CN101876790B - Photocurable resin composition for transparent electrode formation and method for producing transparent electrode - Google Patents
Photocurable resin composition for transparent electrode formation and method for producing transparent electrode Download PDFInfo
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- CN101876790B CN101876790B CN200910215566.5A CN200910215566A CN101876790B CN 101876790 B CN101876790 B CN 101876790B CN 200910215566 A CN200910215566 A CN 200910215566A CN 101876790 B CN101876790 B CN 101876790B
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Abstract
The invention provides a photocurable resin composition for transparent electrode formation capable of counteracting the influence of halation in the formation of a transparent electrode of a PDP, SED or the like, and a method for producing a transparent electrode using the same. The photocurable resin composition for transparent electrode formation includes: a photopolymerization initiator (a) whose transmittance for light having a wavelength of 360 nm is <80%; a resin (b) having an acid radical; a monomer (c) having an ethylenically unsaturated group; and a light absorbent (d) which substantially transmits light in a wavelength range of 300-355 nm and substantially absorbs light in a wavelength range of 360-400 nm.
Description
Technical field
The present invention relates to transparency electrode and form the manufacture method by the transparency electrode of Photocurable resin composition and use said composition, more specifically, relate to and be applicable to form the manufacture method of the transparency electrode formation of plasma display panel transparency electrode by the transparency electrode of Photocurable resin composition and use said composition.
Background technology
Utilize electric discharge to develop to make that a plurality of micro components (cell) oneself is luminous and to form the plasma display panel that shows image (following also referred to as " PDP ".), there is the advantageous feature that display board can't be realized in the past such as picture is large, frivolous, smooth, therefore realizing the universal of plasma display panel.
This PDP is by the display element of header board and the integrated formation of rear plate, wherein header board forms distribution in parallel to each other by the combination electrode of transparency electrode and bus electrode (bus electrode) formation, rear plate forms distribution by addressing electrode (address electrode) in parallel to each other with the state with above-mentioned combination electrode orthogonal, by header board and rear plate are arranged in opposite directions, thereby form illuminating part between the substrate that forms these electrodes.
In the past, the method as the transparency electrode that forms PDP, had stripping method (liftoff method) and etching method etc., and etching method is common method.In this etching method, for example, after forming transparent and electrically conductive film by sputter, evaporation on glass substrate, the coating Photocurable resin composition, form the light-cured resin layer.Then, the glass substrate vacuum suction that will be formed with the light-cured resin layer is upper at the operator's console (stage) of exposure device, via mask (mask), by extra-high-pressure mercury vapour lamp etc., is exposed.Then, with developing liquid developing, form photoetching agent pattern (resist pattern), using this photoetching agent pattern as mask, transparent and electrically conductive film is carried out to etching, thereby form transparency electrode.
Yet all there are following problem in stripping method, etching method: during exposure, exposure light reflects on glass substrate or on the operator's console of exposure device, produces halation (halation) (with reference to patent documentation 1).In the formation of transparency electrode, the Photocurable resin composition and the substrate that are used to form transparency electrode are all transparent, thereby easily be subject to the impact that wire spoke that halation causes changes, particularly on the operator's console of exposure device, be provided with ditch, the sectional hole patterns for vacuum suction, so these ditch patterns etc. can make the wire spoke of the pattern that forms change or make the pattern form variation.
The problem of this halation, be not limited only to PDP, forming surface-conduction-electron emission display (hereinafter to be referred as " SED ".) etc. transparency electrode the time also can produce.
Patent documentation 1: TOHKEMY 2006-276791 communique
Summary of the invention
The present invention completes in view of above-mentioned problem, purpose is to provide and can when forming the transparency electrode of PDP, SED etc., prevents or alleviate the impact of halation and realize highly sensitive transparency electrode formation Photocurable resin composition, and the manufacture method of using the transparency electrode of said composition.
The inventor conducts in-depth research to achieve these goals repeatedly, found that if use specific composition can solve above-mentioned problem, thereby has completed the present invention.Particularly, the invention provides following scheme.
The first embodiment of the present invention is that transparency electrode forms and use Photocurable resin composition, and it comprises: to the light absorber (d) of the light of the Photoepolymerizationinitiater initiater (a) of the transmitance less than 80% of the light of 360nm wavelength, the resin (b) with acidic group, the monomer (c) with ethene unsaturated group and the substantive light that sees through 300～355nm wavelength and substantive absorption 360～400nm wavelength.
The manufacture method that the second embodiment of the present invention is transparency electrode, the method comprises: be formed with coating transparency electrode formation of the present invention Photocurable resin composition on the glass substrate of transparent and electrically conductive film, after the selectivity exposure, develop to form the operation of photoetching agent pattern; Using above-mentioned photoetching agent pattern as mask, above-mentioned transparent and electrically conductive film is carried out to the operation of selective etch; And the operation of peeling off above-mentioned photoetching agent pattern.
According to the present invention, the transparency electrode that can prevent or alleviate the halation impact while can be provided in the transparency electrode that forms PDP, SED etc. forms uses Photocurable resin composition, and the manufacture method of using the transparency electrode of said composition.
Embodiment
Below, embodiments of the present invention are described.In this instructions, " (methyl) acrylic acid " means one or both in acrylic acid and methacrylic acid.Similarly, " (methyl) acrylate " means one or both in acrylate and methacrylate.
" Photocurable resin composition "
Transparency electrode of the present invention forms and (is designated hereinafter simply as " Photocurable resin composition " with Photocurable resin composition.) comprise: to the light absorber (d) of the light of the Photoepolymerizationinitiater initiater (a) of the transmitance less than 80% of the light of 360nm wavelength, the resin (b) with acidic group, the monomer (c) with ethene unsaturated group and the substantive light that sees through 300～355nm wavelength and the substantive 360～400nm of absorption wavelength.Below, each composition contained in Photocurable resin composition of the present invention is described.
[Photoepolymerizationinitiater initiater (a)]
The Photoepolymerizationinitiater initiater (a) that Photocurable resin composition of the present invention contains the transmitance less than 80% of the light of 360nm wavelength is (following also referred to as " (a) composition ".)。
In the situation that form the transparency electrode of PDP, SED etc., sometimes when exposing, the light-cured resin layer reflects on the operator's console of exposure light at exposure device, produce halation.That is, due to exposure light transmission glass substrate, reflect on the operator's console of exposure device, so light (reflected light) also can arrive the zone beyond exposure position, sometimes be difficult to form the pattern of required form.Through the inventor, confirm, the light that is less than the short wavelength of 360nm due to wavelength is absorbed by glass substrate, so in reflected light, contained major part is that wavelength is the above light of 360nm.Therefore, by the light absorber (d) that makes in Photocurable resin composition of the present invention to contain the light that absorbs in fact aftermentioned 360～400nm wavelength, the impact that can alleviate halation.
For the impact that alleviates halation by light absorber (d), as Photoepolymerizationinitiater initiater, can use existing normal optical polymerization initiator on principle, but, in order when suppressing the halation impact, to improve sensitivity, used the Photoepolymerizationinitiater initiater to the transmitance less than 80% of the light of 360nm wavelength in Photocurable resin composition of the present invention.To the transmitance of the light of 360nm wavelength, be more preferably below 70%.The preferred value of transmitance lower limit is 0%.
In addition, in this instructions, the transmitance value in the following manner obtain of Photoepolymerizationinitiater initiater to the light of 360nm wavelength.That is,, in the composition of following comparative example 1, suitable selective light polymerization initiator (make coordinate mass fraction identical), as estimating with resin combination 1.Use slit coater (slit coater) that this evaluation is coated on resin combination 1
evaporation has the glass substrate (Asahi Glass society system, PD200) of ITO upper, then dry under the condition of 65 ℃, 180 seconds on hot plate, obtains having the light-cured resin layer of 2.5 μ m film thicknesses.Then, use extinction photometer (Shimadzu Seisakusho Ltd.'s system, UV-2500PC) to measure the transmitance of this light-cured resin layer to the light of 360nm wavelength, the value recorded is considered as to the transmitance of Photoepolymerizationinitiater initiater.This is because will containing the composition of Photoepolymerizationinitiater initiater, the transmitance of the light of 360nm wavelength roughly not regarded as to 100%.
Photoepolymerizationinitiater initiater as the transmitance less than 80% of this light to the 360nm wavelength, can enumerate: 2, the 4-diethyl thioxanthone, 2, 2-dimethoxy-1, 2-diphenylethane-1-ketone, 2-hydroxyl-1-{4-[4-(2-hydroxy-2-methyl-propiono)-benzyl]-phenyl }-2-methyl-propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butanone-1, 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholine-4-base-phenyl)-butane-1-ketone, two (2, 4, the 6-trimethylbenzoyl)-phenyl phosphine oxide, 1, the 2-acetyl caproyl, 1-[4-(thiophenyl)-2-(O-benzoyl oxime)] etc.In commercially available Photoepolymerizationinitiater initiater, can use KAYACURE DETX-S (Japanese chemical drug society system), IRGACURE 651, IRGACURE 127, IRGACURE 369, IRGACURE 379, IRGACURE 379EG, IRGACURE 819DW, IRGACURE OXE01 (IRGACURE series is by チ バ ス ペ シ ヤ Le テ イ ケ ミ カ Le ズ society system) etc.These Photoepolymerizationinitiater initiaters may be used singly or two or more in combination.
In these Photoepolymerizationinitiater initiaters, from aspects such as sensitivity, consider, be preferably at least one being selected from 2,4-diethyl thioxanthone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butanone-1 and 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholine-4-base-phenyl)-butane-1-ketone.
(a) content of composition is preferably 0.5～30 quality % with respect to the solid constituent of Photocurable resin composition, more preferably 1～20 quality %.Content by making (a) composition, in above-mentioned scope, can obtain sufficient thermotolerance, resistance to chemical reagents, can also make filming performance improve, and it is bad to suppress photocuring.
[resin (b) with acidic group]
It is (following also referred to as " (b) composition " that Photocurable resin composition of the present invention comprises the resin (b) with acidic group.)。As this (b) composition, can preferably use the resin with ethene unsaturated group and acidic group.
As the resin with ethene unsaturated group and acidic group, can enumerate: by (methyl) acrylic acid, fumaric acid, maleic acid, monomethyl fumarate, monomethyl ester, (methyl) acrylic acid 2-hydroxyl ethyl ester, glycol monoethyl ether (methyl) acrylate, ethylene glycol monoethyl ether (methyl) acrylate, (methyl) acrylic acid glyceride, (methyl) acrylamide, vinyl cyanide, methacrylonitrile, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) isobutyl acrylate, (methyl) 2-EHA, (methyl) benzyl acrylate, ethylene glycol bisthioglycolate (methyl) acrylate, diethylene glycol diacrylate, triethylene glycol two (methyl) acrylate, TEG two (methyl) acrylate, butanediol dimethylacrylate, propylene glycol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, tetra methylol propane four (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, 1,6-hexanediol two (methyl) acrylate, the resin of the polymerization gained such as カ Le De epoxy diacrylate, make polyalcohols and monoacid or polyprotonic acid condensation obtain polyester prepolyer, then it is reacted to polyester (methyl) acrylate of gained with (methyl) acrylic acid, after making polyvalent alcohol and the compound with two isocyanate group reacting, then react polyurethane (methyl) acrylate of gained with (methyl) acrylic acid, the epoxy resin such as bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, phenol or cresol-novolac epoxy resin, cresols type epoxy resin, triphenol methane type epoxy resin, poly carboxylic acid poly glycidyl ester, polyvalent alcohol poly glycidyl ester, aliphatics or cycloaliphatic epoxy resin, amine epoxy resin, dihydroxy benzenes type epoxy resin react epoxy (methyl) acrylate resin of gained etc. with (methyl) acrylic acid.And, can also use epoxy (methyl) acrylate resin and the reacted resin of multi-anhydride.
Particularly when the light-cured resin layer of the thinner film that forms 2.0～5.0 μ m, in the resin with ethene unsaturated group and acidic group, the resin that preferably uses (methyl) benzyl acrylate etc. to be obtained by the monomer with phenyl ring and the monomer polymerization with the acidic group such as (methyl) acrylic acid.Preferably 10～90 % by mole, more preferably 30～85 % by mole of ratios that there is the monomer of phenyl ring in this resin.The ratio of the monomer by making to have phenyl ring, in above-mentioned scope, can improve the elching resistant of the photoetching agent pattern that uses Photocurable resin composition to form.In addition, preferably 1～40 % by mole, more preferably 1～30 % by mole of the ratio that there is the monomer of the acidic groups such as (methyl) acrylic acid.The ratio of the monomer by making to have the acidic groups such as (methyl) acrylic acid, in above-mentioned scope, can improve the developability of Photocurable resin composition.
Have ethene unsaturated group and acidic group resin the matter average molecular weight preferably 100～500000, more preferably 3000～250000, further preferably 5000～100000.In addition, there is preferably 80～150 ℃ of the vitrifying points (Tg) of the resin of ethene unsaturated group and acidic group, more preferably 90～140 ℃.By matter average molecular weight, vitrifying point are adjusted to above-mentioned scope, can improve the elching resistant of the photoetching agent pattern that uses Photocurable resin composition to form.
In addition, the acid number preferably 50～200mgKOH/g, the more preferably 60～150mgKOH/g that there is the resin of ethene unsaturated group and acidic group.By its acid number is adjusted to above-mentioned scope, can improve the developability of Photocurable resin composition.
(b) content of composition is preferably 5～95 quality %, 10～80 quality % more preferably with respect to the solid constituent of Photocurable resin composition.Content by making (b) composition, in above-mentioned scope, can easily be obtained the balance of sensitivity, developability, resolution.
[monomer (c) with ethene unsaturated group]
It is (following also referred to as " (c) composition " that Photocurable resin composition of the present invention comprises the monomer (c) with ethene unsaturated group.)。By should (c) composition and the combination of above-mentioned (b) composition, can make the raising of curing property, and easily form pattern.Should in (c) composition, contain monofunctional monomer and polyfunctional monomer.
As monofunctional monomer, can enumerate: (methyl) acrylamide, methylol (methyl) acrylamide, methoxy (methyl) acrylamide, ethoxyl methyl (methyl) acrylamide, propoxyl group methyl (methyl) acrylamide, butoxy methoxy (methyl) acrylamide, N-methylol (methyl) acrylamide (N-methylol (metha) crylamide), N-methylol (methyl) acrylamide (N-hydroxymethyl (metha) crylamide), (methyl) acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2-acrylamide-2-methyl propane sulfonic acid, N-tert-butyl acrylamide sulfonic acid, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) 2-EHA, (methyl) cyclohexyl acrylate, (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) acrylic acid 2-hydroxypropyl acrylate, (methyl) acrylic acid 2-hydroxyl butyl ester, (methyl) acrylic acid-2-phenoxy group-2-hydroxy propyl ester, phthalic acid-2-(methyl) acryloxy-2-hydroxy propyl ester, single (methyl) acrylic acid glyceride, (methyl) tetrahydrofurfuryl acrylate, amino (methyl) acrylic acid dimethyl ester, (methyl) glycidyl acrylate, (methyl) acrylic acid 2,2, the 2-trifluoro ethyl ester, (methyl) acrylic acid 2,2,3,3-tetrafluoro propyl ester, half (methyl) acrylate of phthalic acid derivatives etc.These monofunctional monomers may be used singly or two or more in combination.
On the other hand, as polyfunctional monomer, can enumerate: ethylene glycol bisthioglycolate (methyl) acrylate, diethylene glycol two (methyl) acrylate, TEG two (methyl) acrylate, propylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, butylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, 1,6-hexanediol two (methyl) acrylate, tristane dimethanol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, two (methyl) acrylic acid glyceride, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, dipentaerythritol five acrylate, dipentaerythritol acrylate, pentaerythrite two (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, two (4-(methyl) the acryloxy diethoxy phenyl) propane of 2,2-, two (4-(methyl) the acryloxy polyethoxy phenyl) propane of 2,2-, (methyl) acrylic acid-2-hydroxyl-3-(methyl) acryloxy propyl ester, ethylene glycol diglycidylether two (methyl) acrylate, diethylene glycol diglycidyl ether two (methyl) acrylate, o-phthalic acid diglycidyl ester two (methyl) acrylate, three acrylic acid glyceride, the glycerine polyglycidyl ether gathers (methyl) acrylate, polyurethane (methyl) acrylate (urethane (metha) acrylate) (being toluene diisocyanate), the reactant of trimethyl hexamethylene diisocyanate and hexamethylene diisocyanate and (methyl) acrylic acid 2-hydroxyl ethyl ester, di-2-ethylhexylphosphine oxide (methyl) acrylamide, (methyl) acrylamide methylene ether, the polyfunctional monomers such as condensation product of polyvalent alcohol and N-methylol (methyl) acrylamide, triacryl formal (Triacrylformal) etc.These polyfunctional monomers may be used singly or two or more in combination.
Particularly, when the light-cured resin layer of the thinner film that forms 2.0～5.0 μ m, in the monomer with ethene unsaturated group, preferably trifunctional monomer and bifunctional monomer are used in combination.The mass ratio of trifunctional monomer and bifunctional monomer preferably 10: 90～90: 10, more preferably 30: 70～70: 30, further preferably 40: 60～60: 40.By using such monomer, can improve the elching resistant of the photoetching agent pattern that uses Photocurable resin composition to form.
(c) content of composition is preferably 5～50 quality %, 10～40 quality % more preferably with respect to the solid constituent of Photocurable resin composition.Content by making (c) composition, in above-mentioned scope, can easily be obtained the balance of sensitivity, developability, resolution.
[light absorber (d)]
The light absorber (d) of the light that Photocurable resin composition of the present invention comprises the substantive light through 300～355nm wavelength and the substantive 360～400nm of absorption wavelength is (following also referred to as " (d) composition ".)。
As mentioned above, in the situation that form the transparency electrode of PDP, SED etc., during light-cured resin layer exposure sometimes, exposure light reflects on the operator's console of exposure device, produces halation.Now, the light that is less than the short wavelength of 360nm due to wavelength is absorbed by glass substrate, therefore by the light absorber that makes Photocurable resin composition of the present invention contain the light that absorbs in fact 360～400nm wavelength, even state in the use in the situation to the Photoepolymerizationinitiater initiater of the transmitance less than 80% of the light of 360nm wavelength the impact that also can alleviate halation.In addition, due to the substantive light that sees through 300～355nm wavelength of light absorber, therefore can suppress the reduction of sensitivity.
To the transmitance of the light of 300～355nm wavelength preferably more than 80%, more preferably more than 85%, further preferably more than 90%.In addition, to the transmitance of the light of the 360～400nm wavelength transmitance of the light of 360nm wavelength (particularly to) preferably below 65%, more preferably below 60%.
In this instructions, the transmitance value in the following manner obtain of Photoepolymerizationinitiater initiater to the light of 360nm wavelength.That is, upwards the commentary valency is used composition 2 with adding the light absorber preparation to estimate in composition 1.With respect to (b) composition 100 mass parts, the use level of light absorber is 1 mass parts.Then, will use the transmitance of the light to the 360nm wavelength that the commentary valency measures with composition 1 as IA
360, will use the transmitance of the light to the 360nm wavelength that the commentary valency measures with composition 2 as IB
360the time, the value of gained in following formula (1) is considered as to the transmitance of light absorber to the light of 360nm wavelength.
Transmitance=100-{ (IA
360-IB
360)/IA
360} * 100 ... (1)
In addition, transmitance to the light of 300～355nm wavelength, for example can measure the transmitance of said composition to the light of 320nm wavelength to adding light absorber (make mass fraction identical) in the composition of following comparative example 2, and the relation of corresponding above-mentioned formula (1) and trying to achieve.
As this light absorber, can enumerate the native compounds such as curcumin, oxygen anthrone; The azo-compounds such as the azobenzene of commercially available weld, azobenzene derivatives, azonaphthalene derivant, aryl pyrrolidones or azonaphthalene substituent etc.For absorbing wavelength is set in desired zone, can suitably select length, the substituting group of azo-compound conjugated system.For example, by replacing with electron withdraw groups such as sulfonic group, sulfonate group, sulfo group, carboxyl, cyano group, substituted aryl or alkyl-carbonyl, halogen atoms, absorption region can be set in the short wavelength zone.By by electron donating group-substituted such as substituted-amino, hydroxyl, alkoxy, aryloxy group, absorbing wavelength can be set in the long wavelength zone in addition.These light absorbers may be used singly or two or more in combination.
Consider preferred curcumin in above-mentioned light absorber from the effect aspect of the impact that alleviates halation.
With respect to (b) composition 100 mass parts of Photocurable resin composition, (d) content of composition is preferably 0.1～5 mass parts, 0.3～5 mass parts more preferably.Content by making (d) composition, in above-mentioned scope, can effectively alleviate the impact of halation.
[sensitizer (e)]
For sensitivity, residual film ratio are improved, it is (following also referred to as " (e) composition " that Photocurable resin composition of the present invention can contain sensitizer (e).)。As this (e) composition, can use mercaptan type chain transfer agent, other sensitizer.
As mercaptan type chain transfer agent, can enumerate: sulfydryl organic acid (propionic acid) derivants such as β-mercaptopropionic acid, β-mercaptopropionic acid methyl esters, β-mercaptopropionic acid ethyl ester, β-mercaptopropionic acid 2-Octyl Nitrite, β-mercaptopropionic acid n-octyl, β-mercaptopropionic acid methoxyl butyl ester, β-mercaptopropionic acid octadecane alcohol ester, β-mercaptopropionic acid ester in the different ninth of the ten Heavenly Stems, trimethylolpropane tris (3-sulfydryl propyl ester), pentaerythrite four (3-sulfydryl propyl ester), dipentaerythritol six (3-sulfydryl propyl ester), three [(3-sulfydryl propionyloxy)-ethyl] isocyanuric acid ester; The mercaptoacetic acid derivants such as methyl thioglycolate, mercaptoacetic acid monooctyl ester, mercaptoacetic acid methoxyl butyl ester, ethylene glycol bisthioglycolate (mercaptoacetate), butylene glycol two (mercaptoacetate), trimethylolpropane tris (mercaptoacetate), pentaerythrite four (mercaptoacetate) etc.These mercaptan type chain transfer agents may be used singly or two or more in combination.
On the other hand, as other sensitizer, for example can enumerate: 2,4-diethyl thioxanthone, isopropyl thioxanthone, two (the 4-lignocaine benzylidene) cyclopentanone of 2,3-, two (the 4-dimethylamino benzylidene) cyclohexanone of 2,6-, two (4-dimethylamino the benzylidene)-4-methyl cyclohexanones of 2,6-, Michler's keton, two (the lignocaine)-benzophenones of 4,4-, two (dimethylamino) chalcones of 4,4-, two (lignocaine) chalcones of 4,4-, to dimethylamino cinnamylidene indenone (p-dimethylamino cinnamilidene indanone), to dimethylamino benzal indenone (p-dimethylamino benzilidene indanone), 2-(to the dimethylamino phenyl ethenylidene)-different aphthothiazoles, two (the 4-dimethylamino benzylidene) acetone of 1,3-, 1,3-carbonyl-bis-(4-lignocaine benzylidene) acetone, 3,3-carbonyl-bis-(7-lignocaine cumarin), N-phenyl-N-ehtylethanolamine, the N-phenylethanol amine, N-phenylglycine, N-tolyl diethanolamine, the N-phenylethanol amine, the dimethylaminobenzoic acid isopentyl ester, the diethylamino Benzoic Acid isopentyl ester, 3-phenyl-5-benzoyl mercapto-tetrazole (3-phenyl-5-benzoyl thiotetrazole), 1-phenyl-5-ethoxy carbonyl mercapto-tetrazole (1-phenyl-5-ethoxy carbonyl thiotetrazole) etc.Above-mentioned other sensitizer may be used singly or two or more in combination.
(e) content of composition is preferably 0.01～20 quality %, the more preferably scope of 1～10 quality % with respect to the solid constituent of Photocurable resin composition.Content by making (e) composition, in above-mentioned scope, has the trend of suitable raising sensitivity, can also make residual film ratio improve simultaneously, therefore preferably.
[organic solvent (s)]
In order to improve coating, to adjust viscosity, it is (following also referred to as " (s) composition " that Photocurable resin composition of the present invention preferably contains organic solvent (s).)。
As this organic solvent, for example can enumerate: glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol list positive propyl ether, the diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, Triethylene glycol ethyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol list positive propyl ether, the propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, DPE, the single positive propyl ether of dipropylene glycol, the dipropylene glycol mono-n-butyl ether, Tripropylene glycol monomethyl Ether, (gathering) the alkylene glycol monoalkyl ethers classes such as tripropylene glycol list ether, (gathering) the alkylene glycol monoalkyl ethers acetate esters such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetic acid esters, diethylene glycol monoethyl ether acetic acid esters, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, other ethers such as diethylene glycol dimethyl ether, diethylene glycol MEE, diethylene glycol diethyl ether, tetrahydrofuran, the ketones such as methyl ethyl ketone, cyclohexanone, 2-HEPTANONE, 3-heptanone, the lactic acid alkyl ester classes such as 2 hydroxy propanoic acid methyl esters, 2 hydroxy propanoic acid ethyl ester, 2-hydroxy-2-methyl ethyl propionate, the 3-methoxy methyl propionate, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, the 3-ethoxyl ethyl propionate, ethoxy ethyl acetate, hydroxyl ethyl acetate, 2-hydroxy-3-methyl methyl butyrate, 3-methoxyl butylacetic acid ester, 3-methyl-3-methoxyl butylacetic acid ester, 3-methyl-3-methoxyl butyl propionic ester, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, the formic acid n-pentyl ester, isoamyl acetate, n-butyl propionate, ethyl butyrate, propyl butyrate, isopropyl isobutyrate, the positive butyl ester of butyric acid, methyl pyruvate, ethyl pyruvate, the pyruvic acid n-propyl, methyl acetoacetate, ethyl acetoacetate, other ester classes such as 2-ethyl acetoacetate, the arene such as toluene, dimethylbenzene, the amide-types such as 1-METHYLPYRROLIDONE, DMF, DMA etc.These solvents may be used singly or two or more in combination.
(s) content of composition is not particularly limited, and can according to coated film thickness, suitably set according to the concentration that can be coated with on glass substrate.The viscosity of Photocurable resin composition is 5～500cp, more preferably scope, the further preferred scope of 20～30cp of 10～50cp preferably.In addition, preferably 5～100 quality %, the more preferably scope of 20～50 quality % of the concentration of solid constituent.
[other composition]
Photocurable resin composition of the present invention can add the adjuvants such as thermal polymerization inhibitor, surfactant as required.
As above-mentioned thermal polymerization inhibitor, can be existing known polymerization inhibitor, can enumerate quinhydrones, quinhydrones list ether etc.
As above-mentioned surfactant, can be existing known surfactant, can enumerate the compound of type siloxane, fluorine class etc.
[preparation method of Photocurable resin composition]
Can prepare by the following method by Photocurable resin composition of the present invention: with stirring machine, above-mentioned each composition is mixed, more as required with filtrations such as membrane filters.The Photocurable resin composition made thus when forming the light-cured resin layer of 2.5 μ m film thicknesses, to the transmitance of the light of 360nm wavelength be preferably below 30%, more preferably 5～28%.
In addition, the transmitance of light-cured resin layer can be measured in the following manner: after being coated on glass substrate (Asahi Glass society system, PD200) by Photocurable resin composition, under 60 ℃, the dry light-cured resin layer that obtains 2.5 μ m film thicknesses in 90 seconds, then use extinction photometer (Shimadzu Seisakusho Ltd.'s system, UV-2500PC) to be measured the light-cured resin layer of gained.
" manufacture method of transparency electrode "
The manufacture method of transparency electrode of the present invention comprises: be formed with coating Photocurable resin composition of the present invention on the glass substrate of transparent and electrically conductive film, after the selectivity exposure, developing and form the operation of photoetching agent pattern; Using this photoetching agent pattern as mask, transparent and electrically conductive film is carried out to the operation of selective etch; And the operation of stripping photoresist pattern.
; at first; use the non-contact type apparatus for coating such as contact transfer printing type apparatus for coating, spinner (rotary apparatus for coating), slit coater, curtain coater (curtain coater) such as roll coater, reverse coating machine, bar coating machine (bar coater); be formed with coating Photocurable resin composition of the present invention on the glass substrate of transparent and electrically conductive film; after making its drying, form the light-cured resin layer.
Then, will be formed with the glass substrate vacuum suction of light-cured resin layer on the operator's console of exposure device, via negative mask irradiation ultraviolet radiation, excimer laser isoreactivity energy line, carry out partial exposure.Can use the ultraviolet light sources of emission such as high-pressure mercury-vapor lamp, extra-high-pressure mercury vapour lamp, xenon lamp, carbon arc lamp to be exposed.The energy line amount of irradiating, according to the composition of photosensitive polymer combination and difference, preference is as 5～2000mJ/cm
2left and right.
Then, by with developer solution, the resin bed after exposing being developed, form photoetching agent pattern.Developing method is not particularly limited, such as using infusion process, spray-on process etc.As the concrete example of developer solution, can enumerate the organic developer solutions such as monoethanolamine, diethanolamine, triethanolamine; The aqueous solution of NaOH, potassium hydroxide, sodium carbonate, ammonia, quaternary ammonium salt etc.In addition, cure to be heating and curing after can also carrying out the photoetching agent pattern after developing.After preferably 150～250 ℃ of the temperature of baking and banking up with earth.
Then, using the photoetching agent pattern of formation as mask, transparent and electrically conductive film is carried out to selective etch.Etching is wet etching normally, can be also dry etching.Thereby form transparency electrode by remove photoetching agent pattern with stripper.
[embodiment]
Below, by embodiment, the present invention will be described in more detail, but the present invention is not limited by these embodiment.
<embodiment 1 >
As Photoepolymerizationinitiater initiater, use (a-1) 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butanone-1 (チ バ ス ペ シ ヤ Le テ イ ケ ミ カ Le ズ society system, " IRGACURE 369 ").This Photoepolymerizationinitiater initiater is 40% to the transmitance of the light of 360nm wavelength.
As resin, use the multipolymer (70 ℃ of matter average molecular weight 60000, vitrifying points) of (b-1) benzyl methacrylate/methacrylic acid=80/20.
As monomer, use (c-1) trimethylolpropane triacrylate, (c-2) tristane dimethanol diacrylate.
As light absorber, use (d-1) curcumin.This light absorber is more than 80% to the transmitance of the light of 320nm wavelength, to the transmitance of the light of 360nm wavelength, is 58%.
As sensitizer, use (e-1) trimethylolpropane tris (3-sulfydryl propyl ester).
As surfactant, use (f-1) " グ ラ ノ mono-Le 440 " (chemistry society of common prosperity society system).
Mix propylene glycol monomethyl ether in each composition, make solid component concentration reach 30%, after stirring 2 hours with stirring machine, with 5 μ m membrane filters, filter and make Photocurable resin composition.The use level of each composition is as shown in table 1.In addition, the numerical value in table mean mass fraction unless otherwise specified.
<embodiment 2～4 >
The use level of each composition of replacement as shown in table 1, in addition adopt the method identical with embodiment 1 to prepare Photocurable resin composition.
<comparative example 1 >
Except mismatching light absorber, adopt the method identical with embodiment 1 to prepare Photocurable resin composition.The use level of each composition is as shown in table 2.In addition, the numerical value in table mean mass fraction unless otherwise specified.
<comparative example 2 >
As Photoepolymerizationinitiater initiater, use (a-2) " EAB-F " (hodogaya chemical society system) and (a-3) " B-CIM " (hodogaya chemical society system) with the use level of table 2, in addition the employing method identical with comparative example 1 prepares Photocurable resin composition.
<comparative example 3 >
As Photoepolymerizationinitiater initiater, use level with table 2 is used (a-4) 2-methyl isophthalic acid-(4-methyl mercapto phenyl)-2-morpholino propane-1-ketone (チ バ ス ペ シ ヤ Le テ イ ケ ミ カ Le ズ society system, " IRGACURE 907 "), in addition adopts the method identical with comparative example 1 to prepare Photocurable resin composition.
[table 1]
[table 2]
PGME: propylene glycol monomethyl ether
The evaluation of<transmitance >
Use slit coater that the Photocurable resin composition of preparation in above-described embodiment 1～4, comparative example 1～3 is coated on
evaporation has the glass substrate (Asahi Glass society system, PD200) of ITO upper, then dry under the condition of 65 ℃, 180 seconds on hot plate, obtains having the light-cured resin layer of 2.5 μ m film thicknesses.Use extinction photometer (Shimadzu Seisakusho Ltd.'s system, UV-2500PC) to measure the transmitance of this light-cured resin layer under 320nm, 360nm, 400nm, 440nm.Result is as shown in table 3.
[table 3]
| Wavelength | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| 320nm | 0 | 0 | 0 | 0 | 0 | 40.8 | 0 |
| 360nm | 23.4 | 18.6 | 25.2 | 33.3 | 40.3 | 47.6 | 26.0 |
| 400nm | 81.2 | 78.7 | 85.1 | 88.3 | 98.8 | 67.1 | 83.0 |
| 440nm | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
As known from Table 3, the transmitance of the Photocurable resin composition of embodiment 1～4 under 360nm is (particularly embodiment 1～3 is below 30%) below 35%, is difficult to be subject to the impact from the halation of exposure device operator's console.
The evaluation of<sensitivity, wire spoke variable quantity, residual film ratio >
The glass substrate that will be formed with the light-cured resin layer of gained in above-mentioned transmitance evaluation load on the Cr substrate or black polyethylene substrate (black polyethylene sheet) upper, via the negative mask of top with exposure 2～200mJ/cm
2the elective irradiation ultraviolet ray, have the gap of 300 μ m between the negative mask of this top and light-cured resin layer.Then, use 0.25%Na under 25 ℃
2cO
3carry out 90 seconds spray development and process, the flowing water washing, nitrogen blowing, obtain line and space (line-and-space) pattern of 100 μ m.Then obtain necessary exposure now, and necessary exposure is carried out to following evaluation: necessary exposure is 25mJ/cm
2when following, be ◎; Surpass 25mJ/cm
2and be 50mJ/cm
2when following, be zero; Surpass 50mJ/cm
2time is *.
In addition, in the situation that this necessity exposure, the wire spoke be used on the Cr substrate while exposing deducts the wire spoke while exposing on the black polyethylene substrate, obtains the wire spoke variable quantity.The wire spoke variable quantity is carried out to following evaluation: the wire spoke variable quantity is that 5.0 μ m are zero when following; Surpass 5.0 μ m and be that 10.0 μ m are △ when following; While surpassing 10.0 μ m, be *.
Film thickness change by exposure, the front and back of developing is obtained residual film ratio (%).Residual film ratio is carried out to following evaluation: residual film ratio is 80% to be zero when above; During 70% above less than 80%, be △; During less than 70%, be *.Result is as shown in table 4.
[table 4]
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Necessary exposure (mJ/cm 2) | ○ (50) | ○ (50) | ◎(25) | ○ (50) | ○ (50) | × (150) | × (150) |
| Wire spoke variable quantity (μ m) | ○ (+1.2) | ○ (+1.6) | ○ (+4.5) | △ (+6.0) | × (+11.0) | △ (+7.0) | ○ (+3.0) |
| Residual film ratio (%) | △ (72) | ○ (84) | ○ (86) | ○ (93) | ○ (93) | × (66) | ○ (85) |
As shown in Table 4, use line and the space pattern of the Photocurable resin composition formation of embodiment 1,2, although residual film ratio is little than low wire spoke variable quantity, the wire spoke variable quantity is respectively 1.2 μ m, 1.6 μ m, has effectively suppressed the impact produced by halation.If reduce the use level of light absorber as shown in embodiment 3,4, residual film ratio improves and the increase of wire spoke variable quantity, but has however also obtained the following result preferably of 6.0 μ m.
On the other hand, in the situation that do not coordinate the light absorber of comparative example 1,2, if want to improve sensitivity wire spoke variable quantity increase (that is, the impact that is subject to halation increases), if want to suppress the wire spoke variable quantity sensitivity.In addition, as shown in comparative example 3, even contain light absorber, in the situation that do not use the Photoepolymerizationinitiater initiater of transmitance less than 80% under the 360nm wavelength, although the good value that the wire spoke variable quantity is 3.0 μ m, sensitivity is low.
Claims (5)
1. the manufacture method of a transparency electrode, it comprises: forms and use Photocurable resin composition being formed with on the glass substrate of transparent and electrically conductive film the coating transparency electrode, after the selectivity exposure, the operation of the formation photoetching agent pattern that develops;
Using described photoetching agent pattern as mask, described transparent and electrically conductive film is carried out to the operation of selective etch; And
Peel off the operation of described photoetching agent pattern;
Described transparency electrode forms and comprises with Photocurable resin composition: to light absorber (d) and the sensitizer (e) of the light of the Photoepolymerizationinitiater initiater (a) of the transmitance less than 80% of the light of 360nm wavelength, the resin (b) with acidic group, the monomer (c) with ethene unsaturated group and the substantive light that sees through 300～355nm wavelength and the substantive 360～400nm of absorption wavelength;
The described resin (b) with acidic group resin that monomer with phenyl ring and the monomer polymerization with acidic group obtain of serving as reasons;
Described sensitizer (e) is mercaptan type chain transfer agent.
2. the manufacture method of transparency electrode as claimed in claim 1, it adopts described transparency electrode to form and use Photocurable resin composition, and the transmitance to the light of 360nm wavelength during light-cured resin layer that said composition is 2.5 μ m at the formation film thickness is below 30%.
3. the manufacture method of transparency electrode as claimed in claim 1, described transparency electrode forms with in Photocurable resin composition, with respect to described resin (b) 100 mass parts with acidic group, the content of described light absorber (d) is 0.3～5 mass parts.
4. the manufacture method of transparency electrode as claimed in claim 1, wherein said light absorber (d) contains curcumin.
5. the manufacture method of transparency electrode as claimed in claim 1, wherein said Photoepolymerizationinitiater initiater (a) is selected from least one in following compounds: 2,4-diethyl thioxanthone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butanone-1 and 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholine-4-base-phenyl)-butane-1-ketone.
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| JP2008333308A JP5384929B2 (en) | 2008-12-26 | 2008-12-26 | Photocurable resin composition for forming transparent electrode and method for producing transparent electrode |
| JP2008-333308 | 2008-12-26 |
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| CN102298262B (en) * | 2011-06-16 | 2012-12-05 | 胡海波 | Thermocuring photosensitive resin composition |
| CN104246975B (en) * | 2012-04-27 | 2018-03-30 | 日产化学工业株式会社 | Impression materials with low knockout press |
| EP4038151A1 (en) * | 2019-10-01 | 2022-08-10 | 3D Systems, Inc. | Optically active build materials for 3d printing |
| CN112051710A (en) * | 2020-09-02 | 2020-12-08 | 之江实验室 | High-refractive-index femtosecond laser photoresist based on mercaptoalkene light click polymerization |
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| US6806024B1 (en) * | 1999-03-03 | 2004-10-19 | Ciba Specialty Chemicals Corporation | Oxime derivatives and the use thereof as photoinitiators |
| CN1547683A (en) * | 2001-07-26 | 2004-11-17 | �������⻯ѧƷ�ع�����˾ | Photosensitive resin composition |
| CN1823107A (en) * | 2003-07-16 | 2006-08-23 | 东京应化工业株式会社 | Positive photoresist composition and method of forming resist pattern |
| CN1885163A (en) * | 2005-06-23 | 2006-12-27 | Adms技术株式会社 | Negative resist composition |
| CN101044434A (en) * | 2004-11-04 | 2007-09-26 | 东京应化工业株式会社 | Photosensitive resin composition and photosensitive dry film by the use thereof |
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| JP2003177530A (en) * | 2001-12-13 | 2003-06-27 | Sumitomo Chem Co Ltd | Photosensitive composition |
| JP4151363B2 (en) * | 2002-09-27 | 2008-09-17 | Ｊｓｒ株式会社 | Photosensitive resin composition and method for producing inorganic shaped article using the same |
| JP2008040477A (en) * | 2006-07-11 | 2008-02-21 | Fujifilm Electronic Materials Co Ltd | Colored resin composition and color filter for liquid crystal display element using same |
| JP2008096680A (en) * | 2006-10-11 | 2008-04-24 | Fujifilm Corp | Curable composition for color filter, color filter and method for manufacturing the same |
| JP4921230B2 (en) * | 2007-04-16 | 2012-04-25 | 関西ペイント株式会社 | Negative resist composition for lift-off and pattern forming method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6806024B1 (en) * | 1999-03-03 | 2004-10-19 | Ciba Specialty Chemicals Corporation | Oxime derivatives and the use thereof as photoinitiators |
| CN1547683A (en) * | 2001-07-26 | 2004-11-17 | �������⻯ѧƷ�ع�����˾ | Photosensitive resin composition |
| CN1823107A (en) * | 2003-07-16 | 2006-08-23 | 东京应化工业株式会社 | Positive photoresist composition and method of forming resist pattern |
| CN101044434A (en) * | 2004-11-04 | 2007-09-26 | 东京应化工业株式会社 | Photosensitive resin composition and photosensitive dry film by the use thereof |
| CN1885163A (en) * | 2005-06-23 | 2006-12-27 | Adms技术株式会社 | Negative resist composition |
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