CN105319846A

CN105319846A - Colored curable resin composition

Info

Publication number: CN105319846A
Application number: CN201510299336.7A
Authority: CN
Inventors: 秋山裕次; 井上胜治
Original assignee: Dongwoo Fine Chem Co Ltd
Current assignee: Sumitomo Chemical Co Ltd; Dongwoo Fine Chem Co Ltd
Priority date: 2014-06-05
Filing date: 2015-06-03
Publication date: 2016-02-10
Also published as: TW201604243A; KR20150140231A; TWI664243B; JP2016011419A; KR102110485B1; JP6742698B2

Abstract

The present invention relates to a colored curable resin composition which comprises: a colorant (A), a resin (B), a polymeric compound (C), and a polymerization initiator (D), wherein the colorant (A) contains a red pigment (A-1) and a dye (A-2) which further comprises a xanthene dye and a coumarin dye.

Description

Colored curable resin composition

Technical field

The present invention relates to colored curable resin composition.

Background technology

Colored curable resin composition, such as, can be used for the color filter manufacturing liquid crystal indicator etc.As colored curable resin composition, in Japanese Unexamined Patent Publication 2010-211198 publication, describe a kind of colored curable resin composition, it comprises at least a kind of pigment in the group being selected from and being made up of yellow uitramarine, orange pigment and red pigment and xanthene dye as colorant.

Summary of the invention

The invention provides following [1] ~ [7].

[1] a kind of colored curable resin composition, which contain toner (A), resin (B), polymerizable compound (C) and polymerization initiator (D), colorant (A) comprises red pigment (A-1) and dyestuff (A-2), and dyestuff (A-2) comprises xanthene (xanthene) dyestuff and coumarine dye.

[2] colored curable resin composition Gen Ju [1], wherein, red pigment (A-1) is selected from least one pigment in the group that is made up of paratonere 177, paratonere 242 and paratonere 254.

[3] according to [1] or the colored curable resin composition described in [2], wherein, xanthene dye is the compound represented by formula (1a).

[in formula (1a), R ¹~ R ⁴represent hydrogen atom independently of each other, the univalent saturated hydrocarbon radical of substituent carbon number 1 ~ 20 can be had or the monovalence aromatic hydrocarbyl of substituent carbon number 6 ~ 10 can be had ,-CH contained in this saturated hydrocarbyl ₂-also can by-O-,-CO-or-NR ¹¹-replace.R ¹and R ²also can bonding mutually, the ring comprising nitrogen-atoms is formed, R together with the nitrogen-atoms of their institute's bondings ³and R ⁴also can bonding mutually, the ring comprising nitrogen-atoms is formed together with the nitrogen-atoms of their institute's bondings.

R ⁵represent-OH ,-SO ₃ ^-,-SO ₃h ,-SO ₃ ^-z ⁺,-CO ₂h ,-CO ₂ ^-z ⁺,-CO ₂r ⁸,-SO ₃r ⁸or-SO ₂nR ⁹r ¹⁰.

R ⁶and R ⁷represent the alkyl of hydrogen atom or carbon number 1 ~ 6 independently of each other.

M represents the integer of 0 ~ 5.M is when more than 2, multiple R ⁵can identical also can be different.

A represents the integer of 0 or 1.

X represents halogen atom.

Z ⁺represent ⁺n (R ¹¹) ₄, Na ⁺or K ⁺.

R ⁸represent the univalent saturated hydrocarbon radical of carbon number 1 ~ 20, hydrogen atom contained in this saturated hydrocarbyl also can be replaced by halogen atom.

R ⁹and R ¹⁰represent hydrogen atom independently of each other or the univalent saturated hydrocarbon radical of substituent carbon number 1 ~ 20 can be had ,-CH contained in this representative examples of saturated aliphatic alkyl ₂-also can by-O-,-CO-,-NH-or-NR ⁸-replace, R ⁹and R ¹⁰also 3 ~ 10 member heterocyclic ring containing nitrogens can be formed together with the nitrogen-atoms of their institute's bondings.

R ¹¹represent the univalent saturated hydrocarbon radical of hydrogen atom, carbon number 1 ~ 20 or the aralkyl of carbon number 7 ~ 10 independently of each other.]

[4] according to the colored curable resin composition according to any one of [1] ~ [3], wherein, coumarine dye is the compound represented by formula (Ad2).

[in formula (Ad2), L ^crepresent bivalent hydrocanbon radical or the sulfonyl of carbon number 1 ~ 20, hydrogen atom contained in this alkyl also can be replaced by fluorine atoms.

X ^crepresent oxygen atom or sulphur atom.

R ^1Cand R ^2Crepresent the alkyl can with substituent phenyl or carbon number 1 ~ 20 independently of one another, also can insert oxygen atom between the carbon atom forming this alkyl.

R ^7C~ R ^13Crepresent hydrogen atom, halogen atom, cyano group, nitro, carbamyl, amino-sulfonyl ,-SO independently of one another ₃m ^c,-CO ₂m ^c, hydroxyl, formoxyl, amino, carbon number 1 ~ 20 monovalent hydrocarbon, also can form this alkyl carbon atom between insert oxygen atom, sulphur atom ,-N (R ^14C)-, sulfonyl or carbonyl, hydrogen atom contained in this alkyl also can by halogen atom, cyano group, nitro, carbamyl, amino-sulfonyl ,-SO ₃m ^c,-CO ₂m ^c, hydroxyl, formoxyl or amino to replace.-SO ₃m ^cand-CO ₂m ^cwhen existing multiple respectively, they can be identical, also can be different.

R ^14Crepresent the monovalent hydrocarbon of hydrogen atom or carbon number 1 ~ 20.There is multiple-N (R ^14C)-when, they can be identical, also can be different.

M ^crepresent hydrogen atom or alkali metal atom.]

[5] according to colored curable resin composition according to any one of [1] ~ [4], wherein, xanthene dye and coumarine dye containing being 60:40 ~ 99:1 than (xanthene dye: coumarine dye) according to quality criteria.

[6] color filter, its colored curable resin composition according to any one of [1] ~ [5] is formed.

[7] liquid crystal indicator, wherein, comprises the color filter described in [6].

Embodiment

Colored curable resin composition of the present invention contains toner (A), resin (B), polymerizable compound (C) and polymerization initiator (D).

Colorant (A) comprises red pigment (A-1) and dyestuff (A-2), and dyestuff (A-2) comprises xanthene dye and coumarine dye.

Xanthene dye is preferably 60:40 ~ 99:1 than (xanthene dye: coumarine dye) according to quality criteria with containing of coumarine dye.

At least one in the group being selected from and being made up of solvent (E) and levelling agent (F) is preferably comprised further in colored curable resin composition of the present invention.

Colored curable resin composition of the present invention also can comprise polymerization further and cause auxiliary agent (D1).

In this manual, about the illustrative compound as each composition, as long as no illustrating in advance especially, just can use individually or by multiple combination.

< colorant (A) >

Red pigment (A-1) is not particularly limited, and can use known pigment, such as, list: the red pigment being categorized as pigment according to colo r index (TheSocietyofDyersandColourists publication).

As red pigment, (following, the record of omission C.I. pigment, only records sequence number such as to list C.I. Pigment Red 9.Other too.), 97,105,122,123,144,149,166,168,176,177,180,192,207,209,215,216,224,242,254,255,264,265,272, preferably list C.I. pigment red 149,176,177,207,242,254,255,264,272, more preferably list C.I. paratonere 177,242,254.

In colored curable resin composition of the present invention, when comprising C.I. pigment red 149,176,177,207,242,254,255,264,272 etc. as red pigment (A-1), easily the transmitted spectrum as red color filter is carried out optimization, the brightness of color filter becomes good.

Further, colored curable resin composition of the present invention also can comprise the pigment (A-3) except red pigment (A-1).

As pigment (A-3), list the yellow uitramarines such as C.I. pigment yellow 1,3,12,13,14,15,16,17,20,24,31,53,83,86,93,94,109,110,117,125,128,137,138,139,147,148,150,153,154,166,173,194,214, C.I. pigment orange 13,31,36,38,40,42,43,51,55,59,61,64,65,71, the orange pigments etc. such as 73.

These pigment suitably can be selected according to the spectrophotometric spectra of desired color filter.These pigment can be used alone, and also two or more mixing can be used.

For pigment, also can the process be implemented as follows as required: rosin process, the surface treatment employing the pigment derivative that is imported with acidic groups or basic group etc., grafting process surface of pigments carried out based on macromolecular compound etc., the micronize process carried out based on sulfuric acid particles method etc. or for go deimpurity carry out based on organic solvent and/or water etc. carrying out washing treatment, based on the ion exchange process etc. of ionic impurity and the Transformatin etc. carried out.

The particle diameter of pigment is preferably evenly.By carrying out dispersion treatment containing pigment dispersing agent, thus the dispersible pigment dispersion that pigment is scattered in the state in solution equably can be obtained.

As pigment dispersing agent, such as, list the surfactant etc. of kation system, negative ion system, nonionic system, both sexes, Polyester, polyamines system, acrylic acid series etc.These pigment dispersing agents can also may be combined with two or more individually and use.About pigment dispersing agent, list according to trade name: KP (Shin-Etsu Chemial Co., Ltd's system), Flowlen (common prosperity society chemistry (strain) system), Solsperse (Zeneca (strain) system), EFKA (registered trademark) (BASF AG's system), Ajisper (aginomoto fine chemistry (strain) system), DISPERBYK (registered trademark) (Bi Ke chemistry Inc.) etc.

When using pigment dispersing agent, its consumption is preferably below more than 1% quality 100% quality relative to the total amount of pigment, is more preferably below more than 5% quality 50% quality.When the consumption of pigment dispersing agent is in aforementioned range, then have the tendency of the dispersible pigment dispersion obtaining uniform disperse state.

About the content of red pigment (A-1), relative to the total amount of colorant (A), be preferably 1 ~ 99% quality, be more preferably 5 ~ 98% quality, more preferably 10 ~ 95% quality.

When comprising pigment (A-3), its containing ratio, relative to the total amount of colorant (A), is preferably 0.5 ~ 50% quality, is more preferably 1 ~ 40% quality.

Dyestuff (A-2) comprises xanthene dye and coumarine dye.

Xanthene dye is included in molecule the dyestuff of the compound with xanthene skeleton.As xanthene dye, list C.I. CI 45430,52,87,92,94,289,388, C.I. acid violet 9,30,102, C.I. alkali red 1:1 (rhodamine 6G), 2,3,4,8, C.I. alkali red 1:1 0 (rhodamine B), 11, C.I. alkaline purple 10,11,25, C.I. solvent red 218, C.I. medium red 27, C.I. reactive red 36 (rose bengal B), the xanthene dye etc. recorded in the xanthene dye recorded in Sulfo rhodamine G, Japanese Unexamined Patent Publication 2010-32999 publication and Japanese Patent No. 4492760 publication.

As xanthene dye, preferably comprise the dyestuff of the compound (following, to be sometimes referred to as " compound (1a) ") represented by formula (1a).Compound (1a) also can be its dynamic isomer.

In colored curable resin composition of the present invention, when inclusion compound (1a) is as xanthene dye, the content of the compound (1a) in xanthene dye is preferably more than 50% quality, be more preferably more than 70% quality, more preferably more than 90% quality.Particularly, preferably only use compound (1a) as xanthene dye.

R ⁶and R ⁷represent the alkyl of hydrogen atom or carbon number 1 ~ 6 independently of one another.

A represents the integer of 0 or 1.

X represents halogen atom.

Z ⁺represent ⁺n (R ¹¹) ₄, Na ⁺or K ⁺.

R ⁹and R ¹⁰represent hydrogen atom independently of each other or the univalent saturated hydrocarbon radical of substituent carbon number 1 ~ 20 can be had ,-CH contained in this representative examples of saturated aliphatic alkyl ₂-also can by-O-,-CO-,-NH-or-NR ⁸-replace, R ⁹and R ¹⁰also can bonding mutually, 3 ~ 10 member heterocyclic ring containing nitrogens are formed together with the nitrogen-atoms of their institute's bondings.

As by R ¹~ R ⁴and R ⁸~ R ¹¹the univalent saturated hydrocarbon radical of the carbon number 1 ~ 20 represented, lists the straight-chain alkyl such as methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, dodecyl, cetyl, eicosyl; The branched-chain alkyls such as isopropyl, isobutyl, isopentyl, neopentyl, 2-ethylhexyl; The ester ring type saturated hydrocarbyl of the carbon numbers 3 ~ 20 such as cyclopropyl, cyclopentyl, cyclohexyl, suberyl, ring octyl group, three ring decyls.

R ¹~ R ⁴in carbon number 1 ~ 20 univalent saturated hydrocarbon radical in contained hydrogen atom also can by replacements such as halogen atom such as the aromatic hydrocarbyl of the carbon numbers such as phenyl 6 ~ 10, fluorine atoms.

About R ⁹and R ¹⁰in carbon number 1 ~ 20 univalent saturated hydrocarbon radical in contained hydrogen atom, such as also can be replaced by hydroxyl or halogen atom.

As by R ¹~ R ⁴the monovalence aromatic hydrocarbyl of the carbon number 6 ~ 10 represented, lists phenyl, toluyl groups, xylyl, mesitylene base, propyl group phenyl and butyl phenyl.

As the substituting group that this aromatic hydrocarbyl also can have, list halogen atom ,-R ^8a,-OH ,-OR ^8a,-SO ₃ ^-,-SO ₃h ,-SO ₃ ^-z ⁺,-CO ₂h ,-CO ₂r ^8a,-SR ^8a,-SO ₂r ^8a,-SO ₃r ^8aand-SO ₂nR ^9ar ^10a.Among them, alternatively base, is preferably-SO ₃ ^-,-SO ₃h ,-SO ₃ ^-z _a ⁺and-SO ₂nR ^9ar ^10a, be more preferably-SO ₃ ^-z _a ⁺and-SO ₂nR ^9ar ^10a.As-SO in the case ₃ ^-z _a ⁺, be preferably-SO ₃ ^-+n (R ^11a) ₄.

About comprising R ¹~ R ⁴for the colored curable resin composition of the present invention of the compound (1a) of these groups, the generation of the foreign matter when forming color filter is few, and the excellent heat resistance of the color filter obtained.

As R ¹and R ²the ring formed together with nitrogen-atoms and R ³and R ⁴the ring formed together with nitrogen-atoms, lists following ring.

R ^8a, R ^9aand R ^10arepresent the univalent saturated hydrocarbon radical of carbon number 1 ~ 20 respectively, hydrogen atom contained in this saturated hydrocarbyl also can be replaced by halogen atom.As by R ^8athe saturated hydrocarbyl represented, lists about R ⁸and the straight-chain alkyl exemplified, branched-chain alkyl, ester ring type saturated hydrocarbyl.

As-OR ⁸and-OR ^8a, list the carbon numbers such as methoxyl, ethoxy, propoxyl group, butoxy, amoxy, own oxygen base, heptyl oxygen base, octyl group oxygen base, 2-ethyl hexyl oxy and eicosyl oxygen base respectively and be 1 ~ 20, be preferably the alkoxy of carbon number 1 ~ 8.

As-CO ₂r ⁸and-CO ₂r ^8a, list methoxycarbonyl, ethoxy carbonyl, propoxycarbonyl, tert-butoxycarbonyl, hexyl oxygen base carbonyl and eicosyl oxygen base carbonyl respectively.

As-SR ⁸and-SR ^8a, list methylsulfanyl (sulfanyl), Ethylsulfanyl, butyl sulfanyl, hexyl sulfanyl, decyl sulfanyl and eicosyl sulfanyl respectively.

As-SO ₂r ⁸and-SO ₂r ^8a, list methyl sulphonyl, ethylsulfonyl, butyl sulfonyl, hexyl sulfonyl, decyl sulfonyl and eicosyl sulfonyl respectively.

As-SO ₃r ⁸and-SO ₂r ^8a, list methoxysulfonyl, ethoxysulfonyl, propoxysulfonyl, tert-butoxy sulfonyl, own oxygen base sulfonyl and eicosane oxygen base sulfonyl respectively.

As-SO ₂nR ⁹r ¹⁰and-SO ₂nR ^9ar ^10a, list: sulfamoyl, N-Methylsulfamoyl, N-ethylsulfamovl, N-propylsulfamov, N-isopropylsulfamoyl base, N-Butylsulfamoyl base, N-isobutyl sulfamoyl, N-sec-butyl sulfamoyl, N-tert-butyl group sulfamoyl, N-amyl group sulfamoyl, N-(1-ethyl propyl) sulfamoyl, N-(1,1-dimethyl propyl) sulfamoyl, N-(1,2-dimethyl propyl) sulfamoyl, N-(2,2-dimethyl propyl) sulfamoyl, N-(1-methyl butyl) sulfamoyl, N-(2-methyl butyl) sulfamoyl, N-(3-methyl butyl) sulfamoyl, N-Cyclopentylsulfamoyl base, N-hexyl sulfamoyl, N-(1,3-dimethylbutyl) sulfamoyl, N-(3,3-dimethylbutyl) sulfamoyl, N-heptyl sulfamoyl, N-(1-methylhexyl) sulfamoyl, N-(Isosorbide-5-Nitrae-dimethyl amyl group) sulfamoyl, N-octyl group sulfamoyl, N-(2-ethylhexyl) sulfamoyl, N-(1,5-dimethyl) hexyl sulfamoyl, the monosubstituted sulfamoyls of N-such as N-(1,1,2,2-tetramethyl butyl) sulfamoyl,

N; N-DimethylsuIfamoyl, N; N-ethyl-methyl sulfamoyl, N, N-diethyl amino sulfonyl, N, N-hydroxypropyl methyl sulfamoyl, N; N-isopropyl methyl sulfamoyl, N; N-tertbutyl methyl sulfamoyl, N, N-butyl ethyl sulfamoyl, N, N-two (1-methyl-propyl) sulfamoyl, N; N, the N-bis-such as N-hept-ylmethyl sulfamoyl replace sulfamoyl.

By R ⁹, R ¹⁰, R ^9aand R ^10athe univalent saturated hydrocarbon radical of the carbon number 1 ~ 20 represented also can have substituting group.As this substituting group, list hydroxyl and halogen atom.

R ⁹, R ¹⁰, R ^9aand R ^10aalso can bonding and form 3 ~ 10 member heterocyclic ring containing nitrogens (comprising the heterocycle of the nitrogen-atoms of more than 1 in ring) together with nitrogen-atoms mutually.

As this heterocycle, such as, list following heterocycle.

As R ⁵, be preferably-CO ₂h ,-CO ₂ ^-z ⁺,-CO ₂r ⁸,-SO ₃ ^-,-SO ₃ ^-z ⁺,-SO ₃h and SO ₂nHR ⁹, be more preferably SO ₃ ^-,-SO ₃ ^-z ⁺,-SO ₃h and SO ₂nHR ⁹.

M is preferably the integer of 1 ~ 4, is more preferably 1 and 2.

As by R ⁶and R ⁷the alkyl of the carbon number 1 ~ 6 represented, lists the alkyl of the carbon number 1 ~ 6 among the above-mentioned alkyl enumerated.

As R ⁸and R ¹¹in the aralkyl of carbon number 7 ~ 10, list benzyl, phenylethyl and phenyl butyl.

Z ⁺and Z _a ⁺be respectively ⁺n (R ¹¹) ₄, Na ⁺or K ⁺, be preferably ⁺n (R ¹¹) ₄.

About aforementioned ⁺n (R ¹¹) ₄, preferably 4 R ¹¹among at least 2 be the univalent saturated hydrocarbon radical of carbon number 5 ~ 20, be more preferably the alkyl of carbon number 5 ~ 10.In addition, 4 R ¹¹total carbon number be preferably 20 ~ 80, be more preferably 20 ~ 60.Exist in compound (1a) ⁺n (R ¹¹) ₄when, R ¹¹during for these groups, then can be formed the color filter of few foreign by the colored curable resin composition of the present invention of inclusion compound (1a).

Aforementioned ⁺n (R ^11a) ₄in R ^11apreferably have and R ¹¹carbon number in identical scope.As by R ^11athe object lesson of the saturated hydrocarbyl represented, lists about R ¹¹and the saturated hydrocarbyl exemplified.

As compound (1a), such as, list the compound represented by formula (1-1) ~ formula (1-63).In formula, R ⁸⁶and R ¹⁰⁰represent the univalent saturated hydrocarbon radical of carbon number 1 ~ 20, as its object lesson, list about R ¹¹and the saturated hydrocarbyl exemplified.R ⁸⁶and R ¹⁰⁰be preferably the branched-chain alkyl of carbon number 6 ~ 12, more preferably 2-ethylhexyl.

About compound (1a), preferably R ¹, R ², R ³and R ⁴for the alkyl of hydrogen atom or carbon number 1 ~ 8, R ⁶and R ⁷for hydrogen atom, R ⁵for-SO ₃ ^-,-SO ₃h ,-SO ₃ ^-z ⁺,-SO ₃r ^8bor-SO ₂nR ^9br ^10b(R ^8b, R ^9band R ^10bbe respectively the alkyl of carbon number 1 ~ 4), a is the compound of the formula (1a) of 0, be more preferably the compound of formula (1-41) ~ formula (1-60), be more preferably the compound of formula (1-41), formula (1-43), formula (1-45), formula (1-47), formula (1-49), formula (1-51), formula (1-53), formula (1-55), formula (1-57) and formula (1-59).

Xanthene dye can use commercially available xanthene dye (such as, " ChugaiAminolFastPinkR-H/C " that middle tank formation (strain) is made, " Rhodamin6G " of Taoka Chemical Industries Co. Ltd.).Also by with commercially available xanthene dye for initiation material, with reference to Japanese Unexamined Patent Publication 2010-32999 publication and synthesizing.

Coumarine dye is included in molecule the dyestuff of the compound with coumarin skeleton.As coumarine dye, list 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 Japanese Patent No. 1299948 publication.

Among them, as coumarine dye, the compound (hereinafter sometimes referred to " compound (Ad2) ") preferably represented by formula (Ad2), also comprises its dynamic isomer or their salt.

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

X ^crepresent oxygen atom or sulphur atom.

M ^crepresent hydrogen atom or alkali metal atom.

As by L ^cthe bivalent hydrocanbon radical of the carbon number 1 ~ 20 represented, lists the straight-chain alkyl such as methylene, ethylidene, propylidene, butylidene; The branched-chain alkyl such as isopropylidene, isobutylene; The ester ring type saturated hydrocarbyl of the carbon numbers 3 ~ 20 such as ring propylidene, cyclohexylene; The aromatic hydrocarbyl such as phenylene, naphthylene etc.

L ^cthe bivalent hydrocanbon radical 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 by R ^1Cand R ^2Cthe alkyl of the carbon number 1 ~ 20 represented, lists the straight-chain alkyl such as methyl, ethyl, propyl group, butyl, amyl group, hexyl; The branched-chain alkyls etc. such as isopropyl, isobutyl, 2-ethylhexyl.As this alkyl, be preferably the alkyl of carbon number 1 ~ 8.

As R ^1Cand R ^2Cthe phenyl substituting group that also can have, list halogen atom (fluorine atom etc.), cyano group, nitro, carbamyl, amino-sulfonyl ,-SO ₃m ^c,-CO ₂m ^c, hydroxyl, formoxyl, amino, carbon number 1 ~ 20 the monovalent hydrocarbon alkyl of carbon number 1 ~ 4 (be preferably) etc.

About R ^1Cand R ^2C, the alkyl being preferably carbon number 1 ~ 8 respectively and the phenyl that also can be replaced by the alkyl of carbon number 1 ~ 4.

About by R ^7C~ R ^14Cthe alkyl represented, lists as the R by formula (1a) ¹~ R ⁴and R ⁸~ R ¹¹the saturated hydrocarbyl represented and the straight-chain alkyl, branched-chain alkyl and the ester ring type saturated hydrocarbyl that list, and the aromatic hydrocarbyl such as phenyl, naphthyl.

As by M ^cthe alkali metal atom represented, lists sodium atom, potassium atom etc.

R ^7C~ R ^14Cbe preferably the alkyl of hydrogen atom or carbon number 1 ~ 4 respectively, be more preferably hydrogen atom.

As compound (Ad2), such as, list the compound be expressed from the next.

As the manufacture method of coumarine dye, such as, can according to DyesandPigments (dyestuff and pigment) (2008), the method recorded in 77,556-558. and manufacturing.

Coumarine dye can be the dyestuff of only inclusion compound (Ad2), also can comprise other coumarine dye.Coumarine dye preferably contains compound (Ad2) with the ratio of 70 ~ 100% quality.

About the containing ratio of dyestuff (A-2), relative to the total amount of colorant (A), be preferably 1 ~ 99% quality, be more preferably 2 ~ 95% quality, more preferably 5 ~ 90% quality.

In dyestuff (A-2), xanthene dye compares according to quality criteria with the content of coumarine dye, is generally 60:40 ~ 99:1, is preferably 65:35 ~ 99:1, is more preferably 70:30 ~ 98:2.

About the containing ratio of colorant (A), relative to the total amount of solid content, be preferably 5 ~ 70% quality, be more preferably 10 ~ 60% quality, more preferably 10 ~ 55% quality.When the containing ratio of colorant (A) is in aforementioned range, then can obtain desired light splitting and colour saturation.

" total amount of solid content " refers in this manual, removes the total amount of the composition after solvent (E) from colored curable resin composition of the present invention.The content of the total amount about solid content and each composition relative to it, measures by the known analysis means such as liquid phase chromatography or vapor-phase chromatography.

< resin (B) >

Resin (B) is not particularly limited, but is preferably alkali soluble resin, is more preferably the addition polymer of the structural unit of at least one material in the group having and be derived from and be selected from and be made up of unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides.As such resin, list following resin [K1] ~ [K6] etc.

Resin [K1] is selected from least one (a) (hereinafter sometimes referred to " (a) ") in the group be made up of unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides and has 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) and (b) with can with (a) carry out copolymerization monomer (c) (but, different from (a) and (b).) multipolymer of (hereinafter sometimes referred to " (c) ");

The multipolymer of resin [K3] (a) and (c);

The resin that resin [K4] makes (a) carry out reacting with (b) with the multipolymer of (c) and obtains;

The resin that resin [K5] makes (b) carry out reacting with (a) with the multipolymer of (c) and obtains;

Resin [K6] makes the multipolymer of (b) and (c) and (a) react, and carries out reacting further and the resin that obtains with carboxylic acid anhydrides.

As (a), specifically list: such as, acrylic acid, methacrylic acid, crotonic acid, neighbour, to unsaturated monocarboxylics such as vinyl benzoic acids;

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 dicarboxylics such as 3,6-tetrahydrophthalic acid, dimethyl tetrahydro phthalic acid, Isosorbide-5-Nitrae-cyclohexene dicarboxylic acid;

Methyl-5-norborene-2, the dicyclo unsaturated compound containing carboxyl such as 3-dicarboxylic acid, 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 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) acryloyl-oxyethyl] ester, phthalic acid list [2-(methyl) acryloyl-oxyethyl] ester etc. more than 2 yuan;

The unsaturated acrylate etc. containing hydroxyl and carboxyl in same a part that α-(hydroxymethyl) acrylic acid is such.

Among them, consider with the deliquescent viewpoint of the resin obtained aqueous alkali from the viewpoint of copolyreaction, be preferably acrylic acid, methacrylic acid, maleic anhydride etc.

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

In this manual, what " (methyl) acrylic acid " represented is is selected from the group be made up of acrylic acid and methacrylic acid at least a kind.The token of " (methyl) acryloyl group " and " (methyl) acrylate " etc. also has same meaning.

As (b), list the monomer (b1) (hereinafter sometimes referred to " (b1) ") with Oxyranyle and ethylenic unsaturated bond, the monomer (b2) (hereinafter sometimes referred to " (b2) ") with oxetanylmethoxy and ethylenic unsaturated bond, the monomer (b3) (hereinafter sometimes referred to " (b3) ") etc. with tetrahydrofuran base and ethylenic unsaturated bond.

As (b1), list to have and the unsaturated aliphatic hydrocarbon of straight-chain or branched carried out epoxidation and the monomer of the structure obtained, has and ester ring type unsaturated hydrocarbon is carried out epoxidation and the monomer of the structure obtained.

As (b2), preferably there is the monomer of oxetanylmethoxy and (methyl) acryloxy.As (b2), list: 3-methyl-3-methacryloxymethyl oxetanes, 3-methyl-3-acryloyloxymethyl oxetanes, 3-ethyl-3-methacryloxymethyl oxetanes, 3-ethyl-3-acryloyloxymethyl oxetanes, 3-methyl-3-methacryloxyethyl oxetanes, 3-methyl-3-acryloyl-oxyethyl oxetanes, 3-ethyl-3-methacryloxyethyl oxetanes, 3-ethyl-3-acryloyl-oxyethyl oxetanes etc.

As (b3), preferably there is the monomer of tetrahydrofuran base and (methyl) acryloxy.As (b3), specifically list tetrahydrofurfuryl acrylate (ViscoatV#150, Osaka Organic Chemical Industry Co., Ltd.'s system), tetrahydrofurfuryl methacrylate etc.

As (b), become higher from the viewpoint of reliabilities such as can making the thermotolerance of obtained color filter, chemical-resistant, be preferably (b1).

As (c), list: methyl (methyl) acrylate, ethyl (methyl) acrylate, normal-butyl (methyl) acrylate, sec-butyl (methyl) acrylate, the tert-butyl group (methyl) acrylate, 2-ethylhexyl (methyl) acrylate, dodecyl (methyl) acrylate, lauryl (methyl) acrylate, stearyl (methyl) acrylate, cyclopentyl (methyl) acrylate, cyclohexyl (methyl) acrylate, 2-methylcyclohexyl (methyl) acrylate, three ring [5.2.1.0 ^2,6] decane-8-base (methyl) acrylate (in the art, is called as trivial name " dicyclo pentyl (methyl) acrylate ".In addition, be sometimes referred to as " three ring decyl (methyl) acrylate ".), three ring [5.2.1.0 ^2,6] decene-8-base (methyl) acrylate (in the art, is called as trivial name " double cyclopentenyl (methyl) acrylate ".), (methyl) acrylate such as dicyclo penta alkoxyethyl (methyl) acrylate, isobornyl (methyl) acrylate, adamantyl (methyl) acrylate, allyl (methyl) acrylate, propargyl (methyl) acrylate, phenyl (methyl) acrylate, naphthyl (methyl) acrylate, benzyl (methyl) acrylate;

(methyl) acrylate of the hydroxyls such as 2-hydroxyethyl (methyl) acrylate, 2-hydroxypropyl (methyl) acrylate;

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", two (tert-butoxycarbonyl) dicyclo [2.2.1] hept-2-ene" of 5,6-, the dicyclo unsaturated compounds such as two (cyclohexyl oxygen base carbonyl) dicyclo [2.2.1] hept-2-ene"s of 5,6-,

The dicarbonyl imides derivants such as N-phenylmaleimide, N-N-cyclohexylmaleimide, N-benzyl maleimide, N-succinimido-3-maleimidobenzoate, N-succinimido-4-maleimidobutyric acid ester, N-succinimido-6-maleimidocaproic acid ester, N-succinimido-3-maleimidoproprionic 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.

Among them, from the viewpoint of copolyreaction and thermotolerance, be preferably styrene, vinyltoluene, benzyl (methyl) acrylate, three ring [5.2.1.0 ^2,6] decane-8-base (methyl) acrylate, N-phenylmaleimide, N-N-cyclohexylmaleimide, N-benzyl maleimide, dicyclo [2.2.1] hept-2-ene".

About resin [K1], such as, can described method and the citing document described in the document and manufacture in list of references " 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 1 day March in 1972).

Specifically list following method: be incorporated in reaction vessel by (a) and (b) of ormal weight, polymerization initiator and solvent etc., such as, by with nitrogen by replacement of oxygen, thus be de-oxygen atmosphere, while stir, carry out heating and being incubated.Be explained, polymerization initiator used herein and solvent etc. are not particularly limited, and can use polymerization initiator usually used in this field and solvent.As polymerization initiator, list azo-compound (2,2 '-azoisobutyronitrile, 2,2 '-azo two (2,4-methyl pentane nitrile) etc.) and organic peroxide (benzoyl peroxide etc.), as solvent, if the solvent dissolved by each monomer, solvent (E) as colored curable resin composition of the present invention can be listed and the solvent etc. that describes later.

About obtained multipolymer, can directly use reacted solution, also can use solution that is concentrated or that dilute and obtain, also can use the object that the methods such as utilization precipitates again are taken out in the mode of solid (powder).As the solvent when this polymerization, solvent contained in the colored curable resin composition of the application of the invention, can reacted solution be directly used in the modulation of colored curable resin composition of the present invention, the manufacturing process of colored curable resin composition of the present invention thus can be made to simplify.

As resin (B), specifically list: 3,4-epoxycyclohexyl-methyl (methyl) acrylate/(methyl) acrylic copolymer, 3,4-epoxy radicals three ring [5.2.1.0 ^2.6] resin [K1] such as decyl (methyl) acrylate/(methyl) acrylic copolymer, glycidyl (methyl) acrylate/benzyl (methyl) acrylate/(methyl) acrylic copolymer, glycidyl (methyl) acrylate/styrene/(methyl) acrylic copolymer, 3,4-epoxy radicals three ring [5.2.1.0 ^2.6] decyl (methyl) acrylate/(methyl) acrylic acid/N-N-cyclohexylmaleimide multipolymer, 3,4-epoxy radicals three ring [5.2.1.0 ^2.6] resin [K2] such as decyl (methyl) acrylate/(methyl) acrylic acid/vinyl toluene copolymer, 3-methyl-3-(methyl) acryloyloxymethyl oxetanes/(methyl) acrylic acid/styrol copolymer, the resins [K3] such as benzyl (methyl) acrylate/(methyl) acrylic copolymer, styrene/(methyl) acrylic copolymer, benzyl (methyl) acrylate/tri-ring decyl (methyl) acrylate/(methyl) acrylic copolymer, glycidyl (methyl) acrylate is added and is formed in benzyl (methyl) acrylate/(methyl) acrylic copolymer and the resin obtained, glycidyl (methyl) acrylate is added and is formed in three ring decyl (methyl) acrylate/styrene/(methyl) acrylic copolymers and the resin obtained, glycidyl (methyl) acrylate is added and is formed in three ring decyl (methyl) acrylate/benzyl (methyl) acrylate/(methyl) acrylic copolymers and the resin [K4] such as resin obtained, make the multipolymer of (methyl) acrylic acid and three ring decyl (methyl) acrylate/glycidyl (methyl) acrylate carry out reacting and the resin obtained, make the multipolymer of (methyl) acrylic acid and three ring decyl (methyl) acrylate/styrene/glycidyl (methyl) acrylate carry out reacting and the resin [K5] such as resin obtained, the resin obtained by making the multipolymer of (methyl) acrylic acid and three ring decyl (methyl) acrylate/glycidyl (methyl) acrylate carry out reacting carries out reacting with tetrabydrophthalic anhydride thus the resins such as the resin obtained [K6] etc. further.

Resin (B) is preferably selected from the one in the group be made up of resin [K1], resin [K2] and resin [K3], is more preferably the one in the group being selected from and being made up of resin [K2] and resin [K3].For during these resins, then the developability of colored curable resin composition is excellent.From the view point of the adhesion of the color filter obtained by colored curable resin composition and substrate, more preferably 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.When molecular weight is in aforementioned range, then have following tendency: hardness of film improves, and residual film ratio is also high, unexposed portion is relative to the favorable solubility of developer solution, and 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 according to in and the mode of amount (mg) of the necessary potassium hydroxide of resin (B) 1g carry out the value that measures, such as obtain by using potassium hydroxide aqueous solution to carry out titration.

About the content of resin (B), relative to the total amount of solid content, be preferably 7 ~ 65% quality, be more preferably 13 ~ 60% quality, more preferably 17 ~ 55% quality.When the content of resin (B) is in aforementioned range, then can form colored pattern, have the resolution of colored pattern and the tendency of residual film ratio raising in addition.

< polymerizable compound (C) >

Polymerizable compound (C) is the compound that can utilize the living radical that produced by polymerization initiator (D) and/or acid and polymerization.As this polymerizable compound (C), list the compound etc. of the ethylenic unsaturated bond with polymerism, be preferably (methyl) acrylate compounds.

As the polymerizable compound with 1 ethylenic unsaturated bond, such as, list: nonyl phenyl carbitol acrylate, 2-hydroxyl-3-phenoxypropylacrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxy ethyl methacrylate, NVP etc. and, above-mentioned (a), (b) and (c).

As the polymerizable compound with 2 ethylenic unsaturated bonds, such as list two (acryloyl-oxyethyl) ether, 3-methyl pentanediol two (methyl) acrylate etc. of 1,6-hexanediol two (methyl) acrylate, ethylene glycol bisthioglycolate (methyl) acrylate, neopentyl glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, bisphenol-A.

Polymerizable compound (C) preferably has the polymerizable compound of the ethylenic unsaturated bond of more than 3.As such polymerizable compound, such as, list trimethylolpropane tris (methyl) acrylate, 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) acryloyl-oxyethyl) 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, dipentaerythritol five (methyl) acrylate and dipentaerythritol six (methyl) acrylate is preferably.

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

About the content of polymerizable compound (C), relative to the total amount of solid content, be preferably 7 ~ 65% quality, be more preferably 13 ~ 60% quality, more preferably 17 ~ 55% quality.

About the content ratio [resin (B): polymerizable compound (C)] of resin (B) with polymerizable compound (C), be preferably 20:80 ~ 80:20 according to quality criteria, be more preferably 35:65 ~ 80:20.

When the content of polymerizable compound (C) is in aforementioned range, then have colored pattern formed time residual film ratio and color filter chemical-resistant improve tendency.

< polymerization initiator (D) >

About polymerization initiator (D), if produce living radical, acid etc. by the effect of light and heat, the compound of initiated polymerization then can not be particularly limited to, and can use known polymerization initiator.

As polymerization initiator (D), list O-acyl group oxime compound, alkyl phenones compound, united imidazole, triaizine compounds and acylphosphine oxide compound etc.

As O-acyl group oxime compound, list N-benzoyloxy-1-(4-Phenylsulfanyl phenyl) butane-1-ketone-2-imines, N-benzoyloxy-1-(4-Phenylsulfanyl phenyl) octane-1-ketone-2-imines, N-benzoyloxy-1-(4-Phenylsulfanyl phenyl)-3-cyclopentyl third-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-dioxolane ylmethyl 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 third-1-ketone-2-imines etc.Also Irgacure (registered trademark) OXE01, OXE02 (more than, BASF AG's system) can be used, the commercially available products such as N-1919 (ADEKA Inc.).Wherein, preferably be selected from least a kind in the group be made up of N-benzoyloxy-1-(4-Phenylsulfanyl phenyl) butane-1-ketone-2-imines, N-benzoyloxy-1-(4-Phenylsulfanyl phenyl) octane-1-ketone-2-imines and N-benzoyloxy-1-(4-Phenylsulfanyl phenyl)-3-cyclopentyl third-1-ketone-2-imines, be more preferably N-benzoyloxy-1-(4-Phenylsulfanyl phenyl) octane-1-ketone-2-imines.

As alkyl phenones compound, list 2-methyl-2-morpholinyl-1-(4-methylsulfanyl phenyl)-1-acetone, 2-dimethylamino-1-(4-morpholino phenyl)-2-benzyl-1-butanone, 2-(dimethylamino)-2-[(4-aminomethyl phenyl) methyl]-1-[4-(4-morpholinyl) phenyl]-1-butanone, 2-hydroxy-2-methyl-1-phenyl-1-acetone, 2-hydroxy-2-methyl-1-[4-(2-hydroxyl-oxethyl) phenyl]-1-acetone, 1-hydroxycyclohexylphenylketone, the oligomer of 2-hydroxy-2-methyl-1-(4-isopropenyl phenyl)-1-acetone, α, α-diethoxy acetophenone, benzyl dimethyl ketal etc.Also the commercially available products such as Irgacure (registered trademark) 369,907,379 (more than, BASF AG's system) can be used.

As united imidazole, list 2,2 '-bis-(2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-bis-(2,3-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline is (with reference 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 (with reference to Japanese Patent Publication 48-38403 publication, Japanese Laid-Open Patent Publication 62-174204 publication etc.), 4,4 ', 5, the imidazolium compounds (with reference to Japanese Unexamined Patent Publication 7-10913 publication etc.) etc. that the phenyl alkoxy carbonyl (carboalkoxy) of 5 '-position replaces.Wherein, the compound preferably represented by following formula and their potpourri.

As triaizine compounds, list 2, 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-lignocaine-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, list TMDPO etc.

Further, as polymerization initiator (D), the benzoin compounds such as benzoin, benzoin methylether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether are listed; Benzophenone, o-benzoyl yl benzoic acid methyl esters, 4-phenyl benzophenone, 4-benzoyl-4 '-methyldiphenyl sulfide, 3,3 ', 4,4 '-four (t-butylperoxycarbonyl) 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 ketone, benzyl, phenylglyoxalates methyl esters, luxuriant titanium (titanocene) compound etc.They preferably cause auxiliary agent (D1) (particularly aminated compounds) and carry out combining with described later polymerization and use.

Polymerization initiator (D) preferably comprises the polymerization initiator of at least one in the group being selected from and being made up of alkyl phenones compound, triaizine compounds, acylphosphine oxide compound, O-acyl group oxime compound and united imidazole, is more preferably the polymerization initiator comprising O-acyl group oxime compound.

About the content of polymerization initiator (D), relative to total amount 100 mass parts of resin (B) and polymerizable compound (C), be preferably 0.1 ~ 40 mass parts, be more preferably 1 ~ 30 mass parts.

< polymerization causes auxiliary agent (D1) >

Polymerization causes auxiliary agent (D1): in order to promote to have caused the polymerization of the polymerizable compound of polymerization and the compound that uses or sensitizer by polymerization initiator.When comprising polymerization initiation auxiliary agent (D1), usual and polymerization initiator (D) carries out combining and using.

Cause auxiliary agent (D1) as polymerization, list aminated compounds, alkoxy anthracene compound, thioxanthone compounds and carboxylic acid compound etc.

As aminated compounds, list triethanolamine, 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 be preferably 4, 4 '-bis-(diethylamino) benzophenone.Also the commercially available products such as EAB-F (Baotugu Chemical Industrial Co., Ltd's system) can be used.

As alkoxy anthracene compound, list 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.

As thioxanthone compounds, list ITX, ITX, 2,4-diethyl thioxanthones, 2,4-bis-clopenthixal ketones, the chloro-4-propoxythioxanthone of 1-etc.

As carboxylic acid compound, list Phenylsulfanyl acetic acid, methyl phefzylsulfanyl acetic acid, ethylphenyl sulfanyl acetic acid, Methylethyl phenyl sulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, methoxyphenyl sulfanyl acetic acid, Dimethoxyphenyl sulfanyl acetic acid, chlorophenylsulfanyl acetic acid, dichlorophenyl sulfanyl acetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthio acetic acid, N-naphthyl glycocoll, naphthoxy acetic acid etc.

When using these polymerizations to cause auxiliary agent (D1), about its content, relative to total amount 100 mass parts of resin (B) and polymerizable compound (C), be preferably 0.1 ~ 30 mass parts, be more preferably 1 ~ 20 mass parts.When the amount of polymerization initiation auxiliary agent (D1) is within the scope of this, then can form colored pattern with high sensitivity further, the throughput rate of color filter is tended to improve.

< solvent (E) >

Solvent (E) is not particularly limited, and can use normally used solvent in this field.Such as, list ester solvent and (in molecule, comprise-COO-, do not comprise the solvent of-O-), ether solvents (comprises-O-in molecule, do not comprise the solvent of-COO-), ether-ether solvent (comprising the solvent of-COO-and-O-in molecule), ketone solvent (comprise-CO-in molecule, do not comprise the solvent of-COO-), alcoholic solvent (comprise OH in molecule, do not comprise the solvent of-O-,-CO-and-COO-), aromatic hydrocarbon solvents, amide solvent, dimethyl sulfoxide (DMSO) etc.

As ester solvent, list 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, adnoral acetate, gamma-butyrolacton etc.

As ether solvents, list glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, TC, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl, 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 methyl ethyl ether, diethylene glycol dipropyl ether, dibutyl ethylene glycol ether, methyl phenyl ethers anisole, phenetol, methylanisole etc.

As ether-ether solvent, list methoxy menthyl acetate, 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, butyl carbitol acetate, dipropylene glycol methyl ether acetic acid esters etc.

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

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

As aromatic hydrocarbon solvents, list benzene,toluene,xylene, mesitylene etc.

As amide solvent, list DMF, DMA, 1-METHYLPYRROLIDONE etc.

These solvents can apply separately also can and use two or more.

Wherein, be preferably propylene glycol methyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, 3-ethoxyl ethyl propionate, glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, TC, 3-methoxybutyl acetic acid esters, 3-methoxyl-n-butyl alcohol, 4-hydroxy-4-methyl-2-pentanone, N, dinethylformamide, 1-METHYLPYRROLIDONE etc., be more preferably propylene glycol methyl ether acetate, propylene glycol monomethyl ether, ethylene glycol monobutyl ether, dipropylene glycol methyl ether acetic acid esters, ethyl lactate, 3-methoxybutyl acetic acid esters, 3-methoxyl-n-butyl alcohol, 3-ethoxyl ethyl propionate, 1-METHYLPYRROLIDONE etc.

About the content of solvent (E), relative to the total amount of colored curable resin composition, be preferably 70 ~ 95% quality, be more preferably 75 ~ 92% quality.In other words, the solid content of colored curable resin composition is preferably 5 ~ 30% quality, is more preferably 8 ~ 25% quality.

When the content of solvent (E) is in aforementioned range, then planarization when being coated with improves, and when defining color filter, colour saturation can not be not enough in addition, thus has the tendency that display characteristic becomes good.

< levelling agent (F) >

In colored curable resin composition of the present invention, also can comprise levelling agent (F).

As levelling agent (F), list silicone type surface active agent, fluorine system surfactant and there is the silicone type surface active agent etc. of fluorine atom.They also can have polymerizable group at side chain.

As silicone type surface active agent, list the surfactant etc. in molecule with siloxane bond.Specifically, list ToraysiliconeDC3PA, ToraysiliconeSH7PA, ToraysiliconeDC11PA, ToraysiliconeSH21PA, ToraysiliconeSH28PA, ToraysiliconeSH29PA, ToraysiliconeSH30PA, ToraysiliconeSH8400 (trade name: eastern beautiful DOW CORNING (strain) system), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (Shin-Etsu Chemial Co., Ltd's system), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460 (stepping co-partnership company of figure new high-tech material Japan system) etc.

As fluorine system surfactant, list the surfactant etc. in molecule with fluorocarbon chain.Specifically list: Fluorad (registered trademark) FC430, FluoradFC431 (Sumitomo 3M (strain) system), Megafac (registered trademark) F142D, MegafacF171, MegafacF172, MegafacF173, MegafacF177, MegafacF183, MegafacF554, MegafacR30, MegafacRS-718-K (D1C (strain) system), F-TOP (registered trademark) EF301, F-TOPEF303, F-TOPEF351, F-TOPEF352 (MitsubishiMaterialsElectronicChemicals (strain) system), Surflon (registered trademark) S381, SurflonS382, SurflonSC101, SurflonSC105 (Asahi Glass (strain) system) and E5844 ((strain) DaikinFineChemical studies made) etc.

As the silicone type surface active agent with fluorine atom, list the surfactant etc. in molecule with siloxane bond and fluorocarbon chain.Specifically, Megafac (registered trademark) R08, MegafacBL20, MegafacF475, MegafacF477 and MegafacF443 (D1C (strain) system) etc. are listed.

About the content of levelling agent (F), relative to the total amount of colored curable resin composition, be preferably below more than 0.001% quality 0.2% quality, be preferably below more than 0.002% quality 0.1% quality, be more preferably below more than 0.005% quality 0.07% quality.When the content of levelling agent (F) is in aforementioned range, then the planarization of color filter can be made good.

Other composition > of <

In colored curable resin composition of the present invention, also can comprise filling agent, other macromolecular compound, contiguity promoter, antioxidant, light stabilizer, chain-transferring agent etc. adjuvant well known in the art as required.

The manufacture method > of < colored curable resin composition

About colored curable resin composition of the present invention, such as, by 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) and other composition are mixed thus modulation.

About red pigment, preferably in advance part or all with solvent (E) of this pigment is mixed, use ball mill etc. to carry out disperseing until the mean grain size of this pigment becomes about less than 0.2 μm.

Now, also can as required compounding pigment dispersing agent, resin (B) part or all.By the mode of remaining composition according to the concentration becoming regulation being mixed in the dispersible pigment dispersion obtained by operating like this, thus the colored curable resin composition of target can be modulated.

About dyestuff (A-2), be preferably dissolved in part or all of solvent (E) in advance and modulate solution.Preferably by the filtrator in about 0.01 ~ 1 μm, aperture, this solution is filtered.

Preferably by the filtrator in about 0.01 ~ 10 μm, aperture, mixed colored curable resin composition is filtered.

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 the film with colored pattern, also can be painted film described later.

As the method being manufactured colored pattern by colored curable resin composition of the present invention, list photoetching process, ink-jet method, print process etc.Wherein, photoetching process is preferably.

Photoetching process is: aforementioned colored curable resin composition is coated substrate, drying and form coloring compositions nitride layer, this coloring compositions nitride layer is exposed via photomask, thus the method for development.In photolithography, by not using photomask when exposure, and/or do not develop, thus the painted film of the solidfied material as above-mentioned coloring compositions nitride layer can be formed.

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

As substrate, quartz glass, pyrex, alumina silicate glass can be used, silica-coating is carried out on surface and the glass plate of soda-lime glass obtained etc., or the resin plate such as polycarbonate, polymethylmethacrylate, polyethylene terephthalate, silicon, aforesaid base plate forms aluminium, silver, silver/copper/palldium alloy film etc. and the substrate obtained.On these substrates, also can form other color-filter layer, resin bed, transistor, circuit etc.

About the formation based on photolithographic color filter, known or usual device and condition can be utilized to carry out.Such as can operate as following and make.

First, colored curable resin composition is coated on substrate, by carrying out heat drying (prebake conditions) and/or drying under reduced pressure and removing the volatile ingredients such as solvent thus dry, obtain level and smooth coloring compositions nitride layer.

As coating process, list spin-coating method, slit coating method, slit spin-coating method etc.

Temperature when carrying out heat drying is preferably 30 ~ 120 DEG C, is more preferably 50 ~ 110 DEG C.Heat time is preferably 10 seconds ~ 60 minutes in addition, is more preferably 30 seconds ~ 30 minutes.

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

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

Then, coloring compositions nitride layer exposes via the photomask of the colored pattern for the formation of target.Pattern on this photomask is not particularly limited, and can use the pattern of the purposes corresponding to target.

As the light source used in exposure, be preferably and produce the light source that wavelength is the light of 250 ~ 450nm.Such as, the wave filter that this wavelength region may is removed can be removed by using for the light less than 350nm, or also by using the bandpass filter (band-passfilter) these wavelength region may can taken out optionally to be taken out by the light near 436nm, near 408nm, near 365nm.Specifically, mercury vapor lamp, light emitting diode, metal halide lamp, Halogen lamp LED etc. are listed.

For irradiating parallel rays equably to plane of exposure entirety, or carrying out aligned in position accurately with the substrate being formed with photomask and coloring compositions nitride layer, preferably using the exposure device such as mask aligner and stepping exposure machine (stepper).

Develop by making the coloring compositions nitride layer after exposure be contacted with developer solution, thus form colored pattern on substrate.By development, the unexposed portion of coloring compositions nitride layer is made to be dissolved in developer solution and to remove.As developer solution, be preferably the aqueous solution of the alkali compounds such as potassium hydroxide, sodium bicarbonate, sodium carbonate, tetramethyl ammonium hydroxide.Concentration in the aqueous solution of alkali compounds is preferably 0.01 ~ 10% quality, is more preferably 0.03 ~ 5% quality.Further, developer solution also can comprise surfactant.

Developing method can be revolve the either method covered in submergence (puddle) method, infusion method and spray-on process etc.Also can when developing, substrate be tilted for arbitrary angle further.

After development, preferably wash.

Further, preferably rear baking (post-bake) is carried out to obtained coloring compositions nitride layer.Rear baking temperature is preferably 150 ~ 250 DEG C, is more preferably 160 ~ 235 DEG C.Post-bake times is preferably 1 ~ 120 minute, is more preferably 10 ~ 60 minutes.

According to the present invention, the colored curable resin composition of the color filter that can manufacture solvent resistance and/or excellent heat resistance can be provided.The color filter formed by colored curable resin composition of the present invention is also included within category of the present invention.

This color filter is preferably applied to display device (liquid crystal indicator, organic el device, Electronic Paper etc.) and solid-state imager.

Embodiment

Next enumerate embodiment and illustrate the present invention further.So long as not special record, " % " and " part " in example is % quality and mass parts.

In following synthesis example, the structure of compound utilizes NMR (JMM-ECA-500; Jeol Ltd.'s system) identify.

About the weight-average molecular weight (Mw) of the polystyrene conversion of resin and the mensuration of number-average molecular weight (Mn), GPC method is utilized to carry out under the following conditions.

Device: HLC-8120GPC (eastern Cao (strain) system)

Chromatographic column: TSK-GELG2000HXL

Chromatogram column temperature: 40 DEG C

Solvent: tetrahydrofuran [THF]

Flow velocity: 1.0mL/ minute

Test solution solid concentration; 0.001 ~ 0.01% quality

Injection rate IR: 50 μ L

Detecting device: R1

Correction standard substance: TSKSTANDARDPOLYSTYRENE (TSK polystyrene standard)

F-40、F-4、F-288、A-2500、A-500

(eastern Cao (strain) system)

Using the ratio (Mw/Mn) of the weight-average molecular weight through polystyrene conversion that obtains in above-mentioned and number-average molecular weight as molecular weight distribution.

Synthesis example 1

By two (3-amino-4-hydroxylphenyl) HFC-236fa 10.1 parts and methyl alcohol 51 parts mixing, stir and add 3-ethoxy-3-iminopropanoate hydrochloride 12.6 parts below 5 DEG C.Thereafter, reaction mixture is stirred only 5 hours below 10 DEG C, at room temperature stir only 24 hours, stir only 24 hours at 60 DEG C.After above-mentioned reaction mixture is cooled to room temperature, add 300 parts, water and 270 parts, ethyl acetate, divide and get ethyl acetate layer.In water layer, add 135 parts, ethyl acetate, divide and get ethyl acetate layer.In water layer, add 135 parts, ethyl acetate, divide and get ethyl acetate layer.Ethyl acetate layer is merged, carries out 3 washings with 300 parts, water, by dried over mgso, filter.The distillation of the solvent of filtrate is removed and obtains residue.Utilize column chromatography to be refined by this residue, obtain the compound 14.5 parts represented by formula (pt1).

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

(mass spectrophotometry) ionization mode (mode)=ESI+:m/z=[M+H] ⁺559.1

Accurate molecular weight (ExactMass): 558.1

In a nitrogen atmosphere, by dimethyl sulfoxide (DMSO) 75 parts, the mixing of 8.45 parts, potassium hydroxide, at room temperature stir 0.5 hour.In this potpourri, add 3-methoxyl diphenylamine 25 parts, at room temperature stir 0.5 hour.To in this potpourri, add iodoethane 21.5 parts, at room temperature stir 2 hours.In obtained potpourri, add 4.23 parts, potassium hydroxide, at room temperature stir after 1 hour, add iodoethane 10.8 parts, at room temperature stir 12 hours.In obtained potpourri, add 4.23 parts, potassium hydroxide, at room temperature stir after 1 hour, add iodoethane 10.8 parts, at room temperature stir 2 hours.In obtained potpourri, add 4.23 parts, potassium hydroxide, at room temperature stir after 1 hour, add iodoethane 10.8 parts, at room temperature stir 13 hours.In obtained potpourri, add 158 parts, water and 135 parts, ethyl acetate, divide and get ethyl acetate layer.In water layer, add 90 parts, ethyl acetate, divide and get ethyl acetate layer.Ethyl acetate layer is merged, has carried out 3 washings with 100 parts, water.With magnesium sulfate, this ethyl acetate solution is dry, filter.The distillation of the solvent of this filtrate is removed and obtains the compound 28.4 parts represented by formula (pt3-1).

The qualification > of the compound that < is represented by formula (pt3-1)

(mass spectrophotometry) ionization mode=ESI+:m/z=[M+H] ⁺228.1

Accurate molecular weight: 227.1

In a nitrogen atmosphere, the compound 28.4 parts represented by formula (pt3-1) and methylene chloride 302 parts is mixed.While this mixed liquor is remained 4 ~ 10 DEG C, add Boron tribromide 44.8 parts, then at room temperature stir 12 hours.While added by obtained potpourri in the potpourri of 341 parts, water and methylene chloride 302 parts, 341 parts, water and the temperature of the potpourri of methylene chloride 302 parts are remained 4 ~ 19 DEG C.This potpourri is at room temperature stirred 2 hours, divides and get dichloromethane layer.With 10wt% saline solution 227 parts, 4 washings are carried out to this dichloromethane solution, by dried over mgso, filter.The distillation of the solvent of this filtrate is removed thus obtained the compound 23.3 parts represented by formula (pt4-1).

The qualification > of the compound that < is represented by formula (pt4-1)

(mass spectrophotometry) ionization mode=ESI+:m/z=[M+H] ⁺214.1

Accurate molecular weight: 213.1

In a nitrogen atmosphere, temperature is remained 6 ~ 15 DEG C, while phosphoryl chloride phosphorus oxychloride 25.1 parts is added DMF 47.7 parts.While the temperature of this potpourri is remained 6 ~ 25 DEG C, in this potpourri, add the potpourri of compound 23.3 parts and the DMF 31.4 parts represented by formula (pt4-1).After this potpourri being stirred 2 hours at 40 DEG C, be cooled to room temperature.While temperature to be remained the potpourri that obtained potpourri is added 48wt% sodium hydrate aqueous solution 109 parts and 410 parts, water by 14 ~ 19 DEG C, stir 1 hour.While temperature is remained 12 ~ 17 DEG C, in obtained potpourri, add 35wt% hydrochloric acid 67.2 parts.To in obtained potpourri, add 210 parts, ethyl acetate and zeyssatite (celite), filter.With 10wt% saline solution 233 parts, obtained filtrate is washed twice, by dried over mgso, filter.The distillation of the solvent of obtained filtrate is removed and obtains residue.Utilize column chromatography to be refined by this residue, obtain the compound 23.9 parts represented by formula (pt5-1).

The qualification > of the compound that < is represented by formula (pt5-1)

(mass spectrophotometry) ionization mode=ESI+:m/z=[M+H] ⁺242.1

Accurate molecular weight: 241.1

In a nitrogen atmosphere, the compound 10.9 parts represented by formula (pt5-1), the compound 12.0 parts represented by formula (pt1), piperidines 0.915 part and toluene 83.8 parts is mixed with.

At 100 DEG C, this potpourri is stirred 19 hours.The distillation of the solvent of this mixed liquor is removed and obtains residue.

Utilize column chromatography to be refined by this residue, obtain the compound 10.6 parts represented by formula (Ad2-12).

The qualification > of the compound that < is represented by formula (Ad2-12)

¹H-NMR(CDCl ₃，270MHz)δ1.31(6H)，3.84(4H)，6.58-6.61(4H)，7.16-7.24(4H)，7.31-7.39(6H)，7.46-7.52(4H)，7.55(2H)，7.99(2H)，8.63(2H)

Synthesis example 2

By 2,4-xylidin 42.4 parts, triethylamine 35.4 parts and DMF 132 parts mixing, stir at 50 DEG C.While the temperature of this potpourri is remained 50 ~ 60 DEG C, add iodoethane 56.8 parts, thereafter, stir 65 hours at 60 DEG C.After this potpourri is cooled to room temperature, add 1000 parts, water and toluene 433 parts, divide and get toluene layer.With saturated sodium-chloride water solution 1000 parts, this toluene layer is carried out 3 washings, then utilize Rotary Evaporators to distill and remove solvent.Utilize column chromatography to be refined by obtained residue, obtain the compound 18.8 parts represented by formula (pt2-2).

The qualification > of the compound that < is represented by formula (pt2-2)

(mass spectrophotometry) ionization mode=ESI+:m/z=[M+H] ⁺150.1

Accurate molecular weight: 149.1

In a nitrogen atmosphere, the compound 29.8 parts that will be represented by formula (pt2-2), 3-bromobenzene methyl ether 37.4 parts, acid chloride (II) 1.35 parts, potassium tert-butoxide 33.7 parts, 2,8,9-triisopropyl-2,5,8,9-tetra-azepine-1-phosphabicyclo [3.3.3] undecane (1M toluene solution) 3.42 parts and toluene 520 parts mixing, stir 6 hours at 100 DEG C.After this mixed liquor is cooled to room temperature, be incorporated in 1000 parts, water.After this mixed liquor is filtered, divide and get toluene layer.This toluene solution saturated sodium bicarbonate aqueous solution is washed, by dried over mgso, then filters.Utilize Rotary Evaporators this filtrate to be carried out solvent distillation to remove, utilize column chromatography to be refined by obtained residue, obtain the compound 41.9 parts represented by formula (pt3-2).

The qualification > of the compound that < is represented by formula (pt3-2)

(mass spectrophotometry) ionization mode=ESI+:m/z=[M+H] ⁺256.2

Accurate molecular weight: 255.2

In synthesis example 1, by the compound represented by formula (pt3-1) instead of the compound represented by formula (pt3-2), in addition, implement in the same manner as synthesis example 1, thus obtain the compound represented by formula (pt4-2), formula (pt5-2) and formula (Ad2-14).

The qualification > of each compound of <

The compound represented by formula (pt4-2)

(mass spectrophotometry) ionization mode=ESI+:m/z=[M+H] ⁺242.2

Accurate molecular weight: 241.2

The compound represented by formula (pt5-2)

(mass spectrophotometry) ionization mode=ESI+:m/z=[M+H] ⁺270.2

Accurate molecular weight: 269.1

The compound represented by formula (Ad2-14)

¹H-NMR(CDCl ₃，270MHz)δ1.30(6H)，2.09(6H)，2.39(6H)，3.59(2H)，3.86(2H)，6.42(4H)，7.00(2H)，7.12(2H)，7.18(2H)，7.30-7.37(4H)，7.54(2H)，7.98(2H)，8.62(2H)

Synthesis example 3

By 4-(dibutylamino) salicylide (2.49g, 10mmol), cyan-acetic ester (1.13g, 10mmol) and 2,2-two (3-amino-4-hydroxylphenyl) HFC-236fa (1.83g, 5mmol) is dissolved in n-amyl alcohol (22g, 250mmol), adds benzoic acid (0.41g, 3.4mmol) and stirs 7 hours at 135 DEG C under nitrogen flowing.After reaction terminating, n-amyl alcohol decompression distillation is removed, residue is dissolved in toluene and washes with water.Concentrated after being utilized by toluene layer sodium sulphate to carry out drying, refine with silica gel column chromatography (hexane/ethyl acetate), thus obtain with the yield of 30% compound (1.39g, 1.5mmol) represented by formula (4-44).Utilize ¹h-NMR and confirm the structure of the compound represented by formula (Ad2-11).

The qualification > of the compound that < is represented by formula (Ad2-11)

¹H-NMR(400MHz，CDCl ₃)：0.99(12H，t)，1.36-1.42(8H，m)，1.59-1.67(8H，m)，3.37(8H，t)，6.51(2H，d)，6.63(2H，dd)，7.32(2H，d)，7.41(2H，d)，7.54(2H，d)，7.99(2H，s)，8.61(2H，s)

Synthesis example 4

By two (3-amino-4-hydroxylphenyl) sulfone 4.98 parts and methyl alcohol 28.1 parts mixing, stir and add 3-ethoxy-3-iminopropanoate hydrochloride 8.18 parts lentamente below 10 DEG C.Thereafter, reaction mixture is stirred only 7 hours below 10 DEG C, at room temperature stir only 24 hours, stir only 24 hours at 60 DEG C.After above-mentioned reaction mixture is cooled to room temperature, the crystallization of precipitation obtains as the residue of suction filtration.With this residue of methanol wash, at 60 DEG C of drying under reduced pressure, thus obtain the compound 6.77 parts represented by formula (pt2).

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

(mass spectrophotometry) ionization mode=ESI+:m/z=[M+H] ⁺473.1

Accurate molecular weight: 472.1

By 2,4-xylidin 42.4 parts (0.35 mole), triethylamine 35.4 parts (0.35 mole) and DMF 132 parts mixing, stir at 50 DEG C.While the temperature of this potpourri is remained 50 ~ 60 DEG C, add 1-bromo-2-ethyl hexane 70.2 parts (0.364 mole), thereafter, stir 65 hours at 60 DEG C.After this potpourri is cooled to room temperature, add 1000 parts, water and toluene 433 parts, divide and get toluene layer.

With saturated sodium-chloride water solution 1000 parts, this toluene layer is carried out 3 washings, then utilize Rotary Evaporators and distill removal solvent.Utilize column chromatography to be refined by obtained residue, obtain the compound 50.6 parts represented by formula (pt2-1).

The qualification > of the compound that < is represented by formula (pt2-1)

(mass spectrophotometry) ionization mode=ESI+:m/z=[M+H] ⁺234.2

Accurate molecular weight: 233.2

In a nitrogen atmosphere, the compound 46.7 parts (0.2 mole) that will be represented by formula (pt2-1), 3-bromobenzene methyl ether 37.4 parts (0.2 mole), acid chloride (II) 1.35 parts (0.006 mole), 33.7 parts, tert-butyl alcohol potassium (0.3 mole), 2,8,9-triisopropyl-2,5,8,9-tetra-azepine-1-phosphabicyclo [3.3.3] undecane (1.0M toluene solution) 3.42 parts (0.01 moles) and toluene 520 parts mixing, stir 6 hours at 100 DEG C.After this mixed liquor is cooled to room temperature, be incorporated in 1000 parts, water.

After this mixed liquor is filtered, divide and get toluene layer.With saturated sodium bicarbonate aqueous solution, this toluene solution is washed, by dried over mgso, then filter.Utilize Rotary Evaporators this filtrate to be carried out solvent distillation to remove, utilize column chromatography to be refined by obtained residue, obtain the compound 30.9 parts represented by formula (pt3-3).

The qualification > of the compound that < is represented by formula (pt3-3)

(mass spectrophotometry) ionization mode=ESI+:m/z=[M+H] ⁺340.3

Accurate molecular weight: 339.3

In a nitrogen atmosphere, the compound 17.0 parts (0.05 mole) represented by formula (pt3-3) and methylene chloride 199 parts is mixed.While this mixed liquor is remained 15 ~ 23 DEG C, add Boron tribromide (1.0M dichloromethane solution), make Boron tribromide only identical with the number (0.05 mole) of the compound molal quantity represented by formula (pt3-3).Thereafter, this mixed liquor is at room temperature stirred 8 hours.

This potpourri is incorporated in frozen water 250 parts, divides and get dichloromethane layer.With 250 parts, water, this dichloromethane layer is washed, by dried over mgso, thus filter.Utilize Rotary Evaporators that the distillation of obtained filtrate is eliminated solvent.Utilize column chromatography to be refined by obtained residue, obtain the compound 13.9 parts represented by formula (pt4-3).

The qualification > of the compound that < is represented by formula (pt4-3)

(mass spectrophotometry) ionization mode=ESI+:m/z=[M+H] ⁺326.3

Accurate molecular weight: 325.2

Be mixed with the compound 13.9 parts (0.0427 mole) and DMF 26.4 parts that are represented by formula (pt4-3).While this mixed liquor is remained 23 ~ 55 DEG C, add phosphoryl chloride phosphorus oxychloride 13.1 parts (0.0854 mole).Thereafter, this potpourri is stirred 6 hours at 60 DEG C.After this potpourri is cooled to room temperature, is incorporated in frozen water 150 parts, neutralizes with 48% sodium hydrate aqueous solution.In this potpourri, add 300 parts, ethyl acetate, filter, divide from obtained filtrate and get ethyl acetate layer.With 300 parts, water, this ethyl acetate solution is washed, by dried over mgso, filter.Utilize Rotary Evaporators that solvent is removed in the distillation of obtained filtrate.Utilize column chromatography to be refined by obtained residue, obtain the compound 11.6 parts represented by formula (pt5-3).

The qualification > of the compound that < is represented by formula (pt5-3)

(mass spectrophotometry) ionization mode=ESI+:m/z=[M+H] ⁺354.2

Accurate molecular weight: 353.2

In a nitrogen atmosphere, the compound 9.65 parts (0.0273 mole) represented by formula (pt5-3), the compound 6.14 parts (0.013 mole) represented by formula (pt2), piperidines 0.553 part (0.0065 mole) and toluene 51.1 parts is mixed with.At 100 DEG C, this potpourri is stirred 19 hours.This mixed liquor is incorporated in methyl alcohol 231 parts.The sediment produced is obtained by removing supernatant.Add methyl alcohol 231 parts stirring in this sediment after, this mixed liquor of suction filtration.Wash the residue obtained with methyl alcohol 20 parts, the residue as suction filtration obtains.Utilize column chromatography to be refined by this residue, obtain the compound 9.1 parts represented by formula (Ad2-2).

The qualification > of the compound that < is represented by formula (Ad2-2)

¹H-NMR(CDCl ₃，270MHz)δ0.82-0.92(12H，m)，1.26-1.52(16H，brm)，1.77(2H，brs)，2.05(6H，s)，2.38(6H，s)，3.32-3.42(2H，m)，3.71-3.78(2H，m)，6.42-6.45(4H，m)，7.02(2H，d)，7.11(2H，d)，7.15(2H，s)，7.33(2H，d)，7.66(2H，d)，7.96(2H，dd)，8.39(2H，d)，8.62(2H，s)

Synthesis example 5

1-bromo-2-ethyl hexane is replaced by 1-bromooctane, in addition, operate in the same manner as synthesis example 1, thus obtain the compound represented by formula (pt2-3), formula (pt3-3), formula (pt4-4), formula (pt5-4) and formula (Ad2-4).

The qualification > of the compound that < is represented by formula (pt2-3), formula (pt3-3), formula (pt4-4) and formula (pt5-4)

Table 1

The qualification > of the compound that < is represented by formula (Ad2-4)

¹H-NMR(CDCl ₃，270MHz)δ0.88(6H，t)，1.28-1.32(20H，m)，1.72(4H，brs)，2.07(6H，s)，2.38(6H，s)，3.44(2H，brm)，3.77(2H，brm)，6.39(4H，brs)，6.99(2H，d)，7.12(2H，d)，7.17(2H，s)，7.34(2H，d)，7.66(2H，d)，7.96(2H，dd)，8.39(2H，d)，8.62(2H，s)

Synthesis example 6

By resorcinol (Tokyo HuaCheng Industry Co., Ltd's system) 275 parts and n-hexylamine (Tokyo HuaCheng Industry Co., Ltd's system) 101 parts mixing, remove at 150 ~ 155 DEG C the water generated and stir 20 hours.After cooling, reaction mixture is dissolved in toluene 433 parts, with 1000 parts, the warm water of 40 DEG C, 3 washings is carried out to this toluene solution.In this toluene solution, add anhydrous magnesium sulfate 50 parts and stir, then filtering.The distillation of the solvent of filtrate is removed and obtains crude product.This crude product is dissolved in toluene 234 parts, stirs below 0 DEG C, collecting by filtration crystallization thing.By this crystallization thing at 50 DEG C of drying under reduced pressure, thus obtain the compound 95.7 parts represented by formula (pt3).

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

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

Accurate molecular weight: 193.2

The compound 95.3 parts that will be represented by formula (pt3) and the mixing of 48 parts, water, 80 DEG C of stirrings.Continue, add 1-bromo-2-ethyl hexane (Tokyo HuaCheng Industry Co., Ltd's system) 107 parts, while stir 3 hours at 80 DEG C, then add 48% sodium hydrate aqueous solution 22.4 parts.This potpourri is stirred 18 hours at 110 DEG C.After cooling, use 10% sodium hydrate aqueous solution that the pH of reaction mixture is adjusted to 5, add toluene 130 parts and stir, extract toluene layer out.With 500 parts, warm water, toluene Extract is washed twice, add anhydrous magnesium sulfate 25.0 parts and stir, filter.The distillation of the solvent of filtrate is removed, obtains and comprise the compound that represented by formula (pt4) residue 154 parts as principal ingredient.

The qualification > of the compound that < is represented by formula (pt4)

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

Accurate molecular weight: 305.3

The compound that represented by (pt4) will be comprised as the residue 154 parts of principal ingredient and DMF 597 parts mixing, stir at-6 DEG C ~ 3 DEG C.While liquid temperature to be remained-6 DEG C ~ 3 DEG C, add phosphoryl chloride phosphorus oxychloride (Wako Pure Chemical Industries, Ltd.'s system) 258 parts wherein.After this potpourri is at room temperature stirred 1 hour, stir 4 hours at 60 DEG C.After cooling, reaction mixture is incorporated in frozen water 1500 parts, uses 48% sodium hydrate aqueous solution neutralization.Add toluene 867 parts wherein, extract toluene layer out.With 15% sodium-chloride water solution 1200 parts, this toluene Extract is washed twice.In this toluene extract, add anhydrous magnesium sulfate 60 parts and stir, then filtering.The distillation of the solvent of filtrate is removed and obtains residue.Utilize column chromatography to be refined by this residue, obtain the compound 94.4 parts represented by formula (pt5).

The qualification > of the compound that < is represented by formula (pt5)

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

Accurate molecular weight: 333.3

By two (3-amino-4-hydroxylphenyl) sulfone (Tokyo HuaCheng Industry Co., Ltd's system) 10.6 parts, the compound 25.3 parts represented by formula (pt5), 3.2 parts, benzoic acid (Tokyo HuaCheng Industry Co., Ltd's system), 1-amylalcohol (Tokyo HuaCheng Industry Co., Ltd's system) 184 parts and cyan-acetic ester (Tokyo HuaCheng Industry Co., Ltd's system) 8.59 parts mixing, stir 3 hours at 120 DEG C.The compound 25.4 parts represented by formula (pt5), 3.21 parts, benzoic acid (Tokyo HuaCheng Industry Co., Ltd's system), 1-amylalcohol (Tokyo HuaCheng Industry Co., Ltd's system) 90 parts and cyan-acetic ester (Tokyo HuaCheng Industry Co., Ltd's system) 8.59 parts are mixed in this reaction solution, stir 12 hours at 120 DEG C.After above-mentioned reactant liquor is cooled to room temperature, be incorporated in methyl alcohol 1800 parts, the crystallization of precipitation obtains as the residue of suction filtration.Utilize column chromatography to be refined by this residue, obtain the compound 20.6 parts represented by formula (Ad2-10).Utilize ¹h-NMR confirms structure.

The qualification > of the compound that < is 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

The synthesis > of < 7-diethyl amino coumarin

4-diethylamino salicylide 1.93g (10mmol) represented by formula (pp " 1-1), the diethyl malonate 3.2g (20mmol) represented by formula (pp " 5-1) and piperidinyl-1 mL are dissolved in the absolute ethyl alcohol of 50mL.Then, 6 hours are under reflux conditions stirred while react.After reaction terminating, ethanol is removed in decompression distillation, adds concentrated hydrochloric acid 10mL and glacial acetic acid 10mL in reaction mixture, stirs 6 hours further.After reaction mixture is cooled to room temperature, is incorporated in the frozen water of 200mL and cools further, then, in reaction mixture, dripping 30% quality sodium hydrate aqueous solution, thus the pH of reaction mixture is adjusted to about 5.Reaction mixture is stirred 30 minutes, then generated sediment is filtered, to wash with water and dry.With toluene, obtained sediment is carried out recrystallization, thus obtain the 7-diethyl amino coumarin represented by formula (pp " 2-1).Output is 1.74g (8mmol), and yield is 80%.

The synthesis > of < 7-diethyl amino coumarin-3-aldehyde

To in the reaction vessel adding phosphoryl chloride phosphorus oxychloride 2mL, 0 DEG C, drip dehydration dimethyl formamide 2mL lentamente in a nitrogen atmosphere, be then warming up to room temperature and stir 30 minutes.Then, the 7-diethyl amino coumarin 1.5g (6.91mmol) represented be dissolved in dehydration dimethyl formamide 10mL and be incorporated in reaction vessel by formula (pp " 2-1), stirring 12 hours at 50 DEG C.Reaction mixture is incorporated in the frozen water of 200mL, adds 20% quality sodium hydrate aqueous solution.Generated sediment is filtered, to wash with water and dry.By obtained sediment being carried out recrystallization with ethanol, thus obtain the 7-diethyl amino coumarin-3-aldehyde represented by formula (pp " 3-1).Output is 1.2g (4.89mmol), and yield is 70%.

The synthesis > of < compound (Ad2-16)

By 7-diethyl amino coumarin-3-aldehyde 2g (8.15mmol) represented by formula (pp " 3-1), represented by formula (pp " 4-1) 2, two (3-amino-4-hydroxylphenyl) the HFC-236fa 1.49g (4.08mmol) and sodium acetate 12.6g (163mmol) of 2-is dissolved in glacial acetic acid 40mL, stirs 10 hours at 90 DEG C.Then, reaction mixture is incorporated in the water of 200mL.Generated sediment filtered and is dissolved in methylene chloride, be incorporated in separating funnel together with water and wash.With the dichloromethane layer that dried over sodium sulfate reclaims from separating funnel, then utilize silica gel column chromatography to refine, thus obtain compound (Ad2-16).Output is 1.67g (2.04mmol), and yield is 50%.

Synthesis example 8

By two (3-amino-4-hydroxylphenyl) sulfone 4.98 parts and methyl alcohol 28.1 parts mixing, stir and add 3-ethoxy-3-iminopropanoate hydrochloride 8.18 parts lentamente below 10 DEG C.Thereafter, reaction mixture is stirred 7 hours below 10 DEG C, at room temperature stir 24 hours, stir 24 hours at 60 DEG C.After above-mentioned reaction mixture is cooled to room temperature, the crystallization of precipitation obtains as the residue of suction filtration.With this residue of methanol wash, at 60 DEG C of drying under reduced pressure, thus obtain the compound 6.77 parts represented by formula (pt2).

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

(mass spectrophotometry) ionization mode=ESI+:m/z=[M+H] ⁺473.1

Accurate molecular weight: 472.1

In a nitrogen atmosphere, by 4.64 parts, o-dichlorobenzene 511 parts mixing of m-anisidine 24 parts, 4-iodine m-xylene 99.7 parts, 117 parts, sal tartari, copper powders 27.3 parts, 18-crown ether-6, stir 19 hours at 175 DEG C.Thereafter, add 1.39 parts, o-dichlorobenzene 22.0 parts of 35.1 parts, sal tartari, copper powders 8.19 parts, 18-crown ether-6, stir 17 hours at 175 DEG C.After said mixture is cooled to room temperature, filter.

In filtrate, add 450 parts, ethyl acetate, carried out 3 washings with 2N hydrochloric acid 450 parts, carry out 3 washings with 18wt% sodium-chloride water solution 470 parts.With magnesium sulfate, obtained ethyl acetate solution is dry, filter.Carry out solvent distillation with Rotary Evaporators to filtrate to remove, then utilize column chromatography to be refined by obtained residue, obtain the compound 64.1 parts represented by formula (pt6).

The qualification > of the compound that < is represented by formula (pt6)

(mass spectrophotometry) ionization mode=ESI+:m/z=[M+H] ⁺332.2

Accurate molecular weight: 331.2

The compound 31.7 parts and dehydration methylene chloride 190 parts that are represented by formula (pt6) is mixed in a nitrogen atmosphere at 0 DEG C.Continue, add 17wt% Boron tribromide dichloromethane solution 199 parts, stir 1 hour.Thereafter, at room temperature stir 12 hours.This mixed liquor is incorporated in frozen water 1100 parts, then adds chloroform 740 parts, extracted chloroform layer out.With 18wt% sodium-chloride water solution 470 parts, obtained chloroformic solution is washed twice, then use dried over mgso, filter.Carry out solvent distillation with Rotary Evaporators to filtrate to remove, then utilize column chromatography to be refined by obtained residue, obtain the compound 30 parts represented by formula (pt7).

The qualification > of the compound that < is represented by formula (pt7)

(mass spectrophotometry) ionization mode=ESI+:m/z=[M+H] ⁺318.2

Accurate molecular weight: 317.2

The compound 7.46 parts and DMF 14.4 parts that are represented by formula (pt7) is mixed in a nitrogen atmosphere at 5 ~ 10 DEG C.While the temperature of this potpourri is remained 5 ~ 10 DEG C, add phosphoryl chloride phosphorus oxychloride 7.21 parts.Thereafter, stir 1 hour below 10 DEG C, at room temperature stir 1 hour, stir 1 hour at 80 DEG C.After this reaction mixture is cooled to room temperature, adds frozen water 100 parts, neutralize with 48% sodium hydrate aqueous solution.In this potpourri, add 180 parts, ethyl acetate, continuing adds zeyssatite and stirs.This potpourri is filtered, extracts ethyl acetate layer out.With magnesium sulfate, this ethyl acetate layer is dry, filter.Carry out solvent distillation with Rotary Evaporators to this filtrate to remove, then utilize column chromatography to be refined by obtained residue, obtain the compound 6.26 parts represented by formula (pt8).

The qualification > of the compound that < is represented by formula (pt8)

(mass spectrophotometry) ionization mode=ESI+:m/z=[M+H] ⁺346.2

Accurate molecular weight: 345.2

By the compound 6.01 parts represented by formula (pt8), the compound 4.04 parts represented by formula (pt2), piperidines 0.357 part and toluene 33.4 parts mixing, stir 6 hours at 105 DEG C.After this potpourri is cooled to room temperature, be incorporated in methyl alcohol 153 parts.Sediment is obtained in the mode of the residue of suction filtration.Utilize column chromatography to be refined by obtained residue, obtain the compound 7.76 parts represented by formula (Ad2-13).

The qualification > of the compound that < is represented by formula (Ad2-13)

¹H-NMR(CDCl ₃，270MHz)δ2.13(12H)，2.34(12H)，6.38(2H)，6.52(2H)，6.92-7.02(8H)，7.10(4H)，7.37(2H)，7.67(2H)，7.98(2H)，8.40(2H)，8.64(2H)

Synthesis example 9

The compound 50 parts represented by formula (X-1), isopropyl alcohol (Wako Pure Chemical Industries, Ltd.'s system) 350 parts are at room temperature mixed, in potpourri, drip diethylamine (Tokyo HuaCheng Industry Co., Ltd's system) 18.1 parts with the temperature being no more than 20 DEG C, stir 3 hours at 20 DEG C.Reactant liquor is devoted 10% hydrochloric acid 2100 parts.Obtain obtained precipitate as suction filtration residue, with dry after ion exchange water 373 parts washing, obtain the compound 23.6 parts represented by formula (X-3).Yield is 43%.

The qualification of the compound represented by formula (X-3)

(mass spectrophotometry) ionization mode=ESI ⁺: m/z=[M+H] ⁺442.1

Accurate molecular weight: 441.1

The compound 5.0 parts represented by formula (X-3), 1-METHYLPYRROLIDONE (Wako Pure Chemical Industries, Ltd.'s system) 35 parts are at room temperature mixed, in potpourri, drip di-n-propylamine (Tokyo HuaCheng Industry Co., Ltd's system) 3.4 parts with the temperature being no more than 20 DEG C, be warming up to 80 DEG C and stir 3 hours.After reactant liquor is cooled to room temperature, add concentrated hydrochloric acid 3.4 parts, obtained potpourri is devoted saturated aqueous common salt 315 parts.Obtain obtained precipitate as suction filtration residue, with dry after ion exchange water 630 parts washing, obtain the compound 3.9 parts represented by formula (1-51).Yield is 69%.

The qualification of the compound represented by formula (1-51)

(mass spectrophotometry) ionization mode=ESI ⁺: m/z=[M+H] ⁺507.7

Accurate molecular weight: 506.7

Synthesis example 10

Be nitrogen atmosphere in flask nitrogen being flowed in right amount have reflux condenser, tap funnel and stirring machine, add propylene glycol methyl ether acetate 100 parts, stir and be heated to 85 DEG C.Then, in this flask, use and drip pump cost and drip by by methacrylic acid 19 parts, 3,4-epoxy radicals three ring [5.2.1.0 for about 5 hours ² _, ⁶] decane-8-base acrylate and 3,4-epoxy radicals three ring [5.2.1.0 ² _, ⁶] potpourri (containing than being calculated in molar ratio as 50:50) (trade name " E-DCPA ", Co., Ltd.'s Daicel system) 171 parts of the decane-9-base acrylate solution that is dissolved in propylene glycol methyl ether acetate 40 parts and obtains.On the other hand, using another to drip pump cost about 5 hours will by by polymerization initiator 2, and the solution that 2 '-azo pair (2,4-methyl pentane nitrile) 26 parts is dissolved in propylene glycol methyl ether acetate 120 parts and obtains drips in flask.After the dropping of polymerization initiator terminates, remain identical temperature about 3 hours, be cooled to room temperature thereafter, thus obtain the solution of the multipolymer (resin B 1) of solid content 43.5%.The weight-average molecular weight of the resin B 1 obtained is 8000, and molecular weight distribution is 1.98, and the acid number converted by solid content is 53mg-KOH/g.

[modulation of colored curable resin composition]

Embodiment 1

Colored curable resin composition is obtained by being carried out mixing by following composition:

Mix, the dispersible pigment dispersion that pigment disperses and obtains by use ball mill fully;

Embodiment 2

Embodiment 3

Embodiment 4

Embodiment 5

Embodiment 6

Embodiment 7

Embodiment 8

Embodiment 9

Embodiment 10

Comparative example 1

Comparative example 2

[making of colored pattern]

At the glass substrate (EAGLEXG of 2 inch square; Corning Incorporated's system) on, utilize spin-coating method to be coated with respectively the colored curable resin composition of embodiment 1 ~ 10 and comparative example 1 ~ 2, then define coloring compositions nitride layer 100 DEG C of prebake conditions 3 minutes.

After being cooled to room temperature, the interval of the substrate and quartz glass photomask that are formed with coloring compositions nitride layer is set to 200 μm, uses exposure machine (TME-150RSK; Open up Pu Kang (strain) system), under air atmosphere, with 60mJ/cm ²exposure (365nm benchmark) expose.Be explained, as photomask, employ the photomask of line and spacing (LineandSpace) pattern defining 100 μm.

Coloring compositions nitride layer after exposure is developed within 70 seconds, to be immersed in the aqueous solution that comprises 0.12% nonionic system surfactant and 0.04% potassium hydroxide at 25 DEG C, after washing, in baking oven, toasts 25 minutes after carrying out at 230 DEG C, thus obtain colored pattern.

[determining film thickness]

For obtained colored pattern, use determining film thickness device (DEKTAK3; Japan's vacuum technique (strain) system) and measure thickness.Result is shown in table 2.

[chromaticity evaluation]

For obtained colored pattern, use colour examining machine (OSP-SP-200; Olympus Corp's system) and measure light splitting, use the characteristic function of illuminant-C and the xy chromaticity coordinate (x, y) that determines in the XYZ colour system of CIE and tristimulus values Y.The value of Y is larger then represents that lightness is higher.Result is shown in table 2.

[Evaluation of Heat Tolerance]

Except not exposing via photomask, according to colored pattern make same order, toast after 25 minutes after carrying out at 230 DEG C and made the painted film that thickness is 2.5 μm.

By this painted film 230 DEG C of heating 2 hours, the aberration (Δ Eab*) of the painted film before and after its heating is by using colour examining machine (OSP-SP-200; Olympus Corp's system) and measure.The thermotolerance of the side that Δ Eab value is little is good.Result is shown in table 2.

[Investigation on Photodegradation]

Ultraviolet cutoff wave filter (COLOREDOPTICALGLASSL38 is configured on painted film; HOYA Inc.; The light of below 380nm is removed.), utilize light fastness test machine (SuntestCPS+: Toyo Seiki Inc.), irradiate xenon lamp 48 hours.

Measure the xy chromaticity coordinate (x, y) after pre-irradiation and Y, calculate aberration △ Eab* according to this measured value by the method recorded in JISZ8730:2009 (7. the computing method of aberration), result is shown in table 2.△ Eab* is less then represents that color change is less, if △ Eab* is less than 5, so can say that this painted film is no problem in practical as color filter.

Result is shown in table 2.

[solvent resistance evaluation]

The colourity of the painted film obtained is by using colour examining machine (OSP-SP-200; Olympus Corp's system) and measure.Then, this painted film to be immersed in the excessive METHYLPYRROLIDONE of fixing maintenance 23 DEG C 30 minutes, the colourity of the painted film after submergence is by similarly operating and measuring.

About the metewand of aberration, if Δ Eab* is less than 2, substantially do not find that form and aspect (colorphase) change, show as the good characteristic of color filter, if Δ Eab* is more than 2 and be less than 5, although so find a little form and aspect change, it is degree no problem in the practicality of color filter, if Δ Eab* is more than 5, so can confirm clearly form and aspect change, be as the in-problem degree of color filter.Result is shown in table 2.

Table 2

Utilizability in industry

According to colored curable resin composition of the present invention, the color filter of excellent solvent resistance can be provided.The excellent solvent resistance of the color filter manufactured by this colored curable resin composition, thus can be preferably applied to display device and the solid-state imagers such as liquid crystal indicator, organic el device, Electronic Paper.

Claims

1. a colored curable resin composition, which contain toner (A), resin (B), polymerizable compound (C) and polymerization initiator (D),

Colorant (A) comprises red pigment (A-1) and dyestuff (A-2),

Dyestuff (A-2) comprises xanthene dye and coumarine dye.

2. colored curable resin composition according to claim 1, wherein, red pigment (A-1) is selected from least one pigment in the group that is made up of paratonere 177, paratonere 242 and paratonere 254.

3. colored curable resin composition according to claim 1 and 2, wherein, xanthene dye is the compound represented by formula (1a),

In formula (1a), R ¹~ R ⁴represent hydrogen atom independently of each other, the univalent saturated hydrocarbon radical of substituent carbon number 1 ~ 20 can be had or the monovalence aromatic hydrocarbyl of substituent carbon number 6 ~ 10 can be had,

-CH contained in described saturated hydrocarbyl ₂-also can by-O-,-CO-or-NR ¹¹-replace, R ¹and R ²also can bonding mutually, the ring comprising nitrogen-atoms is formed, R together with the nitrogen-atoms of their institute's bondings ³and R ⁴also can bonding mutually, the ring comprising nitrogen-atoms is formed together with the nitrogen-atoms of their institute's bondings,

R ⁵represent-OH ,-SO ₃ ^-,-SO ₃h ,-SO ₃ ^-z ⁺,-CO ₂h ,-CO ₂ ^-z ⁺,-CO ₂r ⁸,-SO ₃r ⁸or-SO ₂nR ⁹r ¹⁰,

R ⁶and R ⁷represent the alkyl of hydrogen atom or carbon number 1 ~ 6 independently of one another,

M represents the integer of 0 ~ 5, and m is when more than 2, multiple R ⁵can identical also can be different,

A represents the integer of 0 or 1,

X represents halogen atom,

Z ⁺represent ⁺n (R ¹¹) ₄, Na ⁺or K ⁺,

R ⁸represent the univalent saturated hydrocarbon radical of carbon number 1 ~ 20, hydrogen atom contained in this saturated hydrocarbyl also can be replaced by halogen atom,

R ⁹and R ¹⁰represent hydrogen atom independently of each other or the univalent saturated hydrocarbon radical of substituent carbon number 1 ~ 20 can be had ,-CH contained in this representative examples of saturated aliphatic alkyl ₂-also can by-O-,-CO-,-NH-or-NR ⁸-replace, R ⁹and R ¹⁰also can bonding mutually, 3 ~ 10 member heterocyclic ring containing nitrogens are formed together with the nitrogen-atoms of their institute's bondings,

R ¹¹represent the univalent saturated hydrocarbon radical of hydrogen atom, carbon number 1 ~ 20 or the aralkyl of carbon number 7 ~ 10 independently of each other.

4. colored curable resin composition according to claim 1 and 2, wherein, coumarine dye is the compound represented by formula (Ad2),

In formula (Ad2), L ^crepresent bivalent hydrocanbon radical or the sulfonyl of carbon number 1 ~ 20, hydrogen atom contained in this alkyl also can be replaced by fluorine atoms,

X ^crepresent oxygen atom or sulphur atom,

R ^1Cand R ^2Crepresent the alkyl can with substituent phenyl or carbon number 1 ~ 20 independently of one another, also can insert oxygen atom between the carbon atom forming this alkyl,

R ^7C~ R ^13Crepresent hydrogen atom, halogen atom, cyano group, nitro, carbamyl, amino-sulfonyl ,-SO independently of one another ₃m ^c,-CO ₂m ^c, hydroxyl, formoxyl, amino, carbon number 1 ~ 20 monovalent hydrocarbon, also can form this alkyl carbon atom between insert oxygen atom, sulphur atom ,-N (R ^14C)-, sulfonyl or carbonyl, hydrogen atom contained in this alkyl also can by halogen atom, cyano group, nitro, carbamyl, amino-sulfonyl ,-SO ₃m ^c,-CO ₂m ^c, hydroxyl, formoxyl or amino to replace ,-SO ₃m ^cand-CO ₂m ^cwhen existing multiple respectively, they can be identical, also can be different,

R ^14Crepresent the monovalent hydrocarbon of hydrogen atom or carbon number 1 ~ 20, there is multiple-N (R ^14C)-when, they can be identical, also can be different,

M ^crepresent hydrogen atom or alkali metal atom.

5. colored curable resin composition according to claim 1 and 2, wherein, xanthene dye and coumarine dye containing than i.e. xanthene dye: coumarine dye is 60:40 ~ 99:1 according to quality criteria.

6. a color filter, it is formed by the colored curable resin composition described in claim 1 or 2.

7. a liquid crystal indicator, it comprises color filter according to claim 6.