CN102445851A

CN102445851A - Colored photosensitive composition

Info

Publication number: CN102445851A
Application number: CN2011102965212A
Authority: CN
Inventors: 宫芳子; 三浦洋之
Original assignee: Sumitomo Chemical Co Ltd
Current assignee: Sumitomo Chemical Co Ltd
Priority date: 2010-10-05
Filing date: 2011-10-08
Publication date: 2012-05-09
Anticipated expiration: 2031-10-08
Also published as: KR101795815B1; KR20120035862A; JP5825961B2; TWI554827B; TW201234103A; JP2012098712A; CN102445851B

Abstract

The present invention provides a colored photosensitive composition which can be used for obtaining a green color filter that has excellent color separation capability with a red color filter. The colored photosensitive composition comprises colorant, polymeric compound, polymerization initiating agent and dissolvent. The colorant comprises copper halide phthalocyanine paint, zinc halide phthalocyanine paint and quinaphthalone paint.

Description

Coloring photosensitive combination

Technical field

The present invention relates to form the coloring photosensitive combination of the rendered image that is suitable for constituting the color filter that uses in liquid crystal display cells, the solid-state imager.

Background technology

The color filter that uses in the display device such as display panels, electroluminescence panel, plasma display can use coloring photosensitive combination manufacturing.As this coloring photosensitive combination, known have a combinations thing, and it contains colorant, resin, optical polymerism compound, Photoepolymerizationinitiater initiater and solvent, and colorant is C.I. pigment green 36 and C.I. pigment yellow 150 (patent documentation 1).

Patent documentation 1: TOHKEMY 2005-157311 communique.

Summary of the invention

Use in the color filter of the green that above-mentioned coloring photosensitive combination forms, for the color separated ability of red color filter, may not be fully satisfactory.

The present invention provides following [1]～[8].

[1] coloring photosensitive combination, it contains colorant, polymerizable compound, polymerization initiator and solvent, and colorant is the colorant that contains copper halide phthalocyanine color, zinc halide phthalocyanine color and quinophthalone pigment.

[2] coloring photosensitive combination of above-mentioned [1] record, wherein, the content of copper halide phthalocyanine color with respect to content 100 mass parts of zinc halide phthalocyanine color, is 20 mass parts～150 mass parts.

[3] coloring photosensitive combination of above-mentioned [1] record, wherein, the content of quinophthalone pigment with respect to content 100 mass parts of zinc halide phthalocyanine color, is 50 mass parts～200 mass parts.

[4] coloring photosensitive combination of above-mentioned [1] record; Wherein, the content of copper halide phthalocyanine color is with respect to content 100 mass parts of zinc halide phthalocyanine color; Be 20 mass parts～150 mass parts; And the content of quinophthalone pigment with respect to content 100 mass parts of zinc halide phthalocyanine color, is 50 mass parts～200 mass parts.

[5] coloring photosensitive combination of any record in above-mentioned [1]～[4], wherein, the copper halide phthalocyanine color is the C.I. pigment Green 7.

[6] the colored photosensitive resin property composition of any record in above-mentioned [1]～[3], wherein, quinophthalone pigment is C.I. pigment yellow 13 8.

[7] coloring photosensitive combination of any record in above-mentioned [1]～[6] wherein, contains colorant, polymerizable compound, polymerization initiator, solvent and resin.

[8] color filter, its coloring photosensitive combination by any record in above-mentioned [1]～[7] forms.

According to coloring photosensitive combination of the present invention, can obtain and the excellent green color filter of the color separated ability of red color filter.

Embodiment

Coloring photosensitive combination of the present invention is following composition, and it contains colorant (A), polymerizable compound (C), polymerization initiator (D) and solvent (E), and colorant contains copper halide phthalocyanine color, zinc halide phthalocyanine color and quinophthalone pigment.Coloring photosensitive combination of the present invention preferably contains resin (B).

And in this instructions, the compound of enumerating as each composition only otherwise specify, then can use alone or in combination.

The colorant that uses in the coloring photosensitive combination of the present invention (A) contains copper halide phthalocyanine color, zinc halide phthalocyanine color and quinophthalone pigment.

As the copper halide phthalocyanine color, be preferably chlorinated copper phthalocyanine pigment, more preferably the C.I. pigment Green 7.If the copper halide phthalocyanine color is above-mentioned pigment, then owing to reducing near the transmissivity of 600nm, so excellent with the color separated ability of red color filter.

As the zinc halide phthalocyanine color, be preferably C.I. naphthol green 58.

The content of copper halide phthalocyanine color, content 100 mass parts with respect to the zinc halide phthalocyanine color are preferably 20 mass parts～150 mass parts, more preferably 80 mass parts～120 mass parts.If the content of copper halide phthalocyanine color is in above-mentioned scope; Then can be under the state of the transmissivity under the high 520nm of maintenance; Reduce near the transmissivity the 600nm, therefore can obtain with the color separated ability of red color filter excellent, and the green color filter of high brightness.When this green color filter is used as the color filter that in the green pixel of display device such as liquid crystal indicator, is provided with, can improve the color reproducibility of this display device.

Colorant (A) further contains quinophthalone pigment.The content of quinophthalone phthalocyanine color, content 100 mass parts with respect to the zinc halide phthalocyanine color are preferably 50 mass parts～200 mass parts, more preferably 120 mass parts～200 mass parts.As quinophthalone pigment, be preferably C.I. pigment yellow 13 8.Through containing above-mentioned quinophthalone pigment, exist and the excellent trend of the color separated ability of blue color filter.

Above-mentioned pigment can be implemented rosin as required and handle; Use to import the surface treatment that pigment derivative that acidic-group or basic group are arranged, pigment dispersing agent etc. carry out; Grafting through macromolecular compound etc. carries out surface of pigments is handled; Micronize through sulfuric acid micronize method etc. is carried out is handled, or the carrying out washing treatment of utilizing organic solvent, water etc. to carry out that is used to remove impurity, ionic impurity utilize that ion exchange process etc. carries out remove processing etc.In addition, pigment optimization uniform particle diameter.Carry out dispersion treatment through containing pigment dispersing agent, can obtain the dispersible pigment dispersion of the state that pigment disperses equably in solution.

As above-mentioned pigment dispersing agent, can use commercially available surfactant.As surfactant, can enumerate the for example surfactant of type siloxane, fluorine class, ester class, cationic, anionic species, nonionic class, both sexes, polyesters, polyamines class, acrylic compounds and polyurethanes.As above-mentioned surfactant; Except polyoxyethylene alkyl ether class, polyoxyethylene alkyl phenyl ether class, polyethylene glycol di class, sorbitan fatty acid esters class, fatty acid modified polyesters, tertiary amine modified polyurethane, polyethyleneimine: amine etc., can also enumerate KP (SHIN-ETSU HANTOTAI's chemical industry (strain) system) with trade name name, Off ローレ Application (common prosperity society chemistry (strain) is made), ソ Le スパース (ゼネカ (strain) system), EFKA (CIBA society system), アジスパー (monosodium glutamate Off ァイ Application テ Network ノ (strain) system), Disperbyk (PVC ッ Network ケミー society system) etc.They can distinguish alone or in combination 2 kinds with on use.

When using pigment dispersing agent, its consumption is preferably below the 100 quality %, more preferably 5～50 quality % with respect to the gross mass of pigment.If in above-mentioned scope, then there is the trend of the dispersible pigment dispersion of the disperse state that obtains homogeneous in the consumption of pigment dispersing agent.

The content of colorant (A), the solid formation branch with respect to coloring photosensitive combination is preferably 5～60 quality %, more preferably 5～45 quality %.If in above-mentioned scope, then can obtain required beam split, color depth.Wherein, Gu and the formation branch refers to the total of being removed the amount of obtaining of desolvating by coloring photosensitive combination.

Coloring photosensitive combination of the present invention preferably contains resin (B).

As the resin that uses in the coloring photosensitive combination of the present invention (B), be preferably the resin of performance alkali dissolution property.Wherein, alkali dissolution property refers to the character of in the developer solution as the WS of alkali cpd, dissolving.

As the resin of the above-mentioned alkali dissolution property of performance, can enumerate

Resin (B-1): will be selected from least a (a) (below be sometimes referred to as " (a) ") of unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides and have the multipolymer that the compound (b) that carbon number is 2～4 cyclic ether (below be sometimes referred to as " (b) ") is polymerized,

Resin (B-2): can with (a) and (b) monomer of copolymerization (c) (wherein, not having carbon number is 2～4 cyclic ether.) (below be sometimes referred to as " (c) "), (a) and the multipolymer that (b) is polymerized,

Resin (B-3): with (a) and the multipolymer that (c) is polymerized,

Resin (B-4): make (a) and resin that the multipolymer that (c) is polymerized obtains with (b) reaction,

Resin (B-5): make (b) and resin that the multipolymer that (c) is polymerized obtains with (a) reaction etc.

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-vinyl phthalic acid, 4-vinyl phthalic acid, 3,4,5; 6-tetrahydrophthalic acid, 1; 2,3,6-tetrahydrophthalic acid, dimethyl tetrahydro phthalic acid, 1; Unsaturated dicarboxylic classes such as 4-cyclohexene dicarboxylic acid

Methyl-5-ENB-2; 3-dicarboxylic acid, 5-carboxyl dicyclo [2.2.1] hept-2-ene", 5; 6-dicarboxyl dicyclo [2.2.1] hept-2-ene", 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" etc. contain the dicyclo unsaturated compound class of carboxyl

Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5; 6-tetrahydrophthalic anhydride, 1; 2,3,6-tetrahydrophthalic anhydride, dimethyl tetrahydro phthalic anhydride, dicyclo [2.2.1] hept-2-ene"-5; 6-dicarboxylic anhydride unsaturated dicarboxylic acid anhydride classes such as (carbic anhydrides)

Unsaturated list [(methyl) acryloxyalkyl] the ester class of the polybasic carboxylic acids more than 2 yuan such as mono succinate [2-(methyl) acryloxy ethyl] ester, phthalic acid list [2-(methyl) acryloxy ethyl] ester,

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

Wherein, acrylic acid, methacrylic acid, maleic anhydride etc. are considered preferred the use from the viewpoint of copolyreaction property, the viewpoint of alkali dissolution property.

Wherein, in this instructions, " (methyl) acrylic acid " expression is selected from acrylic acid and methacrylic acid at least a kind.Record such as " (methyl) acryloyl group " and " (methyl) acrylic ester " has the same meaning.

(b) be to have the polymerizable compound that carbon number is 2～4 a cyclic ether (for example be selected from oxirane ring, oxetanes ring and tetrahydrofuran ring (tetrahydrofuran ring) at least a kind).(b) preferably having carbon number is 2～4 the cyclic ether and the monomer of ethylenic unsaturated bond, is more preferably that to have carbon number be 2～4 cyclic ether and the monomer of (methyl) acryloxy.

As (b), can enumerate the monomer (b1) that for example has Oxyranyle (below be sometimes referred to as " (b1) "), have the monomer (b2) (below be sometimes referred to as " (b2) ") of oxetanyl and have the monomer (b3) (below be sometimes referred to as " (b3) ") of tetrahydrofuran base.

Have the monomer (b1) of Oxyranyle, refer to polymerizable compound with Oxyranyle.As (b1), can enumerate the monomer (b1-1) that for example has structure that the chain type alkene epoxidation is formed and ethylenic unsaturated bond (below be sometimes referred to as " (b1-1) ") and have structure that the cycloolefin epoxidation is formed and the monomer (b1-2) of ethylenic unsaturated bond (below be sometimes referred to as " (b1-2) ").

As (b1), be preferably monomer with Oxyranyle and ethylenic unsaturated bond, more preferably have the monomer of Oxyranyle and (methyl) acryloxy, further be preferably (b1-2) with (methyl) acryloxy.

As (b1-1), specifically, can enumerate (methyl) acrylic acid glycidyl esters, (methyl) acrylic acid Beta-methyl glycidyl esters, (methyl) propenoic acid beta-ethyl glycidyl esters, glycidyl vinyl ether, adjacent vinyl benzyl glycidyl ether, a vinyl benzyl glycidyl ether, to vinyl benzyl glycidyl ether, Alpha-Methyl-adjacent vinyl benzyl glycidyl ether, an Alpha-Methyl-vinyl benzyl glycidyl ether, Alpha-Methyl-to vinyl benzyl glycidyl ether, 2; Two (the glycidyl oxygen ylmethyl) styrene, 2 of 3-; Two (the glycidyl oxygen ylmethyl) styrene, 2 of 4-, two (the glycidyl oxygen ylmethyl) styrene, 2 of 5-, two (the glycidyl oxygen ylmethyl) styrene, 2 of 6-; 3; 4-three (glycidyl oxygen ylmethyl) styrene, 2,3,5-three (glycidyl oxygen ylmethyl) styrene, 2; 3; 6-three (glycidyl oxygen ylmethyl) styrene, 3,4,5-three (glycidyl oxygen ylmethyl) styrene, 2; 4, the compound of putting down in writing in 6-three (glycidyl oxygen ylmethyl) styrene, the japanese kokai publication hei 7-248625 communique etc.

As (b1-2); Can enumerate VCH list oxide, 1; (for example セロキサイ De 2000 for 2-epoxy-4-vinyl cyclohexane; ダイセ Le chemical industry (strain) system), acrylic acid 3,4-epoxycyclohexyl methyl ester (for example サイ Network ロマー A400, ダイセ Le chemical industry (strain) system), methacrylic acid 3; Compound shown in 4-epoxycyclohexyl methyl ester (for example サイ Network ロマー M100, ダイセ Le chemical industry (strain) system), the formula (I), the compound shown in the formula (II) etc.

[Chemical formula 1]

[in formula (I) and the formula (II), R ¹And R ²Represent that independently of each other hydrogen atom or carbon number are 1～4 alkyl, the hydrogen atom that contains in this alkyl can be replaced by hydroxyl.

X ¹And X ²Represent independently of each other singly-bound ,-R ³-, *-R ³-O-, *-R ³-S-, *-R ³-NH-.

R ³The expression carbon number is 1～6 alkane two bases.

* represent bonding key with O.]

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

As hydroxy alkyl, 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 ¹And R ², preferably enumerate hydrogen atom, methyl, hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, more preferably enumerate hydrogen atom, methyl.

As alkane two bases, can enumerate methylene, 1,2-ethylidene, propane-1,2-two bases, propane-1,3-two bases, butane-1,4-two bases, pentane-1,5-two bases, hexane-1,6-two bases etc.

As X ¹And X ², preferably enumerate singly-bound, methylene, 1,2-ethylidene, *-CH ₂-O-(* representes the bonding key with O) base, *-CH ₂CH ₂-O-base is more preferably enumerated singly-bound, *-CH ₂CH ₂-O-base.

As the compound shown in the formula (I), can enumerate the compound shown in formula (I-1)～formula (I-15) etc.Preferably enumerate formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9), formula (I-11)～formula (I-15).More preferably enumerate formula (I-1), formula (I-7), formula (I-9), formula (I-15).

[Chemical formula 2]

As the compound shown in the formula (II), can enumerate the compound shown in formula (II-1)～formula (II-15) etc.Preferably enumerate formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9), formula (II-11)～formula (II-15).More preferably enumerate formula (II-1), formula (II-7), formula (II-9), formula (II-15).

[chemical formula 3]

Compound shown in compound shown in the formula (I) and the formula (II) can be distinguished independent use.In addition, they also can mix with arbitrary proportion.During mixing, its blending ratio is with molar ratio computing, and preferred formula (I): formula (II) is 5:95～95:5, and more preferably 10:90～90:10 is preferably 20:80～80:20 especially.

Have the monomer (b2) of oxetanyl, refer to polymerizable compound with oxetanyl.As (b2), be preferably monomer with oxa-cyclobutyl and ethylenic unsaturated bond, more preferably have the monomer of oxetanyl and (methyl) acryloxy.As (b2), can enumerate for example 3-methyl-3-(methyl) acryloyl-oxy ylmethyl oxetanes, 3-ethyl-3-(methyl) acryloyl-oxy ylmethyl oxetanes, 3-methyl-3-(methyl) acryloxy ethyl oxetanes and 3-ethyl-3-(methyl) acryloxy ethyl oxetanes.

Have the monomer (b3) of tetrahydrofuran base, refer to polymerizable compound with tetrahydrofuran base.As (b3), be preferably monomer with tetrahydrofuran base and ethylenical unsaturated double bonds, more preferably have the monomer of tetrahydrofuran base and (methyl) acryloxy.

As (b3), specifically, can enumerate acrylic acid tetrahydro furfuryl ester (for example PVC スコート V#150, Osaka organic chemistry industry (strain) system), methacrylic acid tetrahydro furfuryl ester etc.

As (c), for example can enumerate (methyl) alkyl-acrylates such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-butyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate,

(methyl) cyclohexyl acrylate, (methyl) acrylic acid 2-methyl cyclohexane ester, (methyl) acrylic acid three ring [5.2.1.0 ^2,6] (methyl) acrylic acid cyclic alkyl ester classes such as decane-8-base ester (in this technical field,, being called (methyl) acrylic acid dicyclo amyl group ester as trivial name), the two cyclopentyloxy ethyl esters of (methyl) acrylic acid, (methyl) isobornyl acrylate,

(methyl) acrylic acid aryl ester or aralkyl ester classes such as (methyl) phenyl acrylate, (methyl) benzyl acrylate,

Dicarboxylic diesters such as diethyl maleate, DEF, diethyl itaconate,

Hydroxyalkyl acrylate classes such as (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester,

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-two (hydroxymethyl) dicyclo [2.2.1] hept-2-ene"; 5; 6-two (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"; 5; Two (tert-butoxycarbonyl) dicyclo [2.2.1] hept-2-ene"s of 6-; 5; Dicyclo unsaturated compound classes such as two (cyclohexyl oxygen base carbonyl) dicyclo [2.2.1] hept-2-ene"s of 6-

Dicarbapentaborane imide derivative classes such as N-phenylmaleimide, N-cyclohexyl maleimide, N-benzyl maleimide, N-succinimido-3-maleimide benzoic ether, N-succinimido-4-maleimide butyric ester, N-succinimido-6-maleimide capronate, N-succinimido-3-maleimide propionic ester, N-(9-acridinyl) maleimide

Styrene, AMS, a methyl styrene, p-methylstyrene, vinyltoluene, to methoxy styrene, vinyl cyanide, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylic amide, Methacrylamide, vinyl acetate, 1; 3-butadiene, isoprene and 2; 3-dimethyl-1,3-butadiene.

Wherein, styrene, N-phenylmaleimide, N-cyclohexyl maleimide, N-benzyl maleimide, dicyclo [2.2.1] hept-2-ene" etc. are considered preferred from the viewpoint of copolyreaction property and alkali dissolution property.

In the resin (B-1), as the ratio of the structural unit that comes from each monomer, with respect to the total mole number of the structural unit that constitutes resin (B-1), preferably in following scope.

Come from the structural unit of (a): 5～60 moles of % (10～50 moles of % more preferably)

Come from the structural unit of (b): 40～95 moles of % (50～90 moles of % more preferably)

If the ratio of the structural unit of resin (B-1) is in above-mentioned scope, the trend that then exists storage stability, development property, solvent resistance, thermotolerance and physical strength to become good.

As resin (B-1), preferably (b) is the resin of (b1), is more preferably (b) resin for (b1-2).

The citing document of putting down in writing in the method for record and the document during resin (B-1) for example can list of references " the high son that divides closes into the experiment method " (the big grand row work sale room in Tianjin (strain) chemistry is with the 1st edition the 1st printing distribution on March 1st, 1972 of people) prepares.

Specifically, can enumerate (a) of ormal weight and (b), polymerization initiator and solvent etc. join in the reaction vessel, utilizes the nitrogen replace oxygen, carries out deoxidation thus, and the method that stirs, heats, is incubated.And, use therein polymerization initiator and solvent etc. are not limited especially, can use normally used polymerization initiator arbitrarily and solvent in this field.As polymerization initiator, for example can enumerate azo-compound (2,2 '-azobis isobutyronitrile, 2; 2 '-azo two (2; The 4-methyl pentane nitrile) etc.) and organic peroxide (benzoyl peroxide etc.), as solvent, so long as the solvent of each monomer of solubilized gets final product; As the solvent of coloring photosensitive combination, the solvent of stating after can using etc.

And the multipolymer of gained can directly use reacted solution, also can use to concentrate or the solution of dilution, can also use the material that obtains with solid (powder) mode through methods such as depositions again.Particularly during this polymerization, as solvent, through use with after the identical solvent of solvent (E) stated, can directly use reacted solution, thereby can simplify preparation process.

In the resin (B-2), as the ratio of the structural unit that comes from each monomer, with respect to the total mole number of the entire infrastructure unit that constitutes resin (B-2), preferably in following scope.

Come from the structural unit of (a): 2～40 moles of % (5～35 moles of % more preferably)

Come from the structural unit of (b): 2～95 moles of % (5～80 moles of % more preferably)

Come from the structural unit of (c): 1～65 mole of % (1～60 mole of % more preferably)

If the ratio of the structural unit of resin (B-2) is in above-mentioned scope, the trend that then exists storage stability, development property, solvent resistance, thermotolerance and physical strength to become good.

As resin (B-2), preferably (b) is the resin of (b1), is more preferably (b) resin for (b1-2).

Resin (B-2) can be through the method preparation identical with resin (B-1).

In the resin (B-3), as the ratio of the structural unit that comes from each monomer, with respect to the total mole number of the entire infrastructure unit that constitutes resin (B-3), preferably in following scope.

Come from the structural unit of (c): 60～98 moles of % (65～95 moles of % more preferably)

If the ratio of the structural unit of resin (B-3) is in above-mentioned scope, the trend that then exists storage stability, development property, solvent resistance to become good.

Resin (B-3) can be through the method preparation identical with resin (B-1).

Resin (B-4) and resin (B-5) for example can pass through two stage step and prepare.At this moment, can wait with reference to the method for putting down in writing in the method for record in the above-mentioned document " high divide son close into the experiment method " (the big grand row work sale room in Tianjin (strain) chemistry is with the 1st edition the 1st printing distribution on March 1st, 1972 of people), the TOHKEMY 2001-89533 communique and prepare.

For resin (B-4),, likewise obtain (a) and (c) multipolymer with the preparation method of above-mentioned resin (B-1) at first as the phase one.

At this moment, with likewise above-mentioned, the multipolymer of gained can directly use reacted solution, also can use to concentrate or the solution of dilution, can also use the material that obtains with solid (powder) mode through methods such as depositions again.

Come from the ratio of (a) and structural unit (c), with respect to the total molal quantity of the entire infrastructure unit that constitutes above-mentioned multipolymer, preferably in following scope.

Come from the structural unit of (a): 5～50 moles of % (10～45 moles of % more preferably)

Come from the structural unit of (c): 50～95 moles of % (55～90 moles of % more preferably)

Then, as subordinate phase, make a part and the reaction of cyclic ether (b) of the carboxylic acid and the carboxylic acid anhydrides of (a) that come from the gained multipolymer.The reactivity of cyclic ether is high, is difficult to (b) of remained unreacted, therefore, as (b), preferably (b1), further preferably (b1-1).

Specifically; After above-mentioned; Atmosphere in the flask is replaced into air by nitrogen; In flask, add with respect to the molal quantity of (a) be 5～80 moles of % (b), be the carboxyl of 0.001～5 quality % and the catalysts of cyclic ether (for example three (dimethylaminomethyl) phenol) and be the polymerization inhibitor (for example quinhydrones) of 0.001～5 quality % with respect to (a) and (b) and total amount (c) with respect to (a) and (b) and total amount (c); 60～130 ℃ of reactions 1～10 hour, can obtain resin (A-4).And, with polymerizing condition likewise, consider thermal discharge that preparation equipment, polymerization cause etc., can suitably adjust adding method, temperature of reaction.

In addition, at this moment, molal quantity (b) with respect to the molal quantity of (a), is preferably 10～75 moles of %, more preferably 15～70 moles of %.Molal quantity through making (b) is in this scope, and storage stability, solvent resistance and stable on heating balance have the trend that becomes good.

Concrete example as resin (B-4); Can enumerate the resin that the multipolymer that makes (methyl) acrylic acid/(methyl) acrylic acid dicyclo amyl group ester obtains with the reaction of (methyl) acrylic acid glycidyl esters; The resin that the multipolymer that makes (methyl) acrylic acid/(methyl) acrylic acid benzyl ester obtains with the reaction of (methyl) acrylic acid glycidyl esters; The resin that the multipolymer that makes (methyl) acrylic acid/(methyl) acrylic acid cyclohexyl ester obtains with the reaction of (methyl) acrylic acid glycidyl esters; The resin that (methyl) acrylic acid/cinnamic multipolymer is obtained with the reaction of (methyl) acrylic acid glycidyl esters; The resin that the multipolymer that makes (methyl) acrylic acid/(methyl) methyl acrylate obtains with the reaction of (methyl) acrylic acid glycidyl esters; The resin that the multipolymer that makes (methyl) acrylic acid/N-cyclohexyl maleimide obtains with the reaction of (methyl) acrylic acid glycidyl esters; The resin that the multipolymer that makes (methyl) acrylic acid/(methyl) acrylic acid dicyclo amyl group ester/(methyl) acrylic acid benzyl ester obtains with the reaction of (methyl) acrylic acid glycidyl esters; The resin that the multipolymer that makes (methyl) acrylic acid/(methyl) acrylic acid dicyclo amyl group ester/(methyl) acrylic acid cyclohexyl ester obtains with the reaction of (methyl) acrylic acid glycidyl esters; The resin that (methyl) acrylic acid/(methyl) acrylic acid dicyclo amyl group ester/cinnamic multipolymer is obtained with the reaction of (methyl) acrylic acid glycidyl esters; The resin that the multipolymer that makes (methyl) acrylic acid/(methyl) acrylic acid dicyclo amyl group ester/(methyl) methyl acrylate obtains with the reaction of (methyl) acrylic acid glycidyl esters; The resin that the multipolymer that makes (methyl) acrylic acid/(methyl) acrylic acid dicyclo amyl group ester/N-cyclohexyl maleimide obtains with the reaction of (methyl) acrylic acid glycidyl esters; The resin that the multipolymer that makes crotonic acid/(methyl) acrylic acid dicyclo amyl group ester obtains with the reaction of (methyl) acrylic acid glycidyl esters

The resin that the multipolymer that makes crotonic acid/(methyl) acrylic acid benzyl ester obtains with the reaction of (methyl) acrylic acid glycidyl esters; The resin that the multipolymer that makes crotonic acid/(methyl) acrylic acid cyclohexyl ester obtains with the reaction of (methyl) acrylic acid glycidyl esters; The resin that crotonic acid/cinnamic multipolymer is obtained with the reaction of (methyl) acrylic acid glycidyl esters; The resin that the multipolymer that makes crotonic acid/ethyl crotonate obtains with the reaction of (methyl) acrylic acid glycidyl esters; The resin that the multipolymer that makes crotonic acid/N-cyclohexyl maleimide obtains with the reaction of (methyl) acrylic acid glycidyl esters; The resin that the multipolymer that makes crotonic acid/(methyl) acrylic acid dicyclo amyl group ester/(methyl) acrylic acid benzyl ester obtains with the reaction of (methyl) acrylic acid glycidyl esters; The resin that the multipolymer that makes crotonic acid/(methyl) acrylic acid dicyclo amyl group ester/(methyl) acrylic acid cyclohexyl ester obtains with the reaction of (methyl) acrylic acid glycidyl esters; The resin that crotonic acid/(methyl) acrylic acid dicyclo amyl group ester/cinnamic multipolymer is obtained with the reaction of (methyl) acrylic acid glycidyl esters; The resin that the multipolymer that makes crotonic acid/(methyl) acrylic acid dicyclo amyl group ester/ethyl crotonate obtains with the reaction of (methyl) acrylic acid glycidyl esters; The resin that the multipolymer that makes crotonic acid/(methyl) acrylic acid dicyclo amyl group ester/N-cyclohexyl maleimide obtains with the reaction of (methyl) acrylic acid glycidyl esters

The resin that the multipolymer that makes maleic acid/(methyl) acrylic acid dicyclo amyl group ester obtains with the reaction of (methyl) acrylic acid glycidyl esters; The resin that the multipolymer that makes maleic acid/(methyl) acrylic acid benzyl ester obtains with the reaction of (methyl) acrylic acid glycidyl esters; The resin that the multipolymer that makes maleic acid/(methyl) acrylic acid cyclohexyl ester obtains with the reaction of (methyl) acrylic acid glycidyl esters; The resin that maleic acid/cinnamic multipolymer is obtained with the reaction of (methyl) acrylic acid glycidyl esters; The resin that the multipolymer that makes maleic acid/maleic acid methyl esters obtains with the reaction of (methyl) acrylic acid glycidyl esters; The resin that the multipolymer that makes maleic acid/N-cyclohexyl maleimide obtains with the reaction of (methyl) acrylic acid glycidyl esters; The resin that the multipolymer that makes maleic acid/(methyl) acrylic acid dicyclo amyl group ester/(methyl) acrylic acid benzyl ester obtains with the reaction of (methyl) acrylic acid glycidyl esters; The resin that the multipolymer that makes maleic acid/(methyl) acrylic acid dicyclo amyl group ester/(methyl) acrylic acid cyclohexyl ester obtains with the reaction of (methyl) acrylic acid glycidyl esters; The resin that maleic acid/(methyl) acrylic acid dicyclo amyl group ester/cinnamic multipolymer is obtained with the reaction of (methyl) acrylic acid glycidyl esters; The resin that the multipolymer that makes maleic acid/(methyl) acrylic acid dicyclo amyl group ester/maleic acid methyl esters obtains with the reaction of (methyl) acrylic acid glycidyl esters; The resin that the multipolymer that makes maleic acid/(methyl) acrylic acid dicyclo amyl group ester/N-cyclohexyl maleimide obtains with the reaction of (methyl) acrylic acid glycidyl esters

The resin that the multipolymer that makes (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid dicyclo amyl group ester obtains with the reaction of (methyl) acrylic acid glycidyl esters; The resin that the multipolymer that makes (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid benzyl ester obtains with the reaction of (methyl) acrylic acid glycidyl esters; The resin that the multipolymer that makes (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid cyclohexyl ester obtains with the reaction of (methyl) acrylic acid glycidyl esters; The resin that (methyl) acrylic acid/maleic anhydride/cinnamic multipolymer is obtained with the reaction of (methyl) acrylic acid glycidyl esters; The resin that the multipolymer that makes (methyl) acrylic acid/maleic anhydride/(methyl) methyl acrylate obtains with the reaction of (methyl) acrylic acid glycidyl esters; The resin that the multipolymer that makes (methyl) acrylic acid/maleic anhydride/N-cyclohexyl maleimide obtains with the reaction of (methyl) acrylic acid glycidyl esters; The resin that the multipolymer that makes (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid dicyclo amyl group ester/(methyl) acrylic acid benzyl ester obtains with the reaction of (methyl) acrylic acid glycidyl esters; The resin that the multipolymer that makes (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid dicyclo amyl group ester/(methyl) acrylic acid cyclohexyl ester obtains with the reaction of (methyl) acrylic acid glycidyl esters; The resin that (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid dicyclo amyl group ester/cinnamic multipolymer is obtained with the reaction of (methyl) acrylic acid glycidyl esters; The resin that the multipolymer that makes (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid dicyclo amyl group ester/(methyl) methyl acrylate obtains with the reaction of (methyl) acrylic acid glycidyl esters; The resin that the multipolymer that makes (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid dicyclo amyl group ester/N-cyclohexyl maleimide obtains with the reaction of (methyl) acrylic acid glycidyl esters

Make the multipolymer and the methacrylic acid 3 of (methyl) acrylic acid/(methyl) acrylic acid dicyclo amyl group ester; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains; Make the multipolymer and the methacrylic acid 3 of (methyl) acrylic acid/(methyl) acrylic acid benzyl ester; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains; Make the multipolymer and the methacrylic acid 3 of (methyl) acrylic acid/(methyl) acrylic acid cyclohexyl ester; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains; Make (methyl) acrylic acid/cinnamic multipolymer and methacrylic acid 3; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains; Make the multipolymer and the methacrylic acid 3 of (methyl) acrylic acid/(methyl) methyl acrylate; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains; Make the multipolymer and the methacrylic acid 3 of (methyl) acrylic acid/N-cyclohexyl maleimide; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains; Make the multipolymer and the methacrylic acid 3 of (methyl) acrylic acid/(methyl) acrylic acid dicyclo amyl group ester/(methyl) acrylic acid benzyl ester; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains; Make the multipolymer and the methacrylic acid 3 of (methyl) acrylic acid/(methyl) acrylic acid dicyclo amyl group ester/(methyl) acrylic acid cyclohexyl ester; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains; Make (methyl) acrylic acid/(methyl) acrylic acid dicyclo amyl group ester/cinnamic multipolymer and methacrylic acid 3; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains; Make the multipolymer and the methacrylic acid 3 of (methyl) acrylic acid/(methyl) acrylic acid dicyclo amyl group ester/(methyl) methyl acrylate; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains; Make the multipolymer and the methacrylic acid 3 of (methyl) acrylic acid/(methyl) acrylic acid dicyclo amyl group ester/N-cyclohexyl maleimide; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains

Make the multipolymer and the methacrylic acid 3 of crotonic acid/(methyl) acrylic acid dicyclo amyl group ester; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains; Make the multipolymer and the methacrylic acid 3 of crotonic acid/(methyl) acrylic acid benzyl ester; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains; Make the multipolymer and the methacrylic acid 3 of crotonic acid/(methyl) acrylic acid cyclohexyl ester; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains; Make crotonic acid/cinnamic multipolymer and methacrylic acid 3; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains; Make the multipolymer and the methacrylic acid 3 of crotonic acid/ethyl crotonate; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains; Make the multipolymer and the methacrylic acid 3 of crotonic acid/N-cyclohexyl maleimide; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains; Make the multipolymer and the methacrylic acid 3 of crotonic acid/(methyl) acrylic acid dicyclo amyl group ester/(methyl) acrylic acid benzyl ester; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains; Make the multipolymer and the methacrylic acid 3 of crotonic acid/(methyl) acrylic acid dicyclo amyl group ester/(methyl) acrylic acid cyclohexyl ester; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains; Make crotonic acid/(methyl) acrylic acid dicyclo amyl group ester/cinnamic multipolymer and methacrylic acid 3; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains; Make the multipolymer and the methacrylic acid 3 of crotonic acid/(methyl) acrylic acid dicyclo amyl group ester/ethyl crotonate; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains; Make the multipolymer and the methacrylic acid 3 of crotonic acid/(methyl) acrylic acid dicyclo amyl group ester/N-cyclohexyl maleimide; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains

Make the multipolymer and the methacrylic acid 3 of maleic acid/(methyl) acrylic acid dicyclo amyl group ester; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains; Make the multipolymer and the methacrylic acid 3 of maleic acid/(methyl) acrylic acid benzyl ester; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains; Make the multipolymer and the methacrylic acid 3 of maleic acid/(methyl) acrylic acid cyclohexyl ester; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains; Make maleic acid/cinnamic multipolymer and methacrylic acid 3; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains; Make the multipolymer and the methacrylic acid 3 of maleic acid/maleic acid methyl esters; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains; Make the multipolymer and the methacrylic acid 3 of maleic acid/N-cyclohexyl maleimide; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains; Make the multipolymer and the methacrylic acid 3 of maleic acid/(methyl) acrylic acid dicyclo amyl group ester/(methyl) acrylic acid benzyl ester; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains; Make the multipolymer and the methacrylic acid 3 of maleic acid/(methyl) acrylic acid dicyclo amyl group ester/(methyl) acrylic acid cyclohexyl ester; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains; Make maleic acid/(methyl) acrylic acid dicyclo amyl group ester/cinnamic multipolymer and methacrylic acid 3; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains; Make the multipolymer and the methacrylic acid 3 of maleic acid/(methyl) acrylic acid dicyclo amyl group ester/maleic acid methyl esters; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains; Make the multipolymer and the methacrylic acid 3 of maleic acid/(methyl) acrylic acid dicyclo amyl group ester/N-cyclohexyl maleimide; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains

Make the multipolymer and the methacrylic acid 3 of (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid dicyclo amyl group ester; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains, multipolymer and the methacrylic acid 3 that makes (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid benzyl ester; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains, multipolymer and the methacrylic acid 3 that makes (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid cyclohexyl ester; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains, make (methyl) acrylic acid/maleic anhydride/cinnamic multipolymer and methacrylic acid 3; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains, multipolymer and the methacrylic acid 3 that makes (methyl) acrylic acid/maleic anhydride/(methyl) methyl acrylate; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains, multipolymer and the methacrylic acid 3 that makes (methyl) acrylic acid/maleic anhydride/N-cyclohexyl maleimide; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains, multipolymer and the methacrylic acid 3 that makes (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid dicyclo amyl group ester/(methyl) acrylic acid benzyl ester; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains, multipolymer and the methacrylic acid 3 that makes (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid dicyclo amyl group ester/(methyl) acrylic acid cyclohexyl ester; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains, make (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid dicyclo amyl group ester/cinnamic multipolymer and methacrylic acid 3; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains, multipolymer and the methacrylic acid 3 that makes (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid dicyclo amyl group ester/(methyl) methyl acrylate; 4-epoxycyclohexyl methyl ester reaction and the resin that obtains, multipolymer and the methacrylic acid 3 that makes (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid dicyclo amyl group ester/N-cyclohexyl maleimide, 4-epoxycyclohexyl methyl ester react and the resin that obtains etc.

For resin (B-5),, likewise obtain (b) and (c) multipolymer with the preparation method of above-mentioned resin (B-1) as the phase one.

As coming from (b) and structural unit ratio (c), with respect to the total mole number of the entire infrastructure unit that constitutes above-mentioned multipolymer, preferably in following scope.

Come from the structural unit of (b): 5～95 moles of % (10～90 moles of % more preferably)

Come from the structural unit of (c): 5～95 moles of % (10～90 moles of % more preferably)

Further, with the preparation method of resin (B-4) likewise, can obtain through (b) and the cyclic ether that comes from (b) in (c) the multipolymer are reacted with carboxylic acid that (a) is had or carboxylic acid anhydrides.The hydroxyl that reaction through cyclic ether and carboxylic acid or carboxylic acid anhydrides is produced further reacts with carboxylic acid anhydrides.

Consumption with (a) of above-mentioned copolymer reaction with respect to the molal quantity of (b), is preferably 5～80 moles of %.The reactivity of cyclic ether is high, is difficult to (b) of remained unreacted, therefore, as (b), preferably (b1), further preferably (b1-1).

Concrete example as resin (B-5); Can enumerate the resin that the multipolymer that makes (methyl) acrylic acid dicyclo amyl group ester/(methyl) acrylic acid glycidyl esters obtains with the reaction of (methyl) acrylic acid; The resin that the multipolymer that makes (methyl) acrylic acid benzyl ester/(methyl) acrylic acid glycidyl esters obtains with the reaction of (methyl) acrylic acid; The resin that the multipolymer that makes (methyl) acrylic acid cyclohexyl ester/(methyl) acrylic acid glycidyl esters obtains with the reaction of (methyl) acrylic acid; The resin that the multipolymer that makes styrene/(methyl) acrylic acid glycidyl esters obtains with the reaction of (methyl) acrylic acid; The resin that the multipolymer that makes (methyl) methyl acrylate/(methyl) acrylic acid glycidyl esters obtains with the reaction of (methyl) acrylic acid; The resin that the multipolymer that makes N-cyclohexyl maleimide/(methyl) acrylic acid glycidyl esters obtains with the reaction of (methyl) acrylic acid; The resin that the multipolymer that makes (methyl) acrylic acid dicyclo amyl group ester/(methyl) acrylic acid benzyl ester/(methyl) acrylic acid glycidyl esters obtains with the reaction of (methyl) acrylic acid; The resin that the multipolymer that makes (methyl) acrylic acid dicyclo amyl group ester/(methyl) acrylic acid cyclohexyl ester/(methyl) acrylic acid glycidyl esters obtains with the reaction of (methyl) acrylic acid; The resin that the multipolymer that makes (methyl) acrylic acid dicyclo amyl group ester/styrene/(methyl) acrylic acid glycidyl esters obtains with the reaction of (methyl) acrylic acid; The resin that the multipolymer that makes (methyl) acrylic acid dicyclo amyl group ester/(methyl) methyl acrylate/(methyl) acrylic acid glycidyl esters obtains with the reaction of (methyl) acrylic acid; The resin that the multipolymer that makes (methyl) acrylic acid dicyclo amyl group ester/N-cyclohexyl maleimide/(methyl) acrylic acid glycidyl esters obtains with the reaction of (methyl) acrylic acid

The resin that makes multipolymer and the crotonic acid reaction of (methyl) acrylic acid dicyclo amyl group ester/(methyl) acrylic acid glycidyl esters and obtain; The resin that makes multipolymer and the crotonic acid reaction of (methyl) acrylic acid benzyl ester/(methyl) acrylic acid glycidyl esters and obtain; The resin that makes multipolymer and the crotonic acid reaction of (methyl) acrylic acid cyclohexyl ester/(methyl) acrylic acid glycidyl esters and obtain; The resin that makes multipolymer and the crotonic acid reaction of styrene/(methyl) acrylic acid glycidyl esters and obtain; The resin that makes multipolymer and the crotonic acid reaction of ethyl crotonate/(methyl) acrylic acid glycidyl esters and obtain; The resin that makes multipolymer and the crotonic acid reaction of N-cyclohexyl maleimide/(methyl) acrylic acid glycidyl esters and obtain; The resin that makes multipolymer and the crotonic acid reaction of (methyl) acrylic acid dicyclo amyl group ester/(methyl) acrylic acid benzyl ester/(methyl) acrylic acid glycidyl esters and obtain; The resin that makes multipolymer and the crotonic acid reaction of (methyl) acrylic acid dicyclo amyl group ester/(methyl) acrylic acid cyclohexyl ester/(methyl) acrylic acid glycidyl esters and obtain; The resin that makes multipolymer and the crotonic acid reaction of (methyl) acrylic acid dicyclo amyl group ester/styrene/(methyl) acrylic acid glycidyl esters and obtain; The resin that makes multipolymer and the crotonic acid reaction of (methyl) acrylic acid dicyclo amyl group ester/ethyl crotonate/(methyl) acrylic acid glycidyl esters and obtain; The resin that makes multipolymer and the crotonic acid reaction of (methyl) acrylic acid dicyclo amyl group ester/N-cyclohexyl maleimide/(methyl) acrylic acid glycidyl esters and obtain

The resin that makes multipolymer and the maleic acid reaction of (methyl) acrylic acid dicyclo amyl group ester/(methyl) acrylic acid glycidyl esters and obtain; The resin that makes multipolymer and the maleic acid reaction of (methyl) acrylic acid benzyl ester/(methyl) acrylic acid glycidyl esters and obtain; The resin that makes multipolymer and the maleic acid reaction of (methyl) acrylic acid cyclohexyl ester/(methyl) acrylic acid glycidyl esters and obtain; The resin that makes multipolymer and the maleic acid reaction of styrene/(methyl) acrylic acid glycidyl esters and obtain; The resin that makes multipolymer and the maleic acid reaction of maleic acid methyl esters/(methyl) acrylic acid glycidyl esters and obtain; The resin that makes multipolymer and the maleic acid reaction of N-cyclohexyl maleimide/(methyl) acrylic acid glycidyl esters and obtain; The resin that makes multipolymer and the maleic acid reaction of (methyl) acrylic acid dicyclo amyl group ester/(methyl) acrylic acid benzyl ester/(methyl) acrylic acid glycidyl esters and obtain; The resin that makes multipolymer and the maleic acid reaction of (methyl) acrylic acid dicyclo amyl group ester/(methyl) acrylic acid cyclohexyl ester/(methyl) acrylic acid glycidyl esters and obtain; The resin that makes multipolymer and the maleic acid reaction of (methyl) acrylic acid dicyclo amyl group ester/styrene/(methyl) acrylic acid glycidyl esters and obtain; The resin that makes multipolymer and the maleic acid reaction of (methyl) acrylic acid dicyclo amyl group ester/maleic acid methyl esters/(methyl) acrylic acid glycidyl esters and obtain; The resin that makes multipolymer and the maleic acid reaction of (methyl) acrylic acid dicyclo amyl group ester/N-cyclohexyl maleimide/(methyl) acrylic acid glycidyl esters and obtain

The multipolymer that makes (methyl) acrylic acid dicyclo amyl group ester/(methyl) acrylic acid glycidyl esters reacts with (methyl) acrylic acid and maleic anhydride and the resin that obtains; The multipolymer that makes (methyl) acrylic acid benzyl ester/(methyl) acrylic acid glycidyl esters reacts with (methyl) acrylic acid and maleic anhydride and the resin that obtains; The multipolymer that makes (methyl) acrylic acid cyclohexyl ester/(methyl) acrylic acid glycidyl esters reacts with (methyl) acrylic acid and maleic anhydride and the resin that obtains; The multipolymer that makes styrene/(methyl) acrylic acid glycidyl esters reacts with (methyl) acrylic acid and maleic anhydride and the resin that obtains; The multipolymer that makes (methyl) methyl acrylate/(methyl) acrylic acid glycidyl esters reacts with (methyl) acrylic acid and maleic anhydride and the resin that obtains; The multipolymer that makes N-cyclohexyl maleimide/(methyl) acrylic acid glycidyl esters reacts with (methyl) acrylic acid and maleic anhydride and the resin that obtains; The multipolymer that makes (methyl) acrylic acid dicyclo amyl group ester/(methyl) acrylic acid benzyl ester/(methyl) acrylic acid glycidyl esters reacts with (methyl) acrylic acid and maleic anhydride and the resin that obtains; The multipolymer that makes (methyl) acrylic acid dicyclo amyl group ester/(methyl) acrylic acid cyclohexyl ester/(methyl) acrylic acid glycidyl esters reacts with (methyl) acrylic acid and maleic anhydride and the resin that obtains; The multipolymer that makes (methyl) acrylic acid dicyclo amyl group ester/styrene/(methyl) acrylic acid glycidyl esters reacts with (methyl) acrylic acid and maleic anhydride and the resin that obtains; The multipolymer that makes (methyl) acrylic acid dicyclo amyl group ester/(methyl) methyl acrylate/(methyl) acrylic acid glycidyl esters reacts with (methyl) acrylic acid and maleic anhydride and the resin that obtains; The multipolymer that makes (methyl) acrylic acid dicyclo amyl group ester/N-cyclohexyl maleimide/(methyl) acrylic acid glycidyl esters reacts with (methyl) acrylic acid and maleic anhydride and the resin that obtains

Make (methyl) acrylic acid dicyclo amyl group ester/methacrylic acid 3; The resin that the multipolymer of 4-epoxycyclohexyl methyl ester obtains with the reaction of (methyl) acrylic acid; Make (methyl) acrylic acid benzyl ester/methacrylic acid 3; The resin that the multipolymer of 4-epoxycyclohexyl methyl ester obtains with the reaction of (methyl) acrylic acid; Make (methyl) acrylic acid cyclohexyl ester/methacrylic acid 3; The resin that the multipolymer of 4-epoxycyclohexyl methyl ester obtains with the reaction of (methyl) acrylic acid; Make styrene/methacrylic acid 3; The resin that the multipolymer of 4-epoxycyclohexyl methyl ester obtains with the reaction of (methyl) acrylic acid; Make (methyl) methyl acrylate/methacrylic acid 3; The resin that the multipolymer of 4-epoxycyclohexyl methyl ester obtains with the reaction of (methyl) acrylic acid; Make N-cyclohexyl maleimide/methacrylic acid 3; The resin that the multipolymer of 4-epoxycyclohexyl methyl ester obtains with the reaction of (methyl) acrylic acid; Make (methyl) acrylic acid dicyclo amyl group ester/(methyl) acrylic acid benzyl ester/methacrylic acid 3; The resin that the multipolymer of 4-epoxycyclohexyl methyl ester obtains with the reaction of (methyl) acrylic acid; Make (methyl) acrylic acid dicyclo amyl group ester/(methyl) acrylic acid cyclohexyl ester/methacrylic acid 3; The resin that the multipolymer of 4-epoxycyclohexyl methyl ester obtains with the reaction of (methyl) acrylic acid; Make (methyl) acrylic acid dicyclo amyl group ester/styrene/methacrylic acid 3; The resin that the multipolymer of 4-epoxycyclohexyl methyl ester obtains with the reaction of (methyl) acrylic acid; Make (methyl) acrylic acid dicyclo amyl group ester/(methyl) methyl acrylate/methacrylic acid 3; The resin that the multipolymer of 4-epoxycyclohexyl methyl ester obtains with the reaction of (methyl) acrylic acid; Make (methyl) acrylic acid dicyclo amyl group ester/N-cyclohexyl maleimide/methacrylic acid 3; The resin that the multipolymer of 4-epoxycyclohexyl methyl ester obtains with the reaction of (methyl) acrylic acid

Make (methyl) acrylic acid dicyclo amyl group ester/methacrylic acid 3; The reaction of the multipolymer of 4-epoxycyclohexyl methyl ester and crotonic acid and the resin that obtains; Make (methyl) acrylic acid benzyl ester/methacrylic acid 3; The reaction of the multipolymer of 4-epoxycyclohexyl methyl ester and crotonic acid and the resin that obtains; Make (methyl) acrylic acid cyclohexyl ester/methacrylic acid 3; The reaction of the multipolymer of 4-epoxycyclohexyl methyl ester and crotonic acid and the resin that obtains; Make styrene/methacrylic acid 3; The reaction of the multipolymer of 4-epoxycyclohexyl methyl ester and crotonic acid and the resin that obtains; Make ethyl crotonate/methacrylic acid 3; The reaction of the multipolymer of 4-epoxycyclohexyl methyl ester and crotonic acid and the resin that obtains; Make N-cyclohexyl maleimide/methacrylic acid 3; The reaction of the multipolymer of 4-epoxycyclohexyl methyl ester and crotonic acid and the resin that obtains; Make (methyl) acrylic acid dicyclo amyl group ester/(methyl) acrylic acid benzyl ester/methacrylic acid 3; The reaction of the multipolymer of 4-epoxycyclohexyl methyl ester and crotonic acid and the resin that obtains; Make (methyl) acrylic acid dicyclo amyl group ester/(methyl) acrylic acid cyclohexyl ester/methacrylic acid 3; The reaction of the multipolymer of 4-epoxycyclohexyl methyl ester and crotonic acid and the resin that obtains; Make (methyl) acrylic acid dicyclo amyl group ester/styrene/methacrylic acid 3; The reaction of the multipolymer of 4-epoxycyclohexyl methyl ester and crotonic acid and the resin that obtains; Make (methyl) acrylic acid dicyclo amyl group ester/ethyl crotonate/methacrylic acid 3; The reaction of the multipolymer of 4-epoxycyclohexyl methyl ester and crotonic acid and the resin that obtains; Make (methyl) acrylic acid dicyclo amyl group ester/N-cyclohexyl maleimide/methacrylic acid 3; The reaction of the multipolymer of 4-epoxycyclohexyl methyl ester and crotonic acid and the resin that obtains

Make (methyl) acrylic acid dicyclo amyl group ester/methacrylic acid 3; The reaction of the multipolymer of 4-epoxycyclohexyl methyl ester and maleic acid and the resin that obtains; Make (methyl) acrylic acid benzyl ester/methacrylic acid 3; The reaction of the multipolymer of 4-epoxycyclohexyl methyl ester and maleic acid and the resin that obtains; Make (methyl) acrylic acid cyclohexyl ester/methacrylic acid 3; The reaction of the multipolymer of 4-epoxycyclohexyl methyl ester and maleic acid and the resin that obtains; Make styrene/methacrylic acid 3; The reaction of the multipolymer of 4-epoxycyclohexyl methyl ester and maleic acid and the resin that obtains; Make maleic acid methyl esters/methacrylic acid 3; The reaction of the multipolymer of 4-epoxycyclohexyl methyl ester and maleic acid and the resin that obtains; Make N-cyclohexyl maleimide/methacrylic acid 3; The reaction of the multipolymer of 4-epoxycyclohexyl methyl ester and maleic acid and the resin that obtains; Make (methyl) acrylic acid dicyclo amyl group ester/(methyl) acrylic acid benzyl ester/methacrylic acid 3; The reaction of the multipolymer of 4-epoxycyclohexyl methyl ester and maleic acid and the resin that obtains; Make (methyl) acrylic acid dicyclo amyl group ester/(methyl) acrylic acid cyclohexyl ester/methacrylic acid 3; The reaction of the multipolymer of 4-epoxycyclohexyl methyl ester and maleic acid and the resin that obtains; Make (methyl) acrylic acid dicyclo amyl group ester/styrene/methacrylic acid 3; The reaction of the multipolymer of 4-epoxycyclohexyl methyl ester and maleic acid and the resin that obtains; Make (methyl) acrylic acid dicyclo amyl group ester/maleic acid methyl esters/methacrylic acid 3; The reaction of the multipolymer of 4-epoxycyclohexyl methyl ester and maleic acid and the resin that obtains; Make (methyl) acrylic acid dicyclo amyl group ester/N-cyclohexyl maleimide/methacrylic acid 3; The reaction of the multipolymer of 4-epoxycyclohexyl methyl ester and maleic acid and the resin that obtains

Make (methyl) acrylic acid dicyclo amyl group ester/methacrylic acid 3; The multipolymer of 4-epoxycyclohexyl methyl ester and (methyl) acrylic acid react with maleic anhydride and the resin that obtains, make (methyl) acrylic acid benzyl ester/methacrylic acid 3; The multipolymer of 4-epoxycyclohexyl methyl ester and (methyl) acrylic acid react with maleic anhydride and the resin that obtains, make (methyl) acrylic acid cyclohexyl ester/methacrylic acid 3; The multipolymer of 4-epoxycyclohexyl methyl ester and (methyl) acrylic acid react with maleic anhydride and the resin that obtains, make styrene/methacrylic acid 3; The multipolymer of 4-epoxycyclohexyl methyl ester and (methyl) acrylic acid react with maleic anhydride and the resin that obtains, make (methyl) methyl acrylate/methacrylic acid 3; The multipolymer of 4-epoxycyclohexyl methyl ester and (methyl) acrylic acid react with maleic anhydride and the resin that obtains, make N-cyclohexyl maleimide/methacrylic acid 3; The multipolymer of 4-epoxycyclohexyl methyl ester and (methyl) acrylic acid react with maleic anhydride and the resin that obtains, make (methyl) acrylic acid dicyclo amyl group ester/(methyl) acrylic acid benzyl ester/methacrylic acid 3; The multipolymer of 4-epoxycyclohexyl methyl ester and (methyl) acrylic acid react with maleic anhydride and the resin that obtains, make (methyl) acrylic acid dicyclo amyl group ester/(methyl) acrylic acid cyclohexyl ester/methacrylic acid 3; The multipolymer of 4-epoxycyclohexyl methyl ester and (methyl) acrylic acid react with maleic anhydride and the resin that obtains, make (methyl) acrylic acid dicyclo amyl group ester/styrene/methacrylic acid 3; The multipolymer of 4-epoxycyclohexyl methyl ester and (methyl) acrylic acid react with maleic anhydride and the resin that obtains, make (methyl) acrylic acid dicyclo amyl group ester/(methyl) methyl acrylate/methacrylic acid 3; The resin that the multipolymer of 4-epoxycyclohexyl methyl ester and (methyl) acrylic acid obtain with the maleic anhydride reaction, make (methyl) acrylic acid dicyclo amyl group ester/N-cyclohexyl maleimide/methacrylic acid 3, the multipolymer of 4-epoxycyclohexyl methyl ester reacts with (methyl) acrylic acid and maleic anhydride and the resin that obtains etc.

The weight-average molecular weight of the polystyrene conversion of resin (B) is preferably 3000～100000, and more preferably 5000～50000.If the weight-average molecular weight of resin (B) is in above-mentioned scope, the trend that then exists coating to become good in addition, is difficult to produce film and reduces during development, and then the trend that exists when developing the deciduous of non-exposure portion to become good.

The molecular weight distribution of resin (B) [weight-average molecular weight (Mw)/number-average molecular weight (Mn)] is preferably 1.1～6.0, and more preferably 1.2～4.0.If, then there is the excellent trend of development property in above-mentioned scope in molecular weight distribution.

The acid number of resin (B) is preferably 20～150mg/g-KOH, and more preferably 50～135mg/g-KOH is preferably 70～135mg/g-KOH especially.Wherein, acid number is as being used for resin (B) 1g and the value that the amount (mg) of essential potassium hydroxide is measured, and it can carry out titration through the use potassium hydroxide aqueous solution and try to achieve.

When coloring photosensitive combination of the present invention contained resin (B), the content of resin (B) was generally 5～95 quality % with respect to the total amount of resin (B) and polymerizable compound (C), is preferably 20～80 quality %, more preferably 40～60 quality %.If the content of resin (B) is in above-mentioned scope, then the solvent resistance of the pattern of development property, adaptation, curing, mechanical property have the trend that becomes good.

Coloring photosensitive combination of the present invention contains polymerizable compound (C).

Polymerizable compound (C) be can be through producing by polymerization initiator (D) living radical, acid etc. carry out polymeric compounds, can enumerate the compound of the ethylenic unsaturated bond that for example has polymerism, preferably enumerate (methyl) acrylate compounds.

As the polymerizable compound (C) of ethylenic unsaturated bond with 1 polymerism, can enumerate with as above-mentioned (a) and (b) and the identical compound of compound (c) enumerated, wherein, be preferably (methyl) esters of acrylic acid.

Polymerizable compound (C) as ethylenic unsaturated bond with 2 polymerisms; Can enumerate 1; 3-butylene glycol two (methyl) acrylic ester, 1; 3-butylene glycol (methyl) acrylic ester, 1, two (acryloxy ethyl) ethers of 6-hexanediol two (methyl) acrylic ester, ethylene glycol bisthioglycolate (methyl) acrylic ester, diethylene glycol two (methyl) acrylic ester, neopentyl glycol two (methyl) acrylic ester, triethylene glycol two (methyl) acrylic ester, TEG two (methyl) acrylic ester, polyethyleneglycol diacrylate, bisphenol-A, ethoxylation bisphenol-A two (methyl) acrylic ester, ethoxylated neopentylglycol two (methyl) acrylic ester, ethoxylation neopentyl glycol two (methyl) acrylic ester, 3-methyl pentanediol two (methyl) acrylic ester etc.

As the polymerizable compound (C) of ethylenic unsaturated bond, can enumerate the reactant etc. of reactant, caprolactone modification tripentaerythritol seven (methyl) acrylic ester and acid anhydrides of reactant, caprolactone modification dipentaerythritol five (methyl) acrylic ester and acid anhydrides of reactant, caprolactone modification trimethylolpropane tris (methyl) acrylic ester, caprolactone modification pentaerythrite three (methyl) acrylic ester, caprolactone modification three (2-hydroxyethyl) isocyanuric acid ester three (methyl) acrylic ester, caprolactone modification pentaerythrite four (methyl) acrylic ester, caprolactone modification dipentaerythritol five (methyl) acrylic ester, caprolactone modification dipentaerythritol six (methyl) acrylic ester, caprolactone modification tripentaerythritol four (methyl) acrylic ester, caprolactone modification tripentaerythritol five (methyl) acrylic ester, caprolactone modification tripentaerythritol six (methyl) acrylic ester, caprolactone modification tripentaerythritol seven (methyl) acrylic ester, caprolactone modification tripentaerythritol eight (methyl) acrylic ester, caprolactone modification pentaerythrite three (methyl) acrylic ester and acid anhydrides of reactant, tripentaerythritol seven (methyl) acrylic ester and acid anhydrides of reactant, dipentaerythritol five (methyl) acrylic ester and the acid anhydrides of trimethylolpropane tris (methyl) acrylic ester, pentaerythrite three (methyl) acrylic ester, three (2-hydroxyethyl) isocyanuric acid ester three (methyl) acrylic ester, ethoxylated trimethylolpropane three (methyl) acrylic ester, propoxylation trimethylolpropane tris (methyl) acrylic ester, pentaerythrite four (methyl) acrylic ester, dipentaerythritol five (methyl) acrylic ester, dipentaerythritol six (methyl) acrylic ester, tripentaerythritol four (methyl) acrylic ester, tripentaerythritol five (methyl) acrylic ester, tripentaerythritol six (methyl) acrylic ester, tripentaerythritol seven (methyl) acrylic ester, tripentaerythritol eight (methyl) acrylic ester, pentaerythrite three (methyl) acrylic ester and acid anhydrides with 3 above polymerisms.

Wherein, being preferably 3 officials can above monomer, more preferably dipentaerythritol six (methyl) acrylic ester.

The content of polymerizable compound (C), the total amount with respect to resin (B) and polymerizable compound (C) is preferably 5～95 quality %, more preferably 20～80 quality %.If the trend that the content of polymerizable compound (C) in above-mentioned scope, then exists flatness, reliability, the physical strength of the pattern of sensitivity, gained to become good.

Coloring photosensitive combination of the present invention contains polymerization initiator (D).

As polymerism initiating agent (D), so long as can produce living radical, acid etc. through the effect of light, the compound of initiated polymerization gets final product, and does not limit especially, can use known polymerization initiator.

As polymerization initiator (D), be preferably united imidazole, benzene alkyl ketone compound, triaizine compounds, acylphosphine oxide compound, oxime compound.In addition, can use the light cationic polymerization initiators of putting down in writing in the TOHKEMY 2008-181087 communique (for example by

kation and the material that comes from lewis acidic negative ion formation).

As above-mentioned united imidazole, can enumerate 2,2 '-two (2-chlorphenyl)-4,4 ', 5; 5 '-tetraphenyl bisglyoxaline, 2,2 '-two (2, the 3-dichlorophenyl)-4,4 '; 5,5 '-tetraphenyl bisglyoxaline (for example with reference to japanese kokai publication hei 6-75372 communique and japanese kokai publication hei 6-75373 communique), 2,2 '-two (2-chlorphenyl)-4,4 '; 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-two (2-chlorphenyl)-4,4 '; 5,5 '-four (alkoxyl phenyl) bisglyoxaline, 2,2 '-two (2-chlorphenyl)-4,4 '; 5,5 '-four (dialkoxy phenyl) bisglyoxaline, 2,2 '-two (2-chlorphenyl)-4,4 '; 5,5 '-four (tri-alkoxy phenyl) bisglyoxaline (for example with reference to special public clear 48-38403 communique of Japan and japanese kokai publication sho 62-174204 communique), 4,4 ' 5,5 '-phenyl by the substituted imidazolium compounds of alkoxy carbonyl group (for example with reference to japanese kokai publication hei 7-10913 communique.) etc.Preferably enumerate 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-two (2, the 3-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-two (2, the 4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline.

As above-mentioned benzene alkyl ketone compound; The oligomer of diethoxy acetophenone, 2-methyl-2-morpholino-1-(4-methyl sulfane base phenyl) propane-1-ketone, 2-dimethylamino-1-(4-morpholino phenyl)-2-benzyl butane-1-ketone, 2-dimethylamino-1-(4-morpholino phenyl)-2-(4-aminomethyl phenyl methyl) butane-1-ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, benzyldimethylketal, 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 etc. be can enumerate, 2-methyl-2-morpholino-1-(4-methyl sulfane base phenyl) propane-1-ketone, 2-dimethylamino-1-(4-morpholino phenyl)-2-benzyl butane-1-ketone etc. preferably enumerated.Also can use commercially available article such as イ Le ガキュア 369, イ Le ガキュア 907 (above BASF ジャパ Application society system).

As above-mentioned triaizine compounds, can enumerate 2, two (the trichloromethyl)-6-(4-methoxyphenyl) of 4--1,3,5-triazines, 2; Two (the trichloromethyl)-6-(4-methoxyl naphthyl) of 4--1,3,5-triazines, 2, two (the trichloromethyl)-6-piperonyls-1,3 of 4-; 5-triazine, 2, two (the trichloromethyl)-6-(4-methoxyl-styrene) of 4--1,3,5-triazines, 2, two (the trichloromethyl)-6-[2-(5-methylfuran-2-yl) vinyl]-1 of 4-; 3,5-triazine, 2, two (the trichloromethyl)-6-[2-(furans-2-yl) vinyl]-1,3 of 4-; 5-triazine, 2, two (the trichloromethyl)-6-[2-(4-diethylamino-2-aminomethyl phenyl) vinyl] of 4--1,3,5-triazines, 2; Two (the trichloromethyl)-6-[2-(3, the 4-Dimethoxyphenyl) vinyl] of 4--1,3,5-triazines etc.

As above-mentioned acylphosphine oxide compound, can enumerate 2,4,6-trimethylbenzoyl diphenyl phosphine oxide etc.Also can use イ Le ガキュア 819 commercially available article such as (BASF ジャパ Application society systems).

As above-mentioned oxime compound; Can enumerate N-benzoyloxy-1-(4-phenyl sulfane base phenyl) butane-1-ketone-2-imines, N-benzoyloxy-1-(4-phenyl sulfane base phenyl) octane-1-ketone-2-imines, N-acetoxyl group-1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl] ethane-1-imines, N-acetoxyl group-1-[9-ethyl-6-[2-methyl-4-(3; 3-dimethyl-2,4-dioxa cyclopentyl-methyl oxygen base) benzoyl]-9H-carbazole-3-yl] ethane-1-imines etc.Also can use イ Le ガキュア OXE-01, OXE-02 (above BASF ジャパ Application society system), N-1919 commercially available article such as (ADEKA society systems).

And then, as polymerization initiator (D), can enumerate benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethylether, 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 peroxide carbonyl) benzophenone, 2; 4, benzophenone cpds such as 6-tri-methyl benzophenone, 9; Naphtoquinone compounds such as 10-phenanthrenequione, 2-EAQ, camphorquinone, 10-butyl-2-chloro-acridine ketone, dibenzoyl, phenylglyoxylic acid methyl esters, two cyclopentadiene titanium compounds etc.They preferably with after the polymerization stated cause auxiliary agent (D1) (amines of stating particularly) combination and use.

Coloring photosensitive combination of the present invention can contain polymerization and cause auxiliary agent (D1).Polymerization causes auxiliary agent (D1) can be used with polymerization initiator (D) combination, and it is that be used to promote can be by the polymeric compounds or the sensitizer of the polymerizable compound of polymerization initiator initiated polymerization.

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

As amines; Can enumerate triethanolamine, methyldiethanolamine, triisopropanolamine, 4-dimethylaminobenzoic acid methyl esters, 4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid isopentyl ester, benzoic acid 2-dimethylamino ethyl ester, 4-dimethylaminobenzoic acid 2-Octyl Nitrite, N; N-dimethyl-p-toluidine, 4,4 '-two (dimethylamino) benzophenone, 4,4 '-two (diethylamino) benzophenone, 4; 4 '-two (ethylmethylamino) benzophenone etc.; Wherein, be preferably 4,4 '-two (diethylamino) benzophenone.Also can use the commercially available article of EAB-F (hodogaya chemical industry (strain) system) etc.

As thiazolinium compounds, can enumerate the compound shown in formula (III-1)～formula (III-3) etc.

[chemical formula 4]

As the alkoxy anthracene compound, can enumerate 9,10-dimethoxy anthracene, 2-ethyl-9,10-dimethoxy anthracene, 9,10-diethoxy anthracene, 2-ethyl-9,10-diethoxy anthracene, 9,10-dibutoxy anthracene, 2-ethyl-9,10-dibutoxy anthracene etc.

As the thioxanthones compound, can enumerate 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-two clopenthixal ketones, 1-chloro-4-propoxyl group thioxanthones etc.

As carboxylic acid compound, can enumerate phenyl sulfane guanidine-acetic acid, aminomethyl phenyl sulfane guanidine-acetic acid, ethylphenyl sulfane guanidine-acetic acid, Methylethyl phenyl sulfane guanidine-acetic acid, 3,5-dimethylphenyl sulfane guanidine-acetic acid, methoxyphenyl sulfane guanidine-acetic acid, Dimethoxyphenyl sulfane guanidine-acetic acid, chlorphenyl sulfane guanidine-acetic acid, dichlorophenyl sulfane guanidine-acetic acid, N-phenylglycine, phenoxyacetic acid, naphthyl thioacetic acid, N-naphthyl glycocoll, naphthoxy acetic acid etc.

The content of polymerization initiator (D), the total amount with respect to resin (B) and polymerizable compound (C) is preferably 0.1～40 quality %, more preferably 1～30 quality %.

If the content of polymerization initiator (D) is in this scope, then coloring photosensitive combination forms high sensitivity, the trend that exists resistance to chemical reagents, physical strength, the surface smoothing property of the pattern of gained to become good.

When using polymerization to cause auxiliary agent (D1), its consumption is preferably 0.01～50 quality % with respect to the total amount of resin (B) and polymerizable compound (C), more preferably 0.1～40 quality %.In addition, with respect to 1 mole of polymerization initiator (D), be preferably 0.01～10 mole, more preferably 0.01～5 mole.

If polymerization causes the amount of auxiliary agent (D1) in this scope, then the sensitivity of the coloring photosensitive combination of gained further improves, and the productivity of the pattern of gained has the trend of raising.

In addition, coloring photosensitive combination of the present invention can further contain multi-functional thiol's compound (T).This multi-functional thiol's compound (T) is the compound that has 2 above sulfane bases in the molecule.Wherein, if use the compound have more than 2 with the sulfane base of aliphatic alkyl adjacency, then the sensitivity of coloring photosensitive combination of the present invention improves, so preferred.

As multi-functional thiol's compound (T); Can enumerate ethanthiol, the last of the ten Heavenly stems two mercaptan, 1; Two (the methyl sulfane base) benzene of 4-, butylene glycol two (3-sulfane base propionic ester), butylene glycol two (3-sulfane yl acetate), ethylene glycol bis (3-sulfane yl acetate), trimethylolpropane tris (3-sulfane yl acetate), butylene glycol two (3-sulfane base propionic ester), trimethylolpropane tris (3-sulfane base propionic ester), trimethylolpropane tris (3-sulfane yl acetate), pentaerythrite four (3-sulfane base propionic ester), pentaerythrite four (3-sulfane yl acetate), trihydroxy ethyl three (3-sulfane base propionic ester), pentaerythrite four (3-sulfane base butyric ester), 1, two (3-sulfane Ji Dingji oxygen base) butane of 4-etc.

The content of multi-functional thiol's compound (T) with respect to polymerization initiator (D), is preferably 0.5～20 quality %, more preferably 1～15 quality %.If the content of multi-functional thiol's compound (T) is in this scope, then sensitivity improves the trend that exists development property to become good in addition.

Coloring photosensitive combination of the present invention contains solvent (E).As solvent (E), do not limit especially, can use normally used solvent in this field.For example can from ester solvent (molecule contains-COO-, do not contain-O-solvent), ether solvents (molecule contains-O-, do not contain-COO-solvent), ether-ether solvent (molecule contains-COO-and-O-solvent), ketone solvent (molecule contains-CO-, do not contain-COO-solvent), alcoholic solvent, aromatic hydrocarbon solvents, amide solvent and dimethyl sulfoxide (DMSO) beyond the ester solvent beyond the ester solvent, select to use.

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 glycol monomethyl methyl ether, ethylene glycol monomethyl ether, glycol monomethyl propyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, TC, diethylene glycol single-butyl ether, propylene glycol monomethyl ether, propylene glycol list ethylether, propylene glycol list propyl ether, propylene glycol single-butyl ether, 3-methoxyl-1-butanols, 3-methoxyl-3-methyl butanol, tetrahydrofuran, oxinane, 1,4-two alkane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ethers, methyl phenyl ethers anisole, phenetol, methylbenzene methyl ether etc.

As the ether-ether solvent, can enumerate methoxy menthyl acetate, methoxyacetic acid ethyl ester, methoxyacetic acid butyl ester, ethoxy acetate, ethoxy ethyl acetate, 3-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, 3-ethoxyl ethyl propionate, 2-methoxypropionic acid methyl esters, 2-methoxy propyl acetoacetic ester, 2-methoxy propyl propyl propionate, 2-ethoxy-propionic acid methyl esters, 2-ethoxyl ethyl propionate, 2-methoxyl-2 Methylpropionic acid methyl esters, 2-ethoxy-2 Methylpropionic acid ethyl ester, 3-methoxyl butylacetic acid ester, 3-methyl-3-methoxyl butylacetic acid ester, propylene glycol monomethyl ether, propylene glycol list ethylether acetic acid esters, propylene glycol list propyl ether acetic acid esters, monoethylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, TC acetic acid esters, diethylene glycol single-butyl 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, monoethylene glycol, propylene glycol, glycerine etc.

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

As amide solvent, can enumerate N, dinethylformamide, DMAC N,N, N-Methyl pyrrolidone etc.

These solvents can separately or make up more than 2 kinds and use.

In the above-mentioned solvent, consider that from the viewpoint of coating, drying property preferably the boiling point under the 1atm is 120 ℃～180 ℃ a organic solvent.Wherein, be preferably propylene glycol monomethyl ether, propylene glycol monomethyl ether, diethylene glycol methyl ethyl ether, 3-methoxyl butylacetic acid ester, 3-methoxyl-1-butanols etc.

The content of the solvent in the coloring photosensitive combination (E) with respect to coloring photosensitive combination, is preferably 60～95 quality %, more preferably 70～90 quality %.In other words, the solid formation branch of coloring photosensitive combination is preferably 5～40 quality %, more preferably 10～30 quality %.If the content of solvent (E) is in above-mentioned scope, the flatness when then being coated with has the trend that becomes good.

Coloring photosensitive combination of the present invention preferably contains surfactant (F).As surfactant, for example can enumerate siloxane type surfactants, fluorine class surfactant and have the siloxane type surfactants of fluorine atom.Through containing surfactant, the flatness during coating has the trend that becomes good.

As siloxane type surfactants, can enumerate surfactant with siloxane bond.Specifically; Can enumerate トーレシリコー Application DC3PA 、トーレシリコー Application SH7PA 、トーレシリコー Application DC11PA 、トーレシリコー Application SH21PA 、トーレシリコー Application SH28PA 、トーレシリコー Application SH29PA 、トーレシリコー Application SH30PA, polyether modified silicon oil SH8400 (trade name: eastern レダウコーニ Application グ (strain) system); KP321, KP322, KP323, KP324, KP326, KP340, KP341 (SHIN-ETSU HANTOTAI's chemical industry (strain) system), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (モメ Application ティ Block パフォーマ Application スマテリア Le ズジャパ Application contract commercial firm system) etc.

As fluorine class surfactant, can enumerate surfactant with fluorocarbon chain.Specifically; Can enumerate Off ロリナート (registered trademark) FC430, Off ロリナート FC431 (Sumitomo スリーエ system (strain) system); メガ Off ァッ Network (registered trademark) F142D, メガ Off ァッ Network F171, メガ Off ァッ Network F172, メガ Off ァッ Network F173, メガ Off ァッ Network F177, メガ Off ァッ Network F183, メガ Off ァッ Network R30 (DIC (strain) system); エ Off トップ (registered trademark) EF301, エ Off トップ EF303, エ Off トップ EF351, エ Off トップ EF352 (the マテリア of Mitsubishi Le electronics changes into (strain) system), サー Off ロ Application (registered trademark) S381, サー Off ロ Application S382, サー Off ロ Application SC101, サー Off ロ Application SC105 (Asahi Glass (strain) system), E5844 ((strain) ダイキ Application Off ァイ Application ケミカ Le institute system) etc.

As siloxane type surfactants, can enumerate surfactant with siloxane bond and fluorocarbon chain with fluorine atom.Specifically, can enumerate メガ Off ァッ Network (registered trademark) R08, メガ Off ァッ Network BL20, メガ Off ァッ Network F475, メガ Off ァッ Network F477, メガ Off ァッ Network F443 (DIC (strain) system) etc.Be preferably メガ Off ァッ Network (registered trademark) F475.

Surfactant (F) is 0.001 quality %～0.2 quality % with respect to coloring photosensitive combination, is preferably 0.002 quality %～0.1 quality %, more preferably 0.01 quality %～0.05 quality %.If surface-active contents in this scope, then can make the flatness of filming good.

Coloring photosensitive combination of the present invention can contain filling agent, other various adjuvants such as macromolecular compound, driving fit promoter, anti-oxidant, ultraviolet light absorber, light stabilizer, chain-transferring agent as required.

Coloring photosensitive combination of the present invention for example can be prepared as follows.

At first, the pigment of colorant (A) is mixed with solvent (E), the mean grain size of using ball mill etc. to be dispersed to pigment be below the 0.2 μ m about.Can cooperate a part of or whole of pigment dispersing agent, resin (B) this moment as required.In the dispersible pigment dispersion of gained with the concentration of regulation add polymerizable compound (C) and polymerization initiator (D), remainder, other composition and then the solvent (E) that appends as required of the resin (B) that contains as required, can obtain the purpose coloring photosensitive combination thus.

Coloring photosensitive combination of the present invention for example passes through the step shown in following (1)～(4), is processed as color filter.

(1) through coloring photosensitive combination of the present invention is coated on the step that obtains coated film on the substrate,

(2) coated film is made public via mask, the step of coated film after obtaining thus making public,

(3) develop with alkaline developer through the back coated film of will making public, obtain the step of pattern,

(4) through pattern is cured, the step of the pattern that obtains solidifying.

As obtaining method of patterning, can enumerate photoetching process, ink-jet method, print process etc.Wherein, be preferably photoetching process.

Photoetching process is that above-mentioned coloring photosensitive combination is coated on the substrate and carries out drying, via photomask exposure, develops, and obtains method of patterning thus.

As aforesaid substrate, can enumerate for example glass, metal and plastics, can be for tabular, also can be for membranaceous.

As plastics; For example polyolefin such as tygon, polypropylene, norbornene polymer be can enumerate, polyvinyl alcohol (PVA), polyethylene terephthalate, PEN, (methyl) acrylic ester, cellulose esters, polycarbonate, polysulfones, polyethersulfone, polyetherketone, polyphenylene sulfide and polyphenylene oxide gathered.Wherein, (methyl) acrylic acid refers at least a kind that is selected from acrylic acid and methacrylic acid.

On these substrates, can form color filter, various insulation or structures such as conducting film, driving circuit.

According to coloring photosensitive combination of the present invention, can be formed on the more following pattern that solidifies of low temperature.Therefore, when on plastic base, forming pattern, particularly useful.

As coating process to substrate, for example can enumerate, extrusion coated method, direct photogravure rubbing method, reversal photogravure rubbing method, lid are coated with method and metal mold rubbing method.In addition, can use dip coater, roll coater, rod to be coated with apparatus for coating such as machine, spin coater, slit & spin coater, slit coater (being sometimes referred to as metal mold coating machine, curtain flow coater, non-rotary coating machine), ink-jet is coated with.Wherein, preferably using slit coater, spin coater, roll coater to wait is coated with.

As the drying means that is coated on the film on the substrate, can enumerate for example methods such as heat drying, air dry, aeration-drying, drying under reduced pressure.Can make up several different methods carries out.

As baking temperature, be preferably 10～120 ℃, more preferably 25～100 ℃.In addition, as heat time heating time, be preferably 10 seconds～60 minutes, more preferably 30 seconds～30 minutes.

Drying under reduced pressure preferably under the pressure of 50～150Pa, 20～25 ℃ temperature range carries out.

Thickness to dried coating does not limit especially, can wait suitably adjustment according to employed material, purposes, is generally 0.1～20 μ m, is preferably 1～6 μ m.

For dried coating, make public via the photomask that is used to form the purpose pattern.Pattern form on the photomask of this moment is not limited especially, can use and the corresponding pattern form of purpose purposes.

Light source as using in the exposure preferably produces the light source that wavelength is the light of 250～450nm.For example use to stop wavelength to stop less than the light filter of the light of 350nm light to this wavelength region may, or use obtain near the 436nm, near near the BPF. of the light the 408nm, the 365nm optionally obtains the light of these wavelength region may.Specifically, can enumerate mercury lamp, light emitting diode, metal halide lamp, halogen lamp etc.

In order to shine parallel rays equably, or carry out the correct location matches of mask and base material, preferably use devices such as mask aligner, ledex burn-out face.

After the exposure, contact,, develop, can obtain pattern thus established part, the dissolving of for example unexposed portion with developer solution.As developer solution, can be organic solvent, but in order to make the exposure portion of filming be difficult to obtain the pattern of excellent in shape, preferably the WS of alkali compounds owing to developer solution produces dissolving, swelling.

Developing method can be any means in slurry, infusion process, the spray-on process etc.Further, substrate can be with arbitrarily angled inclination during development.

Preferably wash after the development.

As above-mentioned alkali compounds; Can enumerate inorganic alkaline compounds such as NaOH, potassium hydroxide, sodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, sal tartari, soda mint, saleratus, sodium borate, potassium borate, ammonia, and organic basic compound such as TMAH, 2-hydroxyethyl trimethylammonium hydroxide, monomethyl amine, dimethyl amine, Trimethylamine, single ethylamine, diethylamide, triethylamine, single isopropylamine, diisopropylamine, monoethanolamine.Wherein, be preferably potassium hydroxide, soda mint and TMAH.

These inorganic and organic basic compound concentration in the WS are preferably 0.01～10 quality %, more preferably 0.03～5 quality %.

The WS of above-mentioned alkali compounds can contain surfactant.

As surfactant; Can enumerate polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkylaryl ether, other nonionic class surfactant such as polyoxyethylene deriv, ethylene oxide/propylene oxide segmented copolymer, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid ester, fatty acid glyceride, polyoxyethylene fatty acid ester, polyoxyethylene alkyl amine

Anionic species surfactants such as dodecanol sodium sulfovinate, oleyl alcohol sodium sulfovinate, lauryl sodium sulfate, ammonium lauryl sulfate, neopelex, dodecyl sodium naphthalene sulfonate,

Cationic surfactants such as stearic amine hydrochloride, DTAC etc.

Surfactant concentrations in the WS of alkali compounds is preferably 0.01～10 quality %, and more preferably 0.05～8 quality % is preferably 0.1～5 quality % especially.

Further as required, can carry out the back baking.2～240 minutes scope is for example preferably carried out in the back baking under 50～230 ℃.

Coloring photosensitive combination of the present invention can obtain good pattern and color filters such as color depth, luminance brightness, contrast, sensitivity, resolution, thermotolerance.In addition; Can be used to have these color filters or pattern display device in known manner, in the machine relevant such as for example known liquid crystal indicator, organic El device, solid camera head, Electronic Paper with rendered image as the part of its component parts.

[embodiment]

Below through embodiment the present invention is explained more specifically." % " in the example and " part " only otherwise specify are quality % and mass parts.

Synthetic example 1

In flask with stirring machine, thermometer, reflux condensing tube, tap funnel and nitrogen ingress pipe; Import propylene glycol monomethyl ether 182g; After making the interior atmosphere of flask become nitrogen by air; After being warming up to 100 ℃; By tap funnel with in flask, dripping the solution that interpolation azobis isobutyronitrile 3.6g forms in the potpourri of the monomethacrylates that comprises benzyl methacrylate 70.5g (0.40 mole), methacrylic acid 43.0g (0.5 mole), tricyclodecane skeleton (Hitachi changes into (strain) system FA-513M) 22.0g (0.10 mole) and propylene glycol monomethyl ether 136g in 2 hours, further 100 ℃ of continuous stirring 5 hours.Then make the interior atmosphere of flask become air by nitrogen; In flask, add methyl propenoic acid glycidyl base ester 35.5g [0.25 mole, (carboxyl with respect to the methacrylic acid of use in this reaction is 50 moles of %)], three (dimethylaminomethyl) phenol 0.9g and quinhydrones 0.145g; 110 ℃ of successive reactions 6 hours, obtaining solid formation, to divide acid number be the resin solution B1 of 79mgKOH/g.The weight-average molecular weight of measuring the polystyrene conversion that obtains through GPC is 13000, and molecular weight distribution (Mw/Mn) is 2.1.

Synthetic example 2

In flask, import 250 parts of propylene glycol monomethyl ether with stirring machine, thermometer, reflux condensing tube, tap funnel and gas introduction tube.Then, the using gases ingress pipe imports to nitrogen in the flask, and atmosphere in the flask is replaced into nitrogen.Then; After solution in the flask is warming up to 100 ℃; Use tap funnel with 2 hours in flask dropping comprise the potpourri of 150 parts of 152.6 parts of benzyl methacrylates, 41.7 parts of methacrylic acids, 1.5 parts of azobis isobutyronitriles and propylene glycol monomethyl ether; After being added dropwise to complete, further 100 ℃ of continuous stirring 2.5 hours, obtaining weight-average molecular weight Mw was 2.3 * 10 ⁴, solid form be divided into 34 quality %, the solution acid number is the resin solution B2 of 47mg-KOH/g.

The weight-average molecular weight (Mw) of the resin that obtains in the synthetic example and the mensuration of number-average molecular weight (Mn) are used the GPC method, under following condition, carry out.

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

Pillar: SHIMADZU Shim-pack GPC-80M

Column temperature: 40 ℃

Solvent: THF (tetrahydrofuran)

Flow velocity, 1.0mL/min

Detecting device: RI

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

Embodiment 1

[preparation of coloring photosensitive combination]

With pigment: 58 51 parts of C.I. naphthol greens

10 parts of acrylic compounds pigment dispersing agents

20 parts of resin solution B2 (converting) Gu form to divide

267 parts of propylene glycol monomethyl ether

Mix, use ball mill that pigment is fully disperseed and form dispersible pigment dispersion A,

With pigment: 8 81 parts of C.I. pigment yellow 13s

12 parts of acrylic compounds pigment dispersing agents

28 parts of resin solution B2 (converting) Gu form to divide

402 parts of propylene glycol monomethyl ether

Mix, use ball mill that pigment is fully disperseed and form dispersible pigment dispersion B,

With pigment: 29 parts of C.I. pigment Green 7s

5.7 parts of acrylic compounds pigment dispersing agents

11 parts of resin solution B2 (converting) Gu form to divide

173 parts of propylene glycol monomethyl ether

Mix, use ball mill that pigment is fully disperseed and form dispersible pigment dispersion C,

With above-mentioned dispersible pigment dispersion A, dispersible pigment dispersion B, dispersible pigment dispersion C,

Resin: 66 parts of resin solution B1 (converting Gu form to divide),

Polymerizable compound: 57 parts of dipentaerythritol acrylates (Japanese chemical drug (strain) system),

Polymerization initiator: 15 parts of 2-dimethylamino-1-(4-morpholino phenyl)-2-benzyl butane-1-ketone (イ Le ガキュア 369, BASF ジャパ Application society system),

Polymerization causes auxiliary agent: 4.9 parts of 4,4 '-two (diethylamino) benzophenone (EAB-F, hodogaya chemical industry (strain) system),

Solvent: 450 parts of propylene glycol monomethyl ether and

Adjuvant: 6.1 parts of スミエ Port キシ ESCN-195XL (Sumitomo Chemical (strain) system)

Mix, obtain coloring photosensitive combination.

Comparative example

[preparation of coloring photosensitive combination]

For with pigment: 5.5 parts of C.I. pigment green 36s

Pigment: 150 2.4 parts of C.I. pigment yellows

1.2 parts of polyesters pigment dispersing agents

38 parts of propylene glycol monomethyl ether

Mix and use ball mill that pigment is fully disperseed the dispersible pigment dispersion that forms,

Hybrid resin: 6.6 parts of resin solution B1 (converting) Gu form to divide

Polymerizable compound: 5.7 parts of dipentaerythritol acrylates (Japanese chemical drug (strain) system)

Polymerization initiator: 1.5 parts of 2-dimethylamino-1-(4-morpholino phenyl)-2-benzyl butane-1-ketone (イ Le ガキュア 369, BASF ジャパ Application society system)

Polymerization causes auxiliary agent: 0.49 part of 4,4 '-two (diethylamino) benzophenone (EAB-F, hodogaya chemical industry (strain) system)

Adjuvant: 0.61 part of スミエ Port キシ ESCN-195XL (Sumitomo Chemical (strain) system)

Solvent: 38 parts of propylene glycol monomethyl ether,

Obtain coloring photosensitive combination.

< manufacturing of pattern >

Applying PET film on 2 inches square glass plates (eastern レ system Le ミラー 75-T60) is made substrate.In the PET of substrate film side,, before 80 ℃, drying by the fire 2 minutes on the heating plate through spin-coating method coating coloring photosensitive combination.Put cold after, make the 10 μ m that are spaced apart of this substrate that is coated with coloring photosensitive combination and quartz glass system photomask, use exposure machine (TME-150RSK, トプコ Application (strain) system), under atmospheric atmosphere, with 200mJ/cm ²The exposure of (365nm benchmark) is carried out rayed.And, for the irradiation of this moment, the radiating light from ultrahigh pressure mercury lamp is carried out through optical filter (UV-35: Korean and Japanese beam split (strain) is made) to coloring photosensitive combination.As photomask, use to have formed the line of 10～100 μ m and the photomask of space pattern.After the rayed, in tetramethyl-ammonium 0.1% WS, developed in 80 seconds, wash, form pattern with pure water at 23 ℃ of dippings.The thickness of the gained pattern that use determining film thickness device (DEKTAK3, Japanese vacuum technique (strain) system) records is 2 μ m.

To further heat 5 minutes (back baking), the pattern that obtains solidifying with the above-mentioned pattern that likewise forms at 50 ℃.In addition, will further heat 5 minutes (back baking), the pattern that obtains solidifying with the above-mentioned pattern that likewise forms at 100 ℃.The thickness of the pattern that solidifies with the above-mentioned gained that likewise records all is 2 μ m.

< color characteristics evaluation >

For the spectrophotometric spectra of the pattern of gained, use micro-spectral determinator (OSP-SP200 OLYMPUS system) to measure transmissivity (T1) and the transmissivity (T2) under the 520nm under the 600nm.T1 is more little with the ratio (T1/T2) of T2, and then the color separated ability with red color filter is high more, so preferred.The result is as shown in table 1.

[table 1]

The ratio (T1/T2) of T1 and T2

< solvent resistance evaluation >

Drip propylene glycol monomethyl ether 1ml to the pattern that on aforesaid substrate, forms, after static 30 seconds, uses spin coater to rotate 10 seconds under as the condition of 1000rpm, get rid of the propylene glycol monomethyl ether on the pattern at rotating speed.

By measuring the film thickness value that obtains before and after contacting with propylene glycol monomethyl ether, keep through the computes thickness.The thickness conservation rate is high more, and then curable is good more, when repeating to be coated with the coloring photosensitive combination beyond the green, has suppressed the stripping of contained solvent in this coloring photosensitive combination, when therefore making color filter, can prevent colour mixture (mixing).The result is as shown in table 2.

(thickness conservation rate) (%)=(thickness after the contact)/(contact before thickness)

< evaluation of resolution >

To the pattern that obtains, observe through laser microscope (Axio Imager MAT カー Le Star ァイス society system), with the minimum dimension of differentiating as resolution.Resolution is high more, can make high meticulous color filter.The result is as shown in table 2.

[table 2]

Industrial applicibility

According to coloring photosensitive combination of the present invention, can obtain color filter with the excellent green of the color separated ability of red color filter.

Claims

1. coloring photosensitive combination, it contains colorant, polymerizable compound, polymerization initiator and solvent, and colorant is the painted material that contains copper halide phthalocyanine color, zinc halide phthalocyanine color and quinophthalone pigment.

2. the described coloring photosensitive combination of claim 1, wherein, the content of copper halide phthalocyanine color with respect to content 100 mass parts of zinc halide phthalocyanine color, is 20 mass parts～150 mass parts.

3. the described coloring photosensitive combination of claim 1, wherein, the content of quinophthalone pigment with respect to content 100 mass parts of zinc halide phthalocyanine color, is 50 mass parts～200 mass parts.

4. the described coloring photosensitive combination of claim 1; Wherein, the content of copper halide phthalocyanine color is with respect to content 100 mass parts of zinc halide phthalocyanine color; Be 20 mass parts～150 mass parts; And the content of quinophthalone pigment with respect to content 100 mass parts of zinc halide phthalocyanine color, is 50 mass parts～200 mass parts.

5. the described coloring photosensitive combination of claim 1, wherein, the copper halide phthalocyanine color is the C.I. pigment Green 7.

6. the described coloring photosensitive combination of claim 1, wherein, quinophthalone pigment is C.I. pigment yellow 13 8.

7. the described coloring photosensitive combination of claim 1 wherein, contains colorant, polymerizable compound, polymerization initiator, solvent and resin.

8. color filter, it is formed by the described coloring photosensitive combination of claim 1.