CN102207680B - Photosensitive polymer combination - Google Patents

Photosensitive polymer combination Download PDF

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Publication number
CN102207680B
CN102207680B CN201110078470.6A CN201110078470A CN102207680B CN 102207680 B CN102207680 B CN 102207680B CN 201110078470 A CN201110078470 A CN 201110078470A CN 102207680 B CN102207680 B CN 102207680B
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methyl
compound
mass parts
photosensitive polymer
polymer combination
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CN102207680A (en
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武部和男
井上胜治
松浦龙一
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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
    • G03F7/027—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
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • 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
    • G03F7/027—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

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Nonlinear Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Optics & Photonics (AREA)
  • Materials For Photolithography (AREA)
  • Optical Filters (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

The invention provides a kind of photosensitive polymer combination, it comprises resin, photopolymerizable compound, Photoepolymerizationinitiater initiater, photopolymerization containing thioxanthone compounds cause auxiliary agent and solvent, Photoepolymerizationinitiater initiater is the Photoepolymerizationinitiater initiater comprising alpha-amido ketonic compound, united imidazole and oxime compound, and the content of thioxanthone compounds is below more than 80 mass parts 160 mass parts relative to content 100 mass parts of alpha-amido ketonic compound.

Description

Photosensitive polymer combination
Technical field
The present invention relates to photosensitive polymer combination.
Background technology
In display panels in recent years etc., in order to form light spacer (photospacer), use sense photosensitive resin composition.
As such photosensitive polymer combination, known is such as the composition of alpha-amido ketonic compound containing resin, photopolymerizable compound, Photoepolymerizationinitiater initiater and solvent and Photoepolymerizationinitiater initiater.
[patent documentation 1] Japanese Unexamined Patent Publication 2009-134078 publication
Summary of the invention
But the photosensitive polymer combination proposed, for the adaptation of the pattern obtained and substrate, may not fully satisfy the demand in the past.
The present invention relates to following invention.
[1] photosensitive polymer combination, it comprises resin, photopolymerizable compound, Photoepolymerizationinitiater initiater, photopolymerization containing thioxanthone compounds cause auxiliary agent and solvent, Photoepolymerizationinitiater initiater is the Photoepolymerizationinitiater initiater comprising alpha-amido ketonic compound, united imidazole and oxime compound, and the content of thioxanthone compounds is below more than 80 mass parts 160 mass parts relative to content 100 mass parts of alpha-amido ketonic compound.
[2] about the photosensitive polymer combination described in [1], wherein the content of united imidazole is below more than 50 mass parts 400 mass parts relative to content 100 mass parts of alpha-amido ketonic compound.
[3] about the photosensitive polymer combination described in [1] or [2], wherein the content of oxime compound is below more than 10 mass parts 100 mass parts relative to content 100 mass parts of alpha-amido ketonic compound.
[4] about the photosensitive polymer combination described in any one of [1] ~ [3], wherein resin is the resin of the structural unit comprised from the unsaturated compound with cyclic ether structure.
[5] pattern that the photosensitive polymer combination described in any one of [1] ~ [4] is formed is used.
[6] display device of the pattern described in [5] is comprised.
[7] photosensitive polymer combination described in any one of [1] ~ [4] is forming the use in light spacer.
Embodiment
Photosensitive polymer combination of the present invention, auxiliary agent (C1) and solvent (D) is caused containing resin (A), photopolymerizable compound (B), Photoepolymerizationinitiater initiater (C), photopolymerization, Photoepolymerizationinitiater initiater (C) comprises alpha-amido ketonic compound, united imidazole and oxime compound, and photopolymerization causes auxiliary agent (C1) and comprises thioxanthone compounds.Further, in this instructions, about as the illustrative compound of each composition, if no special instructions, can be used alone or in combination.
Photosensitive polymer combination of the present invention contains resin (A).
The resin (A) used in photosensitive polymer combination of the present invention, is preferably the resin of display alkali-solubility.So-called alkali-solubility, refers to the character of dissolving in the developer solution of the aqueous solution as alkali cpd.As the resin of display alkali-solubility, can be listed below:
Resin (A2-1): the multipolymer that at least a kind (a) being selected from unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides (hereinafter sometimes referred to " (a) ") is polymerized with the unsaturated compound (b) (hereinafter sometimes referred to " (b) ") of the cyclic ether structure with carbon number 2 ~ 4,
Resin (A2-2): (wherein, can not there is the cyclic ether structure of carbon number 2 ~ 4 with the monomer (c) of (a) and (b) copolymerization.) (hereinafter sometimes referred to " (c) ") and (a) and (b) be polymerized multipolymer,
Resin (A2-3): the multipolymer that (a) and (c) is polymerized,
Resin (A2-4): make (b) with will the copolymer reaction that is polymerized of (a) and (c) and the resin etc. that obtains.
As resin (A), preferred resin (A2-1) and resin (A2-2).
As (a), specifically can be listed below:
The unsaturated monocarboxylic class such as acrylic acid, methacrylic acid, crotonic acid, o-vinyl benzoic acid, m-vinyl benzoic acid, p-vinyl benzoic acid;
Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2, the unsaturated dicarboxylic classes such as 3,6-tetrahydrophthalic acid, dimethyl tetrahydro phthalic acid, Isosorbide-5-Nitrae-cyclohexene dioctyl phthalate;
Methyl-5-norborene-2, the dicyclo unsaturated compound class containing carboxyl such as 3-dioctyl phthalate, 5-carboxyl dicyclo [2.2.1] hept-2-ene", 5,6-dicarboxyl dicyclo [2.2.1] hept-2-ene"s, 5-carboxyl-5-methyl bicycle [2.2.1] hept-2-ene", 5-carboxyl-5-ethyl dicyclo [2.2.1] hept-2-ene", 5-carboxyl-6-methyl bicycle [2.2.1] hept-2-ene", 5-carboxyl-6-ethyl dicyclo [2.2.1] hept-2-ene";
Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic acid acid anhydride, 4-vinylphthalic acid acid anhydride, 3,4,5,6-tetrabydrophthalic anhydride, 1,2, the unsaturated dicarboxylic class acid anhydrides such as 3,6-tetrabydrophthalic anhydride, dimethyl tetrahydro phthalic anhydride, 5,6-dicarboxyl dicyclo [2.2.1] hept-2-ene" acid anhydrides (carbic anhydride: himic 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;
The unsaturated esters of acrylic acid etc. of hydroxyl and carboxyl is contained in same a part that α-(hydroxymethyl) acrylic acid is such.
In these, from copolyreaction aspect, alkali-solubility aspect, preferably use acrylic acid, methacrylic acid, maleic anhydride etc.
In this instructions, so-called " (methyl) acrylic acid ", represents at least a kind that is selected from acrylic acid and methacrylic acid.The token of " (methyl) acryloyl group " and " (methyl) acrylate " etc. also has same implication.
As (b), the unsaturated compound of at least a kind such as having and be selected from oxirane ring, oxetanes ring and tetrahydrofuran ring (tetrahydrofuran ring) can be enumerated.As (b), preferably there is the cyclic ether structure of carbon number 2 ~ 4 and the monomer of ethylenic unsaturated link, more preferably there is the cyclic ether structure of carbon number 2 ~ 4 and the monomer of (methyl) acryloxy.
As (b), the unsaturated compound (b1) (hereinafter sometimes referred to " (b1) ") such as with epoxy ethyl, the unsaturated compound (b2) (hereinafter sometimes referred to " (b2) ") with oxetanyl, the unsaturated compound (b3) (hereinafter sometimes referred to " (b3) ") etc. with tetrahydrofuran base can be enumerated.
What is called has the unsaturated compound (b1) of epoxy ethyl, refers to the polymerizable compound with epoxy ethyl.(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 link, there is monomer (b1-2) (hereinafter sometimes referred to " (b1-2) ") by the structure of ring type alkene epoxidation and ethylenic unsaturated link.
As (b1), preferably there is the monomer of epoxy ethyl and ethylenic unsaturated link, more preferably there is the monomer of epoxy ethyl and (methyl) acryloxy, preferably there is the monomer of (b1-2) and (methyl) acryloxy further.
As (b1-1), (methyl) glycidyl acrylate specifically can be enumerated, (methyl) propenoic acid beta-methylglycidyl esters, (methyl) propenoic acid beta-ethyl glycidyl ester, glycidyl vinyl ether, o-vinylbenzyl glycidyl base ether, m-vinylbenzyl glycidyl base ether, p-vinylbenzyl glycidyl base ether, Alpha-Methyl-o-vinylbenzyl glycidyl base ether, Alpha-Methyl-m-vinylbenzyl glycidyl base ether, Alpha-Methyl-p-vinylbenzyl glycidyl base ether, two (glycidoxypropyl methyl) styrene of 2,3-, two (glycidoxypropyl methyl) styrene of 2,4-, two (glycidoxypropyl methyl) styrene of 2,5-, two (glycidoxypropyl methyl) styrene of 2,6-, 2,3,4-tri-(glycidoxypropyl methyl) styrene, 2,3,5-tri-(glycidoxypropyl methyl) styrene, 2,3,6-tri-(glycidoxypropyl methyl) styrene, 3,4,5-tri-(glycidoxypropyl methyl) styrene, 2,4,6-tri-(glycidoxypropyl methyl) styrene, the compound etc. recorded in Japanese Unexamined Patent Publication 7-248625 publication.
As (b1-2), vinylcyclohexene monoxide, 1,2-epoxy-4-vinyl cyclohexane (such as CELOXIDE 2000 can be enumerated; Daicel chemical industry (strain) make), acrylic acid 3,4-epoxycyclohexanecarboxylate (such as Cyclomer A400; Daicel chemical industry (strain) make), methacrylic acid 3,4-epoxycyclohexanecarboxylate (such as Cyclomer M100; Daicel chemical industry (strain) make), the compound shown in formula (I), the compound etc. shown in formula (II).
[in formula (I) and formula (II), R 1and R 2represent the alkyl of hydrogen atom or carbon number 1 ~ 4 independently of each other, 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 the alkane 2 basis of carbon number 1 ~ 6.
* the bonding end with O is represented.]
As the alkyl of carbon number 1 ~ 4, 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 can enumerate hydrogen atom, methyl, hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, preferredly can enumerate hydrogen atom, methyl.
As alkane 2 basis, methylene, ethylidene, propane-1,2-bis-base, propane-1,3-bis-base, butane-Isosorbide-5-Nitrae-two base, pentane-1,5-bis-base, hexane-1,6-bis-base etc. can be enumerated.
As X 1and X 2, preferably can enumerate singly-bound, methylene, ethylidene, *-CH 2-O-(* represents the bonding end with O) base, *-CH 2cH 2-O-base, preferredly can enumerate 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 can enumerate formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9), formula (I-11) ~ formula (I-15).Preferredly can enumerate formula (I-1), formula (I-7), formula (I-9), formula (I-15).
As the compound shown in formula (II), the compound etc. shown in formula (II-1) ~ formula (II-15) can be enumerated.Preferably can enumerate formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9), formula (II-11) ~ formula (II-15).Preferredly can enumerate formula (II-1), formula (II-7), formula (II-9), formula (II-15).
Compound shown in compound shown in formula (I) and formula (II), can be used alone separately.In addition, they can mix with arbitrary ratio.When mix, its mixture ratio with molar ratio computing, preferably with formula (I): formula (II) is expressed as 5: 95 ~ 95: 5, is more preferably 10: 90 ~ 90: 10, is particularly preferably 20: 80 ~ 80: 20.
As the unsaturated compound (b2) with oxetanyl, preferably there is the monomer of oxetanyl and ethylenic unsaturated link, more preferably there is the monomer of oxetanyl and (methyl) acryloxy.As (b2), such as 3-methyl-3-methacryloxymethyl oxetanes, 3-methyl-3-acryloyloxymethyl oxetanes, 3-ethyl-3-methacryloxymethyl oxetanes, 3-ethyl-3-acryloyloxymethyl oxetanes, 3-methyl-3-methacryloxyethyl oxetanes, 3-methyl-3-acryloyl-oxyethyl oxetanes, 3-ethyl-3-methacryloxyethyl oxetanes, 3-ethyl-3-acryloyl-oxyethyl oxetanes etc. can be enumerated.
As the unsaturated compound (b3) with tetrahydrofuran base, preferably there is the monomer of tetrahydrofuran base and ethylenic unsaturated link, more preferably there is the monomer of tetrahydrofuran base and (methyl) acryloxy.
As (b3), tetrahydrofurfuryl acrylate (such as Biscoat V#150, Osaka Organic Chemical Industry (strain) system), tetrahydrofurfuryl methacrylate etc. specifically can be enumerated.
As (c), such as, can be listed below:
(methyl) alkyl-acrylates such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-butyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate;
(methyl) cyclohexyl acrylate, (methyl) acrylic acid 2-methyl cyclohexyl, (methyl) acrylic acid three ring [5.2.1.0 2,6] decane-8-base ester (in this technical field, as trivial name, is called (methyl) acrylic acid tetrahydro-dicyclopentadiene base (dicyclopentanyl) ester.), (methyl) acrylate base ester class such as (methyl) acrylic acid tetrahydro-dicyclopentadiene oxygen base (dicyclopentanyloxy) ethyl ester, (methyl) isobornyl acrylate;
(methyl) acrylic acid aryl or aralkyl ester classes such as (methyl) phenyl acrylate, (methyl) benzyl acrylate;
The dicarboxylic diesters such as diethyl maleate, DEF, diethyl itaconate;
(methyl) hydroxyalkyl acrylates 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", uncle 5--butoxy carbonyl dicyclo [2.2.1] hept-2-ene", 5-cyclohexyl oxygen base carbonyl dicyclo [2.2.1] hept-2-ene", 5-phenyloxycarbonyl dicyclo [2.2.1] hept-2-ene", two (uncle-butoxy carbonyl) 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 di carbonyl imide derivant classes such as N-phenylmaleimide, N-N-cyclohexylmaleimide, N-benzyl maleimide, N-succinimido-3-maleimidobenzoyl salt, N-succinimido-4-maleimidobutyrate salt, N-succinimido-6-maleimidohexanoic acid salt, N-succinimido-3-maleimidopropionic acid salt, N-(9-acridinyl) maleimide;
Styrene, α-methyl styrene, m-methyl styrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, vinyl cyanide, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, Methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene etc.
In these, from copolyreaction and alkali-solubility aspect, optimization styrene, N-phenylmaleimide, N-N-cyclohexylmaleimide, N-benzyl maleimide, dicyclo [2.2.1] hept-2-ene" etc.
In resin (A2-1), about the ratio of the structural unit from each monomer, relative to the total molal quantity of the structural unit of formation resin (A2-1), preferably in following scope.
Structural unit from (a): 5 ~ 60 % by mole (being more preferably 10 ~ 50 % by mole)
Structural unit from (b): 40 ~ 95 % by mole (being more preferably 50 ~ 90 % by mole)
If in above-mentioned scope, there is the tendency that storage stability, developability, solvent resistance, thermotolerance and physical strength become good in the ratio of the structural unit of resin (A2-1).
As resin (A2-1), preferably (b) is the resin of (b1), and more preferably (b) is the resin of (b1-2).
Resin (A2-1) can manufacture see, for example the citing document recorded in the method recorded in document " experimental method of Polymer Synthesizing " (grand row work sale room (strain) chemistry in large Tianjin is with people's the 1st edition the 1st printing distribution on March 1st, 1972) and the document.
Specifically can illustrate and the ormal weight of (a) and (b), polymerization initiator and solvent etc. are loaded in reaction vessel, with nitrogen, oxygen be replaced, thus under deoxidation, carry out the method that stirs, heat, be incubated.Further, the polymerization initiator wherein used and solvent etc. are not particularly limited, any material usually used in this field can be used.Such as, as polymerization initiator, azo-compound (2 can be enumerated, 2 '-azoisobutyronitrile, 2,2 '-azo two (2,4-methyl pentane nitrile) etc.), organic peroxide (benzoyl peroxide etc.), as solvent, as long as dissolved by each monomer, solvent described later etc. can be used as the solvent of photosensitive polymer combination.
Further, about the multipolymer obtained, can directly use reacted solution, also can use the solution after concentrated or dilution, the product that the methods such as employing precipitates again are taken out as solid (powder) can also be used.Especially, as solvent during this polymerization, use the solvent identical with solvent described later (D), thus can be used as it is reacted solution, manufacturing process can be made to simplify.
In resin (A2-2), about the ratio of the structural unit from each monomer, relative to the total molal quantity of the entire infrastructure unit of formation resin (A2-2), preferably in following scope.
Structural unit from (a): 2 ~ 40 % by mole (being more preferably 5 ~ 35 % by mole)
Structural unit from (c): 1 ~ 65 % by mole (being more preferably 1 ~ 60 % by mole)
Structural unit from (b): 2 ~ 95 % by mole (being more preferably 5 ~ 80 % by mole)
If in above-mentioned scope, there is the tendency that storage stability, developability, solvent resistance, thermotolerance and physical strength become good in the ratio of the structural unit of resin (A2-2).
As resin (A2-2), preferably (b) is the resin of (b1), and more preferably (b) is the resin of (b1-2).
Resin (A2-2), can adopt the method same with resin (A2-1) to be manufactured.
In resin (A2-3), about the ratio of the structural unit from each monomer, relative to the total molal quantity of the entire infrastructure unit of formation resin (A2-3), preferably in following scope.
Structural unit from (a): 2 ~ 40 % by mole (being more preferably 5 ~ 35 % by mole)
Structural unit from (c): 60 ~ 98 % by mole (being more preferably 65 ~ 95 % by mole)
If the ratio of the structural unit of resin (A2-3) is in above-mentioned scope, there is storage stability, developability, solvent resistance become good tendency.
Resin (A2-3) can adopt the method same with resin (A2-1) to be manufactured.
The resin that resin (A2-4) obtains for making the copolymer reaction of (b) and (a) and (c).
Resin (A2-4) such as can be passed through the operation manufacture of two-stage.In this case, also can with reference to manufactures such as the methods recorded in the method recorded in above-mentioned document " experimental method of Polymer Synthesizing " (grand row work sale room (strain) chemistry in large Tianjin is with people's the 1st edition the 1st printing distribution on March 1st, 1972), Japanese Unexamined Patent Publication 2001-89533 publication.
First, as the first stage, obtain the multipolymer of (a) and (c) in the same manner as the manufacture method of above-mentioned resin (A2-1).
In this case, as described above, the multipolymer obtained can directly use reacted solution, also can use the solution after concentrated or dilution, can also use the product that the methods such as employing precipitates again are taken out as solid (powder).In addition, weight-average molecular weight and the molecular weight distribution [weight-average molecular weight (Mw)/number-average molecular weight (Mn)] of polystyrene conversion similar to the above is preferably.
But, about the ratio of the structural unit from (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.
Structural unit from (a): 5 ~ 50 % by mole (being more preferably 10 ~ 45 % by mole)
Structural unit from (c): 50 ~ 95 % by mole (being more preferably 55 ~ 90 % by mole)
Then, as subordinate phase, the cyclic ether from the carboxylic acid of (a) of the multipolymer obtained and a part for carboxylic acid anhydrides and aforesaid (b) is reacted.Because the reactivity of cyclic ether is high, unreacted (b) is difficult to remaining, therefore as (b), and preferably (b1) or (b2), more preferably (b1-1).
Specifically, after the above, atmosphere in flask is replaced into air by nitrogen, molal quantity relative to (a) is generally (b) of 5 ~ 80 % by mole, relative to (a), b the total amount of () and (c) is generally the carboxyl of 0.001 ~ 5 quality % and the catalysts (such as three (dimethylaminomethyl) phenol etc.) of cyclic ether and relative to (a), b the total amount of () and (c) is generally in polymerization inhibitor (such as quinhydrones etc.) the loading flask of 0.001 ~ 5 quality %, usually react 1 ~ 10 hour at 60 ~ 130 DEG C, resin (A2-4) can be obtained.Further, in the same manner as polymerizing condition, the thermal discharge etc. of manufacturing equipment, polymerization generation can be considered, suitably regulate feed process, temperature of reaction.
In addition, in this case, the molal quantity of (b) is preferably 10 ~ 75 % by mole relative to the molal quantity of (a), is more preferably 15 ~ 70 % by mole.By being this scope, the equilibrium that there is storage stability, developability, solvent resistance, thermotolerance, physical strength and light sensitivity becomes good tendency.
The weight-average molecular weight of the polystyrene conversion of resin (A), is preferably 3,000 ~ 100,000, is more preferably 5,000 ~ 50,000, more preferably 5,000 ~ 25,000, be particularly preferably 5,000 ~ 15,000.If the weight-average molecular weight of resin (A), in above-mentioned scope, exists the tendency that coating becomes good, and be difficult to during development produce film minimizing, and then during development, the extractable of non-pixel portion tends to well.
The molecular weight distribution [weight-average molecular weight (Mw)/number-average molecular weight (Mn)] of resin (A) is preferably 1.1 ~ 6.0, is more preferably 1.2 ~ 4.0.If molecular weight distribution is in above-mentioned scope, there is the tendency of developability excellence.
The acid number of resin (A) is preferably 20 ~ 150mg-KOH/g, is more preferably 40 ~ 135mg-KOH/g, more preferably 50 ~ 135mg-KOH/g, is particularly preferably 50 ~ 90mg-KOH/g.Wherein, acid number carries out measuring the value obtained with the amount (mg) of required potassium hydroxide as by resin (A) 1g, obtains by using potassium hydroxide aqueous solution to carry out titration.
About the content of resin (A), be preferably 5 ~ 95 quality % relative to the total amount of resin (A) and photopolymerizable compound (B), be more preferably 20 ~ 80 quality %, be particularly preferably 40 ~ 60 quality %.If the content of resin (A) is in above-mentioned scope, there is developability, adaptation, solvent resistance, mechanical property become good tendency.
Photosensitive polymer combination of the present invention contains photopolymerizable compound (B).
Photopolymerizable compound (B) to utilize the living radical produced by Photoepolymerizationinitiater initiater (C) to carry out the compound be polymerized, such as having the compound etc. of ethylenic unsaturated link, be preferably (methyl) acrylate compounds.
As the photopolymerizable compound (B) with 1 ethylenic unsaturated link, the compound same with the Compound Phase enumerated as above-mentioned (a), (b) and (c) can be enumerated, wherein, preferred (methyl) esters of acrylic acid.
As the photopolymerizable compound (B) with 2 ethylenic unsaturated links, 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, diglycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, tetraethylene glycol 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 photopolymerizable compound (B) with more than 3 ethylenic unsaturated links, 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, preferably 3 officials can above photopolymerizable compound (B), more preferably dipentaerythritol six (methyl) acrylate.
About the content of photopolymerizable compound (B), be preferably 5 ~ 95 quality % relative to the total amount of resin (A) and photopolymerizable compound (B), be more preferably 20 ~ 80 quality %, be particularly preferably 40 ~ 60 quality %.If the content of photopolymerizable compound (B) is in above-mentioned scope, there is the intensity of pattern after light sensitivity, solidification, flatness, reliability, physical strength become good tendency.
Photosensitive polymer combination of the present invention, containing alpha-amido ketonic compound, united imidazole and oxime compound as Photoepolymerizationinitiater initiater (C), causes auxiliary agent (C1) containing thioxanthone compounds as photopolymerization.About the content of thioxanthone compounds, be preferably below more than 80 mass parts 160 mass parts relative to alpha-amido ketonic compound 100 mass parts.If containing above-mentioned compound in the scope of above-mentioned amount, pattern has excellent adaptation, and when therefore developing, pattern becomes and is difficult to from strippable substrate, also there is the tendency that light sensitivity raises.
As alpha-amido ketonic compound, 2-methyl-2-morpholino-1-(4-methylsulfanyl phenyl) propane-1-ketone, 2-dimethylamino-1-(4-morphlinophenyl)-2-benzyl butane-1-ketone, 2-(dimethylamino)-2-[(4-aminomethyl phenyl) methyl]-1-[4-(4-morpholinyl) phenyl]-1-butanone etc. can be enumerated.The commercially available products such as IRGACURE 369,907,379 (above is Ciba Specialty Chemicals's system) can be used.
As united imidazole, can 2 be enumerated, 2 '-bis-(2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-bis-(2,3-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline is (such as with reference to Japanese Unexamined Patent Publication 6-75372 publication, Japanese Unexamined Patent Publication 6-75373 publication etc.), 2,2 '-bis-(2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-bis-(2-chlorphenyl)-4,4 ', 5,5 '-four (alkoxyl phenyl) bisglyoxaline, 2,2 '-bis-(2-chlorphenyl)-4,4 ', 5,5 '-four (dialkoxy phenyl) bisglyoxaline, 2,2 '-bis-(2-chlorphenyl)-4,4 ', 5,5 '-four (tri-alkoxy phenyl) bisglyoxaline is (such as with reference to Japanese Patent Publication 48-38403 publication, Japanese Laid-Open Patent Publication 62-174204 publication etc.), 4,4 ' 5, the imidazolium compounds that the phenyl of 5 '-position is replaced by alkoxy carbonyl group is (such as with reference to Japanese Unexamined Patent Publication 7-10913 publication etc.) etc.Preferably can enumerate 2,2 '-bis-(2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-bis-(2,3-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-bis-(2,4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline.
As oxime compound, N-benzoyloxy-1-(4-Phenylsulfanyl phenyl) butane-1-ketone-2-imines can be enumerated, N-ethoxy carbonyl Oxy-1-phenyl-propane-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, 3-dimethyl-2, 4-dioxolyl methoxyl) benzoyl }-9H-carbazole-3-base] ethane-1-imines etc.The commercially available product such as IRGACURE OXE-01, OXE-02 (above is Ciba Specialty Chemicals's system), N-1919 (ADEKA Inc.) can be used.
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 Photoepolymerizationinitiater initiater (C), Photoepolymerizationinitiater initiater other than the above can be comprised, from light sensitivity aspect, preferably be substantially devoid of.As Photoepolymerizationinitiater initiater other than the above, as long as pass through the compound of the effect initiated polymerization of light, be then not particularly limited, known Photoepolymerizationinitiater initiater can be used.As Photoepolymerizationinitiater initiater other than the above, such as alpha-hydroxyacetone compounds, alpha-alkoxy base ketonic compound, triaizine compounds, acylphosphine oxide compound etc. can be enumerated.
As alpha-hydroxyacetone compounds, the oligomer etc. of 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 2-hydroxy-2-methyl-1-[4-(2-hydroxyl-oxethyl) phenyl] propane-1-ketone, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-(4-isopropenyl phenyl) propane-1-ketone can be enumerated.
As alpha-alkoxy base ketonic compound, α can be enumerated, α-diethoxy acetophenone, benzyl dimethyl ketal etc.
As 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 acylphosphine oxide compound, TMDPO etc. can be enumerated.The commercially available products such as IRGACURE 819 (Ciba Specialty Chemicals's system) can be used.
Photopolymerization causes auxiliary agent (C1) and can combinationally use with Photoepolymerizationinitiater initiater (C), is the compound of polymerization for the photopolymerizable compound of the polymerization that promotes to have utilized Photoepolymerizationinitiater initiater to cause or sensitizer.
Cause auxiliary agent (C1) as photopolymerization, the photopolymerization that can comprise beyond thioxanthone compounds causes auxiliary agent, from light sensitivity aspect, is preferably substantially devoid of.Cause auxiliary agent as the photopolymerization beyond thioxanthone compounds, known photopolymerization can be used to cause auxiliary agent.Cause auxiliary agent as the photopolymerization beyond thioxanthone compounds, such as amines, thiazolinium compounds, alkoxy anthracene compound, 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 (common name Michler's keton), 4, 4 '-bis-(diethylamino) benzophenone, 4, 4 '-bis-(ethylmethylamino) benzophenone etc., wherein preferably 4, 4 '-bis-(diethylamino) benzophenone.The commercially available products such as EAB-F (hodogaya chemical industry (strain) system) can be used.
As thiazolinium compounds, the compound etc. shown in formula (III-1) ~ formula (III-3) can be enumerated.
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 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, phenoxyethanoic acid, naphthalene sulfenyl acetic acid, N-naphthyl glycocoll, naphthoxy acetic acid etc. can be enumerated.
About alpha-amido ketonic compound, united imidazole, oxime compound and thioxanthone compounds content separately, relative to alpha-amido ketonic compound 100 mass parts, preferably in following scope.
United imidazole, is preferably 50 ~ 400 mass parts, is more preferably 50 ~ 300 mass parts, more preferably 50 ~ 100 mass parts.
Oxime compound, is preferably 10 ~ 100 mass parts, is more preferably 10 ~ 50 mass parts, more preferably 10 ~ 30 mass parts.
Thioxanthone compounds, is preferably 80 ~ 160 mass parts, is more preferably 80 ~ 150 mass parts, more preferably 80 ~ 140 mass parts.
If containing above-claimed cpd in the scope of above-mentioned amount, pattern has excellent adaptation, and therefore during development, pattern is difficult to from strippable substrate, and there is the tendency of light sensitivity raising.
About the total amount of alpha-amido ketonic compound, united imidazole, oxime compound and thioxanthone compounds, relative to total amount 100 mass parts of resin (A) and photopolymerizable compound (B), be preferably 1 ~ 30 mass parts, be more preferably 3 ~ 20 mass parts, more preferably 4 ~ 16 mass parts, are particularly preferably 6 ~ 13 mass parts.If the total amount of alpha-amido ketonic compound, united imidazole, oxime compound and thioxanthone compounds is above-mentioned scope, pattern has excellent adaptation, and therefore during development, pattern is difficult to from strippable substrate.
In addition, photosensitive polymer combination of the present invention can contain multi-functional thiol's compound (T) further.This multi-functional thiol's compound (T) is the compound of the sulfanyl in molecule with more than 2.Wherein, if use have more than 2 with from the compound of the sulfanyl of the carbon atom bonding of aliphatic alkyl, photosensitive polymer combination of the present invention has the tendency of light sensitivity rising.
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 butoxy) butane of 4-etc.
About the content of multi-functional thiol's compound (T), relative to Photoepolymerizationinitiater initiater (C) 100 mass parts, be preferably 0.5 ~ 20 mass parts, be more preferably 1 ~ 15 mass parts.If the content of multi-functional thiol's compound (T) is within the scope of this, there is light sensitivity and raise, and developability becomes good tendency.
The solvent (D) used in photosensitive polymer combination of the present invention, is not particularly limited, and can use normally used solvent in this field.Can from the ketone solvent (solvent containing-CO-) beyond the ether solvents (solvent containing-O-) beyond such as ester solvent (solvent containing-COO-), ester solvent, ether-ether solvent (solvent containing-COO-and-O-), ester solvent, alcoholic solvent, aromatic hydrocarbon solvents, amide solvent, dimethyl sulfoxide (DMSO) etc. choice for use.
As ester solvent, methyl lactate, ethyl lactate, butyl lactate, 2-hydroxy-methyl isobutyl acid, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl isobutyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, Propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, adnoral acetate, gamma-butyrolacton etc. can be enumerated.
As ether solvents, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxyl-n-butyl alcohol, 3-methoxyl-3-methyl butanol, tetrahydrofuran, oxinane, Isosorbide-5-Nitrae-diox, diethylene glycol dimethyl ether, diethyl carbitol, diglycol methyl ethyl ether, diglycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetol, methyl anisole etc. can be enumerated.
As ether-ether solvent, Methoxy Methyl Acetate can be enumerated, Methoxy acetic acid ethyl ester, Methoxy acetic acid butyl ester, ethoxy methyl acetate, ethoxy ethyl acetate, 3-methoxy methyl propionate, 3-methoxypropionate, 3-ethoxypropanoate, 3-ethoxyl ethyl propionate, 2-methoxy methyl propionate, 2-methoxypropionate, 2-methoxy propyl propyl propionate, 2-ethoxypropanoate, 2-ethoxyl ethyl propionate, 2-methoxyl-2 Methylpropionic acid methyl esters, 2-ethoxy-2 Methylpropionic acid ethyl ester, acetic acid 3-methoxybutyl, acetic acid 3-methyl-3-methoxybutyl, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetic acid esters, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetic acid esters, 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, 1,3,5-trimethylbenzene etc. can be enumerated.
As amide solvent, DMF, DMA, 1-METHYLPYRROLIDONE etc. can be enumerated.
These solvents may be used alone, or two or more kinds may be used in combination.
In above-mentioned solvent, from coating, drying property aspect, the boiling point preferably under 1 atmospheric pressure is the organic solvent of more than 120 DEG C less than 180 DEG C.Wherein, preferred propylene glycol monomethyl ether, propylene glycol methyl ether acetate, diglycol methyl ethyl ether, acetic acid 3-methoxybutyl, 3-methoxyl-n-butyl alcohol and comprise the mixed solvent of these organic solvents, more preferably comprise the solvent of at least a kind be selected from diglycol methyl ethyl ether and 3-methoxyl-n-butyl alcohol.
About the content of solvent in photosensitive polymer combination (D), relative to photosensitive polymer combination, be preferably 60 ~ 95 quality %, be more preferably 70 ~ 90 quality %.In other words, the solid state component of photosensitive polymer combination is preferably 5 ~ 40 quality %, is more preferably 10 ~ 30 quality %.Wherein, so-called solid state component, refers to the amount to eliminate solvent (D) from photosensitive polymer combination after.If the content of solvent (D) is in above-mentioned scope, exists and be coated with the high tendency of the flatness of the film of photosensitive polymer combination.
Photosensitive polymer combination of the present invention is preferably containing surfactant (E).As surfactant, such as silicone based surfactants, fluorine system surfactant can be enumerated, there is the silicone based surfactants etc. of fluorine atom.
As silicone based surfactants, the surfactant with siloxane bond can be enumerated.Specifically can enumerate TORAY SILICONE DC3PA, TORAY SILICONE SH7PA, TORAY SILICONE DC11PA, TORAY SILICONE SH21PA, TORAYSILICONE SH28PA, TORAY SILICONE SH29PA, TORAY SILICONESH30PA, polyether modified silicon oil SH8400 (trade name: eastern beautiful DOW CORNING (strain) system), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (SHIN-ETSU HANTOTAI's chemical industry (strain) system), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (stepping contract commercial firm of figure new high-tech material Japan system) etc.
As fluorine system surfactant, the surfactant with fluorocarbon chain can be enumerated.Specifically can enumerate Fluorinert (registered trademark) FC430, Fluorinert FC431 (Sumitomo 3M (strain) system), Megafac (registered trademark) F142D, Megafac F171, Megafac F172, Megafac F173, Megafac F177, Megafac F183, Megafac R30 (DIC (strain) system), F-Top (registered trademark) EF301, F-Top EF303, F-Top EF351, F-Top EF352 (Mitsubishi Materials electronics changes into (strain) system), Surflon (registered trademark) S381, Surflon S382, Surflon SC101, Surflon SC105 (Asahi Glass (strain) system), E5844 ((strain) DAIKIN FINE CHEMICAL studies made) etc.
As the silicone based surfactants with fluorine atom, the surfactant with siloxane bond and fluorocarbon chain can be enumerated.Specifically can enumerate Megafac (registered trademark) R08, Megafac BL20, Megafac F475, Megafac F477, Megafac F443 (DIC (strain) system) etc.Preferably can enumerate Megafac (registered trademark) F475.
About surfactant (E), relative to photosensitive polymer combination, be generally below more than 0.001 quality % 0.2 quality %, be preferably below more than 0.002 quality % 0.1 quality %, be more preferably below more than 0.01 quality % 0.05 quality %.By containing surfactant within the scope of this, the flatness of film can be made good.
In photosensitive polymer combination of the present invention, can as required also with various adjuvants such as filling agent, other macromolecular compounds, closely sealed promoter, antioxidant, ultraviolet light absorber, light stabilizer, chain-transferring agents.
Photosensitive polymer combination of the present invention, is substantially devoid of the colorant such as pigment and dyestuff.That is, in photosensitive polymer combination of the present invention, colorant is generally relative to the content of composition entirety and is less than 1 quality %, is preferably less than 0.5 quality %.
In addition, photosensitive polymer combination of the present invention, if being filled into optical path length is in the quartz cell of 1cm, use spectrophotometer, under the condition measuring wavelength 400 ~ 700nm, measure transmissivity, then average transmittance is more than 70%, is preferably more than 80%.
Photosensitive polymer combination of the present invention, when making film, the average transmittance of film is generally more than 90%, is more preferably more than 95%.This average transmittance be for be heating and curing (such as 100 ~ 250 DEG C, 5 minutes ~ 3 hours) after thickness be the film of 3 μm, mean value when using spectrophotometer to measure under the condition measuring wavelength 400 ~ 700nm.The film of the transparency excellence of visible region can be provided thus.
Photosensitive polymer combination of the present invention, such as described later, by the substrates such as base material such as glass, metal, plastics, define color filter, various insulation or conducting film, driving circuit etc. these substrates on be coated with, can film be formed as.Film is preferably the product after dry and solidification.In addition, also the film obtained can be patterned as required shape, use as pattern.And then, also these films or pattern can be formed as a part for the component parts of display device etc. and use.
First, photosensitive polymer combination of the present invention is coated on base material.
As mentioned above, coating can use the various apparatus for coating such as spin coater, slit and spin coater, slit coater, ink-jet, roll coater, dip coater and carry out.
Then, preferably drying or prebake is carried out, by volatile ingredient removings such as solvents.Thereby, it is possible to obtain level and smooth uncured film.
The thickness of the film of this situation is not particularly limited, and suitably can regulate, be generally about 1 ~ 6 μm according to the material, purposes etc. that use.
And then, to the uncured film obtained, across the mask for the formation of target pattern, the ultraviolet etc. irradiate light, such as being occurred by mercury vapor lamp, light emitting diode.The shape of mask is now not particularly limited, and can enumerate various shape.In addition, about the transmissivity of mask transmittance section, as long as through the light from light source, be just not particularly limited.The width, height etc. of pattern suitably regulate by the transmissivity etc. of mask size, mask transmittance section.
And then, to the uncured film obtained, across the mask for the formation of target pattern, the ultraviolet etc. irradiate light, such as being occurred by mercury vapor lamp, light emitting diode.The shape of mask is now not particularly limited, and can enumerate various shape.In addition, about the transmissivity of mask transmittance section, as long as through the light from light source, be just not particularly limited.The width, height etc. of pattern suitably regulate by the transmissivity etc. of mask size, mask transmittance section.
The light being less than 350nm can be used the filter cutoff this wavelength region may ended by exposure machine in recent years, light near 436nm, near 408nm, near 365nm is used the bandpass filter that these wavelength region may are taken out optionally is taken out, equably parallel rays is irradiated to plane of exposure entirety.Now in order to carry out the correct contraposition of mask and base material, the device such as mask aligner, ledex (ス テ Star パ) can be used.
Then, by making film contact with aqueous alkali, established part such as non-exposed portion being dissolved, develops, thus the pattern form of target can be obtained.
Developing method can be any methods such as liquid hole (liquid contains り) method, infusion process, spray-on process.And then base material can be made to tilt to arbitrary angle when developing.
The aqueous solution of the preferred alkali compounds of the developer solution used in development.
Alkali compounds can be any one of inorganic and organic alkali compounds.
As the concrete example of inorganic alkaline compound, NaOH, potassium hydroxide, sodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, sal tartari, sodium bicarbonate, saleratus, sodium borate, potassium borate, ammonia etc. can be enumerated.
In addition, as organic basic compound, such as tetramethylammonium hydroxide, hydroxide 2-hydroxyethyl trimethyl ammonium, MMA, dimethylamine, trimethylamine, mono aminoethane, diethylamine, triethylamine, single isopropylamine, diisopropylamine, monoethanolamine etc. can be enumerated.
Concentration in the aqueous solution of these inorganic and organic basic compounds, is preferably 0.01 ~ 10 quality %, is more preferably 0.03 ~ 5 quality %.
The aqueous solution of above-mentioned alkali compounds can contain surfactant.
Surfactant can be any one of non-ionization series surfactant, negative ion system surfactant or kation system surfactant.
As nonionic system surfactant, such as polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkylaryl ether, other polyoxyethylene deriv, ethylene oxide/propylene oxide segmented copolymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, fatty acid glyceride, polyoxyethylene fatty acid ester, polyoxyethylene alkyl amine etc. can be enumerated.
As negative ion system surfactant, the higher alcohol sulfate salt that such as lauryl alcohol sodium sulfovinate, oleyl sulfate sodium are such can be enumerated, the alkylsurfuric acid salt that lauryl sodium sulfate, ammonium lauryl sulfate are such, the alkyl aryl sulfonate class etc. that neopelex, dodecyl sodium naphthalene sulfonate are such.
As kation system surfactant, amine salt or quaternary ammonium salt etc. that such as stearyl amine hydrochloride, DTAC are such can be enumerated.
The concentration of the surfactant in alkaline developer, is preferably the scope of 0.01 ~ 10 quality %, is more preferably 0.05 ~ 8 quality %, more preferably 0.1 ~ 5 quality %.
After development, wash, and then cure after can carrying out as required.After cure usually preferably 150 ~ 240 DEG C temperature range, 10 ~ 180 minutes.
The film obtained like this or pattern, can be used as such as liquid crystal indicator light spacer, can the overlay coating (overcoat) of patterning.In addition, when patterned exposure is carried out to uncured film, by using hole formation photomask, can hole be formed, can be used as interlayer dielectric.And then, when uncured film is exposed, do not use photomask, carry out blanket exposure and be heating and curing or be only heating and curing, can hyaline membrane be formed thus.This hyaline membrane can be used as overlay coating.In addition, also can be used for the display device such as touch-screen.The film of high-quality or the display device of pattern can be had thus with high yield manufacture.
Photosensitive polymer combination of the present invention, due to the pattern with the excellent adhesion of substrate can be given, therefore the material forming various film and pattern can be suitable for, such as, for the formation of the hyaline membrane, pattern, light spacer, overlay coating, dielectric film, liquid crystal aligning control projection, lenticule, coating etc. of a part forming color filter and/or array base palte.In addition, also can be used for having these films or pattern as the color filter, array base palte etc. of a part for its component parts, the display device possessing these color filter and/or array base paltes etc. can also be used for, such as liquid crystal indicator, organic el device etc.
Embodiment
By the following examples the present invention is illustrated in greater detail." % " and " part " in example if no special instructions, is then quality % and mass parts.
(synthesis example 1)
In the flask of 1L with reflux cooler, tap funnel and stirrer, make nitrogen flow into 0.02L/ minute and become blanket of nitrogen, load diglycol ethyl-methyl ether 140 mass parts, be heated to 70 DEG C while stirring.Then, by methacrylic acid 40 mass parts, acrylic acid 3,4-epoxy three ring [5.2.1.0 2,6] last of the ten Heavenly stems ester (potpourri of the compound shown in the compound shown in formula (I-1) and formula (II-1), mol ratio=50: 50) 360 mass parts are dissolved in diglycol ethyl-methyl ether 190 mass parts, modulation solution.Dropping liquid pump is used to instill with 4 hours in the flasks of 70 DEG C of insulations by the lysate obtained.
On the other hand, by polymerization initiator 2, two (2,4-methyl pentane nitrile) 30 mass parts of 2 '-azo are dissolved in the solution that diglycol ethyl-methyl ether 240 mass parts obtains, and use other dropping liquid pump with in 5 hours instillation flasks.After the instillation of the solution of polymerization initiator terminates, keep 4 hours at 70 DEG C, then cool to room temperature, obtains multipolymer (Resin A solution a).The solid state component of the Resin A a solution obtained is 42.6 quality %, and the weight-average molecular weight (Mw) of the Resin A a obtained is 8.0 × 10 3, molecular weight distribution (Mw/Mn) is 1.91, and acid number is 60mg-KOH/g (acid number that solid state component converts).
(synthesis example 2)
In the 1L flask with reflux cooler, tap funnel and stirrer, make nitrogen flow into 0.02L/ minute and become blanket of nitrogen, load 3-methoxyl-n-butyl alcohol 200 mass parts and acetic acid 3-methoxybutyl 105 mass parts, be heated to 70 DEG C while stirring.Then, by methacrylic acid 60 mass parts, acrylic acid 3,4-epoxy three ring [5.2.1.0 2,6] last of the ten Heavenly stems ester (mol ratio=50 of the compound shown in the compound shown in formula (I-1) and formula (II-1): the potpourri of 50) 240 mass parts be dissolved in acetic acid 3-methoxybutyl 140 mass parts, modulation solution, uses tap funnel with 4 hours by the flask of this lysate instillation insulation at 70 DEG C.On the other hand, by polymerization initiator 2, two (2,4-methyl pentane nitrile) 30 mass parts of 2 '-azo are dissolved in acetic acid 3-methoxybutyl 225 mass parts, are used by the solution obtained other tap funnel with in 4 hours instillation flasks.After the instillation of the solution of polymerization initiator terminates, keep 4 hours at 70 DEG C, then cool to room temperature, obtains the solution of the multipolymer (Resin A b) of solid state component 32.6 quality %, acid number 34.3mg-KOH/g (the acid number 105mg-KOH/g that solid state component converts).The weight-average molecular weight Mw of the Resin A b obtained is 13,400, and molecular weight distribution (Mw/Mn) is 2.50.
The weight-average molecular weight (Mw) of the Resin A a obtained and Resin A b and the mensuration of number-average molecular weight (Mn) use GPC method to carry out under the following conditions.
Device: K2479 ((strain) Shimadzu Seisakusho Ltd. system)
Post: SHIMADZU Shim-pack GPC-80M
Column temperature: 40 DEG C
Solvent: THF (tetrahydrofuran)
Flow velocity: 1.0mL/ minute
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 ~ 7, reference example 1 and comparative example 1)
The composition of table 1 is mixed, obtains photosensitive polymer combination 1 ~ 9.
[table 1]
Should illustrate, in table 1, resin (A) represents the mass parts that solid state component converts.
Photopolymerizable compound (Ba): dipentaerythritol acrylate (A-DPH; Xin Zhong village chemical industry (strain) makes)
Photopolymerizable compound (Bb): trimethylolpropane triacrylate (A-TMMT; Xin Zhong village chemical industry (strain) makes)
Photoepolymerizationinitiater initiater (Ca): 2,2 '-bis-(o-chlorphenyl)-4,5,4 ', 5 '-tetraphenyl-1,2 '-bisglyoxaline (B-CIM; Hodogaya chemical industry (strain) is made); United imidazole
Photoepolymerizationinitiater initiater (Cb): 2-(dimethylamino)-2-[(4-aminomethyl phenyl) methyl]-1-[4-(4-morpholinyl) phenyl]-1-butanone (IRGACURE 379EG; Ciba Specialty Chemicals's system); Alpha-amido ketonic compound
Photoepolymerizationinitiater initiater (Cc): oxime compound (N-1919; ADEKA society system); Oxime compound
Photoepolymerizationinitiater initiater (Cd): 2-methyl-2-morpholino-1-(4-methylsulfanyl phenyl) propane-1-ketone (IRGACURE 907; Ciba Specialty Chemicals's system); Alpha-amido ketonic compound
Photopolymerization causes auxiliary agent (C1): 2,4-diethyl thioxanthone (KAYACURE DETX-S; Japan's chemical drug (strain) system); Thioxanthone compounds
Solvent (Da): 3-methoxyl-n-butyl alcohol
Solvent (Db): diglycol ethyl-methyl ether
Solvent (Dc): propylene glycol methyl ether acetate
Solvent (Dd): propionic acid 3-ethoxy ethyl ester
Solvent (De); Acetic acid 3-methoxybutyl
Surfactant (E): polyether modified silicon oil (eastern beautiful DOW CORNING (strain) system; SH8400)
Solvent (D) mixes in the mode of " solid state component amount (%) " that the solid state component amount of photosensitive polymer combination is table 1, and the value of solvent composition (Da) ~ (De) in solvent (D) represents the mass ratio in solvent (D).
The content of surfactant (E) represents the mass ratio (%) relative to photosensitive polymer combination total amount.
< pattern forms >
By the glass substrate (#1737 of 2 inch square; Healthy and free from worry (Corning) Inc.) with neutral lotion, water and alcohol successively clean after carry out drying.On this glass substrate, spin coating photosensitive polymer combination, makes with 60mJ/cm 2exposure (365nm benchmark) exposure, development, washing, after cure after thickness be 3.0 μm, secondly in clean baking oven at 80 DEG C prebake 2 minutes.After cooling, what make to be coated with the substrate of this photosensitive polymer combination and quartz glass photomask is spaced apart 200 μm, uses exposure machine (TME-150RSK; Open up Pu Kang (strain) system, light source; Extra-high-pressure mercury vapour lamp), with 60mJ/cm under air atmosphere 2exposure (365nm benchmark) carry out illumination and penetrate.Further, now be make radiating light from extra-high-pressure mercury vapour lamp by optical filter (UV-33 to the irradiation of photosensitive polymer combination; ASAHI TECHNO GLASS (strain) makes) and use.In addition, as photomask, the photomask forming pattern (have the foursquare transmittance section that 1 limit is 13 μm ~ 15 μm, this is foursquare is spaced apart 100 μm, average form 5600) (i.e. transmittance section) is at grade employed.Wherein, the pattern formed at photomask is called optical mask pattern.
After illumination is penetrated, at 23 DEG C, 60 seconds spray development are carried out to the water system developer solution of above-mentioned film containing nonionic system surfactant 0.12% and potassium hydroxide 0.04%, after washing, cure after carrying out 15 minutes in an oven at 235 DEG C, obtain pattern.
< adaptation evaluates >
For the pattern obtained, with optical microscope (Axio Imager MAT; Carl Zeiss (strain) make), the pattern obtained by the optical mask patterns of less than 5 μm is not peeled off and the situation residued in completely on substrate is designated as zero, though by have 1 situation also peeled off be designated as ×, be recorded in table 2.When the pattern obtained by the optical mask patterns of less than 5 μm is residual on substrate, can be judged as that adaptation is good.
< light sensitivity >
Use and there is foursquare transmittance section, this foursquare photomask being spaced apart 100 μm that 1 limit is 13 μm, exposure is replaced with 20mJ/cm respectively 2, 40mJ/cm 2, 60mJ/cm 2and 80mJ/cm 2, obtain pattern in addition as described above.
For each pattern obtained, by three-dimensional non-planar contact surfaces shape calculating system (MicromapMM527N-PS-M100 type; (strain) Ling Hua System Inc.) measure the width of bottom portion.By the value measured by straight line be similar to calculate wide be 31 μm time exposure.Using this calculated value as light sensitivity, remember in table 2.
The value of light sensitivity is less, then the time shutter can be shorter, therefore preferably, if but be less than 20mJ/cm 2, with the fluctuation of exposure, the width of pattern easily changes, not preferred on the contrary.
The transmissivity > of < composition
For the photosensitive polymer combination obtained, use UV, visible light near infrared spectrometer (V-650 respectively; Japan's light splitting (strain) system) (quartz cell, optical path length: 1cm), measure the average transmittance (%) of 400 ~ 700nm.Show the result in table 2.
The transmissivity > of < film
Use the photosensitive polymer combination obtained, be the mode of 3 μm respectively with the thickness after solidification, make film under the following conditions.
By the glass substrate (#1737 of 2 inch square; Corning Incorporated's system) with neutral lotion, water and alcohol successively clean after carry out drying.On this glass substrate, spin coating photosensitive polymer combination is 3.0 μm with the thickness after curing after making, secondly in clean baking oven at 90 DEG C prebake 10 minutes.After cooling, use exposure machine (TME-150RSK; Open up Pu Kang (strain) system, light source; Extra-high-pressure mercury vapour lamp), under air atmosphere, irradiate exposure 60mJ/cm 2the light of (365nm benchmark).Further, now be make radiating light from extra-high-pressure mercury vapour lamp by optical filter (UV-35 to the irradiation of photosensitive polymer combination; Morning sun light splitting (strain) system) and carry out.After illumination is penetrated, flood at 23 DEG C in the water system developer solution comprising nonionic system surfactant 0.12% and potassium hydroxide 0.04%, shake above-mentioned film 60 seconds, develop, then, heat 15 minutes at 235 DEG C in an oven and obtain film.
For the film obtained, use micro-spectral light measurer (OSP-SP200; OLYMPUS Inc.), measure the average transmittance (%) under 400 ~ 700nm.Transmissivity uprises and means that absorption diminishes.Show the result in table 2.
[table 2]
*) content (mass parts) relative to alpha-amido ketonic compound 100 mass parts is represented.
Known as described embodiments, for photosensitive polymer combination of the present invention, the pattern obtained and the adaptation of substrate good.
Use such photosensitive polymer combination to form pattern, utilize them, thus display device etc. can be manufactured with high yield.
industry utilizes possibility
Photosensitive polymer combination of the present invention, due to the pattern with the excellent adhesion of substrate can be provided, therefore be suitable for use in the material forming various film and pattern, such as, be suitable for the hyaline membrane, pattern, light spacer, overlay coating, dielectric film, liquid crystal aligning control projection, lenticule, coating etc. that form the part forming color filter and/or array base palte.In addition, also can be used in and there is these films or pattern as the color filter, array base palte etc. of a part for its component parts and the display device possessing these color filter and/or array base paltes etc., such as liquid crystal indicator, organic el device etc.

Claims (7)

1. a photosensitive polymer combination, it contains resin, photopolymerizable compound, Photoepolymerizationinitiater initiater, photopolymerization containing thioxanthone compounds cause auxiliary agent and solvent, Photoepolymerizationinitiater initiater is the Photoepolymerizationinitiater initiater comprising alpha-amido ketonic compound, united imidazole and oxime compound, and the content of thioxanthone compounds is below more than 80 mass parts 160 mass parts relative to content 100 mass parts of alpha-amido ketonic compound.
2. photosensitive polymer combination as claimed in claim 1, wherein the content of united imidazole is below more than 50 mass parts 400 mass parts relative to content 100 mass parts of alpha-amido ketonic compound.
3. photosensitive polymer combination as claimed in claim 1, wherein the content of oxime compound is below more than 10 mass parts 100 mass parts relative to content 100 mass parts of alpha-amido ketonic compound.
4. photosensitive polymer combination as claimed in claim 1, wherein resin is the resin of the structural unit comprised from the unsaturated compound with cyclic ether structure.
5. the film of the patterning using the photosensitive polymer combination described in claim 1 to be formed.
6. comprise the display device of the film of patterning according to claim 5.
7. photosensitive polymer combination according to claim 1 is forming the use in light spacer.
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