WO2012033119A1 - Résine ayant des propriétés d'adhérence améliorées et feuille - Google Patents

Résine ayant des propriétés d'adhérence améliorées et feuille Download PDF

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Publication number
WO2012033119A1
WO2012033119A1 PCT/JP2011/070338 JP2011070338W WO2012033119A1 WO 2012033119 A1 WO2012033119 A1 WO 2012033119A1 JP 2011070338 W JP2011070338 W JP 2011070338W WO 2012033119 A1 WO2012033119 A1 WO 2012033119A1
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Prior art keywords
resin
sheet
coupling agent
copolymer
aromatic vinyl
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PCT/JP2011/070338
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English (en)
Japanese (ja)
Inventor
荒井　亨
彰 見山
雅也 梅山
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電気化学工業株式会社
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Priority to JP2012532996A priority Critical patent/JPWO2012033119A1/ja
Priority to CN201180052353.0A priority patent/CN103210025B/zh
Priority to KR1020137008976A priority patent/KR20130118866A/ko
Publication of WO2012033119A1 publication Critical patent/WO2012033119A1/fr

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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
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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

Definitions

  • the present invention relates to a resin excellent in adhesiveness with inorganic materials such as glass plates, glass fibers, inorganic fillers, and the like, and a sheet thereof.
  • a resin or a sheet thereof excellent in adhesiveness to an inorganic material such as glass is required for uses such as a solar power generation device (solar cell), a liquid crystal, an EL display member, an EL light emitting device sealing, and an adhesive resin. It has been.
  • conventional resins have not been satisfactory because sufficient adhesiveness cannot be obtained, a method for improving adhesiveness is expensive, and other physical properties are adversely affected.
  • Patent Documents 1 to 4 For example, a method of modifying a silane by adding a silane coupling agent to an EVA resin or a polyolefin resin, kneading and cross-linking (Patent Documents 1 to 4) has been proposed. Although this method improves the adhesion to, for example, glass, the method of kneading a coupling agent into a resin and performing radical crosslinking suppresses crosslinking at the time of sheet molding and reliably crosslinks at the time of sealing. The process window is narrow, and sometimes there are problems in molding processing and poor cross-linking during sealing. Further, the kneading increases the cost, and there is also an adverse effect on the physical properties of the remaining cross-linking agent, cross-linking auxiliary, etc., and a more efficient and stable method for improving adhesiveness has been demanded.
  • Patent Documents 5, 6, 7, and 8 describe a sealing material for a solar power generation device that is obtained by irradiating an electron beam to a resin such as EVA or polyolefin that contains a silane coupling agent or a crosslinking agent.
  • a resin such as EVA or polyolefin that contains a silane coupling agent or a crosslinking agent.
  • its main purpose is electron beam crosslinking for substituting the drawback of crosslinking by peroxide, or adjustment of molding processability by controlling the degree of crosslinking by electron beam.
  • Patent Documents 9 and 10 for the purpose of improving the adhesiveness of a sealing material and suppressing deterioration, an ethylene-based resin is copolymerized with an unsaturated carboxylic acid derivative or an epoxy compound, or modified with these. A method of coating a silane coupling agent is described. However, it is highly technically difficult to copolymerize or modify polar monomers such as carboxylic acid derivatives and epoxy compounds in an olefin resin, and there is a high possibility of sacrificing other physical properties.
  • the present invention has been made in view of the above circumstances, and provides a resin having excellent adhesiveness with an inorganic material such as glass and the like, and capable of imparting adhesiveness in an efficient manner, and a sheet thereof.
  • Another object of the present invention is to provide a sealing material using such a resin or sheet and a solar power generation device including the sealing material.
  • a resin having adhesiveness to an inorganic material such as glass or silicon which is obtained by adding or applying a coupling agent to an aromatic vinyl compound-olefin copolymer and further irradiating with energy.
  • the method of adding or applying the coupling agent is not limited, but in one embodiment, the aromatic vinyl compound-olefin copolymer is formed into a sheet shape, the coupling agent is applied to the surface, and energy irradiation is performed.
  • a resin obtained by adding a coupling agent to an aromatic vinyl compound-olefin copolymer to form a sheet and further irradiating with energy is provided. .
  • the aromatic vinyl compound is styrene, and in another embodiment, the olefin is ethylene.
  • the aromatic vinyl compound-olefin copolymer is a cross-copolymer comprising an aromatic vinyl compound and an olefin.
  • such a cross-copolymer has an olefin-aromatic vinyl compound-aromatic polyene copolymer chain and an aromatic vinyl compound polymer chain, and is a unit derived from an aromatic vinyl compound and an olefin monomer.
  • the content of units derived from aromatic polyene is preferably of copolymer weight. Less than 5% by mass and 0.01% by mass or more, more preferably less than 1% by mass and 0.01% by mass or more.
  • the energy irradiation is electron beam irradiation, for example, generally an electron beam having an acceleration voltage in the range of 10 keV to 5000 keV, preferably 10 keV to 250 keV, more preferably 10 keV to 150 keV.
  • the coupling agent is a silane coupling agent, particularly a silane coupling agent having any functional group of an amino group, a methacryloxy group, and an epoxy group.
  • a sheet produced using the above resin and a sealing material using such a resin or the sheet are provided, and further, such a sealing material is used as a constituent element.
  • a solar power generation device is also provided.
  • the aromatic vinyl compound-olefin copolymer is particularly selected, and a coupling agent is added or applied thereto, and further irradiated with energy, so that it has excellent adhesion to inorganic materials, particularly glass and silicon.
  • Resin or its sheet can be obtained, and such resin or its sheet is useful as, for example, a sealing material for a solar power generation device, a liquid crystal or EL display, a sealing for a light emitting device, and an adhesive resin.
  • the present invention relates to adhesion to inorganic materials such as glass plates, glass fibers, and inorganic fillers, which can be obtained by adding or applying a coupling agent to an aromatic vinyl compound-olefin copolymer and further irradiating with energy. It is a resin or sheet thereof that is excellent in properties and preferably excellent in filling properties.
  • the sheet in the present invention includes the concept of a film, and the thickness thereof is not particularly limited, and generally ranges from 1 ⁇ m to 3 mm.
  • the aromatic vinyl compound-olefin copolymer means a copolymer obtained by copolymerizing each monomer of an aromatic vinyl compound and an olefin, and the content of units derived from these monomers. Denotes a copolymer occupying 70% by mass or more, preferably 90% by mass or more, and most preferably 95% by mass or more of the entire copolymer mass.
  • the manufacturing method of this copolymer is arbitrary.
  • aromatic vinyl compounds include styrene and various substituted styrenes such as p-methylstyrene, m-methylstyrene, o-methylstyrene, ot-butylstyrene, mt-butylstyrene, and pt-butylstyrene. , P-chlorostyrene, o-chlorostyrene and the like.
  • styrene, p-methylstyrene, p-chlorostyrene, particularly preferably styrene is used.
  • the olefin examples include ethylene and an ⁇ -olefin having 3 to 20 carbon atoms, that is, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, and 1-octene.
  • cyclic olefins are also included in the category of olefins, and examples of the cyclic olefins include vinylcyclohexane, cyclopentene, and norbornene.
  • ethylene or a mixture of ethylene and an ⁇ -olefin, ie, propylene, 1-butene, 1-hexene, or 1-octene is used, and more preferably, ethylene is used.
  • the aromatic vinyl compound-olefin copolymer a copolymer of ethylene and styrene is preferable.
  • examples of the aromatic vinyl compound-olefin copolymer include the copolymers described in EP 0 416 815 A2, JP 3659760, and EP 872492B1, each of which is incorporated herein by reference. More preferably, a cross-copolymer is used as the aromatic vinyl compound-olefin copolymer.
  • a cross-copolymer is a copolymer obtained by anionic polymerization in the presence of an olefin-aromatic vinyl compound-aromatic polyene copolymer and an aromatic vinyl compound monomer obtained by coordination polymerization.
  • -Aromatic vinyl compound-A copolymer having an aromatic polyene copolymer chain (may be described as a main chain) and an aromatic vinyl compound polymer chain (may be described as a side chain) .
  • the present cross-copolymer and its production method are described in WO 2000-37517, USP 6559234, or WO 2007-139116, each of which is incorporated herein by reference in its entirety, and is derived from an aromatic vinyl compound and an olefin monomer.
  • the content of the unit to be produced occupies 70% by mass or more of the total copolymer mass, preferably 90% by mass or more, most preferably 95% by mass or more, and the content of the unit derived from the aromatic polyene is preferably It is less than 5% by mass of the combined mass and 0.01% by mass or more, more preferably less than 1% by mass and 0.01% by mass.
  • the aromatic polyene is a monomer having a carbon number of 10 or more and 30 or less, having a plurality of double bonds (vinyl group) and one or a plurality of aromatic groups and capable of coordination polymerization.
  • An aromatic polyene in which one of (vinyl group) is used for coordination polymerization and a double bond left in a polymerized state can be anionically polymerized.
  • any one or a mixture of two or more of orthodivinylbenzene, paradivinylbenzene and metadivinylbenzene is preferably used.
  • a cross copolymer having a main chain of an ethylene-styrene-divinylbenzene copolymer chain and a side chain of a polystyrene chain is used.
  • Examples of the inorganic material in which the adhesiveness of the resin or sheet according to the present invention is a problem include glass, ceramics, metal, and the like, but glass is particularly preferable.
  • the glass may have any form such as powder, fiber, plate, etc., but is preferably plate-like glass.
  • a known coupling agent can be used.
  • a coupling agent include a silane coupling agent, a titanate coupling agent, and an isocyanate coupling agent.
  • a silane coupling agent is used.
  • silane coupling agents can be obtained from Shin-Etsu Chemical Co., Ltd., Dow Corning Co., and Evonik.
  • a silane coupling agent is a silane compound having a functional group and a hydrolytic condensable group in the molecule.
  • the functional group include vinyl groups such as vinyl, methacryloxy, acryloxy, and styryl, amino groups, epoxy groups, mercapto groups, sulfide groups, isocyanate groups, and halogens.
  • the functional group is preferably a vinyl group, amino group, epoxy group, methacryloxy group, or acryloxy group, and most preferably an amino group, methacryloxy group, or epoxy group.
  • these functional groups may be present in the molecule.
  • These coupling agents can be used alone or in combination of two or more.
  • silane coupling agent having a vinyl group as a functional group examples include vinyltrimethoxysilane and vinyltriethoxysilane.
  • An example of a silane coupling agent having a styryl group as a functional group is p-styryltrimethoxysilane.
  • An example of a silane coupling agent having an acryloxy group as a functional group is 3-acryloxypropyltrimethoxysilane.
  • Examples of the silane coupling agent having a methacryloxy group as a functional group include 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, and 3-methacryloxypropylmethyldiethoxysilane. Can be illustrated.
  • Examples of the silane coupling agent having an epoxy group as a functional group include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4 -Epoxycyclohexyl) ethyltrimethoxysilane.
  • silane coupling agent having an amino group as a functional group examples include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2 -(Aminoethyl) -3-aminopropylethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N -2- (aminoethyl) -3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, bis (3-trimethoxysilylpropyl) amine, bis (3-triethoxysilylpropyl) amine, N-
  • the above is an example having a methoxy group or an ethoxy group as a hydrolytic condensable group, but a triisopropoxy group or an acetoxy group can also be used.
  • the amount of the silane coupling agent used is not particularly limited, but when added to the resin by kneading or the like, it is generally used in the range of 0.05% by mass to 10% by mass with respect to the resin. When applied to a resin, it is generally used in the range of 0.1 g / m 2 to 20 g / m 2 .
  • the resin according to the present invention is prepared by a method characterized by adding or applying a coupling agent to an aromatic vinyl compound-olefin copolymer and further irradiating with energy. That is, in the method of adding a coupling agent to an aromatic vinyl compound-olefin copolymer, a known method for adding an additive to a resin is usually used to add the aromatic vinyl compound-olefin copolymer to the aromatic vinyl compound-olefin copolymer. Add coupling agent and knead. Industrially, for example, a twin screw extruder, a Banbury mixer, a roll forming machine, or the like can be used.
  • a sheet is formed by a known molding method such as inflation molding, extrusion molding, T-die molding, calendar molding, roll molding, press molding or the like.
  • a coupling agent is applied.
  • the above-mentioned known methods can be used.
  • a known coating method such as a gravure coating method, a roll coating method, a dip coating method, or a spraying method, Apply coupling agent.
  • the coupling agent may be used after diluted in an appropriate solvent or may be used without dilution.
  • the latter application method is economically superior to the former method in which the coupling agent is added and kneaded, because the amount of coupling agent used can be reduced.
  • the aromatic vinyl compound-olefin copolymer sheet formed by adding or applying the coupling agent as described above is irradiated with energy.
  • energy irradiation include irradiation with electron beams, gamma rays, X-rays, ultraviolet rays, neutron rays, ⁇ rays, infrared rays, visible rays, corona discharge treatment, and plasma treatment. These energy irradiations can be performed using a known apparatus. In a preferred embodiment of the invention, electron beam irradiation is used.
  • the acceleration voltage of the electron beam is generally in the range of 10 keV to 5000 keV, and the irradiation dose is generally in the range of 1 kGy to 500 kGy. This acceleration voltage is appropriately controlled depending on the thickness of the sheet.
  • the purpose of the present invention is to provide adhesion by strengthening the interaction between the resin in the vicinity of the surface and the coupling agent by electron beam treatment. , Preferably 10 keV to 250 keV, more preferably 10 keV to 150 keV.
  • the term “reinforcement of interaction” as used herein refers to enhancement of chemical or physical interaction that leads to adhesion enhancement, such as grafting, cross-linking, chemical reaction, molecular chain entanglement between resins and coupling agents in the vicinity of the surface.
  • corona discharge treatment or plasma treatment particularly preferably corona discharge treatment is used.
  • the specific condition is that the coupling agent used is preferably a silane coupling agent having an epoxy group or an amino group.
  • the corona discharge treatment can be performed with a known apparatus and known conditions.
  • the preferred corona discharge energy is not particularly limited, but is preferably in the range of 0.1 to 1000 mJ / mm 2 .
  • a peel strength (adhesive strength) of 22 N / 25 mm or more, preferably 25 N / 25 mm or more can be achieved.
  • a peel strength of 3N / 6 mm or more can be achieved in the same test for metals such as silicon (including silicon subjected to surface stabilization treatment), aluminum, copper, and solder.
  • Irradiation of energy rays is carried out in the same way whether the aromatic vinyl compound-olefin copolymer is added with a coupling agent and kneaded or applied after forming into a sheet, but the interaction only in the vicinity of the resin surface.
  • crosslinking aids that can be used are known crosslinking aids such as triallyl isocyanurate, triallyl cyanurate, N, N′-phenylenebismaleimide, ethylene glycol di (meth) acrylate, propanediol di (meth) acrylate, Examples include butanediol di (meth) acrylate, hexanediol di (meth) acrylate, nonanediol di (meth) acrylate, and trimethylolpropane tri (meth) acrylate. These crosslinking aids may be used alone or in combination of two or more. When the crosslinking aid is blended, the content is not particularly limited, but it is usually preferably in the range of 0.01 to 5% by mass with respect to the total mass.
  • additives that are used in ordinary resins, for example, heat stabilizers, antioxidants, and the like, as long as the purpose of the present invention is not impaired.
  • An antistatic agent, a filler, a colorant, a lubricant, an antifogging agent, a foaming agent, a flame retardant, a flame retardant aid and the like may be added.
  • the resin of the present invention or the sheet thereof has excellent adhesiveness with an inorganic material such as a wiring metal, silicon, or glass, sealing of a photovoltaic power generation device (solar cell), a liquid crystal, an EL display member, and an EL light emitting device It is useful as an adhesive resin.
  • a photovoltaic power generation device solar cell
  • liquid crystal liquid crystal
  • EL display member an EL light emitting device
  • various sealing members of a solar power generation device (solar cell) which is a preferred application of the resin of the present invention or a sheet thereof, will be described in detail.
  • the adhesive resin sheet of the present invention is used as various sealing members of a solar power generation device (solar cell), particularly as a sealing sheet, the preferred physical properties are A hardness 50 or more and 95 or less, and total light The transmittance is 75% or more in a sheet having a thickness of 1 mm.
  • a styrene-ethylene copolymer satisfying such conditions has a composition having a styrene content of 5 mol% to 40 mol%.
  • a cross-copolymer can be preferably used.
  • a cross-copolymer satisfying this condition is incorporated herein by reference in its entirety, for example, in WO 2007-139116, JP-A 2009-120792, and JP-A 2010-150442. Since the method, the total light transmittance, and the A hardness are described, those skilled in the art can easily manufacture by performing a few trials with reference to these. Specifically, when the aromatic vinyl compound is styrene and the olefin is ethylene, a cross-copolymer that satisfies this condition can be achieved by satisfying the following conditions.
  • the ethylene-styrene-divinylbenzene copolymer used for the production of the cross-copolymer has a styrene content of 5 mol% to 40 mol%, a divinylbenzene content of 0.01 mol% to 3 mol%, and a weight average.
  • the molecular weight is 30,000 to 150,000
  • the mass proportion of the present ethylene-styrene-divinylbenzene copolymer in the finally obtained cross-copolymer is 40% by mass to 95% by mass, preferably 40% by mass to 90%. It is below mass%.
  • the storage elastic modulus of the resin at 120 ° C. is preferably 1 ⁇ 10 4 Pa or more, more preferably It is necessary to be 1 ⁇ 10 5 Pa or more.
  • the storage elastic modulus can be easily obtained using a known viscoelasticity measuring apparatus.
  • the above cross-copolymer can satisfy this condition without performing a crosslinking treatment and can be suitably used in the present invention.
  • the MFR value (200 ° C., weight 98N) of the raw material resin is not particularly limited, but is generally 0.1 g / 10 min or more and 300 g / 10 min or less. If it is lower than this, voids due to poor filling are likely to occur during sealing, and if it is higher than this, there may be a concern about insufficient heat resistance, that is, a creep phenomenon of solar cells or wiring in the environment.
  • This MFR value can be easily estimated by a person skilled in the art from the known literature of the resin to be used, and can also be adjusted by adding a small amount of oil or plasticizer.
  • adhesion to glass is particularly important from the viewpoint of ensuring reliability.
  • peel strength adheresive strength
  • the sheet body is substantially thermoplastic, and therefore, crosslinking and other effects due to electron beam irradiation are inorganic. It is preferably limited to the vicinity of the sheet surface that requires adhesion to a material such as glass. For this purpose, it is generally preferable to control the electron arrival depth by changing the acceleration voltage of the electron beam, or to irradiate only the surface that requires adhesion.
  • the center of the sheet or the surface opposite to the electron beam irradiation surface is substantially not irradiated with the electron beam, and is preferably thermoplastic for the sealing resin sheet for the photovoltaic power generation apparatus.
  • the degree of cross-linking with respect to the entire sheet is substantially low. It is as follows.
  • the gel content is determined according to ASTM D-2765-84.
  • acquires the radical produced
  • the ultraviolet absorber include benzotriazole, triazine, benzophenone, benzoate, oxalic anilide, and malonic ester.
  • the mass ratio of the ultraviolet absorber and the hindered amine light stabilizer is in the range of 1: 100 to 100: 1, and the total mass of the ultraviolet absorber and the hindered amine light stabilizer is the light-proofing agent mass. The range is 0.05 to 5 parts by mass with respect to 100 parts by mass.
  • the light-proofing agent as described above can be obtained, for example, as ADEKA STAB LA series from ADEKA Corporation or as Sumisorb series from Sumika Chemtex Co., Ltd.
  • the sealing material can be blended with any known plasticizer conventionally used for polyvinyl chloride and other resins.
  • the plasticizer preferably used is an oil or an oxygen-containing or nitrogen-containing plasticizer, more preferably a paraffinic oil, a naphthenic oil, an ester plasticizer, an epoxy plasticizer, an ether plasticizer, or Selected from amide plasticizers. These plasticizers can be suitably used because they have relatively good compatibility and are not easily bled, and have a large plasticizing effect that can be evaluated by the degree to which the glass transition temperature is lowered.
  • the compounding amount of the plasticizer is 1 part by mass or more and 20 parts by mass or less, preferably 1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the resin of the present invention or the sheet thereof. If the amount is less than 1 part by mass, the above effects are insufficient. If the amount is more than 20 parts by mass, it may cause bleeding, excessive softening, and excessive stickiness. Moreover, the fluidity
  • Suitable anti-aging agents include, for example, hindered phenol antioxidants, phosphorus heat stabilizers, lactone heat stabilizers, vitamin E heat stabilizers, sulfur heat stabilizers and the like.
  • the usage-amount is 3 parts weight or less with respect to 100 mass parts of resin compositions.
  • the thickness of the sheet for the sealing material of the solar power generation device is not particularly limited, but is generally 30 ⁇ m to 1 mm, preferably 100 ⁇ m to 0.5 mm.
  • known molding methods such as inflation molding, extrusion molding, T-die molding, calendar molding, roll molding, etc. can be employed.
  • the sheet for the sealing material of the photovoltaic power generation apparatus does not necessarily have to be a single layer, and the adhesive resin sheet according to the present invention is applied to a glass bonding surface or a bonding surface with a cell such as a silicon cell.
  • Other suitable resin sheets may be further laminated to form a multilayer structure.
  • the other suitable resin sheet may be an aromatic vinyl compound-olefin copolymer, preferably a cross copolymer sheet, in which the amount of the silane coupling agent is small or not blended,
  • Other resin for example, EVA or other ethylene copolymer sheets may be used.
  • the crosslinking treatment is performed using a coupling agent and a resin sheet. Only the vicinity of the surface of the sheet for strengthening the bonding of the sheet is preferable, and the central part occupying most of the sheet and the opposite side of the adhesive surface to the glass are sealed without substantial cross-linking. It is preferable when used as a stopper. However, when the sheet itself requires high heat resistance or after sealing, it is possible to perform further crosslinking treatment.
  • thermoplasticity of the thermoplastic sealing material of the present invention is important in the process of sealing solar cells by melting and flowing in the sealing process.
  • the subsequent crosslinking conditions are arbitrarily determined depending on the crosslinking agent and crosslinking aid used.
  • the crosslinking agents and crosslinking aids that can be used for the thermoplastic sealing material are those commonly used for ethylene resins, styrene resins, and styrene-ethylene copolymers, and are known.
  • crosslinking agents Preferred crosslinking agents, crosslinking assistants, and crosslinking conditions are described in, for example, JP-T-10-505621 (WO96 / 077681), JP-A-08-139347, and JP-A-2000-183831.
  • the sealing material subjected to such a crosslinking treatment loses the merit of using recyclability, but has a high water vapor barrier property (low water vapor permeability), a high volume resistivity, and does not liberate corrosive substances such as acetic acid. This is advantageous in terms of improving the reliability of the solar cell.
  • Examples of solar cells using the sealing material according to the present invention include solar cells of each type of single crystal silicon, polycrystalline silicon, amorphous silicon, compound, and organic. High water vapor barrier properties (low water vapor permeability), high volume resistivity, and corrosion of acetic acid, etc., even in the case where solar cells adhere to the surface glass, such as thin film solar cells, and the sealing material does not require transparency The point that the active substance is not liberated is advantageous from the viewpoint of improving the reliability of the solar cell.
  • ⁇ Raw resin> The raw material resins used in Examples and Comparative Examples are as follows.
  • the following cross copolymers were produced by the production methods described in WO2000 / 37517 or WO2007139116, the entire contents of which are incorporated herein by reference, and the following compositions were similarly determined by the methods described in these publications.
  • These cross copolymers include an ethylene-styrene-divinylbenzene copolymer chain obtained by anionic polymerization in the presence of an ethylene-styrene-divinylbenzene copolymer obtained by coordination polymerization and a styrene monomer. It is a copolymer having a polystyrene chain.
  • the cross-copolymer in order to define the cross-copolymer, the styrene content, divinylbenzene content, weight average molecular weight (Mw), molecular weight distribution (Mw / Mn) of the ethylene-styrene-divinylbenzene copolymer used, the cross-copolymer
  • Mw weight average molecular weight
  • Mw / Mn molecular weight distribution of the ethylene-styrene-divinylbenzene copolymer used, the cross-copolymer
  • the content of the ethylene-styrene-divinylbenzene copolymer, the molecular weight (Mw) of the polystyrene chain, and the molecular weight distribution (Mw / Mn) are shown.
  • the total styrene content is a total content of the styrene contents contained in the ethylene-styrene-divinylbenzene copolymer chain and the polystyrene chain contained in the cross copolymer.
  • ⁇ Silane coupling agent> The following silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd. was used. ⁇ 3-Aminopropyltriethoxysilane (KBE-903) ⁇ 3-Aminopropyltrimethoxysilane (KBM-903) N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane (KBM-602) ⁇ 3-Glycidoxypropyltrimethoxysilane (KBM-403) ⁇ 3-Methacryloxypropyltrimethoxysilane (KBM-503) Furthermore, the following silane coupling agent manufactured by Evonik was used. ⁇ Bis (3-trimethoxysilylpropyl) amine
  • ⁇ Sheet preparation> As the sample sheet, a 0.4 mm thick sheet formed by a hot press method (temperature 180 ° C., time 3 minutes, pressure 50 kg / cm 2 ) was used.
  • ⁇ Tensile test> In accordance with JIS K-6251, the obtained film was cut into a No. 2 1/2 type test piece shape, and an initial tensile elastic modulus was used at a tensile speed of 500 mm / min using a Shimadzu AGS-100D type tensile tester. The elongation at break and the strength at break were measured.
  • ⁇ Coating method> A silane coupling agent and acetic acid were dissolved in cyclohexane to prepare a solution containing 2% by mass of the coupling agent and 2% by mass of acetic acid. Using a bar coater, the cyclohexane solution was coated on the sheet with a thickness of 45 microns. Then, it was naturally dried all day and night.
  • Example 1 Addition of 0.2 parts by weight of ADEKA Corporation weathering agents LA-52 and LA-36, 0.1 parts by weight of Ciba Japan Co., Ltd. Irganox 1076 to 100 parts by weight of cross copolymer 1 Then, kneading was performed using a Brabender as described above. A sheet having a thickness of 0.4 mm was prepared from the obtained resin kneaded material by the above-described hot pressing method. A silane coupling agent: 3-aminopropyltriethoxysilane was dissolved in cyclohexane at a concentration of 2% by mass and acetic acid 2% by mass to prepare a coating solution.
  • the cyclohexane solution was applied to the prepared sheet with an opening thickness of 45.7 microns using a bar coater. Then, it was dried overnight in a draft. The surface of the obtained sheet on which the coupling agent was applied was irradiated once with an electron beam of 50 kGy at an acceleration voltage of 125 kV. Several days after the irradiation, pressure bonding with glass was performed according to the above. The next day, when the adhesive strength was measured, the adhesive strength was high and the sheet was destroyed. The adhesive strength measured at the time of material breakage was 35 N / 25 mm or more.
  • Examples 2 to 10> The test was conducted in the same manner as in Example 1, except that the sheet resin, the silane coupling agent, and the electron beam irradiation conditions were changed. Test conditions and results are shown in Table 2. Further, Irganox 1076 made by Ciba Japan, which is an antioxidant, was not added to the resin kneaded material using the cross copolymers 4 and 5.
  • Example 11 to 20 As in Example 1, except that when dissolving the silane coupling agent in cyclohexane, a coating solution was prepared without using acetic acid, and the sheet resin, silane coupling agent, and electron beam irradiation conditions were prepared. Others were tested in the same manner. When 3-methacryloxypropyltrimethoxysilane was used, 3-methacryloxypropyltrimethoxysilane was dissolved in cyclohexane at a concentration of 10% by mass to prepare a coating solution. Test conditions and results are shown in Table 2.
  • Examples 21 to 25 The test pieces obtained in the same manner as in Examples 1, 4, 5, and 7 were left to stand for 1000 hours under the conditions of a temperature and humidity of 85 ° C. and a humidity of 85% using a constant temperature and humidity device, and the adhesive strength was measured in the same manner. .
  • the results are shown in Table 4.
  • the adhesive strength was 35 N / 25 mm or more, resulting in material destruction, and substantially the same adhesive strength.
  • Example 22 (same sample as Example 4) also showed an adhesive strength of 35 N / 25 mm or more, resulting in material destruction, rather the adhesive strength increased.
  • Example 26 to 27 As in Example 1, except that when dissolving the silane coupling agent in cyclohexane, a coating solution was prepared without using acetic acid, and the sheet resin and the silane coupling agent were changed. The test was conducted in the same manner except that the corona discharge treatment (corona discharge energy 4 mJ / mm 2 ) was used instead of the line irradiation. Table 5 shows the test conditions and results.
  • Example 28 to 30> As in Example 1, except that when dissolving the silane coupling agent in cyclohexane, a coating solution was prepared without using acetic acid, and the sheet resin and the silane coupling agent were changed. Irradiation or corona treatment was performed. In the adhesion test, tab sheets for solar cells (super soft copper flat-plated wire: lead-free solder, width 6 mm) were used instead of glass, and the sheet was pressure-bonded by the same method. The adhesive strength was measured under 180 ° peeling conditions. Table 6 shows the test conditions and results.

Abstract

La présente invention porte sur : une résine qui peut adhérer à un matériau inorganique tel qu'une plaque de verre et qui est produite par ajout d'un agent de couplage à un copolymère de (composé vinylique aromatique)-oléfine tel qu'un copolymère réticulé comprenant un composé vinylique aromatique et une oléfine ou application de l'agent de couplage sur le copolymère de (composé vinylique aromatique)-oléfine puis exposition du produit ainsi obtenu à de l'énergie telle qu'un faisceau d'électrons ; ou une feuille de la résine. La résine ou la feuille produite à partir de la résine est utile, par exemple, comme matériau d'étanchéité pour un dispositif de production d'énergie solaire ou résine pour le scellement ou la fixation d'un dispositif à cristaux liquides, d'un écran électroluminescent ou d'un dispositif électroluminescent.
PCT/JP2011/070338 2010-09-08 2011-09-07 Résine ayant des propriétés d'adhérence améliorées et feuille WO2012033119A1 (fr)

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JP2015079834A (ja) * 2013-10-16 2015-04-23 大日本印刷株式会社 太陽電池モジュール用の封止材シート及びその製造方法

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JPH06334207A (ja) * 1993-05-27 1994-12-02 Canon Inc 太陽電池モジュール
JPH08283696A (ja) * 1995-04-14 1996-10-29 Haishiito Kogyo Kk 太陽電池封止用シート及びその製造方法
WO2000037517A1 (fr) * 1998-12-22 2000-06-29 Denki Kagaku Kogyo Kabushiki Kaisha Copolymere olefine/styrene/diene reticule, procede de production dudit copolymere et ses utilisations
JP2001119047A (ja) * 1999-10-21 2001-04-27 Du Pont Mitsui Polychem Co Ltd 太陽電池封止材料及び太陽電池モジュール
JP2002537423A (ja) * 1999-02-17 2002-11-05 ザ ダウ ケミカル カンパニー アルファ−オレフィン／ビニルまたはビニリデン芳香族インターポリマー生成物及び複合触媒系を使用して該生成物を製造する方法
JP2009120792A (ja) * 2007-10-23 2009-06-04 Denki Kagaku Kogyo Kk クロス共重合体の製造方法及び得られるクロス共重合体、その用途
JP2009249556A (ja) * 2008-04-09 2009-10-29 Asahi Kasei E-Materials Corp 樹脂封止シート
JP2010150442A (ja) * 2008-12-26 2010-07-08 Denki Kagaku Kogyo Kk 太陽電池封止材

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06334207A (ja) * 1993-05-27 1994-12-02 Canon Inc 太陽電池モジュール
JPH08283696A (ja) * 1995-04-14 1996-10-29 Haishiito Kogyo Kk 太陽電池封止用シート及びその製造方法
WO2000037517A1 (fr) * 1998-12-22 2000-06-29 Denki Kagaku Kogyo Kabushiki Kaisha Copolymere olefine/styrene/diene reticule, procede de production dudit copolymere et ses utilisations
JP2002537423A (ja) * 1999-02-17 2002-11-05 ザ ダウ ケミカル カンパニー アルファ−オレフィン／ビニルまたはビニリデン芳香族インターポリマー生成物及び複合触媒系を使用して該生成物を製造する方法
JP2001119047A (ja) * 1999-10-21 2001-04-27 Du Pont Mitsui Polychem Co Ltd 太陽電池封止材料及び太陽電池モジュール
JP2009120792A (ja) * 2007-10-23 2009-06-04 Denki Kagaku Kogyo Kk クロス共重合体の製造方法及び得られるクロス共重合体、その用途
JP2009249556A (ja) * 2008-04-09 2009-10-29 Asahi Kasei E-Materials Corp 樹脂封止シート
JP2010150442A (ja) * 2008-12-26 2010-07-08 Denki Kagaku Kogyo Kk 太陽電池封止材

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015079834A (ja) * 2013-10-16 2015-04-23 大日本印刷株式会社 太陽電池モジュール用の封止材シート及びその製造方法

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