CN101206402A - Photosensitive resin composition - Google Patents
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- CN101206402A CN101206402A CNA2007101611252A CN200710161125A CN101206402A CN 101206402 A CN101206402 A CN 101206402A CN A2007101611252 A CNA2007101611252 A CN A2007101611252A CN 200710161125 A CN200710161125 A CN 200710161125A CN 101206402 A CN101206402 A CN 101206402A
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Abstract
A photosensitive resin composition of the present invention comprises a binder resin(A), a photopolymerization compound(B), a photopolymerization initiator(C) and solvents(D), wherein the binder resin(A) is a copolymer of unsaturated carboxylic acids and/or unsaturated carboxylic acid anhydrides(A1) and aliphatic polycyclic epoxy compounds(A2). The invention provides a novel photosensitive resin composition keeping a low viscosity in preservation and being capable of forming dividable patterns or coatings excellent in solvent resistance and heat resistance.
Description
Technical field
The present invention relates to photosensitive polymer combination.
Background technology
Be provided with separator to keep the interval of two substrates between the filter substrate of formation display device and the array base palte in liquid crystal indicator or the touch panel etc.This separator uses beaded glass, plastic bead equal sphere particle.
Yet if use such spheroidal particle, this spheroidal particle can disperse on glass substrate out of orderly, so can damage TFT element or electrode etc., in addition, if this spheroidal particle is present in through in the pixel portions, because the incident scattering of light, the contrast of liquid crystal display cells can reduce.Therefore, propose to replace use spheroidal particle and form the scheme of separator by photosensitive polymer combination.According to this method, can form separator in arbitrary site, so can solve the above problems a little.
As such photosensitive polymer combination, known have contain acrylic copolymer and form with composition (patent documentation 1) as the separator of adhesive resin with carboxyl and glycidyl ether, wherein disclose as long as use said composition, just can obtain solvent resistance, spacer pattern that thermotolerance is outstanding.
Patent documentation 1: the spy opens flat 11-133600 communique
But, according to the inventor's research as can be known, contain with the photosensitive polymer combination of aliphatics monocycle epoxy radicals as the resin of constituent, viscosity when it is preserved rises very big, and describedly it is believed that than better as the stable resin of constituent with glycidyl ether with the resin of aliphatics monocycle epoxy radicals as constituent.
In addition, also wish to develop the photosensitive polymer combination that can form pattern with fine live width.
Summary of the invention
The objective of the invention is to, provide viscosity when preserving little and can form the photosensitive polymer combination of pattern with fine live width.
The inventor studies in order to obtain solving the photosensitive polymer combination of above-mentioned problem, found that, the viscosity rising of photosensitive polymer combination when preserving that contains certain binary system multipolymer is little, can form the pattern with fine live width.
That is, the invention provides following [1]～[5].
[1] a kind of photosensitive polymer combination, contain adhesive resin (A), optical polymerism compound (B), Photoepolymerizationinitiater initiater (C) and solvent (D), adhesive resin (A) is the multipolymer that unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydrides (A1) and aliphatics are encircled epoxy compound (A2) more.
[2] about [1] described photosensitive polymer combination, it is to have epoxy radicals on the ring of aliphatics polycyclic compund that aliphatics is encircled epoxy compound (A2) more, and has the compound of unsaturated link.
[3] about [1] or [2] described photosensitive polymer combination, having aliphatics, to encircle the monomer of epoxy radicals (A2) be from at least a compound of selecting the compound of formula (I) expression and the group with the compound composition of formula (II) expression more.
[in formula (I) and formula (II), R represents independently that respectively carbon number that hydrogen atom maybe can replace with hydroxyl be 1～4 alkyl, and X represents independently that respectively it is 1～6 alkylidene that singly-bound maybe can contain heteroatomic carbon number.]
[4] use any pattern that described photosensitive polymer combination forms in [1]～[3].
[5] liquid crystal indicator that contains [4] described pattern.
Embodiment
Below, describe the present invention in detail.
Photosensitive polymer combination of the present invention contains adhesive resin (A), optical polymerism compound (B) and Photoepolymerizationinitiater initiater (C) and then also contains other adjuvants (F), solvent (D) arbitrarily.
Photosensitive polymer combination of the present invention preferred main forms material as pattern, adhesive resin (A), optical polymerism compound (B) and Photoepolymerizationinitiater initiater (C), other adjuvants (F) preferred dissolution or be scattered in the solvent (D) arbitrarily.
The adhesive resin that uses in the photosensitive polymer combination of the present invention (A) is unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydrides (A1) and the multipolymer with monomer (A2) of aliphatics polycycle epoxy radicals, preferably has alkali dissolution.
As above-mentioned unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydrides (A1), specifically for example can enumerate:
Unsaturated monocarboxylic acid classes such as acrylic acid, methacrylic acid, crotonic acid;
Unsaturated dicarboxylic acid classes such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid;
And the acid anhydrides of above-mentioned unsaturated dicarboxylic acid class;
Unsaturated list [2-(methyl) acryloyloxyalkyl] the ester class of the polybasic carboxylic acids more than 2 yuan such as mono succinate [2-(methyl) acrylyl oxy-ethyl] ester, phthalic acid list [2-(methyl) acrylyl oxy-ethyl] ester;
The unsaturated esters of acrylic acid that in a part, contains hydroxyl and carboxyl of α-(hydroxymethyl) acrylic acid and so on etc.
Wherein, from copolyreaction, with respect to the high viewpoint of the dissolubility of aqueous alkali, preferably use acrylic acid, methacrylic acid, maleic anhydride etc.They can use separately, can also make up two or more uses.
It is the compound that has epoxy radicals on the ring of aliphatics polycyclic compund that above-mentioned aliphatics is encircled epoxy compound (A2) more, above-mentioned aliphatics is encircled epoxy compound (A2) more and is preferably had epoxy radicals on the ring of aliphatics polycyclic compund, and has the compound of unsaturated link.
As this aliphatics polycyclic compund, for example can enumerate dicyclo pentane, tristane, norbornane, different norbornane, double-octane, bicyclic nonane, dicyclo undecane, three ring undecanes, dicyclo dodecane, three cyclododecanes etc., preferred carbon number is 8～12 compound, more preferably at least a compound of selecting from the group of the compound formation represented with the compound of formula (I) expression with formula (II).
In formula (I) and formula (II), R represents the alkyl of the carbon number 1～4 that hydrogen atom maybe can replace with hydroxyl respectively independently.
X represents independently that respectively singly-bound maybe can contain the alkylidene of heteroatomic carbon number 1～6.
As R, specifically can enumerate hydrogen atom, alkyl such as methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, 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. contain the alkyl of hydroxyl.Wherein, preferably can enumerate hydrogen atom, methyl, hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, preferredly can enumerate hydrogen atom, methyl.
As X, specifically can enumerate singly-bound, alkylidenes such as methylene, ethylidene, propylidene, oxygen methylene, oxygen ethylidene, oxygen propylidene, sulphur methylene, sulphur ethylidene, sulphur propylidene, aminomethylene, amino ethylidene, amino propylidene etc. contain heteroatomic alkylidene etc.Wherein, preferably can enumerate singly-bound, methylene, ethylidene, oxygen methylene, oxygen ethylidene, preferredly can enumerate singly-bound, oxygen ethylidene.
As compound with formula (I) expression, can enumerate the compound of usefulness formula (I-1)～formula (I-15) expression etc., preferably can enumerate formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9), formula (I-11)～formula (I-15), preferredly can enumerate (I-1), formula (I-7), formula (I-9), (I-15).
As compound with formula (II) expression, can enumerate the compound of usefulness formula (II-1)～formula (II-15) expression etc., preferably can enumerate formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9), formula (II-11)～formula (II-15), preferredly can enumerate (II-1), formula (II-7), formula (II-9), (II-15).
At least a compound of selecting from the group that constitutes with the compound of formula (I) expression with the compound of formula (II) expression can be distinguished separately and uses, can also be with ratio mixing arbitrarily.When mixing, its mixture ratio is represented preferred formula (I) with molar ratio: formula (II) is 5: 95～95: 5, more preferably 10: 90～90: 10, and more preferably 20: 80～80: 20.
The adhesive resin of Shi Yonging (A) is (A1) and multipolymer (A2) in the present invention.
The adhesive resin of Shi Yonging (A) is to make (A1) and (A2) copolymerization and the multipolymer that obtains in the present invention, and is preferred in following scope in mole fraction with respect to the total mole number of the constituent that constitutes above-mentioned multipolymer from the ratio of the constituent of each compound deriving.
From the formation unit that (A1) derives: 5～75 moles of %
From the formation unit that (A2) derives: 25～95 moles of %
In addition, if the ratio of above-mentioned constituent in following scope then more preferably.
From the formation unit that (A1) derives: 10～70 moles of %
From the formation unit that (A2) derives: 30～90 moles of %
If the trend that sharpness, development, solvent resistance, thermotolerance and the physical strength of the pattern that in above-mentioned scope, there is the storage stability of photosensitive polymer combination in the ratio of above-mentioned constituent, obtain from said composition become good.
The method of record and the citing document of putting down in writing in the document were made during above-mentioned adhesive resin (A) for example can list of references " experimental method of Polymer Synthesizing " (the big grand row work sale room in Tianjin (strain) chemistry is with people's first published first impression distribution on March 1st, 1972).
Particularly, the unit (A1) and ormal weight (A2), polymerization initiator and the solvent that constitute multipolymer are put in the reaction vessel, replaced oxygen, do not having under the condition of oxygen thus, stir, heat, be incubated, obtain polymkeric substance thus with nitrogen.Wherein, the polymkeric substance that obtains can directly use reacted solution, can also use to concentrate or the solution of dilution, can also use by the material of methods such as precipitation again as solid (powdery object) taking-up.
The weight-average molecular weight of the polystyrene conversion of above-mentioned adhesive resin (A) is preferred 3000～100000, and more preferably 5000～50000.Adhesive resin (A) if weight-average molecular weight in above-mentioned scope, the trend that exists coating to become good, in addition, be difficult to during development produce " film reduces (Mo Minus り) ", and then the deciduous (order け of non-pixel portion when developing) good, so the trend that sharpness is good is preferred.
The molecular weight distribution of adhesive resin (A) [weight-average molecular weight (Mw)/number-average molecular weight (Mn)] is preferably 1.1～1.6, and more preferably 1.2～4.0.If in above-mentioned scope, there is the trend that development is good, sharpness is outstanding in molecular weight distribution, so preferred.
The content of the adhesive resin that uses in photosensitive polymer combination of the present invention (A) is preferably 5～90 quality % with respect to the solid constituent in the photosensitive polymer combination (being meant the central 25 ℃ of following compositions as solid of composition in the composition) in massfraction, more preferably 10～70 quality %.Adhesive resin (A) if content in above-mentioned scope, dissolubility in developer solution is abundant, is difficult on the substrate of non-pixel portion to produce the development residue, is difficult to produce " the film minimizing " of the pixel portion of exposure portion in addition when developing, the deciduous of non-pixel portion is good, so preferred.
As the optical polymerism compound (B) that contains in the photosensitive polymer combination of the present invention, can enumerate monofunctional monomer, two functional monomers, the above polyfunctional monomer of other trifunctionals.
As the object lesson of monofunctional monomer, can enumerate acrylic acid nonyl phenyl carbitol ester, acrylic acid 2-hydroxyl-3-phenoxy group propyl ester, acrylic acid 2-ethylhexyl carbitol ester, acrylic acid 2-hydroxyl ethyl ester, N-vinyl pyrrolidone etc.
Object lesson as two functional monomers, can enumerate two (methyl) acrylic acid 1, two (acrylyl oxy-ethyl) ethers of 6-hexanediol ester, two (methyl) acrylic acid glycol ester, two (methyl) acrylic acid DOPCP, two (methyl) acrylic acid triglycol ester, bisphenol-A, two (methyl) acrylic acid 3-methyl pentanediol ester etc.
As the object lesson of other polyfunctional monomers more than trifunctional, can enumerate trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, the reaction product of pentaerythrite three (methyl) acrylate and acid anhydrides, the reaction product of dipentaerythritol five (methyl) acrylate and acid anhydrides, the polyfunctional monomer that the trifunctional of the caprolactone modification in the molecule more than 1 is above, the polyfunctional monomer that the trifunctional of the alkylene oxide modification in the molecule more than 3 is above etc.
Wherein, in this manual, caprolactone modification is meant open loop body or the ring-opening polymerization polymer that imports caprolactone between the alcohol position, source of (methyl) acrylate compounds and (methyl) acryloxy.
In addition, the alkylene oxide modification is meant open loop body or its ring-opening polymerization polymer of between the alcohol of (methyl) acrylate compounds position, source and (methyl) acryloxy importing aklylene glycol or its dehydration condensation and alkylene oxide.
As the polyfunctional monomer more than the trifunctional of the caprolactone modification more than 1 in the molecule, for example can enumerate KAYARAD DPCA-20, KAYARAD DPCA-40, KAYARADDPCA-60, KAYARAD DPCA-120 (being Japanese chemical drug (strain) corporate system), NK ester AD-TMP-4CL commercially available products such as (Xin Zhong village chemical industry (strain) systems).
In the middle of the polyfunctional monomer more than the trifunctional of the alkylene oxide modification in molecule more than 3,, can enumerate oxirane, epoxypropane as preferred alkylene oxide.
Wherein, preferably use the above polyfunctional monomer of two senses.These optical polymerism compounds (B) can use separately, can also be also with two or more.
The content of optical polymerism compound (B) is preferably 1～90 quality % with respect to the total amount of adhesive resin (A) and optical polymerism compound (B) in massfraction, more preferably 10～80 quality %.Optical polymerism compound (B) if content in above-mentioned scope, so the trend that exists the intensity of pixel portions or flatness, reliability to become good is preferred.
As the Photoepolymerizationinitiater initiater that in photosensitive polymer combination of the present invention, contains (C), preferably use acetophenone based compound, di-imidazole compound, oxime compound, triazine based compound, acyl group phosphine oxygen based compound.Cause auxiliary agent (C-1) in these Photoepolymerizationinitiater initiaters (C) and with photopolymerization, the sensitivity of the photosensitive polymer combination that obtains thus is higher, thus if use it to form pattern, can improve the throughput rate of pattern, so preferred.
As above-mentioned acetophenone based compound, for example 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, the 1-hydroxycyclohexylphenylketone, 2-methyl isophthalic acid-(4-methyl thio phenyl)-2-morpholino propane-1-ketone, 2-benzyl-2-methylamino-1-(4-morpholino phenyl) butane-1-ketone, 2-(2-methyl-benzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(3-methyl-benzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(4-methyl-benzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(2-Ethylbenzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(2-propyl group benzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(2-butyl benzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(2, the 3-dimethyl benzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(2, the 4-dimethyl benzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(2-benzyl chloride base)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(2-bromobenzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(3-benzyl chloride base)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(4-benzyl chloride base)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(3-bromobenzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(4-bromobenzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(2-methoxy-benzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(3-methoxy-benzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(4-methoxy-benzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(2-methyl-4-methoxy-benzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(2-methyl-4-bromobenzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-(2-bromo-4-methoxy-benzyl)-2-dimethylamino-1-(4-morpholino phenyl)-butanone, 2-hydroxy-2-methyl-1-[4-(1-methyl ethylene) phenyl] oligomer etc. of propane-1-ketone.
As above-mentioned di-imidazolium compounds, for example can enumerate 2,2 '-two (2-chlorphenyls)-4; 4 ', 5,5 '-tetraphenyl di-imidazoles; 2; 2 '-two (2, the 3-dichlorophenyl)-4,4 '; 5,5 '-tetraphenyl di-imidazoles (for example, is opened flat 6-75372 communique with reference to the spy; Te Kaiping 6-75373 communique etc.); 2; 2 '-two (2-chlorphenyl)-4,4 ', 5; 5 '-tetraphenyl di-imidazoles; 2; 2 '-two (2-chlorphenyl)-4,4 ', 5; 5 '-four (alkoxyl phenyl) di-imidazoles; 2; 2 '-two (2-chlorphenyl)-4,4 ', 5; 5 '-four (dialkoxy phenyl) di-imidazoles; 2; 2 '-two (2-chlorphenyl)-4,4 ', 5; 5 '-four (tri-alkoxy phenyl) di-imidazoles (for example; with reference to special public clear 48-38403 communique; the spy opens clear 62-174204 communique etc.); 4,4 ', 5; the imidazolium compounds (for example, opening flat 7-10913 communique etc. with reference to the spy) that the phenyl alkoxy carbonic acyl radical of 5 '-position replaces etc.Preferably can enumerate 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl di-imidazoles, 2,2 '-two (2, the 3-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl di-imidazoles.
As above-mentioned oxime compound, for example can enumerate the compound of O-ethoxy carbonyl-α-oxygen base imino group-1-phenyl-propane-1-ketone, usefulness formula (3) expression, the compound of usefulness formula (4) expression etc.
As above-mentioned triazine based compound, for example can enumerate 2, two (the trichloromethyl)-6-(4-methoxyphenyl)-1 of 4-, 3, the 5-triazine, 2, two (the trichloromethyl)-6-(4-methoxyl naphthyl)-1 of 4-, 3, the 5-triazine, 2, two (the trichloromethyl)-6-piperonyls-1 of 4-, 3, the 5-triazine, 2, two (the trichloromethyl)-6-(4-methoxyl-styrene)-1,3 of 4-, the 5-triazine, 2, two (trichloromethyl)-6-[2-(5-methylfuran-2-yl) vinyl of 4-]-1,3,5-triazines, 2, two (trichloromethyl)-6-[2-(furans-2-yl) vinyl of 4-]-1,3, the 5-triazine, 2, two (trichloromethyl)-6-[2-(4-diethylamino-2-aminomethyl phenyl) vinyl of 4-]-1,3, the 5-triazine, 2, two (trichloromethyl)-6-[2-(3, the 4-Dimethoxyphenyl) vinyl of 4-]-1,3,5-triazine etc.
As above-mentioned acyl group phosphine oxygen based compound, for example can enumerate 2,4,6-trimethylbenzoyl diphenyl phosphine oxygen etc.
In addition, so long as do not damage the degree of effect of the present invention, Photoepolymerizationinitiater initiater commonly used in this field etc. be can also and be used in,, benzoin based compound, benzophenone based compound, thioxanthones based compound, anthracene based compound etc. for example can be enumerated as this Photoepolymerizationinitiater initiater.
More specifically can enumerate compound as described below, can distinguish and use them separately, can also be used in combination two or more.
As above-mentioned benzoin based compound, for example can enumerate benzoin, benzoin methylether, benzoin ethyl ether, benzoin iso-propylether, benzoin isobutyl ether etc.
As above-mentioned benzophenone based compound, for example can enumerate benzophenone, o-benzophenone methyl formate, 4-phenyl benzophenone, 4-benzoyl-4 '-methyldiphenyl base sulfide, 3,3 ', 4,4 '-four (t-butylperoxy carbonyl) benzophenone, 2,4,6-tri-methyl benzophenone etc.
As above-mentioned thioxanthones based compound, for example can enumerate 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-two clopenthixal ketones, 1-chloro-4-propoxyl group thioxanthones etc.
As above-mentioned anthracene based compound, for example can enumerate 9,10-dimethoxy anthracene, 2-ethyl-9,10-dimethoxy anthracene, 9,10-diethoxy anthracene, 2-ethyl-9,10-diethoxy anthracene etc.
In addition, as Photoepolymerizationinitiater initiater also illustration 10-butyl-2-chloro-acridine ketone, 2-EAQ, benzil, 9,10-phenanthrenequione, camphorquinone, phenyl glyoxalic acid methylester, two luxuriant titaniums etc. are arranged.
In addition, have the Photoepolymerizationinitiater initiater of the group that can cause chain transfer, can use the spy and show the Photoepolymerizationinitiater initiater put down in writing in the 2002-544205 communique.
As above-mentioned Photoepolymerizationinitiater initiater, for example can enumerate the Photoepolymerizationinitiater initiater of following formula (5)～(10) with the group that can cause chain transfer.
In addition, can light and/or hot cationic polymerization initiators.
Light and/or hot cationic polymerization initiators can also use by kation and be derived from the material that lewis acidic negative ion constitutes.
As above-mentioned cationic object lesson, can enumerate diphenyl iodine, two (p-methylphenyl) iodine, two (to tert-butyl-phenyl) iodine, two (to octyl phenyl) iodine, two (to the octadecyl phenyl) iodine, two (to octyl group oxygen base phenyl) iodine, two (to octadecyl oxygen base phenyl) iodine, phenyl (to octadecyl 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) sulfonium, dimethyl (methoxyl) sulfonium, dimethyl (ethoxy) sulfonium, dimethyl (propoxyl group) sulfonium, dimethyl (butoxy) sulfonium, dimethyl (octyloxy) sulfonium, dimethyl (octadecane oxygen base) sulfonium, dimethyl (isopropoxy) sulfonium, dimethyl (tert-butoxy) sulfonium, dimethyl (cyclopentyloxy) sulfonium, dimethyl (cyclohexyloxy) sulfonium, dimethyl (fluorine methoxyl) sulfonium, dimethyl (2-chloroethoxy) sulfonium, dimethyl (3-bromine propoxyl group) sulfonium, dimethyl (4-cyano group butoxy) sulfonium, dimethyl (8-nitro octyloxy) sulfonium, dimethyl (18-trifluoromethyl octadecane oxygen base) sulfonium, dimethyl (2-hydroxyl isopropoxy) sulfonium, perhaps 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.
Be derived from lewis acidic anionic object lesson as above-mentioned, can enumerate hexafluorophosphate, hexafluoro arsenate, hexafluoro antimonate or four (pentafluorophenyl group) borate etc.As preferably being derived from lewis acidic negative ion, can enumerate hexafluoro antimonate or four (pentafluorophenyl group) borate.
Above-mentioned kation and be derived from lewis acidic negative ion can combination in any.
Object lesson 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 octyl group oxygen base phenyl) iodine hexafluorophosphate, two (to octadecyl oxygen base phenyl) iodine hexafluorophosphate, phenyl (to octadecyl 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 (methoxyl) sulfonium hexafluorophosphate, dimethyl (ethoxy) sulfonium hexafluorophosphate, dimethyl (propoxyl group) sulfonium hexafluorophosphate, dimethyl (butoxy) sulfonium hexafluorophosphate, dimethyl (octyloxy) sulfonium hexafluorophosphate, dimethyl (octadecane oxygen base) sulfonium hexafluorophosphate, dimethyl (isopropoxy) sulfonium hexafluorophosphate, dimethyl (tert-butoxy) sulfonium hexafluorophosphate, dimethyl (cyclopentyloxy) sulfonium hexafluorophosphate, dimethyl (cyclohexyloxy) sulfonium hexafluorophosphate, dimethyl (fluorine methoxyl) sulfonium hexafluorophosphate, dimethyl (2-chloroethoxy) sulfonium hexafluorophosphate, dimethyl (3-bromine propoxyl group) sulfonium hexafluorophosphate, dimethyl (4-cyano group butoxy) sulfonium hexafluorophosphate, dimethyl (8-nitro octyloxy) sulfonium hexafluorophosphate, dimethyl (18-trifluoromethyl octadecane oxygen base) sulfonium hexafluorophosphate, dimethyl (2-hydroxyl isopropoxy) sulfonium hexafluorophosphate, dimethyl (three (trichloromethyl) methyl) sulfonium hexafluorophosphate;
Diphenyl 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 octyl group oxygen base phenyl) iodine hexafluoro arsenate, two (to octadecyl oxygen base phenyl) iodine hexafluoro arsenate, phenyl (to octadecyl 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 (methoxyl) sulfonium hexafluoro arsenate, dimethyl (ethoxy) sulfonium hexafluoro arsenate, dimethyl (propoxyl group) sulfonium hexafluoro arsenate, dimethyl (butoxy) sulfonium hexafluoro arsenate, dimethyl (octyloxy) sulfonium hexafluoro arsenate, dimethyl (octadecane oxygen base) sulfonium hexafluoro arsenate, dimethyl (isopropoxy) sulfonium hexafluoro arsenate, dimethyl (tert-butoxy) sulfonium hexafluoro arsenate, dimethyl (cyclopentyloxy) sulfonium hexafluoro arsenate, dimethyl (cyclohexyloxy) sulfonium hexafluoro arsenate, dimethyl (fluorine methoxyl) sulfonium hexafluoro arsenate, dimethyl (2-chloroethoxy) sulfonium hexafluoro arsenate, dimethyl (3-bromine propoxyl group) sulfonium hexafluoro arsenate, dimethyl (4-cyano group butoxy) sulfonium hexafluoro arsenate, dimethyl (8-nitro octyloxy) sulfonium hexafluoro arsenate, dimethyl (18-trifluoromethyl octadecane oxygen base) sulfonium hexafluoro arsenate, dimethyl (2-hydroxyl isopropoxy) sulfonium hexafluoro arsenate, dimethyl (three (trichloromethyl) methyl) sulfonium hexafluoro arsenate;
Diphenyl 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 octyl group oxygen base phenyl) iodine hexafluoro antimonate, two (to octadecyl oxygen base phenyl) iodine hexafluoro antimonate, phenyl (to octadecyl 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 (methoxyl) sulfonium hexafluoro antimonate, dimethyl (ethoxy) sulfonium hexafluoro antimonate, dimethyl (propoxyl group) sulfonium hexafluoro antimonate, dimethyl (butoxy) sulfonium hexafluoro antimonate, dimethyl (octyloxy) sulfonium hexafluoro antimonate, dimethyl (octadecane oxygen base) sulfonium hexafluoro antimonate, dimethyl (isopropoxy) sulfonium hexafluoro antimonate, dimethyl (tert-butoxy) sulfonium hexafluoro antimonate, dimethyl (cyclopentyloxy) sulfonium hexafluoro antimonate, dimethyl (cyclohexyloxy) sulfonium hexafluoro antimonate, dimethyl (fluorine methoxyl) sulfonium hexafluoro antimonate, dimethyl (2-chloroethoxy) sulfonium hexafluoro antimonate, dimethyl (3-bromine propoxyl group) sulfonium hexafluoro antimonate, dimethyl (4-cyano group butoxy) sulfonium hexafluoro antimonate, dimethyl (8-nitro octyloxy) sulfonium hexafluoro antimonate, dimethyl (18-trifluoromethyl octadecane oxygen base) sulfonium hexafluoro antimonate, dimethyl (2-hydroxyl isopropoxy) sulfonium hexafluoro antimonate, dimethyl (three (trichloromethyl) methyl) sulfonium hexafluoro antimonate;
Diphenyl 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 octyl group oxygen base phenyl) iodine four (pentafluorophenyl group) borate, two (to octadecyl oxygen base phenyl) iodine four (pentafluorophenyl group) borate, phenyl (to octadecyl 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 (methoxyl) sulfonium four (pentafluorophenyl group) borate, dimethyl (ethoxy) sulfonium four (pentafluorophenyl group) borate, dimethyl (propoxyl group) sulfonium four (pentafluorophenyl group) borate, dimethyl (butoxy) sulfonium four (pentafluorophenyl group) borate, dimethyl (octyloxy) sulfonium four (pentafluorophenyl group) borate, dimethyl (octadecane oxygen base) sulfonium four (pentafluorophenyl group) borate, dimethyl (isopropoxy) sulfonium four (pentafluorophenyl group) borate, dimethyl (tert-butoxy) sulfonium four (pentafluorophenyl group) borate, dimethyl (cyclopentyloxy) sulfonium four (pentafluorophenyl group) borate, dimethyl (cyclohexyloxy) sulfonium four (pentafluorophenyl group) borate, dimethyl (fluorine methoxyl) sulfonium four (pentafluorophenyl group) borate, dimethyl (2-chloroethoxy) sulfonium four (pentafluorophenyl group) borate, dimethyl (3-bromine propoxyl group) sulfonium four (pentafluorophenyl group) borate, dimethyl (4-cyano group butoxy) sulfonium four (pentafluorophenyl group) borate, dimethyl (8-nitro octyloxy) sulfonium four (pentafluorophenyl group) borate, dimethyl (18-trifluoromethyl octadecane oxygen base) sulfonium four (pentafluorophenyl group) borate, dimethyl (2-hydroxyl isopropoxy) sulfonium four (pentafluorophenyl group) borate, dimethyl (three (trichloromethyl) methyl) sulfonium four (pentafluorophenyl group) borate; Preferably can 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 four (pentafluorophenyl group) borate, triphenylsulfonium four (pentafluorophenyl group) borate, three (to tert-butyl-phenyl) sulfonium four (pentafluorophenyl group) borate etc.; Preferredly can 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, or three (to tert-butyl-phenyl) sulfonium four (pentafluorophenyl group) borate etc.
In addition, also can in Photoepolymerizationinitiater initiater, be used in combination photopolymerization and cause auxiliary agent (C-1), can also be with a plurality of photopolymerization initiation auxiliary agents that are used in combination.
Cause auxiliary agent as photopolymerization, can enumerate amines, carboxylic acid compound, multi-functional thiol's compound, use the compound of formula (III) expression etc.As above-mentioned amines, the optimization aromatic amines.As Photoepolymerizationinitiater initiater, preferred amines compound, multi-functional thiol, the compound of using formula (III) to represent.
Cause auxiliary agent (C-1) as photopolymerization, for example can enumerate fatty amine compounds such as triethanolamine, methyldiethanolamine, triisopropanolamine, 4-dimethylaminobenzoic acid methyl esters, 4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid isopentyl ester, 4-dimethylaminobenzoic acid 2-Octyl Nitrite, benzoic acid 2-dimethylamino ethyl ester, N, N-dimethyl-p-toluidine, 4, (the common name of 4 '-two (dimethylamino) benzophenone; Michler's keton), aromatic amines compound such as 4,4 '-two (diethylamino) benzophenone;
Carboxylic acid compounds such as the assorted acetate class of aromatic series such as phenyl thioacetic acid, aminomethyl phenyl thioacetic acid, ethylphenyl thioacetic acid, Methylethyl phenyl thioacetic acid, 3,5-dimethylphenyl thioacetic acid, methoxyphenyl thioacetic acid, Dimethoxyphenyl thioacetic acid, chlorphenyl thioacetic acid, dichlorophenyl thioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthyl thioacetic acid, N-naphthyl aminoacetic acid, naphthoxy acetic acid;
Ethanthiol, the last of the ten Heavenly stems two mercaptan, 1,4-dimethyl sulfydryl benzene, butylene glycol two thiopropionates, butylene glycol dithioglycol acid esters, ethylene glycol bisthioglycolate thioglycolic acid ester, trimethylolpropane tris thioglycolic acid ester, butylene glycol two thiopropionates, trimethylolpropane tris thiopropionate, trimethylolpropane tris thioglycolic acid ester, pentaerythrite tetrathio propionic ester, pentaerythrite tetrathio ethyl glycolate, trihydroxyethyl three sulfo-propionic esters, pentaerythrite four (3-sulfydryl butyric ester), 1, multi-functional thiol's compounds such as two (the 3-sulfydryl butyryl acyloxy) butane of 4-;
With the compound of following formula (III) expression etc.
In formula (III), the dotted line of representing with X is represented the aromatic ring of the carbon number 6～12 that can replace with halogen atom.
Y represents oxygen atom, sulphur atom.
R
1The alkyl of expression carbon number 1～6.
R
2The aryl that the alkyl of the carbon number 1～12 that expression can replace with halogen atom maybe can replace with halogen atom.
As halogen atom, can enumerate fluorine atom, chlorine atom, bromine atoms etc.
As the aromatic ring of carbon number 6～12, can enumerate phenyl ring, naphthalene nucleus etc.
As the aromatic series of the carbon number 6～12 that can replace with 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, cyclohexyl biphenyl, chlordiphenyl ring, bromo biphenyl ring, naphthalene nucleus, chloronaphthalene ring, bromonaphthalene ring etc.
Alkyl as carbon number 1～6, can enumerate methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, 1-methyl-n-pro-pyl, 2-methyl-n-pro-pyl, the tert-butyl group, n-pentyl, 1-methyl-normal-butyl, 2-methyl-normal-butyl, 3-methyl-normal-butyl, 1,1-dimethyl-n-pro-pyl, 1,2-dimethyl-n-pro-pyl, 2,2-dimethyl-n-pro-pyl, n-hexyl, cyclohexyl etc.
Alkyl as the carbon number 1～12 that can replace with 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-pro-pyl, 1,2-dimethyl-n-pro-pyl, 2,2-dimethyl-n-pro-pyl, n-hexyl, cyclohexyl, 1-chloro-normal-butyl, 2-chloro-normal-butyl, 3-chloro-normal-butyl etc.
As can enumerating 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. with the aryl of halogen atom replacement.
As compound with formula (III) expression; specifically can enumerate 2-phenacylidene-3-methyl-naphthalene [2; 1-d] thiazoline; 2-phenacylidene-3-methyl-naphthalene [1; 2-d] thiazoline; 2-phenacylidene-3-methyl-naphthalene [2; 3-d] thiazoline; 2-(2-naphthoyl methylene)-3-methylbenzothiazole quinoline; 2-(1-naphthoyl methylene)-3-methylbenzothiazole quinoline; 2-(2-naphthoyl methylene)-3-methyl-5-phenyl benzothiazole quinoline; 2-(1-naphthoyl methylene)-3-methyl-5-phenyl benzothiazole quinoline; 2-(2-naphthoyl methylene)-3-methyl-5-fluoro benzothiazole quinoline; 2-(1-naphthoyl methylene)-3-methyl-5-fluoro benzothiazole quinoline; 2-(2-naphthoyl methylene)-3-methyl-5-chloro benzothiazole quinoline; 2-(1-naphthoyl methylene)-3-methyl-5-chloro benzothiazole quinoline; 2-(2-naphthoyl methylene)-3-methyl-5-bromo benzothiazole quinoline; 2-(1-naphthoyl methylene)-3-methyl-5-bromo benzothiazole quinoline; 2-(4-dibenzoyl methylene)-3-methylbenzothiazole quinoline; 2-(4-dibenzoyl methylene)-3-methyl-5-phenyl benzothiazole quinoline; 2-(2-naphthalene formyl methylene)-3-methyl-naphthalene [2; 1-d] thiazoline; 2-(2-naphthalene formyl methylene)-3-methyl-naphthalene [1; 2-d] thiazoline; 2-(4-dibenzoyl methylene)-3-methyl-naphthalene [2; 1-d] thiazoline; 2-(4-dibenzoyl methylene)-3-methyl-naphthalene [1; 2-d] thiazoline; 2-(to the fluorobenzoyl methylene)-3-methyl-naphthalene [2; 1-d] thiazoline; 2-(to the fluorobenzoyl methylene)-3-methyl-naphthalene [1; 2-d] thiazoline; 2-phenacylidene-3-methyl-naphthalene [2; 1-d] oxazoline; 2-phenacylidene-3-methyl-naphthalene [1; 2-d] oxazoline; 2-phenacylidene-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-naphthalene formyl methylene)-3-methyl-naphthalene [2; 1-d] oxazoline; 2-(2-naphthalene formyl methylene)-3-methyl-naphthalene [1; 2-d] oxazoline; 2-(4-dibenzoyl methylene)-3-methyl-naphthalene [2; 1-d] oxazoline; 2-(4-dibenzoyl methylene)-3-methyl-naphthalene [1; 2-d] oxazoline; 2-(to the fluorobenzoyl methylene)-3-methyl-naphthalene [2; 1-d] oxazoline; 2-(to the fluorobenzoyl methylene)-3-methyl-naphthalene [1,2-d] oxazoline etc.
Wherein, preferably use 2-(2-naphthoyl the methylene)-3-methylbenzothiazole quinoline of formula (III-1) expression, 2-benzoyl methylene-3-methyl-naphthalene [1 of using formula (III-2) to represent; 2-d] thiazoline and with 2-(4-dibenzoyl methylene)-3-methyl-naphthalene [1,2-d] thiazoline of formula (III-3) expression.
The content of Photoepolymerizationinitiater initiater (C) is preferably 0.1～40 quality % with respect to the total amount of adhesive resin (A) and optical polymerism compound (B) in massfraction, more preferably 1～30 quality %.
In addition, the content that photopolymerization causes auxiliary agent (C-1) is preferably 0.01～50 quality % with benchmark same as described above, more preferably 0.1～40 quality %.
Photoepolymerizationinitiater initiater (C) if total amount in above-mentioned scope, photosensitive polymer combination has high sensitivity, use the flatness on the surface of the intensity of the pixel portions that above-mentioned photosensitive polymer combination forms or above-mentioned pixel that the tendency that becomes good is arranged, so preferred.Except that above-mentioned, photopolymerization cause auxiliary agent (C-1) if amount in above-mentioned scope, raisings advanced-go on foot to the sensitivity of the photosensitive polymer combination that obtains, and uses the throughput rate of above-mentioned photosensitive polymer combination formation pattern substrate that the tendency of raising is arranged, so preferably.
Photosensitive polymer combination of the present invention contains solvent (D).As above-mentioned solvent (D), can enumerate the various organic solvents that use in the field of photosensitive polymer combination, as its object lesson, can enumerate:
The ethylene glycol monoalkyl ether class of glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether and ethylene glycol monobutyl ether and so on;
Diethylene glycol dialkyl ether classes such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dipropyl ether, dibutyl ethylene glycol ether;
Ethylene glycol alkyl ether acetate esters such as methylcellosolve acetate, ethyl cellosolve acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate;
Aklylene glycol alkyl ether acetate esters such as propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetic acid esters, methoxy butyl acetate, acetate methoxyl pentyl 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 methyl ether, propylene glycol ethyl propyl ether;
Propylene glycol alkyl ether propionic acid esters such as propylene glycol monomethyl ether acetate, propylene-glycol ethyl ether propionic ester, propylene glycol propyl ether propionic ester, propylene glycol butyl ether propionic ester;
Butylene glycol monoalkyl ethers such as methoxybutanol, ethoxy butanols, propoxyl group butanols, butoxy butanols;
Butylene glycol monoalky lether acetate esters such as methoxy butyl acetate, acetate ethoxy butyl ester, acetate propoxyl group butyl ester, acetate butoxy butyl ester;
Butylene glycol monoalky lether 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;
Dipropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol MEE;
Benzene,toluene,xylene, mesitylene etc. are aromatic hydrocarbon based;
Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, hexone, cyclohexanone;
Alcohols such as ethanol, propyl alcohol, butanols, hexanol, cyclohexanol, ethylene glycol, glycerine;
Methyl acetate, ethyl acetate, propyl acetate, butyl acetate, 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 glycolic acid butyl ester, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, the 3-hydroxy methyl propionate, 3-hydracrylic acid ethyl ester, 3-hydracrylic acid propyl ester, 3-hydracrylic 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 propoxyl group methyl acetate, propoxyl group ethyl acetate, the propoxyl group propyl acetate, the propoxyl group butyl acetate, the butoxy acetic acid methyl esters, the butoxy acetic acid ethyl ester, the butoxy acetic acid propyl ester, the butoxy acetic acid butyl ester, 2-methoxypropionic acid methyl esters, 2-methoxy propyl acetoacetic ester, 2-methoxy propyl propyl propionate, 2-methoxy propyl acid butyl ester, 2-ethoxy-propionic acid methyl esters, the 2-ethoxyl ethyl propionate, 2-ethoxy-c propyl propionate, 2-ethoxy-c acid butyl ester, 2-butoxy methyl propionate, 2-butoxy ethyl propionate, 2-butoxy propyl propionate, 2-butoxy butyl propionate, 3-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 3-methoxy propyl propyl propionate, 3-methoxy propyl acid butyl ester, 3-ethoxy-propionic acid methyl esters, the 3-ethoxyl ethyl propionate, 3-ethoxy-c propyl propionate, 3-ethoxy-c acid butyl ester, 3-propoxyl group methyl propionate, 3-propoxyl group ethyl propionate, 3-propoxyl group propyl propionate, 3-propoxyl group butyl propionate, 3-butoxy methyl propionate, 3-butoxy ethyl propionate, 3-butoxy propyl propionate, ester classes such as 3-butoxy butyl propionate;
Ring-type such as tetrahydrofuran, pyrans ethers;
Cyclic ester classes such as gamma-butyrolacton etc.
In the middle of above-mentioned solvent, viewpoint from coating, drying property, preferred above-mentioned solvent mid-boiling point is 100 ℃～200 ℃ a organic solvent, more preferably ester classes such as aklylene glycol alkyl ether acetate esters, ketone, butylene glycol alkyl ether acetate esters, butylene glycol monoalkyl ethers, 3-ethoxyl ethyl propionate, 3-methoxypropionic acid methyl esters, further preferred propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, methoxy butyl acetate, methoxybutanol, 3-ethoxyl ethyl propionate, 3-methoxypropionic acid methyl esters.
These solvents (D) can be distinguished use separately, can also mix more than 2 kinds and use.
The content of solvent in the photosensitive polymer combination of the present invention (D) is preferably 60～90 quality % with respect to photosensitive polymer combination in massfraction, more preferably 70～85 quality %.Solvent (D) if content in above-mentioned scope, with spin coater, Feng Xi ﹠amp; When apparatus for coating such as spin coater, slit coating machine (be also referred to as mould sometimes and be coated with machine, curtain formula flow coater), ink-jet were coated with, coating became well, so preferred.
In photosensitive polymer combination of the present invention, can also and use adjuvants (F) such as filling agent, other macromolecular compounds, levelling agent, adhesion promoter, antioxidant, ultraviolet light absorber, preventing flocculation material, chain-transferring agent as required.
As filling agent, specifically can enumerate glass, silicon dioxide, aluminium oxide etc.
As other macromolecular compounds, specifically can enumerate thermoplastic resins such as curable resins such as epoxy resin, maleimide resin or polyvinyl alcohol, polyacrylic acid, polyalkylene glycol monoalkyl ether, polyacrylic acid fluoroalkyl ester, polyester, polyurethane etc.
As levelling agent, can use commercially available surfactant, for example can enumerate surfactants such as silicone-based, fluorine system, ester system, kation system, negative ion system, nonionic system, both sexes etc., they can distinguish use separately, can also make up more than 2 kinds and use.As above-mentioned surfactant, for example can enumerate the polyoxyethylene alkyl ether class, the polyoxyethylene alkyl phenyl ether class, the polyethylene glycol di class, the sorbitan fatty acid ester class, fatty acid modified polyester, the tertiary amine modified polyurethane, polyethyleneimine: amine etc., in addition, can also enumerate commodity KP (SHIN-ETSU HANTOTAI's chemical industry (strain) system) by name, Port リ Off ロ one (common prosperity chemistry (strain) system), エ Off ト Star プ (ト one ケ system プ ロ ダ Network Star corporate system), メ ガ Off ア Star Network (big Japanese ink chemical industry (strain) system), Off ロ ラ one De (Sumitomo 3M (strain) system), ア サ ヒ ガ one De, サ one Off ロ Application (above is rising sun pin (strain) system), ソ Le ス バ one ス (ゼ ネ カ (strain) system), EFKA (EFKA CHEMICALS corporate system), PB821 (aginomoto (strain) system) etc.
As adhesion promoter, the preferred silane based compound, specifically 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 radicals cyclohexyl) ethyl trimethoxy silane, the 3-chloropropylmethyldimethoxysilane, the 3-r-chloropropyl trimethoxyl silane, the 3-methacryloxypropyl trimethoxy silane, 3-sulfydryl propyl trimethoxy silicane etc.
As antioxidant; specifically can enumerate the 2-tert-butyl group-6-(the 3-tert-butyl group-2-hydroxy-5-methyl base benzyl)-4-aminomethyl phenyl acrylate; 2-[1-(2-hydroxyl-3; the 5-di-tert-pentyl-phenyl) ethyl]-4; 6-di-tert-pentyl-phenyl acrylate; 6-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propoxyl group]-2; 4; 8; 10-tetra-tert hexichol [d; f] [1; 3; 2] dioxy phosphorus heterocycle heptene; 3; 9-pair [2-{3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propiono oxygen base }-1; the 1-dimethyl ethyl]-2; 4; 8,10-four oxygen spiral shells [5.5] ten-alkane; 2,2 '-di-2-ethylhexylphosphine oxide (the 6-tert-butyl group-4-methylphenol); 4; 4 '-butylidene two (the 6-tert-butyl group-3-methylphenol); 4; 4 '-thiobis (the 2-tert-butyl group-5-methylphenol); 2,2 '-thiobis (the 6-tert-butyl group-4-methylphenol); dilauryl 3,3 '-thiodipropionate; myristyl 3; 3 '-thiodipropionate; distearyl 3; 3 '-thiodipropionate; pentaerythrite base four (3-lauryl thiopropionate); 1,3,5-three (3; the 5-di-tert-butyl-4-hydroxyl benzyl)-1; 3,5-triazine-2,4; 6 (1H; 3H, 5H)-triketone; 3,3 '; 3 " 5,5 ', 5 "-and six tert-butyl groups-a; a '; a "-(sym-trimethyl benzene base-2,4,6-three bases) three-paracresol; [3-(3 for pentaerythrite four; the 5-di-tert-butyl-hydroxy phenyl) propionic ester]; 2,6 di tert butyl 4 methyl phenol etc.
As ultraviolet light absorber, specifically can enumerate 2-(the 3-tert-butyl group-2-hydroxy-5-methyl base phenyl)-5-chlorobenzotriazole, alkoxy benzene ketone etc.
In addition, as anti flocculant, specifically can enumerate sodium polyacrylate etc.
As chain-transferring agent, can enumerate dodecyl mercaptans, 2,4-diphenyl-4-methyl-1-pentene etc.
Photosensitive polymer combination for example can be coated on as mentioned above and carry out photocuring and development on the base material and form pattern.At first, on the layer that the solid state component by photosensitive polymer combination that said composition is coated on substrate (being generally glass) or forms in advance constitutes, remove volatile ingredient such as desolvate by prebake from the photosensitive polymer combination layer that is coated with, obtain level and smooth filming.The thickness of filming of this moment is generally about 1～6 μ m.By the mask that is used to form target pattern to as the above-mentioned irradiation ultraviolet radiation of filming that obtains.At this moment, the preferred use to whole exposure portion shone parallel rays equably and carried out the such mask aligner or the steeper devices such as (stepper) in accurate location of mask and substrate.After this, make the contact aqueous alkali of filming that finish to solidify make the dissolving of non-exposure portion, develop, obtain the purpose pattern form thus.Developing method can be contain liquid (liquid is contained り) method, infusion process, gunite etc. any.And then when developing, substrate can be inclined to arbitrarily angled.
As coating process, for example by spin-coating method, curtain coating rubbing method, roller rubbing method, slit; Spin-coating method or gap coating method etc. are carried out.Carry out heat drying (prebake) after the coating or behind drying under reduced pressure, heating, making volatile ingredient volatilizations such as solvent, forming the photosensitive polymer combination layer thus.Here, the temperature of heating is generally 70～200 ℃, preferred 80～130 ℃.This photosensitive polymer combination layer contains volatile ingredient hardly.In addition, the thickness of above-mentioned photosensitive polymer combination layer is generally about 1.5～8 μ m.
The developer solution that uses in the development behind pattern exposure normally contains the aqueous solution of alkali compounds and surfactant.
Alkali compounds can be any of inorganic and organic alkali compounds.As the object lesson 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 the object lesson of organic basic compound, can enumerate tetramethyl ammonium hydroxide, hydroxide 2-hydroxyethyl trimethyl ammonium, monomethyl amine, dimethyl amine, Trimethylamine, single ethylamine, diethylamide, triethylamine, single isopropylamine, diisopropylamine, monoethanolamine etc.These inorganic and organic basic compounds can be distinguished separately and use, and can also make up more than 2 kinds and use.The concentration of the alkali compounds in the alkaline-based developer is preferably 0.01～10 quality %, more preferably 0.03～5 quality %.
Surfactant in the alkaline-based developer can be that non-ionization series surfactant, negative ion are that surfactant or kation are any of surfactant.
As nonionic is the object lesson of surfactant, can enumerate polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkylaryl ether, other polyoxyethylene derivs, oxygen ethene/oxypropylene segmented copolymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, fatty acid glyceride, polyoxyethylene fatty acid ester, polyoxyethylene alkyl amine etc.
As negative ion is the object lesson of surfactant, can enumerate the alkyl aryl sulfonate class etc. of alkylsurfuric acid salt, neopelex or dodecyl sodium naphthalene sulfonate and so on of higher alcohol sulfate salt, NaLS or the Texapon Special and so on of lauryl alcohol sodium sulfovinate or oleyl alcohol sodium sulfovinate and so on.
As kation is the object lesson of surfactant, can enumerate stearyl amine hydrochloride or lauryl trimethyl ammonium chloride and so on amine salt or quaternary ammonium salt etc.
These surfactants can be distinguished separately and to use, can also make up more than 2 kinds more than.
The scope of preferred 0.01～10 quality % of surfactant concentrations in the alkaline-based developer, more preferably 0.05～8 quality %, further preferred 0.1～5 quality %.
After development, wash, and then as required also can 150～230 ℃ implement down 10～60 minutes after cure.
Use photosensitive polymer combination of the present invention,, can form pattern on the substrate or on the filter substrate through aforesaid each operation.This pattern is useful as the employed smooth separator of liquid crystal indicator.In addition, when implementing pattern formation exposure to dry coating, using photomask if use the hole to form, can form the hole, is useful as interlayer dielectric.And then, when dry coating is exposed, do not use photomask and by blanket exposure be heating and curing or only can form hyaline membrane by being heating and curing, this hyaline membrane is useful as protective finish, in addition, can also be used for touch panel.
Therefore, by the pattern that will so the obtain display device such as liquid crystal indicator of packing into, can be with the outstanding display device of high finished product rate quality bills of materials.
Photosensitive polymer combination of the present invention, its viscosity when preserving changes little, even if fine pattern also can be separated picture, can form the outstanding pattern of solvent resistance, thermotolerance or films.
Photosensitive polymer combination of the present invention be suitable as for example be used to form constitute protective finish, light separator, dielectric film, liquid crystal aligning control with projection, be used to cooperate the material of hyaline membrane of a part of color filters such as coating of the thickness of colored pattern.
Embodiment
Below, the present invention will be described in more detail by embodiment, but the present invention is not limited by these embodiment.In an embodiment, the % of expression content or use amount and part just are meant quality criteria if not otherwise specified.
Synthesis example 1
In the flask of the 1L that possesses reflux condenser, tap funnel and stirring machine, flow through nitrogen, be nitrogen atmosphere, add 3-methoxyl-1-butanols 200 mass parts and acetate 3-methoxyl butyl ester 105 mass parts, be heated to 70 ℃ while stirring with 0.02L/ minute.Then, it is dissolved in methacrylic acid 60 mass parts, 3,4-epoxy three ring [5.2.1.0
2.6] in decyl acrylate (mol ratio of the compound of representing with the compound of formula (I-1) expression with formula (II-1) is 50: 50 a potpourri) 240 mass parts and acetate 3-methoxyl butyl ester 140 mass parts, modulation solution uses tap funnel that this lysate was dripped in the flask of insulation to 70 ℃ with time of 4 hours.On the other hand, use other tap funnels with time of 4 hours will be in acetate 3-methoxyl butyl ester 225 mass parts solvent polymerization initiating agent 2, the solution that two (2, the 4-methyl pentane nitrile) 30 mass parts of 2 '-azo obtain drips in the flask.After the dropping of the solution of polymerization initiator finishes, kept 4 hours at 70 ℃, be cooled to room temperature subsequently, obtain multipolymer (Resin A solution a) of solid state component 32.6 quality %, acid number 110mg-KOH/g (solid state component conversion).The weight-average molecular weight Mw of the Resin A a that obtains is 13400, and dispersion degree is 2.50.
Synthesis example 2
In the flask of the 1L that possesses reflux condenser, tap funnel and stirring machine, flow through nitrogen, be nitrogen atmosphere, add 3-methoxyl-1-butanols 200 mass parts and acetate 3-methoxyl butyl ester 105 mass parts, be heated to 70 ℃ while stirring with 0.02L/ minute.Then, with methacrylic acid 55 mass parts, 3,4-epoxy three ring [5.2.1.0
2.6] decyl acrylate (mol ratio of the compound of representing with the compound of formula (I-1) expression with formula (II-1) is 50: 50 a potpourri) 175 mass parts and N-cyclohexyl maleimide 70 mass parts are dissolved in acetate 3-methoxyl butyl ester 140 mass parts, modulation solution uses tap funnel that this lysate was dripped in the flask of insulation to 70 ℃ with time of 4 hours.On the other hand, use other tap funnels with time of 4 hours will be in acetate 3-methoxyl butyl ester 225 mass parts solvent polymerization initiating agent 2, the solution that two (2, the 4-methyl pentane nitrile) 30 mass parts of 2 '-azo obtain drips in the flask.After the dropping of the solution of polymerization initiator finishes, kept 70 ℃ at 4 hours, be cooled to room temperature subsequently, obtain the solution of the multipolymer (Resin A b) of solid state component 32.6 quality %, acid number 105mg-KOH/g.The weight-average molecular weight Mw of the Resin A b that obtains is 13600, and dispersion degree is 2.54.
Synthesis example 3
The synthesis example 1 of opening flat 11-133600 communique with the spy is identical, adds 2 in the flask that possesses condenser and stirring machine, two (2, the 4-methyl pentane nitrile) 7 mass parts of 2 '-azo, diethylene glycol dimethyl ether 200 mass parts.Then, add styrene 30 mass parts, methacrylic acid 20 mass parts, glycidyl methacrylate 50 mass parts, after carrying out the nitrogen displacement, beginning is slowly stirred.The temperature of solution is risen to 70 ℃, kept this temperature 5 hours, obtain containing the polymer solution of Resin A c.The polystyrene conversion weight-average molecular weight of the Resin A c that obtains is 24000.
About the weight-average molecular weight (Mw) of above-mentioned binder polymer and the mensuration of number-average molecular weight (Mn), use the GPC method under following condition, to carry out.
Device: K2479 ((strain) Shimadzu Seisakusho Ltd. system)
Post: SHIMADZU Shim-pack GPC-80M
Column temperature: 40 ℃
Solvent: THF (tetrahydrofuran)
Flow velocity: 1.0mL/min
Detecting device: RI
Likening to of the weight-average molecular weight of the polystyrene conversion that will obtain in above-mentioned and number-average molecular weight is dispersion degree (Mw/Mn).
Embodiment 1
Mix 169 parts of the resin solutions (A) (solid state component converts 55 parts) that contain the Resin A a that in synthesis example 1, obtains, 45 parts of dipentaerythritol acrylates (B), 2,2 '-two (2-chlorphenyls)-4,4 ', 5,4 parts of 5 '-tetraphenyl di-imidazoles (C), 0.5 part of 2-(2-naphthyl methylene)-3-methylbenzothiazole quinoline (C-1), pentaerythrite tetrathio propionic ester)-C-1) 3 parts, (F) 0.8 part of IRGANOX3114 (Ciba Specialty Chemicals corporate system), 58 parts of propylene glycol methyl ether acetates, 42 parts of 3-ethoxyethyl group propionic esters, 2 parts of 3-methoxyl-3 parts in 1-butanols and acetate 3-methoxyl butyl esters obtain photosensitive polymer combination 1.
＜pattern forms 〉
Clean 2 inches square glass substrates (イ one グ Le 2000 successively with neutral lotion, water and alcohol; コ one ニ Application グ corporate system), dry then.Spin coating photosensitive polymer combination 1 makes with 100mJ/cm on this glass substrate
2Exposure (405nm) expose, develop, washing, after thickness when curing be 3.0 μ m, then 90 ℃ of prebake 3 minutes in clean stove.After the cooling,, use exposure machine (TME-150RSK according to making the substrate that is coated with this photosensitive polymer combination and the mode that is spaced apart 10 μ m of quartz glass system photomask; TOPCOM (strain) system), under air atmosphere with 100mJ/cm
2Exposure (405nm benchmark) irradiates light.Wherein, the irradiation to polymer resin composition at this moment is that the radiating light from extra-high-pressure mercury vapour lamp is passed through optical filter (LU0400; Morning sun beam split (strain) system), cutting off the following light of 400nm uses.
Wherein, as photomask, use the photomask that has formed following pattern at grade.
Having 1 limit is the foursquare transmittance section (pattern) of 10 μ m, these foursquare 100 μ m that are spaced apart.
Having 1 limit is the foursquare transmittance section (pattern) of 15 μ m, these foursquare 100 μ m that are spaced apart.
After irradiates light, down this substrate above-mentioned filmed to be immersed in to contain in the water system developer solution that nonionic is surfactant 0.12% and potassium hydroxide 0.04% for 25 ℃ and developed 100 seconds, after the washing, in stove, carry out under 220 ℃ 20 minutes after cure.Natural cooling is afterwards with determining film thickness device (DEKTAK3; Japan's vacuum technique (strain) system) measure the thickness of the cured film obtain, the result is 3.0 μ m.
＜storage stability 〉
Be determined at the viscosity of the photosensitive polymer combination 1 that obtains in above-mentioned.In addition, photosensitive polymer combination 1 is sealed in the shading container, in 23 ℃ calibration cell, preserves these 2 weeks of container.
Measure the viscosity of the photosensitive polymer combination 1 after taking care of.The viscosity of trying to achieve according to following formula is changed to 100%.
It is more little that viscosity changes, if for example be that 100～103% scope is exactly good.Wherein, the mensuration of viscosity can be carried out with method as follows.
Wherein, use viscosity meter (VISCOMETER TV-30; East machine industry (strain) system) measures viscosity down at 23 ℃.
＜live width, cross sectional shape 〉
For the cured film that obtains, use scanning electron microscope (S-4000; (strain) Hitachi system) observes, measures live width, shape (cross section).
To with photomask on the corresponding pattern setting-out line of 10 μ m patterns wide be 10.0 μ m.
With regard to cross sectional shape, the angle of the relative substrate of pattern is positive taper less than 90 degree.Wherein, when the angle of the relative substrate of pattern is more than 90 degree, be judged as anti-taper.
If be positive taper, when forming liquid crystal indicator, be difficult to take place the broken string of ITO distribution, so preferred.
＜mechanical property〉(total displacement amount and recovery rate)
For the cured film that obtains, use the little sclerometer (DUH-W201 of dynamic ultra micro; (strain) Shimadzu Seisakusho Ltd. system) measures its total displacement amount (μ m) and elastic displacement (μ m).Obtain recovery rate (%) from these numerical value.The total displacement amount is 0.57 μ m, and recovery rate is 92.9%.
-condition determination-
Test model: load-unload test
Test power: 5gf[SI unit conversion value, 49.0mN]
Loading speed: 0.45gf/sec[SI unit conversion value, 4.41mN/sec]
Retention time: 5sec
Pressure head: frustum of a cone pressure head (diameter 50 μ m)
Recovery rate (%): [elastic displacement (μ m)]/[total displacement amount (μ m)] * 100
＜solvent resistance 〉
In exposure process, except not using the photomask, carry out same operation, making is filmed, and measures its thickness.With in the N-Methyl pyrrolidone that is impregnated into 40 ℃ that obtains filming 40 minutes, measure the thickness behind the dipping.Obtain Thickness Variation according to following formula, with its index as solvent resistance.The value that obtains is 103.9%.
Thickness Variation (%): [thickness behind the dipping (μ m)]/[thickness (μ m) before the dipping] * 100
Above-mentioned Thickness Variation is preferably below 104%.
＜thermotolerance 〉
In exposure process, except not using the photomask, carry out same operation, making is filmed, and measures its thickness.Be placed on obtaining filming in 240 ℃ the clean stove 1 hour, and measured the thickness before and after the heating.Obtain its Thickness Variation according to following formula, with it as stable on heating index.The value that obtains is 98.2%.
Thickness Variation (%): [thickness after the heating (μ m)]/[thickness (μ m) before the heating] * 100
Above-mentioned Thickness Variation is preferably more than 97%.
Embodiment 2
According to the composition shown in the table 1, obtain photosensitive polymer combination 2, with embodiment 1 the same the evaluation.The results are shown in table 2.
Embodiment 3
According to the composition shown in the table 1, obtain photosensitive polymer combination 3, with embodiment 1 the same the evaluation.The results are shown in table 2.
Comparative example 1
According to the composition shown in the table 1, obtain photosensitive polymer combination 4, with embodiment 1 the same the evaluation.The results are shown in table 2.
Comparative example 2
According to the composition shown in the table 1, obtain photosensitive polymer combination 5, with the embodiment 1 the same storage stability of measuring, the result is thickening, so end to estimate.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | ||
| Photosensitive polymer combination | 1 | 2 | 3 | 4 | 5 | |
| Adhesive resin (A) | Resin A a | 55 | 50 | 45 | - | - |
| Resin A b | - | - | - | 55 | - | |
| Resin A c | - | - | - | - | 60 | |
| Optical polymerism compound (B): dipentaerythritol acrylate (KAYARAD DPHA: Japanese chemical drug (strain) system) | 45 | 50 | 55 | 45 | 40 | |
| Photoepolymerizationinitiater initiater (C) | 2,2 '-two (O-chlorphenyls)-4,5,4 ', 5 '-tetraphenyl-1,2 '-di-imidazoles (BCIM; Hodogaya chemical industry (strain) system) | 4 | 4 | 4 | 4 | - |
| 2-methyl-2-morpholino (4-sulphomethyl phenyl) propane-1-ketone (Irgacure-907; Ciba Specialty Chemicals corporate system) | - | - | - | - | 6 | |
| Photoepolymerizationinitiater initiater (C-1) | 2-(2-naphthoyl methylene)-3-methylbenzothiazole quinoline | 0.5 | 0.5 | 0.5 | 0.5 | - |
| Pentaerythrite tetrathio propionic ester (PEMP; Sakai chemical industry (strain) system) | 3 | 3 | 3 | 3 | - | |
| Solvent (D) | Propylene glycol methyl ether acetate | 58 | 58 | 58 | 58 | - |
| 3-ethoxyethyl group propionic ester | 42 | 42 | 42 | 42 | - | |
| 3-methoxyl-1-butanols | 3 | 7 | 10 | 3 | - | |
| Acetate 3-methoxyl butyl ester | 2 | 9 | 17 | 2 | - | |
| Diethylene glycol dimethyl ether | - | - | - | - | 197 | |
| Adjuvant (F) | Antioxidant; 1,3,5-three (3,5-di-t-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6 (1H, 3H, 5H)-triketone (Irganox3114; Ciba Specialty Chemicals corporate system) | 0.8 | 0.8 | 0.8 | 0.8 | - |
Table 2
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | ||
| Photosensitive polymer combination | 1 | 2 | 3 | 4 | 5 | |
| Storage stability (%) | 100 | 101 | 100 | 101 | 107 | |
| Pattern | Live width | 10.0 | 8.9 | 8.2 | 11.6 | - |
| Shape | Positive taper | Positive taper | Positive taper | Positive taper | - | |
| Mechanical property | Total displacement amount (μ m) | 0.57 | 0.73 | 0.67 | 0.50 | - |
| Recovery rate (%) | 92.9 | 77.9 | 75.6 | 88.3 | - | |
| Solvent resistance | (％) | 103.9 | 102.2 | 103.0 | 105.3 | - |
| Thermotolerance | (％) | 98.2 | 98.1 | 98.0 | 98.0 | - |
Embodiment 4
According to the composition shown in the table 3, obtain photosensitive polymer combination 6.
＜pattern forms 〉
Clean 2 inches square glass substrates (イ one グ Le 2000 successively with neutral lotion, water and ethanol; コ one ニ Application グ corporate system), dry then.Spin coating photosensitive polymer combination 1 makes with 40mJ/cm on this glass substrate
2Exposure (365nm) expose, develop, washing, after thickness when curing be 3.0 μ m, then 85 ℃ of prebake 3 minutes in clean stove.Make the 10 μ m that are spaced apart of the substrate that has been coated with this photosensitive polymer combination and quartz glass system photomask after the cooling, use exposure machine (TME-150RSK; TOPCOM (strain) system), under air atmosphere with 40mJ/cm
2Exposure (365nm benchmark) irradiates light.Wherein, the irradiation to polymer resin composition at this moment is that the radiating light from extra-high-pressure mercury vapour lamp is passed through optical filter (UV-31; Morning sun beam split (strain) system).
Wherein, as photomask, use the photomask that forms following pattern at grade.
Having 1 limit is the foursquare transmittance section (pattern) of 10 μ m, these foursquare 100 μ m that are spaced apart.
Having 1 limit is the foursquare transmittance section (pattern) of 15 μ m, these foursquare 100 μ m that are spaced apart.
After irradiates light, down this substrate above-mentioned filmed to be immersed in to contain in the water system developer solution that nonionic is surfactant 0.12% and potassium hydroxide 0.04% for 23 ℃ and developed 40 seconds, after the washing, in stove, carry out under 220 ℃ 20 minutes after cure.Natural cooling is afterwards with determining film thickness device (DEKTAK3; Japan's vacuum technique (strain) system) measure the thickness of the cured film obtain, the result is 3.0 μ m.
Evaluation after pattern forms is identical with embodiment 1.
Comparative example 3
According to the composition shown in the table 3, obtain photosensitive polymer combination 7.With embodiment 4 the same evaluations.
Table 3
| Embodiment 4 | Comparative example 3 | ||
| Polymer resin composition 6 | Polymer resin composition 7 | ||
| Resin (A) | Resin A a (only being solid state component) | 60 | |
| Resin A b (only being solid state component) | 60 | ||
| Resin A c (only being solid state component) | |||
| Polymerizable compound (B) | Dipentaerythritol acrylate (Japanese chemical drug (strain) system KAYARAD DPHA) | 40 | 40 |
| Initiating agent (C) | エ ノ Application, 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl]-1-(O-acetyl group oxime) (CIBA SPECIALTY CHEMICALS corporate system OXE-02) | 2 | 2 |
| Solvent (D) | Propylene glycol methyl ether acetate | 41 | 41 |
| 3-ethoxyethyl group propionic ester | 37 | 37 | |
| 3-methoxyl-1-butanols | 4 | 4 | |
| Acetate 3-methoxyl butyl ester | 0 | 0 | |
| 3-methoxyl-1-butanols+acetate 3-methoxyl butyl ester is from the amount of bringing into of resin (A) | 124 | 124 | |
Table 4
| Embodiment 4 | Comparative example 3 | |||
| Photosensitive polymer combination | 6 | 7 | ||
| Storage stability | 100 | 101 | ||
| Pattern | Live width | μm | 13.1 | 20.0 |
| Shape | Positive taper | Positive taper | ||
From the result of the embodiment shown in the table 2 1～3 as can be known, contain and comprise the photosensitive polymer combination of the present invention that aliphatics is encircled the adhesive resin of epoxy compound more, have good storage stability.In addition, if use photosensitive polymer combination of the present invention, obtain the good pattern of pattern form, mechanical property, solvent resistance, thermotolerance and film.In addition, if compare, can also separate and look like fine pattern with comparative example 1.
In addition, from the result of the embodiment shown in the table 44 as can be known, contain and comprise the photosensitive polymer combination of the present invention that aliphatics is encircled the adhesive resin of epoxy compound more, have good storage stability.In addition, if use photosensitive polymer combination of the present invention, obtain the good pattern of pattern form and film.In addition, if compare, can also separate and look like fine pattern with comparative example 3.
Industrial utilizability
Having good storage stability of photosensitive polymer combination of the present invention; can form the outstanding pattern of pattern form, surface smoothness, mechanical property, heat resistance, solvent resistance and film, can perform well in forming protective finish, light separator, dielectric film, liquid crystal aligning control with projection, be used for the film that the coating etc. of the thickness of cooperation colored pattern is used in display unit.
Claims (5)
1. photosensitive polymer combination, contain adhesive resin (A), optical polymerism compound (B), Photoepolymerizationinitiater initiater (C) and solvent (D), wherein adhesive resin (A) is the multipolymer that unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydrides (A1) and aliphatics are encircled epoxy compound (A2) more.
2. it is to have epoxy radicals on the ring of aliphatics polycyclic compund that photosensitive polymer combination as claimed in claim 1, aliphatics encircle epoxy compound (A2) more, and has the compound of unsaturated link.
3. as claim 1 or 2 described photosensitive polymer combinations, having aliphatics, to encircle the monomer of epoxy radicals (A2) be from at least a compound of selecting the compound of formula (I) expression and the group with the compound composition of formula (II) expression more,
In formula (I) and formula (II), R represents independently that respectively carbon number that hydrogen atom maybe can replace with hydroxyl be 1～4 alkyl, and X represents independently that respectively it is 1～6 alkylidene that singly-bound maybe can contain heteroatomic carbon number.
4. one kind is used any pattern that described photosensitive polymer combination forms in the claim 1～3.
5. liquid crystal indicator that contains the described pattern of claim 4.
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| JP2010039480A (en) * | 2008-07-11 | 2010-02-18 | Sumitomo Chemical Co Ltd | Colored photosensitive resin composition |
| JP2010039481A (en) * | 2008-07-11 | 2010-02-18 | Sumitomo Chemical Co Ltd | Photosensitive resin composition |
| CN102040795A (en) * | 2009-10-15 | 2011-05-04 | 住友化学株式会社 | Resin composition |
| CN102093514A (en) * | 2009-11-25 | 2011-06-15 | 住友化学株式会社 | Resin composition and display device |
| CN102214024A (en) * | 2010-04-08 | 2011-10-12 | 新应材股份有限公司 | Touchpad and manufacturing method thereof as well as touch display panel with touchpad |
| CN102279527A (en) * | 2010-06-08 | 2011-12-14 | 住友化学株式会社 | Photosensitive resin composition |
| CN102289150A (en) * | 2010-06-17 | 2011-12-21 | 住友化学株式会社 | Photosensitve resin composition |
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