WO2011013638A1 - 太陽光発電用樹脂部材の屋外暴露物性改良方法およびそれに用いられる樹脂物性改良剤 - Google Patents
太陽光発電用樹脂部材の屋外暴露物性改良方法およびそれに用いられる樹脂物性改良剤 Download PDFInfo
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- WO2011013638A1 WO2011013638A1 PCT/JP2010/062567 JP2010062567W WO2011013638A1 WO 2011013638 A1 WO2011013638 A1 WO 2011013638A1 JP 2010062567 W JP2010062567 W JP 2010062567W WO 2011013638 A1 WO2011013638 A1 WO 2011013638A1
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- Prior art keywords
- resin
- polymer
- hydroxy
- functional agent
- ester
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- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 125000004018 acid anhydride group Chemical group 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 229920006222 acrylic ester polymer Polymers 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- VPKDCDLSJZCGKE-UHFFFAOYSA-N carbodiimide group Chemical group N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical group CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- NRKOSGXDEITTQE-UHFFFAOYSA-N ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CCOC(=O)CCC1=CC(C)=C(O)C(C(C)(C)C)=C1 NRKOSGXDEITTQE-UHFFFAOYSA-N 0.000 description 1
- KTHPWKZETVERCL-UHFFFAOYSA-N ethyl 3-[3-(benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl]propanoate Chemical compound CC(C)(C)C1=CC(CCC(=O)OCC)=CC(N2N=C3C=CC=CC3=N2)=C1O KTHPWKZETVERCL-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- DOIRQSBPFJWKBE-UHFFFAOYSA-N phthalic acid di-n-butyl ester Natural products CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002215 polytrimethylene terephthalate Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
-
- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
-
- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/48—Stabilisers against degradation by oxygen, light or heat
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
-
- 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 method for improving physical properties of a resin member for photovoltaic power generation and a resin physical property improving agent used therefor. More specifically, in a photovoltaic module using a polymer (hereinafter sometimes referred to as “polymer binding functional agent”) in which a functional agent selected from an ultraviolet absorber, a light stabilizer, and an antioxidant is bound.
- polymer binding functional agent a polymer in which a functional agent selected from an ultraviolet absorber, a light stabilizer, and an antioxidant is bound.
- the present invention relates to a method for improving physical properties of a resin member used, a resin physical property improving agent used therefor, a solid resin composition or a liquid composition, a resin member article having improved physical properties, and a photovoltaic module.
- Solar power generation directly converts solar energy into electrical energy using energy conversion elements such as silicon cell semiconductors.
- energy conversion elements such as silicon cell semiconductors.
- the function of the energy conversion element is lowered and the deterioration further proceeds. Therefore, the energy conversion element is sandwiched between adhesive resin layers called sealing materials and covered with a protective film.
- this sealing material sheet ethylene / vinyl acetate copolymer, ethylene / acrylate copolymer, its carboxylic acid copolymer, ionomer, etc. from adhesiveness, transparency, strength, impact resistance, chemical resistance, etc. Butyral resin is used.
- Resin materials with excellent durability have been selected as the resin materials used for these encapsulants, but since the usage period is very long, coloring and discoloration may occur as they are, or the resin physical properties may deteriorate. Cracks may occur. Therefore, improvement in weather resistance has been demanded.
- Patent Document 1 Japanese Patent Laid-Open No. 9-1161812. It has also been proposed that benzotriazole- and triazine-based UV absorbers, hindered amine light stabilizers, and hindered phenolic antioxidants be blended into ethylene / (meth) acrylic acid copolymers or their ionomers.
- Patent Document 2 Japanese Patent Laid-Open No. 2001-261904.
- Patent Document 3 Japanese Patent Laid-Open No. 2006-36874
- cerium oxide as an ultraviolet absorber
- benzophenone ultraviolet absorber as the ultraviolet absorber
- Patent Document 5 JP-A-2001-19711, Patent Document.
- 6 Japanese Patent Laid-Open No. 2003-253248, and Japanese Patent Laid-Open No. 2005-051833.
- these documents do not disclose that these polymer-binding functional agents are used in combination with a resin member used in a photovoltaic power generation module.
- UV absorbers such as UV absorbers, light stabilizers, and antioxidants are not sufficient in solubility and compatibility with resin materials, particularly polyolefin resin materials.
- the amount added was large, the surface gradually bleeded out during the period of use, or a decrease in transparency appeared.
- these are low molecular weight compounds they may be volatilized when added to the resin material and subjected to heat-kneading, and the effect is reduced when the actual content is reduced. At the same time, this volatilization resulted in material loss, and there was concern that it would cause contamination of the molding machine and the work environment.
- the inventors of the present invention have recently applied the polymer materials obtained by combining the above-described various physical property-improving additives to the polymer and applying them to resin members used in the photovoltaic power generation module.
- the present inventors have found that the above problem can be solved, and have completed the present invention.
- an object of the present invention is to provide a resin physical property improving agent that improves the outdoor exposed physical property of the resin member used in the photovoltaic power generation module.
- Another object of the present invention is to provide a method for improving outdoor exposed physical properties of a resin member used in a photovoltaic power generation module.
- the object of the present invention is to provide a masterbatch comprising a resin physical property improving agent for improving the outdoor exposed physical properties of the resin member used in the solar power generation module.
- Another object of the present invention is to provide a liquid composition used as a coating agent or paint comprising a resin physical property improving agent for improving the outdoor physical properties of the resin member used in the solar power generation module.
- the present invention provides use of a polymer material obtained by combining various physical property-improving additives with a polymer to improve the outdoor physical properties of a resin member used in a solar power generation module. .
- the resin physical property improving agent which improves the outdoor exposure physical property of the resin member used for the photovoltaic module according to the present invention is one or more selected from ultraviolet absorbers, light stabilizers and antioxidants. It is characterized by comprising one or two or more polymer-binding functional agents obtained by binding a functional agent to a polymer.
- the method for improving the outdoor physical properties of the resin member used in the photovoltaic module according to the present invention is to add the resin property improving agent according to the present invention to the resin member used in the photovoltaic module, or It is a method comprising applying or pasting to the surface of the resin material.
- the masterbatch according to the present invention is prepared by mixing the resin physical property improver according to the present invention with the same resin as the resin member or a synthetic resin and / or resin wax having compatibility therewith, and kneading them to form a sheet or pellet. It is formed into a shape of Furthermore, the liquid composition used as a coating agent or paint according to the present invention is characterized in that the resin physical property improver according to the present invention is dispersed or dissolved in a liquid medium together with a film forming material as required.
- the resin material used for the member of the photovoltaic power generation module good durability can be imparted to the resin material used for the member of the photovoltaic power generation module.
- the functional components of UV absorbers, hindered amine light stabilizers, and hindered phenolic antioxidants are chemically bonded to the polymer, so there is no loss due to sublimation or environmental pollution even during heat processing. There is an effect that the effect can be effectively maintained over a long period of time without being caused, and without being eluted with rain water, environmental water, oil or solvent.
- a polymer that is compatible with the resin material used for the members of the photovoltaic power generation module and that has good compatibility a large amount of the functional agent component can be stably added to the resin material. It becomes possible to add.
- the resin physical property improving agent according to the present invention can be easily used by simultaneously adding a plurality of types thereof to the resin material, and is advantageous in that various physical properties of the resin can be improved at the same time.
- Resin members used in photovoltaic modules examples include a sealing material resin, a surface coating resin, and an adhesive resin member.
- the basic configuration of the photovoltaic panel is to sandwich the top and bottom of the photovoltaic cell material (solar cell) with the resin layer of the sealing material, and attach the glass plate to the sealing resin layer on the front side that receives sunlight, A film of a surface coating resin (back sheet) is attached to the sealing resin layer on the back and side surfaces.
- the sealing resin has excellent long-term adhesion to glass, solar cells, and backsheets, is flexible and has excellent solar cell sealing properties, and has high solar ray transmittance and excellent transparency. It is required to have. Furthermore, durability such as heat resistance, high temperature resistance, water / moisture resistance, weather resistance, and reactivity such as easy crosslinkability are required.
- sealing resin having these properties examples include polyolefin polymers, polyether polymers, polyester polymers, polyamide polymers, polyvinyl polymers, polysilicone polymers, polyurethane polymers, and the like. Is mentioned. Among them, polyolefin polymers are preferable, and ethylene copolymer resins have the above-described performance, and are preferable as sealing material resins.
- ethylene / vinyl acetate copolymer ethylene / unsaturated carboxylic acid alkyl (carbon number 1 to 8) ester copolymer, ethylene / unsaturated carboxylic acid copolymer, ethylene / unsaturated carboxylic acid alkyl (carbon number 1 8) Esters / unsaturated carboxylic acid copolymers, and their ionomers, particularly ethylene / vinyl acetate copolymers; ethylene / methyl (meth) acrylate copolymers, ethylene / (meta ) Ethyl acrylate copolymer, etc .; Ethylene, unsaturated such as ethylene, methyl (meth) acrylate, (meth) acrylic acid copolymer, ethylene, ethyl (meth) acrylate, (meth) acrylic acid copolymer Carboxylic acid copolymers and their ionomers, and also polyvinyl butyral resins, urethane resin
- the surface coating resin that is, the back sheet is a resin film that covers the back surface or the side surface, and is directly exposed to the external environment at the installation site. Therefore, in addition to mechanical strength, electrical insulation, chemical resistance, etc., environmental resistance such as heat resistance, water resistance, moisture resistance, salt damage resistance is a very important property.
- the resin known fluororesins, polyolefin resins, polyvinyl resins, poly (meth) acrylic resins, polyether resins, polyester resins, polyamide resins, polycarbonate resins, polysilicon resins, etc. with excellent weather resistance Is mentioned.
- polyester resins, fluorine resins, and cyclic polyolefin resins are preferable.
- polyester resin examples include polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyester films such as polytrimethylene naphthalate and polybutylene naphthalate, and aluminum foil laminated polyester films and metals. Vapor-deposited or silica-deposited polyester films are also used.
- the physical property improving agent according to the present invention can be added to an adhesive used in a photovoltaic power generation module.
- an adhesive used in a known laminating method or melting method is preferably used.
- the laminating adhesive include a dry laminating adhesive, a wet laminating adhesive, a non-solvent laminating adhesive, and a hot melt adhesive depending on the form of the adhesive.
- the resin component of these adhesives include ethylene copolymer resins such as ethylene / vinyl acetate resin, ethylene / acrylic ester resin, ethylene / methacrylic ester resin, acrylic resins such as acrylic ester resin and methacrylate ester resin.
- Rubber resins such as nitrile rubber, chloroprene rubber, styrene / butadiene rubber, styrene-isoprene rubber, hydrogenated resins of these rubber resins, polyester resin, polyurethane resin, polyamide resin, polyamide-imide resin, polyimide resin, silicone Examples thereof include an adhesive such as a resin. Further, a reactive adhesive or self-crosslinking in which a reactive group such as an epoxy group, an isocyanate group, a masked isocyanate group, an alkoxymethyl group, a carbodiimide group, a hydroxyl group, or a carboxyl group is introduced into the polymer chain of the resin component of the adhesive. Mold adhesives.
- crosslinkable adhesives in which known crosslinkers such as epoxy crosslinkers, isocyanate crosslinkers, and alkoxymethylmelamine crosslinkers are used in combination with the above reactive adhesives or self-crosslinkable adhesives.
- polymerizable adhesives including a polymerizable oligomer such as a heat polymerizable adhesive, an ultraviolet curable adhesive, and an electron beam curable adhesive, and a polyfunctional polymerizable monomer can be used.
- the resin component of the melt-extruded adhesive examples include, for example, polyethylene resin, ethylene and acrylic acid, methacrylic acid, their metal salts, vinyl acetate, acrylic acid ester, methacrylic acid ester and other comonomers.
- examples thereof include known thermoplastic resins such as resins, polypropylene resins, and acid-modified polypropylene resins.
- Polymer binding functional agent In the present invention, one obtained by binding one or more functional agents selected from an ultraviolet absorber, a light stabilizer, and an antioxidant to a polymer is referred to as a polymer binding functional agent.
- the functional agent constituting the polymer binding functional agent is selected from an ultraviolet absorber, a light stabilizer, and an antioxidant.
- the ultraviolet absorber include benzotriazole, hydroxyphenyltriazine, benzophenone, benzoate, salicylate, and cyanoacrylate ultraviolet absorbers.
- the light stabilizer include hindered amine light stabilizers.
- Antioxidants include hindered phenol and phosphite antioxidants.
- These functional agents may be used singly or in combination, and it is also preferable to use those having different functions in combination. This is because the multifaceted physical properties such as the sealing material resin can be improved.
- Such use in combination may be performed by using a combination of a plurality of functional agents bonded in the same polymer molecule, or a combination of polymers combined with the respective functional agents. It is also possible to combine both methods.
- the polymer constituting the polymer binding functional agent is preferably selected in consideration of the type of resin member used in the photovoltaic power generation module to be improved, and particularly used in the photovoltaic power generation module. It is preferable to select a polymer that is compatible with the resin member to be formed.
- Preferred polymers include polyolefin polymers, poly (meth) acrylic ester polymers, polyvinyl polymers, polyether polymers, polyester polymers, polyamide polymers, polysilicone polymers, or polyurethane polymers. Examples include polymer chains such as polymers.
- polymer chains include ethylene / vinyl alcohol copolymers having hydroxyl groups as reactive groups, ethylene / vinyl alcohol / vinyl acetate. Copolymer, vinyl alcohol / vinyl butyral copolymer, etc .; ethylene / (meth) acrylic acid copolymer having a carboxylic acid derivative group such as carboxyl group, acid anhydride group, acid halogenide group, lower alkyl ester group, Ethylene / (meth) acrylic acid (carbon number: 1-8) ester / (meth) acrylic acid copolymer, acid halide derivatives thereof, ethylene / maleic anhydride copolymer, ethylene / (meth) acrylic acid lower alkyl (C1-C4) ester copolymer; an ester copolymer having a glycidyl group or a chlorohydrin group And ethylene / (meth) acrylic acid g
- a backsheet resin Even in the case of a backsheet resin, it is preferable in terms of compatibility and physical properties to use the same polymer chain as that resin. Specific examples thereof include a fluorine polymer and a polyolefin polymer. , Polyvinyl polymer, poly (meth) acrylic polymer, polyether polymer, polyester polymer, polyamide polymer, polycarbonate polymer, and polysilicone polymer.
- the back sheet resin is a polyester resin film
- ethylene glycol, trimethylene glycol or butylene glycol is used as the diol
- dicarboxylic acids such as terephthalic acid and naphthalenedicarboxylic acid and their methyl esters and diglycol esters are used as the dicarboxylic acid.
- a polyester chain using a derivative such as benzene or halogenide is preferred.
- the bonding method between the polymer and the functional agent is preferably formed by a reaction between a reactive group introduced into the functional agent residue and the polymer.
- the polymer-binding functional agent used in the present invention may be produced by a known method.
- the method described in JP-A No. 2001-19711, JP-A No. 2003-253248, JP-A No. 2005-051833 and the like can be used. It can be manufactured similarly.
- the functional agent residue which is a chemical structure exhibiting various functionalities, has various reactive groups that can be bonded to the polymer, or has been introduced, and binds to the polymer via the reactive groups. .
- a functional agent residue of a specific compound of a benzotriazole ultraviolet absorber for example, [(3-alkyl (0 to 4 carbon atoms) -4-hydroxy-5- (2H-benzotriazol-2-yl)- Phenyl] residue, [(3-alkyl (0 to 4 carbon atoms) -4-hydroxy-5- (2H-benzotriazol-2-yl) -phenyl] residue, [(2-alkyl (0 to carbon atoms) 4) -3-Hydroxy-4- (2H-benzotriazol-2-yl) -phenyl-oxy] residue, [(2-alkyl (0 to 4 carbon atoms) -3-hydroxy-4- (5-chloro -H-benzotriazol-2-yl) -phenyl-oxy] residues and the like.
- Examples of the reactive group introduced into the ultraviolet absorber residue include -alkylene (1 to 6 carbon atoms) carboxylic acid, its lower alkyl (1 to 6 carbon atoms) ester, acid halide, hydroxyalkyl (1 to 6 carbon atoms).
- bifunctional derivative groups obtained by reacting these with tricarboxylic acid anhydride / monocarboxylic acid, tetracarboxylic acid anhydride, tricarboxylic acid anhydride / monohalogenide, glycidol, diepoxy compound, etc. are mentioned. In the same manner as above, considering one or more reactors
- Examples of the hindered amine light stabilizer having a reactive group include 4-hydroxy-2,2,6,6-tetramethyl-4-piperidine, 4-hydroxy-1,2,2, and the like. 6,6-pentamethyl-4-piperidine, 1-octyloxy-4-hydroxy-2,2,6,6-tetramethyl-4-piperidine, 2,4-bis [N-butyl-N- (1-cyclohexyl) And oxy-2,2,6,6-tetramethylpiperidin-4-yl) amino] -6- (2-hydroxyethylamine) -1,3,5-triazine.
- One or more reactive hindered amine light stabilizers can be combined with the polymer.
- Examples of the reactive group of the hindered phenol antioxidant include 3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionic acid ethyl ester, 3- ( 3-t-butyl-5-methyl-4-hydroxyphenyl) propionic acid ethyl ester, 3,5-di-t-butyl-4-hydroxybenzoic acid ethyl ester and the like.
- One or more reactive hindered phenolic antioxidants can be combined with the polymer.
- a bifunctional derivative is used as a functional agent to be bonded to the polymer chain to introduce it into the main chain of the polymer chain, and 1 for bonding to the side chain or terminal of the polymer. It is preferable to use one having a functional reactive group introduced therein.
- a bifunctional compound in which two functional agents are made reactive is added, and this functional agent is added during the polymerization of the polyester, and a co-condensation reaction is performed together. It is done.
- a functional agent having one hydroxyl group is selected from butanetetracarboxylic anhydride, trimellitic anhydride, pyromellitic. Reaction with acid anhydride, trimellitic acid anhydride / monochloride, etc. to react bifunctional functional agent with two carboxyl groups introduced, and further functional agent with one carboxyl group with glycidol or diepoxy compound
- a bifunctional functional agent having two hydroxyl groups can be preferably used.
- the resin physical property improving agent according to the present invention may be used in the form of a polymer to which a functional agent is bound. However, for ease of use, the physical property of the polymer to which the functional agent is bound should be improved. It is preferable to use it in the form of a master batch which is mixed with a resin member to be prepared or a synthetic resin and / or resin wax having compatibility therewith, kneaded, and molded into, for example, a sheet or pellet form.
- the content of the polymer-binding functional agent in the master batch is appropriately determined in consideration of the required performance, the type and combination of functional agents used, the type of resin member to be applied, and the like.
- the content of the functional agent portion is preferably in the range of 2 to 30% by mass.
- the amount of the master batch added to the resin member used in the photovoltaic module may be appropriately determined in consideration of the required performance, the type and combination of functional agents used, the type of resin member applied, and the like. However, in general, the master batch is added so that the total amount of the functional agent components contained in 100 parts by mass of the resin member is 2 to 30 parts by mass.
- the resin property improving agent according to the present invention is a liquid composition in which a polymer binding functional agent is dispersed or dissolved in an appropriate liquid medium, and this is used as a paint or a coating agent. It is also preferable to do.
- the addition amount of the polymer binding functional agent in the liquid composition may be appropriately determined in consideration of the required performance, the type and combination of functional agents used, the type of resin member to be applied, etc.
- the polymer binding functional agent containing 5 to 95% by mass of the functional agent residue is set to a concentration containing 2 to 30% by mass of the functional agent part.
- a film-forming material may be added to the liquid composition according to this embodiment as necessary.
- liquid medium of the liquid composition according to the present invention examples include ester solvents such as ethyl acetate and butyl acetate, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohesanone, and hydrocarbon solvents such as cyclohexane, methylcyclohexane and xylene.
- Known solvents such as solvents, glycol ether solvents such as propylene glycol monomethyl ether, propylene glycol monoethyl ether and propylene glycol monomethyl ether acetate, and alcohol solvents such as isopropanol and butanol can be used.
- the film-forming material added to the liquid composition according to the present invention as needed include, for example, ethylene and vinyl acetate, acrylic acid ester, methacrylic acid ester, acrylic acid, methacrylic acid and the like.
- Copolymer resins with monomers acrylic resins such as acrylic ester resins and methacrylic ester resins, polyester resins, polyurethane resins, etc., and epoxy resins, isocyanate groups, masked isocyanate groups, alkoxymethyl groups, carbodiimides, etc.
- examples thereof include a reactive resin or a self-crosslinking resin into which a reactive group such as a group, a hydroxyl group or a carboxyl group is introduced.
- known coating film forming materials such as crosslinkable resins using the above reactive resins or self-crosslinking resins in combination with known crosslinking agents such as epoxy crosslinking agents, isocyanate crosslinking agents, and alkoxymethylmelamine crosslinking agents. It is done.
- the polymer-binding functional agent is used as it is, or as a master batch or liquid composition containing the same, to improve the physical properties of the resin material used for the photovoltaic power generation module.
- the amount of may be determined as appropriate.
- the amount of the functional agent component is 0.5 to 15 parts by mass of the ultraviolet absorber content or application amount relative to the resin material, and 0.5 to 20 parts of the light stabilizer.
- the mass part and the antioxidant are preferably 0.1 to 20 parts by mass.
- the functional agents are preferably used in combination.
- a plurality of functional agents bonded in the same polymer molecule may be used, or a polymer in which each functional agent is bonded may be used in combination. You may combine. It is also preferable to use the same kind of functional agent components in combination. For example, it is also preferable to use a benzotriazole-based UV absorber polymer-binding functional agent in combination with a triazine-based UV absorber polymer-binding functional agent.
- the solar cell to which the present invention is applied is not particularly limited, and a known cell is used.
- a silicon system a single crystal, polycrystal, microcrystal, or amorphous silicon film is used in a thin film type, a hybrid type, a tandem type, a spherical type, or the like.
- Known compound systems, dye-sensitized titanium oxide types, organic thin film types, quantum dot types, and the like are used.
- Sealing material sheet high weather resistance / high resin physical property sealing material sheet
- back coat film high weather resistance / high physical property back
- the polymer binding functional agent of the present invention is internally added to improve weather resistance and resin physical properties
- a method for preparing a photovoltaic power generation module using a coated film is performed according to a conventional method.
- the photovoltaic cell module is sandwiched from the front and back surfaces with a high weather resistance and high resin property sealing material sheet containing a polymer binding functional agent, and the whole is sealed. It is coated with a high weather resistance / high resin property sealing material sheet.
- ⁇ Production Example 3> (Example of production of a masterbatch containing a composite of a polymer binding functional agent)
- a functional agent component a master batch of a polymer binding functional agent containing a composite of an ultraviolet absorber, a light stabilizer, and an antioxidant was prepared.
- 32.51 parts of ethylene / ethyl acrylate copolymer resin (ethyl acrylate content: 20% by mass) used as a sealing material resin, 16.56 parts of polymer-bonded UV absorber-1 and polymer bond 16.61 parts of UV absorber-2, 23.90 parts of polymer-bound light stabilizer-1 and 10.42 parts of polymer-bound antioxidant-1 are blended, kneaded, cut, and masterbatch Got.
- the total content of the functional agent component is 20% by mass, and as the functional agent component, hydroxyphenyltriazine-based UV absorber: benzotriazole-based UV absorber: hindered amine-based light stabilizer: hindered phenol-based antioxidant In a composite at 25: 25: 30: 20.
- this is referred to as polymer-binding functional agent composite masterbatch-1.
- ⁇ Production Example 4> (Production Example of Polyvinyl Butyral Resin Master Batch) Using the polyvinyl butyral resin used as the sealing material resin in place of the ethylene-vinyl acetate copolymer resin used in Production Example 1, the polymer-bound ultraviolet absorber-4 obtained in Synthesis Example 6 and Synthesis Example 7 The polymer-bound ultraviolet absorber-5 obtained in 1 above, the polymer-bound light stabilizer-2 obtained in Synthesis Example 8 and the polymer-bound antioxidant 2 obtained in Synthesis Example 9 were blended, kneaded and sheeted. As a result, a polyvinyl butyral resin master batch of each polymer binding functional agent was obtained. This is preferably used for a polyvinyl butyral resin-based sealing material.
- the test piece produced from the obtained sheet showed sufficiently good results in the physical property test. Further, the obtained sheet was heated in a gear oven at 60 ° C., and the blooming phenomenon of the added polymer binding functional agent on the sheet surface was examined from the state of cloudiness on the surface. Naturally, the polymer-binding functional agent sheet did not show any blooming phenomenon to the surface. Similarly, the masterbatch using the polymer-bound ultraviolet absorbers-2 and -4, the polymer-bound light stabilizer-2 and the polymer-bound antioxidant-2 showed the same excellent performance.
- the functional agents such as known low molecular weight UV absorbers used for comparison caused significant blooming of the functional agent on the surface.
- the thermal stability was compared with known low molecular weight UV absorbers, light stabilizers and antioxidants.
- the polymer binding functional agent shows a slight decrease in weight that is thought to be attributable to the polymer component, but almost no weight loss is observed, whereas known UV absorbers, light stabilizers, and antioxidants At about 190 ° C to 200 ° C, there was a significant weight loss due to sublimation, confirming that the conditions of use were limited.
- bonding functional agent produced by the above other synthesis examples and manufacture examples also showed the same outstanding performance.
- Example 1 An ethylene / vinyl acetate copolymer resin-based encapsulant with an internally added polymer-bound composite functional agent used in a photovoltaic power generation module was prepared as follows.
- the ethylene / vinyl acetate copolymer resin (vinyl acetate content: 28%, MFR: 15 g / 10 min) used as a sealing material resin for the photovoltaic module is 49.5 parts, and the weight obtained in Production Example 1 is used.
- the silicon cell module was sandwiched from the front and back with the ethylene / vinyl acetate copolymer resin sealing material sheet obtained above, and the whole was sealed. It was covered with a back sheet made of a polyethylene terephthalate film (high weather resistance and high physical property PET film) having improved weather resistance and resin physical properties by internally adding a polyester-based polymer binding functional agent.
- a glass plate was placed on the upper surface, and the whole was reduced in pressure using an electrothermal laminator and evacuated for 3 minutes. The hot plate was heated to 135 ° C. to soften the resin layer, and pressed to integrate the whole. Next, the hot plate was heated to 150 ° C. and held for 15 minutes to form a cross-linked bond, and the whole was sealed to prepare a photovoltaic power generation module.
- Example 2 An ethylene-ethyl acrylate copolymer resin-based sealing material into which a polymer-bonded composite functional agent used for a photovoltaic power generation module was internally added was prepared as follows. 30% of the polymer binding functional agent composite masterbatch-1 obtained in Production Example 3 was added to 47.5 parts of ethylene / ethyl acrylate copolymer resin (ethyl acrylate content: 20% by mass) as a sealing material resin.
- the silicon cell module was sealed with the above-obtained ethylene-acrylic ester copolymer resin-based sealing material sheet, covered with a highly weather-resistant, high physical property PET film, and a glass plate on the upper surface.
- a vacuum with an electric heating laminator heated and pressed to form a cross-linked bond, and the whole was sealed to prepare a photovoltaic module.
- Example 3 A polyvinyl butyral resin-based encapsulant with an internally added polymer-bonded composite functional agent used for a solar power generation module was prepared in the same manner as in Example 1.
- the polymer-bonded UV absorber-4, polymer-bonded UV absorber-5, polymer-bonded light stabilizer-2, and polymer bond obtained in Production Example 4 were used.
- Each masterbatch containing antioxidant-2 and the additive masterbatch containing the white pigment and multifunctional monomer obtained in Production Example 6 t-butylperoxyisopropyl carbonate and vinyltrimethoxysilane were blended, and After mixing, the mixture was kneaded with an extruder and extruded into a sheet.
- the silicon cell module was sealed with the polyvinyl butyral resin-based sealing material sheet obtained above, covered with a highly weather-resistant and high physical property PET film, a glass plate was placed on the upper surface, and electrothermal heating was performed.
- a solar power generation module was prepared by evacuating with a type laminator, heating and pressing to form a cross-linked bond, and sealing the whole.
- the photovoltaic power generation module according to the present invention has improved compatibility with the resin member of the polymer-bonded composite functional agent, and can add a necessary amount sufficiently. The effect could be sustained effectively over a long period of time without causing contamination and without leaching with rain water, environmental water, oil or solvent.
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Abstract
Description
また、本発明は、太陽光発電モジュールに使用される樹脂部材の屋外暴露物性を改良する方法の提供をその目的としている。
さらに、本発明は、上記の太陽光発電モジュールに使用される樹脂部材の屋外暴露物性を改良する樹脂物性改良剤を含んでなるマスターバッチの提供をその目的としている。
さらに、本発明は、上記の太陽光発電モジュールに使用される樹脂部材の屋外暴露物性を改良する樹脂物性改良剤を含んでなるコーティング剤または塗料として用いられる液体組成物の提供をその目的としている。
さらに、本発明は、重合体に各種の物性改良添加剤を結合させて一体化した高分子材料の、太陽光発電モジュールに使用される樹脂部材の屋外暴露物性を改良するための使用を提供する。
また、本発明による太陽光発電モジュールに使用される樹脂部材の屋外暴露物性を改良する方法は、上記本発明による樹脂物性改良剤を、太陽光発電モジュールに使用される樹脂部材に添加する、または前記樹脂材料の表面に塗付または貼り付けることを含んでなることを特徴とする方法である。
さらに、本発明によるマスターバッチは、上記本発明による樹脂物性改良剤を、前記樹脂部材と同じ樹脂またはそれと相溶性を有する合成樹脂および/または樹脂ワックスと混合し、混練してシート状またはペレット状の形状に成型したことを特徴とする。
さらに本発明によるコーティング剤または塗料として用いられる液体組成物は、上記本発明による樹脂物性改良剤を、必要に応じて皮膜形成材料と共に、液媒体に分散または溶解させてなることを特徴とする。
本発明による樹脂物性改良剤が適用可能な太陽光発電モジュールに使用される樹脂部材としては、封止材樹脂、表面被覆樹脂、および接着剤の樹脂部材が挙げられる。
本発明にあっては、紫外線吸収剤、光安定剤、および酸化防止剤から選ばれる1種または2種以上の機能剤を重合体に結合したものを、重合体結合機能剤と呼ぶ。
本発明による樹脂物性改良剤は、機能剤が結合された重合体の形態で用いられてもよいが、好ましくは使用を容易にするため、機能剤が結合された重合体を、物性を改良しようとする樹脂部材またはそれと相溶性を有する合成樹脂および/または樹脂ワックス類と混合し、混練して、例えばシート状またはペレット状の形状に成型したマスターバッチの形状にして使用することが好ましい。
温度計、攪拌装置、窒素吹き込み器、および減圧装置に連結した還流冷却器を備えた反応容器に、反応性基を有する重合体としてエチレン・メタクリル酸メチル共重合体(メタクリル酸メチル含有量28%、メルトフロー(MFR)450g/10分)357.0g(0.997等量)および反応性基を有する紫外線吸収剤として2-[4-(2-ヒドロキシ-3-(2’-エチルヘキシル)オキシ)-2-ヒドロキシフェニル]-4,6-ビス(2,4-ジメチルフェニル)-1,3,5-トリアジン(分子量:584)160.9g(0.276モル)を仕込み、窒素を吹き込みながら加熱して溶融させた。触媒のオクチル酸すず0.89gおよび2,6-ジ-t-ブチル-4-メチルフェノール(BHT)1.79gを加え、200℃まで昇温した。キシレン50gを滴下しながら、6時間反応し、さらにオクチル酸すず0.89gを追加し、7時間反応させた。反応中に生成したメタノール分は冷却器にて系外に除いた。反応の進行は赤外吸収スペクトルで確認した。反応完了後、減圧してキシレンを留出させた後、冷却し、イソプロピルアルコール中に注入して反応生成物を析出させ、濾過した。イソプロピルアルコールで洗浄し、乾燥させ、「重合体結合紫外線吸収剤-1」を得た。生成物は赤外吸収スペクトルおよびNMRで確認した。紫外線吸収剤残基の含有率は30.2%を示した。
合成例1と同様の反応装置に、エチレン・ビニルアルコール・酢酸ビニル共重合体(質量比;82.1:14.7:3.1、水酸基当量:299.4)375.4g(1.254等量)、キシレン200g、3-[3-(2H-ベンゾトリアゾール-2-イル)-4-ヒドロキシ-5-t-ブチル-フェニル]プロピオン酸エチルエステル(分子量:367.4)182.6g(0.497モル)を仕込み、加熱溶解させた。触媒としてモノブチルすずオキサイドを0.38gおよびBHT0.76g添加して、合成例1と同様に加熱反応させ、「重合体結合紫外線吸収剤-2」を得た。生成物は赤外吸収スペクトルおよびNMRで確認した。紫外線吸収剤残基の含有率は30.1%を示した。
エチレン・メタクリル酸メチル共重合体を378.5g(0.9735等量)および2-[3-ヒドロキシ-4-(2H-ベンゾトリアゾール-2-イル)-フェニル-オキシ]-エチルアルコール(分子量:270.3)165.2g(0.611モル)、触媒としてオクチル酸すず0.87gおよびBHT1.74gを使用した以外は合成例1と同様にして、「重合体結合紫外線吸収剤-3」を得た。生成物は赤外吸収スペクトルおよびNMRで確認した。紫外線吸収剤残基の含有率は30.3%を示した。
エチレン・メタクリル酸メチル共重合体を374.4g(1.046等量)および4-ヒドロキシ-1,2,2,6,6-ペンタメチル-ピペリジン(分子量:171.3)132.0g(0.771モル)、触媒としてテトラブチルチタネート0.75gおよびBHT1.87gを使用した以外は合成例1と同様にして、「重合体結合光安定剤-1」を得た。生成物は赤外吸収スペクトルおよびNMRで確認した。
エチレン・ビニルアルコール・酢酸ビニル共重合体308.0g(1.029当量)および3-(3’,5’-ジ-t-ブチル-4’-ヒドロキシフェニル)プロピオン酸エチルエステル(平均分子量:306.4)234.8g(0.766モル)および触媒としてモノブチルすずオキサイドを0.59gおよびBHT1.17gを使用した以外は合成例2と同様にして、「重合体結合酸化防止剤-1」を得た。生成物は赤外吸収スペクトルおよびNMRで確認した。
エチレン・ビニルアルコール・酢酸ビニル共重合体に変えてポリビニルブチラール樹脂(ビニルアルコール分:20質量%)を使用した以外は合成例2と同様にして、ポリビニルブチラール樹脂系の「重合体結合紫外線吸収剤-4」を合成した。
2-[4-(2-ヒドロキシ-3-(2’-エチルヘキシル)オキシ]-2-ヒドロキシフェニル]-4,6-ビス(2,4-ジメチルフェニル)-1,3,5-トリアジンに無水コハク酸を反応させて得た2-[4-(2-(カルボキシエチルカルボニルオキシ)-3-(2’-エチルヘキシル)オキシ)-2-ヒドロキシフェニル]-4,6-ビス(2,4-ジメチルフェニル)-1,3,5-トリアジンを用いた以外は合成例6と同様にして、ポリビニルブチラール樹脂系の「重合体結合紫外線吸収剤-5」を合成した。
4-ヒドロキシ-1,2,2,6,6-ペンタメチル-ピペリジンに無水コハク酸を反応させて得た1,2,2,6,6-ペンタメチル-ピペリジン-4-オキシカルボニルエチルカルボン酸を用いた以外は合成例6と同様にして、ポリビニルブチラール樹脂系の「重合体結合光安定剤-2」を合成した。
3-(3’,5’-ジ-t-ブチル-4’-ヒドロキシフェニル)プロピオン酸エチルエステルを用いた以外は合成例6と同様にして、ポリビニルブチラール樹脂系の「重合体結合酸化防止剤-2」を合成した。
太陽光発電モジュールの封止材樹脂として使用され得るエチレン・酢酸ビニル共重合樹脂(酢酸ビニル含有量:28%、MFR:15g/10分)33.77部に、合成例1で得られた重合体結合紫外線吸収剤-1の66.23部をミキシングロール(ロール表面温度:120℃)で混練し、シーティングマシーンを用い、シートとして引き出し、裁断して約20cm×20cm×5mmの重合体結合紫外線吸収剤を含むマスターバッチを得た。このマスターバッチはトリアジン系紫外線吸収剤換算で20質量%含有する。以下、重合体結合紫外線吸収剤マスターバッチ-1と称する。
製造例1と同様にして、合成例2~5で得られた重合体結合機能剤の、機能剤成分を20質量%含有するそれぞれのマスターバッチを調製した。重合体結合紫外線吸収剤-2は66.45部、重合体結合紫外線吸収剤-3は66.01部、重合体結合光安定剤-1は79.68部、重合体結合酸化防止剤-1は52.08部をそれぞれ採取し、合計質量が100部になるようにそれぞれエチレン-酢酸ビニル共重合樹脂を配合し、ミキシングロールで混練し、シーティングマシーンを用い、裁断して、それぞれのマスターバッチとした。それぞれ重合体結合紫外線吸収剤マスターバッチ-2、重合体結合紫外線吸収剤マスターバッチ-3、重合体結合光安定剤マスターバッチ-1および重合体結合酸化防止剤マスターバッチ-1と称する。
機能剤成分として、紫外線吸収剤、光安定剤、および酸化防止剤を複合して含有する重合体結合機能剤のマスターバッチを調製した。封止材樹脂として使用されるエチレン・アクリル酸エチル共重合樹脂(アクリル酸エチル含有量:20質量%)32.51部に、重合体結合紫外線吸収剤-1を16.56部、重合体結合紫外線吸収剤-2を16.61部、重合体結合光安定剤-1を23.90部および重合体結合酸化防止剤-1を10.42部配合し、混練し、裁断して、マスターバッチを得た。これは、機能剤成分の総含有量は20質量%で、機能剤成分としてヒドロキシフェニルトリアジン系紫外線吸収剤:ベンゾトリアゾール系紫外線吸収剤:ヒンダートアミン系光安定剤:ヒンダートフェノール系酸化防止剤を25:25:30:20で複合して含有する。以下、これを重合体結合機能剤複合体マスターバッチ-1と称する。
製造例1で使用したエチレン-酢酸ビニル共重合樹脂に代えて封止材樹脂として使用されるポリビニルブチラール樹脂を使用して、合成例6で得た重合体結合紫外線吸収剤-4、合成例7で得た重合体結合紫外線吸収剤-5、合成例8で得た重合体結合光安定剤-2および合成例9で得た重合体結合酸化防止剤-2をそれぞれ配合し、混練してシート化し、それぞれの重合体結合機能剤のポリビニルブチラール樹脂マスターバッチを得た。これはポリビニルブチラール樹脂系封止材に好ましく使用される。
製造例1で使用したエチレン・酢酸ビニル共重合樹脂を40部に、酸化チタン白色顔料を50部およびトリアリルシアヌレートを10部を配合し、2軸押出機で混練して、マスターバッチを得た。以下、これを「添加剤マスターバッチ」と称する。
エチレン・酢酸ビニル共重合樹脂75.0部に重合体結合紫外線吸収剤マスターバッチ-1を7.5部、重合体結合紫外線吸収剤マスターバッチ-3を5.0部、重合体結合光安定剤マスターバッチ-1を7.5部、および重合体結合酸化防止剤マスターバッチ-1を5.0部配合し、ミキシングロールで混練し、熱プレスで成形し、厚さ約1mmのシートを作製した。加熱混練中に重合体結合機能剤は当然ながら昇華するようなことはなく、加工機械への汚染もなかった。
同様に、重合体結合紫外線吸収剤-2、-4、重合体結合光安定剤-2、重合体結合酸化防止剤-2を使用したマスターバッチも同様の優れた性能を示した。
比較に使用した公知の低分子量の紫外線吸収剤などの機能剤は表面に機能剤のブルーミングを大きく起こした。
また、上記したその他の合成例、製造例で作製した重合体結合機能剤を使用したマスターバッチも同様の優れた性能を示した。
太陽光発電モジュールに使用される、重合体結合複合機能剤を内部添加したエチレン・酢酸ビニル共重合樹脂系封止材を以下のようにして調製した。
太陽光発電モジュールの封止材樹脂として使用されるエチレン・酢酸ビニル共重合樹脂(酢酸ビニル含有量:28%、MFR:15g/10分)49.5部に、製造例1で得られた重合体結合紫外線吸収剤マスターバッチ-1を7.5部、製造例2で得られた重合体結合紫外線吸収剤マスターバッチ-3を5.0部、重合体結合光安定剤マスターバッチ-1を7.5部、重合体結合酸化防止剤マスターバッチ-1を5.0部、および製造例5で得られた白色顔料および多官能性モノマーを含む添加剤マスターバッチを20.0部、過酸化物としてt-ブチルパーオキシイソプロピルカーボネートを2.0部およびシランカップリング剤としてビニルトリメトキシシランを0.5部配合し、十分に混合して後、押出機にて100℃で混練し、厚さ1mmのシート状に押出成形した。
太陽光発電モジュールに使用される重合体結合複合機能剤を内部添加したエチレン-アクリル酸エチル共重合樹脂系封止材を以下のようにして調製した。封止材樹脂のエチレン・アクリル酸エチル共重合樹脂(アクリル酸エチル含有量:20質量%)47.5部に、製造例3で得られた重合体結合機能剤複合体マスターバッチ-1を30.0部、および製造例5で得られた白色顔料および多官能性モノマーを含む添加剤マスターバッチを20.0部、過酸化物としてt-ブチルパーオキシイソプロピルカーボネートを2.0部およびシランカップリング剤としてビニルトリメトキシシランを0.5部配合し、十分に混合して後、二軸押出機にて混練し、シート状に押出成形した。
太陽光発電モジュールに使用される、重合体結合複合機能剤を内部添加したポリビニルブチラール樹脂系封止材を実施例1と同様にして調製した。封止材樹脂として使用されるポリビニルブチラール樹脂に、製造例4で得られた重合体結合紫外線吸収剤-4、重合体結合紫外線吸収剤-5、重合体結合光安定剤-2および重合体結合酸化防止剤-2を含むそれぞれのマスターバッチおよび製造例6で得られた白色顔料および多官能性モノマーを含む添加剤マスターバッチ、t-ブチルパーオキシイソプロピルカーボネートおよびビニルトリメトキシシランを配合し、十分に混合して後、押出機にて混練し、シート状に押出成形した。
Claims (27)
- 太陽光発電モジュールに使用される樹脂部材の屋外曝露物性を改良する樹脂物性改良剤であって、紫外線吸収剤、光安定剤、および酸化防止剤から選ばれる1種または2種以上の機能剤を重合体に結合してなる重合体結合機能剤を1種または2種以上を含んでなることを特徴とする樹脂物性改良剤。
- 前記樹脂材料中に添加する、または前記樹脂材料の表面に塗付または貼り付けて用いられる、請求項1に記載の樹脂物性改良剤。
- 前記太陽光発電モジュールに使用される樹脂部材が、封止材樹脂、表面被覆樹脂、および接着剤から選ばれる1種またはそれ以上の樹脂部材である、請求項1に記載の樹脂物性改良剤。
- 前記樹脂部材が、ポリオレフィン系重合体、ポリエーテル系重合体、ポリエステル系重合体、ポリアミド系重合体、ポリビニル系重合体、ポリシリコーン系重合体またはポリウレタン系重合体である、請求項1に記載の樹脂物性改良剤。
- 前記太陽光発電モジュールに使用される封止材樹脂が、エチレン・酢酸ビニル共重合体、エチレン・不飽和カルボン酸アルキル(炭素数1~8)エステル共重合体、エチレン・不飽和カルボン酸共重合体、エチレン・不飽和カルボン酸アルキル(炭素数1~8)エステル・不飽和カルボン酸共重合体、およびそれらのアイオノマー、ポリビニルブチラール系樹脂からなる群から選ばれる1種またはそれ以上の封止材樹脂である、請求項1に記載の樹脂物性改良剤。
- 前記機能剤が、ベンゾトリアゾール系、ヒドロキシフェニルトリアジン系、ベンゾフェノン系、ベンゾエート系、サリシレート系、およびシアノアクリレート系紫外線吸収剤からなる群から選ばれる1種またはそれ以上の紫外線吸収剤である、請求項1に記載の樹脂物性改良剤。
- 前記機能剤が、ヒンダートアミン系光安定剤から選ばれた1種またはそれ以上の光安定剤である、請求項1に記載の樹脂物性改良剤。
- 前記機能剤が、ヒンダートフェノール系酸化防止剤、およびホスファイト系酸化防止剤からなる群から選ばれる1種またはそれ以上の酸化防止剤である、請求項1に記載の樹脂物性改良剤。
- 前記重合体が、ポリオレフィン系重合体、ポリビニル系重合体、ポリエーテル系重合体、ポリエステル系重合体、ポリアミド系重合体、ポリシリコーン系重合体、またはポリウレタン系重合体である、請求項1に記載の樹脂物性改良剤。
- 前記太陽光発電モジュールに使用される樹脂部材が封止材樹脂であり、かつ前記重合体が、エチレン・ビニルアルコール共重合体、エチレン・ビニルアルコール・酢酸ビニル共重合体、ビニルアルコール・ビニルブチラール共重合体;エチレン・(メタ)アクリル酸共重合体、エチレン・(メタ)アクリル酸(炭素数1~8)エステル・(メタ)アクリル酸共重合体、それらの酸ハロゲナイド誘導体、エチレン・無水マレイン酸共重合体、エチレン・(メタ)アクリル酸低級アルキル(炭素数1~4)エステル共重合体;エチレン・(メタ)アクリル酸グリシジルエステル共重合体、およびエチレン・(メタ)アクリル酸アルキル(炭素数1~8)エステル・(メタ)アクリル酸グリシジルエステル共重合体からなる群から選ばれる1種またはそれ以上の重合体を反応させて得られる重合体鎖である、請求項1に記載の樹脂物性改良剤。
- 前記太陽光発電モジュールに使用される樹脂部材がバックシートであり、前記重合体が、フッ素系重合体、ポリオレフィン系重合体、ポリビニル系重合体、ポリ(メタ)アクリル重合体、ポリエーテル系重合体、ポリエステル系重合体、ポリアミド系重合体、ポリカーボネート重合体、またはポリシリコーン系重合体である、請求項1に記載の樹脂物性改良剤。
- 前記機能剤が、ベンゾトリアゾール系紫外線吸収剤、トリアジン系紫外線吸収剤、ベンゾフェノン系紫外線吸収剤、ヒンダートアミン系光安定剤、およびヒンダートフェノール系酸化防止剤からなる群から選ばれる2種以上の機能剤である、請求項1に記載の樹脂物性改良剤。
- 前記重合体と前記機能剤との結合が、前記機能剤残基に導入された反応性基と、前記重合体との反応によって形成され、前記機能剤の残基が紫外線吸収剤、ヒンダートアミン系光安定剤、ヒンダートフェノール系酸化防止剤から選ばれた1種または2種以上の機能剤残基である、請求項1に記載の樹脂部材の物性改良方法。
- 前記機能剤の残基が、[(3-アルキル(炭素数0~4)-4-ヒドロキシ-5-(2H-ベンゾトリアゾール-2-イル)-フェニル]残基、[(3-アルキル(炭素数0~4)-4-ヒドロキシ-5-(2H-ベンゾトリアゾール-2-イル)-フェニル]残基、[(2-アルキル(炭素数0~4)-3-ヒドロキシ-4-(2H-ベンゾトリアゾール-2-イル)-フェニル-オキシ]残基、[(2-アルキル(炭素数0~4)-3-ヒドロキシ-4-(5-クロロ-2H-ベンゾトリアゾール-2-イル)-フェニル-オキシ]残基からなる群から選ばれる1種ないしそれ以上のベンゾトリアゾール系紫外線吸収剤残基であり、
前記反応性基が、-アルキレン(炭素数1~6)カルボン酸、その低級アルキル(炭素数1~6)エステル、酸ハロゲナイド、ヒドロキシアルキル(炭素数1~10)エステル、(2-ヒドロキシ-3-アルキル(炭素数1~20)オキシプロピルエステル、(2-ヒドロキシ-3-フェニル-オキシプロピルエステル;-アルキレン(炭素数1~6)アルコール、-(2-ヒドロキシ-3-アルキルオキシ(炭素数1~20)プロパン、(2-ヒドロキシ-3-フェニールオキシ)プロパン、または(2-ヒドロキシ-3-アルキルカルボニルオキシ(炭素数1~20)プロパンであるか、さらにこれらとトリカルボン酸無水物・モノカルボン酸、テトラカルボン酸無水物、トリカルボン酸無水物・モノハロゲナイド、グリシドール、ジエポキシ化合物とを反応させて得られた2官能性誘導体が有する反応基からなる群から選ばれる1種または2種以上の反応基である、請求項13に記載の樹脂物性改良剤。 - 前記機能剤の残基が、4-(4,6-ビス(アルキル(炭素数0~4)フェニル-1,3,5-トリアジン-2-イル)-(3-ヒドロキシ)-フェニル-オキシ]残基、4-(4,6-ビス(ジフェニル-1,3,5-トリアジン-2-イル)-(3-ヒドロキシ)-フェニル-オキシ]残基からなる群から選ばれる1種または2種以上のトリアジン系紫外線吸収剤残基であり、
上記反応性基が、-アルキレン(炭素数1~6)カルボン酸、その低級アルキル(炭素数1~6)エステル、酸ハロゲナイド、ヒドロキシアルキル(炭素数1~10)エステル、(2-ヒドロキシ-3-アルキル(炭素数1~20)オキシプロピルエステル、(2-ヒドロキシ-3-フェニル-オキシプロピルエステル;-アルキレン(炭素数1~6)アルコール、-(2-ヒドロキシ-3-アルキルオキシ(炭素数1~20)プロパン、(2-ヒドロキシ-3-フェニールオキシ)プロパン、または(2-ヒドロキシ-3-アルキルカルボニルオキシ(炭素数1~20)プロパンであるか、さらにこれらとトリカルボン酸無水物・モノカルボン酸、テトラカルボン酸無水物、トリカルボン酸無水物・モノハロゲナイド、グリシドール、ジエポキシ化合物とを反応させて得られた2官能性誘導体が有する反応基からなる群から選ばれる1種または2種以上の反応基である、請求項13に記載の樹脂物性改良剤。 - 前記機能剤が、4-ヒドロキシ-2,2,6,6-テトラメチル-4-ピペリジン、4-ヒドロキシ-1,2,2,6,6-ペンタメチル-4-ピペリジン、1-オクチルオキシ-4-ヒドロキシ-2,2,6,6-テトラメチル-4-ピペリジン、および2,4-ビス[N-ブチル-N-(1-シクロヘキシルオキシ-2,2,6,6-テトラメチルピペリジン-4-イル)アミノ]-6-(2-ヒドロキシエチルアミン)-1,3,5-トリアジンからなる群から選ばれる1種ないしそれ以上の反応性ヒンダートアミン系光安定剤である、請求項13に記載の樹脂物性改良剤。
- 前記機能剤が、3-(3’,5’-ジ-t-ブチル-4’-ヒドロキシフェニル)プロピオン酸エチルエステル、3-(3-t-ブチル-5-メチル-4-ヒドロキシフェニル)プロピオン酸エチルエステル、および3,5-ジ-t-ブチル-4-ヒドロキシ安息香酸エチルエステルからなる群から選ばれる1種ないしそれ以上の反応性ヒンダートフェノール系酸化防止剤である、請求項13に記載の樹脂物性改良剤。
- 請求項1~17のいずれか一項に記載の樹脂改良剤を、前記樹脂部材と同じ樹脂またはそれと相溶性を有する合成樹脂および/または樹脂ワックスと混合し、混練してシート状またはペレット状の形状に成型したことを特徴とする、マスターバッチ。
- 機能剤残基の含量が5~95質量%である重合体を、機能剤部分の含量が2~30質量%となる量含有してなる、請求項18に記載のマスターバッチ。
- 請求項1~17のいずれか一項に記載の樹脂改良剤を、必要に応じて塗膜形成材料と共に、液媒体に分散または溶解させてなることを特徴とする、液状組成物。
- 前記機能剤成分を2~30質量%含有し、塗料またはコーティング剤として用いられる、請求項20に記載の液状組成物。
- 請求項1~17のいずれか一項に記載の樹脂改良剤を、太陽光発電モジュールに使用される樹脂部材に添加する、または前記樹脂材料の表面に塗付または貼り付けることを含んでなることを特徴とする、太陽光発電モジュールに使用される樹脂部材の屋外曝露物性を改良する方法。
- 請求項18に記載のマスターバッチを太陽光発電モジュールに使用される樹脂部材に添加することを含んでなる、太陽光発電モジュールに使用される樹脂部材の屋外曝露物性を改良する方法。
- 前記マスターバッチを、樹脂部材100質量部あたり機能剤成分として合計で0.1~20質量部の割合で添加する、請求項23に記載の樹脂部材の屋外暴露物性を改良する方法。
- 請求項20に記載の液状組成物を太陽光発電モジュールに使用される樹脂部材表面に塗付することを含んでなる、太陽光発電モジュールに使用される樹脂部材の屋外曝露物性を改良する方法。
- 紫外線吸収剤、光安定剤、および酸化防止剤から選ばれる1種または2種以上の機能剤を重合体に結合してなる化合物の、太陽光発電モジュールに使用される樹脂部材の屋外暴露物性を改良するための使用。
- 請求項22~25のいずれか一項に記載の樹脂部材の屋外暴露物性を改良する方法で得られたことを特徴とする、太陽光発電モジュールに使用される樹脂部材物品。
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JP (1) | JP5576375B2 (ja) |
KR (1) | KR101375399B1 (ja) |
CN (1) | CN102471594B (ja) |
TW (1) | TWI448492B (ja) |
WO (1) | WO2011013638A1 (ja) |
Cited By (7)
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WO2014007150A1 (ja) * | 2012-07-03 | 2014-01-09 | 三菱レイヨン株式会社 | 太陽電池保護シート及び太陽電池モジュール |
JP2015214692A (ja) * | 2014-05-07 | 2015-12-03 | クラレイ ユーロップ ゲゼルシャフト ミット ベシュレンクテル ハフツングKuraray Europe GmbH | 移行性が低い紫外線保護性pvbシート |
US10125251B2 (en) | 2014-06-25 | 2018-11-13 | 3M Innovative Properties Company | Fluoropolymer composition including at least one oligomer |
US10519350B2 (en) | 2015-06-25 | 2019-12-31 | 3M Innovative Properties Company | Copolymer including ultraviolet light-absorbing group and compositions including the same |
US10577467B2 (en) | 2012-12-20 | 2020-03-03 | 3M Innovative Properties Company | Fluoropolymer composition including an oligomer having an ultraviolet absorbing group |
US11110689B2 (en) | 2014-06-25 | 2021-09-07 | 3M Innovative Properties Company | Pressure sensitive adhesive composition including ultraviolet light-absorbing oligomer |
WO2023085082A1 (ja) * | 2021-11-10 | 2023-05-19 | 株式会社Adeka | 樹脂添加剤マスターバッチ、合成樹脂組成物および成形体 |
Families Citing this family (6)
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CN108192003B (zh) * | 2017-12-29 | 2020-01-21 | 中山大学 | 一种自由基化乙烯马来酸酐共聚物及其合成方法 |
CN108484833A (zh) * | 2018-03-07 | 2018-09-04 | 乐凯胶片股份有限公司 | 一种功能树脂、聚烯烃材料、及其制备方法和应用 |
WO2020196044A1 (ja) * | 2019-03-28 | 2020-10-01 | 三井・ダウ ポリケミカル株式会社 | 樹脂ペレット、樹脂ペレットの製造方法及びグラビアインキ |
TWI762175B (zh) * | 2021-02-02 | 2022-04-21 | 臺灣永光化學工業股份有限公司 | 自修復樹脂組成物及其用途 |
KR102425451B1 (ko) * | 2021-09-15 | 2022-07-27 | 한진케미칼 주식회사 | 건축도료 부착증진용 내황변성 열가소성 수지의 제조방법 |
CN116693938A (zh) * | 2022-02-24 | 2023-09-05 | 天津利安隆新材料股份有限公司 | 反应型复合光稳定剂及其应用、光稳定改性高分子材料 |
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WO2014007150A1 (ja) * | 2012-07-03 | 2014-01-09 | 三菱レイヨン株式会社 | 太陽電池保護シート及び太陽電池モジュール |
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JP2015214692A (ja) * | 2014-05-07 | 2015-12-03 | クラレイ ユーロップ ゲゼルシャフト ミット ベシュレンクテル ハフツングKuraray Europe GmbH | 移行性が低い紫外線保護性pvbシート |
US10125251B2 (en) | 2014-06-25 | 2018-11-13 | 3M Innovative Properties Company | Fluoropolymer composition including at least one oligomer |
US11110689B2 (en) | 2014-06-25 | 2021-09-07 | 3M Innovative Properties Company | Pressure sensitive adhesive composition including ultraviolet light-absorbing oligomer |
US10519350B2 (en) | 2015-06-25 | 2019-12-31 | 3M Innovative Properties Company | Copolymer including ultraviolet light-absorbing group and compositions including the same |
WO2023085082A1 (ja) * | 2021-11-10 | 2023-05-19 | 株式会社Adeka | 樹脂添加剤マスターバッチ、合成樹脂組成物および成形体 |
Also Published As
Publication number | Publication date |
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KR101375399B1 (ko) | 2014-03-17 |
JPWO2011013638A1 (ja) | 2013-01-07 |
TWI448492B (zh) | 2014-08-11 |
CN102471594A (zh) | 2012-05-23 |
CN102471594B (zh) | 2015-04-01 |
KR20120045014A (ko) | 2012-05-08 |
TW201109374A (en) | 2011-03-16 |
JP5576375B2 (ja) | 2014-08-20 |
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