CN101738859B - Photosensitive resin composition and display - Google Patents

Photosensitive resin composition and display Download PDF

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Publication number
CN101738859B
CN101738859B CN200910221745.XA CN200910221745A CN101738859B CN 101738859 B CN101738859 B CN 101738859B CN 200910221745 A CN200910221745 A CN 200910221745A CN 101738859 B CN101738859 B CN 101738859B
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methyl
acid
ester
acrylate
butyl
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CN101738859A (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, conventionally in order to form the hyaline layers such as overlay or pattern, can on real estate, pass through the photosensitive resin coating compositions such as method of spin coating or slit & rotary process.
On the other hand, from boosting productivity, adapt to large-scale picture equal angles, also someone has studied the method that forms high-quality uniform coating when can saving photosensitive polymer combination solution.
On this basis, in order to form the film that quality is outstanding, just the selection of solvent species is studied at present.For example, disclose and utilized the scheme that has 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-n-butyl alcohol and acetic acid 3-methoxyl butyl ester.
Patent documentation 1: JP 2008-181087 communique paragraph 91
But, the photosensitive polymer combination that has used above-mentioned solvent is applicable in the situation of slot die (slit die) rubbing method as representational coating process etc., occur sometimes that mist (も や) is uneven, vertical stripe is uneven and nail trace, thereby can not obtain high-quality film.
Summary of the invention
The object of the present invention is to provide a kind ofly can suppress that thereby the generation uneven and nail trace of mist inequality, vertical stripe can form that film entirety is even, the photosensitive polymer combination of high-quality film and used the display device etc. of said composition.
, the invention provides following [1]～[8].
[1] photosensitive polymer combination, wherein,
Contain resin (A), polymerizable compound (B), polymerization initiator (C) and solvent (D),
Solvent (D) is for containing the solvent with two aklylene glycol dialkyl ethers of the alkylidene of carbon number 1～3 and the alkyl of carbon number 1～4 and the alcohol of carbon number 1～6.
[2] according to the photosensitive polymer combination [1] described, wherein,
In solvent (D), solvent total amount contains 30～90 quality % bis-aklylene glycol dialkyl ethers relatively.
[3] according to the photosensitive polymer combination [1] or [2] described, wherein,
The alcohol of the carbon number 1～6 that in solvent (D), solvent total amount contains 10～50 quality % relatively.
[4] according to the photosensitive polymer combination described in any one in [1]～[3], wherein,
Two aklylene glycol dialkyl ethers are diglycol ethyl-methyl ether.
[5] according to the photosensitive polymer combination described in any one in [1]～[4], wherein,
The alcohol of carbon number 1～6 is 3-methoxybutanol.
[6] film, it is to use the film that in [1]～[5], the photosensitive polymer combination described in any one forms.
[7] pattern, it is to use the pattern that in [1]～[5], the photosensitive polymer combination described in any one forms.
[8] display device, wherein,
Comprise at least a kind that from the pattern described in the film [6] Suo Shu and [7], selects.
According to the present invention, can form even, the high-quality film of entirety thereby can suppress the generation uneven and nail trace of mist inequality, vertical stripe.
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, can be used alone or in combination.
As the resin using in photosensitive polymer combination of the present invention (A), can illustrate and there is the deliquescent resin of alkali (A1), there is alkali dissolubility and at light and hanker thering is reactive resin (A2) etc. under at least one party's effect.
As there is the deliquescent resin of alkali (A1), can illustrate at least a kind (a) (being sometimes referred to as below " (a) ") of selecting from unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides and can with multipolymer of the monomer of (a) copolymerization (c) (being sometimes referred to as below " (c) ") etc.
As (a), for example, can specifically enumerate the unsaturated monocarboxylic acid classes such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, p-vinyl benzoic acid;
Isosorbide-5-Nitrae-cyclohexene dicarboxylic acid, methyl-5-norborene-2, the 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, the unsaturated dicarboxylic acid classes such as 3,6-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 2 yuan of above polybasic carboxylic acids such as ester, phthalic acid list [2-(methyl) acryloxy ethyl] ester;
The unsaturated esters of acrylic acid that contains hydroxyl and carboxyl in same a part of α-(methylol) acrylic acid and so on etc.
Wherein, from copolymerization or the deliquescent angle of alkali, 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 cyclohexyl, (methyl) acrylic acid three encircle [5.2.1.0 2.6] decane-8-base ester is (in the art, as trivial name, be called as (methyl) acrylic acid two cyclopentyl esters), (methyl) acrylic acid cyclic alkyl ester class such as (methyl) acrylic acid two cyclopentyloxy ethyl esters, (methyl) isobornyl acrylate;
Cyclohexyl acrylate, acrylic acid 2-methyl cyclohexyl, acrylic acid three encircle [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.), the 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;
The acrylic acid such as phenyl acrylate, benzyl acrylate aryl ester class;
The dicarboxylic diesters such as diethyl maleate, DEF, diethyl itaconate;
The 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 encircles [2.2.1] hept-2-ene", 5-hydroxyl two encircles [2.2.1] hept-2-ene", 5-carboxyl two encircles [2.2.1] hept-2-ene", 5-methylol two encircles [2.2.1] hept-2-ene", 5-(2 '-hydroxyethyl) two ring [2.2.1] hept-2-ene"s, 5-methoxyl two encircles [2.2.1] hept-2-ene", 5-ethoxy two encircles [2.2.1] hept-2-ene", 5,6-dihydroxy two encircles [2.2.1] hept-2-ene", 5,6 dicarboxyls two encircle [2.2.1] hept-2-ene", 5,6-bis-(methylol), two ring [2.2.1] hept-2-ene"s, 5,6-bis-(2 '-hydroxyethyl), two ring [2.2.1] hept-2-ene"s, 5,6-dimethoxy two encircles [2.2.1] hept-2-ene", 5,6-diethoxy two encircles [2.2.1] hept-2-ene", 5-hydroxy-5-methyl base two encircles [2.2.1] hept-2-ene", 5-hydroxyl-5-ethyl two encircles [2.2.1] hept-2-ene", 5-carboxyl-5-methyl bicyclic [2.2.1] hept-2-ene", 5-carboxyl-5-ethyl two encircles [2.2.1] hept-2-ene", 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 encircles [2.2.1] hept-2-ene", 5,6-dicarboxyl two encircles [2.2.1] hept-2-ene" acid anhydrides (humic acid (himic acid) acid anhydride), 5-tertbutyloxycarbonyl two encircles [2.2.1] hept-2-ene", 5-hexamethylene oxygen carbonyl two encircles [2.2.1] hept-2-ene", 5-carbobenzoxy two encircles [2.2.1] hept-2-ene", 5,6-bis-(tertbutyloxycarbonyl), two ring [2.2.1] hept-2-ene"s, the two ring unsaturated compound classes such as 5,6-bis-(hexamethylene oxygen carbonyl), two ring [2.2.1] hept-2-ene"s,
The dicarbapentaborane imide derivative classes such as N-phenylmaleimide, N-N-cyclohexylmaleimide, 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-methyl styrene, a methyl styrene, p-methylstyrene, vinyltoluene, to methoxy styrene, vinyl cyanide, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, Methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene etc.
Wherein, from copolymerization and the deliquescent angle of alkali, optimization styrene, N-phenylmaleimide, N-N-cyclohexylmaleimide, 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 refers to acrylate and/or methacrylate.
Making (a) and (c) in multipolymer that copolymerization obtains, in the time that the total mole number of the constituent of multipolymer described formation is made as to 100 % by mole, calculate in mol%, respectively from (a) and (c) ratio of derivative constituent preferably in following scope.
From (a) derivative structural unit; 2～40 % by mole
From (c) derivative structural unit; 60～98 % by mole
In addition, if the ratio of described constituent is in following scope, more preferably.
From (a) derivative structural unit; 5～35 % by mole
From (c) derivative structural unit; 65～95 % by mole
If described component ratio in above-mentioned scope, has the trend that bin stability, developability, solvent resistance improve.
Described have the deliquescent resin of alkali (A1) and can reference example manufacture as method and the citing document of recording in the document etc. of record in document " experimental method of Polymer Synthesizing " (the large grand row work sale room in Tianjin (strain) chemistry is with the 1st edition the 1st printing distribution on March 1st, 1972 of people).
Particularly, can be illustrated in the unit (a) of the formation multipolymer that adds polymerization initiator, solvent and ormal weight in reaction vessel and (c) etc., by utilizing nitrogen replace oxygen, under the non-existent condition of oxygen, the method that stirs, heats, is incubated.Wherein, polymerization initiator and solvent etc. are as used herein not particularly limited, can use normally used any polymerization initiator and solvent in the field.For example, can use polymerization initiator described later and solvent etc.
In addition, the multipolymer obtaining can directly use reacted solution, also can use the solution after concentrated or dilution, the multipolymer that also can use the 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's (following, in resin (A2), too) can be simplified.
The weight-average molecular weight of the described polystyrene conversion with the deliquescent resin of alkali (A1) is preferably 3,000～100, and 000, more preferably 5,000～50,000.If there is the weight-average molecular weight of the deliquescent resin of alkali (A1) in described scope, there is the trend that coating improves, in addition, also have in the time developing, be difficult for that film attenuate occurs so that in the time developing the good trend of exfoliative of non-pixel portion, so preferably.
The molecular weight distribution [weight-average molecular weight (Mw)/number-average molecular weight (Mn)] with the deliquescent resin of alkali (A1) is preferably 1.1～6.0, and more preferably 1.2～4.0.If molecular weight distribution, in described scope, has the trend that developability is outstanding, so preferably.
Solid constituent in photosensitive polymer combination relatively, the amount with the deliquescent resin of alkali (A1) that can use in photosensitive polymer combination of the present invention calculates and is preferably 5～90 quality %, more preferably 10～70 quality % with mass fraction (factor).If there is the amount of the deliquescent resin of alkali (A1) in described scope, the dissolubility in developer solution is abundant, on the substrate of non-pixel portion, be difficult to produce development residue, in addition, in the time developing, be difficult to the film attenuate of the pixel portion that exposure portion occurs, there is the good trend of deciduous of non-exposed portion, so preferably.
As thering is alkali dissolubility and at light and hanker thering is reactive resin (A2) under at least one party's effect, can enumerating
Resin (A2-1): (a) with (c) with have carbon number 2～4 cyclic ether structure compound (b) (being sometimes referred to as below " (b) ") multipolymer,
Resin (A2-2): the multipolymer that (a) and multipolymer (c) reacted with (b) obtain,
Resin (A2-3): multipolymer (a) and (b) etc.
(b) be the compound with the cyclic ether structure of carbon number 2～4, refer to the polymerizable compound with at least a kind of group selecting from epoxy radicals, oxetanyl (oxetanyl) and tetrahydrofuran base.(b) be preferably the cyclic ether structure with carbon number 2～4 and the compound with ethene carbon-to-carbon unsaturated bond, more preferably there is the cyclic ether structure of carbon number 2～4 and there is acryloyl group or the compound of methacryl.
As (b), for example can enumerate have epoxy radicals monomer (b1) (being sometimes referred to as below " b1 "), have oxetanyl monomer (b2) (being sometimes referred to as below " b2 "), there is monomer of tetrahydrofuran base etc.
(b1) refer to the polymerizable compound with at least a kind of group for example selecting from aliphatic epoxy base and ester ring type epoxy radicals.This monomer with epoxy radicals is preferably has at least a kind of group selecting from aliphatic epoxy base and ester ring type epoxy radicals and the compound with ethene carbon-to-carbon unsaturated bond, more preferably has 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, aliphatic epoxy base refers to oxirane (oxiranyl) base of strand, and ester ring type epoxy radicals refers to have the ring of ester ring type hydrocarbon and the group of the structure that oxirane (oxirane) cyclic condensation forms.
As thering is aliphatic epoxy base and thering is the compound of ethene carbon-to-carbon double bond in (b1) of (A2), compound being represented by following formula of can specifically enumerate diglycidyl (methyl) acrylate, Beta-methyl diglycidyl (methyl) acrylate, β-ethyl diglycidyl (methyl) acrylate, diglycidyl vinyl ether, recording in Unexamined Patent 7-248625 communique etc.
(in formula, R 11and R 13be the alkyl of hydrogen atom or carbon number 1～10 independently respectively, the integer that m is 1～5.)。
As the compound being represented by described formula, for example can enumerate adjacent vinyl benzyl glycidol ether, between vinyl benzyl glycidol ether, to vinyl benzyl glycidol ether, Alpha-Methyl-adjacent vinyl benzyl glycidol ether, an Alpha-Methyl-vinyl benzyl glycidol ether, Alpha-Methyl-to 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 thering is ester ring type epoxy radicals and thering is 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 (for example Celloxide2000; Daicel chemical industry (strain) system), acrylic acid 3,4-epoxy radicals cyclohexyl methyl ester (for example CyclomerA400; Daicel chemical industry (strain) system), methacrylic acid 3,4-epoxy radicals cyclohexyl methyl ester (for example CyclomerM100; Daicel chemical industry (strain) system) or at least a kind of compound selecting from the compound being represented by formula (I) and the compound being represented by formula (II).
[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 respectively singly-bound, C 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 Oxymethylene, oxygen ethylidene, oxygen propylidene etc.
As alkylene oxide group, can enumerate sub-methoxyl, inferior ethoxyl, sub-propoxyl group etc.
As sulphur alkylidene, can enumerate sulphur methylene, sulphur ethylidene, sulphur propylidene etc.
As alkylidene sulfenyl, can enumerate methylene sulfenyl, ethylidene sulfenyl, propylidene sulfenyl etc.
As amino alkylidenyl, can enumerate aminomethylene, amino ethylidene, Aminopropylidene etc.
As alkylidene amino, can enumerate methene amido, ethyleneimino, propylidene amino etc.
As substituent X and X ', can preferably enumerate singly-bound, methylene, ethylidene, Oxymethylene, oxygen ethylidene, can more preferably enumerate singly-bound, oxygen ethylidene.
As the compound being represented by formula (I), can enumerate the compound etc. being represented by formula (I-1)～formula (I-15).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).
As the compound being represented by formula (II), can enumerate the compound etc. being represented by formula (II-1)～formula (II-15).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).
At least a kind of compound selecting from the compound being represented by formula (I) and the compound being represented by formula (II) can be distinguished use separately.In addition, they can be with ratio mixing arbitrarily.In the situation that mixing, its mixture ratio calculates preferred formula (I) taking mol ratio: formula (II) is 5: 95～95: 5, and more preferably 10: 90～90: 10, and then be preferably 20: 80～80: 20.
(b2) as multipolymer (A2-1) and (A2-2) has oxetanyl and has the compound of unsaturated link, 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 Ethyloxetane, 3-ethyl-3-methacryloxyethyl oxetanes, 3-ethyl-3-acryloxy Ethyloxetane etc.
In multipolymer (A2-1), relatively form the total mole number of the constituent of multipolymer (A2-1), calculate preferably in following scope with mole fraction from the ratio of the derivative constituent of each composition.
From (a) derivative structural unit; 2～40 % by mole
From (c) derivative structural unit; 1～65 % by mole
From (b1) or (b2) derivative structural unit; 2～95 % by mole
In addition, if the ratio of described constituent is in following scope, more preferably.
From (a) derivative structural unit; 5～35 % by mole
From (c) derivative structural unit; 1～60 % by mole
From (b1) or (b2) derivative structural unit; 5～80 % by mole
If described component ratio, in above-mentioned scope, has the trend that bin stability, developability, solvent resistance, thermotolerance and physical strength improve.
Described have the deliquescent resin of alkali (A2-1) and can reference example manufacture as method and the citing document of recording in the document etc. of record in document " experimental method of Polymer Synthesizing " (the large grand row work sale room in Tianjin (strain) chemistry is with the 1st edition the 1st printing distribution on March 1st, 1972 of people).
Particularly, can enumerate the unit (a), (c) and the compound (b1) or (b2) that form multipolymer of deriving that adds polymerization initiator, solvent and ormal weight in reaction vessel, by utilizing 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 manufacture in two stages.In this case, also can manufacture with reference to method, the method for recording in JP 2001-89533 communique etc. recorded in above-mentioned document " experimental method of Polymer Synthesizing " (the large grand row work sale room in Tianjin (strain) chemistry is with the 1st edition the 1st printing distribution on March 1st, 1972 of people).
First, as the first stage, similarly carry out with the above-mentioned manufacture method with the deliquescent resin of alkali (A1), obtain multipolymer (, thering is the resin of alkali-soluble).
In this case, can similarly then use with various forms with above-mentioned.In addition, can be suitable for 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, relatively form the total mole number of the constituent of described multipolymer, respectively from (a) and (c) ratio of derivative constituent calculate preferably in following scope with mole fraction.
From (a) derivative structural unit; 5～50 % by mole
From (c) derivative structural unit; 50～95 % by mole
In addition, if the ratio of described constituent is in following scope, more preferably.
From (a) derivative structural unit; 10～45 % by mole
From (c) derivative structural unit; 55～90 % by mole
Then,, as subordinate phase, make to derive from the carboxylic acid of (a) and a part for carboxylic acid anhydrides for the multipolymer obtaining and derive from described (b1) or epoxy radicals or oxetanes radical reaction (b2).
Particularly, after above-mentioned steps, then atmosphere in flask being replaced as to air from nitrogen, is the constituent (b1) of 5～80 % by mole or (b2) to the molal quantity that adds relative constituent (a) in flask; For example relatively the total amount of monomer (a)～(c) is calculated as three dimethylamino methyl phenol of 0.001～5% the catalysts as carboxyl and epoxy radicals or oxetanyl using quality standard; And for example relatively the total amount of monomer (a)～(c) is calculated as 0.001～5% the quinhydrones as polymerization inhibitor, sustained response 1～10 hour at 60～130 DEG C using quality standard.Like this, can obtain resin (A2-2).In addition, can similarly consider manufacturing equipment with polymerizing condition or the calorie value that produces by polymerization etc. is suitably adjusted and added method or temperature of reaction.
In addition, in this case, molal quantity (b1) or (b2) is the molal quantity of (a) relatively, is preferably 10～75 % by mole, more preferably 15～70 % by mole.By within the scope of this, can there is the trend that the balance of bin stability, developability, solvent resistance, thermotolerance, physical strength and light sensitivity improves.
In resin (A2-3), relatively form the total mole number of the constituent of alkali soluble resin (A2-3), calculate preferably in following scope with mole fraction from the ratio of the derivative constituent of each composition.
From (a) derivative structural unit; 5～95 % by mole
From (b1) or (b2) derivative structural unit; 5～95 % by mole
In addition, if the ratio of described constituent is in following scope, more preferably.
From (a) derivative structural unit; 10～90 % by mole
From (b1) or (b2) derivative structural unit; 10～90 % by mole
If described component ratio, in above-mentioned scope, has the trend that bin stability, developability, solvent resistance, thermotolerance and physical strength improve.
Resin (A2-3) can reference example be manufactured as method and the citing document of recording in the document etc. of record in document " experimental method of Polymer Synthesizing " (the large grand row work sale room of Feng (strain) chemistry is with the 1st edition the 1st printing distribution on March 1st, 1972 of people).
Particularly, in reaction vessel, add the unit (a) and the compound (b1) or (b2) that form multipolymer of deriving of polymerization initiator, solvent and ormal weight, by utilizing nitrogen replace oxygen, under the non-existent condition of oxygen, stir, heat, be incubated, obtain thus multipolymer.In addition, the multipolymer obtaining can directly use reacted solution, also can use the solution after concentrated or dilution, the multipolymer that also can use the methods such as utilization precipitates again to take out as solid (powder).
The polymerizable compound (B) containing in photosensitive polymer combination of the present invention, as long as have polymerism, is not particularly limited, for example, can illustrate polyfunctional monomer that 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-, o-, m-, p-methylstyrene, to methoxy styrene, to phenylethylenes such as tert-butoxy styrene, 1-chloro-4-methyl-benzenes;
Butadiene, 2, the 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 cyclohexyl, (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, N-dimethylformamide ,-N, (methyl) acrylamides such as N-propyl amides;
The vinyl compounds such as (methyl) acryloyl aniline, (methyl) vinyl cyanide, acryl aldehyde, vinyl chloride, vinylidene chloride, NVP, vinyl acetate;
The 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, the glycidyl compounds such as 7-epoxy radicals heptyl ester, allyl glycidyl ether, vinyl glycidyl ether etc.
As 2 functional monomers' concrete example, 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.
Polyfunctional monomer that can be above as 3 officials, 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 monomer that 2 officials can be above.
The total amount of resin (A) and polymerizable compound (B) relatively, the amount of polymerizable compound (B) calculates and is preferably 1～70 quality %, more preferably 5～60 quality % with mass fraction.If the amount of polymerizable compound (B) in described scope, has the trend that the intensity of light sensitivity or film and pattern or flatness, reliability, physical strength improve, so preferably.
As the polymerization initiator containing in photosensitive polymer combination of the present invention (C), as long as the compound of initiated polymerization under the effect in light or heat, 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 light and/or the hot cationic polymerization initiators (for example, by (onium) kation and the polymerization initiator that derives from lewis acidic negative ion formation) in JP 2008-181087 communique, recorded.Wherein, di-imidazole compound due to light sensitivity remarkably and more preferably.
As described di-imidazolium compounds, can enumerate 2,2 '-bis-(2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl di-imidazoles, 2,2 '-bis-(2,3-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl di-imidazoles is (for example, with reference to Unexamined Patent 6-75372 communique, Unexamined Patent 6-75373 communique etc.), 2,2 '-bis-(2-chlorphenyls)-4,4 ', 5,5 '-tetraphenyl di-imidazoles, 2,2 '-bis-(2-chlorphenyl)-4,4 ', 5,5 '-tetra-(alkoxyl phenyl) di-imidazoles, 2,2 '-bis-(2-chlorphenyl)-4,4 ', 5,5 '-tetra-(dialkoxy phenyl) di-imidazoles, 2,2 '-bis-(2-chlorphenyl)-4,4 ', 5,5 '-tetra-(tri-alkoxy phenyl) di-imidazoles is (for example, with reference to examined patent publication 48-38403 communique, JP 62-174204 communique etc.), the phenyl of 4,4 ', 5,5 '-position replaced the di-imidazolium compounds that forms (for example, with reference to Unexamined Patent 7-10913 communique etc. by carbonyl alkoxy (calboalcoxy).) etc.Can preferably enumerate 2,2 '-bis-(2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl di-imidazoles, 2,2 '-bis-(2,3-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl di-imidazoles, 2,2 '-bis-(2,4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl di-imidazoles.
As described acetophenone based compound, can enumerate 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-(2,3-dimethyl benzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(2,4-dimethyl benzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(2-chlorobenzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(2-bromobenzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(3-chlorobenzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(4-chlorobenzyl)-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-(the bromo-4-methoxy-benzyl of 2-)-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, 5-triazine, 2, two (the trichloromethyl)-6-(4-methoxyl naphthyl)-1 of 4-, 3, 5-triazine, 2, two (the trichloromethyl)-6-piperonyls (piperonyl)-1 of 4-, 3, 5-triazine, 2, two (the trichloromethyl)-6-(4-methoxyl-styrene)-1 of 4-, 3, 5-triazine, 2, two (trichloromethyl)-6-[2-(5-methylfuran-2-yl) vinyl (ethenyl) of 4-]-1, 3, 5-triazine, 2, two (trichloromethyl)-6-[2-(furans-2-yl) vinyl of 4-]-1, 3, 5-triazine, 2, two (trichloromethyl)-6-[2-(4-diethylamino-2-aminomethyl phenyl) vinyl of 4-]-1, 3, 5-triazine, 2, two (the trichloromethyl)-6-[2-(3 of 4-, 4-Dimethoxyphenyl) vinyl]-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, the compound that can enumerate O-carbethoxyl group-α-oxygen base imino group-1-phenyl-propane-1-ketone, be represented by formula (III), the compound being represented by formula (IV) etc.
In addition go back preferably, and together with described polymerization initiator (C), use polymerization to cause auxiliary agent (C-1).Cause auxiliary agent (C-1) as polymerization, can enumerate the compound being represented by formula (V).
[in formula (V), the dotted line being represented by X represents the aromatic rings of the carbon number 6～12 that can be replaced by halogen atom.
Y represents oxygen atom, sulphur atom.
R 1represent the alkyl of 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.
As the alkyl of 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.
As the alkyl of 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 different because of carbon number, unless otherwise specified, each substituting group is applicable above-mentioned illustration all.In addition, equal either party in available straight or branched.
As the compound being represented by formula (V), can specifically enumerate
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 benzothiazoline,
2-(1-naphthoyl methylene)-3-methyl-5-phenyl benzothiazoline,
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 benzothiazoline,
2-(1-naphthoyl methylene)-3-methyl-5-chloro benzothiazoline,
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 benzothiazoline,
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 fluorobenzoyl methylene)-3-methyl-naphthalene [2,1-d] thiazoline,
2-(to 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 fluorobenzoyl methylene)-3-methyl-naphthalene [2,1-d] oxazoline,
2-(to fluorobenzoyl methylene)-3-methyl-naphthalene [1,2-d] oxazoline etc.
Wherein, can preferably enumerate 2-(2-naphthoyl the methylene)-3-methylbenzothiazole quinoline being represented by formula (V-1), the 2-benzoyl methylene-3-methyl-naphthalene [1 being represented by formula (V-2); 2-d] thiazoline, by formula (V-3) represent 2-(4-dibenzoyl methylene)-3-methyl-naphthalene [1,2-d] thiazoline.
By using these compounds, can make the photosensitive polymer combination obtaining become more ISO.The photosensitive polymer combination obtaining by use forms film or pattern, can make the throughput rate of film or pattern improve, thereby preferably.The compound being represented by formula (V) can the heat when curing (postbake) after film not distil, thus light and heat at least arbitrarily-transparency of fading under the effect of side improves, so preferred.
In addition, cause auxiliary agent (C-1) as polymerization, also can use the compound of at least a kind of expression selecting from formula (VI) and formula (VII).
[in formula (VI) and formula (VII), ring X 1and ring X 2represent independently respectively aromatic rings or the heterocycle of the carbon number 6～12 that can be replaced by halogen atom.Y 1and Y 2represent oxygen atom or sulphur atom.R 1and R 2represent the alkyl of 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 that can be replaced by halogen atom or heterocycle, 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) ring and their derivant etc.
As hydroxyl substituted alkyl, can enumerate methylol, hydroxyethyl, hydroxypropyl, hydroxyl butyl etc.
As hydroxyl substituted aryl, can enumerate hydroxy phenyl, hydroxyl naphthyl etc.
As alkoxy substituted alkyl, can enumerate methoxy, methoxy ethyl, methoxy-propyl, methoxyl butyl, butoxymethyl, ethoxyethyl group, ethoxycarbonyl propyl, propoxyl group butyl etc.
As alkoxy substituted aryl, can enumerate methoxyphenyl, ethoxy naphthyl etc.
The compound being represented by formula (VI) and formula (VII) can specifically be enumerated:
The dialkoxy naphthalene classes such as dimethoxy-naphthalene, diethoxy naphthalene, dipropoxy naphthalene, diisopropoxy naphthalene, dibutoxy naphthalene;
The 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;
The 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 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 '-tetra-(tert-butyl hydroperoxide carbonyl) benzophenone, 2; 4,6-tri-methyl benzophenone etc.
As described thioxanthones based compound, for example, can enumerate ITX, ITX, 2,4-diethyl thioxanthone, 2,4-bis-clopenthixal ketones, the chloro-4-propoxyl group of 1-thioxanthones etc.
As described anthracene based compound, for example, can enumerate 9,10-dimethoxy anthracene, EDMO, 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 the Photoepolymerizationinitiater initiater with the group that chain transfer can occur, also can use spy and show the Photoepolymerizationinitiater initiater of recording in 2002-544205 communique.
The Photoepolymerizationinitiater initiater of the group of chain transfer can be there is as described having, for example, the Photoepolymerizationinitiater initiater of following formula (1)～(6) can be enumerated.
The described Photoepolymerizationinitiater initiater with the group that chain transfer can occur also can be used as the composition use that forms resin (A).
In addition, preferably polymerization initiator-playing use polymerization causes auxiliary agent (C-2) with described.
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 '-bis-(dimethylamino) benzophenone; Michler's keton (Michler ' s ketone)), the aromatic amines compound of 4,4 '-bis-(diethylin) benzophenone and so on.
As carboxylic acid compound, can enumerate the assorted acetic acid class of the 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 resin (A) and polymerizable compound (B) relatively, the amount of polymerization initiator (C) calculates and is preferably 0.1～40 quality %, more preferably 1～30 quality % with mass fraction.
If the total amount of polymerization initiator (C) is within the scope of this, photosensitive polymer combination becomes ISO, use film that this photosensitive polymer combination forms or the intensity of pattern or the lip-deep flatness of film or pattern to there is the trend improving, so preferably.
The total amount of resin (A) and polymerizable compound (B) relatively, polymerization causes auxiliary agent (C-1) and/or use amount (C-2) is calculated and is preferably 0.01～50 quality %, more preferably 0.1～40 quality % with mass fraction.
If polymerization initiation auxiliary agent (C-1) and/or amount (C-2) are within the scope of this, the light sensitivity of the photosensitive polymer combination obtaining can further uprise, use the throughput rate of the pattern substrate of this photosensitive polymer combination formation to improve, so preferably.
Especially in the case of using the compound being represented by formula (V), the amount that the relative polymerization of its amount causes auxiliary agent (C-1) is preferably 50 quality %～100 quality %, more preferably 60 quality %～100 quality %, and then be preferably 65 quality %～100 quality %.If the amount of the compound being represented by formula (V) is within the scope of this, when the photosensitive polymer combination that contains this compound in use forms film, the transparency of film improves, so preferably.
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) for having the compound of more than 2 sulfydryl (sulfanyl) base in molecule.Wherein, have more than 2 the compound with the sulfydryl that the carbon atom of more than 2 aliphatic alkyls is combined, because the light sensitivity of photosensitive polymer combination of the present invention uprises, so preferably in use.
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, trimethylolpropane tris thiopropionate, trimethylolpropane tris thioglycolic acid ester, pentaerythrite tetrathio propionic ester, pentaerythrite tetrathio ethyl glycolate, trihydroxy ethyl three thiopropionates, pentaerythrite four (3-sulfydryl butyric ester), 1, two (3-sulfydryl butyryl acyloxy) butane of 4-etc.
Polymerization initiator (C) relatively, the amount of multi-functional thiol's compound (T) calculates and is preferably 0.5～100 quality %, more preferably 1～90 quality % with mass fraction.In addition, the total amount of adhesive resin (A) and optical polymerism compound (C) relatively, the amount of multi-functional thiol's compound calculates and is preferably 0.1～20 quality %, more preferably 1～10 quality % with mass fraction.If the amount of multi-functional thiol's compound (T), within the scope of this, has the trend that light sensitivity uprises and developability improves, so preferably.
The solvent that the solvent (D) using in photosensitive polymer combination of the present invention is preferably the constituent such as dissolving resin (A), polymerizable compound (B) and polymerization initiator (C) equably and does not react with each composition.In addition, solvent (D) more preferably at least contains the both sides' of specific two aklylene glycol dialkyl ethers and specific alcohol solvent.Wherein, two aklylene glycol dialkyl ethers and alcohol can be distinguished use separately, also can and use two or more.
As two aklylene glycol dialkyl ethers, for the alkyl of the alkylidene of carbon number 1～3 and carbon number 1～4 being contained respectively to 2 above solvents, 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.
Solvent (D) full dose relatively, two aklylene glycol dialkyl ethers preferably contain 30～90 quality %, more preferably contain 30～80 quality %, and then preferably contain 30～70 quality %.If within the scope of this, can suppress the uneven drying of film.That is, the in the situation that of dry coating, conventionally utilize drying under reduced pressure to make solvent seasoning, and owing to there is the trend that shortens drying time, so reduce pressure at short notice.Now, can there is bumping and become the reason of the generation of uneven drying in solvent, but can be by effectively prevent the uneven drying of film with two aklylene glycol dialkyl ethers within the scope of this.
As alcohol, the preferably alcohol of carbon number 1～6.This alcohol can be monohydroxy alcohol, also can be 2 yuan of above polyvalent alcohols.
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, 3-methoxybutanol, glycerine, 2 hydroxy propanoic acid ethyl ester, 2-hydroxy-2-methyl methyl propionate, 2-hydroxy-2-methyl ethyl propionate, 3-hydroxy methyl propionate, 3-hydracrylic acid ethyl ester, 3-hydracrylic acid propyl ester, hydroxy methyl acetate, hydroxyl ethyl acetate, Butyl Glycolate 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 contain 15～40 quality % alcohols relatively.
By containing alcohol in this scope, can obtain fully the dissolubility of resin etc., be simultaneously also adjustablely made into suitable viscosity, thereby realize the homogeneity of the film obtaining.In addition, even in the case of using slit die coating machine to carry out the coating of photosensitive polymer combination, also can prevent the dry of nozzle tip, 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 the ethylene glycol alkyl ether acetate esters such as methyl glycol acetate, ethyl cellosolve acetate, butyl cellosolve acetate, ethoxyethyl acetate(EA);
The 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, acetic acid methoxyl amyl group ester;
More than 7 propylene glycol one alkyl ethers of carbon number such as propylene glycol monobutyl ether;
The 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;
The 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, propandiol butyl ether propionic ester;
More than 7 butylene glycol one alkyl ethers of carbon number such as propoxyl group butanols, butoxy butanols;
The butylene glycol one alkyl ether acetate esters such as methoxy butyl acetate, acetic acid ethoxy butyl ester, acetic acid propoxyl group butyl ester, acetic acid butoxy butyl ester;
The 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;
The ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, hexone, cyclohexanone;
Methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methoxy menthyl acetate, methoxyacetic acid ethyl ester, methoxyacetic acid propyl ester, methoxyacetic acid butyl ester, ethoxy acetate, ethoxy ethyl acetate, ethoxyacetic acid propyl ester, ethoxyacetic acid butyl ester, propoxyl group methyl acetate, propoxyl group ethyl acetate, propoxyl group propyl acetate, propoxyl group butyl acetate, butoxy acetic acid methyl esters, butoxy acetic acid ethyl ester, butoxy acetic acid propyl ester, butoxy acetic acid butyl ester, 2-methoxy methyl propionate, 2-methoxy propyl acetoacetic ester, 2-methoxy propyl propyl propionate, 2-methoxy propyl acid butyl ester, 2-ethoxy-propionic acid methyl esters, 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-methoxy methyl propionate, 3-methoxy propyl acetoacetic ester, 3-methoxy propyl propyl propionate, 3-methoxy propyl acid butyl ester, 3-ethoxy-propionic acid methyl esters, 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, the ester classes such as 3-butoxy butyl propionate,
The more than 7 hydroxyl ester classes of carbon number such as butyl lactate, 3-hydracrylic acid butyl ester, 2-hydroxy-3-methyl methyl butyrate;
The ring-type such as tetrahydrofuran, pyrans ethers;
The cyclic ester classes such as gamma-butyrolacton etc.
In above-mentioned solvent, from the angle of coating, drying property, preferably boiling point is the organic solvent of 100 DEG C～200 DEG C.Wherein, can enumerate aklylene glycol alkyl ether acetate esters, ketone, butylene glycol alkyl ether acetate esters, more than 7 butylene glycol one alkyl ether of carbon number, the ester classes such as 3-ethoxyl ethyl propionate, 3-methoxy methyl propionate, preferably propylene glycol monomethyl ether acetic acid esters, ethoxy propyl acetate, cyclohexanone, methoxy butyl acetate, 3-ethoxyl ethyl propionate, 3-methoxy methyl propionate.
Wherein, preferably only use two above-mentioned aklylene glycol dialkyl ether and alcohol.
Photosensitive polymer combination relatively, the amount of the solvent (D) in photosensitive polymer combination of the present invention calculates and is preferably 60～90 quality %, more preferably 65～85 quality % with mass fraction.If the amount of solvent (D) within the scope of this, is expected to using spin coated machine (spincoater), slit & spin coated machine (slit & spin coater), slit coating agent (slit coater) (sometimes also referred to as mould coating machine (die coater), curtain formula curtain coater (curtain flow coater).), realize good coating when the 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 in fact the colorant such as pigment and dyestuff.,, 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 in fact the following colorant using in this field.
The compound that is divided into dyestuff (Pigment) in color index (Color Index) (The Society of Dyers and Colourists publication) can specifically be enumerated:
C.I. the 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, the 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, the red pigments such as 265;
C.I. pigment blue 15,15:3,15:4,15:6, the blue pigments such as 60;
C.I. pigment violet 1,19,23,29,32,36, the violet pigments such as 38;
C.I. pigment Green 7, the viridine greens such as 36;
C.I. the brown pigments such as bistre 23,25;
C.I. the 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, for example, can illustrate glass, silicon dioxide, aluminium oxide etc.
As other macromolecular compounds, for example, can enumerate the curable resin such as epoxy resin, maleimide resin, the thermoplastic resins such as polyvinyl alcohol (PVA), polyacrylic acid, polyglycol one alkyl ether, poly-fluoroalkyl acrylate, polyester, polyurethane etc.
As surfactant, can use any one in surfactant of silicone-based, fluorine system, ester system, kation system, negative ion system, nonionic system, both sexes etc. etc.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 (Mitsubishi Materials electronics changes into (strain)), Megafac (DIC (strain) system), Off ロ ラ-De (Sumitomo 3M (strain) system), Surfron (AGC beautifies clearly (strain) system), Solsperse (Geneka (strain) system), EFKA (CIBA company 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, 3-aminopropyl triethoxysilane, 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl group methyl dimethoxysilane, 2-(3, 4-epoxy radicals cyclohexyl) ethyl trimethoxy silane, 3-chloropropylmethyldimethoxysilane, 3-r-chloropropyl trimethoxyl silane, 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, 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] dioxa phosphorus (dioxaphosphepine), 3, 9-pair [2-{3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy }-1, 1-dimethyl ethyl]-2, 4, 8, 10-tetra-oxygen volutions [5, 5] undecane, 2, 2 '-di-2-ethylhexylphosphine oxide (6-tert-butyl-4-methyl-Phenol), 4, 4 '-butylidene two (the 6-tert-butyl group-3-methylphenol), 4, 4 '-thiobis (the 2-tert-butyl group-5-methylphenol), 2, 2 '-thiobis (6-tert-butyl-4-methyl-Phenol), dilauryl 3, 3 '-thiodipropionate, myristyl 3, 3 '-thiodipropionate, distearyl acyl group 3, 3 '-thiodipropionate, pentaerythrite base four (3-lauryl thiopropionate), 1, 3, 5-tri-(3, 5-di-tert-butyl-4-hydroxyl benzyl)-1, 3, 5-triazine-2, 4, 6 (1H, 3H, 5H)-triketone, 3, 3 ', 3 ", 5, 5 ', 5 "-six tert-butyl groups-a, a ', a "-(mesitylene-2, 4, 6-tri-bases) three-paracresol, pentaerythrite four [3-(3, 5-di-tert-butyl-hydroxy phenyl) propionic ester], 2, 6-bis--tert-butyl-4-methyl-Phenol 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-(the chloro-2H-benzotriazole-2-of 5-yl) phenyl] propionic ester, 2-[4-[(2-hydroxyl-3-dodecyloxy propyl group) oxygen]-2-hydroxy phenyl]-4, 6-two (2, 4-3,5-dimethylphenyl)-1, 3, 5-triazine, 2-[4-[(2-hydroxyl-3-(2 '-ethyl) hexyl) oxygen]-2-hydroxy phenyl]-4, 6-two (2, 4-3,5-dimethylphenyl)-1, 3, 5-triazine, 2, two (2-hydroxyl-4-butoxy phenyl)-6-(2 of 4-, 4-pair-butoxy phenyl)-1, 3, 5-triazine, 2-(2-hydroxyl-4-[1-carbonyl octyloxy ethoxy] phenyl)-4, two (the 4-phenyl)-1 of 6-, 3, 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, 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) ethanol form macromolecule, N, N ', N ", N " '-tetra-(4, two (butyl-(N-methyl-2 of 6-, 2, 6, 6-tetramethyl piperidine-4-yl) amino) triazine-2-yl)-4, 7-diaza decane-1, 10-diamines, decanedioic acid (Decandioic Acid) and two (2, 2, 6, 6-tetramethyl-1-(octyloxy)-4-piperidyl) ester and 1, the reactant of 1-dimethyl ethyl hydroperoxides, two (1, 2, 2, 6, 6-pentamethyl-4-piperidyl)-[[3, 5-two (1, 1-dimethyl ethyl)-4-hydroxy phenyl] methyl] butylmalonic acid ester, 2, two [N-butyl-N-(1-cyclohexyloxy-2 of 4-, 2, 6, 6-tetramethyl piperidine-4-yl) amino]-6-(2-hydroxyethyl amine)-1, 3, 5-triazine, 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 base material for example the substrate at glass, metal, plastics etc., be formed with coating on these substrates of color filter (color filter), various dielectric film or conducting film, driving circuit etc. and be formed as film.Film is dry and curing film preferably.In addition, also the film obtaining can be patterned as to required form and set it as pattern use.And then the part that also these films and/or pattern can be formed as to 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), under the condition that is 400～700nm at mensuration wavelength with spectrophotometer, measure transmitance, 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.
First, photosensitive polymer combination of the present invention is coated on base material.
As mentioned above, coating can be used the various apparatus for coating such as spin coated machine, slit & spin coated machine, slit coating agent, ink jet printer, roll coater, dip coater to carry out.Wherein, from dissolubility, prevent from being dried, prevent the generation equal angles of foreign matter, preferably utilize the coating of method of spin coating, preferably utilize the coating of slit & spin coated machine and slit coating machine etc.
Then, be preferably dried and/or prebake (prebake) is removed the volatile ingredients such as desolventizing.Like this, can obtain level and smooth uncured film.
Thickness to film is in this case not particularly limited, and can suitably adjust according to the material, the purposes etc. that use, for example, illustrate 1～6 μ m left and right.
And then, via the mask (mask) that is used to form target pattern, the ultraviolet ray for example occurring from mercury lamp, light emitting diode to the uncured film irradiation obtaining etc.Shape to mask is now not particularly limited, and can enumerate various shapes.In addition, live width etc. also can utilize mask size etc. suitably to adjust.
In exposure machine in recent years, the wave filter (filter) that wavelength can be used for blocking (cut) this wavelength domain less than the light of 350nm blocks, or, use the bandpass filter (band-pass filter) that can take out these wavelength domains optionally to take out near near near light 436nm, 408nm, 365nm, thereby irradiate equably parallel rays to plane of exposure entirety.Now, in order to carry out the contraposition accurately of mask and base material, also can use the devices such as mask aligner (mask aligner), ledex (stepper).
Afterwards, can, by making film contact aqueous alkali make for example unexposed portion of established part dissolve and develop, obtain target pattern shape.
Developing method can be any one in dress liquid method, dipping (dipping) method, injection (spray) method etc.And then, also can in the time developing, base material be inclined to angle arbitrarily.
The developer solution using in development is generally the aqueous solution that contains alkali compounds and surfactant.
Alkali compounds can be any one in 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 surfactant that surfactant can be nonionic.
Be surfactant as nonionic, 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.
Be surfactant as negative ion, for example, can enumerate the alkyl aryl sulfonate class of alkylsurfuric acid salt, neopelex or dodecyl sodium naphthalene sulfonate of higher alcohol sulfate salt, NaLS or Texapon Special of lauryl alcohol sodium sulfovinate or oleyl alcohol sodium sulfovinate and so on and so on and so on etc.
Be surfactant as kation, for example, can enumerate amine salt or the quaternary ammonium salt etc. of stearyl amine hydrochloride or lauryl trimethyl ammonium chloride and so on.
The concentration of the surfactant in alkaline developer is preferably the scope of 0.01～10 quality %, more preferably 0.05～8 quality %, and then be preferably 0.1～5 quality %.
After development, wash, and then cure after also can carrying out as required.After the applicable condition of curing be for example the temperature range, 10～180 minutes of 150～230 DEG C.
If hardening resin composition of the present invention uses spectrophotometer measuring for example, film mensuration transmitance to the 3 μ m thickness after (150～250 DEG C, 0.1～3 hour) that are heating and curing under the condition that wavelength is 400～700nm, 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.
The film obtaining like this or pattern for example can be used as the photoinduction gap material (photospacer) using in liquid crystal indicator, the coverlay (over coat) that can form pattern.In addition, in the time that uncured film is carried out to patterned exposure, can form hole with photomask by use hole (hole) formation, thereby can be used as interlayer dielectric.And then, in the time that uncured film is exposed, can, by not using photomask carry out blanket exposure and be heating and curing or be only heating and curing, form hyaline membrane.This hyaline membrane can be used as coverlay.In addition, also can in the display device such as touch panel (touch panel), use.Like this, can possess with high finished product rate manufacture the display device of high-quality film or pattern.
The hyaline membrane, pattern, photoinduction gap material, coverlay, dielectric film, liquid crystal aligning that photosensitive polymer combination of the present invention can especially form in order to be formed for forming the such as hyaline membrane of material of various films and pattern a part for color filter projection, lenticule (microlens) for control, combine colored pattern, the overlay etc. of different thickness and suitably utilize.In addition, also can in possessing these films or pattern color filter, array (array) substrate etc. as a part for its constituent part and then possessing display device such as liquid crystal indicator, the organic El device etc. of these color filters and/or array base palte etc., utilize.
embodiment
Below utilize embodiment to illustrate in greater detail photosensitive polymer combination of the present invention, but the present invention is not limited to these examples.In addition, in following embodiment and comparative example, represent % and part of amount or use amount, unless otherwise specified, all taking quality as standard.
Synthesis example 1
In the 1L flask that possesses reflux cooler, tap funnel and stirring machine, flow into nitrogen with the speed of 0.02L/ minute, become blanket of nitrogen, add 140 parts, diglycol ethyl-methyl ether, be heated to while stirring 70 DEG C.Then,, by 40 parts of methacrylic acids, acrylic acid 3,4-epoxy radicals three is encircled [5.2.1.0 2.6] decyl ester (potpourri of the compound being represented by formula (I-1) mixing at 50: 50 with mol ratio and the compound being represented by formula (II-1).) 360 parts be dissolved in 190 parts, diglycol ethyl-methyl ether, obtain solution, uses dropping liquid pump, with 4 hours, gained lysate is instilled into and is incubated in the flask of 70 DEG C.
On the other hand, by polymerization initiator 2, two (2, the 4-methyl pentane nitriles) 30 parts of 2 '-azo are dissolved in 240 parts, diglycol ethyl-methyl ether, and gained solution is used to other dropping liquid pumps, are instilled in flask with 5 hours.After the instillation of the solution of polymerization initiator finishes, remain at 70 DEG C 4 hours, be then cooled to room temperature, obtain multipolymer (Resin A solution a) of solid constituent 42.6%, acid value 60mg-KOH/g.The weight-average molecular weight (Mw) of the Resin A a obtaining is 8000, and dispersion degree is 1.91.
Synthesis example 2
In the 1L flask that possesses reflux cooler, tap funnel and stirring machine, flow into nitrogen with the speed of 0.02L/ minute, become blanket of nitrogen, add 305 parts, diglycol ethyl-methyl ether, be heated to while stirring 70 DEG C.Then,, by 60 parts of methacrylic acids, acrylic acid 3,4-epoxy radicals three is encircled [5.2.1.0 2.6] decyl ester (potpourri of the compound being represented by formula (I-1) mixing at 50: 50 with mol ratio and the compound being represented by formula (II-1).) 240 parts be dissolved in obtain solution in 140 parts, diglycol ethyl-methyl ether, use tap funnel, with 4 hours, this lysate is instilled into and is incubated in the flask of 70 DEG C.On the other hand, by polymerization initiator 2, two (2, the 4-methyl pentane nitriles) 30 parts of 2 '-azo are dissolved in 225 parts, diglycol ethyl-methyl ether, and gained solution is used to other tap funnels, are instilled in flask with 4 hours.After the instillation of the solution of polymerization initiator finishes, remain at 70 DEG C 4 hours, be then cooled to room temperature, obtain multipolymer (Resin A solution 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 obtaining is 13,600, and dispersion degree is 2.49.
Synthesis example 3
In the 1L flask that possesses reflux cooler, tap funnel and stirring machine, flow into nitrogen with the speed of 0.02L/ minute, become blanket of nitrogen, add 105 parts of 200 parts of 3-methoxyl-n-butyl alcohols and acetic acid 3-methoxyl butyl esters, be heated to while stirring 70 DEG C.Then,, by 60 parts of methacrylic acids, acrylic acid 3,4-epoxy radicals three is encircled [5.2.1.0 2.6] decyl ester (potpourri of the compound being represented by formula (I-1) mixing at 50: 50 with mol ratio and the compound being represented by formula (II-1).) 240 parts be dissolved in obtain solution in 140 parts of acetic acid 3-methoxyl butyl esters, use tap funnel, with 4 hours, this lysate is instilled into and is incubated in the flask of 70 DEG C.On the other hand, by polymerization initiator 2, two (2, the 4-methyl pentane nitriles) 30 parts of 2 '-azo are dissolved in 225 parts of acetic acid 3-methoxyl butyl esters, and gained solution is used to other tap funnels, are instilled in flask with 4 hours.After the instillation of the solution of polymerization initiator finishes, remain at 70 DEG C 4 hours, be then cooled to room temperature, obtain multipolymer (Resin A solution 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 obtaining is 13,400, and dispersion degree is 2.50.
Use GPC method, utilize following condition to carry out the weight-average molecular weight (Mw) of multipolymer (Resin A a～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 DEG C
Solvent; THF (tetrahydrofuran)
Flow velocity; 1.0mL/min
Detecting device; RI
The weight-average molecular weight of the polystyrene conversion obtaining under above-mentioned condition and number-average molecular weight be compared to dispersion degree (Mw/Mn).
Embodiment 1～9, comparative example 1
The composition of mixture table 1, obtains photosensitive polymer combination 1～10.
The uneven > that evaluates of < mist
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 respectively the solution of the photosensitive polymer combination obtaining in embodiment and comparative example.
Then, utilize pressure Reduction Dryer (VCD Microtech (strain) system), degree of decompression is decompressed to 0.5torr, make it dry.On heating plate, prebake 2 minutes at 95 DEG C, forms film.
After cooling, utilize Na lamp (lamp) to irradiate film surface, through Visual Confirmation film coated surface.
Situation that can clear confirmation mist inequality (vaporific inequality) is ×, situation about can slightly confirm is △, situation about almost not confirming is zero.
< nail trace is evaluated >
With above-mentioned similarly form film after, drying under reduced pressure.Then, the corrosion resistant plate of thick 20mm in hole that has diameter 60mm is loaded in being set as on the heating plate of 90 DEG C, prebake 2 minutes thereon, forms film.
After cooling, utilize Na light irradiation film surface, through Visual Confirmation film coated surface.
Can be clear the situation of confirmation nail trace be ×, situation about can slightly confirm is △, situation about almost not confirming is zero.
< gap nozzle drying property is evaluated >
With the above-mentioned film that similarly forms.
Afterwards, do not carry out the washing of nozzle tip and directly place.After 1 minute, do not carry out the washing of nozzle tip and carry out identical coating.
Then, utilize pressure Reduction Dryer (VCD Microtech (strain) system), degree of decompression is decompressed to 0.5torr, make it dry.On heating plate, prebake 2 minutes at 90 DEG C, forms film.
After cooling, utilize Na light irradiation film surface, through Visual Confirmation film coated surface.
Situation that can clear confirmation vertical stripe inequality is ×, situation about can slightly confirm 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 light splitting (strain) system) (quartz cell, optical length; 1cm), measure the mean transmissivity (%) under 400～700nm.
The mean transmissivity > of < pattern
Use each photosensitive polymer combination, make cured film by following steps, 3 microns of the thickness tastes after solidifying.
The square glass substrate that is 5cm by neutral detergent, water and the 2-propyl alcohol washing length of side successively, then dry.Utilize spin coated, coating composition on this substrate, the thickness of the pattern after curing after making becomes 3.0 μ m.Then, utilize pressure Reduction Dryer (VCD Microtech (strain) system), degree of decompression is decompressed to 0.5torr, make it dry, form film.By this film, in heating plate, with 90 DEG C of prebake 2 minutes.Make the interval between substrate and quartz glass photomask processed 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), the film after prebake is exposed.In this exposure, make to pass through optical filter (LUO400 from the radiating light of ultrahigh pressure mercury lamp; Morning sun light splitting (strain) system) irradiate.In addition, used and be used to form the line of 100 μ m and the photomask of space pattern (line and space pattern).After exposure, utilize tetramethylammonium hydroxide aqueous solution (containing 2.38 parts of Tetramethylammonium hydroxide in 100 parts of the aqueous solution) dipping 60 seconds of 23 DEG C, develop, after washing, utilize heating plate after 235 DEG C, to cure 11 minutes, form line and space pattern.
To the each pattern obtaining, use micro-spectral light measurer (OSP-SP200; OLYMPUS company system), measure the mean transmissivity (%) under 400～700nm.
Transmitance uprises to show to absorb and diminishes.
[table 1]
Each composition in 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-1,2-diketone-2-oxime-O-benzoic ether (OXE 01; Qi Ba Japanese firm system)
Polymerization initiator (C) Cb; 2,2 '-bis-(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) PEMP processed)
Cause auxiliary agent C2b; 2-(2-naphthoyl methylene)-3-methylbenzothiazole quinoline
Solvent Da; 3-methoxyl-n-butyl alcohol
Solvent Db: propylene glycol monomethyl ether
Solvent Dc; Diglycol ethyl-methyl ether
Solvent Dd; Propylene glycol monomethyl ether acetic acid esters
Solvent De; Acetic acid 3-methoxyl butyl ester
Solvent Df; 3-ethoxyethyl group propionic ester
As mentioned above, in the time using photosensitive polymer combination of the present invention to form film, even form thicker film in coating, can there is not mist inequality, vertical stripe inequality and nail trace yet, can form the even and level and smooth high-quality film of film entirety.; because boiling point is compared with low and can shorten coating drying time, thereby can realize the raising of throughput rate, on the other hand; also can suppress top dry of gap nozzle (slitnozzle), thereby prevent the generation of the dry foreign matter causing, to 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 film or pattern and utilizing these films or pattern manufacture display device, can improve yield rate.
Utilizability in industry
If utilize the present invention, can form generation, the uniform high-quality film of film entirety that can suppress mist inequality, vertical stripe inequality and nail trace.
In addition, by utilizing photosensitive polymer combination of the present invention, can obtain high-quality display device etc.

Claims (5)

1. a photosensitive polymer combination, wherein,
Contain resin (A), polymerizable compound (B), polymerization initiator (C) and solvent (D),
In solvent (D), solvent total amount, two aklylene glycol dialkyl ethers of the alkylidene with carbon number 1～3 that contains 30～90 quality % and the alkyl of carbon number 1～4 and the 3-methoxybutanol of 10～50 quality % relatively.
2. photosensitive polymer combination according to claim 1, wherein,
Two aklylene glycol dialkyl ethers are diglycol ethyl-methyl ether.
3. a film, it is the film that right to use requires the photosensitive polymer combination described in 1 or 2 to form.
4. a pattern, it is the pattern that right to use requires the photosensitive polymer combination described in 1 or 2 to form.
5. a display device, wherein,
Comprise at least a kind that from film claimed in claim 3 and pattern claimed in claim 4, selects.
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