CN102445851B - Coloring photosensitive combination - Google Patents

Coloring photosensitive combination Download PDF

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CN102445851B
CN102445851B CN201110296521.2A CN201110296521A CN102445851B CN 102445851 B CN102445851 B CN 102445851B CN 201110296521 A CN201110296521 A CN 201110296521A CN 102445851 B CN102445851 B CN 102445851B
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methyl
resin
multipolymer
acid
acrylic acid
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CN102445851A (en
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宫芳子
三浦洋之
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/201—Filters in the form of arrays
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0042—Photosensitive materials with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Optics & Photonics (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Materials For Photolithography (AREA)
  • Optical Filters (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The coloring photosensitive combination that can obtain with the color filter of the green of the color separated ability excellence of red color filter is provided.This coloring photosensitive combination, containing colorant, polymerizable compound, polymerization initiator and solvent, colorant contains halogenated copper phthalocyanine pigment, zinc halide phthalocyanine color and quinophthalone pigments.

Description

Coloring photosensitive combination
Technical field
The present invention relates to the coloring photosensitive combination being formed and be suitable for the rendered image forming the color filter used in liquid crystal display cells, solid-state imager.
Background technology
The color filter used in the display device such as display panels, electroluminescence panel, plasma display can use coloring photosensitive combination to manufacture.As this coloring photosensitive combination, there will be a known following composition, it contains colorant, resin, photopolymerizable 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: Japanese Unexamined Patent Publication 2005-157311 publication.
Summary of the invention
In the color filter of the green using above-mentioned coloring photosensitive combination to be formed, for the color separated ability with red color filter, may not be fully satisfactory.
The invention provides following [1] ~ [8].
[1] coloring photosensitive combination, it contains colorant, polymerizable compound, polymerization initiator and solvent, and colorant is the colorant containing halogenated copper phthalocyanine pigment, zinc halide phthalocyanine color and quinophthalone pigments.
[2] above-mentioned [1] coloring photosensitive combination of recording, wherein, the content of halogenated copper phthalocyanine pigment, relative to content 100 mass parts of zinc halide phthalocyanine color, is 20 mass parts ~ 150 mass parts.
[3] above-mentioned [1] coloring photosensitive combination of recording, wherein, the content of quinophthalone pigments, relative to content 100 mass parts of zinc halide phthalocyanine color, is 50 mass parts ~ 200 mass parts.
[4] above-mentioned [1] coloring photosensitive combination of recording, wherein, the content of halogenated copper phthalocyanine pigment, relative to content 100 mass parts of zinc halide phthalocyanine color, be 20 mass parts ~ 150 mass parts, and the content of quinophthalone pigments, relative to content 100 mass parts of zinc halide phthalocyanine color, be 50 mass parts ~ 200 mass parts.
[5] coloring photosensitive combination that in above-mentioned [1] ~ [4], any one is recorded, wherein, halogenated copper phthalocyanine pigment is C.I. pigment Green 7.
[6] the colored photosensitive resin composition that in above-mentioned [1] ~ [3], any one is recorded, wherein, quinophthalone pigments is C.I. pigment yellow 13 8.
[7] coloring photosensitive combination that in above-mentioned [1] ~ [6], any one is recorded, wherein, containing colorant, polymerizable compound, polymerization initiator, solvent and resin.
[8] color filter, its coloring photosensitive combination recorded by any one in above-mentioned [1] ~ [7] is formed.
According to coloring photosensitive combination of the present invention, the green color filter with the color separated ability excellence of red color filter can be obtained.
Embodiment
Coloring photosensitive combination of the present invention is following composition, it contains colorant (A), polymerizable compound (C), polymerization initiator (D) and solvent (E), and colorant contains halogenated copper phthalocyanine pigment, zinc halide phthalocyanine color and quinophthalone pigments.Coloring photosensitive combination of the present invention is preferably containing resin (B).
And, in this instructions, as the compound that each composition is enumerated, only otherwise special instruction, then can use alone or in combination.
The colorant (A) used in coloring photosensitive combination of the present invention is containing halogenated copper phthalocyanine pigment, zinc halide phthalocyanine color and quinophthalone pigments.
As halogenated copper phthalocyanine pigment, be preferably chlorinated copper phthalocyanine pigment, be more preferably C.I. pigment Green 7.If halogenated copper phthalocyanine pigment is above-mentioned pigment, then due to the transmissivity near 600nm can be reduced, so excellent with the color separated ability of red color filter.
As zinc halide phthalocyanine color, be preferably C.I. naphthol green 58.
The content of halogenated copper phthalocyanine pigment, relative to content 100 mass parts of zinc halide phthalocyanine color, is preferably 20 mass parts ~ 150 mass parts, is more preferably 80 mass parts ~ 120 mass parts.If the content of halogenated copper phthalocyanine pigment is in above-mentioned scope, then can under the state keeping the transmissivity under high 520nm, reduce the transmissivity near 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 arranged in the green pixel of the display device such as liquid crystal indicator, the color reproducibility of this display device can be improved.
Colorant (A) is further containing quinophthalone pigments.The content of quinophthalone phthalocyanine color, relative to content 100 mass parts of zinc halide phthalocyanine color, is preferably 50 mass parts ~ 200 mass parts, is more preferably 120 mass parts ~ 200 mass parts.As quinophthalone pigments, be preferably C.I. pigment yellow 13 8.By containing above-mentioned quinophthalone pigments, there is the trend with the color separated ability excellence of blue color filter.
Above-mentioned pigment can implement rosin process as required; use the surface treatment that the pigment derivative, pigment dispersing agent etc. that are imported with acidic-group or basic group are carried out; by the grafting process that macromolecular compound etc. carries out surface of pigments; by the micronize process that sulfuric acid particles method etc. is carried out; or for removing the carrying out washing treatment utilizing organic solvent, water etc. to carry out of impurity, the removing process etc. utilizing ion exchange process etc. to carry out of ionic impurity.In addition, pigment preferable particle size is homogeneous.By carrying out dispersion treatment containing pigment dispersing agent, the dispersible pigment dispersion of the state that pigment disperses in the solution equably can be obtained.
As above-mentioned pigment dispersing agent, commercially available surfactant can be used.As surfactant, the surfactant of such as type siloxane, fluorine class, ester class, cationic, anionic species, nonionic class, both sexes, polyesters, polyamines class, acrylic compounds and polyurethanes can be enumerated.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 polyurethanes, outside polyethyleneimine: amine etc., can also enumerate with the KP (SHIN-ETSU HANTOTAI's chemical industry (strain) system) of trade name name, フ ロ ー レ Application (common prosperity society chemistry (strain) system), 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 individually or combine two or more to use.
When using pigment dispersing agent, its consumption, relative to the gross mass of pigment, is preferably below 100 quality %, is more preferably 5 ~ 50 quality %.If the consumption of pigment dispersing agent is in above-mentioned scope, then there is the trend obtaining the dispersible pigment dispersion of homogeneous disperse state.
The content of colorant (A), relative to the solid composition of coloring photosensitive combination, is preferably 5 ~ 60 quality %, is more preferably 5 ~ 45 quality %.If in above-mentioned scope, then can obtain required light splitting, color depth.Wherein, solid composition refers to the total being removed desolventizing and the amount of obtaining by coloring photosensitive combination.
Coloring photosensitive combination of the present invention is preferably containing resin (B).
As the resin used in coloring photosensitive combination of the present invention (B), be preferably the resin of performance alkali-solubility.Wherein, alkali-solubility refers to the character of dissolving in the developer solution of the aqueous solution as alkali cpd.
As the resin of the above-mentioned alkali-solubility of performance, can enumerate
Resin (B-1): will at least one (a) (hereinafter sometimes referred to " (a) ") of unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides is selected from and there is the multipolymer that compound (b) (hereinafter sometimes referred to " (b) ") that carbon number is the cyclic ether of 2 ~ 4 is polymerized
Resin (B-2): (wherein, can not there is the cyclic ether that carbon number is 2 ~ 4 with the monomer (c) of (a) and (b) copolymerization.) multipolymer that is polymerized of (hereinafter sometimes referred to " (c) "), (a) and (b),
Resin (B-3): the multipolymer that (a) and (c) is polymerized,
Resin (B-4): the resin that the multipolymer that (a) and (c) is polymerized reacts with (b) and obtains,
Resin (B-5): the resin etc. that the multipolymer that (b) and (c) is polymerized reacts with (a) and obtains.
As (a), specifically, can enumerate acrylic acid, methacrylic acid, crotonic acid, adjacent vinyl benzoic acid, a vinyl benzoic acid, to unsaturated monocarboxylic classes such as vinyl benzoic acids,
Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl tetrahydro phthalic acid, 1, the unsaturated dicarboxylic classes such as 4-cyclohexene dicarboxylic acid
Methyl-5-norborene-2,3-dicarboxylic acid, 5-carboxyl dicyclo [2.2.1] hept-2-ene", 5, the dicyclo unsaturated compound class containing carboxyl such as 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"
Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic acid acid anhydride, 4-vinylphthalic acid acid 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, the unsaturated dicarboxylic acid anhydride classes such as 6-dicarboxylic anhydride (carbic anhydride)
Unsaturated list [(methyl) acryloxyalkyl] the ester class of the polybasic carboxylic acid of mono succinate [2-(methyl) acryloyl-oxyethyl] ester, phthalic acid list [2-(methyl) acryloyl-oxyethyl] ester etc. more than 2 yuan
α-(hydroxymethyl) acrylic acid etc. contain the unsaturated esters of acrylic acid etc. of hydroxyl and carboxyl in same a part.
Wherein, acrylic acid, methacrylic acid, maleic anhydride etc. preferably use from the viewpoint of the viewpoint of copolyreaction, alkali-solubility.
Wherein, in this instructions, " (methyl) acrylic acid " represents at least a kind that is selected from acrylic acid and methacrylic acid." (methyl) acryloyl group " and " (methyl) acrylate " etc. are recorded has the same meaning.
B () has the polymerizable compound that carbon number is the cyclic ether (being such as selected from least a kind of oxirane ring, oxetanes ring and tetrahydrofuran ring (tetrahydrofuran ring)) of 2 ~ 4.B () preferably has carbon number is the cyclic ether of 2 ~ 4 and the monomer of ethylenic unsaturated bond, is more preferably that to have carbon number be the cyclic ether of 2 ~ 4 and the monomer of (methyl) acryloxy.
As (b), the monomer (b3) (hereinafter sometimes referred to " (b3) ") monomer (b1) (hereinafter sometimes referred to " (b1) ") such as with Oxyranyle, the monomer (b2) (hereinafter sometimes referred to " (b2) ") with oxetanyl can enumerated and there is tetrahydrofuran base.
There is the monomer (b1) of Oxyranyle, refer to the polymerizable compound with Oxyranyle.As (b1), can enumerate and such as have the monomer (b1-1) (hereinafter sometimes referred to " (b1-1) ") of the structure of chain type alkene epoxidation and ethylenic unsaturated bond and the monomer (b1-2) (hereinafter sometimes referred to " (b1-2) ") that has the structure of cycloolefin epoxidation and ethylenic unsaturated bond.
As (b1), preferably there is the monomer of Oxyranyle and ethylenic unsaturated bond, be more preferably the monomer with Oxyranyle and (methyl) acryloxy, more preferably have (b1-2) of (methyl) acryloxy.
As (b1-1), specifically, (methyl) glycidyl acrylate can be enumerated, (methyl) propenoic acid beta-methylglycidyl ester, (methyl) propenoic acid beta-ethyl glycidyl base ester, glycidyl vinyl ether, adjacent vinylbenzyl glycidyl base ether, between vinylbenzyl glycidyl base ether, to vinylbenzyl glycidyl base ether, Alpha-Methyl-adjacent vinylbenzyl glycidyl base ether, an Alpha-Methyl-vinylbenzyl glycidyl base ether, Alpha-Methyl-to vinylbenzyl glycidyl base ether, two (glycidyl oxy methyl) styrene of 2,3-, two (glycidyl oxy methyl) styrene of 2,4-, two (glycidyl oxy methyl) styrene of 2,5-, two (glycidyl oxy methyl) styrene of 2,6-, 2,3,4-tri-(glycidyl oxy methyl) styrene, 2,3,5-tri-(glycidyl oxy methyl) styrene, 2,3,6-tri-(glycidyl oxy methyl) styrene, 3,4,5-tri-(glycidyl oxy methyl) styrene, 2,4,6-tri-(glycidyl oxy methyl) styrene, the compound etc. recorded in Japanese Unexamined Patent Publication 7-248625 publication.
As (b1-2), vinyl cyclohexene list oxide, 1 can be enumerated, 2-epoxy-4-vinyl cyclohexane (such as セ ロ キ サ イ De 2000, ダ イ セ Le chemical industry (strain) make), acrylic acid 3,4-epoxycyclohexyl-methyl ester (such as サ イ Network ロ マ ー A400, ダ イ セ Le chemical industry (strain) make), methacrylic acid 3,4-epoxycyclohexyl-methyl ester (such as サ イ Network ロ マ ー M100, ダ イ セ Le chemical industry (strain) system), the compound shown in formula (I), the compound etc. shown in formula (II).
[chemical formula 1]
[in formula (I) and formula (II), R 1and R 2represent that hydrogen atom or carbon number are the alkyl of 1 ~ 4 independently of each other, the hydrogen atom contained in this alkyl can be optionally substituted by a hydroxyl group.
X 1and X 2represent singly-bound ,-R independently of each other 3-, *-R 3-O-, *-R 3-S-, *-R 3-NH-.
R 3represent that carbon number is alkane two base of 1 ~ 6.
* the bonding key with O is represented.]
Be the alkyl of 1 ~ 4 as carbon number, specifically, methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group etc. can be enumerated.
As hydroxy alkyl, 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. can be enumerated.
As R 1and R 2, preferably enumerate hydrogen atom, methyl, hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, more preferably enumerate hydrogen atom, methyl.
As alkane two base, methylene, 1,2-ethylidene, propane-1,2-bis-base, propane-1,3-bis-base, butane-Isosorbide-5-Nitrae-two base, pentane-1,5-bis-base, hexane-1,6-bis-base etc. can be enumerated.
As X 1and X 2, preferably enumerate singly-bound, methylene, 1,2-ethylidene, *-CH 2-O-(* represents the bonding key with O) base, *-CH 2cH 2-O-base, more preferably enumerates singly-bound, *-CH 2cH 2-O-base.
As the compound shown in formula (I), the compound etc. shown in formula (I-1) ~ formula (I-15) can be enumerated.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 formula (I-1), formula (I-7), formula (I-9), formula (I-15) is enumerated.
[chemical formula 2]
As the compound shown in formula (II), the compound etc. shown in formula (II-1) ~ formula (II-15) can be enumerated.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 formula (II-1), formula (II-7), formula (II-9), formula (II-15) is enumerated.
[chemical formula 3]
Compound shown in compound shown in formula (I) and formula (II) can individually use.In addition, they also can mix with arbitrary proportion.During mixing, its blending ratio with molar ratio computing, preferred formula (I): formula (II) is 5:95 ~ 95:5, is more preferably 10:90 ~ 90:10, is particularly preferably 20:80 ~ 80:20.
There is the monomer (b2) of oxetanyl, refer to the polymerizable compound with oxetanyl.As (b2), preferably there is the monomer of oxetanylmethoxy and ethylenic unsaturated bond, be more preferably the monomer with oxetanyl and (methyl) acryloxy.As (b2), such as 3-methyl-3-(methyl) acryloyloxymethyl oxetanes, 3-ethyl-3-(methyl) acryloyloxymethyl oxetanes, 3-methyl-3-(methyl) acryloyl-oxyethyl oxetanes and 3-ethyl-3-(methyl) acryloyl-oxyethyl oxetanes can be enumerated.
There is the monomer (b3) of tetrahydrofuran base, refer to the polymerizable compound with tetrahydrofuran base.As (b3), preferably there is the monomer of tetrahydrofuran base and ethylenical unsaturated double bonds, be more preferably the monomer with tetrahydrofuran base and (methyl) acryloxy.
As (b3), specifically, acrylic acid tetrahydro furfuryl ester (such as PVC ス コ ー ト V#150, Osaka Organic Chemical Industry (strain) system), methacrylic acid tetrahydro furfuryl ester etc. can be enumerated.
As (c), (methyl) alkyl-acrylates such as such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-butyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate can be enumerated
(methyl) cyclohexyl acrylate, (methyl) acrylic acid 2-methyl cyclohexyl, (methyl) acrylic acid three ring [5.2.1.0 2,6] decane-8-base ester is (in this technical field, as trivial name, be called (methyl) acrylic acid Bicvclopentyl ester), (methyl) acrylic acid cyclic alkyl ester class such as (methyl) acrylic acid Bicvclopentyl oxygen base ethyl ester, (methyl) isobornyl acrylate
(methyl) benzyl acrylate or the aralkyl ester classes such as (methyl) phenyl acrylate, (methyl) benzyl acrylate,
The dicarboxylic diesters such as diethyl maleate, DEF, diethyl itaconate,
The 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-bis-(hydroxymethyl) dicyclo [2.2.1] hept-2-ene", 5,6-bis-(2 '-hydroxyethyl) dicyclo [2.2.1] hept-2-ene", 5,6-dimethoxy dicyclo [2.2.1] hept-2-ene", 5,6-diethoxy dicyclo [2.2.1] hept-2-ene", 5-hydroxy-5-methyl base dicyclo [2.2.1] hept-2-ene", 5-hydroxyl-5-ethyl dicyclo [2.2.1] hept-2-ene", 5-hydroxymethyl-5-methyl bicycle [2.2.1] hept-2-ene", 5-tert-butoxycarbonyl dicyclo [2.2.1] hept-2-ene", 5-cyclohexyloxy carbonyl dicyclo [2.2.1] hept-2-ene", 5-phenyloxycarbonyl dicyclo [2.2.1] hept-2-ene", two (tert-butoxycarbonyl) dicyclo [2.2.1] hept-2-ene" of 5,6-, the dicyclo unsaturated compound classes such as two (cyclohexyl oxygen base carbonyl) dicyclo [2.2.1] hept-2-ene"s of 5,6-,
The dicarbonyl imides derivant classes such as N-phenylmaleimide, N-N-cyclohexylmaleimide, N-benzyl maleimide, N-succinimido-3-maleimidobenzoyl ester, N-succinimido-4-malimidobutanoate, N-succinimido-6-maleimidohexanoic acid ester, N-succinimido-3-maleimidopropionic acid ester, N-(9-acridinyl) maleimide
Styrene, α-methyl styrene, a methyl styrene, p-methylstyrene, vinyltoluene, to methoxy styrene, vinyl cyanide, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, Methacrylamide, vinyl acetate, 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene.
Wherein, styrene, N-phenylmaleimide, N-N-cyclohexylmaleimide, N-benzyl maleimide, dicyclo [2.2.1] hept-2-ene" etc. are preferred from the viewpoint of copolyreaction and alkali-solubility.
In resin (B-1), as the ratio of structural unit coming from each monomer, relative to the total mole number of structural unit forming resin (B-1), preferably in following scope.
Come from the structural unit of (a): 5 ~ 60 % by mole (being more preferably 10 ~ 50 % by mole)
Come from the structural unit of (b): 40 ~ 95 % by mole (being more preferably 50 ~ 90 % by mole)
If in above-mentioned scope, then there is the trend that storage stability, developability, solvent resistance, thermotolerance and physical strength become good in the ratio of the structural unit of resin (B-1).
As resin (B-1), preferably (b) is the resin of (b1), is more preferably (b) resin for (b1-2).
Prepared by the citing document recorded in the method that resin (B-1) such as can be recorded in list of references " high point son close into experiment method " (grand row work sale room (strain) chemistry in large Tianjin is with people's the 1st edition the 1st printing distribution on March 1st, 1972) and the document.
Specifically, can enumerate and (a) and (b) of ormal weight, polymerization initiator and solvent etc. are joined in reaction vessel, utilize nitrogen to replace oxygen, carry out deoxidation thus, and carry out the method that stirs, heat, be incubated.And, to the polymerization initiator wherein used and solvent etc. without particular limitation of, normally used arbitrary polymerization initiator and solvent in this field can be used.As polymerization initiator, such as azo-compound (2 can be enumerated, 2 '-azobis isobutyronitrile, 2,2 '-azo two (2,4-methyl pentane nitrile) etc.) and organic peroxide (benzoyl peroxide etc.), as solvent, as long as the solvent of each monomer of solubilized, as the solvent of coloring photosensitive combination, solvent described later etc. can be used.
And the multipolymer of gained can directly use reacted solution, also can using solution that is concentrated or dilution, the material obtained in solid (powder) mode by the method such as precipitating again can also being used.Particularly during this polymerization, as solvent, by using the solvent identical with solvent described later (E), can directly use reacted solution, thus can preparation process be simplified.
In resin (B-2), as the ratio of structural unit coming from each monomer, relative to the total mole number of entire infrastructure unit forming resin (B-2), preferably in following scope.
Come from the structural unit of (a): 2 ~ 40 % by mole (being more preferably 5 ~ 35 % by mole)
Come from the structural unit of (b): 2 ~ 95 % by mole (being more preferably 5 ~ 80 % by mole)
Come from the structural unit of (c): 1 ~ 65 % by mole (being more preferably 1 ~ 60 % by mole)
If in above-mentioned scope, then there is the trend that storage stability, developability, solvent resistance, thermotolerance and physical strength become good in the ratio of the structural unit of resin (B-2).
As resin (B-2), preferably (b) is the resin of (b1), is more preferably (b) resin for (b1-2).
Resin (B-2) can be prepared by the method identical with resin (B-1).
In resin (B-3), as the ratio of structural unit coming from each monomer, relative to the total mole number of entire infrastructure unit forming resin (B-3), preferably in following scope.
Come from the structural unit of (a): 2 ~ 40 % by mole (being more preferably 5 ~ 35 % by mole)
Come from the structural unit of (c): 60 ~ 98 % by mole (being more preferably 65 ~ 95 % by mole)
If the ratio of the structural unit of resin (B-3) is in above-mentioned scope, then there is storage stability, developability, solvent resistance become good trend.
Resin (B-3) can be prepared by the method identical with resin (B-1).
Resin (B-4) and resin (B-5) such as can be prepared through two stage step.Now, can prepare with reference to the method etc. recorded in the method recorded in above-mentioned document " high point son closes into experiment method " (grand row work sale room (strain) chemistry in large Tianjin is with people's the 1st edition the 1st printing distribution on March 1st, 1972), Japanese Unexamined Patent Publication 2001-89533 publication.
For resin (B-4), first as the first stage, obtain the multipolymer of (a) and (c) in the same manner as the preparation method of above-mentioned resin (B-1).
Now, as described above, the multipolymer of gained can directly use reacted solution, also can use solution that is concentrated or dilution, can also use the material obtained in solid (powder) mode by the method such as precipitating again.
Come from the ratio of the structural unit of (a) and (c), relative to the total molal quantity of the entire infrastructure unit of the above-mentioned multipolymer of formation, preferably in following scope.
Come from the structural unit of (a): 5 ~ 50 % by mole (being more preferably 10 ~ 45 % by mole)
Come from the structural unit of (c): 50 ~ 95 % by mole (being more preferably 55 ~ 90 % by mole)
Then, as subordinate phase, a part for the carboxylic acid of (a) coming from gained multipolymer and carboxylic acid anhydrides and the cyclic ether of (b) are reacted.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 the above, atmosphere in flask is replaced into air by nitrogen, adding in flask relative to the molal quantity of (a) is (b) of 5 ~ 80 % by mole, relative to (a), b the total amount of () and (c) is the carboxyl of 0.001 ~ 5 quality % and the catalysts (such as three (dimethylaminomethyl) phenol) of cyclic ether, and relative to (a), b the total amount of () and (c) is the polymerization inhibitor (such as quinhydrones) of 0.001 ~ 5 quality %, 60 ~ 130 DEG C of reactions 1 ~ 10 hour, resin (A-4) can be obtained.And, in the same manner as polymerizing condition, consider Preparation equipment, be polymerized the thermal discharge etc. caused, can suitably adjust adding method, temperature of reaction.
In addition, now, the molal quantity of (b), relative to the molal quantity of (a), is preferably 10 ~ 75 % by mole, is more preferably 15 ~ 70 % by mole.By making the molal quantity of (b) in this scope, the balance of storage stability, solvent resistance and thermotolerance has and becomes good trend.
As the concrete example of resin (B-4), can enumerate and the multipolymer of (methyl) acrylic acid/(methyl) acrylic acid Bicvclopentyl ester and (methyl) glycidyl acrylate be reacted and the resin that obtains, the multipolymer of (methyl) acrylic acid/(methyl) benzyl acrylate and (methyl) glycidyl acrylate are reacted and the resin that obtains, the multipolymer of (methyl) acrylic acid/(methyl) cyclohexyl acrylate and (methyl) glycidyl acrylate are reacted and the resin that obtains, (methyl) acrylic acid/cinnamic multipolymer and (methyl) glycidyl acrylate are reacted and the resin that obtains, the multipolymer of (methyl) acrylic acid/(methyl) methyl acrylate and (methyl) glycidyl acrylate are reacted and the resin that obtains, the multipolymer of (methyl) acrylic acid/N-N-cyclohexylmaleimide and (methyl) glycidyl acrylate are reacted and the resin that obtains, the multipolymer of (methyl) acrylic acid/(methyl) acrylic acid Bicvclopentyl ester/(methyl) benzyl acrylate and (methyl) glycidyl acrylate are reacted and the resin that obtains, the multipolymer of (methyl) acrylic acid/(methyl) acrylic acid Bicvclopentyl ester/(methyl) cyclohexyl acrylate and (methyl) glycidyl acrylate are reacted and the resin that obtains, (methyl) acrylic acid/(methyl) acrylic acid Bicvclopentyl ester/cinnamic multipolymer and (methyl) glycidyl acrylate are reacted and the resin that obtains, the multipolymer of (methyl) acrylic acid/(methyl) acrylic acid Bicvclopentyl ester/(methyl) methyl acrylate and (methyl) glycidyl acrylate are reacted and the resin that obtains, the multipolymer of (methyl) acrylic acid/(methyl) acrylic acid Bicvclopentyl ester/N-N-cyclohexylmaleimide and (methyl) glycidyl acrylate are reacted and the resin that obtains, the multipolymer of crotonic acid/(methyl) acrylic acid Bicvclopentyl ester and (methyl) glycidyl acrylate are reacted and the resin that obtains
The multipolymer of crotonic acid/(methyl) benzyl acrylate and (methyl) glycidyl acrylate are reacted and the resin that obtains, the multipolymer of crotonic acid/(methyl) cyclohexyl acrylate and (methyl) glycidyl acrylate are reacted and the resin that obtains, crotonic acid/cinnamic multipolymer and (methyl) glycidyl acrylate are reacted and the resin that obtains, the multipolymer of crotonic acid/ethyl crotonate and (methyl) glycidyl acrylate are reacted and the resin that obtains, the multipolymer of crotonic acid/N-N-cyclohexylmaleimide and (methyl) glycidyl acrylate are reacted and the resin that obtains, the multipolymer of crotonic acid/(methyl) acrylic acid Bicvclopentyl ester/(methyl) benzyl acrylate and (methyl) glycidyl acrylate are reacted and the resin that obtains, the multipolymer of crotonic acid/(methyl) acrylic acid Bicvclopentyl ester/(methyl) cyclohexyl acrylate and (methyl) glycidyl acrylate are reacted and the resin that obtains, crotonic acid/(methyl) acrylic acid Bicvclopentyl ester/cinnamic multipolymer and (methyl) glycidyl acrylate are reacted and the resin that obtains, the multipolymer of crotonic acid/(methyl) acrylic acid Bicvclopentyl ester/ethyl crotonate and (methyl) glycidyl acrylate are reacted and the resin that obtains, the multipolymer of crotonic acid/(methyl) acrylic acid Bicvclopentyl ester/N-N-cyclohexylmaleimide and (methyl) glycidyl acrylate are reacted and the resin that obtains
The multipolymer of maleic acid/(methyl) acrylic acid Bicvclopentyl ester and (methyl) glycidyl acrylate are reacted and the resin that obtains, the multipolymer of maleic acid/(methyl) benzyl acrylate and (methyl) glycidyl acrylate are reacted and the resin that obtains, the multipolymer of maleic acid/(methyl) cyclohexyl acrylate and (methyl) glycidyl acrylate are reacted and the resin that obtains, maleic acid/cinnamic multipolymer and (methyl) glycidyl acrylate are reacted and the resin that obtains, the multipolymer of maleic acid/methyl maleate and (methyl) glycidyl acrylate are reacted and the resin that obtains, the multipolymer of maleic acid/N-N-cyclohexylmaleimide and (methyl) glycidyl acrylate are reacted and the resin that obtains, the multipolymer of maleic acid/(methyl) acrylic acid Bicvclopentyl ester/(methyl) benzyl acrylate and (methyl) glycidyl acrylate are reacted and the resin that obtains, the multipolymer of maleic acid/(methyl) acrylic acid Bicvclopentyl ester/(methyl) cyclohexyl acrylate and (methyl) glycidyl acrylate are reacted and the resin that obtains, maleic acid/(methyl) acrylic acid Bicvclopentyl ester/cinnamic multipolymer and (methyl) glycidyl acrylate are reacted and the resin that obtains, the multipolymer of maleic acid/(methyl) acrylic acid Bicvclopentyl ester/methyl maleate and (methyl) glycidyl acrylate are reacted and the resin that obtains, the multipolymer of maleic acid/(methyl) acrylic acid Bicvclopentyl ester/N-N-cyclohexylmaleimide and (methyl) glycidyl acrylate are reacted and the resin that obtains
The multipolymer of (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid Bicvclopentyl ester and (methyl) glycidyl acrylate are reacted and the resin that obtains, the multipolymer of (methyl) acrylic acid/maleic anhydride/(methyl) benzyl acrylate and (methyl) glycidyl acrylate are reacted and the resin that obtains, the multipolymer of (methyl) acrylic acid/maleic anhydride/(methyl) cyclohexyl acrylate and (methyl) glycidyl acrylate are reacted and the resin that obtains, (methyl) acrylic acid/maleic anhydride/cinnamic multipolymer and (methyl) glycidyl acrylate are reacted and the resin that obtains, the multipolymer of (methyl) acrylic acid/maleic anhydride/(methyl) methyl acrylate and (methyl) glycidyl acrylate are reacted and the resin that obtains, the multipolymer of (methyl) acrylic acid/maleic anhydride/N-N-cyclohexylmaleimide and (methyl) glycidyl acrylate are reacted and the resin that obtains, the multipolymer of (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid Bicvclopentyl ester/(methyl) benzyl acrylate and (methyl) glycidyl acrylate are reacted and the resin that obtains, the multipolymer of (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid Bicvclopentyl ester/(methyl) cyclohexyl acrylate and (methyl) glycidyl acrylate are reacted and the resin that obtains, (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid Bicvclopentyl ester/cinnamic multipolymer and (methyl) glycidyl acrylate are reacted and the resin that obtains, the multipolymer of (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid Bicvclopentyl ester/(methyl) methyl acrylate and (methyl) glycidyl acrylate are reacted and the resin that obtains, the multipolymer of (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid Bicvclopentyl ester/N-N-cyclohexylmaleimide and (methyl) glycidyl acrylate are reacted and the resin that obtains
Make multipolymer and the methacrylic acid 3 of (methyl) acrylic acid/(methyl) acrylic acid Bicvclopentyl ester, the resin that 4-epoxycyclohexyl-methyl ester reacts and obtains, make multipolymer and the methacrylic acid 3 of (methyl) acrylic acid/(methyl) benzyl acrylate, the resin that 4-epoxycyclohexyl-methyl ester reacts and obtains, make multipolymer and the methacrylic acid 3 of (methyl) acrylic acid/(methyl) cyclohexyl acrylate, the resin that 4-epoxycyclohexyl-methyl ester reacts and obtains, make (methyl) acrylic acid/cinnamic multipolymer and methacrylic acid 3, the resin that 4-epoxycyclohexyl-methyl ester reacts and obtains, make multipolymer and the methacrylic acid 3 of (methyl) acrylic acid/(methyl) methyl acrylate, the resin that 4-epoxycyclohexyl-methyl ester reacts and obtains, make multipolymer and the methacrylic acid 3 of (methyl) acrylic acid/N-N-cyclohexylmaleimide, the resin that 4-epoxycyclohexyl-methyl ester reacts and obtains, make multipolymer and the methacrylic acid 3 of (methyl) acrylic acid/(methyl) acrylic acid Bicvclopentyl ester/(methyl) benzyl acrylate, the resin that 4-epoxycyclohexyl-methyl ester reacts and obtains, make multipolymer and the methacrylic acid 3 of (methyl) acrylic acid/(methyl) acrylic acid Bicvclopentyl ester/(methyl) cyclohexyl acrylate, the resin that 4-epoxycyclohexyl-methyl ester reacts and obtains, make (methyl) acrylic acid/(methyl) acrylic acid Bicvclopentyl ester/cinnamic multipolymer and methacrylic acid 3, the resin that 4-epoxycyclohexyl-methyl ester reacts and obtains, make multipolymer and the methacrylic acid 3 of (methyl) acrylic acid/(methyl) acrylic acid Bicvclopentyl ester/(methyl) methyl acrylate, the resin that 4-epoxycyclohexyl-methyl ester reacts and obtains, make multipolymer and the methacrylic acid 3 of (methyl) acrylic acid/(methyl) acrylic acid Bicvclopentyl ester/N-N-cyclohexylmaleimide, the resin that 4-epoxycyclohexyl-methyl ester reacts and obtains,
Make multipolymer and the methacrylic acid 3 of crotonic acid/(methyl) acrylic acid Bicvclopentyl ester, the resin that 4-epoxycyclohexyl-methyl ester reacts and obtains, make multipolymer and the methacrylic acid 3 of crotonic acid/(methyl) benzyl acrylate, the resin that 4-epoxycyclohexyl-methyl ester reacts and obtains, make multipolymer and the methacrylic acid 3 of crotonic acid/(methyl) cyclohexyl acrylate, the resin that 4-epoxycyclohexyl-methyl ester reacts and obtains, make crotonic acid/cinnamic multipolymer and methacrylic acid 3, the resin that 4-epoxycyclohexyl-methyl ester reacts and obtains, make multipolymer and the methacrylic acid 3 of crotonic acid/ethyl crotonate, the resin that 4-epoxycyclohexyl-methyl ester reacts and obtains, make multipolymer and the methacrylic acid 3 of crotonic acid/N-N-cyclohexylmaleimide, the resin that 4-epoxycyclohexyl-methyl ester reacts and obtains, make multipolymer and the methacrylic acid 3 of crotonic acid/(methyl) acrylic acid Bicvclopentyl ester/(methyl) benzyl acrylate, the resin that 4-epoxycyclohexyl-methyl ester reacts and obtains, make multipolymer and the methacrylic acid 3 of crotonic acid/(methyl) acrylic acid Bicvclopentyl ester/(methyl) cyclohexyl acrylate, the resin that 4-epoxycyclohexyl-methyl ester reacts and obtains, make crotonic acid/(methyl) acrylic acid Bicvclopentyl ester/cinnamic multipolymer and methacrylic acid 3, the resin that 4-epoxycyclohexyl-methyl ester reacts and obtains, make multipolymer and the methacrylic acid 3 of crotonic acid/(methyl) acrylic acid Bicvclopentyl ester/ethyl crotonate, the resin that 4-epoxycyclohexyl-methyl ester reacts and obtains, make multipolymer and the methacrylic acid 3 of crotonic acid/(methyl) acrylic acid Bicvclopentyl ester/N-N-cyclohexylmaleimide, the resin that 4-epoxycyclohexyl-methyl ester reacts and obtains,
Make multipolymer and the methacrylic acid 3 of maleic acid/(methyl) acrylic acid Bicvclopentyl ester, the resin that 4-epoxycyclohexyl-methyl ester reacts and obtains, make multipolymer and the methacrylic acid 3 of maleic acid/(methyl) benzyl acrylate, the resin that 4-epoxycyclohexyl-methyl ester reacts and obtains, make multipolymer and the methacrylic acid 3 of maleic acid/(methyl) cyclohexyl acrylate, the resin that 4-epoxycyclohexyl-methyl ester reacts and obtains, make maleic acid/cinnamic multipolymer and methacrylic acid 3, the resin that 4-epoxycyclohexyl-methyl ester reacts and obtains, make multipolymer and the methacrylic acid 3 of maleic acid/methyl maleate, the resin that 4-epoxycyclohexyl-methyl ester reacts and obtains, make multipolymer and the methacrylic acid 3 of maleic acid/N-N-cyclohexylmaleimide, the resin that 4-epoxycyclohexyl-methyl ester reacts and obtains, make multipolymer and the methacrylic acid 3 of maleic acid/(methyl) acrylic acid Bicvclopentyl ester/(methyl) benzyl acrylate, the resin that 4-epoxycyclohexyl-methyl ester reacts and obtains, make multipolymer and the methacrylic acid 3 of maleic acid/(methyl) acrylic acid Bicvclopentyl ester/(methyl) cyclohexyl acrylate, the resin that 4-epoxycyclohexyl-methyl ester reacts and obtains, make maleic acid/(methyl) acrylic acid Bicvclopentyl ester/cinnamic multipolymer and methacrylic acid 3, the resin that 4-epoxycyclohexyl-methyl ester reacts and obtains, make multipolymer and the methacrylic acid 3 of maleic acid/(methyl) acrylic acid Bicvclopentyl ester/methyl maleate, the resin that 4-epoxycyclohexyl-methyl ester reacts and obtains, make multipolymer and the methacrylic acid 3 of maleic acid/(methyl) acrylic acid Bicvclopentyl ester/N-N-cyclohexylmaleimide, the resin that 4-epoxycyclohexyl-methyl ester reacts and obtains,
Make multipolymer and the methacrylic acid 3 of (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid Bicvclopentyl ester, the resin that 4-epoxycyclohexyl-methyl ester reacts and obtains, make multipolymer and the methacrylic acid 3 of (methyl) acrylic acid/maleic anhydride/(methyl) benzyl acrylate, the resin that 4-epoxycyclohexyl-methyl ester reacts and obtains, make multipolymer and the methacrylic acid 3 of (methyl) acrylic acid/maleic anhydride/(methyl) cyclohexyl acrylate, the resin that 4-epoxycyclohexyl-methyl ester reacts and obtains, make (methyl) acrylic acid/maleic anhydride/cinnamic multipolymer and methacrylic acid 3, the resin that 4-epoxycyclohexyl-methyl ester reacts and obtains, make multipolymer and the methacrylic acid 3 of (methyl) acrylic acid/maleic anhydride/(methyl) methyl acrylate, the resin that 4-epoxycyclohexyl-methyl ester reacts and obtains, make multipolymer and the methacrylic acid 3 of (methyl) acrylic acid/maleic anhydride/N-N-cyclohexylmaleimide, the resin that 4-epoxycyclohexyl-methyl ester reacts and obtains, make multipolymer and the methacrylic acid 3 of (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid Bicvclopentyl ester/(methyl) benzyl acrylate, the resin that 4-epoxycyclohexyl-methyl ester reacts and obtains, make multipolymer and the methacrylic acid 3 of (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid Bicvclopentyl ester/(methyl) cyclohexyl acrylate, the resin that 4-epoxycyclohexyl-methyl ester reacts and obtains, make (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid Bicvclopentyl ester/cinnamic multipolymer and methacrylic acid 3, the resin that 4-epoxycyclohexyl-methyl ester reacts and obtains, make multipolymer and the methacrylic acid 3 of (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid Bicvclopentyl ester/(methyl) methyl acrylate, the resin that 4-epoxycyclohexyl-methyl ester reacts and obtains, make multipolymer and the methacrylic acid 3 of (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid Bicvclopentyl ester/N-N-cyclohexylmaleimide, the resin etc. that 4-epoxycyclohexyl-methyl ester reacts and obtains.
For resin (B-5), as the first stage, obtain the multipolymer of (b) and (c) in the same manner as the preparation method of above-mentioned resin (B-1).
Now, as described above, the multipolymer of gained can directly use reacted solution, also can use solution that is concentrated or dilution, can also use the material obtained in solid (powder) mode by the method such as precipitating again.
As the structural unit ratio coming from (b) and (c), relative to the total mole number of the entire infrastructure unit of the above-mentioned multipolymer of formation, preferably in following scope.
Come from the structural unit of (b): 5 ~ 95 % by mole (being more preferably 10 ~ 90 % by mole)
Come from the structural unit of (c): 5 ~ 95 % by mole (being more preferably 10 ~ 90 % by mole)
Further, in the same manner as the preparation method of resin (B-4), can react to obtain by the carboxylic acid that makes the cyclic ether coming from (b) in the multipolymer of (b) and (c) and (a) have or carboxylic acid anhydrides.Also the reaction by cyclic ether and carboxylic acid or carboxylic acid anhydrides can be made and the hydroxyl produced reacts with carboxylic acid anhydrides further.
With the consumption of (a) of above-mentioned copolymer reaction, relative to the molal quantity of (b), be preferably 5 ~ 80 % by mole.The reactivity of cyclic ether is high, is difficult to (b) of remained unreacted, therefore, as (b), preferably (b1), further preferably (b1-1).
As the concrete example of resin (B-5), can enumerate and the multipolymer of (methyl) acrylic acid Bicvclopentyl ester/(methyl) glycidyl acrylate and (methyl) acrylic acid be reacted and the resin that obtains, the multipolymer of (methyl) benzyl acrylate/(methyl) glycidyl acrylate and (methyl) acrylic acid are reacted and the resin that obtains, the multipolymer of (methyl) cyclohexyl acrylate/(methyl) glycidyl acrylate and (methyl) acrylic acid are reacted and the resin that obtains, the multipolymer of styrene/(methyl) glycidyl acrylate and (methyl) acrylic acid are reacted and the resin that obtains, the multipolymer of (methyl) methyl acrylate/(methyl) glycidyl acrylate and (methyl) acrylic acid are reacted and the resin that obtains, the multipolymer of N-N-cyclohexylmaleimide/(methyl) glycidyl acrylate and (methyl) acrylic acid are reacted and the resin that obtains, the multipolymer of (methyl) acrylic acid Bicvclopentyl ester/(methyl) benzyl acrylate/(methyl) glycidyl acrylate and (methyl) acrylic acid are reacted and the resin that obtains, the multipolymer of (methyl) acrylic acid Bicvclopentyl ester/(methyl) cyclohexyl acrylate/(methyl) glycidyl acrylate and (methyl) acrylic acid are reacted and the resin that obtains, the multipolymer of (methyl) acrylic acid Bicvclopentyl ester/styrene/(methyl) glycidyl acrylate and (methyl) acrylic acid are reacted and the resin that obtains, the multipolymer of (methyl) acrylic acid Bicvclopentyl ester/(methyl) methyl acrylate/(methyl) glycidyl acrylate and (methyl) acrylic acid are reacted and the resin that obtains, the multipolymer of (methyl) acrylic acid Bicvclopentyl ester/N-N-cyclohexylmaleimide/(methyl) glycidyl acrylate and (methyl) acrylic acid are reacted and the resin that obtains
Make the resin that the multipolymer of (methyl) acrylic acid Bicvclopentyl ester/(methyl) glycidyl acrylate and crotonic acid react and obtain, make the resin that the multipolymer of (methyl) benzyl acrylate/(methyl) glycidyl acrylate and crotonic acid react and obtain, make the resin that the multipolymer of (methyl) cyclohexyl acrylate/(methyl) glycidyl acrylate and crotonic acid react and obtain, make the resin that the multipolymer of styrene/(methyl) glycidyl acrylate and crotonic acid react and obtain, make the resin that the multipolymer of ethyl crotonate/(methyl) glycidyl acrylate and crotonic acid react and obtain, make the resin that the multipolymer of N-N-cyclohexylmaleimide/(methyl) glycidyl acrylate and crotonic acid react and obtain, make the resin that the multipolymer of (methyl) acrylic acid Bicvclopentyl ester/(methyl) benzyl acrylate/(methyl) glycidyl acrylate and crotonic acid react and obtain, make the resin that the multipolymer of (methyl) acrylic acid Bicvclopentyl ester/(methyl) cyclohexyl acrylate/(methyl) glycidyl acrylate and crotonic acid react and obtain, make the resin that the multipolymer of (methyl) acrylic acid Bicvclopentyl ester/styrene/(methyl) glycidyl acrylate and crotonic acid react and obtain, make the resin that the multipolymer of (methyl) acrylic acid Bicvclopentyl ester/ethyl crotonate/(methyl) glycidyl acrylate and crotonic acid react and obtain, make the resin that the multipolymer of (methyl) acrylic acid Bicvclopentyl ester/N-N-cyclohexylmaleimide/(methyl) glycidyl acrylate and crotonic acid react and obtain
Make the resin that the multipolymer of (methyl) acrylic acid Bicvclopentyl ester/(methyl) glycidyl acrylate and maleic acid react and obtain, make the resin that the multipolymer of (methyl) benzyl acrylate/(methyl) glycidyl acrylate and maleic acid react and obtain, make the resin that the multipolymer of (methyl) cyclohexyl acrylate/(methyl) glycidyl acrylate and maleic acid react and obtain, make the resin that the multipolymer of styrene/(methyl) glycidyl acrylate and maleic acid react and obtain, make the resin that the multipolymer of methyl maleate/(methyl) glycidyl acrylate and maleic acid react and obtain, make the resin that the multipolymer of N-N-cyclohexylmaleimide/(methyl) glycidyl acrylate and maleic acid react and obtain, make the resin that the multipolymer of (methyl) acrylic acid Bicvclopentyl ester/(methyl) benzyl acrylate/(methyl) glycidyl acrylate and maleic acid react and obtain, make the resin that the multipolymer of (methyl) acrylic acid Bicvclopentyl ester/(methyl) cyclohexyl acrylate/(methyl) glycidyl acrylate and maleic acid react and obtain, make the resin that the multipolymer of (methyl) acrylic acid Bicvclopentyl ester/styrene/(methyl) glycidyl acrylate and maleic acid react and obtain, make the resin that the multipolymer of (methyl) acrylic acid Bicvclopentyl ester/methyl maleate/(methyl) glycidyl acrylate and maleic acid react and obtain, make the resin that the multipolymer of (methyl) acrylic acid Bicvclopentyl ester/N-N-cyclohexylmaleimide/(methyl) glycidyl acrylate and maleic acid react and obtain
Make the resin that the multipolymer of (methyl) acrylic acid Bicvclopentyl ester/(methyl) glycidyl acrylate reacts with (methyl) acrylic acid and maleic anhydride and obtains, make the resin that the multipolymer of (methyl) benzyl acrylate/(methyl) glycidyl acrylate reacts with (methyl) acrylic acid and maleic anhydride and obtains, make the resin that the multipolymer of (methyl) cyclohexyl acrylate/(methyl) glycidyl acrylate reacts with (methyl) acrylic acid and maleic anhydride and obtains, make the resin that the multipolymer of styrene/(methyl) glycidyl acrylate reacts with (methyl) acrylic acid and maleic anhydride and obtains, make the resin that the multipolymer of (methyl) methyl acrylate/(methyl) glycidyl acrylate reacts with (methyl) acrylic acid and maleic anhydride and obtains, make the resin that the multipolymer of N-N-cyclohexylmaleimide/(methyl) glycidyl acrylate reacts with (methyl) acrylic acid and maleic anhydride and obtains, make the resin that the multipolymer of (methyl) acrylic acid Bicvclopentyl ester/(methyl) benzyl acrylate/(methyl) glycidyl acrylate reacts with (methyl) acrylic acid and maleic anhydride and obtains, make the resin that the multipolymer of (methyl) acrylic acid Bicvclopentyl ester/(methyl) cyclohexyl acrylate/(methyl) glycidyl acrylate reacts with (methyl) acrylic acid and maleic anhydride and obtains, make the resin that the multipolymer of (methyl) acrylic acid Bicvclopentyl ester/styrene/(methyl) glycidyl acrylate reacts with (methyl) acrylic acid and maleic anhydride and obtains, make the resin that the multipolymer of (methyl) acrylic acid Bicvclopentyl ester/(methyl) methyl acrylate/(methyl) glycidyl acrylate reacts with (methyl) acrylic acid and maleic anhydride and obtains, make the resin that the multipolymer of (methyl) acrylic acid Bicvclopentyl ester/N-N-cyclohexylmaleimide/(methyl) glycidyl acrylate reacts with (methyl) acrylic acid and maleic anhydride and obtains
Make (methyl) acrylic acid Bicvclopentyl ester/methacrylic acid 3, the resin that multipolymer and (methyl) acrylic acid of 4-epoxycyclohexyl-methyl ester react and obtains, make (methyl) benzyl acrylate/methacrylic acid 3, the resin that multipolymer and (methyl) acrylic acid of 4-epoxycyclohexyl-methyl ester react and obtains, make (methyl) cyclohexyl acrylate/methacrylic acid 3, the resin that multipolymer and (methyl) acrylic acid of 4-epoxycyclohexyl-methyl ester react and obtains, make styrene/methacrylic acid 3, the resin that multipolymer and (methyl) acrylic acid of 4-epoxycyclohexyl-methyl ester react and obtains, make (methyl) methyl acrylate/methacrylic acid 3, the resin that multipolymer and (methyl) acrylic acid of 4-epoxycyclohexyl-methyl ester react and obtains, make N-N-cyclohexylmaleimide/methacrylic acid 3, the resin that multipolymer and (methyl) acrylic acid of 4-epoxycyclohexyl-methyl ester react and obtains, make (methyl) acrylic acid Bicvclopentyl ester/(methyl) benzyl acrylate/methacrylic acid 3, the resin that multipolymer and (methyl) acrylic acid of 4-epoxycyclohexyl-methyl ester react and obtains, make (methyl) acrylic acid Bicvclopentyl ester/(methyl) cyclohexyl acrylate/methacrylic acid 3, the resin that multipolymer and (methyl) acrylic acid of 4-epoxycyclohexyl-methyl ester react and obtains, make (methyl) acrylic acid Bicvclopentyl ester/styrene/methacrylic acid 3, the resin that multipolymer and (methyl) acrylic acid of 4-epoxycyclohexyl-methyl ester react and obtains, make (methyl) acrylic acid Bicvclopentyl ester/(methyl) methyl acrylate/methacrylic acid 3, the resin that multipolymer and (methyl) acrylic acid of 4-epoxycyclohexyl-methyl ester react and obtains, make (methyl) acrylic acid Bicvclopentyl ester/N-N-cyclohexylmaleimide/methacrylic acid 3, the resin that multipolymer and (methyl) acrylic acid of 4-epoxycyclohexyl-methyl ester react and obtains,
Make (methyl) acrylic acid Bicvclopentyl ester/methacrylic acid 3, the resin that the multipolymer of 4-epoxycyclohexyl-methyl ester and crotonic acid react and obtain, make (methyl) benzyl acrylate/methacrylic acid 3, the resin that the multipolymer of 4-epoxycyclohexyl-methyl ester and crotonic acid react and obtain, make (methyl) cyclohexyl acrylate/methacrylic acid 3, the resin that the multipolymer of 4-epoxycyclohexyl-methyl ester and crotonic acid react and obtain, make styrene/methacrylic acid 3, the resin that the multipolymer of 4-epoxycyclohexyl-methyl ester and crotonic acid react and obtain, make ethyl crotonate/methacrylic acid 3, the resin that the multipolymer of 4-epoxycyclohexyl-methyl ester and crotonic acid react and obtain, make N-N-cyclohexylmaleimide/methacrylic acid 3, the resin that the multipolymer of 4-epoxycyclohexyl-methyl ester and crotonic acid react and obtain, make (methyl) acrylic acid Bicvclopentyl ester/(methyl) benzyl acrylate/methacrylic acid 3, the resin that the multipolymer of 4-epoxycyclohexyl-methyl ester and crotonic acid react and obtain, make (methyl) acrylic acid Bicvclopentyl ester/(methyl) cyclohexyl acrylate/methacrylic acid 3, the resin that the multipolymer of 4-epoxycyclohexyl-methyl ester and crotonic acid react and obtain, make (methyl) acrylic acid Bicvclopentyl ester/styrene/methacrylic acid 3, the resin that the multipolymer of 4-epoxycyclohexyl-methyl ester and crotonic acid react and obtain, make (methyl) acrylic acid Bicvclopentyl ester/ethyl crotonate/methacrylic acid 3, the resin that the multipolymer of 4-epoxycyclohexyl-methyl ester and crotonic acid react and obtain, make (methyl) acrylic acid Bicvclopentyl ester/N-N-cyclohexylmaleimide/methacrylic acid 3, the resin that the multipolymer of 4-epoxycyclohexyl-methyl ester and crotonic acid react and obtain,
Make (methyl) acrylic acid Bicvclopentyl ester/methacrylic acid 3, the resin that the multipolymer of 4-epoxycyclohexyl-methyl ester and maleic acid react and obtain, make (methyl) benzyl acrylate/methacrylic acid 3, the resin that the multipolymer of 4-epoxycyclohexyl-methyl ester and maleic acid react and obtain, make (methyl) cyclohexyl acrylate/methacrylic acid 3, the resin that the multipolymer of 4-epoxycyclohexyl-methyl ester and maleic acid react and obtain, make styrene/methacrylic acid 3, the resin that the multipolymer of 4-epoxycyclohexyl-methyl ester and maleic acid react and obtain, make methyl maleate/methacrylic acid 3, the resin that the multipolymer of 4-epoxycyclohexyl-methyl ester and maleic acid react and obtain, make N-N-cyclohexylmaleimide/methacrylic acid 3, the resin that the multipolymer of 4-epoxycyclohexyl-methyl ester and maleic acid react and obtain, make (methyl) acrylic acid Bicvclopentyl ester/(methyl) benzyl acrylate/methacrylic acid 3, the resin that the multipolymer of 4-epoxycyclohexyl-methyl ester and maleic acid react and obtain, make (methyl) acrylic acid Bicvclopentyl ester/(methyl) cyclohexyl acrylate/methacrylic acid 3, the resin that the multipolymer of 4-epoxycyclohexyl-methyl ester and maleic acid react and obtain, make (methyl) acrylic acid Bicvclopentyl ester/styrene/methacrylic acid 3, the resin that the multipolymer of 4-epoxycyclohexyl-methyl ester and maleic acid react and obtain, make (methyl) acrylic acid Bicvclopentyl ester/methyl maleate/methacrylic acid 3, the resin that the multipolymer of 4-epoxycyclohexyl-methyl ester and maleic acid react and obtain, make (methyl) acrylic acid Bicvclopentyl ester/N-N-cyclohexylmaleimide/methacrylic acid 3, the resin that the multipolymer of 4-epoxycyclohexyl-methyl ester and maleic acid react and obtain,
Make (methyl) acrylic acid Bicvclopentyl ester/methacrylic acid 3, the resin that the multipolymer of 4-epoxycyclohexyl-methyl ester reacts with (methyl) acrylic acid and maleic anhydride and obtains, make (methyl) benzyl acrylate/methacrylic acid 3, the resin that the multipolymer of 4-epoxycyclohexyl-methyl ester reacts with (methyl) acrylic acid and maleic anhydride and obtains, make (methyl) cyclohexyl acrylate/methacrylic acid 3, the resin that the multipolymer of 4-epoxycyclohexyl-methyl ester reacts with (methyl) acrylic acid and maleic anhydride and obtains, make styrene/methacrylic acid 3, the resin that the multipolymer of 4-epoxycyclohexyl-methyl ester reacts with (methyl) acrylic acid and maleic anhydride and obtains, make (methyl) methyl acrylate/methacrylic acid 3, the resin that the multipolymer of 4-epoxycyclohexyl-methyl ester reacts with (methyl) acrylic acid and maleic anhydride and obtains, make N-N-cyclohexylmaleimide/methacrylic acid 3, the resin that the multipolymer of 4-epoxycyclohexyl-methyl ester reacts with (methyl) acrylic acid and maleic anhydride and obtains, make (methyl) acrylic acid Bicvclopentyl ester/(methyl) benzyl acrylate/methacrylic acid 3, the resin that the multipolymer of 4-epoxycyclohexyl-methyl ester reacts with (methyl) acrylic acid and maleic anhydride and obtains, make (methyl) acrylic acid Bicvclopentyl ester/(methyl) cyclohexyl acrylate/methacrylic acid 3, the resin that the multipolymer of 4-epoxycyclohexyl-methyl ester reacts with (methyl) acrylic acid and maleic anhydride and obtains, make (methyl) acrylic acid Bicvclopentyl ester/styrene/methacrylic acid 3, the resin that the multipolymer of 4-epoxycyclohexyl-methyl ester reacts with (methyl) acrylic acid and maleic anhydride and obtains, make (methyl) acrylic acid Bicvclopentyl ester/(methyl) methyl acrylate/methacrylic acid 3, the resin that the multipolymer of 4-epoxycyclohexyl-methyl ester reacts with (methyl) acrylic acid and maleic anhydride and obtains, make (methyl) acrylic acid Bicvclopentyl ester/N-N-cyclohexylmaleimide/methacrylic acid 3, the resin etc. that the multipolymer of 4-epoxycyclohexyl-methyl ester reacts with (methyl) acrylic acid and maleic anhydride and obtains.
The weight-average molecular weight of the polystyrene conversion of resin (B) is preferably 3000 ~ 100000, is more preferably 5000 ~ 50000.If the weight-average molecular weight of resin (B) in above-mentioned scope, then exists the trend that coating becomes good, in addition, be difficult to produce film during development and reduce, and then the deciduous that there is non-exposed portion during development becomes good trend.
The molecular weight distribution [weight-average molecular weight (Mw)/number-average molecular weight (Mn)] of resin (B) is preferably 1.1 ~ 6.0, is more preferably 1.2 ~ 4.0.If molecular weight distribution is in above-mentioned scope, then there is the trend of developability excellence.
The acid number of resin (B) is preferably 20 ~ 150mg/g-KOH, is more preferably 50 ~ 135mg/g-KOH, is particularly preferably 70 ~ 135mg/g-KOH.Wherein, acid number be as in and the value that measures of the amount (mg) of resin (B) 1g and required potassium hydroxide, it can carry out titration to try to achieve by using potassium hydroxide aqueous solution.
When coloring photosensitive combination of the present invention contains resin (B), the content of resin (B) is relative to the total amount of resin (B) and polymerizable compound (C), be generally 5 ~ 95 quality %, be preferably 20 ~ 80 quality %, be more preferably 40 ~ 60 quality %.If the content of resin (B) is in above-mentioned scope, then the solvent resistance of the pattern of developability, adaptation, solidification, mechanical property have and become good trend.
Coloring photosensitive combination of the present invention contains polymerizable compound (C).
Polymerizable compound (C) is the compound that the living radical, acid etc. by being produced by polymerization initiator (D) carries out being polymerized, the compound of the ethylenic unsaturated bond such as with polymerism can be enumerated, preferably enumerate (methyl) acrylate compounds.
As the polymerizable compound (C) of ethylenic unsaturated bond with 1 polymerism, the compound same with the Compound Phase enumerated as above-mentioned (a), (b) and (c) can be enumerated, wherein, (methyl) esters of acrylic acid is preferably.
As the polymerizable compound (C) of ethylenic unsaturated bond with 2 polymerisms, can 1 be enumerated, 3-butylene glycol two (methyl) acrylate, 1, 3-butylene glycol (methyl) acrylate, 1, 6-hexanediol two (methyl) acrylate, ethylene glycol bisthioglycolate (methyl) acrylate, diethylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, TEG two (methyl) acrylate, polyethyleneglycol diacrylate, two (acryloyl-oxyethyl) ethers of bisphenol-A, Ethoxylated bisphenol A bis-(methyl) acrylate, ethoxylated neopentylglycol two (methyl) acrylate, ethoxylation neopentyl glycol two (methyl) acrylate, 3-methyl pentanediol two (methyl) acrylate etc.
As the polymerizable compound (C) of ethylenic unsaturated bond with more than 3 polymerisms, trimethylolpropane tris (methyl) acrylate can be enumerated, pentaerythrite three (methyl) acrylate, three (2-hydroxyethyl) isocyanuric acid ester three (methyl) acrylate, ethoxylated trimethylolpropane three (methyl) acrylate, propoxylation trimethylolpropane tris (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, tripentaerythritol four (methyl) acrylate, tripentaerythritol five (methyl) acrylate, tripentaerythritol six (methyl) acrylate, tripentaerythritol seven (methyl) acrylate, tripentaerythritol eight (methyl) acrylate, the reactant of pentaerythrite three (methyl) acrylate and acid anhydrides, the reactant of dipentaerythritol five (methyl) acrylate and acid anhydrides, the reactant of tripentaerythritol seven (methyl) acrylate and acid anhydrides, caprolactone modification trimethylolpropane tris (methyl) acrylate, caprolactone modification pentaerythrite three (methyl) acrylate, caprolactone modification three (2-hydroxyethyl) isocyanuric acid ester three (methyl) acrylate, caprolactone modification pentaerythrite four (methyl) acrylate, caprolactone modification dipentaerythritol five (methyl) acrylate, caprolactone modification dipentaerythritol six (methyl) acrylate, caprolactone modification tripentaerythritol four (methyl) acrylate, caprolactone modification tripentaerythritol five (methyl) acrylate, caprolactone modification tripentaerythritol six (methyl) acrylate, caprolactone modification tripentaerythritol seven (methyl) acrylate, caprolactone modification tripentaerythritol eight (methyl) acrylate, the reactant of caprolactone modification pentaerythrite three (methyl) acrylate and acid anhydrides, the reactant of caprolactone modification dipentaerythritol five (methyl) acrylate and acid anhydrides, the reactant etc. of caprolactone modification tripentaerythritol seven (methyl) acrylate and acid anhydrides.
Wherein, being preferably 3 officials can above monomer, is more preferably dipentaerythritol six (methyl) acrylate.
The content of polymerizable compound (C), relative to the total amount of resin (B) and polymerizable compound (C), is preferably 5 ~ 95 quality %, is more preferably 20 ~ 80 quality %.If the content of polymerizable compound (C) is in above-mentioned scope, then there is sensitivity, the flatness of pattern of gained, reliability, physical strength become good trend.
Coloring photosensitive combination of the present invention contains polymerization initiator (D).
As polymerizing initiator (D), as long as produce living radical, acid etc. by the effect of light, the compound of initiated polymerization, is not particularly limited, and 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 record in Japanese Unexamined Patent Publication 2008-181087 publication light cationic polymerization initiators (such as by kation and the material coming from lewis acidic negative ion formation).
As above-mentioned united imidazole, can 2 be enumerated, 2 '-bis-(2-chlorphenyl)-4, 4 ', 5, 5 '-tetraphenyl bisglyoxaline, 2, 2 '-bis-(2, 3-dichlorophenyl)-4, 4 ', 5, 5 '-tetraphenyl bisglyoxaline (such as with reference to Japanese Unexamined Patent Publication 6-75372 publication and Japanese Unexamined Patent Publication 6-75373 publication), 2, 2 '-bis-(2-chlorphenyl)-4, 4 ', 5, 5 '-tetraphenyl bisglyoxaline, 2, 2 '-bis-(2-chlorphenyl)-4, 4 ', 5, 5 '-four (alkoxyl phenyl) bisglyoxaline, 2, 2 '-bis-(2-chlorphenyl)-4, 4 ', 5, 5 '-four (dialkoxy phenyl) bisglyoxaline, 2, 2 '-bis-(2-chlorphenyl)-4, 4 ', 5, 5 '-four (tri-alkoxy phenyl) bisglyoxaline (such as with reference to Japanese Patent Publication 48-38403 publication and Japanese Laid-Open Patent Publication 62-174204 publication), 4, 4 ' 5, the imidazolium compounds that the phenyl of 5 '-position is replaced by alkoxy carbonyl group is (such as with reference to Japanese Unexamined Patent Publication 7-10913 publication.) etc.Preferably enumerate 2,2 '-bis-(2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-bis-(2,3-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-bis-(2,4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline.
As above-mentioned benzene alkyl ketone compound, diethoxy acetophenone can be enumerated, 2-methyl-2-morpholino-1-(4-methylsulfanyl phenyl) propane-1-ketone, 2-dimethylamino-1-(4-morphlinophenyl)-2-benzyl butane-1-ketone, 2-dimethylamino-1-(4-morphlinophenyl)-2-(4-methylphenylmethyl) 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, the oligomer etc. of 2-hydroxy-2-methyl-1-(4-isopropenyl phenyl) propane-1-ketone, preferably enumerate 2-methyl-2-morpholino-1-(4-methylsulfanyl phenyl) propane-1-ketone, 2-dimethylamino-1-(4-morphlinophenyl)-2-benzyl butane-1-ketone etc.Also the commercially available product such as イ Le ガ キ ュ ア 369, イ Le ガ キ ュ ア 907 (above BASF ジ ャ パ Application society system) can be used.
As above-mentioned triaizine compounds, can 2 be enumerated, two (the trichloromethyl)-6-(4-methoxyphenyl)-1 of 4-, 3, 5-triazine, 2, two (the trichloromethyl)-6-(4-methoxyl naphthyl)-1 of 4-, 3, 5-triazine, 2, two (the trichloromethyl)-6-piperonyl-1 of 4-, 3, 5-triazine, 2, two (the trichloromethyl)-6-(4-methoxyl-styrene)-1 of 4-, 3, 5-triazine, 2, two (the trichloromethyl)-6-[2-(5-methylfuran-2-base) vinyl]-1 of 4-, 3, 5-triazine, 2, two (the trichloromethyl)-6-[2-(furans-2-base) vinyl]-1 of 4-, 3, 5-triazine, 2, two (the trichloromethyl)-6-[2-(4-diethylamino-2-aminomethyl phenyl) vinyl]-1 of 4-, 3, 5-triazine, 2, two (trichloromethyl)-6-[2-(3 of 4-, 4-Dimethoxyphenyl) vinyl]-1, 3, 5-triazine etc.
As above-mentioned acylphosphine oxide compound, TMDPO etc. can be enumerated.Also the commercially available products such as イ Le ガ キ ュ ア 819 (BASF ジ ャ パ Application society system) can be used.
As above-mentioned oxime compound; N-benzoyloxy-1-(4-Phenylsulfanyl phenyl) butane-1-ketone-2-imines, N-benzoyloxy-1-(4-Phenylsulfanyl phenyl) octane-1-ketone-2-imines, N-acetoxyl group-1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base] ethane-1-imines, N-acetoxyl group-1-[9-ethyl-6-[2-methyl-4-(3 can be enumerated; 3-dimethyl-2,4-dioxolyl methyl oxygen base) benzoyl]-9H-carbazole-3-base] ethane-1-imines etc.Also the commercially available product such as イ Le ガ キ ュ ア OXE-01, OXE-02 (above BASF ジ ャ パ Application society system), N-1919 (ADEKA society system) can be used.
And then, as polymerization initiator (D), benzoin can be enumerated, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, the benzoin compounds such as 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, the benzophenone cpds such as 6-tri-methyl benzophenone, 9, 10-phenanthrenequione, 2-EAQ, the naphtoquinone compounds such as camphorquinone, 10-butyl-2-chloro-acridine ketone, dibenzoyl, phenylglyoxylic acid methyl esters, two cyclopentadiene titanium compounds etc.They preferably cause auxiliary agent (D1) (particularly amines described later) combine to use with described later polymerizations.
Coloring photosensitive combination of the present invention can cause auxiliary agent (D1) containing polymerization.Polymerization causes auxiliary agent (D1) and can combine to use with polymerization initiator (D), and it is for promote can by the compound of the polymerization of the polymerizable compound of polymerization initiator initiated polymerization or sensitizer.
Cause auxiliary agent (D1) as polymerization, amines, thiazolinium compounds, alkoxy anthracene compound, thioxanthone compounds, carboxylic acid compound etc. can be enumerated.
As amines, triethanolamine can be enumerated, methyldiethanolamine, triisopropanolamine, 4-dimethylaminobenzoic acid methyl esters, EDMAB, 4-dimethylaminobenzoic acid isopentyl ester, benzoic acid 2-dimethylamino ethyl ester, 4-dimethylaminobenzoic acid 2-Octyl Nitrite, N, N-dimethyl-p-toluidine, 4, 4 '-bis-(dimethylamino) benzophenone, 4, 4 '-bis-(diethylamino) benzophenone, 4, 4 '-bis-(ethylmethylamino) benzophenone etc., wherein, be preferably 4, 4 '-bis-(diethylamino) benzophenone.Also the commercially available product of EAB-F (hodogaya chemical industry (strain) system) etc. can be used.
As thiazolinium compounds, the compound etc. shown in formula (III-1) ~ formula (III-3) can be enumerated
[chemical formula 4]
As alkoxy anthracene compound, 9,10-dimethoxy anthracene, EDMO, 9,10-diethoxy anthracenes, 2-ethyl-9,10-diethoxy anthracene, 9,10-dibutoxy anthracenes, 2-ethyl-9,10-dibutoxy anthracene etc. can be enumerated.
As thioxanthone compounds, ITX, ITX, 2,4-diethyl thioxanthones, 2,4-bis-clopenthixal ketones, the chloro-4-propoxythioxanthone of 1-etc. can be enumerated.
As carboxylic acid compound, Phenylsulfanyl acetic acid, methyl phefzylsulfanyl acetic acid, ethylphenyl sulfanyl acetic acid, Methylethyl phenyl sulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, methoxyphenyl sulfanyl acetic acid, Dimethoxyphenyl sulfanyl acetic acid, chlorophenylsulfanyl acetic acid, dichlorophenyl sulfanyl acetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthio acetic acid, N-naphthyl glycocoll, naphthoxy acetic acid etc. can be enumerated.
The content of polymerization initiator (D), relative to the total amount of resin (B) and polymerizable compound (C), is preferably 0.1 ~ 40 quality %, is more preferably 1 ~ 30 quality %.
If the content of polymerization initiator (D) is in this scope, then coloring photosensitive combination forms high sensitivity, there is the resistance to chemical reagents of the pattern of gained, physical strength, surface smoothness become good trend.
When using polymerization to cause auxiliary agent (D1), its consumption is relative to the total amount of resin (B) and polymerizable compound (C), and preferably 0.01 ~ 50 quality %, is more preferably 0.1 ~ 40 quality %.In addition, relative to polymerization initiator (D) 1 mole, be preferably 0.01 ~ 10 mole, be 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 improves further, the trend that the productivity of the pattern of gained is improved.
In addition, coloring photosensitive combination of the present invention can contain multi-functional thiol's compound (T) further.This multi-functional thiol's compound (T) is the compound in molecule with more than 2 sulfanyls.Wherein, if use the compound with the sulfanyl that more than 2 adjoin with aliphatic alkyl, then the sensitivity of coloring photosensitive combination of the present invention improves, so preferably.
As multi-functional thiol's compound (T), ethanthiol can be enumerated, the last of the ten Heavenly stems two mercaptan, 1, two (methylsulfanyl) benzene of 4-, butylene glycol two (3-sulfanyl propionic ester), butylene glycol two (3-sulfanyl acetic acid esters), ethylene glycol bis (3-sulfanyl acetic acid esters), trimethylolpropane tris (3-sulfanyl acetic acid esters), butylene glycol two (3-sulfanyl propionic ester), trimethylolpropane tris (3-sulfanyl propionic ester), trimethylolpropane tris (3-sulfanyl acetic acid esters), pentaerythrite four (3-sulfanyl propionic ester), pentaerythrite four (3-sulfanyl acetic acid esters), trihydroxy ethyl three (3-sulfanyl propionic ester), pentaerythrite four (3-sulfanyl butyric ester), 1, two (3-sulfanyl butyl oxygen base) butane of 4-etc.
The content of multi-functional thiol's compound (T), relative to polymerization initiator (D), is preferably 0.5 ~ 20 quality %, is more preferably 1 ~ 15 quality %.If the content of multi-functional thiol's compound (T) is in this scope, then sensitivity improves, and there is the trend that developability becomes good in addition.
Coloring photosensitive combination of the present invention contains solvent (E).As solvent (E), without particular limitation of, normally used solvent in this field can be used.Such as can select to use from the ether solvents (containing-O-, solvent not containing-COO-in molecule) beyond ester solvent (containing-COO-, solvent not containing-O-in molecule), ester solvent, the ketone solvent beyond ether-ether solvent (solvent containing-COO-and-O-in molecule), ester solvent (containing-CO-, solvent not containing-COO-in molecule), alcoholic solvent, aromatic hydrocarbon solvents, amide solvent and dimethyl sulfoxide (DMSO).
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, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol list propyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, TC, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl, propylene glycol monopropyl ether, glycol monobutyl ether, 3-methoxyl-n-butyl alcohol, 3-methoxyl-3-methyl butanol, tetrahydrofuran, oxinane, Isosorbide-5-Nitrae-two can be enumerated alkane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, methyl phenyl ethers anisole, phenetol, methylanisole etc.
As ether-ether solvent, methoxy menthyl acetate can be enumerated, ethyl methoxyacetate, methoxyacetic acid butyl ester, ethoxy acetate, ethoxy ethyl acetate, 3-methoxy methyl propionate, 3-methoxypropionate, 3-ethoxypropanoate, 3-ethoxyl ethyl propionate, 2-methoxy methyl propionate, 2-methoxypropionate, 2-methoxy propyl propyl propionate, 2-ethoxypropanoate, 2-ethoxyl ethyl propionate, 2-methoxyl-2 Methylpropionic acid methyl esters, 2-ethoxy-2 Methylpropionic acid ethyl ester, 3-methoxybutyl acetic acid esters, 3-methyl-3-methoxybutyl acetic acid esters, propylene glycol monomethyl ether, propylene glycol monoethyl acetic acid esters, propylene glycol monopropyl ether acetic acid esters, ethylene glycol monomethyl ether acetic acid ester, ethylene glycol monomethyl ether acetate, TC acetic acid esters, diethylene glycol monobutyl ether acetic acid esters etc.
As ketone solvent, 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-HEPTANONE, 3-heptanone, 4-heptanone, 4-methyl-2 pentanone, cyclopentanone, cyclohexanone, isophorone etc. can be enumerated.
As alcoholic solvent, methyl alcohol, ethanol, propyl alcohol, butanols, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerine etc. can be enumerated.
As aromatic hydrocarbon solvents, benzene,toluene,xylene, sym-trimethyl benzene etc. can be enumerated.
As amide solvent, DMF, DMA, 1-METHYLPYRROLIDONE etc. can be enumerated.
These solvents can separately or two or more combination use.
In above-mentioned solvent, from the viewpoint of coating, drying property, the boiling point preferably under 1atm is the organic solvent of 120 DEG C ~ 180 DEG C.Wherein, propylene glycol monomethyl ether, propylene glycol monomethyl ether, diethylene glycol methyl ethyl ether, 3-methoxybutyl acetic acid esters, 3-methoxyl-n-butyl alcohol etc. are preferably.
The content of the solvent (E) in coloring photosensitive combination, relative to coloring photosensitive combination, is preferably 60 ~ 95 quality %, is more preferably 70 ~ 90 quality %.In other words, the solid composition of coloring photosensitive combination, is preferably 5 ~ 40 quality %, is more preferably 10 ~ 30 quality %.If the content of solvent (E) is in above-mentioned scope, then flatness when being coated with has and becomes good trend.
Coloring photosensitive combination of the present invention is preferably containing surfactant (F).As surfactant, such as siloxane type surfactants, fluorine class surfactant can be enumerated and there is the siloxane type surfactants of fluorine atom.By containing surfactant, flatness during coating has and becomes good trend.
As siloxane type surfactants, the surfactant with siloxane bond can be enumerated.Specifically, ト ー レ シ リ コ ー Application DC3PA can be enumerated, 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, the surfactant with fluorocarbon chain can be enumerated.Specifically, Off ロ リ ナ ー ト (registered trademark) FC430 can be enumerated, 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 (Mitsubishi マ テ リ ア 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 (research of (strain) ダ イ キ Application Off ァ イ Application ケ ミ カ Le is made) etc.
As the siloxane type surfactants with fluorine atom, the surfactant with siloxane bond and fluorocarbon chain can be enumerated.Specifically, 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. can be enumerated.Be preferably メ ガ Off ァ ッ Network (registered trademark) F475.
Surfactant (F) is 0.001 quality % ~ 0.2 quality % relative to coloring photosensitive combination, is preferably 0.002 quality % ~ 0.1 quality %, is more preferably 0.01 quality % ~ 0.05 quality %.If surface-active contents is in this scope, then the flatness of film can be made good.
Coloring photosensitive combination of the present invention, can contain the various adjuvants such as filling agent, other macromolecular compound, closely sealed promoter, antioxidant, ultraviolet light absorber, light stabilizer, chain-transferring agent as required.
Coloring photosensitive combination of the present invention such as can be prepared as follows.
First, mixed with solvent (E) by the pigment of colorant (A), the mean grain size using ball mill etc. to be dispersed to pigment is about less than 0.2 μm.Now can coordinate part or all of pigment dispersing agent, resin (B) as required.In the dispersible pigment dispersion of gained, add polymerizable compound (C) and polymerization initiator (D), the remainder of resin (B) contained as required, other composition and then solvent (E) additional as required with the concentration of regulation, object coloring photosensitive combination can be obtained thus.
Coloring photosensitive combination of the present invention such as through the step shown in following (1) ~ (4), is processed as color filter.
(1) by coloring photosensitive combination of the present invention being coated on step substrate obtaining coated film,
(2) coated film is exposed via mask, obtains the step exposing rear coated film thus,
(3) by being developed by coated film alkaline developer after exposure, the step of pattern is obtained,
(4) by being cured by pattern, the step of the pattern solidified is obtained.
As the method obtaining pattern, photoetching process, ink-jet method, print process etc. can be enumerated.Wherein, photoetching process is preferably.
Photoetching process is coated on by above-mentioned coloring photosensitive combination on substrate and carries out drying, via photomask exposure, develops, obtain the method for pattern thus.
As aforesaid substrate, can enumerate such as glass, metal and plastics, can be tabular, also can be membranaceous.
As plastics, the polyolefin such as such as tygon, polypropylene, norbornene polymer can be enumerated, polyvinyl alcohol (PVA), polyethylene terephthalate, PEN, poly-(methyl) acrylate, cellulose esters, polycarbonate, polysulfones, polyethersulfone, polyetherketone, polyphenylene sulfide and polyphenylene oxide.Wherein, (methyl) acrylic acid refers at least a kind that is selected from acrylic acid and methacrylic acid.
These substrates can be formed color filter, various insulation or the structure such as conducting film, driving circuit.
According to coloring photosensitive combination of the present invention, the pattern solidified at lower temperatures can be formed.Therefore, when plastic base is formed pattern, particularly useful.
As the coating process to substrate, can enumerate such as, extrusion coating methods, directly photogravure rubbing method, reversal photogravure rubbing method, lid painting method and metal mold rubbing method.In addition, the apparatus for coating such as dip coater, roll coater, bar coater, spin coater, slit & spin coater, slit coater (being sometimes referred to as metal mold coating machine, curtain flow coater, non-rotating coating machine), ink-jet can be used to be coated with.Wherein, slit coater, spin coater, roll coater etc. is preferably used to be coated with.
As the drying means of the film be coated on substrate, the methods such as such as heat drying, natural drying, aeration-drying, drying under reduced pressure can be enumerated.Multiple method can be combined carry out.
As baking temperature, be preferably 10 ~ 120 DEG C, be more preferably 25 ~ 100 DEG C.In addition, as the heat time, be preferably 10 seconds ~ 60 minutes, be more preferably 30 seconds ~ 30 minutes.
Drying under reduced pressure preferably under the pressure of 50 ~ 150Pa, the temperature range of 20 ~ 25 DEG C carries out.
To the thickness of dried film without particular limitation of, suitably can adjust according to used material, purposes etc., be generally 0.1 ~ 20 μm, be preferably 1 ~ 6 μm.
For dried film, expose via the photomask for the formation of object pattern.To the pattern form on photomask now without particular limitation of, the pattern form corresponding with object purposes can be used.
As the light source used in exposure, preferably produce the light source that wavelength is the light of 250 ~ 450nm.Such as use the light of light filter to this wavelength region may stoping wavelength to be less than the light of 350nm to stop, or use the bandpass filter of the light obtained near 436nm, near 408nm, near 365nm optionally to obtain the light of these wavelength region may.Specifically, mercury lamp, light emitting diode, metal halide lamp, halogen lamp etc. can be enumerated.
In order to parallel rays can be irradiated equably to whole plane of exposure, or carry out the correct location matches of mask and base material, preferably use the device such as mask aligner, ledex.
After exposure, contact with developer solution, established part, such as unexposed portion are dissolved, develops, can pattern be obtained thus.As developer solution, can be organic solvent, but in order to make the exposure portion of film be difficult to produce due to developer solution dissolving, swelling, obtain the pattern of excellent in shape, preferably the aqueous solution of alkali compounds.
Developing method can for any means in slurry, infusion process, spray-on process etc.Further, during development, substrate can with arbitrarily angled inclination.
Preferably wash after development.
As above-mentioned alkali compounds, NaOH can be enumerated, 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, sodium bicarbonate, saleratus, sodium borate, potassium borate, the inorganic alkaline compounds such as ammonia, and Tetramethylammonium hydroxide, 2-hydroxyethyl trimethylammonium hydroxide, monomethyl amine, dimethyl amine, Trimethylamine, MEA, diethylamide, triethylamine, single isopropylamine, diisopropylamine, the organic basic compounds such as monoethanolamine.Wherein, potassium hydroxide, sodium bicarbonate and Tetramethylammonium hydroxide is preferably.
These inorganic and organic basic compound concentration are in aqueous preferably 0.01 ~ 10 quality %, are more preferably 0.03 ~ 5 quality %.
The aqueous solution of above-mentioned alkali compounds can contain surfactant.
As surfactant, polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkylaryl ether, other the 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 can be enumerated
The anionic based surfactants such as dodecanol sodium sulfovinate, oleyl sulfate sodium, lauryl sodium sulfate, ammonium lauryl sulfate, neopelex, dodecyl sodium naphthalene sulfonate,
The cationic based surfactants etc. such as stearic amine hydrochloride, DTAC.
The concentration of the surfactant in the aqueous solution of alkali compounds is preferably 0.01 ~ 10 quality %, is more preferably 0.05 ~ 8 quality %, is particularly preferably 0.1 ~ 5 quality %.
Further as required, rear baking can be carried out.Rear baking is preferred scope of carrying out 2 ~ 240 minutes at 50 ~ 230 DEG C such as.
Coloring photosensitive combination of the present invention, can obtain good pattern and the color filters such as color depth, luminance brightness, contrast, sensitivity, resolution, thermotolerance.In addition, can in known manner for having these color filters or the pattern display device as a part for its component parts, such as, in the machine that known liquid crystal indicator, organic el device, solid camera head, Electronic Paper etc. are relevant to rendered image.
[embodiment]
By the following examples more specific description is carried out to the present invention." % " and " part " in example only otherwise special instruction, is quality % and mass parts.
Synthesis example 1
To having stirring machine, thermometer, reflux condensing tube, in the flask of tap funnel and nitrogen ingress pipe, import propylene glycol monomethyl ether 182g, the atmosphere in flask is made to become after nitrogen from air, after being warming up to 100 DEG C, to be dripped in flask with 2 hours by tap funnel and comprising benzyl methacrylate 70.5g (0.40 mole), methacrylic acid 43.0g (0.5 mole), the solution of azobis isobutyronitrile 3.6g is added in the potpourri of the monomethacrylates of tricyclodecane skeleton (Hitachi changes into (strain) FA-513M processed) 22.0g (0.10 mole) and propylene glycol monomethyl ether 136g, stir 5 hours continuously at 100 DEG C further.Then atmosphere in flask is made to become air from nitrogen, methyl propenoic acid glycidyl base ester 35.5g [0.25 mole, (be 50 % by mole relative to the carboxyl of methacrylic acid used in this reaction)], three (dimethylaminomethyl) phenol 0.9g and quinhydrones 0.145g is added in flask, 110 DEG C of successive reactions 6 hours, obtain the resin solution B1 that solid composition acid number is 79mgKOH/g.The weight-average molecular weight being measured the polystyrene conversion obtained by GPC is 13000, and molecular weight distribution (Mw/Mn) is 2.1.
Synthesis example 2
To in the flask with stirring machine, thermometer, reflux condensing tube, tap funnel and gas introduction tube, import propylene glycol monomethyl ether 250 parts.Then, use gas introduction tube to import in flask by nitrogen, atmosphere in flask is replaced into nitrogen.Then, by after the solution warms to 100 in flask DEG C, tap funnel is used in flask, to drip with 2 hours the potpourri comprising benzyl methacrylate 152.6 parts, methacrylic acid 41.7 parts, azobis isobutyronitrile 1.5 parts and propylene glycol monomethyl ether 150 parts, after being added dropwise to complete, stir 2.5 hours continuously at 100 DEG C further, obtaining weight-average molecular weight Mw is 2.3 × 10 4, solid composition is 34 quality %, solution acid number is 47mg-KOH/g resin solution B2.
The weight-average molecular weight (Mw) of the resin obtained in synthesis example and the mensuration of number-average molecular weight (Mn) use GPC method, carry out under the following conditions.
Device: K2479 ((strain) Shimadzu Seisakusho Ltd. system)
Pillar: SHIMADZU Shim-pack GPC-80M
Column temperature: 40 DEG C
Solvent: THF (tetrahydrofuran)
Flow velocity, 1.0mL/min
Detecting device: RI
Using the ratio (Mw/Mn) of the weight-average molecular weight of polystyrene conversion obtained above and number-average molecular weight as molecular weight distribution.
Embodiment 1
[preparation of coloring photosensitive combination]
By pigment: C.I. naphthol green 5851 parts
Acrylic pigment spreading agent 10 parts
Resin solution B2 (conversion of solid composition) 20 parts
Propylene glycol monomethyl ether 267 parts
Mixing, uses ball mill fully disperseed by pigment and form dispersible pigment dispersion A,
By pigment: C.I. pigment yellow 13 8 81 parts
Acrylic pigment spreading agent 12 parts
Resin solution B2 (conversion of solid composition) 28 parts
Propylene glycol monomethyl ether 402 parts
Mixing, uses ball mill fully disperseed by pigment and form dispersible pigment dispersion B,
By pigment: C.I. pigment Green 7 29 parts
Acrylic pigment spreading agent 5.7 parts
Resin solution B2 (conversion of solid composition) 11 parts
Propylene glycol monomethyl ether 173 parts
Mixing, uses ball mill fully disperseed by pigment and form dispersible pigment dispersion C,
By above-mentioned dispersible pigment dispersion A, dispersible pigment dispersion B, dispersible pigment dispersion C,
Resin: resin solution B1 (conversion of solid composition) 66 parts,
Polymerizable compound: dipentaerythritol acrylate (Japanese chemical drug (strain) system) 57 parts,
Polymerization initiator: 2-dimethylamino-1-(4-morphlinophenyl)-2-benzyl butane-1-ketone (イ Le ガ キ ュ ア 369, BASF ジ ャ パ Application society system) 15 parts,
Polymerization causes auxiliary agent: 4,4 '-bis-(diethylamino) benzophenone (EAB-F, hodogaya chemical industry (strain) is made) 4.9 parts,
Solvent: propylene glycol monomethyl ether 450 parts and
Adjuvant: ス ミ エ Port キ シ ESCN-195XL (Sumitomo Chemical (strain) system) 6.1 parts
Mixing, obtains coloring photosensitive combination.
Comparative example
[preparation of coloring photosensitive combination]
For by pigment: C.I. pigment green 36 5.5 parts
Pigment: C.I. pigment yellow 1502.4 parts
Polyesters pigment dispersing agent 1.2 parts
Propylene glycol monomethyl ether 38 parts
Mix and use the dispersible pigment dispersion that pigment fully disperses by ball mill,
Hybrid resin: resin solution B1 (conversion of solid composition) 6.6 parts
Polymerizable compound: dipentaerythritol acrylate (Japanese chemical drug (strain) system) 5.7 parts
Polymerization initiator: 2-dimethylamino-1-(4-morphlinophenyl)-2-benzyl butane-1-ketone (イ Le ガ キ ュ ア 369, BASF ジ ャ パ Application society system) 1.5 parts
Polymerization causes auxiliary agent: 4,4 '-bis-(diethylamino) benzophenone (EAB-F, hodogaya chemical industry (strain) is made) 0.49 part
Adjuvant: ス ミ エ Port キ シ ESCN-195XL (Sumitomo Chemical (strain) system) 0.61 part
Solvent: propylene glycol monomethyl ether 38 parts,
Obtain coloring photosensitive combination.
The manufacture > of < pattern
PET film that the glass plate of 2 inch square is fitted (eastern レ Le ミ ラ ー 75-T60) makes substrate.In the PET film side of substrate, be coated with coloring photosensitive combination by spin-coating method, on hot plate in 80 DEG C of front bakings 2 minutes.After letting cool, what make this substrate being coated with coloring photosensitive combination and quartz glass photomask is spaced apart 10 μm, uses exposure machine (TME-150RSK, ト プ コ Application (strain) system), under atmospheric atmosphere, with 200mJ/cm 2the exposure of (365nm benchmark) is carried out illumination and is penetrated.And, for the irradiation to coloring photosensitive combination now, the radiating light from ultrahigh pressure mercury lamp is undertaken by optical filter (UV-35: Korean and Japanese light splitting (strain) is made).As photomask, use and define the line of 10 ~ 100 μm and the photomask of space pattern.After illumination is penetrated, in tetramethyl-ammonium 0.1% aqueous solution, within 80 seconds, develop at 23 DEG C of dippings, wash with pure water, form pattern.The thickness of the gained pattern using determining film thickness device (DEKTAK3, Japanese vacuum technique (strain) is made) to record is 2 μm.
By the pattern formed as described above further 50 DEG C of heating 5 minutes (drying afterwards), obtain the pattern solidified.In addition, by the pattern formed as described above further 100 DEG C of heating 5 minutes (drying afterwards), the pattern solidified is obtained.The thickness of the pattern of the gained solidification recorded as described above is all 2 μm.
< color characteristics evaluates >
For the spectrophotometric spectra of the pattern of gained, use micro-spectral determinator (OSP-SP200OLYMPUS system) measures the transmissivity (T1) under 600nm and the transmissivity (T2) under 520nm.The ratio (T1/T2) of T1 and T2 is less, then higher with the color separated ability of red color filter, so preferably.Result is as shown in table 1.
[table 1]
The ratio (T1/T2) of T1 and T2
< solvent resistance evaluates >
Drip propylene glycol monomethyl ether 1ml to the pattern formed on aforesaid substrate, after static 30 seconds, use spin coater to rotate 10 seconds under the condition of rotating speed for 1000rpm, get rid of the propylene glycol monomethyl ether on pattern.
Before and after contacting with propylene glycol monomethyl ether, measure the film thickness value obtained, calculate thickness by following formula and keep.Thickness conservation rate is higher, then curability is better, when repeating to be coated with the coloring photosensitive combination beyond green, inhibits to solvent-laden stripping in this coloring photosensitive combination, when therefore manufacturing color filter, can prevent colour mixture (mixing).Result is as shown in table 2.
(thickness conservation rate) (%)=(thickness after contact)/(thickness before contact)
The evaluation > of < resolution
To the pattern obtained, observed by laser microscope (Axio Imager MAT カ ー Le Star ァ イ ス society system), using the minimum dimension of resolution as resolution.Resolution is higher, can manufacture the color filter of fine.Result is as shown in table 2.
[table 2]
Industrial applicibility
According to coloring photosensitive combination of the present invention, the color filter with the green of the color separated ability excellence of red color filter can be obtained.

Claims (5)

1. coloring photosensitive combination, it contains colorant, polymerizable compound, polymerization initiator and solvent, colorant is the coloring matter containing halogenated copper phthalocyanine pigment, zinc halide phthalocyanine color and quinophthalone pigments, the wherein content of halogenated copper phthalocyanine pigment, relative to content 100 mass parts of zinc halide phthalocyanine color, be 20 mass parts ~ 150 mass parts, and the content of quinophthalone pigments, relative to content 100 mass parts of zinc halide phthalocyanine color, be 50 mass parts ~ 200 mass parts.
2. coloring photosensitive combination according to claim 1, wherein, halogenated copper phthalocyanine pigment is C.I. pigment Green 7.
3. coloring photosensitive combination according to claim 1, wherein, quinophthalone pigments is C.I. pigment yellow 13 8.
4. coloring photosensitive combination according to claim 1, wherein, containing colorant, polymerizable compound, polymerization initiator, solvent and resin.
5. color filter, it is formed by coloring photosensitive combination according to claim 1.
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