CN101738859A - Photosensitive resin composition and display - Google Patents

Photosensitive resin composition and display Download PDF

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Publication number
CN101738859A
CN101738859A CN200910221745A CN200910221745A CN101738859A CN 101738859 A CN101738859 A CN 101738859A CN 200910221745 A CN200910221745 A CN 200910221745A CN 200910221745 A CN200910221745 A CN 200910221745A CN 101738859 A CN101738859 A CN 101738859A
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methyl
acid
ester
acrylate
butyl
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CN101738859B (en
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白川政和
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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
    • Y10S430/1055—Radiation sensitive composition or product or process of making

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials For Photolithography (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The present invention provides a photosensitive resin composition, wherein, the photosensitive resin comprises resin (A), polymeric compound (B), polymerization initiator (C) and solvent (D). The solvent (D) comprises dialkylidene glycol dialkyl ether with alkylidene containing 1-3 carbon atoms and alkyl with 1-4 carbon atoms. The invention also provides a display device with a film or/and a pattern formed by the photosensitive resin according to the invention.

Description

Photosensitive polymer combination and display device
Technical field
The present invention relates to a kind of photosensitive polymer combination and display device.
Background technology
In recent years, carrying out the maximization of substrate size in fields such as display panels, usually in order to form hyaline layer or pattern such as overlay, can be by method of spin coating or slit on real estate; Photosensitive resin coating compositions such as rotary process.
On the other hand, from boosting productivity, adapt to large-scale picture equal angles, also the someone has studied the method that forms high-quality uniform coating when can save photosensitive polymer combination solution.
On this basis, in order to form outstanding the filming of quality, study over against the selection of solvent species at present.For example, disclose and utilized the scheme of having used the photosensitive polymer combination of following material as solvent, described solvent is the potpourri (for example patent documentation 1) of propylene glycol monomethyl ether acetic acid esters, 3-ethoxyethyl group propionic ester, 3-methoxyl-1-butanols and acetate 3-methoxyl butyl ester.
Patent documentation 1: the spy opens 2008-181087 communique paragraph 91
But, the photosensitive polymer combination that has used above-mentioned solvent is applicable under the situation of slot die (slit die) rubbing method as representational coating process etc., take place sometimes that mist (も や) is uneven, vertical stripe is uneven and the nail trace, thereby can not obtain high-quality filming.
Summary of the invention
Thereby the object of the present invention is to provide and a kind ofly can suppress the generation uneven and the nail trace of mist inequality, vertical stripe and can form and film whole even, high-quality photosensitive polymer combination of filming and used the display device etc. of said composition.
That is, the invention provides following [1]～[8].
[1] a kind of photosensitive polymer combination, wherein,
Contain resin (A), polymerizable compound (B), polymerization initiator (C) and solvent (D),
Solvent (D) is the solvent of the alcohol of two aklylene glycol dialkyl ethers of the alkyl that contains alkylidene with carbon number 1～3 and carbon number 1～4 and carbon number 1～6.
[2] according to [1] described photosensitive polymer combination, wherein,
Relative solvent total amount contains 30～90 quality %, two aklylene glycol dialkyl ethers in the solvent (D).
[3] according to [1] or [2] described photosensitive polymer combination, wherein,
Relative solvent total amount contains the alcohol of the carbon number 1～6 of 10～50 quality % in the solvent (D).
[4] according to any described photosensitive polymer combination in [1]～[3], wherein,
Two aklylene glycol dialkyl ethers are diglycol ethyl-methyl ether.
[5] according to any described photosensitive polymer combination in [1]～[4], wherein,
The alcohol of carbon number 1～6 is the 3-methoxybutanol.
[6] a kind of filming, it is to use filming that any described photosensitive polymer combination forms in [1]～[5].
[7] a kind of pattern, it is to use any pattern that described photosensitive polymer combination forms in [1]～[5].
[8] a kind of display device, wherein,
Comprise from [6] described film and [7] described pattern select at least a kind.
According to the present invention, thereby the generation that can suppress mist inequality, vertical stripe inequality and nail trace can form whole even, high-quality filming.
In addition, by utilizing this photosensitive polymer combination, can obtain high-quality display device etc.
Embodiment
Photosensitive polymer combination of the present invention contains resin (A), polymerizable compound (B), polymerization initiator (C) and solvent (D).Wherein, in this manual, as the illustrative compound of each composition unless otherwise specified, then can be used alone or in combination.
As the resin that in photosensitive polymer combination of the present invention, uses (A), but illustration have alkali dissolution resin (A1), have alkali dissolution and at light and pine for having reactive resin (A2) etc. under at least one side's the effect.
As the resin with alkali dissolution (A1), but at least a kind (a) that illustration is selected from unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides (below be sometimes referred to as " (a) ") and can with multipolymer of the monomer (c) of (a) copolymerization (below be sometimes referred to as " (c) ") etc.
As (a), for example can specifically enumerate acrylic acid, methacrylic acid, crotonic acid, neighbour-,-, right-unsaturated monocarboxylic acid classes such as vinyl benzoic acid;
1,4-cyclohexene dicarboxylic acid, methyl-5-norborene-2, unsaturated dicarboxylic acid classes such as 3-dicarboxylic acid;
Maleic acid, fumaric acid, citraconic acid (citraconic acid), mesaconic acid (mesaconicacid), itaconic acid, 3-vinyl phthalic acid (3-vinylphthalic acid), 4-vinyl phthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3, unsaturated dicarboxylic acid classes such as 6-tetrahydrophthalic acid, dimethyl tetrahydro phthalic acid;
The acid anhydrides of these unsaturated dicarboxylic acid classes;
Mono succinate [2-(methyl) acryloxy ethyl]] unsaturated list [(methyl) acryloxyalkyl] the ester class of the polybasic carboxylic acid more than 2 yuan such as ester, phthalic acid list [2-(methyl) acryloxy ethyl] ester;
The unsaturated esters of acrylic acid that in a part, contains hydroxyl and carboxyl of α-(methylol) acrylic acid and so on etc.
Wherein, from the angle of copolymerization or alkali dissolution, preferably use acrylic acid, methacrylic acid, maleic anhydride etc.
As (c), can enumerate (methyl) alkyl-acrylates such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-butyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate;
(methyl) cyclohexyl acrylate, (methyl) acrylic acid 2-methyl cyclohexane ester, (methyl) acrylic acid three ring [5.2.1.0 2.6] (methyl) acrylic acid cyclic alkyl ester classes such as decane-8-base ester (in the art,, being called as (methyl) acrylic acid two cyclopentyl esters as trivial name), (methyl) acrylic acid two cyclopentyloxy ethyl esters, (methyl) isobornyl acrylate;
Cyclohexyl acrylate, acrylic acid 2-methyl cyclohexane ester, acrylic acid three ring [5.2.1.0 2.6] decane-8-base ester (in this technical field, as trivial name, is called as acrylic acid two cyclopentyl esters.), acrylic acid cyclic alkyl ester class such as acrylic acid two cyclopentyloxy ethyl esters, isobornyl acrylate;
(methyl) acrylic acid aryl ester classes such as (methyl) phenyl acrylate, (methyl) benzyl acrylate;
Acrylic acid such as phenyl acrylate, benzyl acrylate aryl ester class;
Dicarboxylic diesters such as diethyl maleate, DEF, diethyl itaconate;
Hydroxyalkyl acrylate classes such as (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) acrylic acid 2-hydroxypropyl acrylate;
Two ring [2.2.1] hept-2-ene"s, 5-methyl bicyclic [2.2.1] hept-2-ene", 5-ethyl two ring [2.2.1] hept-2-ene"s, 5-hydroxyl two ring [2.2.1] hept-2-ene"s, 5-carboxyl two ring [2.2.1] hept-2-ene"s, 5-methylol two ring [2.2.1] hept-2-ene"s, 5-(2 '-hydroxyethyl) two ring [2.2.1] hept-2-ene"s, 5-methoxyl two ring [2.2.1] hept-2-ene"s, 5-ethoxy two ring [2.2.1] hept-2-ene"s, 5,6-dihydroxy two ring [2.2.1] hept-2-ene"s, 5,6 dicarboxyls, two ring [2.2.1] hept-2-ene"s, 5,6-two (methylol) two ring [2.2.1] hept-2-ene"s, 5,6-two (2 '-hydroxyethyl) two ring [2.2.1] hept-2-ene"s, 5,6-dimethoxy two ring [2.2.1] hept-2-ene"s, 5,6-diethoxy two ring [2.2.1] hept-2-ene"s, 5-hydroxy-5-methyl base two ring [2.2.1] hept-2-ene"s, 5-hydroxyl-5-ethyl two ring [2.2.1] hept-2-ene"s, 5-carboxyl-5-methyl bicyclic [2.2.1] hept-2-ene", 5-carboxyl-5-ethyl two ring [2.2.1] hept-2-ene"s, 5-methylol-5-methyl bicyclic [2.2.1] hept-2-ene", 5-carboxyl-6-methyl bicyclic [2.2.1] hept-2-ene", 5-carboxyl-6-ethyl two ring [2.2.1] hept-2-ene"s, 5,6-dicarboxyl two ring [2.2.1] hept-2-ene" acid anhydrides (humic acid (himic acid) acid anhydride), 5-tertbutyloxycarbonyl two ring [2.2.1] hept-2-ene"s, 5-hexamethylene oxygen carbonyl two ring [2.2.1] hept-2-ene"s, 5-carbobenzoxy two ring [2.2.1] hept-2-ene"s, 5,6-two (tertbutyloxycarbonyl) two ring [2.2.1] hept-2-ene"s, 5, two ring unsaturated compound classes such as 6-two (hexamethylene oxygen carbonyl) two ring [2.2.1] hept-2-ene"s;
Dicarbapentaborane imide derivative classes such as N-phenylmaleimide, N-cyclohexyl maleimide, N-benzyl maleimide, N-succinimido (succinimidyl)-3-maleimide benzoic ether, N-succinimido-4-maleimide butyric ester, N-succinimido-6-maleimide capronate, N-succinimido-3-maleimide propionic ester, N-(9-acridinyl (acridinyl)) maleimide;
Styrene, α-Jia Jibenyixi, a methyl styrene, p-methylstyrene, vinyltoluene, to methoxy styrene, vinyl cyanide, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, Methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene etc.
Wherein, from the angle of copolymerization and alkali dissolution, optimization styrene, N-phenylmaleimide, N-cyclohexyl maleimide, N-benzyl maleimide, two ring [2.2.1] hept-2-ene"s etc.
(a) and (c) can be used alone or in combination.
In addition, in this manual, (methyl) acrylate is meant acrylate and/or methacrylate.
Make (a) and (c) in the multipolymer that copolymerization obtains, when the total mole number of the constituent that will constitute described multipolymer is made as 100 moles of %, calculate with mole %, the ratio from (a) and the constituent of (c) deriving preferably is in the following scope respectively.
The structural unit of deriving from (a); 2～40 moles of %
The structural unit of deriving from (c); 60～98 moles of %
In addition, if the ratio of described constituent is in the following scope, then more preferably.
The structural unit of deriving from (a); 5～35 moles of %
The structural unit of deriving from (c); 65～95 moles of %
If described component ratio is in above-mentioned scope, then has the trend that bin stability, development, solvent resistance improve.
Described resin (A1) with alkali dissolution but reference example reaches the citing document of putting down in writing as the method for record in document " experimental method of Polymer Synthesizing " (the big grand row work sale room in Tianjin (strain) chemistry is with the 1st edition the 1st printing distribution on March 1st, 1972 of people) in the document wait and make.
Particularly, can be illustrated in the unit (a) of the formation multipolymer that adds polymerization initiator, solvent and ormal weight in the reaction vessel and (c) etc., by utilizing the nitrogen replace oxygen, under the non-existent condition of oxygen, stir, the method for heating, insulation.Wherein, polymerization initiator and solvent etc. as used herein are not particularly limited, can use normally used in the field any polymerization initiator and solvent.For example, can use polymerization initiator described later and solvent etc.
In addition, the multipolymer that obtains can directly use reacted solution, also can use concentrate or dilution after solution, the multipolymer that also can use methods such as utilization precipitates again to take out as solid (powder).Especially by using solvent described later (D) as solvent when its polymerization, and reacted solution can be directly used, thereby manufacturing process (below, in resin (A2), too) can be simplified.
The weight-average molecular weight of the polystyrene conversion of described resin (A1) with alkali dissolution is preferably 3,000～100, and 000, more preferably 5,000～50,000.If having the weight-average molecular weight of the resin (A1) of alkali dissolution is in the described scope, then has the trend that coating improves, in addition, also have be difficult for that when developing the film attenuate takes place so that when developing the good trend of stripping off property of non-pixel portion, so preferred.
Molecular weight distribution [weight-average molecular weight (Mw)/number-average molecular weight (Mn)] with resin (A1) of alkali dissolution is preferably 1.1～6.0, and more preferably 1.2～4.0.If molecular weight distribution in described scope, then has the outstanding trend of development, so preferred.
Solid constituent in the relative photosensitive polymer combination, the amount of the resin with alkali dissolution (A1) that can use in photosensitive polymer combination of the present invention calculates with mass fraction (factor) and is preferably 5～90 quality %, more preferably 10～70 quality %.If the amount of resin (A1) with alkali dissolution is in described scope, then the dissolubility in developer solution is abundant, on the substrate of non-pixel portion, be difficult to produce the development residue, in addition, when developing, be difficult to take place the film attenuate of the pixel portion of exposure portion, so the good trend of deciduous with non-exposed portion is preferred.
As having alkali dissolution and at light and pine for having reactive resin (A2) under at least one side's the effect, can enumerating
Resin (A2-1): (a) with (c) with the multipolymer of compound (b) (below be sometimes referred to as " (b) ") with cyclic ether structure of carbon number 2～4,
Resin (A2-2): make (a) and multipolymer (c) with (b) reaction obtain multipolymer,
Resin (A2-3): (a) with (b) multipolymer etc.
(b) be compound, be meant polymerizable compound with at least a kind of group from epoxy radicals, oxetanyl (oxetanyl) and tetrahydrofuran base, selecting with cyclic ether structure of carbon number 2～4.(b) be preferably cyclic ether structure with carbon number 2～4 and compound, more preferably have the cyclic ether structure of carbon number 2～4 and have acryloyl group or the compound of methacryl with ethene carbon-to-carbon unsaturated bond.
As (b), for example can enumerate monomer (b1) with epoxy radicals (below be sometimes referred to as " b1 "), have oxetanyl monomer (b2) (below be sometimes referred to as " b2 "), have the monomer of tetrahydrofuran base etc.
(b1) be meant polymerizable compound with at least a kind of group for example from aliphatic epoxy base and ester ring type epoxy radicals, selecting.This monomer with epoxy radicals is preferably has at least a kind of group selecting and the compound with ethene carbon-to-carbon unsaturated bond from aliphatic epoxy base and ester ring type epoxy radicals, more preferably have at least a kind of structure selecting and have acryloyl group or the compound of methacryl from aliphatic epoxy base and ester ring type epoxy radicals.
At this, the aliphatic epoxy base is meant oxirane (oxiranyl) base of strand, and the ester ring type epoxy radicals is meant the group of the structure that ring with ester ring type hydrocarbon and oxirane (oxirane) cyclic condensation form.
As having the aliphatic epoxy base and having the compound of ethene carbon-to-carbon double bond in (b1) of (A2), can specifically enumerate diglycidyl (methyl) acrylate, Beta-methyl diglycidyl (methyl) acrylate, β-ethyl diglycidyl (methyl) acrylate, diglycidyl vinyl ether, open compound of representing by following formula of putting down in writing in the flat 7-248625 communique etc. the spy.
(in the formula, R 11And R 13Be the alkyl of hydrogen atom or carbon number 1～10 independently respectively, m is 1～5 integer.)。
As the compound of representing by described formula, for example can enumerate adjacent vinyl benzyl glycidol ether, between the vinyl benzyl glycidol ether, to the vinyl benzyl glycidol ether, Alpha-Methyl-adjacent vinyl benzyl glycidol ether, an Alpha-Methyl-vinyl benzyl glycidol ether, Alpha-Methyl-to the vinyl benzyl glycidol ether, 2,3-2-glycidyl oxygen ylmethyl styrene, 2,4-2-glycidyl oxygen ylmethyl styrene, 2,5-2-glycidyl oxygen ylmethyl styrene, 2,6-2-glycidyl oxygen ylmethyl styrene, 2,3,4-three-glycidyl oxygen ylmethyl styrene, 2,3,5-three-glycidyl oxygen ylmethyl styrene, 2,3,6-three-glycidyl oxygen ylmethyl styrene, 3,4,5-three-glycidyl oxygen ylmethyl styrene, 2,4,6-three-glycidyl oxygen ylmethyl styrene etc.
As having the ester ring type epoxy radicals and having the compound of ethene carbon-to-carbon double bond in (b1) of (A2), can enumerate vinyl cyclohexene monoxide 1,2-epoxy radicals-4-vinyl cyclohexane (Celloxide2000 for example; Daicel chemical industry (strain) system), acrylic acid 3,4-epoxy radicals cyclohexyl methyl ester (CyclomerA400 for example; Daicel chemical industry (strain) system), methacrylic acid 3,4-epoxy radicals cyclohexyl methyl ester (CyclomerM100 for example; Daicel chemical industry (strain) system) or from compound reach at least a kind of compound selecting the compound of representing by formula (II) by formula (I) expression.
Figure G200910221745XD00081
[in formula (I) and formula (II), R and R ' represent hydrogen atom respectively or the alkyl of the carbon number 1～4 that can be replaced by hydroxyl independently.
X and X ' represent singly-bound, C respectively independently 1～6Alkylidene, oxygen base-C 1～6Alkylidene, sulfenyl-C 1-6Alkylidene, amino-C 1-6Alkylidene, C 1～6Alkylidene-oxygen base, C 1～6Alkylidene-sulfenyl or C 1～6Alkylidene-amino.]
As alkyl, can specifically enumerate methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group etc.
As hydroxy alkyl, can enumerate hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxyl n-pro-pyl, 2-hydroxyl n-pro-pyl, 3-hydroxyl n-pro-pyl, 1-hydroxyl isopropyl, 2-hydroxyl isopropyl, 1-hydroxyl normal-butyl, 2-hydroxyl normal-butyl, 3-hydroxyl normal-butyl, 4-hydroxyl normal-butyl etc.
As substituent R and R ', can preferably enumerate hydrogen atom, methyl, methylol, 1-hydroxyethyl, 2-hydroxyethyl, can more preferably enumerate hydrogen atom, methyl.
As alkylidene, can enumerate methylene, ethylidene, propylidene etc.
As oxyalkylene, can enumerate oxygen methylene, oxygen ethylidene, oxygen propylidene etc.
As alkylene oxide group, can enumerate inferior methoxyl, inferior ethoxyl, inferior propoxyl group etc.
As the sulphur alkylidene, can enumerate sulphur methylene, sulphur ethylidene, sulphur propylidene etc.
As the alkylidene sulfenyl, can enumerate methylene sulfenyl, ethylidene sulfenyl, propylidene sulfenyl etc.
As amino alkylidenyl, can enumerate aminomethylene, amino ethylidene, amino propylidene etc.
As alkylidene amino, can enumerate methene amido, ethyleneimino, propylidene amino etc.
As substituent X and X ', can preferably enumerate singly-bound, methylene, ethylidene, oxygen methylene, oxygen ethylidene, can more preferably enumerate singly-bound, oxygen ethylidene.
As compound, can enumerate by the compound of formula (I-1)～formula (I-15) expression etc. by formula (I) expression.Can preferably enumerate formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9), formula (I-11)～formula (I-15).Can more preferably enumerate formula (I-1), formula (I-7), formula (I-9), formula (I-15).
Figure G200910221745XD00091
As compound, can enumerate by the compound of formula (II-1)～formula (II-15) expression etc. by formula (II) expression.Can preferably enumerate formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9), formula (II-11)～formula (II-15).Can more preferably enumerate formula (II-1), formula (II-7), formula (II-9), formula (II-15).
Figure G200910221745XD00101
Reach at least a kind of compound selecting the compound of representing by formula (II) from compound and can distinguish use separately by formula (I) expression.In addition, they can be with ratio mixing arbitrarily.Under the situation of mixing, its mixture ratio calculates preferred formula (I) with mol ratio: formula (II) is 5: 95～95: 5, more preferably 10: 90～90: 10, and then be preferably 20: 80～80: 20.
As multipolymer (A2-1) and the having oxetanyl and have the compound of unsaturated link of (b2) (A2-2), for example can enumerate 3-methyl-3-methacryloxy methyl oxetanes, 3-methyl-3-acryloyl-oxy ylmethyl oxetanes, 3-ethyl-3-methacryloxy methyl oxetanes, 3-ethyl-3-acryloyl-oxy ylmethyl oxetanes, 3-methyl-3-methacryloxyethyl oxetanes, 3-methyl-3-acryloxy ethyl oxetanes, 3-ethyl-3-methacryloxyethyl oxetanes, 3-ethyl-3-acryloxy ethyl oxetanes etc.
In multipolymer (A2-1), constitute the total mole number of the constituent of multipolymer (A2-1) relatively, the ratio of the constituent of deriving from each composition calculates with mole fraction and preferably is in the following scope.
The structural unit of deriving from (a); 2～40 moles of %
The structural unit of deriving from (c); 1～65 mole of %
From (b1) or the structural unit of (b2) deriving; 2～95 moles of %
In addition, if the ratio of described constituent is in the following scope, then more preferably.
The structural unit of deriving from (a); 5～35 moles of %
The structural unit of deriving from (c); 1～60 mole of %
From (b1) or the structural unit of (b2) deriving; 5～80 moles of %
If described component ratio is in above-mentioned scope, then has the trend that bin stability, development, solvent resistance, thermotolerance and physical strength improve.
Described resin (A2-1) with alkali dissolution but reference example reaches the citing document of putting down in writing as the method for record in document " experimental method of Polymer Synthesizing " (the big grand row work sale room in Tianjin (strain) chemistry is with the 1st edition the 1st printing distribution on March 1st, 1972 of people) in the document wait and make.
Particularly, can enumerate the unit (a), (c) that add deriving of polymerization initiator, solvent and ormal weight and constitute multipolymer in reaction vessel reaches (b1) or compound (b2), by utilizing the nitrogen replace oxygen, under the non-existent condition of oxygen, the method that stirs, heats, is incubated.
Resin (A2-2) for example can be through the operation manufacturing in two stages.In this case, also can be with reference to the method for in above-mentioned document " experimental method of Polymer Synthesizing " (the grand row work sale room in big Tianjin (strain) chemistry is with the 1st edition the 1st printing distribution on March 1st, 1972 of people), putting down in writing, open the method for putting down in writing in the 2001-89533 communique the spy and wait and make.
At first,, similarly carry out, obtain multipolymer (that is the resin that, has alkali-soluble) with the manufacture method of the above-mentioned resin with alkali dissolution (A1) as the phase one.
In this case, can similarly then use with above-mentioned with various forms.In addition, can be suitable for the weight-average molecular weight and the molecular weight distribution [weight-average molecular weight (Mw)/number-average molecular weight (Mn)] of polystyrene conversion same as described above.
Wherein, constitute the total mole number of the constituent of described multipolymer relatively, calculate with mole fraction from the ratio of (a) and the constituent of (c) deriving respectively and preferably be in the following scope.
The structural unit of deriving from (a); 5～50 moles of %
The structural unit of deriving from (c); 50～95 moles of %
In addition, if the ratio of described constituent is in the following scope, then more preferably.
The structural unit of deriving from (a); 10～45 moles of %
The structural unit of deriving from (c); 55～90 moles of %
Then, as subordinate phase, a part that makes the carboxylic acid of (a) that derive from the multipolymer that obtains and carboxylic acid anhydrides with derive from described (b1) or epoxy radicals (b2) or oxetanes radical reaction.
Particularly, then atmosphere in the flask is replaced as air from nitrogen after above-mentioned steps, the molal quantity that adds relative constituent (a) in flask is the constituent (b1) of 5～80 moles of % or (b2); For example relatively the total amount of monomer (a)～(c) is calculated as 0.001～5% three dimethylamino methyl phenol as the catalysts of carboxyl and epoxy radicals or oxetanyl with quality standard; And for example relatively the total amount of monomer (a)～(c) was calculated as 0.001～5% the quinhydrones as polymerization inhibitor with quality standard, 60～130 ℃ of following sustained responses 1～10 hour.Like this, can obtain resin (A2-2).In addition, can similarly consider manufacturing equipment with polymerizing condition or wait by the calorie value that polymerization produces and suitably to adjust adding method or temperature of reaction.
In addition, in this case, (b1) or the relative molal quantity of (a) of molal quantity (b2), be preferably 10～75 moles of %, more preferably 15～70 moles of %.By in this scope, can have the trend that the balance of bin stability, development, solvent resistance, thermotolerance, physical strength and light sensitivity improves.
In resin (A2-3), constitute the total mole number of the constituent of alkali soluble resin (A2-3) relatively, the ratio of the constituent of deriving from each composition calculates with mole fraction and preferably is in the following scope.
The structural unit of deriving from (a); 5～95 moles of %
From (b1) or the structural unit of (b2) deriving; 5～95 moles of %
In addition, if the ratio of described constituent is in the following scope, then more preferably.
The structural unit of deriving from (a); 10～90 moles of %
From (b1) or the structural unit of (b2) deriving; 10～90 moles of %
If described component ratio is in above-mentioned scope, then has the trend that bin stability, development, solvent resistance, thermotolerance and physical strength improve.
Resin (A2-3) but reference example reaches the citing document of putting down in writing as the method for record in document " experimental method of Polymer Synthesizing " (the grand row work sale room of big Feng (strain) chemistry is with the 1st edition the 1st printing distribution on March 1st, 1972 of people) in the document wait and make.
Particularly, the unit (a) that derives the formation multipolymer that adds polymerization initiator, solvent and ormal weight in reaction vessel reaches (b1) or compound (b2), by utilizing the nitrogen replace oxygen, under the non-existent condition of oxygen, stir, heat, be incubated, obtain multipolymer thus.In addition, the multipolymer that obtains can directly use reacted solution, also can use concentrate or dilution after solution, the multipolymer that also can use methods such as utilization precipitates again to take out as solid (powder).
The polymerizable compound that contains in photosensitive polymer combination of the present invention (B) then is not particularly limited as long as have polymerism, but the polyfunctional monomer that for example illustration monofunctional monomer, 2 functional monomers, 3 officials can be above etc.
As monofunctional monomer, can enumerate (methyl) acrylate such as nonyl phenyl carbitol (methyl) acrylate, (methyl) acrylic acid 2-hydroxyl-3-phenoxy propyl ester, 2-ethylhexyl carbitol (methyl) acrylate, (methyl) acrylic acid 2-(2-ethoxy ethoxy) ethyl ester, caprolactone (methyl) acrylate, ethoxyquin nonyl phenol (methyl) acrylate, propoxylation nonyl phenol (methyl) acrylate;
Styrene, α-, adjacent-,-, p-methylstyrene, to methoxy styrene, to phenylethylenes such as tert-butoxy styrene, 1-chloro-4-methyl-benzenes;
Butadiene, 2, dienes such as 3-dimethyl butadiene, isoprene;
(methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) 2-ethylhexyl acrylate, (methyl) acrylic acid Lauryl Ester, (methyl) dodecylacrylate, (methyl) stearyl acrylate base ester, (methyl) acrylic acid two cyclopentyl esters, (methyl) isobornyl acrylate, (methyl) cyclohexyl acrylate, (methyl) acrylic acid 2-methyl cyclohexane ester, (methyl) acrylic acid two cyclohexyls, (methyl) acrylic acid adamantane esters, (methyl) acrylic acid allyl ester, (methyl) acrylic acid propargyl (プ ロ バ ギ Le) ester, (methyl) phenyl acrylate, (methyl) acrylic acid naphthalene ester, (methyl) acrylic acid anthryl (anthracenyl) ester, (methyl) acrylic acid ring pentyl ester, (methyl) acrylic acid furyl (furyl) ester, (methyl) acrylic acid tetrahydrofuran base ester, (methyl) acrylic acid pyranose (pyranyl) ester, (methyl) benzyl acrylate, (methyl) acrylic acid phenacyl (phenacyl) ester, (methyl) acrylic acid tolyl ester, (methyl) acrylic acid 1,1,1-trifluoroethyl ester, (methyl) acrylic acid perfluor ethyl ester, (methyl) acrylic acid perfluor n-pro-pyl ester, (methyl) acrylic acid perfluor isopropyl esters, (methyl) acrylic acid trityl group ester, (methyl) acrylic acid adamantane esters, (methyl) alkyl acrylates such as (methyl) acrylic acid cumyl ester, (methyl) acrylic acid cycloalkyl ester or (methyl) acrylic acid aryl ester;
(methyl) acrylic acid hydroxyalkyl acrylates such as (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) acrylic acid 2-hydroxypropyl acrylate;
(methyl) propylene-acid amides ,-N, the N-dimethylformamide ,-N, (methyl) acrylamides such as N-propyl amides;
Vinyl compounds such as (methyl) acryloyl aniline, (methyl) vinyl cyanide, acryl aldehyde, vinyl chloride, vinylidene chloride, N-vinyl pyrrolidone, vinyl acetate;
Unsaturated dicarboxylic diester such as diethyl maleate, DEF, diethyl itaconate;
Diglycidyl (methyl) acrylate, α-ethyl diglycidyl (methyl) acrylate, α-n-pro-pyl diglycidyl (methyl) acrylate, α-normal-butyl diglycidyl (methyl) acrylate, (methyl) acrylic acid 3,4-epoxy radicals butyl ester, (methyl) acrylic acid 3,4-epoxy radicals heptyl ester, (methyl) acrylic acid α-ethyl-6, glycidyl compounds such as 7-epoxy radicals heptyl ester, allyl glycidyl ether, vinyl glycidyl ether etc.
Concrete example as 2 functional monomers, can enumerate 1,3-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, polyglycol two (methyl) acrylate, two (acryloxy ethyl) ethers of bisphenol-A, ethoxylation bisphenol-A two (methyl) acrylate, ethoxylated neopentylglycol two (methyl) acrylate, ethoxylation neopentyl glycol two (methyl) acrylate, 3-methyl pentanediol two (methyl) acrylate etc.
As the above polyfunctional monomer of 3 officials energy, can enumerate trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) acrylate, three (2-hydroxyethyl) chlorinated isocyanurates 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) chlorinated isocyanurates 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 of caprolactone modification tripentaerythritol seven (methyl) acrylate and acid anhydrides etc.Wherein, preferably use the above monomer of 2 officials energy.
The total amount of relative resin (A) and polymerizable compound (B), the amount of polymerizable compound (B) are calculated with mass fraction and are preferably 1～70 quality %, more preferably 5～60 quality %.If the amount of polymerizable compound (B) is in the described scope, then has light sensitivity or film and trend that the intensity of pattern or flatness, reliability, physical strength improve, so preferred.
As the polymerization initiator that in photosensitive polymer combination of the present invention, contains (C), so long as under the effect of light or heat the compound of initiated polymerization, then be not particularly limited, can use known polymerization initiator.
As polymerization initiator (C), for example preferred di-imidazole compound, acetophenone based compound, triazine based compound, acyl group phosphine oxygen based compound, oxime compound.In addition, also can use the spy and open the light put down in writing in the 2008-181087 communique and/or hot cationic polymerization initiators (for example by (onium) kation with derive from the polymerization initiator that lewis acidic negative ion constitutes).Wherein, the di-imidazole compound since light sensitivity remarkably and more preferably.
As described di-imidazolium compounds, can enumerate 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl di-imidazoles, 2,2 '-two (2, the 3-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl di-imidazoles (for example with reference to the spy open flat 6-75372 communique, the spy opens flat 6-75373 communique etc.), 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl di-imidazoles, 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-four (alkoxyl phenyl) di-imidazoles, 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-four (dialkoxy phenyl) di-imidazoles, 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-four (tri-alkoxy phenyl) di-imidazoles (is for example opened clear 62-174204 communique etc. with reference to special public clear 48-38403 communique, spy.), the phenyl of 4,4 ', 5,5 '-position replaces the di-imidazolium compounds form by carbonyl alkoxy (calboalcoxy) and (for example opens flat 7-10913 communique etc. with reference to the spy.) etc.Can preferably enumerate 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl di-imidazoles, 2,2 '-two (2, the 3-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl di-imidazoles, 2,2 '-two (2, the 4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl di-imidazoles.
As described acetophenone based compound; can enumerate the diethoxy acetophenone; 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone; benzyl dimethyl ketal; 2-hydroxyl-1-[4-(2-hydroxyl-oxethyl) phenyl]-2-methylpropane-1-ketone; 2-hydroxyl-1-{4-[4-(2-hydroxy-2-methyl-propiono)-benzyl]-phenyl }-2-methyl-propane-1-ketone; 1-hydroxy-cyclohexyl phenyl ketone; 2-methyl isophthalic acid-(4-methyl thio-phenyl)-2-morpholino propane-1-ketone; 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl) butane-1-ketone; 2-(2-methyl-benzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone; 2-(3-methyl-benzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone; 2-(4-methyl-benzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone; 2-(2-Ethylbenzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone; 2-(2-propyl group benzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone; 2-(2-butyl benzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone; 2-(2; the 3-dimethyl benzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone; 2-(2, the 4-dimethyl benzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone; 2-(2-benzyl chloride base)-2-dimethylamino-1-(4-morpholino phenyl)-butanone; 2-(2-bromobenzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone; 2-(3-benzyl chloride base)-2-dimethylamino-1-(4-morpholino phenyl)-butanone; 2-(4-benzyl chloride base)-2-dimethylamino-1-(4-morpholino phenyl)-butanone; 2-(3-bromobenzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone; 2-(4-bromobenzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone; 2-(2-methoxy-benzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone; 2-(3-methoxy-benzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone; 2-(4-methoxy-benzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone; 2-(2-methyl-4-methoxy-benzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone; 2-(2-methyl-4-bromobenzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone; 2-(2-bromo-4-methoxy-benzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone; 2-hydroxy-2-methyl-1-[4-(1-methyl ethylene) phenyl] oligomer etc. of propane-1-ketone.
As described triazine based compound, can enumerate 2, two (the trichloromethyl)-6-(4-methoxyphenyl)-1 of 4-, 3, the 5-triazine, 2, two (the trichloromethyl)-6-(4-methoxyl naphthyl)-1 of 4-, 3, the 5-triazine, 2, two (the trichloromethyl)-6-piperonyls (piperonyl)-1 of 4-, 3, the 5-triazine, 2, two (the trichloromethyl)-6-(4-methoxyl-styrene)-1,3 of 4-, the 5-triazine, 2, two (trichloromethyl)-6-[2-(5-methylfuran-2-yl) vinyl (ethenyl) of 4-]-1,3,5-triazines, 2, two (trichloromethyl)-6-[2-(furans-2-yl) vinyl of 4-]-1,3, the 5-triazine, 2, two (trichloromethyl)-6-[2-(4-diethylamino-2-aminomethyl phenyl) vinyl of 4-]-1,3, the 5-triazine, 2, two (trichloromethyl)-6-[2-(3, the 4-Dimethoxyphenyl) vinyl of 4-]-1,3,5-triazine etc.
As described acyl group phosphine oxygen series initiators, can enumerate 2,4,6-trimethylbenzoyl diphenyl phosphine oxygen etc.
As described oxime compound, can enumerate O-carbethoxyl group-α-oxygen base imino group-1-phenyl-propane-1-ketone, by the compound of formula (III) expression, by the compound of formula (IV) expression etc.
Figure G200910221745XD00171
In addition, also preferably use polymerization to cause auxiliary agent (C-1) with described polymerization initiator (C).Cause auxiliary agent (C-1) as polymerization, can enumerate compound by formula (V) expression.
Figure G200910221745XD00181
[in the formula (V), the dotted line of being represented by X is represented the aromatic rings of the carbon number 6～12 that can be replaced by halogen atom.
Y represents oxygen atom, sulphur atom.
R 1The alkyl of expression carbon number 1～6.
R 2The alkyl of the carbon number 1～12 that expression can be replaced by halogen atom or the aryl that can be replaced by halogen atom.]
As halogen atom, can enumerate fluorine atom, chlorine atom, bromine atoms etc.
As the aromatic rings of carbon number 6～12, can enumerate phenyl ring, naphthalene nucleus etc.
As the aromatic rings of the carbon number 6～12 that can be replaced by halogen atom, can enumerate phenyl ring, methyl phenyl ring, dimethyl phenyl ring, ethyl phenyl ring, propyl group phenyl ring, butyl phenyl ring, amyl group phenyl ring, hexyl phenyl ring, cyclohexyl phenyl ring, chlorobenzene ring, dichloro phenyl ring, bromobenzene ring, dibromo phenyl ring, phenyl phenyl ring, chlorphenyl phenyl ring, bromophenyl phenyl ring, naphthalene nucleus, chloronaphthalene ring, bromonaphthalene ring etc.
Alkyl as carbon number 1～6, can enumerate methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, 1-methyl n-pro-pyl, 2-methyl n-pro-pyl, the tert-butyl group, n-pentyl, 1-methyl normal-butyl, 2-methyl normal-butyl, 3-methyl normal-butyl, 1,1-dimethyl n propyl group, 1,2-dimethyl n propyl group, 2,2-dimethyl n propyl group, n-hexyl, cyclohexyl etc.
Alkyl as the carbon number 1～12 that can be replaced by halogen atom, can enumerate methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, 1-methyl n-pro-pyl, 2-methyl n-pro-pyl, the tert-butyl group, n-pentyl, 1-methyl normal-butyl, 2-methyl normal-butyl, 3-methyl normal-butyl, 1,1-dimethyl n propyl group, 1,2-dimethyl n propyl group, 2,2-dimethyl n propyl group, n-hexyl, cyclohexyl, 1-chloro-n-butyl, 2-chloro-n-butyl, 3-chloro-n-butyl etc.
As the aryl that can be replaced by halogen atom, can enumerate phenyl, chlorphenyl, dichlorophenyl, bromophenyl, dibromo phenyl, chloro-bromobenzene base, xenyl, chlorodiphenyl, DCBP base, bromophenyl, dibromo phenyl, naphthyl, chloronaphthyl, methylnaphthyl, dichloro naphthyl, bromonaphthalene base, dibromo naphthyl etc.
In addition, in this manual, in any chemical structural formula, though because of the carbon number difference is different, unless otherwise specified, all applicable above-mentioned illustration of each substituting group.In addition, the either party in all available straight or branched.
As compound, can specifically enumerate by formula (V) expression
2-benzoyl methylene-3-methyl-naphthalene [2,1-d] thiazoline,
2-benzoyl methylene-3-methyl-naphthalene [1,2-d] thiazoline,
2-benzoyl methylene-3-methyl-naphthalene [2,3-d] thiazoline,
2-(2-naphthoyl methylene)-3-methylbenzothiazole quinoline,
2-(1-naphthoyl methylene)-3-methylbenzothiazole quinoline,
2-(2-naphthoyl methylene)-3-methyl-5-phenyl benzothiazole quinoline,
2-(1-naphthoyl methylene)-3-methyl-5-phenyl benzothiazole quinoline,
2-(2-naphthoyl methylene)-3-methyl-5-fluoro benzothiazole quinoline,
2-(1-naphthoyl methylene)-3-methyl-5-fluoro benzothiazole quinoline,
2-(2-naphthoyl methylene)-3-methyl-5-chloro benzothiazole quinoline,
2-(1-naphthoyl methylene)-3-methyl-5-chloro benzothiazole quinoline,
2-(2-naphthoyl methylene)-3-methyl-5-bromo benzothiazole quinoline,
2-(1-naphthoyl methylene)-3-methyl-5-bromo benzothiazole quinoline,
2-(4-dibenzoyl base (biphenoyl) methylene)-3-methylbenzothiazole quinoline,
2-(4-dibenzoyl methylene)-3-methyl-5 phenyl benzothiazole quinoline,
2-(2-naphthoyl methylene)-3-methyl-naphthalene [2,1-d] thiazoline,
2-(2-naphthoyl methylene)-3-methyl-naphthalene [1,2-d] thiazoline,
2-(4-dibenzoyl methylene)-3-methyl-naphthalene [2,1-d] thiazoline,
2-(4-dibenzoyl methylene)-3-methyl-naphthalene [1,2-d] thiazoline,
2-(to the fluorobenzoyl methylene)-3-methyl-naphthalene [2,1-d] thiazoline,
2-(to the fluorobenzoyl methylene)-3-methyl-naphthalene [1,2-d] thiazoline,
2-benzoyl methylene-3-methyl-naphthalene [2,1-d] oxazoline,
2-benzoyl methylene-3-methyl-naphthalene [1,2-d] oxazoline,
2-benzoyl methylene-3-methyl-naphthalene [2,3-d] oxazoline,
2-(2-naphthoyl methylene)-3-Jia base benzoxazole quinoline,
2-(1-naphthoyl methylene)-3-Jia base benzoxazole quinoline,
2-(2-naphthoyl methylene)-3-methyl-5-Ben base benzoxazole quinoline,
2-(1-naphthoyl methylene)-3-methyl-5-Ben base benzoxazole quinoline,
2-(2-naphthoyl methylene)-3-methyl-5-Fu benzoxazole quinoline,
2-(1-naphthoyl methylene)-3-methyl-5-Fu benzoxazole quinoline,
2-(2-naphthoyl methylene)-3-methyl-5-chloro benzoxazole quinoline,
2-(1-naphthoyl methylene)-3-methyl-5-chloro benzoxazole quinoline,
2-(2-naphthoyl methylene)-3-methyl-5-bromoxynil oxazoline quinoline,
2-(1-naphthoyl methylene)-3-methyl-5-bromoxynil oxazoline quinoline,
2-(4-dibenzoyl methylene)-3-Jia base benzoxazole quinoline,
2-(4-dibenzoyl methylene)-3-methyl-5-Ben base benzoxazole quinoline,
2-(2-naphthoyl methylene)-3-methyl-naphthalene [2,1-d] oxazoline,
2-(2-naphthoyl methylene)-3-methyl-naphthalene [1,2-d] oxazoline,
2-(4-dibenzoyl methylene)-3-methyl-naphthalene [2,1-d] oxazoline,
2-(4-dibenzoyl methylene)-3-methyl-naphthalene [1,2-d] oxazoline,
2-(to the fluorobenzoyl methylene)-3-methyl-naphthalene [2,1-d] oxazoline,
2-(to the fluorobenzoyl methylene)-3-methyl-naphthalene [1,2-d] oxazoline etc.
Wherein, can preferably enumerate by 2-(2-naphthoyl the methylene)-3-methylbenzothiazole quinoline of formula (V-1) expression, by the 2-benzoyl methylene-3-methyl-naphthalene [1 of formula (V-2) expression; 2-d] thiazoline, by 2-(4-dibenzoyl methylene)-3-methyl-naphthalene [1,2-d] thiazoline of formula (V-3) expression.
Figure G200910221745XD00201
By using these compounds, can make the photosensitive polymer combination that obtains become more ISO.The photosensitive polymer combination that obtains by use forms and films or pattern, can make to film or the throughput rate of pattern improves, thereby preferred.Heat in the time of can not curing (postbake) because of after filming by the compound of formula (V) expression distils, thus light and heat at least arbitrarily-transparency of fading under the effect of side improves, so preferably.
In addition, cause auxiliary agent (C-1), also can use the compound of at least a kind of expression from formula (VI) and formula (VII), selecting as polymerization.
Figure G200910221745XD00211
[in formula (VI) and the formula (VII), ring X 1And ring X 2The aromatic rings or the heterocycle of the expression carbon number 6～12 that can be replaced by halogen atom independently respectively.Y 1And Y 2Expression oxygen atom or sulphur atom.R 1And R 2The alkyl of expression carbon number 1～12 or the aryl of carbon number 6～12.These alkyl and aryl can be replaced by the alkoxy of halogen atom, hydroxyl or carbon number 1～6.]
As the aromatic rings or the heterocycle that can be replaced by halogen atom, can enumerate phenyl ring, methyl phenyl ring, dimethyl phenyl ring, ethyl phenyl ring, propyl group phenyl ring, butyl phenyl ring, amyl group phenyl ring, hexyl phenyl ring, cyclohexyl phenyl ring, chlorobenzene ring, dichloro phenyl ring, bromobenzene ring, dibromo phenyl ring, phenyl phenyl ring, chlorphenyl phenyl ring, bromophenyl phenyl ring, naphthalene nucleus, chloronaphthalene ring, bromonaphthalene ring, phenanthrene ring, bend (chrysene) ring, fluoranthene ring, benzo [a] pyrene ring, benzo (e) pyrene ring, perylene (perylene) encircles and their derivant etc.
As the hydroxyl substituted alkyl, can enumerate methylol, hydroxyethyl, hydroxypropyl, hydroxyl butyl etc.
As the hydroxyl substituted aryl, can enumerate hydroxy phenyl, hydroxyl naphthyl etc.
As the alkoxy substituted alkyl, can enumerate methoxy, methoxy ethyl, methoxy-propyl, methoxyl butyl, butoxymethyl, ethoxyethyl group, ethoxycarbonyl propyl, propoxyl group butyl etc.
As the alkoxy substituted aryl, can enumerate methoxyphenyl, ethoxy naphthyl etc.
Compound by formula (VI) and formula (VII) expression can specifically be enumerated:
Dialkoxy naphthalene classes such as dimethoxy-naphthalene, diethoxy naphthalene, dipropoxy naphthalene, diisopropoxy naphthalene, dibutoxy naphthalene;
Dialkoxy anthracene classes such as dimethoxy anthracene, diethoxy anthracene, dipropoxy anthracene, diisopropoxy anthracene, dibutoxy anthracene two amoxy anthracenes, two own oxygen base anthracenes, methoxy ethoxy anthracene, methoxy propoxy anthracene, methoxyl isopropoxy anthracene, methoxyl butoxy anthracene, ethoxy propoxyl group anthracene, ethoxy isopropoxy anthracene, ethoxy butoxy anthracene, propoxyl group isopropoxy anthracene, propoxyl group butoxy anthracene, isopropoxy butoxy anthracene;
Dialkoxy naphthonaphthalene classes such as dimethoxy naphtho-naphthalene, diethoxy naphthonaphthalene, dipropoxy naphthonaphthalene, diisopropoxy naphthonaphthalene, dibutoxy naphthonaphthalene etc.
In addition, as above-mentioned polymerization initiator (C), also can use Photoepolymerizationinitiater initiater.
As Photoepolymerizationinitiater initiater, for example can enumerate benzoin based compound, benzophenone based compound, thioxanthones based compound, anthracene based compound etc.
As the benzoin based compound, for example can enumerate benzoin, benzoin methylether, benzoin ethyl ether, benzoin iso-propylether, benzoin isobutyl ether etc.
As described benzophenone based compound; for example can enumerate benzophenone, adjacent benzophenone methyl formate, 4-phenyl benzophenone, 4-benzoyl-4 '-methyldiphenyl base sulfide, 3; 3 '; 4; 4 '-four (tert-butyl hydroperoxide carbonyl) benzophenone, 2; 4,6-tri-methyl benzophenone etc.
As described thioxanthones based compound, for example can enumerate 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-two clopenthixal ketones, 1-chloro-4-propoxyl group thioxanthones etc.
As described anthracene based compound, for example can enumerate 9,10-dimethoxy anthracene, 2-ethyl-9,10-dimethoxy anthracene, 9,10-diethoxy anthracene, 2-ethyl-9,10-diethoxy anthracene etc.
And then, also can use 10-butyl-2-chloro-acridine ketone, 2-EAQ, dibenzoyl, 9,10-phenanthrenequione, camphorquinone, phenyl glyoxalic acid methylester, luxuriant titanium (titanocene) compound etc. are as Photoepolymerizationinitiater initiater.
As Photoepolymerizationinitiater initiater, also can use the spy and show the Photoepolymerizationinitiater initiater put down in writing in the 2002-544205 communique with group that chain transfer can take place.
As described Photoepolymerizationinitiater initiater, for example can enumerate the Photoepolymerizationinitiater initiater of following formula (1)～(6) with group that chain transfer can take place.
Figure G200910221745XD00231
Described Photoepolymerizationinitiater initiater with group that chain transfer can take place also can be used as the composition that constitutes resin (A) and uses.
In addition, preferably with described polymerization initiator-playing the use polymerization causes auxiliary agent (C-2).
Cause auxiliary agent (C-2) as polymerization, can enumerate amines and carboxylic acid compound etc.
As amines, can enumerate triethanolamine, first for fatty amine compounds such as diethanolamine, triisopropanolamines, 4-dimethylamino methyl benzoate, 4-dimethylamino ethyl benzoate, 4-dimethylamino isoamyl benzoate, 4-dimethylamino benzoic acid 2-ethylhexyl, benzoic acid 2-dimethylamino ethyl ester, N, N-dimethyl-p-toluidine, 4, (the common name of 4 '-two (dimethylamino) benzophenone; Michler's keton (Michler ' s ketone)), the aromatic amines compound of 4,4 '-two (diethylin) benzophenone and so on.
As carboxylic acid compound, can enumerate the assorted acetate class of aromatic series such as phenyl thioacetic acid, aminomethyl phenyl thioacetic acid, ethylphenyl thioacetic acid, Methylethyl phenyl thioacetic acid, 3,5-dimethylphenyl thioacetic acid, methoxyphenyl thioacetic acid, Dimethoxyphenyl thioacetic acid, chlorphenyl thioacetic acid, dichlorophenyl thioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthyl thioacetic acid, N-naphthyl glycocoll, naphthoxy acetic acid.
The total amount of relative resin (A) and polymerizable compound (B), the amount of polymerization initiator (C) are calculated with mass fraction and are preferably 0.1～40 quality %, more preferably 1～30 quality %.
If the total amount of polymerization initiator (C) is in this scope, then photosensitive polymer combination becomes ISO, that uses that this photosensitive polymer combination forms films or the intensity of pattern or film or the lip-deep flatness of pattern has the trend that improves, so preferred.
The total amount of relative resin (A) and polymerizable compound (B), polymerization cause auxiliary agent (C-1) and/or use amount (C-2) is preferably 0.01～50 quality %, more preferably 0.1～40 quality % with mass fraction calculating.
If polymerization causes auxiliary agent (C-1) and/or amount (C-2) is in this scope, the light sensitivity of the photosensitive polymer combination that then obtains can further uprise, and uses the throughput rate of the pattern substrate of this photosensitive polymer combination formation to improve, so preferred.
Especially under the situation of using the compound of representing by formula (V), the amount that the relative polymerization of its amount causes auxiliary agent (C-1) is preferably 50 quality %～100 quality %, 60 quality %～100 quality % more preferably, and then be preferably 65 quality %～100 quality %.If the amount by the compound of formula (V) expression is in this scope, when then the photosensitive polymer combination that contains this compound in use formed and films, the transparency of filming improved, so preferred.
In addition, photosensitive polymer combination of the present invention also can further contain multi-functional thiol's compound (T).This multi-functional thiol's compound (T) is for having the compound of 2 above sulfydryls (sulfanyl) base in molecule.Wherein, have more than 2 in use under the situation of compound of the sulfydryl that combines with the carbon atom of aliphatic alkyl more than 2, because the light sensitivity of photosensitive polymer combination of the present invention uprises, so preferred.
As multi-functional thiol's compound (T), can specifically enumerate hexane two mercaptan, decane two mercaptan, 1,4-dimethyl sulfydryl benzene, the two thiopropionates of butylene glycol, the two thioglycolic acid esters of butylene glycol, ethylene glycol bis thioglycolic acid ester, trimethylolpropane tris thioglycolic acid ester, the two thiopropionates of butylene glycol, the trimethylolpropane tris thiopropionate, trimethylolpropane tris thioglycolic acid ester, pentaerythrite tetrathio propionic ester, pentaerythrite tetrathio ethyl glycolate, trihydroxy ethyl three sulfo-propionic esters, pentaerythrite four (3-sulfydryl butyric ester), 1, two (3-sulfydryl butyryl acyloxy) butane of 4-etc.
Relative polymerization initiator (C), the amount of multi-functional thiol's compound (T) calculate with mass fraction and are preferably 0.5～100 quality %, more preferably 1～90 quality %.In addition, the total amount of relative adhesive resin (A) and optical polymerism compound (C), the amount of multi-functional thiol's compound calculates with mass fraction and is preferably 0.1～20 quality %, more preferably 1～10 quality %.If the amount of multi-functional thiol's compound (T) is in this scope, then has the trend that light sensitivity uprises and development property improves, so preferred.
The solvent that in photosensitive polymer combination of the present invention, uses (D) be preferably dissolving resin (A), polymerizable compound (B) and polymerization initiator constituents such as (C) equably and also not with the solvent of each composition reaction.In addition, solvent (D) more preferably contains the both sides' of two specific aklylene glycol dialkyl ethers and specific alcohol solvent at least.Wherein, two aklylene glycol dialkyl ethers and alcohol can be distinguished use separately, also can be also with more than 2 kinds.
As two aklylene glycol dialkyl ethers, for the alkyl with the alkylidene of carbon number 1～3 and carbon number 1～4 contains solvent more than 2 respectively, alkylidene and alkyl are identical or different respectively.
As two such aklylene glycol dialkyl ethers, for example can enumerate diethylene glycol dimethyl ether, diglycol ethylhexyl ether, diethyl carbitol, diglycol di-n-propyl ether, diglycol isopropyl methyl ether, diglycol butyl methyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol ethyl-methyl ether, dipropylene glycol diethyl ether, dipropylene glycol methyl-propyl ether, dipropylene glycol butyl methyl ether, dipropylene glycol ethyl propyl ether, dipropylene glycol butyl ethyl ether, dipropylene glycol butyl propyl ether, dipropylene glycol butyl oxide etc.Wherein, preferred diglycol ethyl-methyl ether.
Relative solvent (D) full dose, two aklylene glycol dialkyl ethers preferably contain 30～90 quality %, more preferably contain 30～80 quality %, and then preferably contain 30～70 quality %.If in this scope, the uneven drying that can suppress to film then.That is, under the situation of dry coating, utilize drying under reduced pressure to make solvent seasoning usually, and owing to have the trend that shortens drying time, so reduce pressure at short notice.At this moment, bumping can take place and become the reason of the generation of uneven drying in solvent, but can prevent the uneven drying of filming effectively by use two aklylene glycol dialkyl ethers in this scope.
As alcohol, the alcohol of preferred carbon number 1～6.This alcohol can be monohydroxy alcohol, also can be the polyvalent alcohol more than 2 yuan.
As such alcohol, can enumerate methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, hexanol, cyclohexanol, propylene glycol monomethyl ether, propylene-glycol ethyl ether, propylene glycol propyl ether, ethylene glycol, glycol monomethyl ether, ethylene glycol monoethyl ether, propyl cellosolve, ethylene glycol monobutyl ether (EGMBE), methyl lactate, ethyl lactate, propyl lactate, 2-methyllactic acid methyl esters, diacetone alcohol, the 3-methoxybutanol, glycerine, the 2 hydroxy propanoic acid ethyl ester, 2-hydroxy-2-methyl methyl propionate, 2-hydroxy-2-methyl ethyl propionate, the 3-hydroxy methyl propionate, 3-hydracrylic acid ethyl ester, 3-hydracrylic acid propyl ester, hydroxy methyl acetate, hydroxyl ethyl acetate, glycolic acid butyl ester etc.Wherein, preferred 3-methoxybutanol.
Solvent (D) total amount preferably contains 10～50 quality % alcohols, and then preferably contains 10～45 quality % alcohols, and then more preferably contains 15～40 quality % alcohols relatively.
By containing alcohol in this scope, can obtain the dissolubility of resin etc. fully, also can be adjusted to suitable viscosity simultaneously, thereby realize the homogeneity of filming that obtains.In addition, even using slit die coating machine to carry out also can preventing the drying of nozzle tip under the situation of coating of photosensitive polymer combination, thereby suppress foreign matter that dry thing causes separate out and prevent reliably the vertical stripe that foreign matter causes.
In addition, as required, also can further and use following solvent.
For example can enumerate ethylene glycol alkyl ether acetate esters such as methyl glycol acetate, ethyl cellosolve acetate, butyl cellosolve acetate, ethoxyethyl acetate(EA);
Aklylene glycol alkyl ether acetate esters such as propylene glycol monomethyl ether acetic acid esters, ethoxy propyl acetate, propylene glycol one propyl ether acetic acid esters, methoxy butyl acetate, acetate methoxyl amyl group ester;
Propylene glycol one alkyl ethers of carbon number more than 7 such as propylene glycol monobutyl ether;
Propylene glycol dialkyl ethers such as Propylene Glycol Dimethyl Ether, propylene glycol diethyl ether, propylene glycol ethyl-methyl ether, propylene glycol dipropyl ether, propylene glycol propyl group methyl ether, propylene glycol ethyl propyl ether;
Propylene glycol alkyl ether propionic acid esters such as propylene glycol monomethyl ether acetate, propylene-glycol ethyl ether propionic ester, propylene glycol propyl ether propionic ester, propylene glycol butyl ether propionic ester;
Butylene glycol one alkyl ethers of carbon number more than 7 such as propoxyl group butanols, butoxy butanols;
Butylene glycol one alkyl ether acetate esters such as methoxy butyl acetate, acetate ethoxy butyl ester, acetate propoxyl group butyl ester, acetate butoxy butyl ester;
Butylene glycol one alkyl ether propionic acid esters such as propionic acid methoxyl butyl ester, propionic acid ethoxy butyl ester, propionic acid propoxyl group butyl ester, propionic acid butoxy butyl ester;
Benzene,toluene,xylene, mesitylene etc. are aromatic hydrocarbon based;
Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, hexone, cyclohexanone;
Methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methoxy menthyl acetate, the methoxyacetic acid ethyl ester, the methoxyacetic acid propyl ester, the methoxyacetic acid butyl ester, ethoxy acetate, ethoxy ethyl acetate, the ethoxyacetic acid propyl ester, the ethoxyacetic acid butyl ester, the propoxyl group methyl acetate, propoxyl group ethyl acetate, the propoxyl group propyl acetate, the propoxyl group butyl acetate, the butoxy acetic acid methyl esters, the butoxy acetic acid ethyl ester, the butoxy acetic acid propyl ester, the butoxy acetic acid butyl ester, 2-methoxypropionic acid methyl esters, 2-methoxy propyl acetoacetic ester, 2-methoxy propyl propyl propionate, 2-methoxy propyl acid butyl ester, 2-ethoxy-propionic acid methyl esters, the 2-ethoxyl ethyl propionate, 2-ethoxy-c propyl propionate, 2-ethoxy-c acid butyl ester, 2-butoxy methyl propionate, 2-butoxy ethyl propionate, 2-butoxy propyl propionate, 2-butoxy butyl propionate, 3-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 3-methoxy propyl propyl propionate, 3-methoxy propyl acid butyl ester, 3-ethoxy-propionic acid methyl esters, the 3-ethoxyl ethyl propionate, 3-ethoxy-c propyl propionate, 3-ethoxy-c acid butyl ester, 3-propoxyl group methyl propionate, 3-propoxyl group ethyl propionate, 3-propoxyl group propyl propionate, 3-propoxyl group butyl propionate, 3-butoxy methyl propionate, 3-butoxy ethyl propionate, 3-butoxy propyl propionate, ester classes such as 3-butoxy butyl propionate;
The hydroxyl ester classes of carbon number more than 7 such as butyl lactate, 3-hydracrylic acid butyl ester, 2-hydroxy-3-methyl methyl butyrate;
Ring-type such as tetrahydrofuran, pyrans ethers;
Cyclic ester classes such as gamma-butyrolacton etc.
In above-mentioned solvent, from the angle of coating, drying property, preferred boiling point is 100 ℃～200 ℃ a organic solvent.Wherein, can enumerate aklylene glycol alkyl ether acetate esters, ketone, butylene glycol alkyl ether acetate esters, butylene glycol one alkyl ether of carbon number more than 7, ester classes such as 3-ethoxyl ethyl propionate, 3-methoxypropionic acid methyl esters, preferred propylene glycol monomethyl ether acetic acid esters, ethoxy propyl acetate, cyclohexanone, methoxy butyl acetate, 3-ethoxyl ethyl propionate, 3-methoxypropionic acid methyl esters.
Wherein, preferably only use two above-mentioned aklylene glycol dialkyl ether and alcohol.
Relative photosensitive polymer combination, the amount of the solvent in the photosensitive polymer combination of the present invention (D) calculate with mass fraction and are preferably 60～90 quality %, more preferably 65～85 quality %.If the amount of solvent (D) is in this scope, then be expected to using spin coated machine (spincoater), Xia Feng ﹠amp; Spin coated machine (slit﹠amp; Spin coater), slit coating agent (slit coater) (is also referred to as mould coating machine (die coater), curtain formula curtain coater (curtain flow coater) sometimes.), realize good coating during various apparatus for coating such as spraying (ink jet), roll coater (roll coater), dip coater (dip coater).
Photosensitive polymer combination of the present invention does not contain colorants such as pigment and dyestuff in fact.That is, in photosensitive polymer combination of the present invention, the content of the colorant of composition in its entirety calculates preferably less than 1 quality % with mass fraction relatively.More preferably less than 0.5 quality %.
For example, photosensitive polymer combination of the present invention does not contain the following colorant that uses in fact in this field.
The compound that is divided into dyestuff (Pigment) in the color index (Color Index) (The Society of Dyers and Colourists publication) can specifically be enumerated:
C.I. yellow uitramarine such as pigment yellow 1,3,12,13,14,15,16,17,20,24,31,53,83,86,93,94,109,110,117,125,128,137,138,139,147,148,150,153,154,166,173,194,214;
C.I. pigment orange 13,31,36,38,40,42,43,51,55,59,61,64,65,71, orange pigment such as 73;
C.I. Pigment Red 9,97,105,122,123,144,149,166,168,176,177,180,192,209,215,216,224,242,254,255,264, red pigments such as 265;
C.I. pigment blue 15,15:3,15:4,15:6, blue pigments such as 60;
C.I. pigment violet 1,19,23,29,32,36, violet pigments such as 38;
C.I. pigment Green 7, viridine greens such as 36;
C.I. brown pigments such as bistre 23,25;
C.I. black pigment such as pigment black 1,7.
Also can be as required also with various adjuvants such as filling agent, other macromolecular compounds, surfactant, adhesion promoter, antioxidant, ultraviolet light absorber, light stabilizer, chain-transferring agents in photosensitive polymer combination of the present invention.
As filling agent, but for example illustration glass, silicon dioxide, aluminium oxide etc.
As other macromolecular compounds, for example can enumerate curable resins such as epoxy resin, maleimide resin, thermoplastic resins such as polyvinyl alcohol (PVA), polyacrylic acid, polyglycol one alkyl ether, poly-fluoroalkyl acrylate, polyester, polyurethane etc.
As surfactant, can use in the surfactant etc. of silicone-based, fluorine system, ester system, kation system, negative ion system, nonionic system, both sexes etc. any one.Particularly, can use polyethylene oxide alkyl ethers class, polyoxyethylene alkyl phenyl ethers, polyethylene glycol di class, sorbitan fatty acid ester class, fatty acid modified polyesters, tertiary amine modified polyurethane, polyethyleneimine: amine etc., in addition, also can use commercially available surfactant.For example, trade name KP (SHIN-ETSU HANTOTAI's chemical industry (strain) system), Polyflow (common prosperity chemistry (strain) system), エ Off ト Star プ (the Mitsubishi Materials electronics changes into (strain)), Megafac (DIC (strain) system), Off ロ ラ-De (Sumitomo 3M (strain) system), Surfron (AGC beautifies (strain) system clearly), Solsperse (Geneka (strain) system), EFKA (CIBA corporate system), AjisperPB821 (aginomoto (strain) system) etc.
As adhesion promoter, for example can enumerate vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (2-methoxy ethoxy) silane, N-(2-aminoethyl)-3-aminopropyl methyl dimethoxysilane, N-(2-aminoethyl)-3-aminopropyl trimethoxysilane, the 3-aminopropyl triethoxysilane, the 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl group methyl dimethoxysilane, 2-(3,4-epoxy radicals cyclohexyl) ethyl trimethoxy silane, the 3-chloropropylmethyldimethoxysilane, the 3-r-chloropropyl trimethoxyl silane, the 3-methacryloxypropyl trimethoxy silane, 3-sulfydryl propyl trimethoxy silicane etc.
As antioxidant; for example can enumerate the 2-tert-butyl group-6-(the 3-tert-butyl group-2-hydroxy-5-methyl base benzyl)-4-aminomethyl phenyl acrylate; 2-[1-(2-hydroxyl-3; the 5-di-tert-pentyl-phenyl) ethyl]-4; 6-di-tert-pentyl-phenyl acrylate; 6-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propoxyl group]-2; 4; 8; 10-tetra-tert dibenzo [d; f] [1; 3; 2] two oxa-phosphorus (dioxaphosphepine); 3; 9-pair [2-{3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy }-1, the 1-dimethyl ethyl]-2,4; 8; 10-four oxygen volution [5,5] undecanes; 2,2 '-di-2-ethylhexylphosphine oxide (the 6-tert-butyl group-4-methylphenol); 4; 4 '-butylidene two (the 6-tert-butyl group-3-methylphenol); 4; 4 '-thiobis (the 2-tert-butyl group-5-methylphenol); 2,2 '-thiobis (the 6-tert-butyl group-4-methylphenol); dilauryl 3,3 '-thiodipropionate; myristyl 3; 3 '-thiodipropionate; distearyl acyl group 3; 3 '-thiodipropionate; pentaerythrite base four (3-lauryl thiopropionate); 1,3,5-three (3; the 5-di-tert-butyl-4-hydroxyl benzyl)-1; 3,5-triazine-2,4; 6 (1H; 3H, 5H)-triketone; 3,3 '; 3 " 5,5 ', 5 "-and six tert-butyl groups-a; a '; a "-(mesitylene-2,4,6-three bases) three-paracresol; [3-(3 for pentaerythrite four; the 5-di-tert-butyl-hydroxy phenyl) propionic ester]; 2,6-two-tert-butyl group-4-methylphenol etc.
As ultraviolet light absorber, for example can enumerate 2-(2-hydroxyl-5-tert-butyl-phenyl)-2H-benzotriazole, octyl group-3-[3-tertiary butyl-4-hydroxy-5-(5-chloro-2H-benzotriazole-2-yl) phenyl] propionic ester, 2-[4-[(2-hydroxyl-3-dodecyloxy propyl group) oxygen]-the 2-hydroxy phenyl]-4,6-two (2, the 4-3,5-dimethylphenyl)-1,3, the 5-triazine, 2-[4-[(2-hydroxyl-3-(2 '-ethyl) hexyl) oxygen]-the 2-hydroxy phenyl]-4,6-two (2, the 4-3,5-dimethylphenyl)-1,3, the 5-triazine, 2, two (2-hydroxyl-4-the butoxy phenyl)-6-(2 of 4-, 4-pair-butoxy phenyl)-1,3, the 5-triazine, 2-(2-hydroxyl-4-[1-carbonyl octyloxy ethoxy] phenyl)-4, two (the 4-phenyl)-1 of 6-, 3, the 5-triazine, 2-(2H-benzotriazole-2-yl)-4, two (1-methyl isophthalic acid-phenylethyl) phenol of 6-, 2-(2H-benzotriazole-2-yl)-6-(1-methyl isophthalic acid-phenylethyl)-4-(1,1,3, the 3-tetramethyl butyl) phenol, 2-(the 3-tert-butyl group-2-hydroxy-5-methyl base phenyl)-5-chlorobenzotriazole, alkoxy benzophenone etc.
As light stabilizer, for example can enumerate by succinic acid and (4-hydroxyl-2,2,6,6-tetramethyl piperidine-1-yl) macromolecule that forms of ethanol, N, N '; N ", N " and '-four (4, two (butyl-(N-methyl-2; 2,6, the 6-tetramethyl piperidine-4-yl) amino) triazines-2-yl of 6-)-4; 7-diaza decane-1,10-diamines; decanedioic acid (Decandioic Acid) and two (2,2; 6,6-tetramethyl-1-(octyloxy)-4-piperidyl) esters and 1, the reactant of 1-dimethyl ethyl hydroperoxides; two (1,2,2,6,6-pentamethyl-4-piperidyl)-[[3,5-two (1, the 1-dimethyl ethyl)-4-hydroxy phenyls] methyl] butylmalonic acid ester, 2,4-two [N-butyl-N-(1-cyclohexyloxy-2,2,6,6-tetramethyl piperidine-4-yl) amino]-6-(2-hydroxyethyl amine)-1,3,5-triazines, two (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, methyl (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate etc.
As chain-transferring agent, for example can enumerate dodecyl mercaptans, 2,4-diphenyl-4-methyl-1-pentene etc.
As described later, photosensitive polymer combination of the present invention for example can by on the base material for example at the substrate of glass, metal, plastics etc., be formed with on these substrates of color filter (color filter), various dielectric film or conducting film, driving circuit etc. coating and form and film.Preferred dry and the filming of solidifying of filming.In addition, also filming of obtaining can be patterned as required form and it is used as pattern.And then, also these can be filmed and/or a part that pattern forms the constituent part of display device etc. is used.
In addition, if hardening resin composition of the present invention is filled in the quartz cell that optical length is 1cm (cell), measure transmitance with spectrophotometer measuring under the condition that wavelength is 400～700nm, then mean transmissivity is preferably more than 70%, more preferably more than 75%.Like this, can be formed on the transparent pattern in visible region or film.
At first, photosensitive polymer combination of the present invention is coated on the base material.
As mentioned above, coating can be used spin coated machine, Xia Feng ﹠amp; Various apparatus for coating such as spin coated machine, slit coating agent, ink jet printer, roll coater, dip coater carry out.Wherein, from dissolubility, prevent drying, prevent the generation equal angles of foreign matter, preferably utilize the coating of method of spin coating, promptly preferably utilize Xia Feng ﹠amp; The coating of spin coated machine and slit coating machine etc.
Then, preferably carry out drying and/or prebake (prebake) and come to remove volatile ingredient such as desolvate.Like this, can obtain level and smooth uncured filming.
In this case the thickness of filming is not particularly limited, can suitably adjusts according to the material that uses, purposes etc., for example about illustration 1～6 μ m.
And then, via the mask that is used to form target pattern (mask), the ultraviolet ray that for example takes place to the uncured irradiation of filming that obtains etc. from mercury lamp, light emitting diode.Shape to mask at this moment is not particularly limited, and can enumerate different shape.In addition, live width etc. also can utilize mask size etc. suitably to adjust.
In the exposure machine in recent years, wavelength can be blocked less than the wave filter (filter) that the light of 350nm is used to block (cut) this wavelength domain, perhaps, use the bandpass filter (band-pass filter) that to take out these wavelength domains optionally to take out near near near the light the 436nm, the 408nm, the 365nm, thereby shine parallel rays equably to plane of exposure integral body.At this moment, in order to carry out the contraposition accurately of mask and base material, also can use mask aligner (mask aligner), ledex devices such as (stepper).
Afterwards, can obtain the target pattern shape by making the contact aqueous alkali of filming make for example unexposed dissolving of established part and developing.
Developing method can be any one in dress liquid method, dipping (dipping) method, injection (spray) method etc.And then, also can when developing, base material be inclined to angle arbitrarily.
The developer solution that uses in development is generally the aqueous solution that contains alkali compounds and surfactant.
Alkali compounds can be any one in the inorganic and organic alkali compounds.
As the concrete example of inorganic alkaline compound, can enumerate 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.
In addition, as organic basic compound, for example can enumerate Tetramethylammonium hydroxide, 2-hydroxyethyl trimethylammonium hydroxide, monomethyl amine, dimethylamine, trimethylamine, monoethyl amine, diethylamine, triethylamine, an isopropylamine, diisopropylamine, monoethanolamine etc.
These inorganic and organic basic compound concentration in alkaline-based developer are preferably 0.01～10 quality %, more preferably 0.03～5 quality %.
It is that surfactant, negative ion are that surfactant and kation are any one in the surfactant that surfactant can be nonionic.
As nonionic is surfactant, for example can enumerate polyethylene oxide alkyl ethers, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyethylene oxide derivatives, 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.
As negative ion is surfactant, for example can enumerate the alkyl aryl sulfonate class etc. of alkylsurfuric acid salt, neopelex or dodecyl sodium naphthalene sulfonate and so on of higher alcohol sulfate salt, NaLS or the Texapon Special and so on of lauryl alcohol sodium sulfovinate or oleyl alcohol sodium sulfovinate and so on.
As kation is surfactant, for example can enumerate the amine salt of stearyl amine hydrochloride or lauryl trimethyl ammonium chloride and so on or quaternary ammonium salt etc.
Surfactant concentrations in the alkaline developer is preferably the scope of 0.01～10 quality %, 0.05～8 quality % more preferably, and then be preferably 0.1～5 quality %.
After development, wash, and then cure after also can carrying out as required.After the suitable condition of curing for example be 150～230 ℃ temperature range, 10～180 minutes.
If hardening resin composition of the present invention uses spectrophotometer in the mensuration transmitance of measuring under the condition that wavelength is 400～700nm 3 μ m thickness after be heating and curing (for example 150～250 ℃, 0.1～3 hour) of filming, then transmitance is preferably more than 90%, more preferably more than 95%.Like this, can be formed on the transparent pattern in visible region or film.
Obtain like this film or pattern for example can be used as the photoinduction gap material (photospacer) that uses, the coverlay (over coat) that can form pattern in liquid crystal indicator.In addition, filming when carrying out patterned exposure, can form the hole with photomask by using hole (hole) to form, thereby can be used as interlayer dielectric uncured.And then, filming when exposing, can form hyaline membrane by not using photomask to carry out blanket exposure and being heating and curing or only being heating and curing to uncured.This hyaline membrane can be used as coverlay.In addition, also can in touch panel display device such as (touch panel), use.Like this, can possess high-quality filming or the display device of pattern with the high finished product rate manufacturing.
Photosensitive polymer combination of the present invention can for the material that is formed for forming various films and pattern for example the hyaline membrane hyaline membrane, pattern, photoinduction gap material, coverlay, dielectric film, liquid crystal aligning control that especially constitute the part of color filter with the colored pattern of the different thickness of projection, lenticule (microlens), combination, overlay etc. and suitably utilize.In addition, also can film or pattern for example utilizes in liquid crystal indicator, the organic El device etc. as the color filter of the part of its constituent part, array (array) substrate etc. and then the display device that possesses these color filters and/or array base palte etc. possessing these.
Embodiment
Below utilize embodiment to illustrate in greater detail photosensitive polymer combination of the present invention, but the present invention is not limited by these embodiment.In addition, in following embodiment and comparative example, the % of expression amount or use amount and part unless otherwise specified, all are standard with the quality.
Synthesis example 1
In possessing the 1L flask of reflux cooler, tap funnel and stirring machine, flow into nitrogen with 0.02L/ minute speed, become blanket of nitrogen, add 140 parts in diglycol ethyl-methyl ether, be heated to 70 ℃ while stirring.Then, with 40 parts of methacrylic acids, acrylic acid 3,4-epoxy radicals three ring [5.2.1.0 2.6] decyl ester (and with mol ratio 50: 50 mix by the compound of formula (I-1) expression and by the potpourri of the compound of formula (II-1) expression.) 360 parts be dissolved in 190 parts in the diglycol ethyl-methyl ether, obtain solution uses the dropping liquid pump, with 4 hours, the gained lysate is instilled into is incubated in 70 ℃ flask.
Figure G200910221745XD00341
On the other hand, with polymerization initiator 2, two (2, the 4-methyl pentane nitrile) 30 parts of 2 '-azo are dissolved in 240 parts in the diglycol ethyl-methyl ether, and gained solution is used other dropping liquid pumps, are instilled in the flask with 5 hours.After the instillation of the solution of polymerization initiator finishes, remain on 70 ℃ following 4 hours, be cooled to room temperature then, obtain multipolymer (Resin A solution a) of solid constituent 42.6%, acid value 60mg-KOH/g.The weight-average molecular weight of the Resin A a that obtains (Mw) is 8000, and dispersion degree is 1.91.
Synthesis example 2
In possessing the 1L flask of reflux cooler, tap funnel and stirring machine, flow into nitrogen with 0.02L/ minute speed, become blanket of nitrogen, add 305 parts in diglycol ethyl-methyl ether, be heated to 70 ℃ while stirring.Then, with 60 parts of methacrylic acids, acrylic acid 3,4-epoxy radicals three ring [5.2.1.0 2.6] decyl ester (and with mol ratio 50: 50 mix by the compound of formula (I-1) expression and by the potpourri of the compound of formula (II-1) expression.) 240 parts be dissolved in obtain solution in 140 parts in the diglycol ethyl-methyl ether, use tap funnel, with 4 hours, this lysate be instilled into be incubated in 70 ℃ flask.On the other hand, with polymerization initiator 2, two (2, the 4-methyl pentane nitrile) 30 parts of 2 '-azo are dissolved in 225 parts in the diglycol ethyl-methyl ether, and gained solution is used other tap funnels, are instilled in the flask with 4 hours.After the instillation of the solution of polymerization initiator finishes, remain on 70 ℃ following 4 hours, be cooled to room temperature then, obtain the solution of the multipolymer (Resin A b) of solid constituent 32.6%, acid value 110mg-KOH/g (solid constituent conversion).The weight-average molecular weight Mw of the Resin A b that obtains is 13,600, and dispersion degree is 2.49.
Synthesis example 3
In possessing the 1L flask of reflux cooler, tap funnel and stirring machine, flow into nitrogen with 0.02L/ minute speed, become blanket of nitrogen, add 105 parts of 3-methoxyl-200 parts in 1-butanols and acetate 3-methoxyl butyl esters, be heated to 70 ℃ while stirring.Then, with 60 parts of methacrylic acids, acrylic acid 3,4-epoxy radicals three ring [5.2.1.0 2.6] decyl ester (and with mol ratio 50: 50 mix by the compound of formula (I-1) expression and by the potpourri of the compound of formula (II-1) expression.) 240 parts be dissolved in obtain solution in 140 parts of the acetate 3-methoxyl butyl esters, use tap funnel, with 4 hours, this lysate be instilled into be incubated in 70 ℃ flask.On the other hand, with polymerization initiator 2, two (2, the 4-methyl pentane nitrile) 30 parts of 2 '-azo are dissolved in 225 parts of the acetate 3-methoxyl butyl esters, and gained solution is used other tap funnels, are instilled in the flask with 4 hours.After the instillation of the solution of polymerization initiator finishes, remain on 70 ℃ following 4 hours, be cooled to room temperature then, obtain the solution of the multipolymer (Resin A c) of solid constituent 32.6%, acid value 110mg-KOH/g (solid constituent conversion).The weight-average molecular weight Mw of the Resin A c that obtains is 13,400, and dispersion degree is 2.50.
Use the GPC method, utilize following condition to carry out multipolymer (the Resin A a～weight-average molecular weight (Mw) Ac) and the mensuration of number-average molecular weight (Mn).
Device; K2479 ((strain) Shimadzu Seisakusho Ltd. system)
Post; SHIMADZU Shim-pack GPC-80M
Column temperature; 40 ℃
Solvent; THF (tetrahydrofuran)
Flow velocity; 1.0mL/min
Detecting device; RI
The weight-average molecular weight and the likening to of number-average molecular weight of the polystyrene conversion that obtains under the above-mentioned condition are dispersion degree (Mw/Mn).
Embodiment 1～9, comparative example 1
The composition of mixture table 1 obtains photosensitive polymer combination 1～10.
＜mist is uneven to be estimated 〉
On the square ITO film forming glass substrate of length of side 15cm, use slit coating machine (Zhuo Mo-100 ITOCHU produces machine (strain) system), become the condition of 5.5 μ m with the thickness after solidifying, be coated in the solution of the photosensitive polymer combination that obtains in embodiment and the comparative example respectively.
Then, utilize drying under reduced pressure machine (VCD Microtech (strain) system), degree of decompression is decompressed to 0.5torr, make its drying.On heating plate, 95 ℃ of following prebake 2 minutes, formation was filmed.
After the cooling, utilize Na lamp (lamp) irradiation film surface, through the Visual Confirmation film coated surface.
Situation that can clear affirmation mist inequality (vaporific inequality) is *, situation about can confirm slightly is △, situation about almost not confirming is zero.
＜nail trace evaluation 〉
With above-mentioned similarly form film after, drying under reduced pressure.Then, in being set on 90 ℃ the heating plate, prebake is 2 minutes thereon with the corrosion resistant plate mounting of thick 20mm in hole that has diameter 60mm, and formation is filmed.
After the cooling, utilize Na light irradiation film surface, through the Visual Confirmation film coated surface.
Can be clear the situation of affirmation nail trace be *, situation about can confirm slightly is △, situation about almost not confirming is zero.
＜gap nozzle drying property is estimated 〉
Film with above-mentioned similarly formation.
Afterwards, do not carry out the washing of nozzle tip and directly placement.After 1 minute, do not carry out the washing of nozzle tip and carry out identical coating.
Then, utilize drying under reduced pressure machine (VCD Microtech (strain) system), degree of decompression is decompressed to 0.5torr, make its drying.On heating plate, 90 ℃ of following prebake 2 minutes, formation was filmed.
After the cooling, utilize Na light irradiation film surface, through the Visual Confirmation film coated surface.
Situation that can clear affirmation vertical stripe inequality is *, situation about can confirm slightly is △, situation about almost not confirming is zero.
The mean transmissivity of＜composition 〉
To each photosensitive polymer combination, use UV, visible light near infrared spectrometer (V-650; Japan's beam split (strain) system) (quartz cell, optical length; 1cm), the mean transmissivity (%) under mensuration 400～700nm.
The mean transmissivity of＜pattern 〉
Use each photosensitive polymer combination, make cured film, 3 microns of the thickness flavors after the curing by following steps.
Be the square glass substrate of 5cm with neutral detergent, water and the 2-propyl alcohol washing length of side successively, dry then.Utilize spin coated, coating composition on this substrate, the thickness of the pattern after curing after making becomes 3.0 μ m.Then, utilize drying under reduced pressure machine (VCD Microtech (strain) system), degree of decompression is decompressed to 0.5torr, make its drying, formation is filmed.This is filmed, in heating plate, with 90 ℃ of prebake 2 minutes.Make the interval between substrate and the quartz glass system photomask become 10 μ m, use exposure machine (TME-150RSK; Open up Pu Kang (strain) system, light source; Ultrahigh pressure mercury lamp), under air atmosphere, with 100mJ/cm 2Exposure (405nm standard), filming after the prebake exposed.In this exposure, make radiating light pass through optical filter (LUO400 from ultrahigh pressure mercury lamp; Morning sun beam split (strain) system) shines.In addition, the line that is used to form 100 μ m and the photomask of space pattern (line and space pattern) have been used.After exposure, utilize 23 ℃ tetramethylammonium hydroxide aqueous solution (in 100 parts of aqueous solution, containing 2.38 parts of Tetramethylammonium hydroxide) dipping 60 seconds, develop, after the washing, utilize heating plate after 235 ℃, to cure 11 minutes, form line and space pattern.
To each pattern that obtains, use micro-spectral light measurer (OSP-SP200; The OLYMPUS corporate system), the mean transmissivity (%) under mensuration 400～700nm.
Transmitance uprises and shows that absorption diminishes.
[table 1]
Figure G200910221745XD00371
Each composition in the table 1 as described below.
Polymerizable compound (B); Dipentaerythritol acrylate (KAYARAD DPHA; Japan's chemical drug (strain) system)
Polymerization initiator (C) Ca; 1-(4-phenyl sulfydryl phenyl) octane-1, the 2-diketone-(OXE 01 for 2-oxime-O-benzoic ether; Vapour crust Japanese firm system)
Polymerization initiator (C) Cb; 2,2 '-two (2-chlorphenyl)-4,4 '-5,5 '-tetraphenyl-1,2 '-di-imidazoles (B-CIM; Hodogaya chemical (strain) system)
Cause auxiliary agent C2a; Pentaerythrite four propionic esters (SC organic chemistry (strain) system PEMP)
Cause auxiliary agent C2b; 2-(2-naphthoyl methylene)-3-methylbenzothiazole quinoline
Solvent Da; 3-methoxyl-1-butanols
Solvent Db: propylene glycol monomethyl ether
Solvent Dc; Diglycol ethyl-methyl ether
Solvent Dd; Propylene glycol monomethyl ether acetic acid esters
Solvent De; Acetate 3-methoxyl butyl ester
Solvent Df; 3-ethoxyethyl group propionic ester
As mentioned above, when using photosensitive polymer combination formation of the present invention to film, even form in coating under the situation of thicker film, mist inequality, vertical stripe inequality and nail trace can not take place yet, can form even and level and smooth high-quality the filming of integral body of filming.Promptly, can shorten coating drying time because boiling point is lower, thereby can realize the raising of throughput rate, on the other hand, also can suppress the drying on the top of gap nozzle (slitnozzle), thereby prevent the generation of the foreign matter that drying causes, sneaking into and vertical stripe in coated film.
In addition, the favorable solubility of resin and various compositions can improve bin stability.
By using such photosensitive polymer combination to form to film or pattern and utilize these to film or pattern is made display device, can improve yield rate.
Utilizability on the industry
If utilize the present invention, then can form and to suppress the mist inequality, vertical stripe is uneven and follows closely the generation of trace, whole uniformly high-quality the filming of filming.
In addition, by utilizing photosensitive polymer combination of the present invention, can obtain high-quality display unit etc.

Claims (8)

1. photosensitive polymer combination, wherein,
Contain resin (A), polymerizable compound (B), polymerization initiator (C) and solvent (D),
Solvent (D) is the solvent of the alcohol of two aklylene glycol dialkyl ethers of the alkyl that contains alkylidene with carbon number 1～3 and carbon number 1～4 and carbon number 1～6.
2. photosensitive polymer combination according to claim 1, wherein,
In the solvent (D), relative solvent total amount contains the two aklylene glycol dialkyl ethers of 30～90 quality %.
3. photosensitive polymer combination according to claim 1 and 2, wherein,
In the solvent (D), relative solvent total amount contains the alcohol of the carbon number 1～6 of 10～50 quality %.
4. according to any described photosensitive polymer combination in the claim 1～3, wherein,
Two aklylene glycol dialkyl ethers are diglycol ethyl-methyl ether.
5. according to any described photosensitive polymer combination in the claim 1～4, wherein,
The alcohol of carbon number 1～6 is the 3-methoxybutanol.
6. film for one kind, it is to use filming that any described photosensitive polymer combination forms in the claim 1～5.
7. pattern, it is to use any pattern that described photosensitive polymer combination forms in the claim 1～5.
8. display device, wherein,
Comprise accessory rights requirement 6 described film and the described pattern of claim 7 in select at least a kind.
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