CN104298072A

CN104298072A - Colored curable resin composition

Info

Publication number: CN104298072A
Application number: CN201410333674.3A
Authority: CN
Inventors: 芦田彻; 土谷崇夫
Original assignee: Sumitomo Chemical Co Ltd
Current assignee: Dongwoo Fine Chem Co Ltd
Priority date: 2013-07-16
Filing date: 2014-07-14
Publication date: 2015-01-21
Anticipated expiration: 2034-07-14
Also published as: CN104298072B; TWI624499B; KR20150009447A; JP6432931B2; JP2015038603A; KR102215069B1; TW201512270A

Abstract

The invention relates to a colored curable resin composition, comprising a compound shown by a formula (A-I), a resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a solution (E). [In the formula (A-I), X- indicates negative ions containing boron atoms or aluminum atoms; A indicates groups shown by formulas (A-VI-1) or (A-VI-2); and ''*'' indicates bonding arms with carbon atoms.] The formula (A-I) is as shown in the specification.

Description

Colored curable resin composition

Technical field

The present invention relates to a kind of colored curable resin composition.

Background technology

As the colored curable resin composition forming color filter contained in liquid crystal indicator etc., solid-state imager etc., in No. 2012/053211st, International Publication, describe the colored curable resin composition of compound shown in contained (A-III-1).

Summary of the invention

The invention provides following [1] ~ [6].

[1] colored curable resin composition, its compound shown in contained (A-I), resin (B), photopolymerizable compound (C), Photoepolymerizationinitiater initiater (D) and solvent (E).

[in formula (A-I), X ^-represent the negative ion comprising boron atom or aluminium atom.A expression (A-VI-1) or the group shown in formula (A-VI-2)." * " represents the bonding arm with carbon atom.

R ¹~ R ¹⁸represent saturated hydrocarbyl or the halogen atom of hydrogen atom, carbon number 1 ~ 10 independently of one another.

R ¹⁹and R ²⁰represent hydrogen atom ,-R independently of one another ^26aor the aromatic hydrocarbyl of carbon number 6 ~ 10, or, R ¹⁹and R ²⁰and together with the nitrogen-atoms of their bondings representative ring.

R ²¹and R ²²represent hydrogen atom ,-R independently of one another ^26aor the aromatic hydrocarbyl of carbon number 6 ~ 10, or, R ²¹and R ²²and together with the nitrogen-atoms of their bondings representative ring.

R ²³and R ²⁴represent hydrogen atom ,-R independently of one another ^26aor the aromatic hydrocarbyl of carbon number 6 ~ 10, or, R ²³and R ²⁴and together with the nitrogen-atoms of their bondings representative ring.

R ²⁵and R ²⁶represent hydrogen atom ,-R independently of one another ^26aor the aromatic hydrocarbyl of carbon number 6 ~ 10, or, R ²⁵and R ²⁶and together with the nitrogen-atoms of their bondings representative ring.

At R ¹⁹~ R ²⁶in, hydrogen atom contained in described aromatic hydrocarbyl can by halogen atom ,-R ^26a,-OH ,-OR ^26a,-SO ₃ ^-,-SO ₃na ,-CO ₂h ,-CO ₂r ^26a,-SO ₃h ,-SO ₃r ^26aor-SO ₂nHR ^28areplace.

R ^26arepresent the saturated hydrocarbyl of carbon number 1 ~ 10.Hydrogen atom contained in this saturated hydrocarbyl can by-OR ^27a(in formula, R ^27arepresent the saturated hydrocarbyl of carbon number 1 ~ 10), halogen atom or benzene sulfonic acid alkali metal salt replace.

R ^28arepresent hydrogen atom ,-R ^26a,-CO ₂r ^26aor the aromatic hydrocarbyl of carbon number 6 ~ 10, hydrogen atom contained in this aromatic hydrocarbyl can by-R ^26aor-OR ^27areplace.]

[2] colored curable resin composition Gen Ju [1], it also comprises blue pigment.

[3] according to [1] or the colored curable resin composition described in [2], it is bag antioxidant (H) also.

[4] film, it is that colored curable resin composition according to any one of [1] ~ [3] is formed.

[5] color filter, it is that colored curable resin composition according to any one of [1] ~ [3] is formed.

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

According to colored curable resin composition of the present invention, the color filter of excellent heat resistance can be obtained.

Embodiment

Compound (hereinafter also referred to compound (A-I)) shown in colored curable resin composition of the present invention contained (A-I) is as colorant (A).Compound (A-I) also comprises its dynamic isomer.

[in formula (A-I), X ^-represent the negative ion comprising boron atom or aluminium atom.

A expression (A-VI-1) or the group shown in formula (A-VI-2), " * " represents the bonding arm with carbon atom.

At R ¹⁹~ R ²⁶in, hydrogen atom contained in aromatic hydrocarbyl can by halogen atom ,-R ^26a,-OH ,-OR ^26a,-SO ₃ ^-,-SO ₃na ,-CO ₂h ,-CO ₂r ^26a,-SO ₃h ,-SO ₃r ^26aor-SO ₂nHR ^28areplace.

At R ¹~ R ¹⁸, R ^26aand R ^27ain, as the saturated hydrocarbyl of carbon number 1 ~ 10, can enumerate: methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, n-pentyl, n-hexyl, n-heptyl, n-octyl, decyl, 1-methyl butyl, 1,1,3,3-tetramethyl butyl, 1,5-dimethylhexanyl, 1,6-dimethyl heptyl, 2-ethylhexyl and 1,1,5,5-tetramethylhexyl etc.

As R ¹~ R ¹⁸, the saturated hydrocarbyl of preferred hydrogen atom and carbon number 1 ~ 4, the more preferably alkyl of hydrogen atom and carbon number 1 ~ 4, further preferred hydrogen atom and methyl.

At R ¹⁹~ R ²⁶in, as the aromatic hydrocarbyl of carbon number 6 ~ 10, can phenyl, naphthyl etc. be enumerated.

As-OR ^27a, can enumerate: methoxyl, ethoxy, propoxyl group, butoxy, amoxy, own oxygen base, heptan oxygen base, octyloxy, 2-ethyl hexyl oxy and eicosane oxygen base.

As-CO ₂r ^26a, can enumerate: methoxycarbonyl, ethoxy carbonyl, propoxycarbonyl, tert-butoxycarbonyl, hexyloxy carbonyl and eicosane oxygen base carbonyl.

As-SO ₃r ^26a, can enumerate: mesyloxy, ethanesulfonyloxy group, own sulfonyloxy, the last of the ten Heavenly stems sulfonyloxy etc.

As-SO ₂nHR ^28a, can enumerate: sulfamoyl, first sulfamoyl, second sulfamoyl, third sulfamoyl, isopropyl sulfamoyl, fourth sulfamoyl, isobutyl sulfamoyl, penta sulfamoyl, isoamyl sulfamoyl, new penta sulfamoyl, ring penta sulfamoyl, own sulfamoyl, hexamethylene sulfamoyl, heptan sulfamoyl, ring sulfamoyl in heptan, pungent sulfamoyl, 2-ethyl hexyl sulfamoyl, 1, the own sulfamoyl of 5-dimethyl, the pungent sulfamoyl of ring, the ninth of the ten Heavenly Stems sulfamoyl, the last of the ten Heavenly stems sulfamoyl, three ring sulfamoyls in the last of the ten Heavenly stems, methoxy propyl sulfamoyl, ethoxy-c sulfamoyl, propoxyl group third sulfamoyl, isopropoxy third sulfamoyl, own oxygen base third sulfamoyl, 2-ethyl hexyl oxy third sulfamoyl, the own sulfamoyl of methoxyl, 3-phenyl-1-methyl-prop sulfamoyl etc.

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

As the alkaline metal in benzene sulfonic acid alkali metal salt, sodium, potassium etc. can be enumerated.

In formula (A-I), preferably make R ¹⁹~ R ²⁶in at least one be-R ^26a, the more preferably alkyl of carbon number 1 ~ 4.

As the kation shown in above formula, such as following radicals can be enumerated.

As the group shown in formula (A-VI-1), such as following radicals can be enumerated.

As the group shown in formula (A-VI-2), such as following radicals can be enumerated.

X ^-represent the negative ion comprising boron atom or aluminium atom.As X ^-, from the view point of improving thermotolerance further, preferably comprise the negative ion of boron atom.

As containing boron anion and containing aluminium negative ion, can the negative ion shown in enumerative (4).

[in formula (4), W ¹, W ²represent that there is 2 are released proton to protic substituting group substituent group from 1 valency independently of one another.M represents boron atom or aluminium atom.]

As having 2 are released proton to protic substituting group substituent group from 1 valency, can enumerate from there are at least 21 valencys to 2 of the compound of protic substituting group (such as hydroxyl, carboxyl etc.) to the group of protic substituting group being released respectively proton.

This compound is preferably: can have substituent catechol, can have substituent 2,3-dihydroxy naphthlene, substituent 2 can be had, 2 '-xenol, substituent 3-hydroxy-2-naphthoic acid can be had, substituent 2-hydroxyl-1-naphthoic acid can be had, substituent 1-hydroxy-2-naphthoic acid can be had, substituent dinaphthol can be had, substituent salicylic acid can be had, substituent diphenylglycollic acid can be had maybe can have substituent mandelic acid.

In above-mentioned preferred compound, alternatively base, can enumerate: halogen atom, haloalkyl, hydroxyl, amino, nitro, alkoxy etc.

Substituent salicylic acid can be had as above-mentioned, can enumerate: salicylic acid, 3-cresotinic acid, 3-tert-butyl salicylic acid, 3-aminosalicylic acid, 3-chloro-salicylic acid, 4-bromo ortho-oxybenzoic acid, 3-methoxysalicylic acid, 3-Nitrosalicylic Acid, 4-trifluoromethyl salicylic acid, 3, 5-di-tert-butyl salicylic acid, 3, 5-dibromosalicylic acid, 3, 5-dichlorosalicylic acid, 3, 5, 6-tri-chloro-salicylic acid, 3-hydroxyl salicylic acid (2, 3-dihydroxy-benzoic acid), 4-hydroxyl salicylic acid (2, 4-dihydroxy-benzoic acid), 5-hydroxyl salicylic acid (2, 5-dihydroxy-benzoic acid), 6-hydroxyl salicylic acid (2, 6-dihydroxy-benzoic acid) etc.

Substituent diphenylglycollic acid can be had, the example etc. that can be listed below as above-mentioned.

Substituent mandelic acid can be had, the example etc. that can be listed below as above-mentioned.

In formula (4), preferably make W ¹, W ²independently of one another for having COO ^-and O ^-the alternatively aromatic hydrocarbyl of the carbon number 6 ~ 10 of base.

As the negative ion shown in formula (4), the negative ion shown in following formula can be enumerated, that is, there is each substituent negative ion (BC-1) shown in table 1 ~ negative ion (BC-24) and respectively with negative ion (BC-25) ~ negative ion (BC-28) etc. that formula (BC-25) ~ formula (BC-28) represents.

[in formula, M represents boron atom or aluminium atom.]

[table 1]

Negative ion	R ⁶¹	R ⁶²	R ⁶³	R ⁶⁴
					Negative ion (BC-1)	H	H	H	H
Negative ion (BC-2)	OH	H	H	H
					Negative ion (BC-3)	H	OH	H	H
Negative ion (BC-4)	H	H	OH	H
					Negative ion (BC-5)	H	H	H	OH
Negative ion (BC-6)	Cl	H	H	H
					Negative ion (BC-7)	H	Cl	H	H
Negative ion (BC-8)	H	H	Cl	H
					Negative ion (BC-9)	H	H	H	Cl
Negative ion (BC-10)	Br	H	H	H
					Negative ion (BC-11)	H	Br	H	H
Negative ion (BC-12)	H	H	Br	H
					Negative ion (BC-13)	H	H	H	Br
Negative ion (BC-14)	NH ₂	H	H	H
					Negative ion (BC-15)	H	NH ₂	H	H
Negative ion (BC-16)	H	H	NH ₂	H
					Negative ion (BC-17)	H	H	H	NH ₂
Negative ion (BC-18)	H	tBu	H	tBu
					Negative ion (BC-19)	H	Cl	H	Cl
Negative ion (BC-20)	H	Br	H	Br
					Negative ion (BC-21)	H	I	H	I
Negative ion (BC-22)	H	OH	OH	H
					Negative ion (BC-23)	OH	H	OH	H
Negative ion (BC-24)	Cl	Cl	H	Cl

[in formula (BC-25) ~ formula (BC-28), M represents boron atom or aluminium atom.]

As the negative ion shown in formula (4), preferred anionic (BC-1), negative ion (BC-2), negative ion (BC-3), negative ion (BC-25), negative ion (BC-26), negative ion (BC-27), more preferably negative ion (BC-1), negative ion (BC-2), negative ion (BC-25), more preferably negative ion (BC-1), negative ion (BC-2).

Compound (A-I) is by by the compound (also this compound being called compound (A-II) below) shown in formula (A-II) with mixed with the salt that alkaline metal is formed by the negative ion shown in formula (4) and manufacture.As alkaline metal, lithium, sodium and potassium etc. can be enumerated.

[in formula (A-II), R ¹~ R ⁸, R ¹⁹~ R ²²and A represents implication same as described above respectively.]

The mixing of the salt formed by the negative ion shown in formula (4) and alkaline metal and compound (A-II) both can be made to be dissolved in above-mentioned solvent to carry out, both also can not be made to dissolve and directly mix.

As solvent, can enumerate: DMF, DMA, 1-METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO), acetonitrile, ethyl acetate, toluene, methyl alcohol, ethanol, isopropyl alcohol, acetone, tetrahydrofuran, diox, water and chloroform etc.

Wherein, preferred DMF, DMA, 1-METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO), methyl alcohol, ethanol, isopropyl alcohol and water.

When solvent is water, also the acid such as acetic acid, hydrochloric acid can be added.

The salt formed by the negative ion shown in formula (4) and alkaline metal and the mixing temperature of compound (A-II) be preferably 0 DEG C ~ 150 DEG C, be more preferably 10 DEG C ~ 120 DEG C, more preferably 20 DEG C ~ 100 DEG C.

Incorporation time is preferably 1 hour ~ 72 hours, is more preferably 2 hours ~ 24 hours, more preferably 3 hour ~ and 12 hours.

When adopting the solvent molten with aqueous phase, reaction mixture being stirred 1 ~ 3 hour as required further, then utilizing and filter and obtain precipitate, compound (A-I) can be obtained thus.Also can ion exchange water be utilized to wash gained compound (A-I) as required.

When adopting the solvent immiscible with water, reaction mixture being mixed with ion exchange water and stirs 1 ~ 3 hour further as required, then utilize separatory and obtain organic layer, the solution of inclusion compound (A-I) can be obtained thus.Also can ion exchange water be utilized to wash this solution as required.By removing desolventizing in the solution from inclusion compound (A-I), compound (A-I) can be obtained.

And then, also compound (A-I) can be dissolved in acetonitrile, ethyl acetate, toluene, methyl alcohol, ethanol, isopropyl alcohol, acetone, chloroform equal solvent and to utilize recrystallization to refine it.

Colored curable resin composition inclusion compound (A-I) of the present invention, resin (B), polymerizable compound (C), polymerization initiator (D) and solvent (E).

Colored curable resin composition of the present invention preferably comprises levelling agent (F), antioxidant (H) further, and then, more preferably comprise antioxidant (H).

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

In this manual, when being not particularly limited, the compound enumerated as each composition can be used alone or combinationally use multiple

< colorant (A) >

Colored curable resin composition inclusion compound (A-I) of the present invention is as colorant (A).

Colorant (A) can be used alone compound (A-I), but in order to reach the object of toning, namely in order to be adjusted dichroism, other dyestuff (A1), pigment (P) or their potpourri can also be comprised further.

As dyestuff (A1), can enumerate the dyestuffs such as oil-soluble dyes, acid dyes, basic-dyeable fibre, can be any dyestuff in direct dyes and mordant dye.Above-mentioned acid dyes can be amine salt, sulfamide derivative.

As dyestuff (A1), the compound being classified as dyestuff in " Colour Index " (The Society of Dyers and Colourists (Britain dyer author association) publication), the dye known be recorded in " dyeing notes " (Se Ran society) can be set forth in.In addition, different according to chemical constitution, can enumerate: azo dyes, cyanine dye, triphenhlmethane dye, xanthene dye, phthalocyanine dye, naphthoquinone dyestuff, quinoneimine dye, methine type dye, azomethine dyes, squarylium cyanine dyes, acridine dye, styryl dye, coumarine dye, quinoline dye and nitro dye etc.In these dyestuffs, preferably with an organic solvent soluble dye as dyestuff (A1).

As dyestuff (A1), specifically can enumerate:

C.I. (following record of omitting C.I. solvent yellow, only records numbering to solvent yellow 4.With regard to other dyestuff, for exist in title common ground dyestuff, also omit the record of this common ground.)、14、15、23、24、38、62、63、68、82、94、98、99、162；

C.I. solvent red 45,49,125,130,218;

C.I. solvent orange 2,7,11,15,26,56;

C.I. solvent blue 4,5,37,67,70,90;

C.I. the C.I. solvent dye such as solvent green 4,5,7,34,35,

C.I. Indian yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251,

C.I. azogeramine, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 195, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 289, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 388, 394, 401, 412, 417, 418, 422, 426,

C.I. acid orange 6,7,8,10,12,26,50,51,52,56,62,63,64,74,75,94,95,107,108,169,173;

C.I. acid violet 6B, 7,9,17,19,30,102;

C.I. Blue VRS 8,29,42,59,60,62,70,72,74,82,87,92,100,102,113,117,120,126,130,131,142,151,154,158,161,166,167,168,170,171,184,187,192,199,210,229,234,236,242,243,256,259,267,285,296,315,335;

C.I. the C.I. acid dyes such as acid green 16,58,63,65,80,104,105,106,109,

C.I. direct Huang 2,33,34,35,38,39,43,47,50,54,58,68,69,70,71,86,93,94,95,98,102,108,109,129,136,138,141;

C.I. directly red 79,82,83,84,91,92,96,97,98,99,105,106,107,172,173,176,177,179,181,182,184,204,207,211,213,218,220,221,222,232,233,234,241,243,246,250;

C.I. direct orange 26,34,39,41,46,50,52,56,57,61,64,65,68,70,96,97,106,107;

C.I. direct purple 47,52,54,59,60,65,66,79,80,81,82,84,89,90,93,95,96,103,104;

C.I. direct indigo plant 1, 2, 6, 8, 15, 22, 25, 41, 57, 71, 76, 78, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196, 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 242, 243, 244, 245, 246, 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293,

C.I. the C.I. direct dyes such as direct green 25,27,31,32,34,37,63,65,66,67,68,69,72,77,79,82,

C.I. the C.I. disperse dyes such as disperse yellow 54,76,

C.I. alkali red 1:1,10;

C.I. alkali blue 1,3,5,7,9,19,24,25,26,28,29,40,41,54,58,59,64,65,66,67,68;

C.I. Viride Nitens 1; Deng C.I. basic-dyeable fibre,

C.I. reactive yellow 2,76,116;

C.I. reactive orange 16;

C.I. reactive red 36; Deng C.I. reactive dye,

C.I. medium Huang 5,8,10,16,20,26,30,31,33,42,43,45,56,61,62,65;

C.I. medium red 1,2,4,9,12,14,17,18,19,22,23,24,25,26,27,30,32,33,36,37,38,39,41,43,45,46,48,53,56,63,71,74,85,86,88,90,94,95;

C.I. medium orange 3,4,5,8,12,13,14,20,21,23,24,28,29,32,34,35,36,37,42,43,47,48;

C.I. medium purple 1,2,4,5,7,14,22,24,30,31,32,37,40,41,44,45,47,48,53,58;

C.I. medium indigo plant 1,2,3,7,9,12,13,15,16,19,20,21,22,26,30,31,39,40,41,43,44,49,53,61,77,83,84;

C.I. the C.I. mordant dye such as medium green 4,10,15,26,29,33,34,35,41,43,53,

C.I. reducing dye such as C.I. such as vat green 1 grade; Etc..

Wherein, preferred blue dyes, cudbear and orchil.

These dyestuffs can be used alone and also can be used in combination of two or more.

As pigment (P), be not particularly limited, known pigment can be used, the pigment being classified as pigment (pigment) in " Colour Index " (The Society of Dyers and Colourists publishes) can be set forth in.

As pigment (P), can enumerate: 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 such as 73;

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

C.I. pigment blue 15,15:3,15:4,15:6, the blue pigments such as 60;

C.I. pigment violet 1,19,23,29,32,36, the violet pigments such as 38;

C.I. pigment Green 7,36, the viridine greens such as 58;

C.I. the brown such as pigment brown 23,25;

C.I. the black pigment etc. such as pigment black 1,7.

Pigment (P) be preferably phthalocyanine color Ji triazine dioxin pigment, be more preferably and be selected from C.I. pigment blue 15: 6 and pigment Violet 23 at least one.By comprising above-mentioned pigment, easily realizing the optimization of transmitted spectrum, the thermotolerance of color filter, photostability and chemical reagent resistance can be made to become good.

For pigment, can also as required and implement rosin process, use be imported with surface treatment that the pigment derivative of acidic groups or basic group etc. carries out, the grafting process utilizing macromolecular compound etc. to carry out surface of pigments, the micronize process utilizing sulfuric acid particles method etc. to carry out or the carrying out washing treatment utilizing organic solvent, water etc. to carry out to remove impurity, the removing process etc. that utilized ion exchange process etc. to be removed by ionic impurity.Preferably make the uniform particle sizes of each pigment.

As above-mentioned pigment (P), pigment can be used in a solvent dispersed and the dispersible pigment dispersion obtained.

Dispersible pigment dispersion obtains by hybrid pigment in a solvent and pigment dispersing agent.

In above-mentioned mixing, when mixing two or more pigment, they separately can be mixed, also can by multiple mixing.

As above-mentioned pigment dispersing agent, can be any spreading agent in cationic pigment dispersing agent, anionic species pigment dispersing agent, nonionic class pigment dispersing agent and both sexes pigment dispersing agent, the pigment dispersing agent etc. of polyesters, polyamines class, acrylic compounds etc. can be enumerated.These pigment dispersing agents can be used alone and also can be used in combination of two or more.As pigment dispersing agent, can enumerate: commodity are called KP (Shin-Etsu Chemial Co., Ltd's system), Floren (Kyoeisha Chemical Co., Ltd.'s system), Solsperse (Zeneca Inc.), EFKA (BASF AG's system), Ajisper (Ajinomoto Fine-Techno Co.Int. system), Disperbyk (Bye Chemie Inc.) etc.

When using pigment dispersing agent, its consumption is preferably below 100 mass parts relative to pigment 100 mass parts, is more preferably more than 5 mass parts and below 50 mass parts.When above-mentioned scope, there is the tendency that can obtain the dispersible pigment dispersion of homogeneous disperse state in the consumption of pigment dispersing agent.

Relative to the total amount of colorant (A), the containing ratio of compound (A-I) is preferably more than 1 quality % and below 100 quality %, be more preferably more than 10 quality % and below 100 quality %.

Relative to the total amount of solid constituent, the containing ratio of colorant (A) is preferably more than 5 quality % and below 70 quality %, be more preferably more than 5 quality % and below 60 quality %, more preferably more than 5 quality % and below 50 quality %.When the containing ratio of colorant (A) is in above-mentioned scope, light splitting and the colour saturation of expectation can be obtained.

Described " total amount of solid constituent " in this instructions refers to the total amount of the composition in colored curable resin composition of the present invention except desolventizing (E).The total amount of solid constituent and each composition measure by known analytical approach such as such as liquid chromatography or gas chromatography etc. relative to the content of the total amount of solid constituent.

< resin (B) >

As resin (B), there is no particular restriction, but preferred bases soluble resin (B).

Alkali soluble resin (B) (hereinafter also referred to " resin (B) ") is for comprising the multipolymer of the structural unit from least one monomer (a) be selected from unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides.

As such resin (B), following resin [K1] ~ [K6] etc. can be enumerated.

Resin [K1]: the multipolymer being selected from least one monomer (a) (hereinafter also referred to " (a) ") in unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides, being formed with the monomer (b) (hereinafter also referred to " (b) ") of the cyclic ether structure and ethylenic unsaturated bond with carbon number 2 ~ 4;

Resin [K2]: (a), (b) and the multipolymer that can be formed from the monomer (c) of (a) copolymerization (they are different with (a) and (b)) (hereinafter also referred to " (c) ");

Resin [K3]: the multipolymer that (a) and (c) are formed;

Resin [K4]: the resin that the multipolymer that (a) and (c) are formed reacts with (b);

Resin [K5]: the resin that the multipolymer that (b) and (c) are formed reacts with (a);

Resin [K6]: the multipolymer that (b) and (c) are formed reacts and the resin reacted with carboxylic acid anhydrides further with (a).

As (a), specifically can enumerate: acrylic acid, methacrylic acid, crotonic acid, adjacent vinyl benzoic acid, a vinyl benzoic acid, to unsaturated monocarboxylic classes 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, 1,2,3,6-tetrahydrophthalic acid, dimethyl tetrahydro phthalic acid, 1, the unsaturated dicarboxylic class such as 4-cyclohexene dicarboxylic acid;

Methyl-5-norborene-2, the dicyclo unsaturated compound class 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 class 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] the ester class 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;

α-(hydroxymethyl) acrylic acid etc. contain the unsaturated esters of acrylic acid etc. of hydroxyl and carboxyl in same a part.

In these monomers, from viewpoint and the deliquescent viewpoint of gained resin in aqueous alkali of copolyreaction, as (a), preferred acrylic acid, methacrylic acid, maleic anhydride etc.

B () refers to: have the cyclic ether structure (being such as selected from least one in 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, described " (methyl) acrylic acid " represents at least one be selected from acrylic acid and methacrylic acid.The statement of " (methyl) acryloyl group " and " (methyl) acrylate " etc. also has same implication.

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

As (b1), can enumerate such as: there is the monomer (b1-1) (hereinafter also referred to " (b1-1) ") of unsaturated aliphatic hydrocarbon through the structure of epoxidation of straight-chain or branched, there is the monomer (b1-2) (hereinafter also referred to " (b1-2) ") of ester ring type unsaturated hydrocarbon through the structure of epoxidation.

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

As (b1-2), can enumerate: vinyl cyclohexene list oxide, 1,2-epoxy-4-vinyl cyclohexane (such as, Celloxide2000; Daicel Co., Ltd. system), (methyl) acrylic acid 3,4-epoxycyclohexanecarboxylate (such as, Cyclomer A400; Daicel Co., Ltd. system), (methyl) acrylic acid 3,4-epoxycyclohexanecarboxylate (such as, Cyclomer M100; Daicel Co., Ltd. system), the compound shown in formula (II) and the compound etc. shown in formula (III).

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

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

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

" * " represents the bonding arm with O.]

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

As the alkyl that hydrogen atom is optionally substituted by a hydroxyl group, can enumerate: hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxyl-1-Methylethyl, 2-hydroxyl-1-Methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl etc.

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

As the alkylidene of carbon number 1 ~ 6, can enumerate: methylene, ethylidene, 1,2-propylidene, 1,3-propylidene, Isosorbide-5-Nitrae-butylidene, 1,5-pentylidene, 1,6-hexylidene etc.

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

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

As the compound shown in formula (III), can enumerate: the compound etc. shown in any chemical formula in formula (III-1) ~ formula (III-15).Wherein, compound shown in preferred formula (III-1), formula (III-3), formula (III-5), formula (III-7), formula (III-9) or formula (III-11) ~ formula (III-15), more preferably formula (III-1), formula (III-7), formula (III-9) or the compound shown in formula (III-15).

Compound shown in formula (II) and the compound shown in formula (III) can independently use, and also the compound combination shown in the compound shown in formula (II) and formula (III) can be used.When they being combinationally used, the ratio that contains of the compound shown in formula (II) and the compound shown in formula (III) is preferably 5: 95 ~ 95: 5 with molar basis, is more preferably 10: 90 ~ 90: 10, more preferably 20: 80 ~ 80: 20.

As (b2), more preferably there is the monomer of oxetanylmethoxy and (methyl) acryloxy.As (b2), can enumerate: 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), more preferably there is the monomer of tetrahydrofuran base and (methyl) acryloxy.As (b3), specifically can enumerate: tetrahydrofurfuryl acrylate (such as, Viscoat V#150, Osaka Organic Chemical Industry Co., Ltd.'s system), tetrahydrofurfuryl methacrylate etc.

As (b), from the view point of the reliability such as thermotolerance, chemical reagent resistance improving gained color filter further, preferably (b1).And then, from the view point of the excellent storage stability making colored curable resin composition, more preferably (b1-2).

As (c), can enumerate such as: (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-butyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) 2-EHA, (methyl) dodecylacrylate, (methyl) lauryl acrylate, (methyl) stearyl acrylate ester, (methyl) acrylic acid ring pentyl ester, (methyl) cyclohexyl acrylate, (methyl) acrylic acid 2-methyl cyclohexyl, (methyl) acrylic acid three ring [5.2.1.0 ^2,6] decane-8-base ester (in the art, as its trivial name, is called as " (methyl) acrylic acid dicyclo pentyl ester ".In addition, be also referred to as " (methyl) acrylic acid three ring ester in the last of the ten Heavenly stems "), (methyl) acrylic acid three ring [5.2.1.0 ^2,6] decene-8-base ester (in the art, as its trivial name, be called as " (methyl) acrylic acid dicyclopentenyloxyethyl methacrylate "), (methyl) esters of acrylic acid such as (methyl) acrylic acid dicyclo amoxy ethyl ester, (methyl) isobornyl acrylate, (methyl) acrylic acid diamantane ester, (methyl) allyl acrylate, (methyl) propargylacrylate, (methyl) phenyl acrylate, (methyl) acrylic acid naphthalene ester, (methyl) benzyl acrylate;

Hydroxyl (methyl) esters of acrylic acids such as (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester;

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

Dicyclo [2.2.1] hept-2-ene", 5-methyl bicycle [2.2.1] hept-2-ene", 5-ethyl dicyclo [2.2.1] hept-2-ene", 5-hydroxyl dicyclo [2.2.1] hept-2-ene", 5-hydroxymethyl dicyclo [2.2.1] hept-2-ene", 5-(2 '-hydroxyethyl) dicyclo [2.2.1] hept-2-ene", 5-methoxyl dicyclo [2.2.1] hept-2-ene", 5-ethoxy dicyclo [2.2.1] hept-2-ene", 5,6-dihydroxy dicyclo [2.2.1] hept-2-ene", 5,6-bis-(hydroxymethyl) dicyclo [2.2.1] hept-2-ene", 5,6-bis-(2 '-hydroxyethyl) dicyclo [2.2.1] hept-2-ene", 5,6-dimethoxy dicyclo [2.2.1] hept-2-ene", 5,6-diethoxy dicyclo [2.2.1] hept-2-ene", 5-hydroxy-5-methyl base dicyclo [2.2.1] hept-2-ene", 5-hydroxyl-5-ethyl dicyclo [2.2.1] hept-2-ene", 5-hydroxymethyl-5-methyl bicycle [2.2.1] hept-2-ene", 5-tert-butoxycarbonyl dicyclo [2.2.1] hept-2-ene", 5-cyclohexyloxy 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 compound classes such as two (cyclohexyloxy carbonyl) dicyclo [2.2.1] hept-2-ene"s of 5,6-,

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

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

In these monomers, from the view point of copolyreaction and thermotolerance, optimization styrene, vinyltoluene, (methyl) benzyl acrylate, (methyl) acrylic acid three ring [5.2.1.0 ^2,6] decane-8-base ester, N-phenylmaleimide, N-N-cyclohexylmaleimide, N-benzyl maleimide, dicyclo [2.2.1] hept-2-ene".

With regard to resin [K1], in the entire infrastructure unit forming resin [K1], the ratio from the structural unit of each monomer is preferably:

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

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

Be more preferably:

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

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

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

Resin [K1] can manufacture see, for example the citing document recorded in the method recorded in document " experimental method of Polymer Synthesizing " (grand row work sale room (strain) chemistry in large Tianjin is with people's the 1st edition the 1st printing distribution on March 1st, 1972) and the document.

As the concrete manufacture method of resin [K1], can enumerate: (a) and (b) of ormal weight, polymerization initiator and solvent etc. are added in reaction vessel, utilize nitrogen displace oxygen, form depleted gas atmosphere thus, carry out the method heating and be incubated while stirring.It should be noted that, polymerization initiator used herein and solvent etc. are not particularly limited, and can use polymerization initiator usually used in this field and solvent etc.As polymerization initiator, azo-compound (2 can be enumerated, 2 '-azoisobutyronitrile, 2,2 '-azo two (2,4-methyl pentane nitrile) etc.), organic peroxide (benzoyl peroxide etc.), as solvent, as long as dissolve the solvent of each monomer, the solvent (E) as colored curable resin composition of the present invention such as solvent of aftermentioned middle record can be set forth in.

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

With regard to resin [K2], in the entire infrastructure unit forming resin [K2], the ratio from the structural unit of each monomer is preferably:

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

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

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

Be more preferably:

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

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

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

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

Except also using (c) of ormal weight, in the same manner as the method can recorded with the manufacture method as resin [K1], manufacture resin [K2].

With regard to resin [K3], in the entire infrastructure unit forming resin [K3], the ratio from the structural unit of each monomer is preferably:

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

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

Be more preferably:

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

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

Manufacture in the same manner as the method that resin [K3] can be recorded with the manufacture method as resin [K1].

Resin [K4] manufactures by following method: after obtaining the multipolymer of (a) and (c), and the cyclic ether of the carbon number 2 ~ 4 that (b) is had adds and is formed in the carboxylic acid and/or carboxylic acid anhydrides that (a) have.

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

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

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

Relative to (a) 100 moles, the consumption of (b) is preferably 5 ~ 80 moles, is more preferably 10 ~ 75 moles.By making the consumption of (b) in this scope, there is following tendency: the balance of the solvent resistance of the storage stability of colored curable resin composition, developability when forming pattern and gained pattern, thermotolerance, physical strength and sensitivity is good.Because the reactivity of cyclic ether is high, not easily remaining unreacted (b), therefore as (b) that be used for resin [K4], be preferably (b1), further preferred (b1-1).

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

The reaction conditionss such as charging process, temperature of reaction and time can being considered manufacturing equipment, suitably adjusting by being polymerized the thermal value etc. caused.It should be noted that, about polymerizing condition, manufacturing equipment can being considered similarly, by being polymerized the thermal value that causes etc., charging process, temperature of reaction suitably being adjusted.

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

Relative to the total mole number of the entire infrastructure unit of the above-mentioned multipolymer of formation, the ratio from the structural unit of (b) and (c) is preferably respectively:

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

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

Be more preferably:

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

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

And then, the cyclic ether from (b) had by the carboxylic acid that makes (a) have under the condition identical with the manufacture method of resin [K4] or carboxylic acid anhydrides and the multipolymer that formed by (b) and (c) is reacted, and can obtain resin [K5].

5 ~ 80 moles are preferably relative to (b) 100 moles with the consumption of (a) of above-mentioned copolymer reaction.Because the reactivity of cyclic ether is high, not easily remaining unreacted (b), therefore as (b) that be used for resin [K5], be preferably (b1), further preferred (b1-1).

Resin [K6] is resin resin [K5] being reacted with carboxylic acid anhydrides further and obtains.Make cyclic ether and carboxylic acid or carboxylic acid anhydrides react and produce hydroxyl, and this hydroxyl and carboxylic acid anhydrides are reacted.

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

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

Resin (B) is preferably selected from the one in resin [K1], resin [K2] and resin [K3], is more preferably the one be selected from resin [K2] and resin [K3].When resin (B) is for these resins, the developability of colored curable resin composition is excellent.From the view point of the adaptation between colored pattern and substrate, further preferred resin [K2].

The weight-average molecular weight of the polystyrene conversion of resin (B) is preferably 3,000 ~ 100, and 000, be more preferably 5,000 ~ 50,000, more preferably 5,000 ~ 30,000.When molecular weight is in above-mentioned scope, there is following tendency: hardness of film improves, and residual film ratio is also high, the favorable solubility of unexposed portion in developer solution, 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.Here, acid number be as in and the amount (mg) of potassium hydroxide required for 1g resin (B) and the value that measures, obtain by such as using potassium hydroxide aqueous solution to carry out titration.

Relative to the total amount of solid constituent, the content of resin (B) is preferably 7 ~ 65 quality %, is more preferably 13 ~ 60 quality %, more preferably 17 ~ 55 quality %.The content of resin (B), when above-mentioned scope, exists and can form colored pattern and the tendency of the resolution of colored pattern and residual film ratio raising.

< polymerizable compound (C) >

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

As the polymerizable compound with 1 ethylenic unsaturated bond, can enumerate: nonyl phenyl carbitol acrylate, acrylic acid 2-hydroxyl-3-phenoxy-propyl, 2-ethylhexyl carbitol acrylate, acrylic acid 2-hydroxy methacrylate, NVP etc.; And above-mentioned (a), (b) and (c).

As the polymerizable compound with 2 ethylenic unsaturated bonds, can enumerate: 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.

Wherein, polymerizable compound (C) preferably has the polymerizable compound of more than 3 ethylenic unsaturated bonds.As such polymerizable compound, can enumerate: 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, preferred dipentaerythritol five (methyl) acrylate and dipentaerythritol six (methyl) acrylate.

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

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

Resin (B) is preferably 20: 80 ~ 80: 20 with the content ratio [resin (B): polymerizable compound (C)] of polymerizable compound (C) in quality criteria, is more preferably 35: 65 ~ 80: 20.

When the content of polymerizable compound (C) is in above-mentioned scope, the tendency that residual film ratio during existence formation colored pattern and the chemical reagent resistance of color filter improve.

< polymerization initiator (D) >

Polymerization initiator (D) as long as can produce the compound of living radical, acid etc. and initiated polymerization under the effect of light, heat, is then not particularly limited, can uses known polymerization initiator.

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

Above-mentioned O-acyl group oxime compound is the compound with structure shown in formula (d1).Below, " * " represents bonding arm.

As above-mentioned O-acyl group oxime compound, can enumerate: N-benzoyloxy-1-(4-Phenylsulfanylphenyl) butane-1-ketone-2-imines, N-benzoyloxy-1-(4-Phenylsulfanylphenyl) octane-1-ketone-2-imines, N-benzoyloxy-1-(4-Phenylsulfanylphenyl)-3-cyclopentyl propane-1-ketone-2-imines, N-acetoxyl group-1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base] ethane-1-imines, N-acetoxyl group-1-[9-ethyl-6-{2-methyl-4-(3, 3-dimethyl-2, 4-dioxolyl methoxyl) benzoyl }-9H-carbazole-3-base] ethane-1-imines, N-acetoxyl group-1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base]-3-cyclopentyl propane-1-imines, N-benzoyloxy-1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base]-3-cyclopentyl propane-1-ketone-2-imines etc.Also the commercially available product such as IRGACURE OXE01, OXE02 (above is BASF AG's system), N-1919 (ADEKA Inc.) can be used.Wherein, O-acyl group oxime compound is preferably selected from least one in N-benzoyloxy-1-(4-Phenylsulfanylphenyl) butane-1-ketone-2-imines, N-benzoyloxy-1-(4-Phenylsulfanylphenyl) octane-1-ketone-2-imines and N-benzoyloxy-1-(4-Phenylsulfanylphenyl)-3-cyclopentyl propane-1-ketone-2-imines, is more preferably N-benzoyloxy-1-(4-Phenylsulfanylphenyl) octane-1-ketone-2-imines.When using these O-acyl group oxime compounds, there is the tendency that can obtain the color filter of high brightness.

Abovementioned alkyl benzophenone compound is for having the compound of structure shown in structure shown in formula (d2) or formula (d3).In these structures, phenyl ring also can have substituting group.

As the compound with structure shown in formula (d2), can enumerate: 2-methyl-2-morpholino-1-(4-methyl mercapto phenyl) propane-1-ketone, 2-dimethylamino-1-(4-morphlinophenyl)-2-benzyl butane-1-ketone, 2-(dimethylamino)-2-[(4-aminomethyl phenyl) methyl]-1-[4-(4-morpholinyl) phenyl] butane-1-ketone etc.Also can use IRGACURE369,907, the commercially available product such as 379 (above for BASF AG's system).

As the compound with structure shown in formula (d3), can enumerate: oligomer, α, α-diethoxy acetophenone, the benzil dimethyl ketal etc. of 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 2-hydroxy-2-methyl-1-[4-(2-hydroxyl-oxethyl) phenyl] propane-1-ketone, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-(4-isopropenyl phenyl) propane-1-ketone.

From the view point of sensitivity, as alkyl phenones compound, preferably there is the compound of structure shown in formula (d2).

Above-mentioned united imidazole is the compound shown in formula (d5).

[in formula (d5), R ^13b~ R ^18bexpression can have the aryl of substituent carbon number 6 ~ 10.]

As the aryl of carbon number 6 ~ 10, can enumerate: phenyl, tolyl, xylyl, ethylphenyl and naphthyl etc., be preferably phenyl.

Alternatively base, can enumerate: the alkoxy etc. of halogen atom, carbon number 1 ~ 4.As halogen atom, fluorine atom, chlorine atom, bromine atoms, atomic iodine etc. can be enumerated, be preferably chlorine atom.As the alkoxy of carbon number 1 ~ 4, methoxyl, ethoxy, propoxyl group, butoxy etc. can be enumerated, be preferably methoxyl.

As united imidazole, can enumerate: 2, 2 '-bis-(2-chlorphenyl)-4, 4 ', 5, 5 '-tetraphenyl bisglyoxaline, 2, 2 '-bis-(2, 3-dichlorophenyl)-4, 4 ', 5, 5 '-tetraphenyl bisglyoxaline is (see Japanese Unexamined Patent Publication 6-75372 publication, Japanese Unexamined Patent Publication 6-75373 publication), 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 (see Japanese Patent Publication 48-38403 publication, Japanese Laid-Open Patent Publication 62-174204 publication), 4, 4 ', 5, the imidazolium compounds (see Japanese Unexamined Patent Publication 7-10913 publication) etc. that the phenyl of 5 '-position is replaced by alkoxy carbonyl group and obtains.Wherein, the compound shown in preferred following formula and their potpourri.

As above-mentioned triaizine compounds, can enumerate: 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-diethylamino-2-aminomethyl phenyl) vinyl]-1 of 4-, 3, 5-triazine, 2, two (trichloromethyl)-6-[2-(3 of 4-, 4-Dimethoxyphenyl) vinyl]-1, 3, 5-triazine etc.

As above-mentioned acylphosphine oxide compound, TMDPO etc. can be enumerated.

In addition, as polymerization initiator (D), can enumerate: the benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; Benzophenone, o-benzoyl yl benzoic acid methyl esters, 4-phenyl benzophenone, 4-benzoyl-4 '-dimethyl diphenyl sulfide, 3,3 ', 4,4 '-four (tert-butyl hydroperoxide carbonyl) benzophenone, 2, the benzophenone cpds such as 4,6-tri-methyl benzophenone; The naphtoquinone compounds such as 9,10-phenanthrenequione, 2-EAQ, camphorquinone; 10-butyl-2-chloro-acridine ketone, benzil, phenylglyoxalates methyl esters, two cyclopentadiene titanium compounds etc.

These polymerization initiators preferably cause auxiliary agent (D1) (particularly amine) combinationally use with described later polymerizations.

Polymerization initiator (D) preferably comprises the polymerization initiator of at least one be selected from 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.

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

< polymerization causes auxiliary agent (D1) >

Polymerization causes the compound or sensitizer that auxiliary agent (D1) is polymerization for promoting the polymerizable compound caused by polymerization initiator.When comprising polymerization and causing auxiliary agent (D1), usual and polymerization initiator (D) combinationally uses.

Cause auxiliary agent (D1) as polymerization, can enumerate: amines, alkoxy anthracene compound, thioxanthone compounds and carboxylic acid compound etc.

As above-mentioned amines, can enumerate: 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, 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 above-mentioned alkoxy anthracene compound, can enumerate: 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 above-mentioned thioxanthone compounds, can enumerate: ITX, ITX, 2,4-diethyl thioxanthones, 2,4-bis-clopenthixal ketones, the chloro-4-propoxythioxanthone of 1-etc.

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

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

< solvent (E) >

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

As ester solvent, can enumerate: 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, can enumerate: ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol list propyl 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, 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, diethylene glycol dibutyl ether, methyl phenyl ethers anisole, phenetol, methylanisole etc.

As ether-ether solvent, can enumerate: 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, acetic acid 3-methoxybutyl, acetic acid 3-methyl-3-methoxybutyl, propylene glycol monomethyl ether, propylene glycol monoethyl acetic acid esters, propylene glycol monopropyl ether acetic acid esters, ethylene glycol monomethyl ether acetic acid ester, ethylene glycol monomethyl ether acetate, TC acetic acid esters, diethylene glycol monobutyl ether acetic acid esters, dipropylene glycol methyl ether acetic acid esters etc.

As ketone solvent, can enumerate: 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, can enumerate: methyl alcohol, ethanol, propyl alcohol, butanols, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerine etc.

As aromatic hydrocarbon solvents, can enumerate: benzene,toluene,xylene, sym-trimethyl benzene etc.

As amide solvent, can enumerate: DMF, DMA, 1-METHYLPYRROLIDONE etc.

These solvents can be used alone and also can be used in combination of two or more.

Wherein, preferred propylene glycol monomethyl ether, ethyl lactate, propylene glycol monomethyl ether, 3-ethoxyl ethyl propionate, ethylene glycol monomethyl 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., more preferably propylene glycol monomethyl ether, 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.

Relative to the total amount of colored curable resin composition, the content of solvent (E) is preferably 70 ~ 95 quality %, is more preferably 75 ~ 92 quality %.In other words, the solid constituent of colored curable resin composition is preferably 5 ~ 30 quality %, is more preferably 8 ~ 25 quality %.When the content of solvent (E) is in above-mentioned scope, there is following tendency: flatness during coating is good, and make display characteristic good owing to can not there is colour saturation deficiency when forming color filter.

< levelling agent (F) >

As levelling agent (F), can enumerate: organosilicone surfactants, fluorine class surfactant and there is the organosilicone surfactants etc. of fluorine atom.These levelling agents also can have polymerizable group at side chain.

As organosilicone surfactants, the surfactant etc. with siloxane bond can be set forth in molecule.Specifically can enumerate: Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (trade name; Dong Li DOW CORNING Co., Ltd. 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 (Momentive Performance Materials Janpan contract commercial firm system) etc.

As above-mentioned fluorine class surfactant, the surfactant etc. with fluorocarbon chain can be set forth in molecule.Specifically can enumerate: Fluorad (registered trademark) FC430, Fluorad FC431 (Sumitomo3M Limited. system), Megafac (registered trademark) F142D, Megafac F171, Megafac F172, Megafac F173, Megafac F177, Megafac F183, Megafac F554, Megafac R30, Megafac RS-718-K (Dainippon Ink Chemicals's system), EFtop (registered trademark) EF301, EFtop EF303, EFtop EF351, EFtop EF352 (Mitsubishi Materials Electronic Chemicals Co., Ltd. make), Surflon (registered trademark) S381, Surflon S382, Surflon SC101, Surflon SC105 (Asahi Glass Co., Ltd's system) and E5844 (Daikin Fine Chemical Laboratory Co., Ltd. make) etc.

As the above-mentioned organosilicone surfactants with fluorine atom, the surfactant etc. with siloxane bond and fluorocarbon chain can be set forth in molecule.Specifically can enumerate: Megafac (registered trademark) R08, Megafac BL20, Megafac F475, Megafac F477 and Megafac F443 (Dainippon Ink Chemicals's system) etc.

When containing levelling agent (F), its content is preferably more than 0.001 quality % relative to the total amount of colored curable resin composition and below 0.2 quality %, be more preferably more than 0.002 quality % and below 0.1 quality %, more preferably more than 0.005 quality % and below 0.07 quality %.When the content of levelling agent (F) is in above-mentioned scope, the flatness of color filter can be made to become good.

< antioxidant (H) >

From improving the thermotolerance of colorant and sunproof viewpoint, preferably antioxidant is used alone or in combination two or more.As antioxidant, as long as industrial normally used antioxidant, be then not particularly limited, phenol antioxidant, phosphorus antioxidants and sulphur class antioxidant etc. can be used.

As above-mentioned phenol antioxidant, can enumerate: Irganox1010 (Irganox1010: pentaerythrite four [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester], BASF Co., Ltd. system), Irganox1076 (Irganox1076: octadecyl-3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester, BASF Co., Ltd. system), Irganox1330 (Irganox1330:3,3 ', 3 ", 5,5 ', 5 "-six tert-butyl group-a, a ', a "-(sym-trimethyl benzene-2,4,6-tri-base) three paracresol, BASF Co., Ltd. system), Irganox3114 (Irganox3114:1,3,5-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl)-1,3,5-triazines-2,4,6 (1H, 3H, 5H)-triketone, BASF Co., Ltd. system), Irganox3790 (Irganox3790:1,3,5-tri-((the 4-tert-butyl group-3-hydroxyl-2,6-xylyl) methyl)-1,3,5-triazines-2,4,6 (1H, 3H, 5H)-triketone, BASF Co., Ltd. system), Irganox1035 (Irganox1035: thiodiethyl two [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester], BASF Co., Ltd. system), Irganox1135 (two (1,1-the dimethyl ethyl)-4-hydroxy phenylpropionic acid C7-C9 pendant alkyl group ester of Irganox1135:3,5-, BASF Co., Ltd. system), Irganox1520L (two (pungent butylthiomethyl) orthoresol of Irganox1520L:4,6-, BASF Co., Ltd. system), Irganox3125 (Irganox3125, BASF Co., Ltd. system), Irganox565 (two (just pungent sulfenyl)-6-(4-hydroxyl 3 ', 5 '-di-tert-butyl amido)-1,3,5-triazines of Irganox565:2,4-, BASF Co., Ltd. system), ADK STAB AO-80 (two (2-(3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy)-1, the 1-dimethyl ethyl)-2 of ADK STAB AO-80:3,9-, 4, 8,10-tetra-oxaspiro (5,5) undecane, ADEKA Corp.'s system), Sumilizer BHT (Sumilizer BHT, Sumitomo Chemical Co's system), Sumilizer GA-80 (Sumilizer GA-80, Sumitomo Chemical Co's system), Sumilizer GS (Sumilizer GS, Sumitomo Chemical Co's system), Cyanox1790 (Cyanox1790, Cytec Inc.) and Vitamin E (Eisai Co., Ltd. system) etc.

As above-mentioned phosphorus antioxidants, can enumerate: Irgafos168 (Irgafos168: tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester, BASF Co., Ltd. system), Irgafos12 (Irgafos12: three [2-[[2,4,8,10-, tetra--tert-butyl group dibenzo [d, f] [1,3,2] dioxa phosphine-6-base] oxygen] ethyl] amine, BASF Co., Ltd. system), Irgafos38 (Irgafos38: phosphorous acid two (two (1,1-the dimethyl ethyl)-6-aminomethyl phenyl of 2,4-) ethyl ester, BASF Co., Ltd. system), ADK STAB329K (ADEKA Corp.'s system), ADK STAB PEP36 (ADEKA Corp.'s system), ADK STAB PEP-8 (ADEKA Corp.'s system), Sandstab P-EPQ (Clariant Inc.), Weston618 (Weston618, GE Inc.), Weston619G (Weston619G, GE Inc.), Ultranox626 (Ultranox626, GE Inc.) and Sumilizer GP (Sumilizer GP:6-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propoxyl group]-2,4,8,10-tetra--tert-butyl group dibenzo [d, f] [1.3.2] dioxaphosphepin English in heptan) (Sumitomo Chemical Co's system) etc.

As above-mentioned sulphur class antioxidant, can enumerate: the β-alkylmercaptopropionates compound etc. of the polyvalent alcohols such as the dialkyl thiodipropionate compounds such as dilauryl thiodipropionate, thio-2 acid two myristin or distearylthiodi-propionate and four [methylene (3-dodecylthio) propionic ester] methane.

Other composition of < >

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

The manufacture method > of < colored curable resin composition

Colored curable resin composition of the present invention can by by the colorants (A) such as compound (A-I), resin (B), polymerizable compound (C), polymerization initiator (D) and solvent (E) and as required and use levelling agent (F), polymerization cause auxiliary agent (D1) and other composition mixing prepare.

When comprising pigment (P), preferably in advance by part or all of the mixing of pigment with solvent (E), and ball mill etc. is utilized to disperse, until the mean grain size of pigment reaches the degree of less than 0.2 μm.Now, also the part or all of of above-mentioned pigment dispersing agent, resin (B) can be coordinated as required.By mixing all the other compositions and make these all the other compositions reach normal concentration in the dispersible pigment dispersion obtained like this, target coloration hardening resin composition can be prepared.

Preferably in advance the dyestuff of colorant (A) is dissolved in solvent (E) part or all of in prepare solution.Aperture is preferably utilized to be that the filtrator of about 0.01 ~ 1 μm filters this solution.

Aperture is preferably utilized to be that the filtrator of about 0.01 ~ 10 μm filters mixed colored curable resin composition.

The manufacture method > of < color filter

As the method being manufactured colored pattern by colored curable resin composition of the present invention, can enumerate: photoetching process, ink-jet method, print process etc.Wherein, preferred light lithography.Photoetching process is following method: above-mentioned colored curable resin composition is coated substrate, makes it dry and forms coloring compositions nitride layer, exposing across photomask, develop this coloring compositions nitride layer.In photolithography, yet can not use photomask when exposing and/or not develop, forming the solidfied material as above-mentioned coloring compositions nitride layer and painted film thus.The colored pattern of such formation, painted film are color filter of the present invention.

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

As substrate, can use: quartz glass, pyrex, alumina silicate glass, surface application have the glass plate of the soda-lime glass of silicon dioxide etc.; The resin plate of polycarbonate, polymethylmethacrylate, polyethylene terephthalate etc.; Silicon substrate; Aforesaid substrate is formed the substrate of aluminium, silver, silver/copper/palldium alloy film etc.These substrates can also be formed other color-filter layer, resin bed, transistor, circuit etc.

Utilize the formation of photolithographic each color pixel can carry out under known or usual device, condition.Such as, can make as described below.

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

As coating process, can enumerate: spin-coating method, slot coated method, slit spin-coating method etc.

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

When carrying out drying under reduced pressure, preferably to carry out in the temperature range of 20 DEG C ~ 25 DEG C under the pressure of 50Pa ~ 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, expose facing to colour cell compound layer across the photomask for the formation of target coloration pattern.Pattern on this photomask is not particularly limited, and can use the pattern corresponding to intended applications.

As the light source for exposing, the light source of the light of preferred emission 250 ~ 450nm wavelength.Such as, the wave filter of this wavelength coverage of interception can be used the light being less than 350nm to block, or the bandpass filter these wavelength coverages derived can be used to carry out selectivity derivation to the light near 436nm, near 408nm, near 365nm.Specifically, as light source, mercury lamp, light emitting diode, metal halide lamp, Halogen lamp LED etc. can be enumerated.

In order to can parallel rays be irradiated equably to plane of exposure entirety or make photomask carry out contraposition exactly with the substrate being formed with coloring compositions nitride layer, preferably use the exposure device such as mask aligner and stepper.

Make the coloring compositions nitride layer after exposure contact with developer solution and develop, colored pattern can be formed on substrate thus.Make the unexposed portion of coloring compositions nitride layer be dissolved in developer solution and be removed by carrying out developing.As developer solution, preference is as the aqueous solution of the alkali compounds such as potassium hydroxide, sodium bicarbonate, sodium carbonate, Tetramethylammonium hydroxide.These alkali compounds concentration is in aqueous preferably 0.01 ~ 10 quality %, is more preferably 0.03 ~ 5 quality %.And then, also can comprise surfactant in developer solution.

Developing method can be any means in paddling process (paddle method), infusion process and gunite etc.In addition, substrate can also be tilted to when developing arbitrarily angled.

Preferably wash after development.

And then, preferably rear baking is carried out to gained colored pattern.Rear baking temperature is preferably 150 ~ 250 DEG C, more preferably 160 ~ 235 DEG C.Post-bake times is preferably 1 ~ 120 minute, more preferably 10 ~ 60 minutes.

The colored curable resin composition of the application of the invention, can produce the color filter that thermotolerance is particularly excellent.This color filter is as being useful for display device (liquid crystal indicator, organic el device, Electronic Paper etc.) and the color filter of solid-state imager.

Embodiment

Below, utilize embodiment to illustrate in more detail the present invention, but the present invention is not by the restriction of these embodiments.In example, when being not particularly limited, represent that " % " and " part " of content or use amount is quality criteria.

In following example, the structure of compound is by mass spectrophotometry (LC; Agilent system 1200 type, MASS; Agilent LC/MSD type) confirm.

Synthesis example 1

In 2.00 parts, NaOH (Wako Pure Chemical Industries, Ltd.'s system), add methyl alcohol 50 parts and make it dissolve.Then, add 2,6-DHBA (Tokyo HuaCheng Industry Co., Ltd's system) 15.41 parts and boric acid (Wako Pure Chemical Industries, Ltd.'s system) 3.09 parts, stirred 8.5 hours in 65 DEG C.After this mixed liquor is cooled to room temperature, obtain precipitate by suction filtration, and utilize ion exchange water 237 parts to wash, obtain the compound shown in formula (BC-1-Na) 10.90 parts.

Synthesis example 2

Basic Blue7 (Tokyo HuaCheng Industry Co., Ltd) 5.1 parts is dissolved in 100 parts, water, adds the solution being dissolved with compound (BC-1-Na) 3.4 parts while stirring.After carrying out stirring for 3 hours, the crystal that collecting by filtration is separated out carrying out is washed, dry, obtain the dyestuff shown in formula (A-I-1) 8.0 parts with the form of blue colored crystal.

Synthesis example 3

In the flask possessing reflux condenser, tap funnel and stirring machine, pass into appropriate nitrogen and form nitrogen atmosphere, adding propylene glycol monomethyl ether 100 parts, be heated to 85 DEG C while stirring.Then, dropping pump is used to drip methacrylic acid 19 parts, acrylic acid 3,4-epoxy three ring [5.2.1.0 in this flask through about 5 hours ^2,6] decane-8-base ester and acrylic acid 3,4-epoxy three ring [5.2.1.0 ^2,6] decane-9-base ester potpourri (containing than with molar ratio computing for 50: 50) (trade name " E-DCPA ", Daicel Co., Ltd. system) 171 parts of solution be dissolved in propylene glycol monomethyl ether 40 parts.On the other hand, use another to drip pump and dripped polymerization initiator 2 in flask through about 5 hours, two (2,4-methyl pentane nitrile) the 26 parts of solution be dissolved in propylene glycol monomethyl ether 120 parts of 2 '-azo.After the dropping of polymerization initiator terminates, be held in this temperature about 3 hours, be then cooled to room temperature, obtain the solution of the copolymer resin (B-1) of solid constituent 43.5%.The acid number that the weight-average molecular weight of gained resin (B-1) is 8000, molecular weight distribution is 1.98, solid constituent converts is 53mg-KOH/g, and has following structural unit.

The weight-average molecular weight (Mw) of the polystyrene conversion of resin and the mensuration of number-average molecular weight (Mn) are carried out under the following conditions by GPC method.

Device: HLC-8120GPC (TOSOH Co., Ltd's system)

Chromatographic column: TSK-GELG2000HXL

Column temperature: 40 DEG C

Solvent: THF

Flow velocity: 1.0mL/min

Test solution solid component concentration: 0.001 ~ 0.01 quality %

Injection rate IR: 50 μ L

Detecting device: RI

Correction standard substance: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (TOSOH Co., Ltd's system)

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

Synthesis example 4

Get propylene glycol monomethyl ether 250.4 parts in the flask possessing stirring apparatus, tap funnel, condenser, thermometer, gas introduction tube, stir while carry out nitrogen displacement limit, and be warming up to 120 DEG C.Then, by methacrylic acid 37.4 parts, benzyl methacrylate 61.3 parts, glycidyl methacrylate 18.5 parts and there is tricyclodecane skeleton monomethacrylates (Hitachi Chemical Co., Ltd. FA-513M) 19.2 parts of monomer mixtures formed in add tert-butyl hydroperoxide (NOF Corp PERBUTYL O) 6.13 parts.This potpourri was dropped in flask by tap funnel through 2 hours, then continues stirring 2 hours in 120 DEG C, carried out slaking (aging).Then, air is replaced into by flask, after three (dimethylaminomethyl) phenol (DMP-30) 0.9 part and quinhydrones 0.145 part are put into 10.6 parts, acrylic acid, again they are put in the potpourri after above-mentioned slaking, continue reaction 6 hours in 120 DEG C, obtain the solution of the multipolymer (resin (B-2)) that solid constituent is 38.4 quality %, acid number is 122mg-KOH/g.The weight-average molecular weight Mw of gained resin (B-2) is 10700, molecular weight distribution is 2.18.

Weight-average molecular weight and molecular weight distribution measure according to the method same with resin (B-1).

[preparation of colored curable resin composition]

Embodiment 1

Following component is mixed, obtains colored curable resin composition.

Colorant (A): the dyestuff shown in formula (A-I-1) 24 parts;

Alkali soluble resin (B): resin (B-2) (solid constituent conversion) 60 parts;

Polymerizable compound (C): dipentaerythritol acrylate (KAYARAD (registered trademark) DPHA; Nippon Kayaku K. K's system) 40 parts;

Polymerization initiator (D): N-benzoyloxy-1-(4-Phenylsulfanylphenyl) octane-1-ketone-2-imines (IRGACURE (registered trademark) OXE-01; BASF AG's system; O-acyl group oxime compound) 10 parts;

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

Solvent (E): ethyl lactate 413 parts; And

Levelling agent (F): polyether modified silicon oil (Toray Silicone SH8400; Dong Li DOW CORNING Co., Ltd. system) 0.2 part.

Embodiment 2

By (A) colorant: C.I. pigment blue 15: 6 (pigment) 4.48 parts

Acrylic pigment spreading agent 1.76 parts

Propylene glycol monomethyl ether 29.8 parts

Mixing, and use ball mill that pigment is fully disperseed, and then mix following each component, obtain colored curable resin composition.

Colorant (A): the dyestuff shown in formula (A-I-1) 10 parts;

Alkali soluble resin (B): resin (B-2) (solid constituent conversion) 60 parts;

Solvent (E): propylene glycol monomethyl ether 300 parts;

Solvent (E): ethyl lactate 250 parts; And

Comparative example 1

Following component is mixed, obtains colored curable resin composition.

Colorant (A): the dyestuff shown in formula (A-III-1) 26 parts;

Alkali soluble resin (B): resin (B-1) (solid constituent conversion) 53 parts;

Polymerizable compound (C): dipentaerythritol acrylate (KAYARAD (registered trademark) DPHA; Nippon Kayaku K. K's system) 16 parts;

Polymerization initiator (D): N-benzoyloxy-1-(4-Phenylsulfanylphenyl) octane-1-ketone-2-imines (IRGACURE (registered trademark) OXE-01; BASF AG's system; O-acyl group oxime compound) 4 parts;

Solvent (E): propylene glycol monomethyl ether 120 parts;

Solvent (E): 4-hydroxy-4-methyl-2-pentanone 480 parts; And

Levelling agent (F): polyether modified silicon oil (Toray Silicone SH8400; Dong Li DOW CORNING Co., Ltd. system) 0.15 part.

[making of color filter]

Spin-coating method is utilized this colored curable resin composition to be coated the glass substrate (#1737 of 2 inch square; Corning Inc.) on, then carry out 3 minutes prebake conditions in 100 DEG C, define coloring compositions nitride layer.After cooling, use exposure machine (TME-150RSK; Topcon Co., Ltd's system) in atmospheric atmosphere with 150mJ/cm ²exposure (365nm benchmark) expose.Wherein, photomask is not used.Toast after coloring compositions nitride layer after exposure is carried out 20 minutes with 180 DEG C in an oven, made color filter (thickness 2.8 μm) thus.

[Evaluation of Heat Tolerance]

By the coated film of photosensitive composition in 230 DEG C of heating 20 minutes, use colour examining machine (OSP-SP-200; OLYMPUS Inc.) to coated film before heating after aberration (Δ Eab*) measure.Implement above-mentioned Evaluation of Heat Tolerance to the coated film obtained in embodiment 1 and embodiment 2, result shows: aberration (Δ Eab*) is respectively 9.7 and 5.7.

In addition, implement Evaluation of Heat Tolerance similarly for comparative example 1, result shows: aberration (Δ Eab*) is 12.1.Known: the color filter formed by colored curable resin composition of the present invention has excellent thermotolerance.

Utilizability in industry

According to colored curable resin composition of the present invention, the color filter of excellent heat resistance can be provided.This color filter is as being useful for display device (liquid crystal indicator, organic el device, Electronic Paper etc.) and the color filter of solid-state imager.

Claims

1. a colored curable resin composition, its compound shown in contained (A-I), resin (B), photopolymerizable compound (C), Photoepolymerizationinitiater initiater (D) and solvent (E),

In formula (A-I), X ^-represent the negative ion comprising boron atom or aluminium atom,

A expression (A-VI-1) or the group shown in formula (A-VI-2), " * " represents the bonding arm with carbon atom,

R ¹~ R ¹⁸represent saturated hydrocarbyl or the halogen atom of hydrogen atom, carbon number 1 ~ 10 independently of one another,

R ¹⁹and R ²⁰represent hydrogen atom ,-R independently of one another ^26aor the aromatic hydrocarbyl of carbon number 6 ~ 10, or, R ¹⁹and R ²⁰and together with the nitrogen-atoms of their bondings representative ring,

R ²¹and R ²²represent hydrogen atom ,-R independently of one another ^26aor the aromatic hydrocarbyl of carbon number 6 ~ 10, or, R ²¹and R ²²and together with the nitrogen-atoms of their bondings representative ring,

R ²³and R ²⁴represent hydrogen atom ,-R independently of one another ^26aor the aromatic hydrocarbyl of carbon number 6 ~ 10, or, R ²³and R ²⁴and together with the nitrogen-atoms of their bondings representative ring,

R ²⁵and R ²⁶represent hydrogen atom ,-R independently of one another ^26aor the aromatic hydrocarbyl of carbon number 6 ~ 10, or, R ²⁵and R ²⁶and together with the nitrogen-atoms of their bondings representative ring,

At R ¹⁹~ R ²⁶in, hydrogen atom contained in described aromatic hydrocarbyl can by halogen atom ,-R ^26a,-OH ,-OR ^26a,-SO ₃ ^-,-SO ₃na ,-CO ₂h ,-CO ₂r ^26a,-SO ₃h ,-SO ₃r ^26aor-SO ₂nHR ^28areplace,

R ^26arepresent the saturated hydrocarbyl of carbon number 1 ~ 10, hydrogen atom contained in this saturated hydrocarbyl can by-OR ^27a, halogen atom or benzene sulfonic acid alkali metal salt replace, formula-OR ^27ain, R ^27arepresent the saturated hydrocarbyl of carbon number 1 ~ 10,

R ^28arepresent hydrogen atom ,-R ^26a,-CO ₂r ^26aor the aromatic hydrocarbyl of carbon number 6 ~ 10, hydrogen atom contained in this aromatic hydrocarbyl can by-R ^26aor-OR ^27areplace.

2. colored curable resin composition according to claim 1, it also comprises blue pigment.

3. colored curable resin composition according to claim 1 and 2, it also comprises antioxidant (H).

4. a film, it is formed by the colored curable resin composition described in claim 1 or 2.

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

6. a display device, it comprises color filter according to claim 5.