify.

As the method being manufactured colored pattern by colored curable resin composition of the present invention, photoetching process, ink-jet method, print process etc. can be enumerated.Wherein, preferred light lithography.Photoetching process is following method: above-mentioned colored curable resin composition is coated substrate, makes it dry and forms coloring compositions nitride layer, this coloring compositions nitride layer being exposed, development across photomask.

In photoetching process, by not using photomask when exposing and/or do not develop, the painted film of the solidfied material as above-mentioned coloring compositions nitride layer can be formed.The colored pattern formed like this, painted film are color filters of the present invention.

The thickness of the color filter made is not particularly limited, and suitably can regulate according to object, purposes etc., such as, 0.1 ~ 30 μm, is preferably 0.1 ~ 20 μm, more preferably 0.5 ~ 6 μm.

As substrate, quartz glass, pyrex, alumina silicate glass, effects on surface can be used to have carried out the glass plates such as the soda-lime glass of silica dioxide coating; The resin plates such as polycarbonate, polymethylmethacrylate, polyethylene terephthalate; Silicon, on aforesaid substrate, define the substrate of aluminium, silver, silver/copper/palldium alloy film etc.On these substrates, other colour filters, resin bed, transistor, circuit etc. can be formed.

Formation based on photolithographic colored pattern can be undertaken by known or usual device, condition.Such as, can make as follows.

First, by being coated on substrate by colored curable resin composition, heat drying (prebake) and/or drying under reduced pressure and make it dry except volatile ingredients such as desolventizings, obtain level and smooth coloring compositions nitride layer.

As coating process, method of spin coating, slot coated method, slit and method of spin coating etc. can be enumerated.

Temperature when carrying out heat drying is preferably 30 ~ 120 DEG C, is more preferably 50 ~ 110 DEG C.In addition as the heat time, be preferably 10 second ~ 60 minutes, be more preferably 30 second ~ 30 minutes.

When carrying out drying under reduced pressure, preferably carry out under the pressure of 50 ~ 150Pa, in the temperature range of 20 ~ 25 DEG C.

The thickness of coloring compositions nitride layer is not particularly limited, as long as suitably select according to the thickness of the color filter of target.

Then, across the photomask for the formation of target coloration pattern, coloring compositions nitride layer is exposed.Pattern on this photomask is not particularly limited, and uses the pattern corresponding to intended applications.

As the light source used in exposure, preferably send the light source of the light of the wavelength of 250 ~ 450nm.Such as, the filter intercepts of this wavelength region may of intercepting can be used optionally to take out the light near 436nm, near 408nm, near 365nm lower than the light of 350nm or the bandpass filter of these wavelength region may of use taking-up.Specifically, mercury lamp, light emitting diode, metal halide lamp, Halogen lamp LED etc. can be enumerated.

Due to can parallel rays be irradiated equably to plane of exposure entirety or carry out photomask and the correct aligned in position of substrate defining coloring compositions nitride layer, therefore preferably use the exposure device such as mask aligner and ledex.

Develop by making the coloring compositions nitride layer after exposure contact with developer solution, substrate forms colored pattern.By development, the unexposed portion of coloring compositions nitride layer dissolves and is removed in developer solution.As developer solution, such as, the aqueous solution of the alkali compounds such as preferred potassium hydroxide, sodium bicarbonate, sodium carbonate, tetramethyl ammonium hydroxide.Concentration in the aqueous solution of these alkali compounds is preferably 0.01 ~ 10 quality %, is more preferably 0.03 ~ 5 quality %.Developer solution can also contain surfactant.

Developing method can be any one in paddle board method, infusion process and spray-on process etc.Can also by substrate with arbitrary angular slope when developing.

Preferably wash after development.

Further, cure after preferably the colored pattern obtained being carried out.Rear stoving temperature is preferably 150 ~ 250 DEG C, is more preferably 160 ~ 235 DEG C.After the time of curing be preferably 1 ~ 120 minute, be more preferably 10 ~ 60 minutes.

Utilize colored curable resin composition of the present invention, the color filter that brightness is excellent especially can be manufactured.This color filter is useful as the color filter used in display device (liquid crystal indicator, organic el device, Electronic Paper etc.) and solid-state imager.Wherein, useful as color filter for liquid crystal display, particularly as LED is useful as the color filter of the liquid crystal indicator of backlight.

Embodiment

Below, by embodiment, colored curable resin composition of the present invention is described in more detail.

" % " and " part " in example refers to quality % and mass parts without special provision.

In following synthesis example, by mass spectrophotometry (LC; Agilent system 1200 type, MASS; Agilent LC/MSD type) or ultimate analysis (VARIO-EL; (elemental (strain) system)) identify compound.

(synthesis example 1)

Following reaction is carried out under nitrogen atmosphere.In the flask possessing condenser pipe and stirring apparatus, after dropping into potassium rhodanide 36.3 parts and 160 parts, acetone, at room temperature stir 30 minutes.Then, with 10 minutes instillation chlorobenzoyl chloride (Tokyo change into (strain) Inc.) 50 parts.After dropping terminates, at room temperature stir 2 hours further.Then, after reaction mixture ice bath is cooled, instillation N-ethyl-ortho-toluidine (Tokyo changes into (strain) Inc.) 45.7 parts.After dropping terminates, at room temperature stir 30 minutes further.Then, after being cooled by reaction mixture ice bath, 30% sodium hydrate aqueous solution 34.2 parts is instilled.After dropping terminates, at room temperature stir 30 minutes further.Then, at room temperature chloroacetic acid 35.3 parts is instilled.After dropping terminates, stir 7 hours under heated reflux condition.Then, reaction mixture is placed after being cooled to room temperature, after reaction solution being injected 120 parts, tap water, add toluene 200 parts and stir 30 minutes.Then stop stirring, leave standstill 30 minutes, result is separated into organic layer and water layer.After water layer is discarded by separatory operation, with 1 equivalent hydrochloric acid 200 parts washing organic layer, then with the washing of 200 parts, tap water, finally with saturated aqueous common salt 200 parts washing.Add appropriate saltcake and after stirring 30 minutes to organic layer, filter and organic layer after the moisture that is removed.With evaporator, the organic layer distillation obtained is removed desolventizing, obtain weak yellow liquid.The weak yellow liquid obtained is refined by column chromatography.At reduced pressure conditions 60 DEG C of dryings refine after weak yellow liquid, obtain the compound 52 parts represented by formula (B-I-1).Yield is 50%.

Following reaction is carried out under nitrogen atmosphere.In the flask possessing condenser pipe and stirring apparatus, compound represented by throw-in type (B-I-1) 9.3 parts, 4, after 4 '-bis-(diethylamino) benzophenone (Tokyo changes into (strain) Inc.) 10 parts and toluene 20.0 parts, then, add phosphorous oxychloride 14.8 parts and stir 3 hours at 95 ~ 100 DEG C.Then, after reaction mixture is cooled to room temperature, with isopropyl alcohol 170 parts dilution.Then, after the reaction solution after dilution is injected saturated aqueous common salt 300 parts, add toluene 100 parts and stir 30 minutes.Then stop stirring, leave standstill 30 minutes, result is separated into organic layer and water layer.After water layer is discarded by separatory operation, with saturated aqueous common salt 300 parts washing organic layer.Add appropriate saltcake and after stirring 30 minutes to organic layer, filter and organic layer after the moisture that is removed.With evaporator, the organic layer distillation obtained is removed desolventizing, obtain bluish violet solid.60 DEG C of dry bluish violet solids at reduced pressure conditions further, obtain the compound 19.8 parts represented by formula (A-II-1).Yield is 100%.

The qualification of the compound represented by formula (A-II-1)

(mass spectrum) ionization mode=ESI+:m/z=601.3 [M-Cl] ⁺

Exact mass: 636.3

Following reaction is carried out under nitrogen atmosphere.In the flask possessing condenser pipe and stirring apparatus; compound represented by throw-in type (A-II-1) 10 parts, two (trifluoromethane sulfonyl group) imide li (Tokyo changes into (strain) Inc.) 4.5 parts and N; after dinethylformamide 100 parts, stir 3 hours at 50 ~ 60 DEG C.Then, after reaction mixture is cooled to room temperature, was added drop-wise in 2000 parts, tap water with 1 hour while stirring, obtains skipper suspension.Filter the suspension obtained, obtain blue-green solid.60 DEG C of dry blue-green solid at reduced pressure conditions further, obtain the compound 11.3 parts represented by formula (Ab2-1).Yield is 82%.

Compound 0.35g represented by formula (Ab2-1) is dissolved in chloroform and volume is set to 250cm ³, by 2cm wherein ³with ion exchange water dilution, volume is set to 100cm ³(concentration: 0.028g/L), uses spectrophotometer (quartz colorimetric utensil, optical length; 1cm) determine absorption spectrum.This compound shows absorbance 2.9 (arbitrary unit) at maximum absorption wavelength λ max=628nm.

(synthesis example 2)

Following reaction is carried out under nitrogen atmosphere.In the flask possessing condenser pipe and stirring apparatus, after dropping into potassium rhodanide 11 parts and 39.4 parts, acetone, at room temperature stir 30 minutes.Then, with 10 minutes instillation chlorobenzoyl chlorides 13 parts.After dropping terminates, at room temperature stir 2 hours further.Then, after reaction solution ice bath is cooled, instillation two (2-ethylhexyl) amine 23 parts.After dropping terminates, at room temperature stir 30 minutes further.Then, after being cooled by reaction solution ice bath, 30% sodium hydrate aqueous solution 30 parts is instilled.After dropping terminates, at room temperature stir 30 minutes further.Then, at room temperature chloroacetic acid 9.2 parts is instilled.After dropping terminates, stir 7 hours under heated reflux condition.Then, reaction solution is placed after being cooled to room temperature, after reaction solution being injected 13 parts, tap water, add 26 parts, ethyl acetate and stir 30 minutes.Then stop stirring, leave standstill 30 minutes, result is separated into organic layer and water layer.After water layer is discarded by separatory operation, with 1 equivalent hydrochloric acid 13 parts washing organic layer, then with the washing of 13 parts, tap water, finally with saturated aqueous common salt 13 parts washing.Add appropriate saltcake and after stirring 30 minutes to organic layer, filter and organic layer after the moisture that is removed.With evaporator, the organic layer distillation obtained is removed desolventizing, obtain weak yellow liquid.60 DEG C of dry weak yellow liquids at reduced pressure conditions further, obtain the compound 14 parts represented by formula (B-I-2).Yield is 48%.

Following reaction is carried out under nitrogen atmosphere.In the flask possessing condenser pipe and stirring apparatus, after dropping into n-amyl alcohol 1000 parts, 3-aminochlotononitlile 133 parts and N-Cyanoacetyl-N '-(2-ethyl hexyl acyl group) hydrazine 250 parts, stir 2 hours under heated reflux condition.Then, after adding zinc chloride 166.4 parts, stir 4 hours under heated reflux condition further.Then, concentrated hydrochloric acid 225 parts is instilled.After dropping terminates, n-amyl alcohol is distilled removing together with water vapor.The suspension that suction filtration is residual, washes residual component with water, obtains faint yellow solid.60 DEG C of dry faint yellow solids at reduced pressure conditions further, obtain the compound 215 parts represented by formula (C-II-1).Yield is 71%.

Following reaction is carried out under nitrogen atmosphere.In the flask possessing condenser pipe and stirring apparatus, after the compound represented by throw-in type (C-II-1) 120 parts, 1200 parts, glacial acetic acid and concentrated hydrochloric acid 1200 parts, at room temperature stir 30 minutes.Then, after reaction solution ice bath is cooled, add 23% sodium nitrite in aqueous solution 28.5 parts and stir 3 hours, obtaining bronzing suspension.After the bronzing suspension that suction filtration obtains.Wash residual component with water, obtain red brown solid.60 DEG C of dry red brown solid at reduced pressure conditions further, obtain the compound 120 parts represented by formula (C-I-1).Yield is 90%.

Following reaction is carried out under nitrogen atmosphere.In the flask possessing condenser pipe and stirring apparatus, add concentrated hydrochloric acid 2 parts, acetic acid 7 parts and the compound represented by formula (C-I-1) 1.5 parts and at room temperature stir 30 minutes.Then, add compound 1.6 parts represented by formula (B-I-2) and 0.5 part, water in reaction solution after, at room temperature stir 30 minutes.Then, add sulfaminic acid 0.05 part in reaction solution after, at room temperature stir 20 minutes.Then, add 30% sodium hydrate aqueous solution 7 parts in reaction solution after, stir 4 hours at 60 DEG C.Then, reaction solution is placed after being cooled to room temperature, after reaction solution being injected 15 parts, tap water, add 15 parts, ethyl acetate and stir 30 minutes.Then stop stirring, leave standstill 30 minutes, result is separated into organic layer and water layer.After water layer is discarded by separatory operation, with evaporator, the organic layer distillation obtained removed desolventizing, obtain blue-green solid.Refine blue-green solid with silica gel column chromatography further, obtain the compound 1.2 parts represented by formula (Ac1-7).Yield is 36%.

Compound 0.35g represented by formula (Ac1-7) is dissolved in chloroform and volume is set to 250cm ³, by 2cm wherein ³with ion exchange water dilution, volume is set to 100cm ³(concentration: 0.028g/L), uses spectrophotometer (quartz colorimetric utensil, optical length; 1cm) measure absorption spectrum.This compound shows absorbance 2.6 (arbitrary unit) at λ max=621nm.

The qualification of the compound represented by formula (Ac1-7)

(mass spectrum) ionization mode=ESI+:m/z=684.4 [M+H] ⁺

Exact mass: 683.4

(synthesis example 3)

Following reaction is carried out under nitrogen atmosphere.In the flask possessing condenser pipe and stirring apparatus, after dropping into 2-bromo-3 '-nitro-acetophenone (Tokyo changes into (strain) Inc.) 5 parts and 50% isopropanol water solution 50 parts, at room temperature stir 30 minutes.Then, potassium rhodanide 3 parts was added with 10 minutes.After dropping terminates, at room temperature stir 3 hours further.Then, 50 parts, tap water is instilled.After dropping terminates, at room temperature stir 30 minutes further.After filtering out the yellow solid of precipitation, refine the yellow solid obtained by column chromatography.The yellow solid that 60 DEG C of dryings are refining at reduced pressure conditions, obtains the compound 4.2 parts represented by formula (B-II-21).Yield is 92%.

Following reaction is carried out under nitrogen atmosphere.In the flask possessing condenser pipe and stirring apparatus, after the compound represented by throw-in type (B-II-13) 5 parts and ethanol 50 parts, at room temperature stir 30 minutes.Then, respectively with instillation piperidines (Tokyo changes into (strain) Inc.) 2.9 parts in 10 minutes and 1.4 parts, glacial acetic acid.After dropping terminates, stir 2 hours under heated reflux condition further.Reaction liquid is placed after being cooled to room temperature, instillation 70 parts, tap water.After dropping terminates, at room temperature stir 30 minutes further.After filtering out the yellow solid of precipitation, refine the yellow solid obtained by column chromatography.At reduced pressure conditions 60 DEG C of dryings refine after yellow solid, obtain the compound 4.2 parts represented by formula (B-I-21).Yield is 64%.

Following reaction is carried out under nitrogen atmosphere.In the flask possessing condenser pipe and stirring apparatus, compound represented by throw-in type (B-I-21) 10.4 parts, 4, after 4 '-bis-(diethylamino) benzophenone (Tokyo changes into (strain) Inc.) 10 parts and toluene 20.0 parts, then, add phosphorous oxychloride 14.8 parts and stir 3 hours at 95 ~ 100 DEG C.Then, after reaction mixture is cooled to room temperature, with isopropyl alcohol 170 parts dilution.Then, after the reaction solution after dilution is injected saturated aqueous common salt 300 parts, add toluene 100 parts and stir 30 minutes.Then stop stirring, leave standstill 30 minutes, result is separated into organic layer and water layer.After water layer is discarded by separatory operation, with saturated aqueous common salt 300 parts washing organic layer.Add appropriate saltcake and after stirring 30 minutes to organic layer, filter and organic layer after the moisture that is removed.With evaporator, the organic layer distillation obtained is removed desolventizing, obtain bluish violet solid.The bluish violet solid obtained is refined by column chromatography.At reduced pressure conditions 60 DEG C of dryings refine after bluish violet solid, obtain the compound 10.2 parts represented by formula (A-II-21).Yield is 52%.

The qualification of the compound represented by formula (A-II-21)

(mass spectrum) ionization mode=ESI+:m/z=596.3 [M-Cl] ⁺

Exact mass: 631.3

Following reaction is carried out under nitrogen atmosphere.In the flask possessing condenser pipe and stirring apparatus; compound represented by throw-in type (A-II-21) 10 parts, two (trifluoromethane sulfonyl group) imide li (Tokyo changes into (strain) Inc.) 5.9 parts and N; after dinethylformamide 30 parts, stir 3 hours at 40 DEG C.Then, after reaction mixture is cooled to room temperature, was added drop-wise in 500 parts, tap water with 1 hour while stirring, obtains skipper suspension.Filter the suspension obtained, obtain blue-green solid.60 DEG C of dry blue-green solid at reduced pressure conditions further, obtain the compound 11.5 parts represented by formula (Ab2-21).Yield is 83%.

Compound 0.35g represented by formula (Ab2-21) is dissolved in chloroform and volume is set to 250cm ³, by 2cm wherein ³with ion exchange water dilution, volume is set to 100cm ³(concentration: 0.028g/L), uses spectrophotometer (quartz colorimetric utensil, optical length; 1cm) measure absorption spectrum.This compound shows absorbance 3.0 (arbitrary unit) at λ max=634nm.

(synthesis example 4)

Following reaction is carried out under nitrogen atmosphere.In the flask possessing condenser pipe and stirring apparatus, after dropping into potassium rhodanide 33 parts and 160 parts, acetone, at room temperature stir 30 minutes.Then, with 10 minutes instillation 2-methyl benzoyl chlorides (Tokyo changes into (strain) Inc.) 50 parts.After dropping terminates, at room temperature stir 2 hours further.Then, after reaction mixture ice bath is cooled, instillation N-ethyl-ortho-toluidine (Tokyo changes into (strain) Inc.) 41.6 parts.After dropping terminates, at room temperature stir 30 minutes further.Then, after being cooled by reaction mixture ice bath, 30% sodium hydrate aqueous solution 34.2 parts is instilled.After dropping terminates, at room temperature stir 30 minutes further.Then, chloroacetic acid 32.1 parts is instilled under room temperature.After dropping terminates, stir 7 hours under heated reflux condition.Then, reaction mixture is placed after being cooled to room temperature, after reaction solution being injected 120 parts, tap water, add toluene 200 parts and stir 30 minutes.Then stop stirring, leave standstill 30 minutes, result is separated into organic layer and water layer.After water layer is discarded by separatory operation, with 1 equivalent hydrochloric acid 200 parts washing organic layer, then with the washing of 200 parts, tap water, finally with saturated aqueous common salt 200 parts washing.

Add appropriate saltcake and after stirring 30 minutes to organic layer, filtered and organic layer after removing moisture.With evaporator, the organic layer distillation obtained is removed desolventizing, obtain weak yellow liquid.The weak yellow liquid obtained is refined by column chromatography.At reduced pressure conditions 60 DEG C of dryings refine after weak yellow liquid, obtain the compound 40.5 parts represented by formula (B-I-9).Yield is 41%.

Following reaction is carried out under nitrogen atmosphere.In the flask possessing condenser pipe and stirring apparatus, compound represented by throw-in type (B-I-9) 9.7 parts, 4, after 4 '-bis-(diethylamino) benzophenone (Tokyo changes into (strain) Inc.) 10 parts and toluene 20 parts, then, add phosphorous oxychloride 14.8 parts and stir 3 hours at 95 ~ 100 DEG C.Then, after reaction mixture is cooled to room temperature, with isopropyl alcohol 170 parts dilution.Then, after the reaction solution after dilution is injected saturated aqueous common salt 300 parts, add toluene 100 parts and stir 30 minutes.Then stop stirring, leave standstill 30 minutes, result is separated into organic layer and water layer.After water layer is discarded by separatory operation, with saturated aqueous common salt 300 parts washing organic layer.Add appropriate saltcake and after stirring 30 minutes to organic layer, filter and organic layer after the moisture that is removed.With evaporator, the organic layer distillation obtained is removed desolventizing, obtain bluish violet solid.The bluish violet solid obtained is refined by column chromatography.At reduced pressure conditions 60 DEG C of dryings refine after bluish violet solid, obtain the compound 15.1 parts represented by formula (A-II-9).Yield is 75%.

The qualification of the compound represented by formula (A-II-9)

(mass spectrum) ionization mode=ESI+:m/z=615.4 [M-Cl] ⁺

Exact mass: 650.3

Following reaction is carried out under nitrogen atmosphere.In the flask possessing condenser pipe and stirring apparatus; compound represented by throw-in type (A-II-9) 10 parts, two (trifluoromethane sulfonyl group) imide li (Tokyo changes into (strain) Inc.) 5.7 parts and N; after dinethylformamide 30 parts, stir 3 hours at 40 DEG C.Then, after reaction mixture is cooled to room temperature, was added drop-wise in 500 parts, tap water with 1 hour while stirring, obtains skipper suspension.Filter the suspension obtained, obtain blue-green solid.60 DEG C of dry blue-green solid at reduced pressure conditions further, obtain the compound 13.2 parts represented by formula (Ab2-9).Yield is 96%.

Compound 0.35g represented by formula (Ab2-9) is dissolved in chloroform and volume is set to 250cm ³, by 2cm wherein ³with ion exchange water dilution, volume is set to 100cm ³(concentration: 0.028g/L), uses spectrophotometer (quartz colorimetric utensil, optical length; 1cm) measure absorption spectrum.This compound shows absorbance 2.7 (arbitrary unit) at λ max=627nm.

(synthesis example 5)

By 10 parts, 4-amino-3-hydroxy formic acid (Tokyo changes into industry (strain) system), 4-(diethylamino) salicylide (Tokyo changes into industry (strain) system) 12.8 parts, 2.73 parts, benzoic acid (Tokyo changes into industry (strain) system), 1-amylalcohol (Tokyo changes into industry (strain) system) 157 parts and cyan-acetic ester (Tokyo changes into industry (strain) system) 7.43 parts of mixing, stir 3 hours at 120 DEG C.Add cyan-acetic ester (Tokyo changes into industry (strain) system) 7.46 parts, 2.79 parts, benzoic acid (Tokyo changes into industry (strain) system), 1-amylalcohol (Tokyo changes into industry (strain) system) 49.8 parts and 4-(diethylamino) salicylide (Tokyo changes into industry (strain) system) 12.7 parts, stir 14 hours at 120 DEG C.Add cyan-acetic ester (Tokyo changes into industry (strain) system) 3.76 parts, 1.41 parts, benzoic acid (Tokyo changes into industry (strain) system), 1-amylalcohol (Tokyo changes into industry (strain) system) 52.5 parts and 4-(diethylamino) salicylide (Tokyo changes into industry (strain) system) 6.35 parts, stir 8 hours at 120 DEG C.After above-mentioned reactant liquor is cooled to room temperature, obtain the crystal of separating out with the form of the residue of suction filtration.In this residue, add tetrahydrofuran 140 parts, after stirring 1 hour at 70 DEG C, obtain insolubles with the form of the residue of suction filtration.In this residue, add tetrahydrofuran 120 parts, after stirring 1 hour at 70 DEG C, obtain insolubles with the form of the residue of suction filtration.In this residue, add DMF 340 parts, after making it dissolve, leave standstill at 0 DEG C ~ 5 DEG C 90 DEG C of heating.The crystal of separating out is obtained with the form of the residue of suction filtration.At 60 DEG C by this residue drying under reduced pressure, obtain the compound 5.69 parts represented by formula (Ad1-1).With ¹h-NMR confirms structure.

The qualification > of the compound represented by < formula (Ad1-1)

¹H-NMR(500MHz,DMSO-d6)：1.14(6H,t),3.47(4H,q),6.57(1H,d),6.78(1H,dd),7.68(1H,d),7.79(1H,d),7.96(1H,dd),8.15(1H,d),8.80(1H,s),13.11(1H,s).

(synthesis example 6)

By resorcinol (Tokyo changes into industry (strain) system) 275 parts and n-hexylamine (Tokyo changes into industry (strain) system) 101 parts of mixing, the waterside that limit removing generates is stirred 20 hours at 150 ~ 155 DEG C.After placing cooling, reaction mixture is dissolved in toluene 433 parts, the warm water 1000 part of this toluene solution with 40 DEG C is washed 3 times.In this toluene solution, add anhydrous magnesium sulfate 50 parts and after stirring, filter.Distillation removes the solvent of filtrate and obtains crude product.This crude product is dissolved in toluene 234 parts, stirs below 0 DEG C, crystallization thing is filtered, by this has been recovery.By this crystallization thing at 50 DEG C of drying under reduced pressure, obtain the compound 95.7 parts represented by formula (pt1).

The qualification > of the compound represented by < formula (pt1)

(mass spectrum) ionization mode=ESI+:m/z=[M+H] ⁺194.2

Exact mass: 193.2

By the compound 95.3 parts represented by formula (pt1) and the mixing of 48.0 parts, water, 80 DEG C of stirrings.Then, while add the bromo-2-ethyl hexane of 1-(Tokyo changes into industry (strain) system) 107 parts of limits after 3 hours, to add 48% sodium hydrate aqueous solution 22.4 parts 80 DEG C of stirrings.This potpourri is stirred 18 hours at 110 DEG C.After placing cooling, with 10% sodium hydrate aqueous solution, the pH of reaction mixture is adjusted to 5, adds toluene 130 parts and stir, extracting toluene layer.With 500 parts, warm water, toluene extract is washed 2 times, add anhydrous magnesium sulfate 25 parts and stir, filter.The solvent of distillation removing filtrate, obtains containing the residue 154 part of the compound represented by formula (pt2) as major component.

The qualification > of the compound represented by < formula (pt2)

(mass spectrum) ionization mode=ESI+:m/z=[M+H] ⁺306.3

Exact mass: 305.3

Using containing the compound represented by the formula obtained (pt2) as the residue 154 parts of major component and DMF 597 parts mixing ,-6 DEG C ~ 3 DEG C stirrings.While liquid temperature is remained on-6 DEG C ~ 3 DEG C limits to add phosphorus oxychloride (pharmaceutical worker industry (strain) system pure with light) 258 parts wherein.After this potpourri is at room temperature stirred 1 hour, stir 4 hours at 60 DEG C.After placing cooling, reaction mixture is added in 1500 parts, ice, use 48% sodium hydrate aqueous solution to neutralize.Add toluene 867 parts wherein, extracting toluene layer.With 15% sodium-chloride water solution 1200 parts washing, 2 these toluene extracts.In this toluene extract, add anhydrous magnesium sulfate 60 parts and after stirring, filter.Distillation removes the solvent of filtrate and obtains residue.Refine this residue by column chromatography, obtain the compound 94.4 parts represented by formula (pt3).

The qualification > of the compound represented by < formula (pt3)

(mass spectrum) ionization mode=ESI+:m/z=[M+H] ⁺334.3

Exact mass: 333.3

By the compound 25.3 parts represented by two (3-amino-4-hydroxylphenyl) sulfone (Tokyo changes into industry (strain) system) 10.6 parts, formula (pt3), 3.2 parts, benzoic acid (Tokyo changes into industry (strain) system), 1-amylalcohol (Tokyo changes into industry (strain) system) 184 parts and cyan-acetic ester (Tokyo changes into industry (strain) system) 8.59 parts of mixing, stir 3 hours at 120 DEG C.Compound represented by hybrid in this reaction solution (pt3) 25.4 parts, 3.21 parts, benzoic acid (Tokyo changes into industry (strain) system), 1-amylalcohol (Tokyo changes into industry (strain) system) 90 parts and cyan-acetic ester (Tokyo changes into industry (strain) system) 8.59 parts, stir 12 hours at 120 DEG C.After above-mentioned reactant liquor is cooled to room temperature, be added in methyl alcohol 1800 parts, obtain the crystal of separating out with the form of the residue of suction filtration.Refine this residue by column chromatography, obtain the compound 20.6 parts represented by formula (Ad2-10).Pass through ¹h-NMR confirms structure.

The qualification > of the compound represented by < formula (Ad2-10)

¹H-NMR(500MHz,DMSO-d ₆)：0.85(6H,t),0.87(6H,t),0.87(6H,t),1.20～1.40(28H),1.56(4H,tt),1.75(2H,ttt),3.34(4H,d),3.43(4H,t),6.55(2H,d),6.79(2H,dd),7.64(2H,d),7.91(2H,d),8.01(2H,dd),8.36(2H,d),8.73(2H,s)

(synthesis example 7)

In the flask possessing reflux condenser, tap funnel and stirrer, flow into appropriate nitrogen and be replaced into blanket of nitrogen, adding propylene glycol methyl ether acetate 371 parts, be heated to 85 DEG C while stirring.Then, 54 parts, acrylic acid, 3,4-epoxy three ring [5.2.1.0 are made ^2,6] decane-8-base acrylate and 3,4-epoxy three ring [5.2.1.0 ^2,6] 225 parts, the potpourri (containing than taking molar ratio computing as 50:50) of decane-9-base acrylate, vinyltoluene (isomer mixture) 81 parts be dissolved in propylene glycol methyl ether acetate 80 parts and be prepared into mixed solution, instilled in flask by this mixed solution with 4 hours.

On the other hand, make polymerization initiator 2,2-azo two (2,4-methyl pentane nitrile) 30 parts be dissolved in propylene glycol methyl ether acetate 160 parts and obtain solution, dripped this solution with 5 hours.After the dropping of initiator solution terminates, after keeping 4 hours at 85 DEG C, be cooled to room temperature, (resin B is solution a) to obtain multipolymer.The solid constituent of resin B a solution is 37%, and the viscosity measured by Brookfield viscometer (23 DEG C) is 246mPas.The weight-average molecular weight of resin B a is 1.06 × 10 ⁴, the acid number that solid constituent converts is 115mg-KOH/g, and molecular weight distribution is 2.01.

Resin B a has following structural unit.

Use GPC method, carry out the weight-average molecular weight (Mw) of resin and the mensuration of number-average molecular weight (Mn) under the following conditions.

Device; K2479 ((strain) Shimadzu Seisakusho Ltd. system)

Post; SHIMADZU Shim-pack GPC-80M

Column temperature; 40 DEG C

Solvent; THF (tetrahydrofuran)

Flow velocity; 1.0mL/min

Detecting device; RI

Correction standard substance; TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (eastern Cao (strain) system)

Using by the weight-average molecular weight of polystyrene conversion obtained above and the ratio (Mw/Mn) of number-average molecular weight as molecular weight distribution.

The preparation > of < dispersible pigment dispersion

Preparation example 1

By viridine green (A2): C.I. pigment Green 7 (pigment; λ max=660nm) 27 parts,

Acrylic acid series pigment dispersing agent 12 parts,

Resin (B): methacrylic acid/benzylmethacrylate copolymers (copolymerization ratio (mass ratio); 30/70, Mw; 1.2 × 10 ⁴) (solid constituent conversion) 9.5 parts and

Solvent (E): propylene glycol methyl ether acetate 180 parts

Mixing, uses ball mill that pigment is fully disperseed, has prepared dispersible pigment dispersion 1 thus.

Preparation example 2

Except by C.I. pigment Green 7 (pigment) instead of C.I. naphthol green 58 (pigment; λ max=675nm) beyond, carry out the operation same with preparation example 1, prepare dispersible pigment dispersion 2.

Embodiment 1 ~ 8 and comparative example 1 ~ 2

The preparation > of < colored curable resin composition

By each composition mixing of table 2, obtain green coloring hardening resin composition.In table 2, the value of the number display solid constituent conversion of resin.

Table 2

< blue dyes (A1) >

Aa; Compound (λ max=628nm) represented by formula (Ab2-1)

Ab; Compound (λ max=621nm) represented by formula (Ac1-7)

Ac; Compound (λ max=634nm) represented by formula (Ab2-21)

Ad; Compound (λ max=627nm) represented by formula (Ab2-9)

Ae; C.I. Blue VRS (λ max=639nm)

Af; Compound (λ max=453nm) represented by formula (Ad1-1)

Ag; Compound (λ max=455nm) represented by formula (Ad2-10)

< resin (B) >

Ba; Resin B a

< polymerizable compound (C) >

Dipentaerythritol acrylate (KAYARAD (registered trademark) DPHA; Japan's chemical drug (strain) system)

< polymerization initiator (D) >

N-benzoyloxy-1-(4-phenylmercapto phenyl) octane-1-ketone-2-imines (irgacure (registered trademark) OXE-01; BASF AG's system; O-acyl group oxime compound)

< solvent (E) >

Ea; Propylene glycol methyl ether acetate

Eb; Ethyl lactate

Ec; 4-hydroxy-4-methyl-2-pentanone

< levelling agent (F) >

Polyether modified silicone oil (toray silicone SH8400; The beautiful DOW CORNING in east (strain) system)

The making > of < colored pattern

At the glass substrate (eagle 2000 that 5cm is square; Corning Incorporated's system) on, after spin-coating method coating colored curable resin composition, form coloring compositions nitride layer 100 DEG C of prebake 3 minutes.After placing cooling, the substrate being formed with coloring compositions nitride layer and quartz glass photomask be set to 100 μm, use exposure machine (TME-150RSK; Open up Pu Kang (strain) system), under air atmosphere, carry out illumination with light quantity (365nm benchmark) and penetrated.As photomask, use the photomask defining 100 μm of live width/intermittent patterns.By postradiation for light coloring compositions nitride layer in the water system developer solution containing nonionic system surfactant 0.12% and potassium hydroxide 0.04% 24 DEG C of immersion development 60 seconds, after washing, in an oven, cure after carrying out 30 minutes at 210 DEG C.

Colored pattern is obtained by the colored curable resin composition of embodiment 1 ~ 8 and comparative example 1.For the colored curable resin composition of comparative example 2, the removing based on the unexposed portion of the coloring compositions nitride layer of development is carried out insufficient, could not obtain colored pattern.Pattern is in table 3 formed in hurdle, and the situation obtaining colored pattern is recited as zero, do not have getable situation be recited as ×.

< determining film thickness >

To the colored pattern obtained, with determining film thickness device (DEKTAK3; Japan's vacuum technique (strain) system) measure thickness.

< chromaticity evaluation >

To the film obtained, with colour examining machine (OSP-SP-200; Olympus (strain) is made) measure light splitting, and measure with the characteristic function of illuminant-C xy chromaticity coordinate in the XYZ colour system of CIE (x, y) with tristimulus values Y.The value of Y is larger, represents that brightness is higher.Result is shown in table 3.

Table 3

Utilizability in industry

Utilize colored curable resin composition of the present invention, the color filter of brightness excellence can be manufactured.

Claims

1. a colored curable resin composition, it contains colorant, resin, polymerizable compound and polymerization initiator,

2. colored curable resin composition according to claim 1, wherein,

The containing ratio of blue dyes is more than 0.1 quality % and below 20 quality % relative to the total content of colorant.

3. colored curable resin composition according to claim 1 and 2, wherein,

Blue dyes for being selected from the compound represented by formula (Ab1), at least a kind of dyestuff in methine dye well azomethine dyes,

In formula, R ^1A~ R ^8Aseparately represent the alkyl of hydrogen atom, halogen atom, nitro, hydroxyl, carbon number 1 ~ 20, wherein, oxygen atom can be inserted, R between the carbon atom forming this alkyl ^4Acan with R ^5Amutual bonding and form-NH-,-S-or-SO ₂-,

R ^9A~ R ^12Aseparately represent: hydrogen atom; By the alkyl of carbon number 1 ~ 20 that is amino or that can be replaced by halogen atom, can insert oxygen atom between the carbon atom forming this alkyl; The aralkyl that can be substituted; The aryl that maybe can be substituted,

R ^9Acan with R ^10Abonding and form ring together with the nitrogen-atoms of their institute's bonding, R ^11Acan with R ^12Abonding and form ring together with the nitrogen-atoms of their institute's bonding,

A represents the aromatic heterocycle that the aromatic hydrocarbyl that can be substituted maybe can be substituted,

G ^g-represent counter anion,

G represents 0 or arbitrary natural number, when g is 0, represents not have counter anion.

4. colored curable resin composition according to claim 1 and 2, wherein,

Polymerization initiator is the polymerization initiator containing O-acyl group oxime compound.

5. a color filter, its colored curable resin composition according to any one of claim 1 or 2 is formed.

6. a display device, it comprises color filter described in claim 5.