WO2011065234A1 - ポリフッ化ビニリデン系樹脂組成物、フィルム、バックシート及び太陽電池モジュール - Google Patents
ポリフッ化ビニリデン系樹脂組成物、フィルム、バックシート及び太陽電池モジュール Download PDFInfo
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- WO2011065234A1 WO2011065234A1 PCT/JP2010/070088 JP2010070088W WO2011065234A1 WO 2011065234 A1 WO2011065234 A1 WO 2011065234A1 JP 2010070088 W JP2010070088 W JP 2010070088W WO 2011065234 A1 WO2011065234 A1 WO 2011065234A1
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- WIPO (PCT)
- Prior art keywords
- polyvinylidene fluoride
- mass
- resin composition
- film
- inorganic pigment
- Prior art date
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- 229920002981 polyvinylidene fluoride Polymers 0.000 title claims abstract description 121
- 239000002033 PVDF binder Substances 0.000 title claims abstract description 119
- 239000011342 resin composition Substances 0.000 title claims abstract description 67
- 239000001023 inorganic pigment Substances 0.000 claims abstract description 76
- 239000011347 resin Substances 0.000 claims abstract description 66
- 229920005989 resin Polymers 0.000 claims abstract description 66
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 36
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 36
- 239000000843 powder Substances 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 28
- 239000008188 pellet Substances 0.000 claims description 24
- 239000002245 particle Substances 0.000 claims description 22
- 238000004898 kneading Methods 0.000 claims description 17
- -1 polyethylene terephthalate Polymers 0.000 claims description 8
- 238000010998 test method Methods 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 4
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 4
- 238000007873 sieving Methods 0.000 claims description 2
- 230000007547 defect Effects 0.000 abstract description 38
- 238000002156 mixing Methods 0.000 abstract description 22
- 239000006185 dispersion Substances 0.000 abstract description 18
- 238000011156 evaluation Methods 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 12
- 239000000049 pigment Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 9
- 239000006087 Silane Coupling Agent Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 238000012216 screening Methods 0.000 description 4
- 239000006104 solid solution Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 239000012986 chain transfer agent Substances 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000007429 general method Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000001055 blue pigment Substances 0.000 description 2
- 239000001058 brown pigment Substances 0.000 description 2
- 230000003915 cell function Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- CRHLEZORXKQUEI-UHFFFAOYSA-N dialuminum;cobalt(2+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Al+3].[Co+2].[Co+2] CRHLEZORXKQUEI-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- CZWLNMOIEMTDJY-UHFFFAOYSA-N hexyl(trimethoxy)silane Chemical compound CCCCCC[Si](OC)(OC)OC CZWLNMOIEMTDJY-UHFFFAOYSA-N 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000010309 melting process Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000003566 sealing material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 239000012463 white pigment Substances 0.000 description 2
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920001479 Hydroxyethyl methyl cellulose Polymers 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical compound OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 0.000 description 1
- 229910000004 White lead Inorganic materials 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- DKJWBYAHPHQBPD-UHFFFAOYSA-N hexyl(methoxy)silane Chemical compound CCCCCC[SiH2]OC DKJWBYAHPHQBPD-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- RYZCLUQMCYZBJQ-UHFFFAOYSA-H lead(2+);dicarbonate;dihydroxide Chemical compound [OH-].[OH-].[Pb+2].[Pb+2].[Pb+2].[O-]C([O-])=O.[O-]C([O-])=O RYZCLUQMCYZBJQ-UHFFFAOYSA-H 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001579 optical reflectometry Methods 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- YPVDWEHVCUBACK-UHFFFAOYSA-N propoxycarbonyloxy propyl carbonate Chemical compound CCCOC(=O)OOC(=O)OCCC YPVDWEHVCUBACK-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/16—Homopolymers or copolymers or vinylidene fluoride
-
- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
- C08L33/12—Homopolymers or copolymers of methyl methacrylate
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/048—Encapsulation of modules
- H01L31/049—Protective back sheets
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- 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
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/16—Homopolymers or copolymers of vinylidene fluoride
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/66—Substances characterised by their function in the composition
- C08L2666/72—Fillers; Inorganic pigments; Reinforcing additives
-
- 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 polyvinylidene fluoride resin composition, a polyvinylidene fluoride resin film, a back sheet for a solar cell module, and a solar cell module. More specifically, the present invention relates to a resin composition for forming a weather resistant film constituting a back sheet of a solar cell module and a weather resistant film formed using this resin composition.
- PVDF Polyvinylidene fluoride
- base materials such as plastic plates for interiors and exteriors of various buildings and automobiles, and metal plates, and as an insulating material for parts of electrical and electronic equipment. It is used.
- PVDF has attracted attention as a weather-resistant film material constituting a back sheet of a photovoltaic power generation module (see, for example, Patent Document 1). Since solar cell modules are required to have long-term durability outdoors, generally, a transparent substrate made of glass or the like, a sealing material made of a thermoplastic resin sheet such as ethylene vinyl acetate copolymer (EVA), light, etc. A photovoltaic cell and a back sheet, which are electromotive elements, are laminated in this order, and laminated and integrated by a method such as pressure heating.
- EVA ethylene vinyl acetate copolymer
- This solar cell backsheet is used in the lowermost layer of the solar cell module for the purpose of protecting solar cells and wiring.
- the solar cell backsheet increases the reflectance of sunlight and increases the power generation efficiency of the solar cell module. An effect is also required.
- the white sheet is mainly used, and the white pigment is normally mix
- a solar cell backsheet has been proposed in which a small amount of a colored inorganic pigment for toning is blended in addition to a white pigment in order to increase the hiding power of the film (see, for example, Patent Document 3).
- the backsheet has long-term weather resistance, heat resistance, etc.
- Other performances such as water vapor barrier properties and gas barrier properties are also required.
- the above-described conventional white PVDF film has a problem in that the dispersibility of white pigments such as titanium oxide and inorganic pigments for toning is poor, and these are aggregates and defects are easily generated in the film. is there.
- the present invention is a polyvinylidene fluoride resin composition, film having good dispersibility of inorganic pigments, hardly causing defects due to poor dispersion when a film is formed, and having practical mechanical strength characteristics,
- the main object is to provide a backsheet and a solar cell module.
- the present inventor has made the resin component a mixed system of PVDF and polymethyl methacrylate (hereinafter abbreviated as PMMA), and has relatively high melt fluidity.
- PMMA polymethyl methacrylate
- the polyvinylidene fluoride resin composition according to the present invention comprises 100 parts by mass of a resin component comprising two types of polyvinylidene fluoride: a total of 50 to 95% by mass and polymethyl methacrylate: 5 to 50% by mass; It contains 7 to 40 parts by weight of a white inorganic pigment and 0.01 to 7 parts by weight of an inorganic pigment for toning, and at least one of the two types of polyvinylidene fluoride is JIS K 7210 MFR (Melt Flow Rate) measured at a temperature of 230 ° C. and a load of 3.8 kg by method A is 3 to 35 g / 10 min. Polymethyl methacrylate is heated to 230 ° C.
- JIS K 7210 MFR Melt Flow Rate
- one of the two types of polyvinylidene fluoride may be a pellet and the other may be a powder.
- the polyvinylidene fluoride in the pellet body for example, one having an average particle diameter (median diameter) of 1 to 6 mm measured by a dry sieving test method defined in JIS K 0069 is used.
- the vinylidene for example, one having an average particle diameter (median diameter) of 3 to 30 ⁇ m measured by a laser diffractometer stipulated in JIS Z 8825-1 is used, and the ratio of pellets in the entire polyvinylidene fluoride is 40 to 97.
- the mass% and the powder ratio can be 3 to 60 mass%.
- the white inorganic pigment those having an average particle diameter (median diameter) of 0.1 to 2 ⁇ m as measured by a laser diffraction apparatus defined in JIS Z 8825-1, for example, can be used. Further, as the inorganic pigment for toning, for example, those having an average particle diameter (median diameter) of 0.1 to 2 ⁇ m measured by a laser diffractometer specified in JIS Z 8825-1 can be used.
- the polyvinylidene fluoride-based resin film according to the present invention is obtained by melt-kneading the above-mentioned polyvinylidene fluoride-based resin composition in a temperature range of 150 to 260 ° C. and then extruding it.
- the solar cell module backsheet according to the present invention is obtained by laminating the aforementioned polyvinylidene fluoride resin film and a polyethylene terephthalate resin film. Furthermore, the solar cell module according to the present invention uses the above-described back sheet.
- two types of PVDF are used in combination, and at least one of them has a relatively high melt fluidity, so that the dispersibility of the inorganic pigment is improved, there are few defects due to poor dispersion, and the weather resistance is improved.
- a polyvinylidene fluoride resin film having excellent and practical mechanical strength characteristics and suitable as a back sheet for a solar cell module can be obtained.
- the polyvinylidene fluoride resin composition (hereinafter also simply referred to as a resin composition) according to the first embodiment of the present invention will be described.
- a resin composition of the present embodiment at least a white inorganic pigment and a toning inorganic pigment are blended in a resin component composed of two types of PVDF and PMMA having different forms.
- PVDF 50 to 95% by mass in total in resin components
- PVDF is excellent in weather resistance and heat resistance, and is a main component of the resin composition of the present embodiment.
- MFR MFR of less than 3 g / 10 min
- the dispersion of the white inorganic pigment and the toning inorganic pigment with respect to PVDF is lowered, and defects when formed into a film are likely to occur.
- both types of PVDF have an MFR exceeding 35 g / 10 min, the mechanical performance such as the tensile strength of the film is lowered and the moldability is also lowered.
- one or both of PVDF has an MFR (Melt Flow Rate) measured at a temperature of 230 ° C. and a load of 3.8 kg according to A method of JIS K 7210 at 3 to 35 g / Use 10 min of resin.
- the MFR of PVDF is preferably 5 to 30 g / 10 min, more preferably 10 to 25 g / 10 min.
- one of the two types of PVDF is a pellet and the other is a powder.
- a pellet body and powder together, it becomes possible to obtain a high shearing force necessary for highly dispersing the pigment in the melting process of the raw material resin in the melt-kneading (compound) step.
- the powder one having an average particle diameter (median diameter) of 3 to 30 ⁇ m measured with a laser diffractometer of JIS Z 8825-1 “Particle size analysis—Laser diffraction method—Part 1: Measurement principle” is used. It is desirable to do. Thereby, the shear force in the melting process can be increased without deteriorating the handleability.
- the ratio of the pellet body to the powder in the entire PVDF is 40 to 97 mass% for the pellet body and 3 to 60 mass% for the powder.
- the proportion of the pellets is increased and the proportion of the powder is less than 3% by mass of the whole, dispersion and mixing of PVDF, the white inorganic pigment, and the inorganic pigment for toning may not be sufficient, resulting in a nonuniform composition.
- the proportion of the pellet body is small and the powder exceeds 60% by mass, the melting of PVDF is completed in a short time during the heat-kneading, so that the dispersion mixing of the white inorganic pigment and the inorganic pigment for toning is performed. Insufficient progress may result in pigment aggregates.
- a more preferable range of the ratio of the pellet body to the powder in the entire PVDF is 60 to 80% by mass for the pellet body and 20 to 40% by mass for the powder.
- the PVDF blended in the resin composition of the present embodiment may be in the range of MFR as described above, and a commercially available resin can also be used. Specifically, a homopolymer of vinylidene fluoride is preferable. However, a copolymer obtained by copolymerizing vinylidene fluoride as a main component and other fluorine-containing monomers in a range of 50% by mass or less may be used. Examples of the fluorine-containing monomer that forms a copolymer with vinylidene fluoride include known fluorine-containing monomers such as hexafluoropropylene, tetrafluoroethylene, hexafluoroisobutylene, and various fluoroalkyl vinyl ethers.
- the method for producing these resins is not particularly limited, and polymerization is performed by a general method such as suspension polymerization or emulsion polymerization.
- a closed reactor is equipped with a solvent such as water, a polymerization initiator, a suspension.
- the reactor is degassed by degassing to charge the gaseous vinylidene fluoride monomer, while controlling the reaction temperature, It can be produced by a method such as advancing polymerization.
- inorganic peroxides and organic peroxides such as persulfate are usually used, and examples thereof include di-normal propyl peroxydicarbonate (NPP) and diisopropyl peroxydicarbonate. It is done.
- Chain transfer agents include acetone, isopropyl acetate, ethyl acetate, diethyl carbonate, dimethyl carbonate, ethyl carbonate, propionic acid, trifluoroacetic acid, trifluoroethyl alcohol, formaldehyde dimethyl acetal, 1,3-butadiene epoxide, 1,4-dioxane. , ⁇ -butyl lactone, ethylene carbonate, vinylene carbonate and the like, and acetone, ethyl acetate and the like are preferably used because they are particularly easy to obtain and handle.
- suspending agent examples include water-soluble cellulose ethers such as partially saponified polyvinyl alcohol, methyl cellulose, and hydroxyethyl cellulose, water-soluble polymers such as acrylic acid polymers, and gelatin.
- the MFR of PVDF can be adjusted by the polymerization temperature, the type and amount of polymerization initiator, the type and amount of chain transfer agent, and the like. For example, when the polymerization initiator and the chain transfer agent are the same type, the MFR can be increased by increasing the polymerization temperature.
- the proportion of PVDF in the resin component is 50 to 95% by mass in total of the pellet body and the powder.
- the blending ratio of PVDF is less than 50% by mass, the dispersion of the pigment is lowered, and defects are easily generated when a film is formed.
- the blending ratio of PVDF in the resin component exceeds 95% by mass, mechanical performance such as film strength is lowered.
- the preferred range of the PVDF content in the resin component is 50 to 90% by mass (PMMA: 10 to 50% by mass), more preferably 60 to 85% by mass (PMMA: 15 to 40% by mass). .
- PMMA 5 to 50% by mass in the resin component
- the adhesiveness necessary for laminating with another substrate can be imparted.
- the blending amount of PMMA in the resin component is less than 5% by mass, sufficient adhesiveness cannot be obtained, or mechanical properties such as film strength are deteriorated.
- the blending amount of PMMA in the resin component exceeds 50% by mass, the weather resistance of the film itself is lowered, and the weather resistance required for the solar battery back sheet may not be obtained. Therefore, the PMMA content in the resin component is 5 to 50% by mass.
- PMMA blended in the resin composition of the present embodiment is not particularly limited, but is preferably composed mainly of methyl methacrylate produced by ACH method, modified ACH method, direct method, ethylene method, or the like.
- a resin excellent in weather resistance is preferred.
- main monomers that can be copolymerized with methyl methacrylate include ethyl (meth) acrylate, 2-propyl (meth) acrylate, and n-propyl (meth) acrylate.
- butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and the like can be mentioned.
- the PMMA used in the resin composition of the present embodiment has an MFR (MeltMeflow rate) of 2 to 20 g / 10 min measured according to JIS K 7210 Method A at a temperature of 230 ° C. and a load of 10 kg. Since PMMA having an MFR in this range has good compatibility with PVDF, it can have appropriate strength and flexibility without generating defects due to segregation of the resin when formed into a film.
- the MFR of PMMA is preferably 4 to 15 g / 10 min, more preferably 6 to 12 g / 10 min.
- the white inorganic pigment is blended, for example, in order to ensure the concealability required for a film used for a solar cell module backsheet.
- the amount of the white inorganic pigment is less than 7 parts by mass per 100 parts by mass of the resin component, sufficient concealability and visible light reflectance cannot be obtained.
- the blending amount of the white inorganic pigment exceeds 40 parts by mass per 100 parts by mass of the resin component, the mechanical strength when formed into a film is reduced, or appearance defects due to poor dispersion increase. Accordingly, the blending amount of the white inorganic pigment is 7 to 40 parts by mass with respect to 100 parts by mass of the resin component composed of PVDF and PMMA.
- the blending amount of the white inorganic pigment is preferably 10 to 35 parts by weight, more preferably 15 to 30 parts by weight, per 100 parts by weight of the resin component.
- the white inorganic pigment preferably has an average particle diameter (median diameter) measured by a laser diffraction apparatus specified in JIS Z 8825-1 of 0.1 to 2 ⁇ m, more preferably 0.20 to 1 ⁇ m. Thereby, the dispersibility at the time of melt-kneading becomes favorable, and a film with few appearance defects can be obtained.
- the material of the white inorganic pigment blended in the resin composition of the present embodiment is not particularly limited, and examples thereof include magnesium oxide, barium sulfate, titanium oxide, basic lead carbonate, and zinc oxide.
- examples thereof include magnesium oxide, barium sulfate, titanium oxide, basic lead carbonate, and zinc oxide.
- rutile crystal titanium dioxide having a large refractive index and coloring power and a small photocatalytic activity.
- the white inorganic pigment is preferably titanium oxide whose particle surface is coated with alumina and / or silica.
- the dispersion of the white inorganic pigment in the film is further improved, the PVDF is prevented from being thermally decomposed by catalytic action during the heat-kneading and film formation in the production of the resin composition, and when the film is used outdoors. It is possible to prevent deterioration of the light beam and ensure weather resistance.
- Inorganic pigment for toning 0.01 to 7 parts by mass with respect to 100 parts by mass of resin component
- the inorganic pigment for toning is blended in order to finely adjust the color tone when formed into a film and to improve heat resistance.
- the blending amount of the inorganic pigment for toning is less than 0.01 parts by mass per 100 parts by mass of the resin component, the coloring power and the heat resistance improvement effect cannot be sufficiently obtained.
- the blending amount of the inorganic pigment for toning exceeds 7 parts by mass per 100 parts by mass of the resin component, it becomes difficult to uniformly disperse in the resin, and the appearance defect of the film increases.
- the blending amount of the inorganic pigment for toning is 0.01 to 7 parts by mass with respect to 100 parts by mass of the resin component composed of PVDF and PMMA.
- the blending amount of the inorganic pigment for toning is preferably 0.1 to 5 parts by mass, more preferably 0.5 to 3 parts by mass per 100 parts by mass of the resin component.
- the average particle diameter of the inorganic pigment for toning is preferably from 0.1 to 2 ⁇ m, more preferably from the viewpoint of having sufficient coloring power and concealing property and suppressing the formation of aggregated particles. 20 to 1 ⁇ m.
- the average particle diameter is a median diameter measured by a laser diffractometer stipulated in JIS Z 8825-1.
- the material of the inorganic pigment for toning blended in the resin composition of the present embodiment is not particularly limited, but for example, oxides of chromium, zinc, iron, nickel, aluminum, cobalt, manganese, copper and the like
- a complex oxide pigment or the like in which several kinds selected from among them are solid-dissolved by firing can be used. Further, one or several complex oxide pigments can be mixed and used.
- this toning inorganic pigment it is preferable to coat the surface of this toning inorganic pigment with a silane coupling agent before blending.
- a silane coupling agent various silane coupling agents can be used.
- n-hexylmethoxysilane having a reactive functional group as a hexyl group and a hydrolyzable group as a methoxy group has a drawback when a film is formed. It is effective in suppressing the occurrence.
- the resin composition of the present embodiment can be obtained, for example, by melt-kneading the above-described pelletized PVDF and powdered PVDF, PMMA, white inorganic pigment, toning inorganic pigment, and the like by a general method.
- the kneading method is not particularly limited, and various mixers or kneaders equipped with a heating device such as a twin-screw extruder, a continuous type and a batch type kneader can be used.
- a twin-screw extruder a continuous type and a batch type kneader
- the most suitable apparatus for melt kneading from the viewpoint of versatility is a twin screw extruder.
- a polyvinylidene fluoride resin film can be obtained by melt-kneading the resin composition of this embodiment in the temperature range of 150 to 260 ° C. and then extrusion molding.
- the film forming method is not particularly limited and can be formed by a general method, but a method of forming a film using a T-die for film by an extruder is preferable.
- the raw material may be supplied by using the resin composition prepared by melt-kneading by the above-mentioned method, but the individual raw materials are mixed and directly fed to a single-screw or twin-screw extruder for melting.
- the film may be formed by kneading and extrusion molding through a film T-die.
- the temperature of the melt kneading is less than 150 ° C, the amount of heat necessary for melting the PDVF may be insufficient, and if it exceeds 260 ° C, the PDVF may be thermally decomposed. Therefore, the temperature during melt-kneading is in the range of 150 to 260 ° C.
- the polyvinylidene fluoride resin film formed by the above-described method can be used as a back sheet for a solar cell module by laminating and bonding polyethylene terephthalate (PET) films. Bonding of these films can be performed using various adhesives.
- PET polyethylene terephthalate
- This back sheet can be suitably used for a solar cell module.
- a sheet of thermoplastic resin such as EVA called a sealing material
- the back sheet using a film made of the resin composition of the present embodiment is , And can be bonded by a hot press at 100 to 150 ° C.
- the resin composition of the present embodiment two types of PDVF having different forms such as a pellet and a powder are used in combination, and one or both MFRs are set to 3 to 35 g / 10 min.
- a high shear force necessary for highly dispersing the pigment can be obtained.
- the dispersibility of the white inorganic pigment and the toning inorganic pigment can be improved, and there are few defects due to poor dispersion, and a film having excellent weather resistance and mechanical strength characteristics can be obtained.
- the resin composition of the present embodiment is the same as the resin composition of the first embodiment described above except that two types of PVDF having different melt flow characteristics are blended.
- PVDF 50 to 95% by mass in total in resin components
- two types of PVDF PVDF1 and PVDF2 having different melt flow characteristics are used. These resins may be in the form of pellets or powders, and may be used by mixing them.
- the melt flow characteristics of the respective raw resin components shown below are values measured by the MFR (Melt Flow Rate) measurement method defined in the A method of JIS K 7210 unless otherwise specified.
- PVDF1 One of the two types of PVDF (PVDF1) has an MFR measured at a temperature of 230 ° C. and a load of 3.8 kg of 3 to 35 g / 10 min, preferably 5 to 30 g / 10 min, more preferably 10 to 25 g / 10 min. Use one.
- the other (PDVF2) has an MFR of 2 to 30 g / 10 min, preferably 10 to 27 g / 10 min, more preferably 15 to 25 g / 10 min measured at a temperature of 230 ° C. and a load of 10 kg.
- PVDF2 has a remarkably low MFR, and does not fall within the range described in the above-mentioned JIS under the same measurement conditions as PVDF1, so it is shown by a measurement value at a higher load.
- PVDF1 with an MFR of 3 to 35 g / 10 min when the temperature is 230 ° C. and the load is 3.8 kg is measured at a temperature of 230 ° C. and a load of 10 kg.
- MFR is 50 to 160 g / 10 min.
- the dispersibility of the inorganic pigment when melt kneaded is improved.
- the PVDF1 temperature is 230 ° C. and the MFR at a load of 3.8 kg is less than 3 g / 10 min
- the dispersibility of the inorganic pigment in the resin composition is lowered, and defects in the film are likely to occur.
- MFR on this condition in PVDF1 exceeds 35 g / 10min, while dispersibility of an inorganic pigment will fall, the tensile strength when it will be set as a film will fall.
- the dispersion of the white inorganic pigment and the inorganic pigment for toning is dispersed. Can be improved. Thereby, there are few defects due to poor dispersion, and a film excellent in weather resistance and mechanical strength characteristics can be obtained.
- the dispersibility of the pigment can be further improved by using one of two types of PDVFs having different melt flow characteristics as a pellet and the other as a powder, so that a film with extremely few defects can be realized. .
- Example 1 (1) Preparation of inorganic pigment for toning: Black inorganic pigment powder made of chromium, manganese and copper oxide solid solution: 0.8 kg, brown pigment powder made of zinc, iron, nickel and aluminum oxide solid solution: An inorganic pigment for toning was produced by mixing 6 kg of blue pigment powder consisting of cobalt aluminate: 0.6 kg with a dry mixer. Next, 0.03 kg of n-hexyltrimethoxysilane was added to a mixed solution of 0.1 mass% acetic acid aqueous solution: 0.3 kg and ethanol: 0.3 kg to prepare a silane coupling agent solution.
- the inorganic pigment for toning was prepared to the mixer, and the silane coupling agent solution was dripped and mixed, stirring. After mixing, the product was taken out, dried in a dryer, and then pulverized into a powder.
- the average particle diameter (median diameter) of the obtained inorganic pigment for toning was 0.3 ⁇ m.
- Resin component A resin having the following physical properties was used as the resin component.
- MFR was measured by the measuring method prescribed
- the average particle diameter (median diameter) is determined by the dry screening test method of JIS K 0069 “Chemical product screening test method” for pellets, and JIS Z 8825-1 “Particle size analysis-laser diffraction method- Measurement was performed with a laser diffraction apparatus of “Part 1: measurement principle”.
- a pellet-shaped resin composition was obtained through a strand die having a hole diameter of 3 mm and 3 holes.
- the composition of each component of the obtained resin composition is PVDF (A) 60 mass parts, PVDF (B) 20 mass parts, PMMA 20 mass parts, white inorganic pigment 20 mass parts, for toning
- the inorganic pigment was 3 parts by mass.
- Example 2 Comparative Examples 1, 2, 9 to 12 Evaluation was performed in the same manner as in Example 1 except that the supply amount of the quantitative feeder of each raw material component was adjusted to change the composition ratio of each component in the resin composition.
- PVDF (A) for pellets and PVDF (B) for powder PVDF resins having MFR of 5 g / 10 min, 33 g / 10 min, 1 g / 10 min, and 40 g / 10 min at a temperature of 230 ° C. and a load of 3.8 kg, respectively. Evaluation was performed in the same manner as in Example 1 except that it was used.
- Examples 6 and 7, Comparative Examples 5 and 6) As the PMMA resin, the same method as in Example 1 described above except that MFR at a temperature of 230 ° C. and a load of 10 kg is 4 g / 10 min, 18 g / 10 min, 1 g / 10 min, and 25 g / 10 min, respectively. Was evaluated.
- Example 7 The PVDF resin was evaluated in the same manner as in Example 1 except that 80 parts by mass of powdered PVDF (B) was used without using pelletized PVDF (A).
- Example 8 Evaluation was performed in the same manner as in Example 1 except that PVDF (B) in powder form was not used as PVDF resin but only 80 parts by mass of PVDF (A) in pellet form was used.
- the resin compositions of Examples 1 to 14 have a significantly reduced number of film defects compared to the resin compositions of Comparative Examples 1 to 12 that are outside the scope of the present invention. It was. As a result, when two types of PVDF, a pellet body and a powder having an MFR within a specific range, are used in combination, there are few defects due to poor dispersion, excellent weather resistance, practical mechanical strength characteristics, It was confirmed that a polyvinylidene fluoride resin film suitable as a module back sheet was obtained.
- a polyvinylidene fluoride resin composition using two types of PVDF having different melt flow characteristics was prepared, and the film characteristics were evaluated.
- Example 21 (1) Preparation of pigment for toning: Black inorganic pigment powder composed of oxide solid solution of chromium, manganese and copper: 0.8 kg, Brown pigment powder composed of oxide solid solution of zinc, iron, nickel and aluminum: 1.6 kg A blue pigment powder composed of cobalt aluminate: 0.6 kg was mixed with a dry mixer to produce an inorganic pigment for toning. Next, 0.03 kg of n-hexyltrimethoxysilane was added to a mixed solution of 0.1 mass% acetic acid aqueous solution: 0.3 kg and ethanol: 0.3 kg to prepare a silane coupling agent solution.
- the inorganic pigment for toning was prepared to the mixer, and the silane coupling agent solution was dripped and mixed, stirring. After mixing, the product was taken out, dried in a dryer, and then pulverized into a powder.
- the average particle diameter (median diameter) of the obtained inorganic pigment for toning was 0.3 ⁇ m.
- Resin component The following resin was used for the resin component.
- MFR was measured by the measuring method prescribed
- ⁇ PVDF1> A polyvinylidene fluoride resin having an MFR (temperature: 230 ° C., load: 3.8 kg) of 20 g / 10 min.
- ⁇ PVDF2> A polyvinylidene fluoride resin having an MFR (temperature: 230 ° C., load: 10 kg) of 20 g / 10 min.
- inorganic pigment for toning which was surface-coated with the silane coupling agent described above: 3 kg and titanium dioxide powder of rutile crystal as white inorganic pigment (median diameter: 0.3 ⁇ m): 20 kg Were mixed with a mixer.
- composition of each component in the obtained resin composition is as follows: PVDF1 is 35 parts by mass (28% by mass), PVDF2 is 45 parts by mass (37% by mass), PMMA is 20 parts by mass (16% by mass), and the white inorganic pigment is 20 parts by mass (16% by mass) and 3 parts by mass (2% by mass) of the toning pigment were used.
- Example 22 to 27 Comparative Examples 21 to 26 Evaluation was carried out in the same manner as in Example 21 described above, except that the feed rate of the quantitative feeder for each raw material component was adjusted to change the composition ratio of each component in the resin composition.
- Example 28 and 29, Comparative Examples 27 and 28 The examples described above except that polyvinylidene fluoride resin having MFR at a temperature of 230 ° C. and a load of 3.8 kg of 5 g / 10 min, 33 g / 10 min, 2 g / 10 min, and 40 g / 10 min, respectively, was used for PVDF1. Evaluation was performed in the same manner as in No. 21.
- Example 30 and 31 Comparative Examples 29 and 30
- PVDF2 polyvinylidene fluoride resin having MFR at a temperature of 230 ° C. and a load of 10 kg of 4 g / 10 min, 30 g / 10 min, 1 g / 10 min, and 35 g / 10 min, respectively, as in Example 21 described above. Evaluation was performed in the same manner.
- Example 21 As PMMA, Example 21 described above was used except that a polymethyl methacrylate resin having MFR of 2 g / 10 min, 20 g / 10 min, 1 g / 10 min, and 27 g / 10 min at a temperature of 230 ° C. and a load of 10 kg was used. Evaluation was performed in the same manner.
- Examples 34 to 37, Comparative Examples 33 to 36 Evaluation was carried out in the same manner as in Example 21 except that the blending ratio of the white inorganic pigment or the toning inorganic pigment was changed.
- the evaluation results of Examples 34 to 37 and Comparative Examples 33 to 36 are summarized in Table 7 below.
- the resin compositions of Examples 21 to 37 had a greatly reduced number of film defects compared to the compositions of Comparative Examples 21 to 36 that were outside the scope of the present invention. .
- the resin compositions of Examples 21 to 37 had a greatly reduced number of film defects compared to the compositions of Comparative Examples 21 to 36 that were outside the scope of the present invention.
- the resin compositions of Examples 21 to 37 had a greatly reduced number of film defects compared to the compositions of Comparative Examples 21 to 36 that were outside the scope of the present invention.
- two types of PVDF having different melt flow characteristics are used in combination, there are few defects due to poor dispersion, excellent weather resistance, practical mechanical strength characteristics, and suitable for use as a back sheet for solar cell modules. It was confirmed that a vinylidene resin film was obtained.
- the polyvinylidene fluoride resin composition of the present invention has very few defects due to poor dispersion of the pigment, and a film having excellent weather resistance and total light reflectance of visible light can be obtained, it is particularly useful for backsheets of solar cell modules. As a material, it can be expected to contribute to the extension of the lifetime of solar cells. Moreover, since the film obtained from the resin composition of this invention has high heat resistance and insulation, it can also be utilized as a protective film in the electric / electronic field, an interior / exterior protective film for buildings and automobiles.
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Abstract
Description
この組成物では、2種類のポリフッ化ビニリデンのうち、一方をペレット体とし、他方を粉体としてもよい。
その場合、ペレット体のポリフッ化ビニリデンとして、例えばJIS K 0069で規定されている乾式ふるい分け試験法により測定した平均粒子径(メジアン径)が1~6mmのものを使用すると共に、粉体のポリフッ化ビニリデンとして、例えばJIS Z 8825-1に規定されているレーザー回折装置により測定した平均粒子径(メジアン径)が3~30μmのものを使用し、ポリフッ化ビニリデン全体におけるペレット体の割合を40~97質量%、粉体の割合を3~60質量%とすることができる。
又は、JIS K 7210のA法により、温度を230℃、荷重を3.8kgとして測定したMFR(Melt Flow Rate)が3~35g/10minであるポリフッ化ビニリデンと、JIS K 7210のA法により、温度を230℃、荷重を10kgとして測定したMFR(Melt Flow Rate)が2~30g/10minであるポリフッ化ビニリデンと、を含有させてもよい。
また、白色無機顔料としては、例えばJIS Z 8825-1に規定されているレーザー回折装置により測定した平均粒子径(メジアン径)が0.1~2μmのものを使用することができる。
更に、調色用無機顔料としては、例えばJIS Z 8825-1に規定されているレーザー回折装置により測定した平均粒子径(メジアン径)が0.1~2μmのものを使用することができる。
また、本発明に係る太陽電池モジュール用バックシートは、前述したポリフッ化ビニリデン系樹脂フィルムと、ポリエチレンテレフタレート系樹脂フィルムとを積層したものである。
更に、本発明に係る太陽電池モジュールは、前述したバックシートを用いたものである。
先ず、本発明の第1の実施形態に係るポリフッ化ビニリデン系樹脂組成物(以下、単に樹脂組成物ともいう。)について説明する。本実施形態の樹脂組成物は、形態が異なる2種類のPVDFとPMMAとからなる樹脂成分に、少なくとも、白色無機顔料及び調色用無機顔料が配合されている。
PVDFは、耐候性及び耐熱性に優れており、本実施形態の樹脂組成物の主成分である。しかしながら、配合するPVDFを、2種類ともMFRが3g/10min未満のものにすると、PVDFに対する白色無機顔料及び調色用無機顔料の分散が低下し、フィルムとした時の欠点が発生しやすくなる。一方、PVDFを、2種類ともMFRが35g/10minを超えるものにすると、フィルムの引っ張り強度等の機械的性能が低下すると共に、成形性が低下する。
PVDFにPMMA配合すると、フィルムなどに加工した際に、他の基材と積層するために必要な接着性を付与することができる。しかしながら、樹脂成分中のPMMAの配合量が5質量%未満の場合、十分な接着性が得られなかったり、フィルム強度等の機械的特性が低下したりする。一方、樹脂成分中のPMMAの配合量が50質量%超になると、フィルム自体の耐候性が低下し、太陽電池バックシートに必要な耐候性が得られない虞がある。よって、樹脂成分中のPMMA含有量は5~50質量%とする。
白色無機顔料は、例えば太陽電池モジュール用バックシートに使用されるフィルムに必要とされる隠蔽性を確保するために配合されている。しかしながら、白色無機顔料の配合量が樹脂成分100質量部あたり7質量部未満であると、十分な隠蔽性や可視光の光線反射率が得られない。一方、白色無機顔料の配合量が樹脂成分100質量部あたり40質量部を超えると、フィルムにしたときの機械的強度が低下したり、分散不良による外観欠陥の発生が多くなったりする。よって、白色無機顔料の配合量は、PVDFとPMMAからなる樹脂成分100質量部に対して7~40質量部とする。
調色用無機顔料は、フィルムにしたときの色調を微調整すると共に、耐熱性を向上させるために配合されている。しかしながら、調色用無機顔料の配合量が樹脂成分100質量部あたり0.01質量部未満であると、着色力や耐熱性向上効果が十分に得られない。一方、調色用無機顔料の配合量が樹脂成分100質量部あたり7質量部を超えると、樹脂中に均一に分散させることが困難になり、フィルムの外観欠陥が増加する。よって、調色用無機顔料の配合量は、PVDFとPMMAからなる樹脂成分100質量部に対して0.01~7質量部とする。なお、調色用無機顔料の配合量は、樹脂成分100質量部あたり、0.1~5質量部であることが好ましく、更に好ましくは0.5~3質量部である。
本実施形態の樹脂組成物は、例えば前述したペレット体のPVDFと粉体のPVDF、PMMA、白色無機顔料及び調色用無機顔料等を一般的な方法で溶融混練することにより得られる。その混練方法は特に限定されるものではないが、二軸押出機、連続式及びバッチ式のニーダー等の加熱装置を備えた各種混合機又は混練機を使用することができる。なお、汎用性の面から溶融混練に最適な装置は、二軸押出機である。
本実施形態の樹脂組成物は、150~260℃の温度範囲で溶融混練した後、押出成形することにより、ポリフッ化ビニリデン系樹脂フィルムを得ることができる。その製膜方法は特に限定されるものではなく、一般的な方法で製膜できるが、押出機によりフィルム用Tダイを用いて製膜する方法が好ましい。その際、原料の供給は、前述した方法で溶融混練して作成した樹脂組成物を用いてもよいが、個々の原料を混合して、直接単軸又は二軸の押出機に供給して溶融混練し、フィルム用Tダイを通して押出成形することにより製膜してもよい。
前述した方法で形成されたポリフッ化ビニリデン系樹脂フィルムは、ポリエチレンテレフタレート(PET)系フィルムを積層し、貼り合わせることにより、太陽電池モジュール用のバックシートとすることができる。これらのフィルムの貼り合わせには、各種接着剤による接着が可能である。
次に、本発明の第2の実施形態に係るポリフッ化ビニリデン系樹脂組成物について説明する。本実施形態の樹脂組成物は、溶融流動特性が異なる2種類のPVDFを配合している以外は、前述した第1の実施形態の樹脂組成物と同様である。
本実施形態の樹脂組成物では、溶融流動特性が異なる2種類のPVDF(PVDF1及びPVDF2)を使用する。これらの樹脂はペレット形状のものでも粉状のものであってもよく、これらを混合して用いてもよい。なお、以下に示す各原料樹脂成分の溶融流動特性は、特に断らない限り、JIS K 7210のA法に規定されたMFR(Melt Flow Rate)の測定法により測定した値である。
(1)調色用無機顔料の調製
クロム、マンガン及び銅の酸化物固溶体からなる黒色の無機顔料粉末:0.8kg、亜鉛、鉄、ニッケル及びアルミニウムの酸化物固溶体からなる茶色顔料粉末:1.6kg、アルミン酸コバルトからなる青色顔料粉末:0.6kgを、乾式の混合機で混ぜ合わせて、調色用無機顔料を製造した。次に、0.1質量%酢酸水溶液:0.3kgとエタノール:0.3kgの混合液に、n-ヘキシルトリメトキシシラン:0.03kgを添加し、シランカップリング剤溶液を調製した。そして、調色用無機顔料をミキサーに仕込み、攪拌しながら、シランカップリング剤溶液を滴下して混合した。混合後、取り出して、乾燥機にて乾燥した後、粉砕して粉末状にした。得られた調色用無機顔料の平均粒子径(メジアン径)は、0.3μmであった。
樹脂成分には、下記の物性を有する樹脂を用いた。なお、MFRはJIS K 7210のA法に規定された測定法により測定した。また、平均粒子径(メジアン径)は、ペレット体はJIS K 0069「化学製品のふるい分け試験方法」の乾式ふるい分け試験方法で、粉体はJIS Z 8825-1「粒子径解析-レーザー回折法-第1部:測定原理」のレーザー回折装置により測定した。
MFR(温度:230℃、荷重:3.8kg)が20g/10minで、平均粒子径(メジアン径)が3mmであるペレット体のポリフッ化ビニリデン樹脂。
<PVDF(B)>
MFR(温度:230℃、荷重:3.8kg)が20g/10minで、平均粒子径(メジアン径)が10μmである粉体のポリフッ化ビニリデン樹脂。
<PMMA>
MFR(温度:230℃、荷重:10kg)が9g/10minであるポリメタクリル酸メチル樹脂。
先ず、前述したシランカップリング剤で表面コートした調色用無機顔料:3kgと、白色無機顔料としてルチル型結晶の二酸化チタン粉末(メジアン径:0.3μm):20kgをミキサーにて混合した。次に、樹脂組成物調製のための混練装置として、スクリュー径30mm、L/D=40の二軸押出機に、前述した調色用無機顔料、PVDF(A)、PVDF(B)及びPMMAを、それぞれ個別の定量フィーダーにて、各成分の配合比に対応する速度で供給して溶融混練した。その後、穴径3mm、3穴のストランドダイを通してペレット状の樹脂組成物を得た。そして、得られた樹脂組成物の各成分の組成は、PVDF(A)が60質量部、PVDF(B)が20質量部、PMMAが20質量部、白色無機顔料が20質量部、調色用無機顔料が3質量部であった。
得られた樹脂組成物を、スクリュー径40mm、L/D=30の単軸押出機に幅400mmのTダイを取り付けた製膜機にて、スクリュー回転数:35rpm、バレル設定温度:240℃で押出し、フィルム幅:300mm、平均厚さ:18μmのフィルムを製膜した。得られたフィルムの欠点の評価として、巻き取ったフィルム(幅300mm×長さ2000m)について、欠点検出器を用いて50m2内の欠点数を評価した。なお、本実施例では、欠点数評価の目安として、フィルムの欠点サイズが0.05mm以上のものの個数を数えた。
得られたフィルムについて、JIS K 7127に規定されている方法で、引張り強度を測定した。なお、引張り強度の測定では、試料幅を10mm、チャック間距離を40mmとした。また、併せて、JIS K 7105に準拠して、可視光の全光線反射率を評価した。
各原料成分の定量フィーダーの供給量を調整して、樹脂組成物中の各成分の組成比率を変更した以外は、実施例1と同様の方法で評価を行った。
ペレット体のPVDF(A)及び粉体のPVDF(B)として、温度:230℃、荷重3.8kgにおけるMFRが、それぞれ5g/10min、33g/10min、1g/10min、40g/10minのPVDF樹脂を用いた以外は、前述した実施例1と同様の方法で評価を行った。
PMMAの樹脂として、温度:230℃、荷重:10kgにおけるMFRが、それぞれ4g/10min、18g/10min、1g/10min、25g/10minのものを用いた以外は、前述した実施例1と同様の方法で評価を行った。
PVDF樹脂として、ペレット体のPVDF(A)を用いず、粉体のPVDF(B)のみを80質量部用いた以外は、前述した実施例1と同様の方法で評価を行った。
PVDF樹脂として、粉体のPVDF(B)を用いず、ペレット体のPVDF(A)のみを80質量部用いた以外は、前述した実施例1と同様の方法で評価を行った。
(1)調色用顔料の調製
クロム、マンガン及び銅の酸化物固溶体からなる黒色の無機顔料粉末:0.8kg、亜鉛、鉄、ニッケル及びアルミニウムの酸化物固溶体からなる茶色顔料粉末:1.6kg、アルミン酸コバルトからなる青色顔料粉末:0.6kgを、乾式の混合機で混ぜ合わせて、調色用無機顔料を製造した。次に、0.1質量%酢酸水溶液:0.3kgとエタノール:0.3kgの混合液に、n-ヘキシルトリメトキシシラン:0.03kgを添加し、シランカップリング剤溶液を調製した。そして、調色用無機顔料をミキサーに仕込み、攪拌しながら、シランカップリング剤溶液を滴下して混合した。混合後、取り出して、乾燥機にて乾燥した後、粉砕して粉末状にした。得られた調色用無機顔料の平均粒子径(メジアン径)は、0.3μmであった。
樹脂成分には、下記の樹脂を用いた。なお、MFRはJIS K 7210のA法に規定された測定法により測定した。
<PVDF1>
MFR(温度:230℃、荷重:3.8kg)が20g/10minであるポリフッ化ビニリデン樹脂。
<PVDF2>
MFR(温度:230℃、荷重:10kg)が20g/10minであるポリフッ化ビニリデン樹脂。
<PMMA>
MFR(温度:230℃、荷重:10kg)が9g/10minであるポリメタクリル酸メチル樹脂。
先ず、前述したシランカップリング剤で表面コートした調色用無機顔料:3kgと、白色無機顔料としてルチル型結晶の二酸化チタン粉末(メジアン径:0.3μm):20kgをミキサーにて混合した。次に、樹脂組成物調製のための混練装置として、スクリュー径30mm、L/D=40の二軸押出機に、前述した調色用無機顔料、PVDF1、PVDF2及びPMMAを、それぞれ個別の定量フィーダーにて、各成分の配合比に対応する速度で供給して溶融混練した。その後、穴径3mm、3穴のストランドダイを通してペレット状の樹脂組成物を得た。
得られた樹脂組成物を、スクリュー径40mm、L/D=30の単軸押出機に幅400mmのTダイを取り付けた製膜機にて、スクリュー回転数:35rpm、バレル設定温度:240℃で押出し、フィルム幅:300mm、平均厚さ:18μmのフィルムを製膜した。得られたフィルムの欠点の評価として、巻き取ったフィルム(幅300mm×長さ2000m)について、欠点検出器を用いて50m2内の欠点数を評価した。なお、本実施例では、欠点数評価の目安として、フィルムの欠点サイズが0.05mm以上のものの個数を数えた。
得られたフィルムについて、JIS K 7127に規定されている方法で、引張り強度を測定した。なお、引張り強度の測定では、試料幅を10mm、チャック間距離を40mmとした。また、併せて、JIS K 7105に準拠して、可視光の全光線反射率を評価した。
各原料成分の定量フィーダーの供給量を調整して、樹脂組成物中の各成分の組成比率を変更した以外は、前述した実施例21と同様の方法で評価を行った。
PVDF1に、温度:230℃、荷重:3.8kgにおけるMFRが、それぞれ、5g/10min、33g/10min、2g/10min、40g/10minであるポリフッ化ビニリデン樹脂を用いた以外は、前述した実施例21と同様の方法で、評価を行った。
PVDF2に、温度:230℃、荷重:10kgにおけるMFRが、それぞれ、4g/10min、30g/10min、1g/10min、35g/10minであるポリフッ化ビニリデン樹脂を用いた以外は、前述した実施例21と同様の方法で、評価を行った。
PMMAとして、温度:230℃、荷重:10kgにおけるMFRが、それぞれ、2g/10min、20g/10min、1g/10min、27g/10minであるポリメチルメタクリレート樹脂を用いた以外は、前述した実施例21と同様の方法で、評価を行った。
白色無機顔料又は調色無機顔料の配合比率を変更した以外は、前述した実施例21と同様の方法で、評価を行った。これらの実施例34~37及び比較例33~36の評価結果を、下記表7にまとめて示す。
Claims (9)
- 2種類のポリフッ化ビニリデン:合計で50~95質量%及びポリメタクリル酸メチル:5~50質量%からなる樹脂成分を100質量部と、
白色無機顔料を7~40質量部と、
調色用無機顔料を0.01~7質量部と、を含有し、
2種類のポリフッ化ビニリデンのうち少なくとも1種は、JIS K 7210のA法により、温度を230℃、荷重を3.8kgとして測定したMFR(Melt Flow Rate)が3~35g/10minであり、
ポリメタクリル酸メチルは、JIS K 7210のA法により、温度を230℃、荷重を10kgにして測定したMFR(Melt flow rate)が2~20g/10minであるポリフッ化ビニリデン系樹脂組成物。 - 2種類のポリフッ化ビニリデンは、一方がペレット体であり、他方が粉体であることを特徴とする請求項1に記載のポリフッ化ビニリデン系樹脂組成物。
- ペレット体のポリフッ化ビニリデンは、JIS K 0069で規定されている乾式ふるい分け試験法により測定した平均粒子径(メジアン径)が1~6mmであり、
粉体のポリフッ化ビニリデンは、JIS Z 8825-1に規定されているレーザー回折装置により測定した平均粒子径(メジアン径)が3~30μmであり、
ポリフッ化ビニリデン全体におけるペレット体の割合が40~97質量%、粉体の割合が3~60質量%であることを特徴とする請求項2に記載のポリフッ化ビニリデン系樹脂組成物。 - JIS K 7210のA法により、温度を230℃、荷重を3.8kgとして測定したMFR(Melt Flow Rate)が3~35g/10minであるポリフッ化ビニリデンと、
JIS K 7210のA法により、温度を230℃、荷重を10kgとして測定したMFR(Melt Flow Rate)が2~30g/10minであるポリフッ化ビニリデンと、
を含有することを特徴とする請求項1乃至3のいずれか1項に記載のポリフッ化ビニリデン系樹脂組成物。 - 白色無機顔料は、JIS Z 8825-1に規定されているレーザー回折装置により測定した平均粒子径(メジアン径)が0.1~2μmであることを特徴とする請求項1乃至4のいずれか1項に記載のポリフッ化ビニリデン系樹脂組成物。
- 調色用無機顔料は、JIS Z 8825-1に規定されているレーザー回折装置により測定した平均粒子径(メジアン径)が0.1~2μmであることを特徴とする請求項1乃至5のいずれか1項に記載のポリフッ化ビニリデン系樹脂組成物。
- 請求項1~6のいずれか1項に記載のポリフッ化ビニリデン系樹脂組成物を、150~260℃の温度範囲で溶融混練した後、押出成形して得たポリフッ化ビニリデン系樹脂フィルム。
- 請求項7に記載のポリフッ化ビニリデン系樹脂フィルムと、ポリエチレンテレフタレート系樹脂フィルムとを積層した太陽電池モジュール用バックシート。
- 請求項8に記載のバックシートを用いた太陽電池モジュール。
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EP10833081.2A EP2508563B1 (en) | 2009-11-30 | 2010-11-11 | Polyvinylidene fluoride resin composition, film, back sheet, and solar cell module |
JP2011543205A JP5763548B2 (ja) | 2009-11-30 | 2010-11-11 | ポリフッ化ビニリデン系樹脂組成物、フィルム、バックシート及び太陽電池モジュール |
KR1020127006724A KR101752178B1 (ko) | 2009-11-30 | 2010-11-11 | 폴리불화비닐리덴계 수지조성물, 필름, 백시트 및 태양전지 모듈 |
CN201080054038.7A CN102666715B (zh) | 2009-11-30 | 2010-11-11 | 聚偏氟乙烯系树脂组合物、薄膜、背板及太阳能电池组件 |
US13/501,276 US8722791B2 (en) | 2009-11-30 | 2010-11-11 | Polyvinylidene fluoride resin composition, film, back sheet, and solar cell module |
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CN108164889A (zh) * | 2017-11-22 | 2018-06-15 | 山东华夏神舟新材料有限公司 | 高强度高韧性pvdf太阳能背板膜材料及其制备方法 |
CN108164889B (zh) * | 2017-11-22 | 2019-12-27 | 山东华夏神舟新材料有限公司 | 高强度高韧性pvdf太阳能背板膜材料及其制备方法 |
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US8722791B2 (en) | 2014-05-13 |
EP2508563A4 (en) | 2013-05-15 |
JPWO2011065234A1 (ja) | 2013-04-11 |
CN102666715A (zh) | 2012-09-12 |
US20120196971A1 (en) | 2012-08-02 |
JP5763548B2 (ja) | 2015-08-12 |
EP2508563B1 (en) | 2017-04-26 |
CN102666715B (zh) | 2014-06-25 |
KR20120102038A (ko) | 2012-09-17 |
TW201129624A (en) | 2011-09-01 |
EP2508563A1 (en) | 2012-10-10 |
KR101752178B1 (ko) | 2017-06-29 |
TWI490261B (zh) | 2015-07-01 |
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