CN103210025A - Resin having improved adhesion properties, and sheet - Google Patents
Resin having improved adhesion properties, and sheet Download PDFInfo
- Publication number
- CN103210025A CN103210025A CN2011800523530A CN201180052353A CN103210025A CN 103210025 A CN103210025 A CN 103210025A CN 2011800523530 A CN2011800523530 A CN 2011800523530A CN 201180052353 A CN201180052353 A CN 201180052353A CN 103210025 A CN103210025 A CN 103210025A
- Authority
- CN
- China
- Prior art keywords
- resin
- coupling agent
- aromatic vinyl
- based compound
- copolymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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- 239000011347 resin Substances 0.000 title claims abstract description 85
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- 239000007822 coupling agent Substances 0.000 claims abstract description 43
- -1 aromatic vinyl compound Chemical class 0.000 claims abstract description 40
- 239000011521 glass Substances 0.000 claims abstract description 26
- 229910010272 inorganic material Inorganic materials 0.000 claims abstract description 13
- 239000011147 inorganic material Substances 0.000 claims abstract description 13
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- 150000001875 compounds Chemical class 0.000 claims description 15
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- 125000003700 epoxy group Chemical group 0.000 claims description 7
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- 238000013329 compounding Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
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- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 5
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/16—Chemical modification with polymerisable compounds
- C08J7/18—Chemical modification with polymerisable compounds using wave energy or particle radiation
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/048—Encapsulation of modules
- H01L31/0481—Encapsulation of modules characterised by the composition of the encapsulation material
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
- C09K2200/0615—Macromolecular organic compounds, e.g. prepolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09K2200/0617—Polyalkenes
- C09K2200/062—Polyethylene
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
- C09K2200/0615—Macromolecular organic compounds, e.g. prepolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09K2200/0632—Polystyrenes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Abstract
The present invention discloses: a resin which can adhere to an inorganic material such as a glass sheet and is produced by adding a coupling agent to an (aromatic vinyl compound)-olefin copolymer such as a cross-copolymer comprising an aromatic vinyl compound and an olefin or applying the coupling agent onto the (aromatic vinyl compound)-olefin copolymer and then irradiating the resulting product with an energy such as an electron beam; or a sheet of the resin. The resin or the sheet produced from the resin is useful as, for example, a sealing material for a solar power generation device or a resin for sealing or bonding a liquid crystal, an EL display or a light-emitting device.
Description
Technical field
The present invention relates to and inorganic materials for example resin excellent in adhesion and the sheet material thereof of sheet glass, glass fibre, mineral filler etc.
Background technology
At present, the encapsulation of device of solar generating (solar cell), liquid crystal, EL display member, EL light-emitting device, bonding with purposes such as resin need with inorganic materials for example resin excellent in adhesion or its sheet material of glass.But present resin or can not get sufficient cementability perhaps improves the method cost height of cementability, perhaps other physical propertiess is produced detrimentally affects etc., can't be satisfactory.
For example, proposed in EVA resinoid, polyolefin resin to add silane coupling agent and mixing, implemented crosslinked and carry out silane-modified method (patent documentation 1～4).For example improved cementability with glass by this method, but to suppress crosslinked man-hour in order adding in sheet forming, to make it positively crosslinked when the encapsulation because coupling agent rubbed into resin, the method for carrying out radical crosslinking, its processing window is narrow, occurs problem, when encapsulation crosslinked bad of forming process aspect sometimes.In addition because be rub into, so cost raises, also consider residual linking agent, crosslinking coagent etc. in addition to the detrimentally affect of physical properties, require to develop more efficient and stable cementability raising method.
In addition, record a kind of packaged material of device of solar generating in the patent documentation 5,6,7,8, it be by to compounding resins such as the EVA of silane coupling agent or linking agent, polyolefine irradiation electron rays obtain, but be crosslinked for the electron rays that replaces being implemented by superoxide the defective when crosslinked, thereby main purpose is to adjust the moulding processibility by electron rays control degree of crosslinking.
On the other hand, record a kind of method in the patent documentation 9,10, this method is for the purpose of the cementability that improves packaged material, inhibition deterioration, to vinyl resins copolymerization olefinically unsaturated carboxylic acid derivatives, epoxy compounds, perhaps carry out modification with them, and then the silane-coating coupling agent.But to the above-mentioned carboxylic acid derivative of olefine kind resin copolymerization, epoxy compounds isopolarity monomer or the technical difficulty height that carries out modification, the possibility of sacrificing other physical propertiess is big.
The prior art document
Patent documentation
Patent documentation 1: Japanese Patent Publication 62-14111 communique
Patent documentation 2: TOHKEMY 2004-214641 communique
Patent documentation 3: TOHKEMY 2006-36875 communique
Patent documentation 4: TOHKEMY 2007-318008 communique
Patent documentation 5: Japanese kokai publication hei 6-334207 communique
Patent documentation 6: TOHKEMY 2001-119047 communique
Patent documentation 7: Japanese kokai publication hei 8-283696 communique
Patent documentation 8: TOHKEMY 2009-249556 communique
Patent documentation 9: TOHKEMY 2002-235047 communique
Patent documentation 10: TOHKEMY 2002-235049 communique
Summary of the invention
The present invention In view of the foregoing finishes, purpose be to provide with inorganic materials for example glass etc. have excellent cementability and can give resin and the sheet material thereof of cementability by high efficiency method.
In addition, the present invention also aims to provide and use such resin or the packaged material of sheet material and the device of solar generating that comprises this packaged material.
According to major programme of the present invention, a kind of resin that has with the cementability of inorganic materials such as glass, silicon is provided, this resin is that aromatic vinyl based compound-olefinic copolymer is added or the coating coupling agent, and then carries out energy exposure and obtain.The interpolation of coupling agent or the method for coating are unqualified, in one embodiment, provide a kind of resin, this resin is by aromatic vinyl based compound-olefinic copolymer is shaped to sheet, at its surface coated coupling agent, and then carry out energy exposure and obtain; In addition, in another embodiment, provide a kind of resin, this resin is to add coupling agent in aromatic vinyl based compound-olefinic copolymer, is shaped to sheet, and then carries out energy exposure and obtain.
In the such scheme, the aromatic vinyl based compound is vinylbenzene in one embodiment, and alkene is ethene in another embodiment.In another embodiment, aromatic vinyl based compound-olefinic copolymer be contain aromatic vinyl based compound and alkene and cross-linking copolymer (cross copolymer).In one embodiment, this cross-linking copolymer has alkene-aromatic vinyl based compound-aromatic polyene copolymer chain and aromatic vinyl based compound polymer chain, the content of the unit of being derived by aromatic vinyl based compound and olefinic monomer accounts for more than the 70 quality % of all copolymer qualities, is preferably more than the 90 quality %, most preferably is more than the 95 quality %, and the content of the unit of being derived by aromatic polyene preferably is lower than 5 quality % of copolymer quality and more than the 0.01 quality %, more preferably less than 1 quality % and more than 0.01 quality %.
In addition, according to another embodiment, above-mentioned energy exposure is electron rays irradiation, for example generally is that acceleration voltage is 10keV～5000keV, is preferably 10keV～250keV, the electron rays of the scope of 10keV～150keV more preferably.
In addition, in an embodiment again, coupling agent is silane coupling agent, particularly has the silane coupling agent of any functional group in amino, methacryloxy, the epoxy group(ing).
According to another aspect of the present invention, the sheet material that uses above-mentioned resin to make is provided, and uses such resin or the packaged material of its sheet material, and then also provide and comprise that such packaged material is as the device of solar generating of integrant.
By like this particularly selecting aromatic vinyl based compound-olefinic copolymer, to its interpolation or coating coupling agent, and then carry out energy exposure, can access resin excellent in adhesion or its sheet material with inorganic materials, particularly glass, silicon, such resin or its sheet material for example as packaged material, liquid crystal, the EL of device of solar generating show, the encapsulation of light-emitting device, bonding be useful with resin.
Embodiment
[adhesive resin and sheet material thereof]
The present invention is such resin or its sheet material: it can obtain by aromatic vinyl based compound-olefinic copolymer being added or being coated with coupling agent and then carrying out energy exposure, excellent in adhesion with inorganic materials such as sheet glass, glass fibre, mineral fillers, preferably fillibility is also excellent in addition.Sheet material among the present invention comprises the concept of film, and its thickness is not particularly limited, and is generally the scope of 1 μ m～3mm.
In this specification sheets, aromatic vinyl based compound-olefinic copolymer refers to multipolymer that each monomer copolymerizable of aromatic vinyl based compound and alkene is obtained, refers to that content by the unit of these monomer derived accounts for more than the 70 quality % of all copolymer qualities, is preferably more than the 90 quality %, most preferably is the multipolymer more than the 95 quality %.The preparation method of this multipolymer is arbitrarily.
As the aromatic vinyl based compound, can enumerate vinylbenzene and various substituted phenylethylene, for example p-methylstyrene, a vinyl toluene, o-methyl styrene, o-tert-butyl vinylbenzene, a t-butyl styrene, to t-butyl styrene, to chloro-styrene, chloro styrene etc.From industrial point of view, preferably use vinylbenzene, p-methylstyrene, to chloro-styrene, especially preferably use vinylbenzene.
As alkene, can enumerate ethene, carbonatoms is 3～20 alpha-olefin, i.e. propylene, 1-butylene, 1-hexene, 4-methyl-1-pentene, 1-octene.Among the present invention, also comprise cyclic olefin in the category of alkene, as the example of this cyclic olefin, can enumerate vinyl cyclohexane or cyclopentenes, norbornylene etc.Preferred use ethene or ethene and alpha-olefin are the mixture of propylene, 1-butylene, 1-hexene or 1-octene etc., more preferably use ethene.
As aromatic vinyl based compound-olefinic copolymer, optimal ethylene and cinnamic multipolymer.
In a preferred embodiment of the invention, as aromatic vinyl based compound-olefinic copolymer, can enumerate the multipolymer of putting down in writing in EP0416815A2, JP3659760, EP872492B1 communique, whole records of above-mentioned communique are incorporated herein by indicating the source respectively.
As aromatic vinyl based compound-olefinic copolymer, further preferably use cross-linking copolymer.Cross-linking copolymer refers to carry out the multipolymer that anionoid polymerization obtains under the coexistence of the alkene that obtains by polycoordination-aromatic vinyl based compound-aromatic polyene multipolymer and aromatic vinyl based compound monomer, is the multipolymer with alkene-aromatic vinyl based compound-aromatic polyene copolymer chain (being recited as main chain sometimes) and aromatic vinyl based compound polymer chain (being recited as side chain sometimes).This cross-linking copolymer and preparation method thereof is recorded among WO2000-37517, USP6559234 or the WO2007-139116, whole records of above-mentioned communique are incorporated herein by indicating the source respectively, the content of the unit of being derived by aromatic vinyl based compound and olefinic monomer accounts for more than the 70 quality % of all copolymer qualities, is preferably more than the 90 quality %, most preferably is more than the 95 quality %, the content of the unit of being derived by aromatic polyene preferably is lower than 5 quality % of copolymer quality and more than 0.01 quality %, more preferably is lower than 1 quality % and more than 0.01 quality %.Herein, aromatic polyene refer to carbonatoms be 10～30, have a plurality of pairs of keys (vinyl) but and the monomer of single or multiple aromatic group polycoordinations, be that in two keys (vinyl) 1 is used to polycoordination and has carried out the aromatic polyene that two bond energys residual under the state of polymerization carry out anionoid polymerization.Preferred use adjacent Vinylstyrene, to Vinylstyrene and between any mixture more than a kind or 2 kinds in the Vinylstyrene.And then, in the cross-linking copolymer, most preferably use main chain to be ethene-styrene diethylene benzene copoly mer chain and the side chain cross-linking copolymer as polystyrene chain.
The cementability of resin of the present invention or sheet material becomes the inorganic materials of problem can enumerate glass, pottery, metal etc., is preferably glass especially.As glass, have Powderedly, fibrous, tabular etc., form is arbitrarily, but is preferably tabular glass.
Among the present invention, can use known coupling agent.As such coupling agent, can enumerate silane coupling agent, titante coupling agent, isocyanates coupling agent, preferably use silane coupling agent.Such silane coupling agent can be bought from Shin-Etsu Chemial Co., Ltd, Dow Corning Corporation, EVONIK company.Silane coupling agent refers to that intramolecularly has the silane compound of functional group and hydrolytic condensation group.As functional group, can enumerate vinyl such as vinyl, methacryloxy, acryloxy, styryl, amino, epoxy group(ing), sulfydryl, thioether group, isocyanate group, halogen group etc.If consider and the high adhesion of glass, as functional group, be preferably vinyl, amino, epoxy group(ing), methacryloxy, acryloxy, most preferably be amino, methacryloxy, epoxy group(ing).Above-mentioned functional group can have single or multiple at intramolecularly.These coupling agents can use more than a kind or 2 kinds.
Have vinyl and for example can enumerate vinyltrimethoxy silane, vinyltriethoxysilane as the silane coupling agent of functional group.Having styryl can enumerate the styryl Trimethoxy silane as the silane coupling agent of functional group.Have acryloxy and can enumerate 3-acryloxy propyl trimethoxy silicane as the silane coupling agent of functional group.Have methacryloxy and can enumerate 3-methacryloxypropyl trimethoxy silane, 3-methacryloxypropyl triethoxyl silane, 3-methacryloxypropyl methyl dimethoxysilane, 3-methacryloxypropyl methyldiethoxysilane as the silane coupling agent of functional group.Have epoxy group(ing) and can enumerate 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl-triethoxysilicane, 3-glycidoxy propyl group methyldiethoxysilane, 2-(3,4-epoxycyclohexyl as the silane coupling agent of functional group) ethyl trimethoxy silane.Have amino and can enumerate the 3-TSL 8330 as the silane coupling agent of functional group, the 3-aminopropyltriethoxywerene werene, the N-2-(amino-ethyl)-3-aminopropyl methyl dimethoxysilane, the N-2-(amino-ethyl)-3-aminopropyl ethyl dimethoxy silane, the N-2-(amino-ethyl)-3-aminopropyl methyldiethoxysilane, the N-2-(amino-ethyl)-the 3-TSL 8330, the N-2-(amino-ethyl)-the 3-aminopropyltriethoxywerene werene, N-phenyl-3-TSL 8330, two (3-trimethoxy-silylpropyl) amine, two (3-triethoxysilylpropyltetrasulfide) amine, N-normal-butyl-3-TSL 8330.
More than be to have methoxyl group, oxyethyl group as the example of hydrolytic condensation group, also can use three isopropoxies, acetoxyl group.
The usage quantity of silane coupling agent is not particularly limited, and when adding in the resin by mixing grade, in general, uses in the scope that with respect to resin is 0.05 quality %～10 quality %.When coating resin, in general at 0.1g/m
2～20g/m
2Scope in use.
Resin of the present invention adds or coating coupling agent and then the method for carrying out energy exposure are modulated aromatic vinyl based compound-olefinic copolymer by being characterised in that.That is, for the method for in aromatic vinyl based compound-olefinic copolymer, adding coupling agent, adopt the known method that is often used in interpolation additive in the resin in aromatic vinyl based compound-olefinic copolymer, to add coupling agent, and carry out mixing.Industrial aspect for example can be used twin screw extruder, Banbury formula mixing machine, roller shaper etc.Then, undertaken sheet materialization by known methods of forming such as inflation moulding, extrusion moulding, T mold forming, calendering formation, roller moulding, extrusion formings.
On the other hand, for the method at aromatic vinyl based compound-olefinic copolymer coating coupling agent, at first, with aromatic vinyl based compound-olefinic copolymer sheet materialization, then, the coating coupling agent.Sheet materialization can be used above-mentioned known method, on the sheet material that obtains, uses for example known coating processes such as intaglio plate coating method, rolling method or dip coating, spray method, the coating coupling agent.At this moment, coupling agent can be diluted in the appropriate solvent and use, and just also can not dilute and use.The latter's coating process with the former the interpolation coupling agent, carry out mixing method and compare, can reduce the usage quantity of coupling agent, economy is more excellent.
Then, to adding as described above or coating coupling agent and aromatic vinyl based compound-olefinic copolymer sheet material of forming carries out energy exposure.As employed energy exposure, can enumerate the irradiation of electron rays, gamma-rays, X ray, ultraviolet ray, neutron ray, alpha-ray, infrared rays, visible rays etc. or Corona discharge Treatment, Cement Composite Treated by Plasma.Above-mentioned energy exposure can use known device to carry out.In preferred implementation of the present invention, use the electron rays irradiation.As the acceleration voltage of electron rays, generally use the scope of 10keV～5000keV, irradiation dose is generally the scope of 1kGy～500kGy.This acceleration voltage is according to the suitably controls such as thickness of sheet material.Among the present invention, purpose is to handle near the strengthening surface resin and thereby cementability is given in the interaction between coupling agent by electron rays, and in order to realize this purpose, the acceleration voltage of electron rays is low for well, be preferably 10keV～250keV, more preferably 10keV～150keV.Alleged strengthening phase mutual effect herein refers to strengthen chemical or the physical property interactions relevant with strengthening cementability such as winding of the resin, the grafting between coupling agent of near surface for example, crosslinked, chemical reaction, molecular chain.
In addition, can adopt Corona discharge Treatment, Cement Composite Treated by Plasma under given conditions, especially preferably adopt Corona discharge Treatment.Certain conditions refers to that employed coupling agent is preferably the such condition of silane coupling agent with epoxy group(ing) or amino.Corona discharge Treatment can be carried out under known device and known condition.Preferred corona discharge energy is not particularly limited, and is preferably 0.1～1000mJ/mm
2Scope.
If to adding or coating coupling agent and aromatic vinyl based compound-olefinic copolymer sheet material of forming carries out such energy exposure, then can realize high-adhesive-strength to inorganic materials, for example, can in 90 ° of stripping tests that utilize the stripping test of floating roll method to carry out, realize more than the 22N/25mm, be preferably the stripping strength (bonding strength) more than the 25N/25mm glass.In addition, in same test, can realize stripping strength more than the 3N/6mm to metals such as silicon (comprise and implemented the silicon that surface stabilization is handled), aluminium, copper, scolding tin.
No matter be to have carried out under the mixing situation in aromatic vinyl based compound-olefinic copolymer in that coupling agent is added to, still after sheet materialization, carried out under the situation of coating, the irradiation of energy line is all similarly carried out, but for only strengthening under near the situation of the interactional purpose the resin surface, consider the preferred scheme that adopts the coating coupling agent from the high low degree aspect of the utilising efficiency of coupling agent.
Among the present invention, can further add or be coated with crosslinking coagent as required.The crosslinking coagent that can use is known crosslinking coagent, for example can enumerate cyanacrylate, triallylcyanurate, N,, N '-penylene bismaleimides, ethylene glycol bisthioglycolate (methyl) acrylate, propylene glycol two (methyl) acrylate, butyleneglycol two (methyl) acrylate, hexylene glycol two (methyl) acrylate, nonanediol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate etc.Above-mentioned crosslinking coagent can use a kind separately, also can will be used in combination more than 2 kinds.Under the situation of compounding crosslinking coagent, its content is not particularly limited, and is the scope of 0.01～5 quality % with respect to adding up to quality optimization usually.
In resin of the present invention or the sheet material that constituted by this resin, in addition, can be in the scope of harmless purpose of the present invention, add the additive that is generally used for resin, for example thermo-stabilizer, antioxidant, antistatic agent, weighting agent, tinting material, lubricant, antifogging agent, whipping agent, fire retardant, flame retardant etc. as required.
Resin of the present invention or its sheet material because of with distribution excellent in adhesion with inorganic materials such as metal, silicon or glass, so as the encapsulation of device of solar generating (solar cell), liquid crystal, EL display member, EL light-emitting device, bonding be useful with resin.Below, be elaborated with member for the various encapsulation as the device of solar generating (solar cell) of the preferable use of resin of the present invention or its sheet material.
[packaged material and device of solar generating]
The adhesive resin sheet material of the invention described above is being used under the situation of sheet material with member, particularly encapsulation as the various encapsulation of device of solar generating (solar cell), its preferred physical properties is that A hardness is more than 50 and below 95, and total light transmittance is more than 75% when the sheet material of thickness 1mm.The styrene-ethylene copolymers that satisfies such condition has the composition that styrene content is 5 moles of %～40 mole %.
In addition, for this kind purposes, can preferably use cross-linking copolymer.The cross-linking copolymer that satisfies this condition has been put down in writing its composition, preparation method and total light transmittance, A hardness in for example WO2007-139116 communique, TOHKEMY 2009-120792 communique, TOHKEMY 2010-150442 communique (its full content is incorporated herein by indicating the source), just can easily prepare so those skilled in the art carry out some tests by the reference foregoing.Particularly, the cross-linking copolymer that satisfies this condition is that vinylbenzene, alkene are under the situation of ethene at the aromatic vinyl based compound, can realize by satisfying following condition.For example, for the preparation of the styrene content of the ethene-styrene diethylene benzene copoly mer of cross-linking copolymer be that 5 moles of %～40 mole %, Vinylstyrene content are that 0.01 mole of %～3 mole %, weight-average molecular weight are 30,000～150,000, the shared quality ratio of this ethene-styrene diethylene benzene copoly mer is 40 quality %～95 quality %, is preferably 40 quality %～90 quality % in the cross-linking copolymer that finally obtains.As under the situation of packaged material, in order stably to keep solar power generation unit, distribution being exposed under the condition of direct sunlight in summer etc., need suitable thermotolerance.Use this packaged material, do not carry out the crosslinked of resin in fact, utilize under the situation that thermoplasticity encapsulates, the storage modulus of resin is preferably 1 * 10 during 120 ° of C
4More than the Pa, further preferably 1 * 10
5Be necessary more than the Pa.This storage modulus can use known determination of viscoelasticity device to try to achieve easily.Also this condition can be satisfied even above-mentioned cross-linking copolymer carries out crosslinking Treatment, the present invention can be applicable to.
And then the MFR value of material resin (200 ° of C, load 98N) is not particularly limited, and in general is more than 0.1g/10 minute and below 300g/10 minute.If lower than this numerical value, then in when encapsulation, be easy to generate by filling the bad space that causes, if than this numerical value height, then the solar battery cell under the environment, the creep of distribution namely may appear in thermotolerance deficiency sometimes.So long as those skilled in the art just can easily infer this MFR value by the known document of employed resin, in addition can by add a spot of oil, softening agent is adjusted.
In addition, as the various encapsulation member of device of solar generating (solar cell), particularly encapsulation sheet material, consider from guaranteeing the reliability aspect, with the cementability particularly important of glass.Preferably in 90 ° of stripping tests that utilize the stripping test of floating roll method to carry out, show the stripping strength (bonding strength) more than the 25N/25mm.
And then, encapsulation sheet material as device of solar generating (solar cell), for encapsulation preferred sheet body be essentially thermoplastic, therefore preferably with the electron rays irradiation to the influence of crosslinked grade be limited to need with near the inorganic materials for example sheet surface of glass cementation.So, in general preferably control the arrival degree of depth of electronics by the acceleration voltage that changes electron rays, or only the bonding face of needs shone.Do not shone by electron rays in fact but be thermoplastic for device of solar generating opposing face of preferred sheet material central part or electron rays shadow surface for the potting resin sheet material.Only strengthened in the interactional preference of near surface, low in fact with respect to the degree of crosslinking of sheet material integral body, be generally below 50% in the evaluation of carrying out with the gel content with respect to sheet material integral body, be preferably below 30% especially.This gel content is obtained by ASTM D-2765-84.
In addition, in the preferred implementation as the packaged material of device of solar generating (solar cell), compounding is by the UV light absorber that transform light energy is become harmless heat energy and catch the photostabilizer that the hindered amine light stabilizer of the free radical that generates by photoxidation constitutes.As UV light absorber, can enumerate benzotriazole category, triazines, benzophenone, benzoates, oxanilide class or malonic ester class.The mass ratio of UV light absorber and hindered amine light stabilizer is the scope of 1:100～100:1, total amount with the quality of UV light absorber and hindered amine light stabilizer is the photostabilizer quality, its usage quantity is the scope of 0.05～5 mass parts with respect to resin quality 100 mass parts.Photostabilizer as above can be bought as ADK STAB LA series from for example Asahi Denka Co., Ltd., perhaps buys as SUMISORB series from Sumika Chemtex Co., Ltd..
And then the purpose for improving as the characteristic of packaged material can add following softening agent, anti-aging agent as required.
＜softening agent 〉
In the packaged material, can compounding be used for known any softening agent of polyvinyl chloride or other resins at present.The preferred softening agent that uses is oil or contains oxygen or nitrogenous class softening agent, more preferably is selected from paraffinic oil, naphthenic oil, ester plasticizer, epoxy plasticiser, ethers softening agent or amides softening agent.
The intermiscibility of these softening agent is relatively good and be difficult to ooze out, in addition can be also big by the plasticized effect that the degree that second-order transition temperature reduces is estimated, can preferably use.
The compounding amount of softening agent is with respect to resin of the present invention or its sheet material 100 mass parts, and softening agent is more than 1 mass parts and below 20 mass parts, is preferably more than 1 mass parts and below 10 mass parts.When being lower than 1 mass parts, above-mentioned effect deficiency, what when being higher than 20 mass parts, cause sometimes oozing out, overbate, cause thus shows stickingly excessively etc.In addition, by the compounding softening agent, the flowability of packaged material is improved.When particularly the MFR value of employed resin is low, by in above-mentioned scope, adding softening agent, can be adjusted to as the suitable MFR value of packaged material.
＜anti-aging agent 〉
As suitable anti-aging agent, for example can enumerate hindered phenol anti-oxidants, Phosphorus thermo-stabilizer, lactone thermo-stabilizer, vitamin-E type thermal stabilizing agent, sulphur type thermal stabilizing agent etc.Its usage quantity is with respect to resin combination 100 mass parts, below 3 mass parts.
＜film, sheet material 〉
Used for packing material sheet material as device of solar generating is not particularly limited its thickness, is generally 30 μ m～1mm, is preferably 100 μ m～0.5mm.In order to prepare such resin sheet, can adopt the known methods of forming such as inflation moulding, extrusion moulding, T mold forming, calendering formation, roller moulding.
In addition, used for packing material sheet material as device of solar generating need not be individual layer, can be with adhesive resin sheet material of the present invention as the glass cementation face, perhaps with the bonding plane of unit such as silion cell, further stacked other suitable resin sheets and make multi-ply construction.Herein, as other suitable resin sheets, can be that the compounding amount of silane coupling agent is few or do not have the aromatic vinyl based compound-olefinic copolymer of compounding, be preferably the sheet material of cross-linking copolymer, also can be other resins, for example sheet material of EVA, other ethene copolymers.
＜crosslinked
The packaged material of the device of solar generating that uses resin sheet of the present invention and obtain, if consider the simplification of packaging process and the recirculation of device of solar generating, then preferably only near the sheet surface of the combination that is used for strengthening coupling agent and resin sheet, carry out crosslinking Treatment, account for sheet material most centre portions, do not carry out substantial crosslinked and be thermoplasticity for for packaged material, being preferred with the opposing face of the bonding plane of glass.But, require owing to sheet material self also can carry out the above crosslinking Treatment of this degree under the stable on heating situation of height or after the encapsulation.In general crosslinking Treatment is to add linking agent, crosslinking coagent in this thermoplasticity packaged material, and the condition compacted under below crosslinking temperature is film, sheet material, carries out crosslinked in solar battery cell encapsulation back in predetermined crosslinked condition.The thermoplasticity of thermoplasticity packaged material of the present invention in packaging process by fusion, flow and be important with the operation of solar battery cell encapsulation.Thereafter crosslinked condition at random determines according to employed linking agent, crosslinking coagent.The linking agent, the crosslinking coagent that can be used for this thermoplasticity packaged material are the materials that is generally used for vinyl resins, styrene resin, styrene-ethylene copolymers, are known.Preferred cross-linking agents, crosslinking coagent, crosslinked condition are recorded in for example flat 10-505621(WO96/07681 of Japanese Unexamined Patent Application Publication), in the Japanese kokai publication hei 08-139347 communique, TOHKEMY 2000-183381 communique.The packaged material that has carried out such crosslinking Treatment can lose the advantage of the such use aspect of recirculation, but high water vapor barrier (low water vapor transmission rate (WVTR)), high volume specific resistance and not corrosives aspect such as free acetic acid be favourable for the reliability that improves solar cell.
Solar cell as using packaged material of the present invention can example illustrate silicon single crystal class, polysilicon class, amorphous silicon class, compounds, the various forms of like this solar cells of organic class.Solar battery cells such as thin-film solar cells are sealed at Watch glass, do not require that packaged material has in the form of the transparency, high water vapor barrier (low water vapor transmission rate (WVTR)), high volume specific resistance and not corrosives aspect such as free acetic acid also be favourable for the reliability that improves solar cell.
Embodiment
Below, by embodiment the present invention is described, but these embodiment do not limit the present invention.
＜material resin 〉
The material resin that uses in embodiment, the comparative example is as described below.
Following cross-linking copolymer is to adopt the preparation method of WO2000/37517 or WO2007139116 communique (its full content is incorporated herein by indicating the source) record to prepare, and following composition is tried to achieve by the method for these communiques records equally.These cross-linking copolymers are multipolymers that anionoid polymerization obtains by carrying out under the coexistence of the ethene-styrene diethylene benzene copoly mer that is obtained by polycoordination and styrene monomer, that have ethene-styrene diethylene benzene copoly mer chain and polystyrene chain.
Below, in order to stipulate cross-linking copolymer, provide content, the molecular weight (Mw) of polystyrene chain, the molecular weight distribution (Mw/Mn) of the ethene-styrene diethylene benzene copoly mer in the styrene content, Vinylstyrene content, weight-average molecular weight (Mw), molecular weight distribution (Mw/Mn), cross-linking copolymer of employed ethene-styrene diethylene benzene copoly mer.In addition, total styrene content be the styrene content that comprises in the ethene-styrene diethylene benzene copoly mer chain that will comprise in the cross-linking copolymer and the polystyrene chain add and and content.
Cross-linking copolymer 1:
The styrene content of ethene-styrene diethylene benzene copoly mer is 15 moles of %,
Vinylstyrene content is 0.040 mole of %,
Mw=70000、Mw/Mn=2.2，
The content of ethene-styrene diethylene benzene copoly mer is 67 quality %,
The Mw=35000 of polystyrene chain, Mw/Mn=1.2,
Total styrene content is 60 quality %.
Cross-linking copolymer 2:
The styrene content of ethene-styrene diethylene benzene copoly mer is 25 moles of %,
Vinylstyrene content is 0.035 mole of %,
Mw=90000、Mw/Mn=2.3，
The content of ethene-styrene diethylene benzene copoly mer is 67 quality %,
The Mw=44000 of polystyrene chain, Mw/Mn=1.2,
Total styrene content is 70 quality %.
Cross-linking copolymer 3:
The styrene content of ethene-styrene diethylene benzene copoly mer is 23 moles of %,
Vinylstyrene content is 0.035 mole of %, Mw=103000, Mw/Mn=2.2,
The content of ethene-styrene diethylene benzene copoly mer is 52 quality %,
The Mw=35000 of polystyrene chain, Mw/Mn=1.2,
Total styrene content is 75 quality %.
Cross-linking copolymer 4:
The styrene content of ethene-styrene diethylene benzene copoly mer is 24 moles of %,
Vinylstyrene content is 0.030 mole of %,
Mw=115000、Mw/Mn=2.2，
The content of ethene-styrene diethylene benzene copoly mer is 77 quality %,
The Mw=26000 of polystyrene chain, Mw/Mn=1.2.
Cross-linking copolymer 5:
The styrene content of ethene-styrene diethylene benzene copoly mer is 10 moles of %,
Vinylstyrene content is 0.040 mole of %,
Mw=105000、Mw/Mn=2.2，
The content of ethene-styrene diethylene benzene copoly mer is 85 quality %,
The Mw=22000 of polystyrene chain, Mw/Mn=1.2.
Ethylene-styrene copolymer 1:
Styrene content is 41 quality %(16 mole %),
Mw=120000、Mw/Mn=2.2。
Above-mentioned ethylene-styrene copolymer is by preparation method's preparation of JP3659760 communique record.
The physical properties of the resin that uses gathers and is shown in table 1.
[table 1]
-※: total crystallization melting heat is below 50J/g
＜silane coupling agent 〉
The silane coupling agent that uses following Shin-Etsu Chemial Co., Ltd to make.
3-aminopropyltriethoxywerene werene (KBE-903)
3-TSL 8330 (KBM-903)
The N-2-(amino-ethyl)-3-aminopropyl methyl dimethoxysilane (KBM-602)
3-glycidoxypropyltrime,hoxysilane (KBM-403)
3-methacryloxypropyl trimethoxy silane (KBM-503)
And then, the silane coupling agent that uses following EVONIK company to make.
Two (3-trimethoxy-silylpropyl) amine
＜sheet material is made 〉
Sample sheets is used by heating and pressurizing method (180 ° of C of temperature, 3 minutes time, pressure 50kg/cm
2) thickness of moulding is the sheet material of 0.4mm.
＜add mixing method 〉
The PL2000 type that uses Brabender PLASTI-CORDER(Brabender company to make), the about 45g of the total of resin and additive 180 ° of C with 100rpm mixing 5 minutes, is prepared resin combination.
＜tension test 〉
Based on JIS K-6251, the film that obtains is cut into type testing plate shape No. 2 No. 1/2, use the AGS-100D of Shimadzu Seisakusho Ltd. type tensile testing machine, measure initial tensile modulus, elongation at break, breaking tenacity with the draw speed of 500mm/min.
＜coating method 〉
Silane coupling agent, acetic acid are dissolved in hexanaphthene, and the modulation coupling agent is that 2 quality %, acetic acid are the solution of 2 quality %.Use rod to be coated with machine, with 45 microns thickness cyclohexane solution is coated on the sheet material.Then, make its seasoning diel.
＜electron rays irradiation 〉
Use the rugged electric EB device TYPE:CB250/15/180L of rock, implement the irradiation of the irradiation dose (kGy) of 1 appointment with the acceleration voltage of 125kV.Under the situation of the sheet material that is obtained by coating method, coated face is implemented irradiation.
＜with the crimping of glass
Be that 25mm, length are the surface of the sheet glass of 60mm with the acetone cleaning width, make it fully dry.It is that 25mm, length are 60mm that sheet material is cut into width, not make mode driving fit that bubble enters on sheet glass.Then, in heated oven, apply the load of 0.03MPa, in 160 ° of C crimping 15 minutes.
＜determining bonding strength 〉
Use the AGS-100D of Shimadzu Seisakusho Ltd. type tensile testing machine, utilize the floating roll method, under 90 ° of stripping conditions, measure with the draw speed of 100mm/min.
＜gel content 〉
According to ASTM D-2765-84, obtain as described below.That is, (the about 1mm of size) wraps in the stainless steel mesh bag of 100 purposes with the 1.0g polymkeric substance of precision weighing, carries out precision weighing.It is extracted about 5 hours in boiling xylene after, reclaim mesh bag, dry more than 10 hours in 90 ° of C in a vacuum.Fully after the cooling, the precision weighing mesh bag is calculated gel content in the polymkeric substance by following formula.
Gel content=(quality of residual polymkeric substance in the mesh bag/initial polymer quality) * 100
＜embodiment 1 〉
With respect to 100 mass parts cross-linking copolymers 1, add each 0.2 mass parts of weather resisting agent LA-52, LA-36 that Asahi Denka Co., Ltd. makes, as the IRGANOX1076 that 0.1 mass parts CIBA JAPAN Co., Ltd. of antioxidant makes, it is mixing to use Brabender to carry out as described above.The mixing thing of the resin that obtains is made into the sheet material of 0.4mm thickness by above-mentioned heating and pressurizing method.
With respect to hexanaphthene, dissolve silane coupling agent with the concentration of 2 quality %: the 3-aminopropyltriethoxywerene werene, with the concentration dissolving acetic acid of 2 quality %, modulation coating solution.Use rod to be coated with machine, with the sheet material coating above-mentioned cyclohexane solution of 45.7 microns opening thickness in above-mentioned making.Then, dry diel in stink cupboard (draft).
With the acceleration voltage of 125kV, the coupling agent coated face of the sheet material that obtains is carried out the electron rays irradiation of a 50kGy.After the irradiation a few days, carry out the crimping with glass as mentioned above.
Second day, carry out determining bonding strength, as a result the material damage of bonding strength height, sheet material.The bonding strength of measuring when reaching material damage is more than the 35N/25mm.
＜embodiment 2～10 〉
Similarly to Example 1, just changed the resin, silane coupling agent, electron rays illuminate condition of sheet material and tested.Test conditions and the results are shown in table 2.In addition, in having used the mixing thing of resin of cross-linking copolymer 4 and 5, do not add the IRGANOX1076 as CIBA JAPAN Co., Ltd. manufacturing of antioxidant.
＜embodiment 11～20 〉
Similarly to Example 1, when just dissolving silane coupling agent in hexanaphthene, do not use acetic acid, in addition modulation coating solution, and then resin, silane coupling agent, the electron rays illuminate condition of change sheet material, are similarly tested.Under the situation of using the 3-methacryloxypropyl trimethoxy silane, with respect to hexanaphthene, with the concentration dissolving 3-methacryloxypropyl trimethoxy silane of 10 quality %, modulation coating solution.Test conditions and the results are shown in table 2.
＜comparative example 1～6 〉
Same with embodiment, just not to sheet material irradiation electron rays, just carry out the adhesive test with glass.Test conditions and the results are shown in table 3.
＜comparative example 7～9 〉
Same with embodiment, just do not use coupling agent, behind the irradiation electron rays, carry out the adhesive test with glass.Test conditions and the results are shown in table 3.
＜comparative example 10～12 〉
Same with embodiment, just do not use coupling agent, do not shine electron rays yet, just carry out the adhesive test with glass.Test conditions and the results are shown in table 3.
[table 2]
[table 3]
＜embodiment 21～25 〉
To in the fixed temperature and humidity device, after 1000 hours, similarly carry out the mensuration of bonding strength in placement under the condition of 85 ° of C of temperature, humidity 85% with the test film that embodiment 1,4,5,7 similarly obtains.It the results are shown in table 4.Be same sample with embodiment 1,5,7,18 respectively at embodiment 21,23,24,25() in, showing the bonding strength that 35N/25mm is above, material damage shows equal in fact bonding strength.Embodiment 22(and embodiment 4 are same sample) also show the bonding strength that 35N/25mm is above, material damage, but bonding strength increases.
[table 4]
＜embodiment 26～27 〉
Similarly to Example 1, when just in hexanaphthene, dissolving silane coupling agent, do not use acetic acid, and modulation coating solution, and then resin, the silane coupling agent of change sheet material, the electron rays irradiation is changed to Corona discharge Treatment, and (the corona discharge energy is 4mJ/mm
2), in addition, similarly test.Test conditions and the results are shown in table 5.
[table 5]
＜embodiment 28～30 〉
Similarly to Example 1, when just in hexanaphthene, dissolving silane coupling agent, do not use acetic acid, and modulation coating solution, and then resin, the silane coupling agent of change sheet material, carry out electron rays irradiation or corona treatment.In the adhesive test, replace glass and use used for solar batteries joint line (ultra-soft matter copper straight angle plate wire: Pb-free solder, width 6mm), use the same method and the sheet material crimping.Being determined under 180 ° of stripping conditions of bonding strength carried out.Test conditions and the results are shown in table 6.
[table 6]
Can be confirmed by above result, by aromatic vinyl based compound-olefinic copolymer is carried out coupling agent treatment, and then carry out electron rays irradiation or corona treatment, thereby significantly increase with the cementability of glass, metal.
Claims (13)
1. a resin that has with the cementability of inorganic materials is that aromatic vinyl based compound-olefinic copolymer is added or the coating coupling agent, and then carries out energy exposure and obtain.
2. resin as claimed in claim 1, wherein, the aromatic vinyl based compound is vinylbenzene.
3. resin as claimed in claim 1 or 2, wherein, alkene is ethene.
4. resin as claimed in claim 1, wherein, aromatic vinyl based compound-olefinic copolymer be contain aromatic vinyl based compound and alkene and cross-linking copolymer.
5. as each the described resin in the claim 1～4, wherein, energy line is electron rays.
6. as each the described resin in the claim 1～5, wherein, inorganic materials is glass.
7. as each the described resin in the claim 1～6, wherein, coupling agent is silane coupling agent.
8. resin as claimed in claim 7, wherein, silane coupling agent has any in amino, epoxy group(ing) or the methacryloxy.
9. as each the described resin in the claim 1～8, be that aromatic vinyl based compound-olefinic copolymer is shaped to sheet, at its surface coated coupling agent, and then carry out energy exposure and obtain.
10. as each the described resin in the claim 1～8, be in aromatic vinyl based compound-olefinic copolymer, to add coupling agent, be shaped to sheet, and then carry out energy exposure and obtain.
11. a sheet material is by each the described resin formation in the claim 1～10.
12. a packaged material, right to use require each described resin or the described sheet material of claim 11 in 1～10 to form.
13. a device of solar generating comprises that the described packaged material of claim 12 is as integrant.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010-200645 | 2010-09-08 | ||
| JP2010200645 | 2010-09-08 | ||
| JP2011-147238 | 2011-07-01 | ||
| JP2011147238 | 2011-07-01 | ||
| PCT/JP2011/070338 WO2012033119A1 (en) | 2010-09-08 | 2011-09-07 | Resin having improved adhesion properties, and sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103210025A true CN103210025A (en) | 2013-07-17 |
| CN103210025B CN103210025B (en) | 2015-02-25 |
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| CN201180052353.0A Expired - Fee Related CN103210025B (en) | 2010-09-08 | 2011-09-07 | Resin having improved adhesion properties, and sheet |
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| Country | Link |
|---|---|
| JP (1) | JPWO2012033119A1 (en) |
| KR (1) | KR20130118866A (en) |
| CN (1) | CN103210025B (en) |
| WO (1) | WO2012033119A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2015079834A (en) * | 2013-10-16 | 2015-04-23 | 大日本印刷株式会社 | Sealing-material sheet for solar battery module use, and method for manufacturing the same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001119047A (en) * | 1999-10-21 | 2001-04-27 | Du Pont Mitsui Polychem Co Ltd | Solar cell sealing material and solar battery module |
| JP2009249556A (en) * | 2008-04-09 | 2009-10-29 | Asahi Kasei E-Materials Corp | Resin sealing sheet |
| JP2010150442A (en) * | 2008-12-26 | 2010-07-08 | Denki Kagaku Kogyo Kk | Sealing material for solar cell |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06334207A (en) * | 1993-05-27 | 1994-12-02 | Canon Inc | Solar cell module |
| JPH08283696A (en) * | 1995-04-14 | 1996-10-29 | Haishiito Kogyo Kk | Sheet for sealing solar cell and its production |
| JP4398591B2 (en) * | 1998-12-22 | 2010-01-13 | 電気化学工業株式会社 | Cross-copolymerized olefin-styrene-diene copolymer, production method thereof and use thereof |
| AR022608A1 (en) * | 1999-02-17 | 2002-09-04 | Dow Chemical Co | AROMATIC INTERPOLIMERIC PRODUCT OF ALFA-OLEFINA / VINYL OR VINYLIDENE AND PROCESS FOR THEIR DEVELOPMENT THROUGH MULTIPLE CATALYSTING SYSTEMS |
| JP5058764B2 (en) * | 2007-10-23 | 2012-10-24 | 電気化学工業株式会社 | CROSS COPOLYMER MANUFACTURING METHOD, OBTAINED CROSS COPOLYMER, AND USE THEREOF |
-
2011
- 2011-09-07 CN CN201180052353.0A patent/CN103210025B/en not_active Expired - Fee Related
- 2011-09-07 KR KR1020137008976A patent/KR20130118866A/en not_active Application Discontinuation
- 2011-09-07 JP JP2012532996A patent/JPWO2012033119A1/en not_active Withdrawn
- 2011-09-07 WO PCT/JP2011/070338 patent/WO2012033119A1/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001119047A (en) * | 1999-10-21 | 2001-04-27 | Du Pont Mitsui Polychem Co Ltd | Solar cell sealing material and solar battery module |
| JP2009249556A (en) * | 2008-04-09 | 2009-10-29 | Asahi Kasei E-Materials Corp | Resin sealing sheet |
| JP2010150442A (en) * | 2008-12-26 | 2010-07-08 | Denki Kagaku Kogyo Kk | Sealing material for solar cell |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103210025B (en) | 2015-02-25 |
| WO2012033119A1 (en) | 2012-03-15 |
| KR20130118866A (en) | 2013-10-30 |
| JPWO2012033119A1 (en) | 2014-01-20 |
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