CN101792568A - Cured film - Google Patents

Cured film Download PDF

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Publication number
CN101792568A
CN101792568A CN201010003757A CN201010003757A CN101792568A CN 101792568 A CN101792568 A CN 101792568A CN 201010003757 A CN201010003757 A CN 201010003757A CN 201010003757 A CN201010003757 A CN 201010003757A CN 101792568 A CN101792568 A CN 101792568A
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China
Prior art keywords
methyl
cured film
acid
monomer
solvent
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Chinese (zh)
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武部和男
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D131/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Coating compositions based on derivatives of such polymers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements

Abstract

The invention provides a cured film, which is a cured film obtained by a resin composition. The resin composition contains a resin (A), a surfactant (B) and a solvent (C), the resin composition substantively does not contain polymerization monomers and colorants, and the content of the surfactant (B) relative to the solid component is 0.005 mass% to 0.5 mass%.

Description

Cured film
Technical field
The present invention relates to a kind of cured film.
Background technology
Display panels in recent years etc. is carrying out the maximization of substrate size, thereby the real estate that is formed with colour element, semiconductor element etc. usually utilizes rotary coating method, Xia Feng ﹠amp for the concavo-convex planarization substrate surface of burying its surface; Rotation (slit﹠amp; Spin) coating such as method forms.
On the other hand, from the productivity raising, to the reciprocity viewpoint of answering of large-scale picture, inquired into the limit curable resin composition solution has been carried out the method that province liquefaction limit forms the cured film of high-quality homogeneous.
As the method for the cured film that forms high-quality homogeneous, for example proposed to utilize and used 3-methoxyl group-1-butanols and 3-methoxyl group butylacetic acid ester to form the method (for example patent documentation 1) of cured film as the resin combination of solvent specific resin.
Patent documentation 1: the spy opens the 2006-193718 communique
But, if will use the resin combination of above-mentioned solvent to be applicable to slot die (slit die) (being also referred to as non-rotating (spinless)) coating method as representational coating process etc., then when solvent evaporation, cause the bumping of the small bubble that contains in the resin combination, thereby such bumping makes sometimes bubble the defective of crater (crater) shape occur causing in film coated surface.
Summary of the invention
The object of the present invention is to provide generation of defective that a kind of bumping that suppresses solvent causes etc. and the outstanding cured film of flatness on the whole.
That is, the invention provides following [1]～[9].
[1]. a kind of cured film, it is the cured film that is obtained by resin combination, described resin combination contains resin (A), tensio-active agent (B) and solvent (C) and does not contain polymerizable monomer and tinting material in fact, and the relative solids component amount of the content of tensio-active agent (B) is 0.005 quality %～0.5 quality %.
[2]. according to [1] described cured film, wherein,
Tensio-active agent (B) is to contain the tensio-active agent that is selected from least a kind of atom in Siliciumatom and the fluorine atom.
[3]. according to [1] or [2] described cured film, wherein,
Resin (A) is the multipolymer that unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydrides (A1) are obtained with monomer (A2) polymerization of the ring-type ehter bond with carbon number 2～4.
[4]. according to [3] described cured film, wherein,
Monomer (A2) with ring-type ehter bond of carbon number 2～4 is the monomer with epoxy ethyl.
[5]. according to [3] or [4] described cured film, wherein,
Monomer (A2) with ring-type ehter bond of carbon number 2～4 is the monomer with aliphatics polycycle epoxy group(ing).
[6]. according to any described cured film in [3]～[5], wherein,
Monomer (A2) with ring-type ehter bond of carbon number 2～4 is at least a kind of compound that is selected from the compound shown in compound shown in the formula (I) and the formula (II).
[in formula (I) and formula (II), R 1And R 2The alkyl of the carbon number 1～4 of representing hydrogen atom respectively independently or can being replaced by hydroxyl,
X 1And X 2Represent independently respectively singly-bound, carbon number 1～6 alkylidene group or-(CH 2) S-X '-(CH 2) t-, X ' is-S-,-O-or-NH-, s and t represent 0～6 integer respectively independently, wherein, s+t=6.]
[7]. according to any described cured film in [1]～[6], wherein,
Solvent (C) is for containing the solvent of diethylene glycol butyl ether acetic ester.
[8]. according to [7] described cured film, wherein,
Solvent (C) is the solvent of 1～40 quality % for the content of the diethylene glycol butyl ether acetic ester of relative solvent total amount.
[9]. a kind of display unit, it contains any described cured film in [1]～[8].
Embodiment
Cured film of the present invention is obtained by resin combination, and described resin combination contains resin (A), tensio-active agent (B) and solvent (C) and the relative solids component amount of content that do not contain polymerizable monomer and tinting material and tensio-active agent (B) in fact is 0.005 quality %～0.5 quality %.At this, the solids component amount is meant the summation of removing the composition that desolvates in the resin combination.
The resin combination of Shi Yonging contains resin (A), tensio-active agent (B) and solvent (C) in the present invention.
The resin (A) that uses in the present invention is not particularly limited, preferably also under the effect of at least any one party of light and heat, demonstrates reactive resin.
As resin (A), but the following multipolymer of illustration [K1]～[K4] etc.
[K1] multipolymer for unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydrides (A1) (following be recited as simply sometimes " (A1) ") and the monomer (A2) with ring-type ehter bond of carbon number 2～4 (following be recited as simply sometimes " (A2) ") are polymerized.
[K2] is for making (A1) and the multipolymer that (A2) is polymerized with monomer (A3).At this, monomer (A3) (following be recited as simply sometimes " (A3) ") for can with (A1) and/or (A2) monomer of copolymerization, be non-(A1) and/or (A2) monomer.
[K3] reacts the multipolymer that obtains for the ring-type ehter bond of a part that makes the carboxyl that derives from (A1) in (A1) and multipolymer (A3) and the carbon number 2～4 that derives from (A2).
[K4] (A1) with (A3) multipolymer.
Wherein, resin (A) be preferably [K1] (A1) with the multipolymer that (A2) is polymerized.
As unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydrides (A1), for example can enumerate aliphatics unsaturated carboxylic acid and/or aliphatics unsaturated carboxylic acid anhydrides etc.Particularly, can enumerate
Unsaturated monocarboxylic acid classes such as vinylformic acid, methacrylic acid, Ba Dousuan;
Unsaturated dicarboxylic acid classes such as toxilic acid, fumaric acid, citraconic acid, methylfumaric acid, methylene-succinic acid; And
The acid anhydrides of these unsaturated dicarboxylic acid classes;
Unsaturated list ((methyl) acryloxyalkyl) the ester class of the polycarboxylic acid that divalents such as mono succinate [2-(methyl) acryloxy ethyl] ester, phthalic acid list [2-(methyl) acryloxy ethyl] ester are above;
5-carboxyl dicyclo [2.2.1] hept-2-ene", 5,6-dicarboxyl dicyclo [2.2.1] hept-2-ene", 5-carboxyl-5-methyl bicycle [2.2.1] hept-2-ene", 5-carboxyl-5-methyl bicycle [2.2.1] hept-2-ene", 5-carboxyl-5-ethyl dicyclo [2.2.1] hept-2-ene", 5-carboxyl-6-methyl bicycle [2.2.1] hept-2-ene", 5-carboxyl-6-ethyl dicyclo [2.2.1] hept-2-ene", 5,6-dicarboxyl dicyclo [2.2.1] hept-2-ene" anhydride (norbornene dicarboxylic anhydride (Himic anhydride)) etc. contains dicyclo [2.2.1] the hept-2-ene" class of carboxyl or carboxylic acid anhydride;
Vinylformic acid α-(methylol) ester etc. contains the unsaturated esters of acrylic acid of hydroxyl and carboxyl etc. in a part.
Wherein, from the point of copolymerization and alkali dissolution, preferred vinylformic acid, methacrylic acid or maleic anhydride etc.
They can use more than 2 kinds alone or in combination.Wherein, in this manual, short of explanation especially in advance all can be used alone or in combination illustrative compound, composition, agent etc. more than 2 kinds.
In addition, in this manual, " (methyl) vinylformic acid " is meant at least a kind that selects from vinylformic acid and methacrylic acid." (methyl) acryl " reaches marks such as " (methyl) acrylate " and also has identical meaning.
The monomer (A2) of ring-type ehter bond with carbon number 2～4 is as long as for example have at least a kind of group selecting the group (for example epoxy ethyl, oxetanyl and tetrahydrofuran base) from the ring-type ehter bond with carbon number 2～4, and then is preferably the monomer with unsaturated link(age).
As (A2), for example can enumerate monomer, monomer, have the monomer of tetrahydrofuran base etc. with oxetanyl with epoxy ethyl.
Described monomer with epoxy ethyl for example is meant the polymerizable compound with at least a kind of group selecting from aliphatic epoxy base and ester ring type epoxy group(ing).
Monomer with epoxy ethyl is preferably has at least a kind of group selecting and the compound with unsaturated link(age) from aliphatic epoxy base and ester ring type epoxy group(ing).
The aliphatic epoxy base is meant to have the group that makes the structure that the chain type alkene epoxidation forms.
As compound with aliphatic epoxy base, particularly, can enumerate Racemic glycidol (methyl) acrylate, Beta-methyl Racemic glycidol (methyl) acrylate, β-ethyl Racemic glycidol (methyl) acrylate, Racemic glycidol vinyl ether, the spy open put down in writing in the flat 7-248625 communique by the compound of following formula (III) expression etc.
Figure G2010100037578D00051
(in formula (III), R 11～R 13The alkyl of representing hydrogen atom or carbonatoms 1～10 respectively independently, m are 1～5 integer.)。
At this, as alkyl, but illustration methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, the tertiary butyl, 1-methyl n-propyl, 2-methyl n-propyl, the tertiary butyl, 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.
Wherein, in all chemical structural formulas, though because of the carbon number difference is different, short of explanation especially in advance, the illustration of substituting group etc. can similarly be suitable in this specification sheets integral body.In addition, all can adopt two kinds of straight chain or ramose.
As described compound by formula (III) expression, for example can enumerate adjacent vinyl benzyl glycidyl ether, between the vinyl benzyl glycidyl ether, to the vinyl benzyl glycidyl ether, the adjacent vinyl benzyl glycidyl ether of Alpha-Methyl, vinyl benzyl glycidyl ether between Alpha-Methyl, Alpha-Methyl is to the vinyl benzyl glycidyl ether, 2,3-2-glycidyl oxygen ylmethyl vinylbenzene, 2,4-2-glycidyl oxygen ylmethyl vinylbenzene, 2,5-2-glycidyl oxygen ylmethyl vinylbenzene, 2,6-2-glycidyl oxygen ylmethyl vinylbenzene, 2,3,4-three-glycidyl oxygen ylmethyl vinylbenzene, 2,3,5-three-glycidyl oxygen ylmethyl vinylbenzene, 2,3,6-three-glycidyl oxygen ylmethyl vinylbenzene, 3,4,5-three-glycidyl oxygen ylmethyl vinylbenzene, 2,4,6-three-glycidyl oxygen ylmethyl vinylbenzene etc.
The ester ring type epoxy group(ing) is meant to have the group that makes the structure that the ring type alkene epoxidation forms.
As monomer, for example can enumerate the monomer with aliphatics monocyclic epoxy group(ing), monomer etc. with aliphatics polycycle epoxy group(ing) with ester ring type epoxy group(ing).Monomer with aliphatics monocyclic epoxy group(ing) is meant the polymerizable compound of the group with structure that the ring type alkene that has the epoxidation monocycle forms.In addition, the monomer with aliphatics polycycle epoxy group(ing) is meant the polymerizable compound of the group with structure that the ring type alkene that has the epoxidation polycyclic forms.Monomer with these epoxy group(ing) preferably has epoxy group(ing) and has the compound of unsaturated link(age) at least a kind the ring of selecting from aliphatics monocyclic epoxy group(ing) and aliphatics polycycle epoxy group(ing), more preferably has at least a kind of selecting and have the compound of (methyl) acryloxy from aliphatics monocyclic epoxy group(ing) and aliphatics polycycle epoxy group(ing).
As the ring type alkene of described monocycle, for example can enumerate cyclopentenes, tetrahydrobenzene, suberene, cyclooctene etc.Wherein, the compound of preferred carbon number 5～7.
As monomer, particularly, can enumerate the single oxide compound 1 of vinyl cyclohexene, 2-epoxy group(ing)-4-vinyl cyclohexane (Celloxide2000 for example with aliphatics monocyclic epoxy group(ing); Daicel chemical industry (strain) system), vinylformic acid 3,4-epoxy group(ing) cyclohexyl methyl ester (CyclomerA400 for example; Daicel chemical industry (strain) system), methacrylic acid 3,4-epoxy group(ing) cyclohexyl methyl ester (CyclomerM100 for example; Daicel chemical industry (strain) system) etc.
As the ring type alkene of described polycyclic, for example can enumerate dicyclo amylene, tricyclo decene, norbornylene, different norbornylene, dicyclo octene, Bicyclononene, dicyclo undecane alkene, three ring undecane alkene, dicyclo dodecane alkene, three cyclododecane alkene etc.Wherein, the compound of preferred carbon number 8～12.
As monomer with described aliphatics polycycle epoxy group(ing), for example can enumerate from vinylformic acid 3,4-epoxy group(ing) norcamphyl ester, methacrylic acid 3, at least a kind of compound selecting in 4-epoxy group(ing) norcamphyl ester, the compound etc. by the compound of formula (I) expression and formula (II) expression.
[in formula (I) and formula (II), R 1And R 2The alkyl of the carbonatoms 1～4 of representing hydrogen atom respectively independently or can being replaced by hydroxyl.
X 1And X 2Represent independently respectively singly-bound, carbon number 1～6 alkylidene group or-(CH 2) S-X '-(CH 2) t-, X ' is-S-,-O-or-NH-, s and t represent 0～6 integer respectively independently, wherein, s+t=6.]
As R 1And R 2, particularly, can enumerate hydrogen atom; Alkyl such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, the tertiary butyl;
Hydroxyl substituted alkyls such as methylol, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxymethyl ethyl, 1-hydroxyl-1-methylethyl, 1-hydroxyl butyl, 2-hydroxyl butyl, 3-hydroxyl butyl, 4-hydroxyl butyl.
Wherein, preferred hydrogen atom, methyl, methylol, 1-hydroxyethyl, 2-hydroxyethyl.More preferably hydrogen atom, methyl.
As X 1And X 2, can specifically enumerate singly-bound; Alkylidene groups such as methylene radical, ethylidene, propylidene;
Sulfo-alkylidene group, oxyalkylene, imido grpup alkylidene group etc. contain heteroatomic alkylidene group.But particular instantiation oxygen methylene radical, oxygen ethylidene, oxygen propylidene, thio-methylene, sulfo-ethylidene, sulfo-propylidene, imido grpup methylene radical, imido grpup ethylidene, imido grpup propylidene etc.
Wherein, preferred singly-bound, methylene radical, ethylidene, oxygen methylene radical or oxygen ethylidene.More preferably singly-bound, oxygen ethylidene.
From by at least a kind of compound selecting the compound of formula (I) expression and the compound by formula (II) expression preferably from by at least a kind of compound selecting the compound of following formula (I ') expression and the compound by formula (II ') expression.
In formula (I ') and formula (II '), R 1 'And R 2 'Respectively with described R 1And R 2Synonym.
As compound, can enumerate by the compound of formula (I-1)～formula (I-15) expression etc. by formula (I) expression.Formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9), formula (I-11)～formula (I-15) can be preferably enumerated, formula (I-1), formula (I-7), formula (I-9), formula (I-15) can be more preferably enumerated.
Figure G2010100037578D00081
As compound by formula (II) expression, can enumerate by the compound of formula (II-1)～formula (II-15) expression etc., formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9), formula (II-11)～formula (II-15) can be preferably enumerated, formula (II-1), formula (II-7), formula (II-9), formula (II-15) can be more preferably enumerated.
Reach at least a kind of compound selecting the compound of representing by formula (II) from compound and can distinguish use separately by formula (I) expression.In addition, also can mix by arbitrary ratio.Under the blended situation, this mixture ratio calculates with mol ratio, preferred formula (I): formula (II) is 5: 95～95: 5, more preferably 10: 90～90: 10, and then be preferably 20: 80～80: 20.
Described monomer with oxetanyl is meant the polymerizable compound that for example has oxetanyl.Monomer with oxetanyl is preferably the compound that has oxetanyl and have unsaturated link(age), more preferably has oxetanyl and has the compound of (methyl) acryloxy.
As monomer, can specifically enumerate 3-methyl-3-methacryloxy methyl trimethylene oxide, 3-methyl-3-acryloyl-oxy ylmethyl trimethylene oxide, 3-ethyl-3-methacryloxy methyl trimethylene oxide, 3-ethyl-3-acryloyl-oxy ylmethyl trimethylene oxide, 3-methyl-3-methacryloxyethyl trimethylene oxide, 3-methyl-3-acryloxy ethyl trimethylene oxide, 3-ethyl-3-methacryloxyethyl trimethylene oxide or 3-ethyl-3-acryloxy ethyl trimethylene oxide etc. with oxetanyl.
Described monomer with tetrahydrofuran base is meant the polymerizable compound that for example has tetrahydrofuran base.Monomer with tetrahydrofuran base is preferably the compound that has tetrahydrofuran base and have unsaturated link(age), more preferably has tetrahydrofuran base and has the compound of (methyl) acryloxy.
As monomer, can specifically enumerate tetrahydrofurfuryl acrylate (for example VISCOAT V#150, Osaka organic chemistry industry (strain) system), tetrahydrofurfuryl methacrylate etc. with tetrahydrofuran base.
As polymerisable monomer (A3), for example can enumerate
(methyl) alkyl-acrylates such as (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) n-butyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate;
(methyl) cyclohexyl acrylate, (methyl) vinylformic acid 2-methyl cyclohexane ester, (methyl) vinylformic acid three ring [5.2.1.0 2,6] decane-8-base ester (in this technical field,, is called as (methyl) vinylformic acid two cyclopentyl esters as trivial name.), (methyl) vinylformic acid cyclic alkyl ester class such as (methyl) vinylformic acid two cyclopentyl oxygen ethyl esters, (methyl) isobornyl acrylate;
(methyl) vinylformic acid aryl ester classes such as (methyl) phenyl acrylate, (methyl) vinylformic acid benzyl ester;
Vinylformic acid aryl ester classes such as phenyl acrylate, vinylformic acid benzyl ester;
Dicarboxylic diesters such as ethyl maleate, DEF, diethyl itaconate;
Hydroxyalkyl acrylate classes such as (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester;
Dicyclo [2.2.1] hept-2-ene", 5-methyl bicycle [2.2.1] hept-2-ene", 5-ethyl dicyclo [2.2.1] hept-2-ene", 5-hydroxyl dicyclo [2.2.1] hept-2-ene", 5-methylol dicyclo [2.2.1] hept-2-ene", 5-(2 '-hydroxyethyl) dicyclo [2.2.1] hept-2-ene", 5-methoxyl group dicyclo [2.2.1] hept-2-ene", 5-oxyethyl group dicyclo [2.2.1] hept-2-ene", 5,6-dihydroxyl dicyclo [2.2.1] hept-2-ene", 5,6-two (methylol) dicyclo [2.2.1] hept-2-ene", 5,6-two (2 '-hydroxyethyl) dicyclo [2.2.1] hept-2-ene", 5,6-dimethoxy dicyclo [2.2.1] hept-2-ene", 5,6-diethoxy dicyclo [2.2.1] hept-2-ene", 5-hydroxy-5-methyl base dicyclo [2.2.1] hept-2-ene", 5-hydroxyl-5-ethyl dicyclo [2.2.1] hept-2-ene", 5-methylol-5-methyl bicycle [2.2.1] hept-2-ene", 5-tert-butoxycarbonyl dicyclo [2.2.1] hept-2-ene", 5-cyclohexyl oxygen carbonyl dicyclo [2.2.1] hept-2-ene", 5-carbobenzoxy dicyclo [2.2.1] hept-2-ene", 5,6-two (tertbutyloxycarbonyl) dicyclo [2.2.1] hept-2-ene", 5, dicyclo unsaturated compound classes such as 6-two (cyclohexyl oxygen carbonyl) dicyclo [2.2.1] hept-2-ene";
N-alkyl maleimides such as N-methyl maleimide, N-ethyl maleimide, N-propyl group maleimide;
N-cycloalkyl maleimides such as N-cyclopentyl maleimide, N-cyclohexyl maleimide, N-ring octyl group maleimide;
The crosslinked carbon-ring type base of N-substituted maleimide amine such as N-adamantyl maleimide, N-norcamphyl maleimide;
N-aryl maleimides such as N-phenylmaleimide;
N-aralkyl maleimides such as N-benzyl maleimide;
Dicarbapentaborane imide derivative classes such as N-succinimido-3-maleimide benzoic ether, N-succinimido-4-maleimide butyric ester, N-succinimido-6-maleimide capronate, N-succinimido-3-maleimide propionic ester, N-(9-acridyl) maleimide;
Vinylbenzene, alpha-methyl styrene, a vinyl toluene, p-methylstyrene, Vinyl toluene, to methoxy styrene, vinyl cyanide, methacrylonitrile, vinylchlorid, vinylidene chloride, acrylamide, Methacrylamide, vinyl acetate, 1,3-divinyl, isoprene, 2,3-dimethyl-1,3-butadiene etc.
Wherein, from the point of copolymerization and alkaline hydrolysis, optimization styrene, N-phenylmaleimide, N-cyclohexyl maleimide, N-benzyl maleimide, dicyclo [2.2.1] hept-2-ene" etc.
Such resin (A) can be made method of for example putting down in writing and the citing document of putting down in writing in the document in document " laboratory method of Polymer Synthesizing " (the grand work sale room (strain) of going in big Tianjin is chemical with the 1st edition the 1st printing distribution on March 1st, 1972 of people) as reference.
Particularly, in reaction vessel, add to constitute the monomer (A1) of multipolymer and (A2), specified amount, polymerization starter and the solvent of (A3) arbitrarily, by using the nitrogen replace oxygen, under the condition that does not have oxygen, by stirring, heat, being incubated, obtain polymkeric substance.Polymerizing conditions such as adding method, temperature of reaction and time can consider producing apparatus, utilize polymeric thermal value etc. suitably to adjust.
Polymerization starter and solvent also can use at normally used polymerization starter in this field and solvent as used herein.For example can use polymerization starter described later and solvent (C) etc.
In addition, the multipolymer that obtains can directly use reacted solution, also can use the solution that concentrates or dilute, the solid (powder) that also can use methods such as utilizing redeposition to take out.
Especially when carrying out this polymerization,, can directly use reacted solution, thereby can simplify manufacturing process by using solvent described later (C) as solvent.
Multipolymer [K1] preferably each monomeric ratio constitutes the monomeric total mole number of multipolymer [K1] relatively, calculates with molar fraction, is in following scope.
(A1) 5～95 moles of %, more preferably 10～90 moles of %
(A2) 5～95 moles of %, more preferably 10～90 moles of %.
If molar fraction is in this scope, the trend that then exists package stability, development, solvent resistance, thermotolerance and physical strength to improve.
In addition, multipolymer [K2] preferably each monomeric ratio constitutes the monomeric total mole number of multipolymer [K2] relatively, calculates with molar fraction, is in following scope.
(A1) 2～40 moles of %, more preferably 5～35 moles of %
(A2) 2～95 moles of %, more preferably 5～80 moles of %
(A3) 1～65 mole of %, more preferably 1～60 mole of %.
If molar fraction is in this scope, the trend that then exists package stability, development, solvent resistance, thermotolerance and physical strength to improve.
Multipolymer [K3] can experience the operation manufacturing in two stages.
At first, with above-mentioned method similarly make (A1) thereby and (A3) copolymerization obtain multipolymer.
In this case, the preferred monomeric total mole number that constitutes resin relatively of each monomeric ratio calculates with molar fraction, is in following scope.
(A1) 5～50 moles of %, more preferably 10～45 moles of %
(A3) 50～95 moles of %, more preferably 55～90 moles of %.
Then, make the part and the epoxy group(ing), oxetanyl or the tetrahydrofuran (THF) radical reaction that derive from (A2) of the carboxylic acid and/or the carboxylic acid anhydride of (A1) that derive from (A1) and multipolymer (A3).
For this reason, then, atmosphere in the flask is replaced as air from nitrogen, will (A2), in catalysts and the polymerization retarder adding flask, for example under 60～130 ℃, sustained reaction 1～10 hour.Reaction conditionss such as adding method, temperature of reaction and time can be considered producing apparatus and utilize polymeric thermal value etc. suitably to adjust.
The mole number of this moment (A2) is the mole number of (A1) relatively, is suitably for 5～80 moles of %, is preferably 10～75 moles of %, more preferably 15～70 moles of %.
If each monomeric ratio is in this scope, the trend that then exists the balance of package stability, development, solvent resistance, thermotolerance, physical strength and sensitivity to improve.
Catalysts for example is fit to use the catalysts of the catalysts that is used as carboxyl and epoxy group(ing), oxetanyl or tetrahydrofuran base.But particular instantiation three dimethylaminomethyl phenol etc.
But the usage quantity of catalysts is the total amount of illustration relative (A1)～(A3) for example, calculates with quality standard, is about 0.001～5 quality %.
But polymerization retarder is the illustration quinhydrones for example.
But the usage quantity of polymerization retarder is the total amount of illustration relative (A1)～(A3) for example, calculates with quality standard, is about 0.001～5 quality %.
Multipolymer [K4] preferably each monomeric ratio constitutes the monomeric total mole number of multipolymer [K4] relatively, calculates with molar fraction, is in following scope.
(A1) 2～40 moles of %, more preferably 5～35 moles of %
(A2) 60～98 moles of %, more preferably 65～95 moles of %
If molar fraction is in this scope, the trend that then exists package stability, solvent resistance, thermotolerance and physical strength to improve.
The weight-average molecular weight of the polystyrene conversion of resin (A) is preferably 3,000～100, and 000, more preferably 5,000～50,000.If the weight-average molecular weight of resin (A) is in this scope, the trend that then exists coating to improve.
The dispersity (molecular weight distribution) of resin (A) [weight-average molecular weight (Mw)/number-average molecular weight (Mn)] is preferably 1.1～6.0, and more preferably 1.2～4.0.If dispersity is in this scope, then there is the outstanding trend of coating.
Solids component in the relative resin combination of content of the resin (A) that can use in resin combination of the present invention calculates with massfraction, is preferably 5～99 quality %, more preferably 10～70 quality %.If the content of resin (A) is in this scope, the trend that then exists solvent resistance, thermotolerance and physical strength to improve.
The tensio-active agent (B) that uses in the present invention is not particularly limited, but for example illustration contains the tensio-active agent of at least a kind of atom selecting from Siliciumatom and fluorine atom.Particularly, can to enumerate silicone-based tensio-active agent, fluorine be tensio-active agent, have the silicone-based tensio-active agent of fluorine atom etc.Wherein, the silicone-based tensio-active agent that preferably has fluorine atom.By using such tensio-active agent (B), can work mutually with other compositions and the content thereof in the resin combination, be suppressed at the generation of the small bubble that contains in the composition.As a result, the bumping in the time of can suppressing solvent evaporation effectively.
As the silicone-based tensio-active agent, can enumerate tensio-active agent with siloxane bond.Particularly, Toray Silicon DC3PA, same SH7PA, same DC11PA, same SH21PA, same SH28PA, same 29SHPA, same SH30PA, polyether modified silicon oil SH8400 (trade(brand)name: Toray Silicon; The beautiful DOW CORNING in east (strain) system), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (SHIN-ETSU HANTOTAI's chemical industry (strain) system), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (MomentivePerformanceMaterials Japan contract commercial firm system) etc.
As fluorine is tensio-active agent, can enumerate the tensio-active agent with fluorohydrocarbon chain.Particularly, can enumerate Fo Luolinate (Off ロ リ Na one ト) (registered trademark) FC430, same FC431 (Sumitomo 3M (strain) system), Megafac (registered trademark) F142D, same F171, same F172, same F173, same F177, same F183, same R30, F489 (DIC (strain) system), EFTOP (registered trademark) EF301, same EF303, same EF351, same EF352 (the Mitsubishi Materials electronics changes into (strain) system), Surfron (registered trademark) S381, same S382, same SC101, same SC105 (rising sun whistle (strain) system), E5844 ((strain) Daikin Fine Chemical institute system), BM-1000, BM-1100 (is trade(brand)name: BM Chemie corporate system) etc.
As silicone-based tensio-active agent, can enumerate tensio-active agent with siloxane bond and fluorohydrocarbon chain with fluorine atom.Particularly, can enumerate Megafac (Co., Ltd.) R08, same BL20, same F475, same F477, same F443 (DIC (strain) system) etc.Can preferably enumerate Megafac (registered trademark) F475.
The solids component amount of tensio-active agent (B) resin combination of the present invention relatively, be 0.005 quality %～0.5 quality %, be preferably 0.01 quality %～0.2 quality %, 0.01 quality %～0.1 quality % more preferably, and then be preferably 0.01 quality %～0.07 quality %.By containing tensio-active agent in this scope, can make flatness good, simultaneously as mentioned above, also can prevent bumping effectively.
As the solvent (C) that uses in the present invention, can enumerate the various organic solvents that in the field of resin combination, use.
As concrete example, can enumerate the ethylene glycol monoalkyl ether class of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether and ethylene glycol monobutyl ether and so on;
Glycol ether dialkyl ethers such as diglyme, diethyl carbitol, glycol ether ethyl-methyl ether, glycol ether dipropyl ether, glycol ether dibutyl ether;
Ethylene glycol alkyl oxide acetate esters such as methylcellosolve acetate, ethyl cellosolve acetate (ethyl cellosolve acetate), ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate;
Aklylene glycol alkyl oxide acetate esters such as propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetic ester, methoxyl group butylacetic acid ester, methoxyl group amyl group acetic ester;
Propylene-glycol monoalky lether classes such as propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether;
Propylene glycol dialkyl ethers such as Propylene Glycol Dimethyl Ether, propylene glycol diethyl ether, propylene glycol ethyl-methyl ether, propylene glycol dipropyl ether, propylene glycol propyl group methyl ether, propylene glycol ethyl propyl ether;
Propylene glycol alkyl ether propionic acid esters such as propylene glycol monomethyl ether acetate, propylene-glycol ethyl ether propionic ester, propylene glycol propyl ether propionic ester, propylene glycol butyl ether propionic ester;
Butyleneglycol monoalkyl ethers such as methoxybutanol, oxyethyl group butanols, propoxy-butanols, butoxy butanols;
Butyleneglycol monoalky lether acetate esters such as methoxyl group butylacetic acid ester, oxyethyl group butylacetic acid ester, propoxy-butylacetic acid ester, butoxy butylacetic acid ester;
Butyleneglycol monoalky lether propionic acid esters such as methoxyl group butyl propionic ester, oxyethyl group butyl propionic ester, propoxy-butyl propionic ester, butoxy butyl propionic ester;
Dipropylene glycol dialkyl ethers such as dipropylene glycol dme, dipropylene glycol diethyl ether, dipropylene glycol methyl ethyl ether;
Benzene,toluene,xylene and mesitylene etc. are aromatic hydrocarbon based;
Ketones such as ethyl methyl ketone, acetone, methyl amyl ketone, hexone, pimelinketone;
Alcohols such as ethanol, propyl alcohol, butanols, hexanol, hexalin, ethylene glycol and glycerine;
Methyl acetate, ethyl acetate, propyl acetate, butylacetate, the 2 hydroxy propanoic acid ethyl ester, 2-hydroxy-2-methyl methyl propionate, 2-hydroxy-2-methyl ethyl propionate, hydroxy methyl acetate, hydroxyl ethyl acetate, the oxyacetic acid butyl ester, methyl lactate, ethyl lactate, propyl lactate, n-Butyl lactate, the 3-hydroxy methyl propionate, 3-hydroxy-propionic acid ethyl ester, 3-hydroxy-propionic acid propyl ester, 3-hydroxy-propionic acid butyl ester, 2-hydroxy-3-methyl methyl-butyrate, methoxy menthyl acetate, the methoxyacetic acid ethyl ester, the methoxyacetic acid propyl ester, the methoxyacetic acid butyl ester, ethoxy acetate, ethoxy ethyl acetate, the ethoxyacetic acid propyl ester, the ethoxyacetic acid butyl ester, the propoxy-methyl acetate, the propoxy-ethyl acetate, the propoxy-propyl acetate, the propoxy-butylacetate, the butoxy acetic acid methyl esters, the butoxy acetic acid ethyl ester, the butoxy acetic acid propyl ester, the butoxy acetic acid butyl ester, 2-methoxypropionic acid methyl esters, 2-methoxy propyl acetoacetic ester, 2-methoxy propyl propyl propionate, 2-methoxy propyl acid butyl ester, 2-ethoxy-propionic acid methyl esters, the 2-ethoxyl ethyl propionate, 2-ethoxy-c propyl propionate, 2-ethoxy-c acid butyl ester, 2-butoxy methyl propionate, 2-butoxy ethyl propionate, 2-butoxy propyl propionate, 2-butoxy butyl propionate, 3-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 3-methoxy propyl propyl propionate, 3-methoxy propyl acid butyl ester, 3-ethoxy-propionic acid methyl esters, the 3-ethoxyl ethyl propionate, 3-ethoxy-c propyl propionate, 3-ethoxy-c acid butyl ester, 3-propoxy-methyl propionate, 3-propoxy-ethyl propionate, 3-propoxy-propyl propionate, 3-propoxy-butyl propionate, 3-butoxy methyl propionate, 3-butoxy ethyl propionate, 3-butoxy propyl propionate, ester classes such as 3-butoxy butyl propionate;
Cyclic ether such as tetrahydrofuran (THF), pyrans base class;
Cyclic ester classes such as gamma-butyrolactone etc.
Solvent (C) is preferably the solvent that contains the diethylene glycol butyl ether acetic ester.
In addition, the viewpoint from coating, drying property and bumping prevent except the diethylene glycol butyl ether acetic ester, and then preferably contains aklylene glycol alkyl oxide acetate esters; Alcohols such as methoxybutanol and oxyethyl group butanols; Ketones such as pimelinketone; Ester classes such as 3-ethoxyl ethyl propionate, 3-methoxypropionic acid methyl esters, 3-methoxy menthyl acetate, 3-ethoxy ethyl acetate, 3-methoxyacetic acid butyl ester, 3-ethoxyacetic acid butyl ester.
The relative resin combination of content of solvent (C) calculates with massfraction, is preferably 60～90 quality %, more preferably 65～85 quality %.If the content of solvent (C) is in this scope, then when utilizing various apparatus for coating described later to be coated with, coating might improve.
The relative solvent of content of especially preferred diethylene glycol butyl ether acetic ester calculates with massfraction, is 1～40 quality %, more preferably 5～25 quality %.
The resin combination of Shi Yonging does not contain polymerizable monomer in fact in the present invention.In the resin combination of Shi Yonging, the content of the polymerizable monomer of composition in its entirety for example calculates with massfraction relatively, less than 1 quality %, preferably less than 0.5 quality % in the present invention.As polymerizable monomer, can enumerate monofunctional monomer, 2 functional monomers or the polyfunctional monomer more than the 3 officials energy etc. with unsaturated link(age).
As monofunctional monomer, can enumerate nonyl phenyl Trivalin SF (methyl) acrylate, (methyl) vinylformic acid 2-hydroxyl-3-phenoxy propyl ester, 2-ethylhexyl Trivalin SF (methyl) acrylate, (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinylformic acid Lauryl Ester, (methyl) stearyl acrylate acid esters, (methyl) vinylformic acid 2-(2-ethoxy ethoxy) ethyl ester, (methyl) vinylformic acid tetrahydrofuran base ester, caprolactone (methyl) acrylate, ethoxylated nonylphenol (methyl) acrylate, propoxylation nonylphenol (methyl) acrylate or N-vinyl pyrrolidone etc.
As 2 functional monomers, can enumerate 1,3-butyleneglycol two (methyl) acrylate, 1,3-butyleneglycol (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, ethylene glycol bisthioglycolate (methyl) acrylate, glycol ether two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, triglycol two (methyl) acrylate, Tetraglycol 99 two (methyl) acrylate, polyethyleneglycol diacrylate, two (acryloxy ethyl) ethers of dihydroxyphenyl propane, ethoxylation dihydroxyphenyl propane two (methyl) acrylate, ethoxylated neopentylglycol two (methyl) acrylate, ethoxylation neopentyl glycol two (methyl) acrylate or 3-methyl pentanediol two (methyl) acrylate etc.
As the above polyfunctional monomer of 3 officials energy, can enumerate trimethylolpropane tris (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, three (2-hydroxyethyl) isocyanuric acid ester three (methyl) acrylate, ethoxylated trimethylolpropane three (methyl) acrylate, propoxylation trimethylolpropane tris (methyl) acrylate, tetramethylolmethane 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 tetramethylolmethane 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 tetramethylolmethane three (methyl) acrylate, caprolactone modification three (2-hydroxyethyl) isocyanuric acid ester three (methyl) acrylate, caprolactone modification tetramethylolmethane 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 tetramethylolmethane three (methyl) acrylate and acid anhydrides, the reactant of caprolactone modification Dipentaerythritol five (methyl) acrylate and acid anhydrides, or the reactant of caprolactone modification tripentaerythritol seven (methyl) acrylate and acid anhydrides etc.
The resin combination of Shi Yonging does not contain tinting materials such as pigment and dyestuff in fact in the present invention.In the resin combination of Shi Yonging, the content of the tinting material of composition in its entirety calculates with massfraction relatively, usually less than 1 quality %, preferably less than 0.5 quality % in the present invention.
Also contain from carboxylic acid anhydride in the resin combination that can use in the present invention and have at least a kind of compound selecting the compound of at least 2 carboxyls.As compound, for example can enumerate polybasic acid anhydride, polycarboxylic acid etc. with 2 carboxyls.
As carboxylic acid anhydride, also can preferably use the commercially available epoxy curing agent that comprises colourless acid anhydrides.Particularly, can enumerate AdecahardnerEH-700 (trade(brand)name (as follows), rising sun electrochemical industry (strain) system), リ カ シ ッ De-HH, same MH-700 (new Japanese physics and chemistry (strain) system), エ ピ キ ニ ア 126, same YH-306, same DX-126 (oiling シ エ Le エ Port キ シ (strain) system) etc.
As polybasic acid anhydride, for example can enumerate
Aliphatic dicarboxylic acid acid anhydrides such as itaconic anhydride, succinyl oxide, citraconic anhydride, dodecenyl succinic anhydride, tricarballylic acid acid anhydride, maleic anhydride, hexahydro phthalic anhydride, methyl tetrahydrophthalic anhydride, norbornene dicarboxylic acids, norbornene dicarboxylic anhydride;
1,2,3, aliphatics polycarboxylic acid dianhydrides such as 4-butane tetracarboxylic acid dianhydride, pentamethylene tetracarboxylic dianhydride;
Aromatic series polybasic acid anhydrides such as Tetra hydro Phthalic anhydride, pyromellitic acid dianhydride, trimellitic acid 1,2-anhydride, benzophenone tetracarboxylic dianhydride;
Ethylene glycol bis trimellitic acid, glycerine three trimellitic acids etc. contain ester group acid anhydrides etc.
Wherein, from transparent high viewpoint in the visible region, preferred Tetra hydro Phthalic anhydride, trimellitic acid 1,2-anhydride.
As polycarboxylic acid, for example can enumerate
Aliphatics polycarboxylic acids such as succsinic acid, pentanedioic acid, hexanodioic acid, BTCA, toxilic acid, methylene-succinic acid;
Hexahydro-phthalic acid, 1,2-hexahydrobenzoic acid, 1,2, alicyclic polycarboxylic acids such as 4-hexanaphthene tricarboxylic acid, pentamethylene tetracarboxylic acid;
Phthalic acid, m-phthalic acid, terephthalic acid, trihemellitic acid, pyromellitic acid, 1,4,5, aromatic series polycarboxylic acids such as 8-naphthalene tetracarboxylic acid, benzophenone tetracid etc.
Wherein, from transparent high viewpoint in the visible region, preferred phthalic acid, trihemellitic acid.
In the present invention in the resin combination of Shi Yonging from carboxylic acid anhydride and have the total amount of the relative resin of content (A) of at least a kind of compound selecting the compound of at least 2 carboxyls, calculate with massfraction, be preferably 0.1～20 quality %, more preferably 1～15 quality %.If this compound is in this scope, the reliability of filming is improved.
The resin combination of Shi Yonging also can contain cationic polymerization initiators in the present invention.
As cationic polymerization initiators, also can use comprise positively charged ion with from lewis acidic anionic cationic polymerization initiators.
As cationic concrete example, can enumerate phenylbenzene iodine, two (p-methylphenyl) iodine, two (to tert-butyl-phenyl) iodine, two (to octyl phenyl) iodine, two (to the octadecyl phenyl) iodine, two (to octyloxyphenyl) iodine, two (to octadecane oxygen base phenyl) iodine, phenyl (to octadecane oxygen base phenyl) iodine, (p-methylphenyl) (p-isopropyl phenyl) iodine, triphenylsulfonium, three (p-methylphenyl) sulfonium, three (p-isopropyl phenyl) sulfonium, three (2, the 6-3,5-dimethylphenyl) sulfonium, three (to tert-butyl-phenyl) sulfonium, three (to cyano-phenyl) sulfonium, three (rubigan) sulfoniums or dimethyl (three (trichloromethyl) methyl) sulfonium etc.
As preferred cation, can enumerate two (p-methylphenyl) iodine, (p-methylphenyl) (p-isopropyl phenyl) iodine, two (to tert-butyl-phenyl) iodine, triphenylsulfonium or three (to tert-butyl-phenyl) sulfonium etc.
From lewis acidic anionic concrete example, can enumerate hexafluorophosphate, hexafluoro arsenate, hexafluoro antimonate or four (pentafluorophenyl group) borate etc. as described.From lewis acidic negatively charged ion, can enumerate hexafluoro antimonate or four (pentafluorophenyl group) borate as preferably.
These positively charged ions reach and can at random make up from lewis acidic negatively charged ion.
Concrete example as cationic polymerization initiators, can enumerate diphenyl iodine hexafluorophosphate, two (p-methylphenyl) iodine hexafluorophosphate, two (to tert-butyl-phenyl) iodine hexafluorophosphate, two (to octyl phenyl) iodine hexafluorophosphate, two (to the octadecyl phenyl) iodine hexafluorophosphate, two (to octyloxyphenyl) iodine hexafluorophosphate, two (to octadecane oxygen base phenyl) iodine hexafluorophosphate, phenyl (to octadecane oxygen base phenyl) iodine hexafluorophosphate, (p-methylphenyl) (p-isopropyl phenyl) iodine hexafluorophosphate, methyl naphthalene iodide hexafluorophosphate, ethyl naphthalene iodide hexafluorophosphate, the triphenylsulfonium hexafluorophosphate, three (p-methylphenyl) sulfonium hexafluorophosphate, three (p-isopropyl phenyl) sulfonium hexafluorophosphate, three (2, the 6-3,5-dimethylphenyl) sulfonium hexafluorophosphate, three (to tert-butyl-phenyl) sulfonium hexafluorophosphate, three (to cyano-phenyl) sulfonium hexafluorophosphate, three (rubigan) sulfonium hexafluorophosphate, dimethyl naphthyl sulfonium hexafluorophosphate, diethyl naphthyl sulfonium hexafluorophosphate, dimethyl (three (trichloromethyl) methyl) sulfonium hexafluorophosphate;
Phenylbenzene iodine hexafluoro arsenate, two (p-methylphenyl) iodine hexafluoro arsenate, two (to tert-butyl-phenyl) iodine hexafluoro arsenate, two (to octyl phenyl) iodine hexafluoro arsenate, two (to the octadecyl phenyl) iodine hexafluoro arsenate, two (to octyloxyphenyl) iodine hexafluoro arsenate, two (to octadecane oxygen base phenyl) iodine hexafluoro arsenate, phenyl (to octadecane oxygen base phenyl) iodine hexafluoro arsenate, (p-methylphenyl) (p-isopropyl phenyl) iodine hexafluoro arsenate, methyl naphthalene iodide hexafluoro arsenate, ethyl naphthalene iodide hexafluoro arsenate, the triphenylsulfonium hexafluoro arsenate, three (p-methylphenyl) sulfonium hexafluoro arsenate, three (p-isopropyl phenyl) sulfonium hexafluoro arsenate, three (2, the 6-3,5-dimethylphenyl) sulfonium hexafluoro arsenate, three (to tert-butyl-phenyl) sulfonium hexafluoro arsenate, three (to cyano-phenyl) sulfonium hexafluoro arsenate, three (rubigan) sulfonium hexafluoro arsenate, dimethyl naphthyl sulfonium hexafluoro arsenate, diethyl naphthyl sulfonium hexafluoro arsenate, dimethyl (three (trichloromethyl) methyl) sulfonium hexafluoro arsenate;
Phenylbenzene iodine hexafluoro antimonate, two (p-methylphenyl) iodine hexafluoro antimonate, two (to tert-butyl-phenyl) iodine hexafluoro antimonate, two (to octyl phenyl) iodine hexafluoro antimonate, two (to the octadecyl phenyl) iodine hexafluoro antimonate, two (to octyloxyphenyl) iodine hexafluoro antimonate, two (to octadecane oxygen base phenyl) iodine hexafluoro antimonate, phenyl (to octadecane oxygen base phenyl) iodine hexafluoro antimonate, (p-methylphenyl) (p-isopropyl phenyl) iodine hexafluoro antimonate, methyl naphthalene iodide hexafluoro antimonate, ethyl naphthalene iodide hexafluoro antimonate, the triphenylsulfonium hexafluoro antimonate, three (p-methylphenyl) sulfonium hexafluoro antimonate, three (p-isopropyl phenyl) sulfonium hexafluoro antimonate, three (2, the 6-3,5-dimethylphenyl) sulfonium hexafluoro antimonate, three (to tert-butyl-phenyl) sulfonium hexafluoro antimonate, three (to cyano-phenyl) sulfonium hexafluoro antimonate, three (rubigan) sulfonium hexafluoro antimonate, dimethyl naphthyl sulfonium hexafluoro antimonate, diethyl naphthyl sulfonium hexafluoro antimonate, dimethyl (three (trichloromethyl) methyl) sulfonium hexafluoro antimonate;
Phenylbenzene iodine four (pentafluorophenyl group) borate, two (p-methylphenyl) iodine four (pentafluorophenyl group) borate, two (to tert-butyl-phenyl) iodine four (pentafluorophenyl group) borate, two (to octyl phenyl) iodine four (pentafluorophenyl group) borate, two (to the octadecyl phenyl) iodine four (pentafluorophenyl group) borate, two (to octyloxyphenyl) iodine four (pentafluorophenyl group) borate, two (to octadecane oxygen base phenyl) iodine four (pentafluorophenyl group) borate, phenyl (to octadecane oxygen base phenyl) iodine four (pentafluorophenyl group) borate, (p-methylphenyl) (p-isopropyl phenyl) iodine four (pentafluorophenyl group) borate, methyl naphthalene iodide four (pentafluorophenyl group) borate, ethyl naphthalene iodide four (pentafluorophenyl group) borate, triphenylsulfonium four (pentafluorophenyl group) borate, three (p-methylphenyl) sulfonium four (pentafluorophenyl group) borate, three (p-isopropyl phenyl) sulfonium four (pentafluorophenyl group) borates, three (2, the 6-3,5-dimethylphenyl) sulfonium four (pentafluorophenyl group) borate, three (to tert-butyl-phenyl) sulfonium four (pentafluorophenyl group) borate, three (to cyano-phenyl) sulfonium four (pentafluorophenyl group) borate, three (rubigan) sulfonium four (pentafluorophenyl group) borate, dimethyl naphthyl sulfonium four (pentafluorophenyl group) borate, diethyl naphthyl sulfonium four (pentafluorophenyl group) borate, dimethyl (three (trichloromethyl) methyl) sulfonium four (pentafluorophenyl group) borate etc.
Can preferably enumerate two (p-methylphenyl) iodine hexafluorophosphates, (p-methylphenyl) (p-isopropyl phenyl) iodine hexafluorophosphate, two (to tert-butyl-phenyl) iodine hexafluorophosphate, the triphenylsulfonium hexafluorophosphate, three (to tert-butyl-phenyl) sulfonium hexafluorophosphate, two (p-methylphenyl) iodine hexafluoro arsenate, (p-methylphenyl) (p-isopropyl phenyl) iodine hexafluoro arsenate, two (to tert-butyl-phenyl) iodine hexafluoro arsenate, the triphenylsulfonium hexafluoro arsenate, three (to tert-butyl-phenyl) sulfonium hexafluoro arsenate, two (p-methylphenyl) iodine hexafluoro antimonate, (p-methylphenyl) (p-isopropyl phenyl) iodine hexafluoro antimonate, two (to tert-butyl-phenyl) iodine hexafluoro antimonate, the triphenylsulfonium hexafluoro antimonate, three (to tert-butyl-phenyl) sulfonium hexafluoro antimonate, two (p-methylphenyl) iodine four (pentafluorophenyl group) borate, (p-methylphenyl) (p-isopropyl phenyl) iodine four (pentafluorophenyl group) borate, two (to tert-butyl-phenyl) iodine, triphenylsulfonium four (pentafluorophenyl group) borate, three (to tert-butyl-phenyl) sulfonium four (pentafluorophenyl group) borate etc.
Can more preferably enumerate two (p-methylphenyl) iodine hexafluoro antimonates, (p-methylphenyl) (p-isopropyl phenyl) iodine hexafluoro antimonate, two (to tert-butyl-phenyl) iodine hexafluoro antimonate, the triphenylsulfonium hexafluoro antimonate, three (to tert-butyl-phenyl) sulfonium hexafluoro antimonate, two (p-methylphenyl) iodine four (pentafluorophenyl group) borate, (p-methylphenyl) (p-isopropyl phenyl) iodine four (pentafluorophenyl group) borate, two (to tert-butyl-phenyl) iodine four (pentafluorophenyl group) borate, triphenylsulfonium four (pentafluorophenyl group) borate, three (to tert-butyl-phenyl) sulfonium four (pentafluorophenyl group) borate etc.
The solids component amount of the relative resin combination of content of cationic polymerization initiators is calculated with massfraction, is preferably 0.1～40 quality %, more preferably 1～30 quality %.
If the total amount of cationic polymerization initiators then has the trend that can shorten set time in above-mentioned scope.
As required, in the resin combination that also can use in the present invention and with in addition macromolecular compound of weighting agent, resin (A), connecting airtight promotor, antioxidant, UV light absorber, photostabilizer, aggegation prevents additives such as agent, chain-transfer agent.
As weighting agent, can enumerate glass, silicon-dioxide, aluminum oxide etc.
As resin (A) macromolecular compound in addition, can enumerate curable resin or polyvinyl alcohol, polyacrylic acid, polyalkylene glycol monoalkyl ethers such as Resins, epoxy, maleimide resin, gather thermoplastic resins such as fluoroalkyl acrylate, polyester, urethane etc.
As connecting airtight promotor, the preferred silane based compound.Particularly, can enumerate vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (2-methoxy ethoxy) silane, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, N-(2-amino-ethyl)-3-TSL 8330, the 3-aminopropyltriethoxywerene werene, the 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl group methyl dimethoxysilane, 2-(3,4-epoxy group(ing) cyclohexyl) ethyl trimethoxy silane, the 3-chloropropylmethyldimethoxysilane, the 3-r-chloropropyl trimethoxyl silane, the 3-methacryloxypropyl trimethoxy silane, 3-sulfydryl propyl trimethoxy silicane etc.
As antioxidant; can enumerate the 2-tertiary butyl-6-(the 3-tertiary butyl-2-hydroxy-5-methyl base benzyl)-4-aminomethyl phenyl acrylate; 2-[1-(2-hydroxyl-3; the 5-di-tert-pentyl-phenyl) ethyl]-4; 6-di-tert-pentyl-phenyl acrylate; 6-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propoxy-]-2; 4; 8; 10-tetra-tert dibenzo [d; f] [1; 3; 2] two oxa-phosphides (Off オ ス Off エ ピ Application); 3; 9-pair [2-{3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy }-1; the 1-dimethyl ethyl]-2,4,8; 10-four oxygen spiral shells [5; 5] undecane; 2,2 '-methylene-bis (the 6-tertiary butyl-4-methylphenol); 4,4 '-butylidene two (the 6-tertiary butyl-3-methylphenol); 4; 4 '-thiobis (the 2-tertiary butyl-5-methylphenol); 2; 2 '-thiobis (the 6-tertiary butyl-4-methylphenol); dilauryl 3,3 '-thiodipropionate; myristyl 3,3 '-thiodipropionate; distearyl acyl group 3; 3 '-thiodipropionate; tetramethylolmethane four (3-lauryl thiopropionate); 1; 3,5-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl)-1; 3; 5-triazine-2,4,6-(1H; 3H; 5H)-triketone; 3,3 ', 3 "; 5; 5 ', 5 "-six tertiary butyls-A1 ', a "-(mesitylene-2; 4; 6-three bases) three p-cresol; tetramethylolmethane four [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester]; 2,6 di tert butyl 4 methyl phenol etc.
As UV light absorber, can enumerate 2-(2-hydroxyl-5-tert-butyl-phenyl)-2H-benzotriazole, octyl group-3-[3-tertiary butyl-4-hydroxy-5-(5-chloro-2H-benzotriazole-2-yl) phenyl] propionic ester, 2-[4-[(2-hydroxyl-3-dodecyloxy propyl group) oxygen]-the 2-hydroxy phenyl]-4,6-two (2, the 4-3,5-dimethylphenyl)-1,3, the 5-triazine, 2-[4-[(2-hydroxyl-3-(2 '-ethyl) hexyl) oxygen]-the 2-hydroxy phenyl]-4,6-two (2, the 4-3,5-dimethylphenyl)-1,3, the 5-triazine, 2, two (2-hydroxyl-4-the butoxy phenyl)-6-(2 of 4-, 4-pair-butoxy phenyl)-1,3, the 5-triazine, 2-(2-hydroxyl-4-[1-carbonyl octyloxy oxyethyl group] phenyl)-4, two (the 4-phenyl)-1 of 6-, 3, the 5-triazine, 2-(2H-benzotriazole-2-yl)-4, two (1-methyl isophthalic acid-phenylethyl) phenol of 6-, 2-(2H-benzotriazole-2-yl)-6-(1-methyl isophthalic acid-phenylethyl)-4-(1,1,3, the 3-tetramethyl butyl) phenol, 2-(the 3-tertiary butyl-2-hydroxy-5-methyl base phenyl)-5-chlorobenzotriazole or alkoxy benzene ketone etc.
As photostabilizer, can enumerate and comprise succsinic acid and (4-hydroxyl-2,2,6,6-tetramethyl piperidine-1-yl) the alcoholic acid polymer, N, N '; N ", N " and '-four (4, two (butyl-(N-methyl-2; 2,6, the 6-tetramethyl piperidine-4-yl) amino) triazines-2-yl of 6-)-4; 7-diaza decane-1,10-diamines; sebacic acid and two (2,2; 6,6-tetramethyl--1-(octyloxy)-4-piperidyl) esters and 1, the reactant of 1-dimethyl ethyl hydroperoxide; two (1,2,2,6,6-pentamethyl--4-piperidyl)-[[3,5-two (1, the 1-dimethyl ethyl)-4-hydroxy phenyls] methyl] butyl malonic acid ester, 2,4-two [N-butyl-N-(1-cyclohexyloxy-2,2,6,6-tetramethyl piperidine-4-yl) amino]-6-(2 hydroxy ethylamine)-1,3,5-triazines, two (1,2,2,6,6-pentamethyl--4-piperidyl) sebate or methyl (1,2,2,6,6-pentamethyl--4-piperidyl) sebate etc.
Prevent agent as aggegation, can enumerate sodium polyacrylate etc.
As chain-transfer agent, can enumerate lauryl mercaptan, 2,4-phenylbenzene-4-methyl-1-pentene etc.
The preferred solids component amount of the resin combination of Shi Yonging is about 10～30 quality % in the present invention, 12～28 quality % more preferably, and then be preferably 15～25 quality %.By being in this scope, utilize various coating processes, even especially utilize the slit method, also be difficult to take place defective etc., can form smooth cured film.
In addition, if the resin combination of Shi Yonging is filled in the quartzy box of light path 1cm and uses spectrophotometer to measure transmitance under the condition of wavelength 400～700nm in the present invention, then average transmittances is generally more than 70%, is preferably more than 80%.
The resin combination of Shi Yonging is when becoming cured film in the present invention, and the average transmittances of cured film is generally more than 90%, is preferably more than 95%.This average transmittances is the cured film of the thickness 3 μ m after (for example 100～250 ℃, 5 minutes～3 hours) of being heating and curing relatively, uses spectrophotometer, surveys periodic mean value under the condition of wavelength 400～700nm.Like this, can be provided at the transparent outstanding cured film of visible region.
For example as described later, can be by at base material substrates such as glass, metal, plastics for example, be formed with the resin combination that coating is used in the present invention on these substrates of colour filter, various insulation or conducting film, driving circuit etc., become smooth cured film.This cured film solidified cured film that normally has been dried.In addition, also the part of these cured film as the constituent part of display unit etc. can be formed.
Method for making to cured film describes.
At first, at base material or comprise the resin combination that coating is used in the present invention on the layer of solids component of preformed resin combination.
Coating process is not particularly limited, for example can uses spin coater (spin coater), Xia Feng ﹠amp; Rotary coating machine (slit﹠amp; Spin coater), slit coater (slit coater) (being also sometimes referred to as die head coating machine (die coater), the mobile varnishing machine (curtain flow coater) of curtain formula, non-rotating coating machine (spinless coater)), ink-jet (ink jet), roller coating machine (roll coater), dip coater apparatus for coating such as (dip coater) carry out.
Wherein, from solvability, drying prevent, the preventing etc. of foreign matter, preferably utilize the coating of being undertaken by the slot coated method, promptly utilize Xia Feng ﹠amp; Rotary coating machine and slit coater etc.
Then, preferably carry out drying or prebake and remove volatile component such as desolvate.Like this, can obtain level and smooth cured films.Be particularly suited for carrying out drying under reduced pressure.Drying under reduced pressure herein can be illustrated under the pressure about 50～150Pa, carry out in about 20～25 ℃ the temperature range.
The thickness of cured films to this moment is not particularly limited, and can utilize the material, purposes etc. of use suitably to adjust, but for example about illustration 0.1～30 μ m, about preferred 1～20 μ m, and then about preferred 1～6 μ m.
By after carrying out after the drying, curing, can obtain cured film such as planarization film.After cure for example preferred 150～230 ℃ temperature range, 10～180 minutes.
The resin combination of Shi Yonging is especially preferably for by using slit coater to be coated with to form film and the film that forms on substrate being carried out drying under reduced pressure make cured film such as planarization film and use in the present invention.
If utilize the present invention, but the generation limit of the defective that the bumping of limit inhibition solvent causes etc. forms the outstanding cured film of flatness on the whole.
In addition, by using such cured film, can obtain high-quality display unit.
Cured film of the present invention can be preferably at transparent film for example, especially constituting utilization in the transparent film etc. of a part of colour filter or array substrate.In addition, also these transparent films can be used as planarization film, can for example utilize in liquid crystal indicator, the organic El device etc. as the display unit that possesses colour filter, array substrate etc., these planarization films, colour filter and/or array substrate etc. of the part of its constituent part possessing planarization film etc., the display unit that possesses high-quality planarization film with the high rate of finished products manufacturing becomes possibility.
Embodiment
Below utilize embodiment that resin combination of the present invention is described in detail, but the present invention is not limited by these embodiment.In addition, in following embodiment and comparative example, the % of expression content or usage quantity and part are quality standard unless otherwise specified.
Resin A a's is synthetic
In the 1L flask that possesses reflux cooler, instillation funnel and stirrer, flowed into nitrogen, become nitrogen atmosphere, add 3-methoxyl group-1-butanols 59 mass parts and 3-methoxyl group butylacetic acid ester 81 mass parts, be heated to 70 ℃ while stirring with 0.02L/ minute.
Then, with 40 mass parts methacrylic acids, 360 mass parts 3,4-epoxy group(ing) three ring [5.2.1.0 2.6] decyl acrylate (by the compound of formula (I-1) expression and by 50: 50 the mixture of mol ratio of the compound of formula (II-1) expression) is dissolved in 80 mass parts 3-methoxyl group-1-butanols and 110 mass parts 3-methoxyl group butylacetic acid esters, obtain solution.Use the instillation pump,, this lysate is instiled to being incubated in 70 ℃ flask with 4 hours.
Figure G2010100037578D00261
On the other hand, with 36 mass parts polymerization starters 2,2 '-azo two (2, the 4-methyl pentane nitrile) is dissolved in 101 mass parts 3-methoxyl group-1-butanols and the 139 mass parts 3-methoxyl group butylacetic acid esters, with another pump that instils,, gained solution is instiled in flask with 5 hours.After the instillation of the solution of polymerization starter finishes, kept 4 hours down at 70 ℃, be cooled to room temperature then, obtain multipolymer (Resin A solution a) of solids component 42.5 quality %, acid number 56mg-KOH/g.The weight-average molecular weight of the Resin A a that obtains (Mw) is 7.6 * 10 3, dispersity is 2.01.
Resin A b's is synthetic
In the 1L flask that possesses reflux cooler, instillation funnel and stirrer, flowed into nitrogen, become nitrogen atmosphere, add 3-methoxyl group-1-butanols 56 mass parts and 3-methoxyl group butylacetic acid ester 84 mass parts, be heated to 70 ℃ while stirring with 0.02L/ minute.
Then, with 40 mass parts methacrylic acids, 360 mass parts 3,4-epoxy group(ing) three ring [5.2.1.0 2.6] decyl acrylate (by the compound of formula (I-1) expression and by 50: 50 the mixture of mol ratio of the compound of formula (II-1) expression) is dissolved in 76 mass parts 3-methoxyl group-1-butanols and 114 mass parts 3-methoxyl group butylacetic acid esters, obtain solution.Use the instillation funnel,, this lysate is instiled to being incubated in 70 ℃ flask with 4 hours.
On the other hand, with 14 mass parts polymerization starters 2,2 '-azo two (2, the 4-methyl pentane nitrile) is dissolved in 96 mass parts 3-methoxyl group-1-butanols and the 144 mass parts 3-methoxyl group butylacetic acid esters, with another funnel that instils,, gained solution is instiled in flask with 4 hours.After the instillation of the solution of polymerization starter finishes, kept 4 hours down at 70 ℃, be cooled to room temperature then, obtain the solution of the multipolymer (Resin A b) of solids component 42.3 quality %, acid number 57mg-KOH/g (solids component conversion).The weight-average molecular weight Mw of the Resin A b that obtains is 1.9 * 10 4, dispersity is 2.65.
Use the GPC method, under the following conditions, measure the weight-average molecular weight (Mw) and the number-average molecular weight (Mn) of above-mentioned resin.
Device; K2479 ((strain) Tianjin, island is made made)
Post; SHIMADZU Shim-pack GPC-80M
Column temperature; 40 ℃
Solvent; THF (tetrahydrofuran (THF))
Flow velocity; 1.0mL/min
Detector; RI
Likening to of the weight-average molecular weight of the polystyrene conversion that will obtain in above-mentioned and number-average molecular weight is dispersity (Mw/Mn).
Embodiment 1
Mix the resin solution (A) 235 parts (solids component converts 100 parts) contain the Resin A a that obtains, be 0.8 part of (B) 0.01 part of Megafac F-489 ((strain) DIC system), Irganox3114 (vapour crust Japan (strain) system) and the solvent (weight ratio of diethylene glycol butyl ether acetic ester, 3-methoxyl group butylacetic acid ester and 3-methoxyl group-1-butanols is 10: 45: 45) of tensio-active agent as fluorine, obtaining solid component concentration is the resin combination 1 of 19.3 quality %.
Embodiment 2
Mix 0.8 part of resin solution (A) 235 parts of (solids component converts 100 parts), (B) 0.05 part of Megafac F-489 ((strain) DIC system), the Irganox3114 (vapour crust Japan (strain) system) and the solvent (weight ratio of diethylene glycol butyl ether acetic ester, 3-methoxyl group butylacetic acid ester and 3-methoxyl group-1-butanols is 10: 45: 45) that contain the Resin A a that obtains, obtaining solid component concentration is the resin combination 2 of 19.3 quality %.
Embodiment 3
Mix 0.8 part of resin solution (A) 236 parts of (solids component converts 100 parts), (B) 0.01 part of Megafac F-489 ((strain) DIC system), the Irganox3114 (vapour crust Japan (strain) system) and the solvent (weight ratio of diethylene glycol butyl ether acetic ester, 3-methoxyl group butylacetic acid ester and 3-methoxyl group-1-butanols is 20: 40: 40) that contain the Resin A b that obtains, obtaining solid component concentration is the resin combination 3 of 19.3 quality %.
Embodiment 4
Mix 0.8 part of resin solution (A) 236 parts of (solids component converts 100 parts), (B) 0.05 part of Megafac F-489 ((strain) DIC system), the Irganox3114 (vapour crust Japan (strain) system) and the solvent (weight ratio of diethylene glycol butyl ether acetic ester, 3-methoxyl group butylacetic acid ester and 3-methoxyl group-1-butanols is 10: 45: 45) that contain Resin A b, obtaining solid component concentration is the resin combination 4 of 19.3 quality %.
Embodiment 5
Mix 0.8 part of resin solution (A) 236 parts of (solids component converts 100 parts), (B) 0.05 part of Megafac F-489 ((strain) DIC system), the Irganox3114 (vapour crust Japan (strain) system) and the solvent (weight ratio of diethylene glycol butyl ether acetic ester, 3-methoxyl group butylacetic acid ester and 3-methoxyl group-1-butanols is 20: 40: 40) that contain the Resin A b that obtains, obtaining solid component concentration is the resin combination 5 of 19.3 quality %.
Embodiment 6
Mix the resin solution (A) 236 parts (solids component converts 100 parts) contain the Resin A b that obtains, as 0.8 part of (B) 0.05 part of SH8400 (eastern beautiful DOW CORNING (strain) system), Irganox3114 (vapour crust Japan (strain) makes) and the solvent (weight ratio of diethylene glycol butyl ether acetic ester, 3-methoxyl group butylacetic acid ester and 3-methoxyl group-1-butanols is 10: 45: 45) of silicone-based tensio-active agent, obtaining solid component concentration is the resin combination 6 of 19.3 quality %.
Embodiment 7
Mix resin solution (A) 236 parts of (solids component converts 100 parts), (B) 0.05 part of (B) 0.05 part of Megafac F-489 ((strain) DIC system), the SH8400 (eastern beautiful DOW CORNING (strain) system), 0.8 part of Irganox3114 (vapour crust Japan (strain) system) and the solvent (weight ratio of diethylene glycol butyl ether acetic ester, 3-methoxyl group butylacetic acid ester and 3-methoxyl group-1-butanols is 10: 45: 45) that contain the Resin A b that obtains, obtaining solid component concentration is the resin combination 7 of 19.3 quality %.
Embodiment 8
Mix 0.8 part of resin solution (A) 235 parts of (solids component converts 100 parts), (B) 0.01 part of Megafac F-489 ((strain) DIC system), the Irganox3114 (vapour crust Japan (strain) system) and the solvent (weight ratio of diethylene glycol butyl ether acetic ester, 3-methoxyl group butylacetic acid ester and 3-methoxyl group-1-butanols is 1: 49.5: 49.5) that contain the Resin A a that obtains, obtain resin combination 8.
Embodiment 9
Mix 0.8 part of resin solution (A) 235 parts of (solids component converts 100 parts), (B) 0.01 part of Megafac F-489 ((strain) DIC system), the Irganox3114 (vapour crust Japan (strain) system) and the solvent (weight ratio of diethylene glycol butyl ether acetic ester, 3-methoxyl group butylacetic acid ester and 3-methoxyl group-1-butanols is 40: 30: 30) that contain the Resin A a that obtains, obtain resin combination 9.
Comparative example 1
Mix 0.8 part of resin solution (A) 235 parts of (solids component converts 100 parts), the Irganox3114 (vapour crust Japan (strain) system) and the solvent (weight ratio of diethylene glycol butyl ether acetic ester, 3-methoxyl group butylacetic acid ester and 3-methoxyl group-1-butanols is 10: 45: 45) that contain Resin A a, obtaining solid component concentration is the resin combination 10 of 19.3 quality %.
The resin combination that obtains in embodiment 1～9 and comparative example 1 is carried out following evaluation respectively.
＜bumping evaluation 〉
With the glass substrate (the system Eagle2000 of Corning Incorporated) of neutral detergent, water and alcohol washing 5cm * 5cm, carry out drying then successively.On this glass substrate, use rotary coating machine, with 600rpm, the condition in 10 seconds, the resin combination of coating embodiment 1～9 and comparative example 1.Then,, be decompressed to 130Pa, make its drying with drying under reduced pressure machine (VCD MICROTECH (strain) system).After the cooling, with reflection-type optical microscopic examination film coated surface.It is the results are shown in table 2.
The situation that bumping will not take place is made as zero, the situation that bumping takes place is made as *.
Wherein, for the situation that bumping takes place,, end the evaluation of tomography difference owing to do not obtain level and smooth filming.
＜tomography difference is estimated 〉
Estimate making of substrate
With each composition of the mixed shown in the table 1, obtain colored resin composition 1.
[table 1]
C.I. pigment Blue 15: 6 5.48 part
C.I. pigment Violet 23 0.35 part
Pigment dispersing agent 2.04 part
Methacrylic acid benzyl ester/Sipacril 2739OF (quality ratio of components 65/35, polystyrene conversion weight-average molecular weight 25,000) 7.38 part
Dipentaerythritol acrylate (Japanese chemical drug (strain) system KAYARAD DPHA) 7.38 part
2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butanone (vapour crust Japan (strain) system I-369) 1.77 part
C.I. pigment Blue 15: 6 5.48 part
4,4 '-diethylamino benzophenone (hodogaya chemical (strain) system EAB-F) 0.59 part
Polyether modified silicone (eastern beautiful DOW CORNING (strain) system SH8400) 0.01 part
The 3-ethoxyl ethyl propionate 15.00 part
Propylene glycol methyl ether acetate 60.00 part
With the glass substrate (the system Eagle2000 of Corning Incorporated) of neutral detergent, water and alcohol washing 5cm * 5cm, carry out drying then successively.On this glass substrate, use rotary coating machine, coating colored resin composition 1.Then, in cleaning oven (clean oven), with 90 ℃ of prebake 3 minutes.After the cooling, make the substrate that has been coated with this colored resin composition 1 and the interval of silica glass system photomask become 100 μ m, with under the air atmosphere, 100mJ/cm 2Exposure (365nm standard), use exposure machine (TME-150RSK; ト プ コ Application (strain) system, light source; Ultrahigh pressure mercury lamp) carries out rayed.Wherein, Ci Shi the irradiation to colored resin composition is to make the radiating light from ultrahigh pressure mercury lamp pass through optical filter (UV-35; Rising sun Techno Glass (strain) system) uses.In addition, as photomask, use the photomask that is formed with pattern (alternately having transmittance section and light shielding part is respectively the linear pattern of 100 μ m) at grade.
After carrying out rayed, above-mentioned filming be impregnated under 23 ℃ that to contain nonionic be tensio-active agent 0.12% with 80 seconds of water system developing solution of sodium hydroxide 0.04% and develop, after the washing, in baking oven, carry out curing after 20 minutes with 220 ℃, make the evaluation substrate of space (space) portion of coloring line (line) portion that alternately has 100 μ m and 100 μ m.The thickness of colored resin composition is 1.36 μ m.
On this estimates with substrate, use rotary coating machine, with the resin combination of 600rpm, the condition in 10 seconds coating embodiment 1～9.Then, be decompressed to 1.0torr with drying under reduced pressure machine (MICROTECH (strain) system), make its drying, mounting is in setting on 95 ℃ the hot-plate (hot plate) then, and prebake is 2 minutes thereon, and formation is filmed.And then, with 230 ℃ of heating 20 minutes, make its curing.After the cooling, use contact pin type film thickness gauge (Veeco corporate system DEKTAK 6M), measure maximum film thickness and minimum thickness, calculate tomography poor (=maximum film thickness-minimum thickness).It is the results are shown in table 2.
If the tomography difference less than the thickness of substrate, then is good.
The average transmittances of＜film 〉
Use each resin combination, carry out as described below, make cured film, the thickness after it is solidified becomes 3 μ m.With glycol ether n-butyl ether acetic ester letdown resin composition, make solids component become 20 quality %.Be coated with rotary coating method, making it solidify the back thickness becomes 3 μ m, carries out 100 ℃ * 10 minutes prebake, is heating and curing with 220 ℃ * 20 minutes then.
To each cured film that obtains, use micro-spectral light measurer (OSP-SP200; The OLYMPUS corporate system), the average transmittances (%) under mensuration 400～700nm.
Transmitance uprises and shows that absorption diminishes.
[table 2]
Figure G2010100037578D00311
In the table 2, the content of tensio-active agent (%) is the content (%) of the solids component amount of apparent surface's promoting agent, and the content of diethylene glycol butyl ether acetic ester (quality %) is the content (quality %) of the diethylene glycol butyl ether acetic ester of relative solvent total amount.
The average transmittances (%) of wavelength 400～700nm when in addition, average transmittances (%) is 3 μ m thickness.
Utilizability on the industry
Cured film of the present invention large-area be smooth on the whole, defective that the bumping of solvent causes etc. can occur hardly. In addition, the overlay etc. that owing to have high permeability, can be preferred for diaphragm (overcoat), dielectric film, is used for the thickness of corresponding colored pattern uses in the purposes such as planarization film of the uses such as display unit.

Claims (9)

1. cured film, it is the cured film that is obtained by resin combination, described resin combination contains resin (A), tensio-active agent (B) and solvent (C) and does not contain polymerizable monomer and tinting material in fact, and the relative solids component amount of the content of tensio-active agent (B) is 0.005 quality %～0.5 quality %.
2. cured film according to claim 1, wherein,
Tensio-active agent (B) is to contain the tensio-active agent that is selected from least a kind of atom in Siliciumatom and the fluorine atom.
3. cured film according to claim 1 and 2, wherein,
Resin (A) is the multipolymer that unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydrides (A1) are obtained with monomer (A2) polymerization of the ring-type ehter bond with carbon number 2～4.
4. cured film according to claim 3, wherein,
Monomer (A2) with ring-type ehter bond of carbon number 2～4 is the monomer with epoxy ethyl.
5. according to claim 3 or 4 described cured film, wherein,
Monomer (A2) with ring-type ehter bond of carbon number 2～4 is the monomer with aliphatics polycycle epoxy group(ing).
6. according to any described cured film in the claim 3～5, wherein,
Monomer (A2) with ring-type ehter bond of carbon number 2～4 is at least a kind of compound that is selected from the compound shown in compound shown in the formula (I) and the formula (II),
Figure F2010100037578C00011
In formula (I) and formula (II), R 1And R 2The alkyl of the carbon number 1～4 of representing hydrogen atom respectively independently or can being replaced by hydroxyl,
X 1And X 2Represent independently respectively singly-bound, carbon number 1～6 alkylidene group or-(CH 2) s-X '-(CH 2) t-, X ' is-S-,-O-or-NH-, s and t represent 0～6 integer respectively independently, wherein, s+t=6.
7. according to any described cured film in the claim 1～6, wherein,
Solvent (C) is for containing the solvent of diethylene glycol butyl ether acetic ester.
8. cured film according to claim 7, wherein,
Solvent (C) is the solvent of 1～40 quality % for the content of the diethylene glycol butyl ether acetic ester of relative solvent total amount.
9. display unit, it contains any described cured film in the claim 1～8.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107272331A (en) * 2016-03-30 2017-10-20 住友化学株式会社 Hardening resin composition and cured film

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW200813635A (en) * 2006-05-16 2008-03-16 Nissan Chemical Ind Ltd Positive type photosensitive resin composition and porous film obtained therefrom
CN101490170A (en) * 2006-07-27 2009-07-22 大赛璐化学工业株式会社 Curable resin composition and method for forming cured coating film

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4305608B2 (en) * 2002-03-11 2009-07-29 Ｊｓｒ株式会社 Color filter protective film composition and protective film
JP2005031642A (en) * 2003-06-19 2005-02-03 Chisso Corp Positive radiation-sensitive polymer composition, thin film using the composition and element using the thin film
JP2005283786A (en) * 2004-03-29 2005-10-13 Jsr Corp Curing composition for antireflection film of microlens and antireflective layered product for microlens using the same
US7799509B2 (en) * 2005-06-04 2010-09-21 Samsung Electronics Co., Ltd. Photosensitive resin composition, method of manufacturing a thin-film transistor substrate, and method of manufacturing a common electrode substrate using the same
KR101371878B1 (en) * 2007-05-11 2014-03-07 가부시끼가이샤 다이셀 Photo- and/or thermo-curable copolymer, curable resin compositions, and cured articles

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW200813635A (en) * 2006-05-16 2008-03-16 Nissan Chemical Ind Ltd Positive type photosensitive resin composition and porous film obtained therefrom
CN101490170A (en) * 2006-07-27 2009-07-22 大赛璐化学工业株式会社 Curable resin composition and method for forming cured coating film

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107272331A (en) * 2016-03-30 2017-10-20 住友化学株式会社 Hardening resin composition and cured film
CN107272331B (en) * 2016-03-30 2021-09-24 住友化学株式会社 Curable resin composition and cured film

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