JP4803317B2 - Easy-adhesive polyester film for solar cell and back sheet using the same - Google Patents
Easy-adhesive polyester film for solar cell and back sheet using the same Download PDFInfo
- Publication number
- JP4803317B2 JP4803317B2 JP2010257656A JP2010257656A JP4803317B2 JP 4803317 B2 JP4803317 B2 JP 4803317B2 JP 2010257656 A JP2010257656 A JP 2010257656A JP 2010257656 A JP2010257656 A JP 2010257656A JP 4803317 B2 JP4803317 B2 JP 4803317B2
- Authority
- JP
- Japan
- Prior art keywords
- polyester film
- mass
- solar cells
- adhesive polyester
- coating layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- 229920006267 polyester film Polymers 0.000 title claims description 98
- 239000000853 adhesive Substances 0.000 title claims description 78
- 239000011247 coating layer Substances 0.000 claims description 69
- 230000001070 adhesive effect Effects 0.000 claims description 61
- 125000001931 aliphatic group Chemical group 0.000 claims description 48
- 239000004417 polycarbonate Substances 0.000 claims description 48
- 229920000515 polycarbonate Polymers 0.000 claims description 48
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 43
- 239000003566 sealing material Substances 0.000 claims description 40
- 239000010410 layer Substances 0.000 claims description 37
- 239000003431 cross linking reagent Substances 0.000 claims description 33
- -1 aliphatic diamine Chemical class 0.000 claims description 32
- 229920005862 polyol Polymers 0.000 claims description 32
- 150000003077 polyols Chemical class 0.000 claims description 29
- 238000002835 absorbance Methods 0.000 claims description 24
- 229920005989 resin Polymers 0.000 claims description 24
- 239000011347 resin Substances 0.000 claims description 24
- 239000000470 constituent Substances 0.000 claims description 21
- 239000005056 polyisocyanate Substances 0.000 claims description 21
- 229920001228 polyisocyanate Polymers 0.000 claims description 21
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000000758 substrate Substances 0.000 claims description 13
- 239000004970 Chain extender Substances 0.000 claims description 10
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 10
- 239000012948 isocyanate Substances 0.000 claims description 10
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 10
- 150000002513 isocyanates Chemical class 0.000 claims description 9
- 230000009477 glass transition Effects 0.000 claims description 8
- 238000010030 laminating Methods 0.000 claims description 8
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 8
- 150000001718 carbodiimides Chemical class 0.000 claims description 7
- 238000002329 infrared spectrum Methods 0.000 claims description 6
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 5
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 4
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical group CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 2
- 239000002245 particle Substances 0.000 description 64
- 239000010408 film Substances 0.000 description 46
- 229920005749 polyurethane resin Polymers 0.000 description 46
- 239000000243 solution Substances 0.000 description 46
- 238000000034 method Methods 0.000 description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 37
- 239000007787 solid Substances 0.000 description 36
- 238000000576 coating method Methods 0.000 description 34
- 239000011248 coating agent Substances 0.000 description 32
- 150000002009 diols Chemical class 0.000 description 28
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 24
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 21
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 18
- 229920000139 polyethylene terephthalate Polymers 0.000 description 17
- 239000005020 polyethylene terephthalate Substances 0.000 description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 14
- 239000002184 metal Substances 0.000 description 14
- 238000006116 polymerization reaction Methods 0.000 description 13
- 239000004094 surface-active agent Substances 0.000 description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
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- 239000000203 mixture Substances 0.000 description 12
- 229920000728 polyester Polymers 0.000 description 12
- 238000001035 drying Methods 0.000 description 11
- 239000007788 liquid Substances 0.000 description 11
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- 229920001730 Moisture cure polyurethane Polymers 0.000 description 10
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 150000003839 salts Chemical group 0.000 description 9
- 239000000523 sample Substances 0.000 description 9
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 9
- 229910052710 silicon Inorganic materials 0.000 description 9
- 239000010703 silicon Substances 0.000 description 9
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 8
- 238000004132 cross linking Methods 0.000 description 8
- 230000007423 decrease Effects 0.000 description 8
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 229920002799 BoPET Polymers 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 7
- 239000010954 inorganic particle Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000010409 thin film Substances 0.000 description 7
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 239000012295 chemical reaction liquid Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000012975 dibutyltin dilaurate Substances 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 6
- 239000000741 silica gel Substances 0.000 description 6
- 229910002027 silica gel Inorganic materials 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000004566 IR spectroscopy Methods 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 5
- 238000009775 high-speed stirring Methods 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 229920001225 polyester resin Polymers 0.000 description 5
- 239000004645 polyester resin Substances 0.000 description 5
- 229920002620 polyvinyl fluoride Polymers 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000001723 curing Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000003475 lamination Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 229920005672 polyolefin resin Polymers 0.000 description 4
- 239000000565 sealant Substances 0.000 description 4
- 125000005372 silanol group Chemical group 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
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- 239000012496 blank sample Substances 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
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- XTUSEBKMEQERQV-UHFFFAOYSA-N propan-2-ol;hydrate Chemical compound O.CC(C)O XTUSEBKMEQERQV-UHFFFAOYSA-N 0.000 description 3
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- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 2
- XSCLFFBWRKTMTE-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)cyclohexane Chemical compound O=C=NCC1CCCC(CN=C=O)C1 XSCLFFBWRKTMTE-UHFFFAOYSA-N 0.000 description 2
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
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- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
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- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
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- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
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- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
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- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
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- 238000005342 ion exchange Methods 0.000 description 1
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- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 238000007759 kiss coating Methods 0.000 description 1
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- 229910052749 magnesium Inorganic materials 0.000 description 1
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- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
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- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- WBSRHBNFOLDTGU-UHFFFAOYSA-N nonane-1,8-diol Chemical compound CC(O)CCCCCCCO WBSRHBNFOLDTGU-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012858 packaging process Methods 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
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- 239000003755 preservative agent Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000047 product Substances 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
- 238000007763 reverse roll coating Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000012945 sealing adhesive Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000004368 synchrotron infrared microspectroscopy Methods 0.000 description 1
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- RKBCYCFRFCNLTO-UHFFFAOYSA-N triisopropylamine Chemical compound CC(C)N(C(C)C)C(C)C RKBCYCFRFCNLTO-UHFFFAOYSA-N 0.000 description 1
- 150000004072 triols Chemical class 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
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- 239000011667 zinc carbonate Substances 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
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Classifications
-
- 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
Landscapes
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Laminated Bodies (AREA)
- Photovoltaic Devices (AREA)
Description
本発明は、太陽電池用易接着性ポリエステルフィルムおよびそれを用いたバックシートに関する。詳しくは、太陽電池用バックシートの封止剤に接する面に用いた際に、高温高湿下においても封止剤との接着に優れたポリエステルフィルム、およびそれを用いたバックシートに関する。 The present invention relates to an easily adhesive polyester film for solar cells and a back sheet using the same. Specifically, the present invention relates to a polyester film excellent in adhesion to a sealant even under high temperature and high humidity when used on a surface of a solar cell backsheet that is in contact with the sealant, and a backsheet using the polyester film.
近年、地球温暖化の原因となる石油エネルギーに代わる、エネルギー手段として、太陽電池が注目を浴びており、その需要が高まっている。太陽電池は太陽光のエネルギーを直接電気に換える太陽光発電システムであり、太陽電池素子として、単結晶シリコン、多結晶シリコン、アモルファスシリコンなどの半導体や、化合物系、あるいは有機物系色素など使用されている。このような太陽電池素子単体を一般的に数枚〜数十枚の太陽電池素子を直列、並列に配線し、長期間(約20年以上)に亘って素子を保護するため種々のパーケージングが行われ、ユニット化されている。このパッケージに組み込まれたユニットを太陽電池モジュールと呼ぶ。 In recent years, solar cells have attracted attention as an energy means to replace petroleum energy that causes global warming, and the demand for solar cells has increased. A solar cell is a solar power generation system that directly converts solar energy into electricity. As a solar cell element, semiconductors such as single crystal silicon, polycrystalline silicon, and amorphous silicon, compound-based materials, and organic dyes are used. Yes. In order to protect such elements over a long period of time (approximately 20 years or more), such a solar cell element is generally wired in series or in parallel with several to several tens of solar cell elements. Done and unitized. A unit incorporated in this package is called a solar cell module.
ここで、太陽電池モジュールは、一般的に太陽光が当たる面をガラスで覆い、太陽電子素子を封止材で間隙を埋め、裏面をバックシートと呼ばれる耐熱、耐候性プラスチック材料などの複数の層構成からなる保護シートで保護された構成になっている。太陽電池素子を充填する封止材としてはエチレン・酢酸ビニル共重合体樹脂(以下、EVA)やポリビニルブチラール樹脂(以下、PVB)などのオレフィン系樹脂が用いられる。これらの封止材を用い、上記ガラス基板/封止材/太陽電池素子/封止材/バックシートの構成で重ね合わせ、真空ラミネーターなどで加熱圧着することによりモジュールが作製される。封止材には、太陽電池素子を接着固定するとともに、外部からの湿気の侵入を防ぎ、太陽電池素子を保護する役割がある。 Here, a solar cell module generally covers a surface to which sunlight is applied with glass, fills a gap with a sealing material for a solar electronic element, and has a plurality of layers such as a heat-resistant and weather-resistant plastic material called a back sheet on the back surface. It is the structure protected by the protective sheet which consists of a structure. As a sealing material filling the solar cell element, an olefin resin such as ethylene / vinyl acetate copolymer resin (hereinafter EVA) or polyvinyl butyral resin (hereinafter PVB) is used. Using these sealing materials, a module is produced by superposing the glass substrate / sealing material / solar cell element / sealing material / back sheet and then heat-pressing with a vacuum laminator or the like. The sealing material has a role of adhering and fixing the solar cell element, preventing moisture from entering from the outside, and protecting the solar cell element.
太陽電池用バックシートとしては、太陽電池素子側(封止材側)からポリエステルフィルム/接着剤/ポリエステルフィルム(着色)/金属、または、金属酸化物系薄膜層(防湿層)/接着剤/フッ素フィルム(防汚層)などの積層構成を有したものが提案されている。バックシートには太陽電池素子を外部の湿気や汚染から長期にわたり、保護する役目がある。そのため、封止材と直接的に接する太陽電池素子側のポリエステルフィルムと封止材との接着性は重要である。しかしながら、表面未処理のポリエステルフィルムでは、十分な接着性が得られず、改善することが求められている。ポリエステルフィルムの接着性を改善させる方法として、樹脂や架橋剤を含む接着層を設けることが提案されている(特許文献1〜4)。 As a solar cell backsheet, from the solar cell element side (encapsulant side) to polyester film / adhesive / polyester film (colored) / metal or metal oxide thin film layer (moisture-proof layer) / adhesive / fluorine Those having a laminated structure such as a film (antifouling layer) have been proposed. The backsheet serves to protect the solar cell element from external moisture and contamination over a long period of time. Therefore, the adhesiveness between the sealing material and the polyester film on the solar cell element side that is in direct contact with the sealing material is important. However, the surface untreated polyester film cannot obtain sufficient adhesiveness and is required to be improved. As a method for improving the adhesion of the polyester film, it has been proposed to provide an adhesive layer containing a resin or a crosslinking agent (Patent Documents 1 to 4).
屋外で過酷な環境条件下で使用される太陽電池モジュールは、20年以上の長寿命化が期待されている。そのため、部材として用いられる封止材易接着フィルムにおいても、初期接着性だけでなく、高温高湿下でも長期間、接着性を保持することが必要であると考えられた。しかしながら、上記特許文献に開示されるような太陽電池用易接着性ポリエステルフィルムは、いまだ接着性が不十分であり、特に高温高湿下の長期間の使用においては接着強度の低下は避けられないものであった。 Solar cell modules that are used outdoors under severe environmental conditions are expected to have a lifespan of 20 years or longer. Therefore, it was considered that not only the initial adhesiveness but also the adhesive easily adhesive film used as a member needs to maintain the adhesive property for a long period of time under high temperature and high humidity. However, the easy-adhesive polyester film for solar cells as disclosed in the above patent document still has insufficient adhesiveness, and a decrease in adhesive strength is unavoidable particularly in long-term use under high temperature and high humidity. It was a thing.
加えて、封止材には、生産性の向上や劣化防止の観点から架橋剤、紫外線吸収剤などの添加剤を含む多様な組成物種が用いられるようになってきた。また、用いる封止材により多様なパッケージング工程が採用されるようになってきている。例えば、スタンダードキュアタイプとされる封止材では、加熱圧着(例えば90〜130℃で5〜10分)の仮接着後に熱処理(例えば140〜160℃で30〜50分)を行い、ゆっくりと封止材を硬化させる接着条件が採用される。一方、ファストキュアタイプとされる封止材では、短時間で加熱圧着(例えば140〜160℃で15〜20分)を行い、急速に封止材を硬化させる接着条件が採用される。そのため、多様な封止材に対しても同程度の接着性を示す汎用性の高さだけでなく、多様な接着条件にも対応し得る汎用性の高い易接着性フィルムが求められている。 In addition, various composition types including additives such as a crosslinking agent and an ultraviolet absorber have come to be used for the sealing material from the viewpoint of improving productivity and preventing deterioration. Also, various packaging processes have been adopted depending on the sealing material used. For example, in the case of a sealing material of the standard cure type, heat treatment (for example, 30 to 50 minutes at 140 to 160 ° C.) is performed after temporary bonding by thermocompression bonding (for example, 90 to 130 ° C. for 5 to 10 minutes), and sealing is performed slowly. Adhesive conditions for curing the stop material are employed. On the other hand, in a fast-curing type sealing material, an adhesive condition is adopted in which thermocompression bonding (for example, 15 to 20 minutes at 140 to 160 ° C.) is performed in a short time and the sealing material is rapidly cured. Therefore, there is a demand for a highly versatile and easy-to-adhere film that can cope with various bonding conditions as well as high versatility that exhibits the same level of adhesion to various sealing materials.
本発明は上記課題に鑑み、過酷な環境下にも耐え得る強度な接着性を有し、従来避けられないと考えられてきた高温高湿下における接着性の低下をほとんど引き起こさず、多様な封止材に対しても良好な接着性を有する太陽電池用易接着性ポリエステルフィルムを提供するものである。 In view of the above problems, the present invention has strong adhesiveness that can withstand harsh environments, hardly causes deterioration of adhesiveness under high temperature and high humidity, which has been conventionally considered to be unavoidable, and has various sealing properties. It is an object of the present invention to provide an easily adhesive polyester film for solar cells that has good adhesion to a stopper.
本発明者は上記課題を解決するため鋭意検討を行った結果、少なくとも片面に塗布層を有するポリエステルフィルムであって、脂肪族系ポリカーボネートポリオールを構成成分とするウレタン樹脂を主成分とし、赤外分光スペクトルにおいて脂肪族系ポリカーボネート成分由来の1460cm−1付近の吸光度(A1460)とウレタン成分由来の1530cm−1付近の吸光度(A1530)との比率(A1460/A1530)が0.50〜1.55である塗布層を用いることにより、各種封止材・接着条件を用いる場合であっても過酷な環境下にも耐え得る強度な接着性を奏し、高温高湿下でも優れた接着性を奏することを見出し、本発明に至ったものである。 As a result of intensive studies to solve the above problems, the present inventor has found that a polyester film having a coating layer on at least one surface, the main component is a urethane resin having an aliphatic polycarbonate polyol as a constituent component, and infrared spectroscopy. In the spectrum, the ratio (A 1460 / A 1530 ) of the absorbance (A 1460 ) near 1460 cm −1 derived from the aliphatic polycarbonate component to the absorbance (A 1530 ) near 1530 cm −1 derived from the urethane component is 0.50 to 1 .55 is a coating layer that provides strong adhesiveness that can withstand harsh environments even when using various sealing materials and bonding conditions, and has excellent adhesiveness even under high temperature and high humidity conditions. As a result, the present invention has been found.
前記の課題は、以下の解決手段により達成することができる。
(1)少なくとも片面に塗布層を有する、基材厚みが20μm〜500μmのポリエステルフィルムであって、前記塗布層が、脂肪族系ポリカーボネートポリオールを構成成分とするウレタン樹脂と架橋剤を主成分とし、前記塗布層の赤外分光スペクトルにおいて脂肪族系ポリカーボネート成分由来の1460cm−1付近の吸光度(A1460)とウレタン成分由来の1530cm−1付近の吸光度(A1530)との比率(A1460/A1530)が0.50〜1.55であることを特徴とする太陽電池用易接着性ポリエステルフィルム。
(2)前記架橋剤が、メラミン系架橋剤、イソシアネート系架橋剤、カルボジイミド系架橋剤、オキサゾリン系架橋剤から選ばれた少なくとも1種の架橋剤である、前記太陽電池用易接着性ポリエステルフィルム。
(3)前記塗布層中の前記架橋剤の含有量が、ウレタン樹脂に対して、5質量%以上90質量%以下である、前記太陽電池用易接着性ポリエステルフィルム。
(4)前記脂肪族ポリカーボネートポリオールの数平均分子量が1500〜4000である、前記太陽電池用易接着性ポリエステルフィルム。
(5)前記ウレタン樹脂が、脂肪族ポリカーボネートポリオールと、ポリイソシアネートと、鎖延長剤を構成成分として含み、鎖延長剤が炭素数4〜10の脂肪族系ジオールもしくは炭素数4〜10の脂肪族系ジアミンである、前記太陽電池用易接着性ポリエステルフィルム。
(6)前記ウレタン樹脂のカラス転移点温度が0℃未満である、前記太陽電池用易接着性ポリエステルフィルム。
(7)前記ウレタン樹脂が、構成成分としてカルボン酸基もしくはカルボン酸塩基を有するポリオールを全ポリイソシアネート中3〜60モル%含む、前記太陽電池用易接着性ポリエステルフィルム。
(8)エチレン酢酸ビニル共重合体もしくはポリビニルブチラール樹脂を主成分とする封止材の積層に用いる、前記太陽電池用易接着性ポリエステルフィルム。
(9)前記太陽電池用易接着性ポリエステルフィルムを最表層に積層した太陽電池用バックシート。
(10)前記太陽電池バックシートの塗布層面に封止材を積層してなる太陽電池モジュール。
The above-described problem can be achieved by the following solution means.
(1) A polyester film having a coating layer on at least one side and having a substrate thickness of 20 μm to 500 μm, wherein the coating layer is mainly composed of a urethane resin having an aliphatic polycarbonate polyol as a constituent component and a crosslinking agent, The ratio (A 1460 / A 1530 ) of the absorbance (A 1460 ) near 1460 cm −1 derived from the aliphatic polycarbonate component and the absorbance (A 1530 ) near 1530 cm −1 derived from the urethane component in the infrared spectrum of the coating layer. ) Is 0.50 to 1.55, an easily adhesive polyester film for solar cells.
(2) The solar cell easily adhesive polyester film, wherein the crosslinking agent is at least one crosslinking agent selected from a melamine crosslinking agent, an isocyanate crosslinking agent, a carbodiimide crosslinking agent, and an oxazoline crosslinking agent.
(3) The said easily adhesive polyester film for solar cells whose content of the said crosslinking agent in the said application layer is 5 to 90 mass% with respect to urethane resin.
(4) The said easily adhesive polyester film for solar cells whose number average molecular weights of the said aliphatic polycarbonate polyol are 1500-4000.
(5) The urethane resin contains an aliphatic polycarbonate polyol, a polyisocyanate, and a chain extender as components, and the chain extender is an aliphatic diol having 4 to 10 carbon atoms or an aliphatic having 4 to 10 carbon atoms. The easily adhesive polyester film for solar cells, which is a diamine.
(6) The said easily adhesive polyester film for solar cells whose crow transition point temperature of the said urethane resin is less than 0 degreeC.
(7) The said easily adhesive polyester film for solar cells in which the said urethane resin contains 3-60 mol% of polyol which has a carboxylic acid group or a carboxylate group as a structural component in all the polyisocyanates.
(8) The easy-adhesive polyester film for solar cells, which is used for laminating a sealing material mainly composed of an ethylene vinyl acetate copolymer or a polyvinyl butyral resin.
(9) A solar cell backsheet in which the easily adhesive polyester film for solar cells is laminated on the outermost layer .
( 10) A solar cell module obtained by laminating a sealing material on the coating layer surface of the solar cell backsheet.
本発明の太陽電池用易接着性ポリエステルフィルムは多様な封止材・接着条件であっても強固な接着性を奏し、特に、高温高湿下での接着性(耐湿熱性)に優れる。そのため、好ましい実施態様としては、上記高温、高湿処理での接着性が、当初の接着性と同等に維持される。本発明の好ましい実施態様としては、本発明の太陽電池用易接着性ポリエステルフィルムをバックシートの部材として用いた場合、封止材との接着性が良好である。 The easily-adhesive polyester film for solar cells of the present invention exhibits strong adhesion even under various sealing materials and adhesion conditions, and is particularly excellent in adhesion (humidity heat resistance) under high temperature and high humidity. Therefore, as a preferred embodiment, the adhesiveness at the high temperature and high humidity treatment is maintained at the same level as the initial adhesiveness. As a preferred embodiment of the present invention, when the easily adhesive polyester film for solar cells of the present invention is used as a member of a back sheet, the adhesiveness with a sealing material is good.
(ポリエステルフィルム)
本発明で基材を構成するポリエステル樹脂は、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレン−2,6−ナフタレート、ポリメチレンテレフタレート、および共重合成分として、例えば、ジエチレングリコール、ネオペンチルグリコール、ポリアルキレングリコールなどのジオール成分や、アジピン酸、セバチン酸、フタル酸、イソフタル酸、2,6−ナフタレンジカルボン酸などのジカルボン酸成分などを共重合したポリエステル樹脂などを用いることができる。
(Polyester film)
The polyester resin constituting the substrate in the present invention includes polyethylene terephthalate, polybutylene terephthalate, polyethylene-2,6-naphthalate, polymethylene terephthalate, and copolymerization components such as diethylene glycol, neopentyl glycol, and polyalkylene glycol. A diol component, a polyester resin copolymerized with a dicarboxylic acid component such as adipic acid, sebacic acid, phthalic acid, isophthalic acid, or 2,6-naphthalenedicarboxylic acid can be used.
本発明で好適に用いられるポリエステル樹脂は、主に、ポリエチレンテレフタレート、ポリプロピレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレートの少なくとも1種を構成成分とする。これらのポリエステル樹脂の中でも、物性とコストのバランスからポリエチレンテレフタレートが最も好ましい。また、これらのポリエステルフィルムは二軸延伸することで耐薬品性、耐熱性、機械的強度などを向上させることができる。 The polyester resin suitably used in the present invention mainly contains at least one of polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate as a constituent component. Among these polyester resins, polyethylene terephthalate is most preferable from the balance between physical properties and cost. Moreover, these polyester films can improve chemical resistance, heat resistance, mechanical strength, etc. by biaxially stretching.
また、本発明のポリエステルフィルムは、単層のポリエステルフィルムであっても良いし、最外層と中心層を有する、少なくとも3層からなるポリエステルフィルムであっても良い。 The polyester film of the present invention may be a single-layer polyester film or a polyester film having at least three layers having an outermost layer and a center layer.
本発明において3層構成とする場合、最外層(上記2種3層の場合はA層)に粒子を含有し、中心層(上記2種3層の場合はB層)には実質的に粒子を含まなくてもよい。A層に粒子を含有させるのが好ましいとした理由は、本発明のポリエステルフィルムを太陽電池用の部材とした場合、金属、または、金属酸化物系薄膜層や塗布層等の防湿機能層、防汚機能層などを積層するなど後加工工程でのハンドリング性を向上させるためである。最外層に粒子を添加する場合は、加工性に適した十分なハンドリング性が得られる。 In the case of a three-layer structure in the present invention, particles are contained in the outermost layer (A layer in the case of the above-mentioned two types and three layers), and particles are substantially contained in the central layer (B layer in the case of the above two types and three layers) May not be included. The reason why it is preferable to include particles in the A layer is that when the polyester film of the present invention is used as a member for a solar cell, a metal or a moisture-proof functional layer such as a metal oxide thin film layer or a coating layer, This is for improving the handling property in the post-processing step such as laminating a fouling functional layer. When particles are added to the outermost layer, sufficient handling properties suitable for processability can be obtained.
また、B層には実質的に粒子を含まないことが好ましいとした理由は、滑剤粒子、特に無機粒子の凝集体による突起の生成確率を低減させるためである。また係る構成をとることで、透明性の高いフィルムを得ることができ、シースルー型太陽電池など透明性が求められる分野にも好適である。 The reason why it is preferable that the B layer substantially does not contain particles is to reduce the probability of formation of protrusions due to aggregates of lubricant particles, particularly inorganic particles. Further, by adopting such a configuration, a highly transparent film can be obtained, which is suitable for a field requiring transparency, such as a see-through solar cell.
なお、「不活性粒子が実質上含有されていない」とは、例えば、無機粒子の場合、蛍光X線分析で粒子に由来する元素を定量分析した際に、50ppm未満、好ましくは10ppm未満、最も好ましくは検出限界以下となる含有量を意味する。これは積極的に粒子を添加させなくても、外来異物由来のコンタミ成分や、原料樹脂あるいはフィルムの製造工程におけるラインや装置に付着した汚れが剥離して、フィルム中に混入する場合があるためである。 Note that “substantially free of inert particles” means, for example, in the case of inorganic particles, when the element derived from the particles is quantitatively analyzed by fluorescent X-ray analysis, it is less than 50 ppm, preferably less than 10 ppm. Preferably, the content is below the detection limit. This is because even if particles are not added positively, contaminants derived from foreign substances and raw material resin or dirt attached to the line or equipment in the film manufacturing process may be peeled off and mixed into the film. It is.
これらの各層には、必要に応じて、ポリエステル中に各種添加剤を含有させることができる。添加剤としては、例えば、酸化防止剤、耐光剤、ゲル化防止剤、有機湿潤剤、帯電防止剤、紫外線吸収剤、界面活性剤などが挙げられる。 These layers may contain various additives in the polyester as necessary. Examples of the additive include an antioxidant, a light resistance agent, an antigelling agent, an organic wetting agent, an antistatic agent, an ultraviolet absorber, and a surfactant.
最外層に含まれる粒子の種類及び含有量は、無機粒子であっても、有機粒子であってもよく、特に限定されるものではないが、シリカ、二酸化チタン、タルク、カオリナイト等の金属酸化物、炭酸カルシウム、リン酸カルシウム、硫酸バリウムなどのポリエステルに対し不活性な無機粒子が例示される。これらの不活性な無機粒子は、いずれか一種を単独で用いてもよく、また2種以上を併用してもよい。 The type and content of the particles contained in the outermost layer may be inorganic particles or organic particles, and are not particularly limited, but include metal oxidation such as silica, titanium dioxide, talc, and kaolinite. Examples thereof include inorganic particles that are inert to polyesters such as products, calcium carbonate, calcium phosphate, and barium sulfate. Any one of these inert inorganic particles may be used alone, or two or more thereof may be used in combination.
前記の粒子は、平均粒子径が0.1〜3.5μmであることが好ましい。前記平均粒子径の下限は、0.5μmがより好ましく、0.8μmがさらに好ましく、1.0μmがよりさらに好ましい。また、前記平均粒子の上限は、3.0μmであることがより好ましく、2.8μmであることがよりさらに好ましい。平均粒子径が0.1μm未満では十分なハンドリング性が得られない。3.5μmを越えると粗大突起が生成しやすくなる。 The particles preferably have an average particle size of 0.1 to 3.5 μm. The lower limit of the average particle diameter is more preferably 0.5 μm, further preferably 0.8 μm, and still more preferably 1.0 μm. Further, the upper limit of the average particle is more preferably 3.0 μm, still more preferably 2.8 μm. If the average particle size is less than 0.1 μm, sufficient handling properties cannot be obtained. When it exceeds 3.5 μm, coarse protrusions are likely to be generated.
また、これらの粒子は多孔質粒子、特に多孔質シリカが好ましい。多孔質粒子はフィルム製膜工程での延伸時に扁平型に変型しやすく、透明性の低下が小さいため、好ましい。 These particles are preferably porous particles, particularly porous silica. The porous particles are preferable because they are easily deformed into a flat shape when stretched in the film forming process and the decrease in transparency is small.
最外層の無機粒子の含有量は最外層を構成するポリエステルに対し、0.01〜0.20質量%であることが好ましい。前記濃度の下限は、0.02質量%がより好ましく、0.03質量%がさらに好ましい。また前記濃度の上限は、0.15質量%がより好ましく、0.10質量%がさらに好ましい。0.01質量%未満では十分なハンドリング性が得られない。0.2質量%を越えると透明性が低下し、好ましくない。 The content of inorganic particles in the outermost layer is preferably 0.01 to 0.20 mass% with respect to the polyester constituting the outermost layer. The lower limit of the concentration is more preferably 0.02% by mass, and further preferably 0.03% by mass. Further, the upper limit of the concentration is more preferably 0.15% by mass, and further preferably 0.10% by mass. If it is less than 0.01% by mass, sufficient handling properties cannot be obtained. If it exceeds 0.2% by mass, the transparency is lowered, which is not preferable.
前記粒子の平均粒子径の測定は下記方法によって求めることができる。
粒子を電子顕微鏡または光学顕微鏡で写真を撮り、最も小さい粒子1個の大きさが2〜5mmとなるような倍率で、300〜500個の粒子の最大径(多孔質シリカの場合は凝集体の粒径)を測定し、その平均値を平均粒子径とする。また、積層フィルムの被覆層中の粒子の平均粒子径を求める場合は、透過型電子顕微鏡(TEM)を用いて、倍率12万倍で積層フィルムの断面を撮影し、粒子の最大径を求めることができる。
The average particle diameter of the particles can be measured by the following method.
The particles are photographed with an electron microscope or an optical microscope, and the maximum diameter of 300-500 particles (in the case of porous silica, the aggregate size) is such that the size of one smallest particle is 2-5 mm. Particle diameter) is measured, and the average value is taken as the average particle diameter. Moreover, when calculating | requiring the average particle diameter of the particle | grains in the coating layer of a laminated film, the cross section of a laminated film is image | photographed by 120,000 times magnification using a transmission electron microscope (TEM), and the largest diameter of a particle | grain is calculated | required. Can do.
ポリエステルに上記粒子を配合する方法としては、公知の方法を採用し得る。例えば、ポリエステルを製造する任意の段階において添加することができるが、好ましくはエステル化の段階、もしくはエステル交換反応終了後、重縮合反応開始前の段階でエチレングリコール等に分散させたスラリーとして添加し、重縮合反応を進めてもよい。またベント付き混練押出機を用いエチレングリコールまたは水などに分散させた粒子のスラリーとポリエステル原料とをブレンドする方法、または混練押出機を用い、乾燥させた粒子とポリエステル原料とをブレンドする方法などによって行うことができる。 As a method of blending the above particles with polyester, a known method can be adopted. For example, it can be added at any stage for producing the polyester, but it is preferably added as a slurry dispersed in ethylene glycol or the like at the stage of esterification or after the end of the ester exchange reaction and before the start of the polycondensation reaction. The polycondensation reaction may proceed. Also, a method of blending a slurry of particles dispersed in ethylene glycol or water with a vented kneading extruder and a polyester raw material, or a method of blending dried particles and a polyester raw material using a kneading extruder It can be carried out.
本発明の基材となるポリエステルフィルムの厚みは20〜500μmであり、より好ましくは25〜450μmであり、さらに好ましくは30〜300μmである。基材厚みが薄いと、熱収縮の影響が大きく、高温高湿処理後の接着性が低下する場合がある。厚いとロールとして巻き取りができなくなってしまう。 The thickness of the polyester film used as the base material of the present invention is 20 to 500 μm, more preferably 25 to 450 μm, and still more preferably 30 to 300 μm. When the substrate thickness is thin, the influence of heat shrinkage is large, and the adhesiveness after high temperature and high humidity treatment may be reduced. If it is thick, it cannot be wound as a roll.
(塗布層)
本発明の太陽電池用易接着性ポリエステルフィルムには、脂肪族系ポリカーボネートポリオールを構成成分とするウレタン樹脂と架橋剤を主成分とした塗布層が形成され、赤外分光法による測定で、脂肪族系ポリカーボネート成分由来の1460cm−1付近の吸光度(A1460)とウレタン成分由来の1530cm−1付近の吸光度(A1530)の比率(A1460/A1530)がが0.50〜1.55であることが重要である。ここで、「主成分」とは、塗布層に含まれる全固形成分中として50質量%以上、より好ましくは70質量%以上含有することを意味する。
(Coating layer)
In the easily adhesive polyester film for solar cells of the present invention, a coating layer mainly composed of a urethane resin having a aliphatic polycarbonate polyol as a constituent component and a crosslinking agent is formed, and an aliphatic layer is measured by infrared spectroscopy. The ratio (A 1460 / A 1530 ) of the absorbance (A 1460 ) near 1460 cm −1 derived from the polycarbonate-based polycarbonate component to the absorbance (A 1530 ) near 1530 cm −1 derived from the urethane component is 0.50 to 1.55. This is very important. Here, the “main component” means that it is contained in an amount of 50% by mass or more, more preferably 70% by mass or more as the total solid component contained in the coating layer.
上記特許文献2〜5のように、従来の技術常識では塗布層の耐久性を向上させる点からは塗布層形成において架橋構造を積極的に導入し、剛直で強硬な塗布層にすることが望ましいと考えられていた。しかし、本発明では脂肪族系ポリカーボネートポリオールを構成成分とするポリウレタン樹脂を赤外分光法による吸光度を一定の範囲に制御することで、強固な接着性を奏し、かつ高温高湿熱下での接着性を向上させるという顕著な効果を見出し、本発明に至った。このような構成により、接着性を向上させることの機序はよくわからないが、本発明者は次のように考えている。 As in the above Patent Documents 2 to 5, it is desirable that the conventional technical common sense positively introduces a cross-linking structure in the formation of the coating layer in order to improve the durability of the coating layer, thereby forming a rigid and strong coating layer. It was thought. However, in the present invention, the polyurethane resin comprising an aliphatic polycarbonate polyol as a constituent component controls the absorbance by infrared spectroscopy within a certain range, thereby exhibiting strong adhesion and adhesion under high temperature and high humidity heat. As a result, the inventors have found a remarkable effect of improving the quality of the present invention and have reached the present invention. Although the mechanism of improving adhesiveness with such a configuration is not well understood, the present inventor thinks as follows.
例えば、モジュールのパッケージングに際して、ガラス基板/封止材/塗布層を有するポリエステルフィルム(塗布層)を積層した構成で高温で加熱圧着が行われる。この際、高温接着時のポリエステルフィルムの熱収縮により、ポリエステルフィルム(塗布層)と封止材の間に応力が生じる。特に、係る応力の発生も多様な封止材の種類・接着条件によって変化しうる。特に、高い温度が長時間かかるスタンダードキュアタイプでは熱収縮に伴う応力変化が大きくなる。その結果、上記応力が緩和し切れず、封止材との接着性が低下すると考えられた。さらに、係る積層体を高温高湿下においた場合、加水分解により、塗布層の劣化が進行する。その結果、上記応力に耐え切れず、封止材が剥離し、高温高湿下での接着性が低下すると考えられた。そのため、封止材との強固な密着性や高温高湿下での接着性を高度に保持するためには、単に塗布層を強固に架橋することで耐久性を付与するのではなく、耐熱、耐加水分解性を保持した成分で、かつ、上記応力に耐えうる柔軟性を備えることが望ましいと考えられる。しかし、単に柔軟性を有するだけでは、ファストキュアタイプのように短時間で高温加熱圧着させる場合、塗布層に部分的に溶解した封止材が侵食し、特に高温高湿処理後のポリエステルフィルム基材との接着性が低下すると考えられる。そのためこれら相反する特性を両立させることが最も望ましい。 For example, when the module is packaged, thermocompression bonding is performed at a high temperature in a configuration in which a glass film / a sealing material / a polyester film having a coating layer (coating layer) is laminated. Under the present circumstances, stress arises between a polyester film (coating layer) and a sealing material by the thermal contraction of the polyester film at the time of high temperature adhesion. In particular, the generation of such stress can also vary depending on various kinds of sealing materials and bonding conditions. In particular, in the standard cure type that takes a high temperature for a long time, the stress change accompanying the thermal contraction becomes large. As a result, it was considered that the stress could not be alleviated and the adhesiveness with the sealing material was lowered. Furthermore, when such a laminated body is placed under high temperature and high humidity, degradation of the coating layer proceeds due to hydrolysis. As a result, it was considered that the above stress could not be endured, the sealing material was peeled off, and the adhesiveness under high temperature and high humidity was lowered. Therefore, in order to maintain high adhesion to the sealing material and high adhesiveness under high temperature and high humidity, instead of simply imparting durability by firmly crosslinking the coating layer, heat resistance, It is considered desirable to have a component that retains hydrolysis resistance and to be flexible enough to withstand the stress. However, if it is simply flexible, when it is subjected to high-temperature thermocompression bonding in a short time as in the fast cure type, the sealing material partially dissolved in the coating layer will be eroded, especially the polyester film base after high-temperature and high-humidity treatment. It is considered that the adhesiveness with the material is lowered. Therefore, it is most desirable to make these conflicting characteristics compatible.
本発明では、脂肪族系ポリカーボネートポリオールを構成成分とするウレタン樹脂と架橋剤を主成分とする塗布層であって、赤外分光法による測定される脂肪族系ポリカーボネート成分由来の1460cm−1付近の吸光度(A1460)とウレタン成分由来の1530cm−1付近の吸光度(A1530)の比率(A1460/A1530)が0.50〜1.55とすることで、上記特性を両立させるものである。すなわち、耐加水分解性を有する脂肪族ポリカーボネート成分と、強硬性を奏するウレタン成分を所定の割合で共存させ、さらに架橋剤を添加することで、上記特性の両立を図るものである。これにより、高温での熱接着時のフィルムの熱収縮による応力を緩和することができるため、様々な封止材・接着条件であっても強固な接着性を得ることができ、その後の高温高湿の環境下でも、耐熱、耐加水分解性を保持しているため、塗布層の劣化を防止できると考えている In the present invention, the coating layer is mainly composed of a urethane resin having an aliphatic polycarbonate polyol as a constituent component and a cross-linking agent as a main component, and the coating layer is in the vicinity of 1460 cm −1 derived from an aliphatic polycarbonate component measured by infrared spectroscopy. By making the ratio (A 1460 / A 1530 ) of the absorbance (A 1460 ) and the absorbance (A 1530 ) in the vicinity of 1530 cm −1 derived from the urethane component 0.50 to 1.55, the above characteristics can be achieved. . That is, the above characteristics can be achieved by coexisting an aliphatic polycarbonate component having hydrolysis resistance and a urethane component exhibiting toughness at a predetermined ratio and further adding a crosslinking agent. This makes it possible to relieve stress due to thermal shrinkage of the film during thermal bonding at high temperatures, so that strong adhesiveness can be obtained even under various sealing materials and bonding conditions. We believe that the coating layer can be prevented from deteriorating because it retains heat resistance and hydrolysis resistance even in wet environments.
ここで、1460cm−1付近の吸光度(A1460)は、脂肪族系ポリカーボネート成分に含まれるメチレン基にC−H結合に特有の変角振動に由来する。よって、1460cm−1付近の吸光度(A1460)の大きさは塗布層に存在するウレタン樹脂を構成する脂肪族系ポリカーボネートポリオール成分量に依存する。一方、1530cm−1付近の吸光度(A1530)は、ウレタン成分に含まれるN−H結合に特有の変角振動に由来する。よって、1530cm−1付近の吸光度(A1530)の大きさは塗布層に存在するウレタン樹脂を構成するウレタン成分量に依存する。そのため、これらの吸光度比率(A1460/A1530)は、それぞれ異なる特性を有する両成分を特定の割合で共存していることを示すものである。本発明では、前記比率(A1460/A1530)が0.50〜1.55であるが、前記比率(A1460/A1530)の下限は好ましくは0.60であり、より好ましくは0.70である。また、前記比率(A1460/A1530)の上限は好ましくは1.45であり、より好ましくは1.35であり、さらに好ましくは1.25である。前記比率(A1460/A1530)が、0.50未満の場合は、強硬なウレタン成分が多くなりすぎ、塗布層の応力緩和が低下するため耐湿熱性が低下する。また、前記比率(A1460/A1530)が、1.55を越える場合は、柔軟な脂肪族系ポリカーボネートの脂肪族成分が多くなりすぎ、塗布層の強度が低下するため塗膜強度や耐湿熱性が低下する。 Here, the absorbance in the vicinity of 1460 cm −1 (A 1460 ) is derived from the bending vibration specific to the C—H bond in the methylene group contained in the aliphatic polycarbonate component. Therefore, the magnitude of the absorbance (A 1460 ) near 1460 cm −1 depends on the amount of the aliphatic polycarbonate polyol component constituting the urethane resin present in the coating layer. On the other hand, the absorbance (A 1530 ) in the vicinity of 1530 cm −1 is derived from the bending vibration specific to the N—H bond contained in the urethane component. Therefore, the magnitude of the absorbance (A 1530 ) near 1530 cm −1 depends on the amount of the urethane component constituting the urethane resin present in the coating layer. Therefore, these absorbance ratios (A 1460 / A 1530 ) indicate that both components having different characteristics coexist in a specific ratio. In the present invention, the ratio (A 1460 / A 1530 ) is 0.50 to 1.55, but the lower limit of the ratio (A 1460 / A 1530 ) is preferably 0.60, more preferably 0.00. 70. The upper limit of the ratio (A 1460 / A 1530 ) is preferably 1.45, more preferably 1.35, and even more preferably 1.25. When the ratio (A 1460 / A 1530 ) is less than 0.50, the amount of the hard urethane component is excessive, and the stress relaxation of the coating layer is lowered, so that the heat and moisture resistance is lowered. In addition, when the ratio (A 1460 / A 1530 ) exceeds 1.55, the aliphatic component of the flexible aliphatic polycarbonate is excessively increased, and the strength of the coating layer is lowered, so that the coating strength and moisture and heat resistance are reduced. Decreases.
本発明は、上記態様により、封止材との強度な接着性を奏し、高温高湿下での接着性(耐湿熱性)を向上させることができる。さらに、本発明の構成を以下に詳細する。 According to the aspect described above, the present invention can exhibit strong adhesiveness with a sealing material and can improve adhesiveness (moisture heat resistance) under high temperature and high humidity. Further, the configuration of the present invention will be described in detail below.
(ウレタン樹脂)
本発明のウレタン樹脂は、構成成分として、少なくともポリオール成分、ポリイソシアネート成分を含み、さらに必要に応じて鎖延長剤を含む。本発明のウレタン樹脂は、これら構成成分が主としてウレタン結合により共重合された高分子化合物である。本発明では、ウレタン樹脂の構成成分として脂肪族系ポリカーボネートポリオールを有することを特徴とする。本発明の塗布層に脂肪族系ポリカーボネートポリオールを構成成分とするウレタン樹脂を含有させることで、耐湿熱性を向上させることができる。なお、これらウレタン樹脂の構成成分は、核磁気共鳴分析などにより特定することが可能である。
(Urethane resin)
The urethane resin of the present invention includes at least a polyol component and a polyisocyanate component as constituent components, and further includes a chain extender as necessary. The urethane resin of the present invention is a polymer compound in which these constituent components are mainly copolymerized by urethane bonds. In this invention, it has an aliphatic polycarbonate polyol as a structural component of a urethane resin. Heat-moisture resistance can be improved by including a urethane resin containing an aliphatic polycarbonate polyol as a constituent component in the coating layer of the present invention. The components of these urethane resins can be specified by nuclear magnetic resonance analysis or the like.
本発明のウレタン樹脂の構成成分であるジオール成分には、耐熱、耐加水分解性に優れる脂肪族系ポリカーボネートポリオールを含有させる必要がある。本発明の太陽光による黄変防止の点から脂肪族系ポリカーボネートポリオールを用いることが好ましい。 The diol component, which is a constituent component of the urethane resin of the present invention, needs to contain an aliphatic polycarbonate polyol having excellent heat resistance and hydrolysis resistance. From the viewpoint of preventing yellowing by sunlight of the present invention, it is preferable to use an aliphatic polycarbonate polyol.
脂肪族系ポリカーボネートポリオールとしては、脂肪族系ポリカーボネートジオール、脂肪族系ポリカーボネートトリオールなどが挙げられるが、好適には脂肪族系ポリカーボネートジオールを用いることができる。本発明のウレタン樹脂の構成成分である脂肪族系ポリカーボネートジオールとしては、例えば、エチレングリコール、プロピレングリコール、1,3−プロパンジオール、1,4−ブタンジオール、1,5−ペンタンジオール、3−メチル−1,5−ペンタンジオール、1,6−ヘキサンジオール、1,9−ノナンジオール、1,8−ノナンジオール、ネオペンチルグリコール、ジエチレングリコール、ジプロピレングリコール、1,4−シクロヘキサンジオール、1,4−シクロヘキサンジメタノールなどのジオール類の1種または2種以上と、例えば、ジメチルカーボネート、ジフェニルカーボネート、エチレンカーボネート、ホスゲンなどのカーボネート類とを反応させることにより得られる脂肪族系ポリカーボネートジオールなどが挙げられる。脂肪族系ポリカーボネートジオールの数平均分子量としては、好ましくは1500〜4000であり、より好ましくは2000〜3000である。脂肪族系ポリカーボネートジオールの数平均分子量が小さい場合は、相対的にウレタン樹脂を構成する脂肪族系ポリカーボネート成分の比率が小さくなる。そのため、前記比率(A1460/A1530)を前述の範囲にするためには、脂肪族系ポリカーボネートジオールの数平均分子量を上記範囲で制御することが好ましい。脂肪族系ポリカーボネートジオールの数平均分子量が大きいと、脂肪族系ポリカーボネート成分由来の1460cm−1付近の吸光度(A1460)が増加し、脂肪族成分が増加してしまうため、接着性や高温高湿処理後の強度が低下する場合がある。脂肪族系ポリカーボネートジオールの数平均分子量が小さいと強硬なウレタン成分が増加し、基材の熱収縮による応力を緩和できなくなり、接着性が低下する場合がある。 Examples of the aliphatic polycarbonate polyol include aliphatic polycarbonate diols and aliphatic polycarbonate triols, and aliphatic polycarbonate diols can be preferably used. Examples of the aliphatic polycarbonate diol that is a constituent of the urethane resin of the present invention include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 3-methyl. -1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 1,8-nonanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanediol, 1,4- Aliphatic polycarbonate diols obtained by reacting one or more diols such as cyclohexanedimethanol with carbonates such as dimethyl carbonate, diphenyl carbonate, ethylene carbonate, and phosgene. It is below. The number average molecular weight of the aliphatic polycarbonate diol is preferably 1500 to 4000, and more preferably 2000 to 3000. When the number average molecular weight of the aliphatic polycarbonate diol is small, the ratio of the aliphatic polycarbonate component constituting the urethane resin is relatively small. Therefore, in order to make the ratio (A 1460 / A 1530 ) within the above range, it is preferable to control the number average molecular weight of the aliphatic polycarbonate diol within the above range. If the number average molecular weight of the aliphatic polycarbonate diol is large, the absorbance (A 1460 ) near 1460 cm −1 derived from the aliphatic polycarbonate component increases, and the aliphatic component increases. The strength after processing may be reduced. When the number average molecular weight of the aliphatic polycarbonate diol is small, a strong urethane component increases, and stress due to thermal shrinkage of the base material cannot be relieved, and adhesiveness may be lowered.
本発明のウレタン樹脂の構成成分であるポリイソシアネートとしては、例えば、キシリレンジイソシアネート等の芳香族脂肪族ジイソシアネート類、イソホロンジイソシアネート及び4,4−ジシクロヘキシルメタンジイソシアネート、1,3−ビス(イソシアネートメチル)シクロヘキサン等の脂環式ジイソシアネート類、ヘキサメチレンジイソシアネート、および2,2,4−トリメチルヘキサメチレンジイソシアネート等の脂肪族ジイソシアネート類、あるいはこれらの化合物を単一あるいは複数でトリメチロールプロパン等とあらかじめ付加させたポリイソシアネート類が挙げられる。芳香族イソシアネートを使用した場合、黄変の問題があり、好ましくない場合がある。また、脂肪族系と比較して、強硬な塗膜になるため、基材の熱収縮による応力を緩和できなくなり、接着性が低下する場合がある。 Examples of the polyisocyanate that is a component of the urethane resin of the present invention include aromatic aliphatic diisocyanates such as xylylene diisocyanate, isophorone diisocyanate and 4,4-dicyclohexylmethane diisocyanate, and 1,3-bis (isocyanatomethyl) cyclohexane. Such as alicyclic diisocyanates such as hexamethylene diisocyanate and aliphatic diisocyanates such as 2,2,4-trimethylhexamethylene diisocyanate; Isocyanates. When aromatic isocyanate is used, there is a problem of yellowing, which may not be preferable. Moreover, since it becomes a hard coating film compared with an aliphatic type | system | group, it becomes impossible to relieve | moderate the stress by the heat shrink of a base material, and adhesiveness may fall.
鎖延長剤としては、エチレングリコール、ジエチレングリコール、1,4−ブタンジオール、ネオペンチルグリコール及び1,6−ヘキサンジオール等のグリコール類、グリセリン、トリメチロールプロパン、およびペンタエリスリトール等の多価アルコール類、エチレンジアミン、ヘキサメチレンジアミン、およびピペラジン等のジアミン類、モノエタノールアミンおよびジエタノールアミン等のアミノアルコール類、チオジエチレングルコール等のチオジグリコール類、あるいは水が挙げられる。ただし、主鎖の短い鎖延長剤を用いると、ウレタン成分由来の1530cm−1付近の吸光度(A1530)が増し、塗布層の柔軟性が低下する場合がある。よって、鎖延長剤としては主鎖の長いものが好ましい。また、塗布層の柔軟性を付与する点では、脂肪族系で主鎖の炭素数が4〜10の長さのジオールやジアミンの鎖延長剤が好ましい。これらの点から、本発明に用いる鎖延長剤としては、1,4−ブタンジオール、1,6−ヘキサンジオール、ヘキサメチレンジアミンなどが好適である。すなわち、ウレタン成分由来の1530cm−1付近の吸光度の低下を防ぐために、1,4−ブタンジオール、1,6−ヘキサンジオール、ヘキサメチレンジアミンなどの直鎖で分子量の大きいものが好ましい。 Chain extenders include glycols such as ethylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol and 1,6-hexanediol, polyhydric alcohols such as glycerin, trimethylolpropane, and pentaerythritol, ethylenediamine Diamines such as hexamethylenediamine and piperazine, aminoalcohols such as monoethanolamine and diethanolamine, thiodiglycols such as thiodiethylene glycol, and water. However, when a chain extender having a short main chain is used, the absorbance (A 1530 ) in the vicinity of 1530 cm −1 derived from the urethane component increases, and the flexibility of the coating layer may decrease. Therefore, a chain extender having a long main chain is preferable. Moreover, the point which provides the softness | flexibility of an application layer has preferable the chain extender of the diol and the diamine whose length of carbon number of a main chain is 4-10. From these points, 1,4-butanediol, 1,6-hexanediol, hexamethylenediamine and the like are preferable as the chain extender used in the present invention. That is, in order to prevent a decrease in absorbance in the vicinity of 1530 cm −1 derived from the urethane component, linear and high molecular weight materials such as 1,4-butanediol, 1,6-hexanediol, and hexamethylenediamine are preferable.
本発明の塗布層は、水系の塗布液を用い後述のインラインコート法により設けることが好ましい。そのため、本発明のウレタン樹脂は水溶性であることが望ましい。なお、前記の「水溶性」とは、水、または水溶性の有機溶剤を50質量%未満含む水溶液に対して溶解することを意味する。 The coating layer of the present invention is preferably provided by an in-line coating method described later using an aqueous coating solution. Therefore, it is desirable that the urethane resin of the present invention is water-soluble. The “water-soluble” means that it dissolves in water or an aqueous solution containing less than 50% by mass of a water-soluble organic solvent.
ウレタン樹脂に水溶性を付与させるためには、ウレタン分子骨格中にスルホン酸(塩)基又はカルボン酸(塩)基を導入(共重合)することができる。スルホン酸(塩)基は強酸性であり、その吸湿性能により耐湿性を維持するのが困難な場合があるので、弱酸性であるカルボン酸(塩)基を導入するのが好適である。また、ポリオキシアルキレン基などのノニオン性基を導入することもできる。 In order to impart water solubility to the urethane resin, a sulfonic acid (salt) group or a carboxylic acid (salt) group can be introduced (copolymerized) into the urethane molecular skeleton. Since the sulfonic acid (salt) group is strongly acidic and it may be difficult to maintain moisture resistance due to its hygroscopic performance, it is preferable to introduce a weakly acidic carboxylic acid (salt) group. Moreover, nonionic groups, such as a polyoxyalkylene group, can also be introduced.
ウレタン樹脂にカルボン酸(塩)基を導入するためには、例えば、ポリオール成分として、ジメチロールプロピオン酸、ジメチロールブタン酸などのカルボン酸基を有するポリオール化合物を共重合成分として導入し、塩形成剤により中和する。塩形成剤の具体例としては、アンモニア、トリメチルアミン、トリエチルアミン、トリイソプロピルアミン、トリ−n−プロピルアミン、トリ−n−ブチルアミンなどのトリアルキルアミン類、N−メチルモルホリン、N−エチルモルホリンなどのN−アルキルモルホリン類、N−ジメチルエタノールアミン、N−ジエチルエタノールアミンなどのN−ジアルキルアルカノールアミン類が挙げられる。これらは単独で使用できるし、2種以上併用することもできる。 In order to introduce a carboxylic acid (salt) group into a urethane resin, for example, as a polyol component, a polyol compound having a carboxylic acid group such as dimethylolpropionic acid or dimethylolbutanoic acid is introduced as a copolymer component to form a salt. Neutralize with an agent. Specific examples of the salt forming agent include trialkylamines such as ammonia, trimethylamine, triethylamine, triisopropylamine, tri-n-propylamine, tri-n-butylamine, N such as N-methylmorpholine and N-ethylmorpholine. -N-dialkylalkanolamines such as alkylmorpholines, N-dimethylethanolamine, N-diethylethanolamine and the like. These can be used alone or in combination of two or more.
水溶性を付与するために、カルボン酸(塩)基を有するポリオール化合物を共重合成分として用いる場合は、ウレタン樹脂中のカルボン酸(塩)基を有するポリオール化合物の組成モル比は、ウレタン樹脂の全ポリイソシアネート成分を100モル%としたときに、3〜60モル%であることが好ましく、5〜40モル%であることが好ましい。前記組成モル比が3モル%未満の場合は、水分散性が困難になる場合がある。また、前記組成モル比が60モル%を超える場合は、耐水性が低下するため耐湿熱性が低下する場合がある。 In order to impart water solubility, when a polyol compound having a carboxylic acid (salt) group is used as a copolymerization component, the composition molar ratio of the polyol compound having a carboxylic acid (salt) group in the urethane resin is the same as that of the urethane resin. When the total polyisocyanate component is 100 mol%, it is preferably 3 to 60 mol%, more preferably 5 to 40 mol%. If the composition molar ratio is less than 3 mol%, water dispersibility may be difficult. Moreover, when the said composition molar ratio exceeds 60 mol%, since water resistance falls, moist heat resistance may fall.
本発明のウレタン樹脂のガラス転移点温度は0℃未満が好ましく、より好ましくは−5℃未満である。ガラス転移点温度が0℃未満の場合は、加圧接着の際に部分的に溶融したEVAやPVBなどのオレフィン樹脂と粘度が近くなり、部分的混合による強固な接着性の向上に寄与し、塗布層の応力緩和の点から好適な柔軟性を奏しやすく好ましい。 The glass transition temperature of the urethane resin of the present invention is preferably less than 0 ° C, more preferably less than -5 ° C. When the glass transition temperature is less than 0 ° C., the viscosity is close to that of partially melted olefin resin such as EVA or PVB at the time of pressure bonding, contributing to the improvement of strong adhesiveness by partial mixing, From the viewpoint of stress relaxation of the coating layer, it is preferable because it is easy to achieve suitable flexibility.
本発明のウレタン樹脂には高温高湿後の接着性を向上させるために、樹脂自体に架橋基を導入しても良い。塗液の経時安定性や架橋密度向上効果からシラノール基が好ましい。 In the urethane resin of the present invention, a crosslinking group may be introduced into the resin itself in order to improve adhesion after high temperature and high humidity. A silanol group is preferred from the viewpoint of the stability over time of the coating solution and the effect of improving the crosslinking density.
本発明のウレタン樹脂以外の樹脂でも、接着性を向上させるために含有させても良い。例えば、ポリエーテル、または、ポリエステルを構成成分とするウレタン樹脂、アクリル樹脂、ポリエステル樹脂などが挙げられる。 A resin other than the urethane resin of the present invention may be contained in order to improve adhesiveness. For example, a urethane resin, an acrylic resin, a polyester resin, or the like containing polyether or polyester as a constituent component can be used.
(添加剤)
本発明において、塗布層中に架橋剤を含有させなければならない。架橋剤を含有させることにより、高温高湿下での接着性を更に向上させることが可能になる。また、短時間で高温加熱圧着させる場合にEVAの侵食による基材密着性の低下を防ぐことができる。そのため、各種の接着条件においても対応可能な汎用性の高い易接着性を奏することができる。架橋剤としては、カルボン酸基、水酸基、アミノ基などと反応して、アミド結合、ウレタン結合、ウレア結合を形成するものが高温高湿処理で劣化しにくいため好ましい。逆に、エステル結合、エーテル結合を伴う場合は加水分解性を有する場合があり好ましくない。本発明で好適に用いられる架橋剤としては、メラミン系、イソシアネート系、カルボジイミド系、オキサゾリン系等が挙げられる。これらの中で、塗液の経時安定性、高温高湿処理下の接着性向上効果からイソシアネート系、カルボジイミド系、が好ましい。さらに、塗布層に適度な柔軟性を奏し、塗布層の応力緩和作用を好適に付与する点で、イソシアネート系架橋剤を用いることが特に好ましい。また、架橋反応を促進させるため、触媒等を必要に応じて適宜使用される。
(Additive)
In the present invention, the coating layer must contain a crosslinking agent. By including a crosslinking agent, it becomes possible to further improve the adhesiveness under high temperature and high humidity. Moreover, when making it heat-press by high temperature for a short time, the fall of the base-material adhesiveness by EVA erosion can be prevented. Therefore, highly versatile and easy-to-adhere that can be applied under various bonding conditions. As the crosslinking agent, those that react with a carboxylic acid group, a hydroxyl group, an amino group, etc. to form an amide bond, a urethane bond, or a urea bond are preferable because they are not easily deteriorated by high-temperature and high-humidity treatment. Conversely, when an ester bond or an ether bond is involved, it may be hydrolyzable, which is not preferable. Examples of the crosslinking agent suitably used in the present invention include melamine-based, isocyanate-based, carbodiimide-based, and oxazoline-based. Among these, an isocyanate type and a carbodiimide type are preferable from the viewpoint of the stability over time of the coating liquid and the effect of improving the adhesiveness under high temperature and high humidity treatment. Furthermore, it is particularly preferable to use an isocyanate-based crosslinking agent from the viewpoint that the coating layer has appropriate flexibility and suitably imparts the stress relaxation action of the coating layer. Moreover, in order to promote a crosslinking reaction, a catalyst etc. are used suitably as needed.
架橋剤の含有量としては、ウレタン樹脂に対して、5質量%以上90質量%以下が好ましい。より好ましくは、10質量%以上50質量%以下である。少ない場合には、塗布層の高温高湿下での強度が低下し、接着性が低下する場合があり、多い場合には、塗布層の樹脂の柔軟性が低下し、常温、高温高湿下での接着性が低下する場合がある。 As content of a crosslinking agent, 5 mass% or more and 90 mass% or less are preferable with respect to a urethane resin. More preferably, it is 10 mass% or more and 50 mass% or less. If the amount is small, the strength of the coating layer under high temperature and high humidity may decrease, and the adhesiveness may decrease. Adhesiveness may be reduced.
本発明において、塗膜強度を向上させるために、2種類の架橋剤を混合させても良い。また、架橋反応を促進させるため、触媒等を必要に応じて適宜使用される。 In the present invention, two kinds of crosslinking agents may be mixed in order to improve the coating film strength. Moreover, in order to promote a crosslinking reaction, a catalyst etc. are used suitably as needed.
本発明において、塗布層中に粒子を含有させることもできる。粒子は(1)シリカ、カオリナイト、タルク、軽質炭酸カルシウム、重質炭酸カルシウム、ゼオライト、アルミナ、硫酸バリウム、カーボンブラック、酸化亜鉛、硫酸亜鉛、炭酸亜鉛、二酸化チタン、サチンホワイト、珪酸アルミニウム、ケイソウ土、珪酸カルシウム、水酸化アルミニウム、加水ハロイサイト、炭酸マグネシウム、水酸化マグネシウム、等の無機粒子、(2)アクリルあるいはメタアクリル系、塩化ビニル系、酢酸ビニル系、ナイロン、スチレン/アクリル系、スチレン/ブタジエン系、ポリスチレン/アクリル系、ポリスチレン/イソプレン系、ポリスチレン/イソプレン系、メチルメタアクリレート/ブチルメタアクリレート系、メラミン系、ポリカーボネート系、尿素系、エポキシ系、ウレタン系、フェノール系、ジアリルフタレート系、ポリエステル系等の有機粒子が挙げられる。 In the present invention, particles may be contained in the coating layer. Particles are (1) silica, kaolinite, talc, light calcium carbonate, heavy calcium carbonate, zeolite, alumina, barium sulfate, carbon black, zinc oxide, zinc sulfate, zinc carbonate, titanium dioxide, satin white, aluminum silicate, diatomaceous earth Inorganic particles such as soil, calcium silicate, aluminum hydroxide, hydrous halloysite, magnesium carbonate, magnesium hydroxide, (2) acrylic or methacrylic, vinyl chloride, vinyl acetate, nylon, styrene / acrylic, styrene / Butadiene, polystyrene / acrylic, polystyrene / isoprene, polystyrene / isoprene, methyl methacrylate / butyl methacrylate, melamine, polycarbonate, urea, epoxy, urethane, phenol, di Rirufutareto systems include organic particles of polyester or the like.
前記粒子は、平均粒径が1〜500nmのものが好適である。平均粒子径は特に限定されないが、フィルムの透明性を維持する点から1〜100nmであれば好ましい。 The particles preferably have an average particle size of 1 to 500 nm. Although an average particle diameter is not specifically limited, If it is 1-100 nm from the point which maintains the transparency of a film, it is preferable.
前記粒子は、平均粒径の異なる粒子を2種類以上含有させても良い。 The particles may contain two or more kinds of particles having different average particle diameters.
なお、上記の平均粒径は、透過型電子顕微鏡(TEM)を用いて、倍率12万倍で積層フィルムの断面を撮影し、塗布層の断面に存在する10ヶ以上の粒子の最大径を測定し、それらの平均値として求めることができる。 In addition, said average particle diameter measures the maximum diameter of the 10 or more particle | grains which exist in the cross section of a coating layer by image | photographing the cross section of a laminated film at a magnification of 120,000 times using a transmission electron microscope (TEM). And can be obtained as an average value of them.
粒子の含有量としては、0.5質量%以上20質量%以下が好ましい。少ない場合は、十分な耐ブロッキング性を得ることができない。また、対スクラッチ性が悪化してしまう。多い場合は、塗膜強度が低下する。 As content of particle | grains, 0.5 mass% or more and 20 mass% or less are preferable. When the amount is small, sufficient blocking resistance cannot be obtained. Further, scratch resistance is deteriorated. When the amount is large, the coating film strength decreases.
塗布層には、コート時のレベリング性の向上、コート液の脱泡を目的に界面活性剤を含有させることもできる。界面活性剤は、カチオン系、アニオン系、ノニオン系などいずれのものでも構わないが、シリコン系、アセチレングリコール系又はフッ素系界面活性剤が好ましい。これらの界面活性剤は、封止材との接着性を損なわない程度の範囲、例えば、塗布液中に0.005〜0.5質量%の範囲で含有させることも好ましい。 The coating layer may contain a surfactant for the purpose of improving leveling properties during coating and defoaming the coating solution. The surfactant may be any of cationic, anionic and nonionic surfactants, but is preferably a silicon-based, acetylene glycol-based or fluorine-based surfactant. These surfactants are preferably contained in a range that does not impair the adhesiveness to the sealing material, for example, in the range of 0.005 to 0.5% by mass in the coating solution.
塗布層に他の機能性を付与するために、封止材との接着性を損なわない程度の範囲で、各種の添加剤を含有させても構わない。前記添加剤としては、例えば、蛍光染料、蛍光増白剤、可塑剤、紫外線吸収剤、顔料分散剤、抑泡剤、消泡剤、防腐剤、帯電防止剤等が挙げられる。 In order to impart other functionality to the coating layer, various additives may be contained within a range that does not impair the adhesion with the sealing material. Examples of the additive include fluorescent dyes, fluorescent brighteners, plasticizers, ultraviolet absorbers, pigment dispersants, foam suppressors, antifoaming agents, preservatives, and antistatic agents.
本発明において、ポリエステルフィルム上に塗布層を設ける方法としては、溶媒、粒子、樹脂を含有する塗布液をポリエステルフィルムに塗布、乾燥する方法が挙げられる。溶媒として、トルエン等の有機溶剤、水、あるいは水と水溶性の有機溶剤の混合系が挙げられるが、好ましくは、環境問題の点から水単独あるいは水に水溶性の有機溶剤を混合したものが好ましい。 In the present invention, examples of the method for providing the coating layer on the polyester film include a method in which a coating solution containing a solvent, particles and a resin is applied to the polyester film and dried. Examples of the solvent include organic solvents such as toluene, water, and a mixed system of water and a water-soluble organic solvent. Preferably, water alone or a mixture of a water-soluble organic solvent and water is used from the viewpoint of environmental problems. preferable.
(太陽電池用易接着性ポリエステルフィルムの製造)
本発明の光学用易接着性ポリエステルフィルムの製造方法について、ポリエチレンテレフタレート(以下、PETと略記する)フィルムを例にして説明するが、当然これに限定されるものではない。
(Manufacture of easily adhesive polyester film for solar cells)
The method for producing an optically easy-adhesive polyester film of the present invention will be described using a polyethylene terephthalate (hereinafter abbreviated as PET) film as an example, but is not limited to this.
PET樹脂を十分に真空乾燥した後、押出し機に供給し、Tダイから約280℃の溶融PET樹脂を回転冷却ロールにシート状に溶融押出しし、静電印加法により冷却固化せしめて未延伸PETシートを得る。前記未延伸PETシートは、単層構成でもよいし、共押出し法による複層構成であってもよい。また、PET樹脂中に不活性粒子を実質的に含有させないことが好ましい。 After sufficiently drying the PET resin in a vacuum, it is supplied to an extruder, melted and extruded at about 280 ° C. from a T-die into a rotating cooling roll into a sheet, cooled and solidified by an electrostatic application method, and unstretched PET. Get a sheet. The unstretched PET sheet may have a single layer structure or a multilayer structure by a coextrusion method. Moreover, it is preferable not to contain an inert particle substantially in PET resin.
得られた未延伸PETシートを、80〜120℃に加熱したロールで長手方向に2.5〜5.0倍に延伸して、一軸延伸PETフィルムを得る。さらに、フィルムの端部をクリップで把持して、70〜140℃に加熱された熱風ゾーンに導き、幅方向に2.5〜5.0倍に延伸する。引き続き、160〜240℃の熱処理ゾーンに導き、1〜60秒間の熱処理を行ない、結晶配向を完了させる。 The obtained unstretched PET sheet is stretched 2.5 to 5.0 times in the longitudinal direction with a roll heated to 80 to 120 ° C. to obtain a uniaxially stretched PET film. Furthermore, the edge part of a film is hold | gripped with a clip, it guide | induces to the hot air zone heated at 70-140 degreeC, and is extended | stretched 2.5 to 5.0 times in the width direction. Then, it guide | induces to the heat processing zone of 160-240 degreeC, and heat-processes for 1 to 60 seconds, and completes crystal orientation.
このフィルム製造工程の任意の段階で、PETフィルムの少なくとも片面に、塗布液を塗布し、前記塗布層を形成する。塗布層はPETフィルムの両面に形成させても特に問題はない。塗布液中の樹脂組成物の固形分濃度は、2〜35重量%であることが好ましく、特に好ましくは4〜15重量%である。 In an arbitrary stage of the film manufacturing process, a coating solution is applied to at least one surface of the PET film to form the coating layer. There is no particular problem even if the coating layer is formed on both sides of the PET film. The solid content concentration of the resin composition in the coating solution is preferably 2 to 35% by weight, particularly preferably 4 to 15% by weight.
この塗布液をPETフィルムに塗布するための方法は、公知の任意の方法を用いることができる。例えば、リバースロールコート法、グラビアコート法、キスコート法、ダイコーター法、ロールブラッシュ法、スプレーコート法、エアナイフコート法、ワイヤーバーコート法、パイプドクター法、含浸コート法、カーテンコート法、などが挙げられる。これらの方法を単独で、あるいは組み合わせて塗工する。 Any known method can be used as a method for applying the coating solution to the PET film. For example, reverse roll coating method, gravure coating method, kiss coating method, die coater method, roll brush method, spray coating method, air knife coating method, wire bar coating method, pipe doctor method, impregnation coating method, curtain coating method, etc. It is done. These methods are applied alone or in combination.
本発明においては、塗布層は未延伸あるいは一軸延伸後のPETフィルムに前記塗布液を塗布、乾燥した後、少なくとも一軸方向に延伸し、次いで熱処理を行って形成させる。フィルム製膜時に塗布層を形成するインラインコート法により塗布層とポリエステルフィルム基材との密着性はより向上するため高温高湿後の封止材と密着性を向上させる点で好ましい。また、塗布層に高温の熱処理を施すことは、塗布層に含まれる架橋剤が反応し、耐湿熱性により好適な塗布層が形成する点で好ましい。 In the present invention, the coating layer is formed by coating the coating solution on an unstretched or uniaxially stretched PET film, drying it, stretching in at least a uniaxial direction, and then performing a heat treatment. Since the adhesion between the coating layer and the polyester film substrate is further improved by the in-line coating method for forming the coating layer during film formation, it is preferable in terms of improving the adhesion with the sealing material after high temperature and high humidity. In addition, it is preferable to apply a high-temperature heat treatment to the coating layer in that a cross-linking agent contained in the coating layer reacts to form a more suitable coating layer due to moisture and heat resistance.
本発明において、最終的に得られる塗布層の厚みは好ましくは10〜3000nm、より好ましくは10〜1000nm、さらに好ましくは10〜500nm、よりさらに好ましくは10〜400nmである。また、塗布層の乾燥後の塗布量は、好ましくは0.01〜3g/m2、より好ましくは0.01〜1g/m2、さらに好ましくは0.01〜0.5g/m2、よりさらに好ましくは0.01〜0.4g/m2である。塗布層の塗布量が0.01g/m2未満であると、接着性に対する効果がほとんどなくなる。一方、塗布量が3g/m2を越えると、耐ブロッキング性が低下してしまう。 In the present invention, the thickness of the finally obtained coating layer is preferably 10 to 3000 nm, more preferably 10 to 1000 nm, still more preferably 10 to 500 nm, and still more preferably 10 to 400 nm. The coating amount after drying of the coating layer is preferably 0.01 to 3 g / m 2, more preferably 0.01 to 1 g / m 2, more preferably 0.01 to 0.5 g / m 2, more More preferably, it is 0.01-0.4 g / m < 2 >. When the coating amount of the coating layer is less than 0.01 g / m 2 , the effect on adhesiveness is almost lost. On the other hand, when the coating amount exceeds 3 g / m 2 , the blocking resistance is lowered.
(太陽電池用バックシート)
本発明の太陽電池用バックシートは前記塗布層を有するポリエステルフィルムを構成部材とする。特に、封止材と直接的に接する最表層に用いることが好ましい。係る構成により本発明の太陽電池用バックシートは封止材との強固な密着性を奏することができ、長期にわたる過酷な環境下においても良好な密着性を奏する。そのため、太陽電池素子の防湿性保持やバリア性向上に寄与しうる。
(Back sheet for solar cell)
The back sheet for solar cell of the present invention comprises a polyester film having the coating layer as a constituent member. In particular, it is preferably used for the outermost layer that is in direct contact with the sealing material. With such a configuration, the solar cell backsheet of the present invention can exhibit strong adhesion to the encapsulant, and can exhibit good adhesion even under harsh environments over a long period of time. Therefore, it can contribute to moisture proof maintenance and barrier property improvement of the solar cell element.
本発明の太陽電池用バックシートの態様としては、例えば、前記塗布層を有するポリエステルフィルム/接着剤/金属箔又は金属系薄膜層を有するフィルム/接着剤/ポリフッ化ビニルフイルム又はポリエステル系高耐久防湿フィルムといった構成が例示される。また本発明のポリエステルフィルムは両面に前記塗布層を有する構成であっても構わない。本発明の塗布層は封止材以外の構成とも良好な接着性を奏しうる。ここで金属箔又は金属系薄膜層を有するフィルムとしては、水蒸気バリア性を有するものが好適に用いることができる。 As an aspect of the back sheet for solar cells of the present invention, for example, a polyester film / adhesive / metal foil having a coating layer or a film / adhesive / polyvinyl fluoride film having a metal-based thin film layer or a polyester-based highly durable moisture-proof A configuration such as a film is exemplified. Further, the polyester film of the present invention may have a configuration having the coating layer on both sides. The coating layer of the present invention can exhibit good adhesiveness with configurations other than the sealing material. Here, as the film having a metal foil or a metal thin film layer, a film having a water vapor barrier property can be suitably used.
前記金属の種類としてはアルミニウム、錫、マグネシウム、銀、ステンレスなどが挙げられるが中でもアルミニウム、銀が比較的高い反射率を有し、工業的に入手しやすいため好適である。金属層は金属箔をして使用しても良いし、ポリエステルフィルム等に薄膜として積層してもよい。これら金属を薄膜として積層する方法としては真空蒸着法、スパッタリング法、イオンプレーティング法、プラズマ気相成長法(CVD)等を用いることができる。 Examples of the metal include aluminum, tin, magnesium, silver, and stainless steel. Among them, aluminum and silver are preferable because they have a relatively high reflectance and are easily available industrially. The metal layer may be used as a metal foil, or may be laminated as a thin film on a polyester film or the like. As a method of laminating these metals as a thin film, a vacuum deposition method, a sputtering method, an ion plating method, a plasma vapor deposition method (CVD), or the like can be used.
本発明においては前記塗布層を有するポリエステルフィルム、金属箔又は金属系薄膜層を有するフィルム、ポリフッ化ビニルフイルム又はポリエステル系高耐久防湿フィルムの各層間を、真空吸引等により一体化して加熱圧着するラミネ−ション法等の通常の成形法を利用し、上記の各層を一体成形体として加熱圧着成形して、太陽電池用バックシートを製造することができる。上記において、各フィルム間の接着性等を高めるために、接着剤を介して積層するのが好ましい。接着剤としては例えば(メタ)アクリル系樹脂、オレフィン系樹脂、ビニル系樹脂、その他等の樹脂をビヒクルの主成分とする加熱溶融型接着剤、溶剤型接着剤、光硬化型接着剤等が挙げられる。 In the present invention, each layer of the polyester film having the coating layer, the metal foil or the metal-based thin film layer, the polyvinyl fluoride film or the polyester-based high durability moisture-proof film is integrally laminated by vacuum suction or the like and heat-pressed. The solar cell backsheet can be produced by thermocompression-molding each of the above-mentioned layers as an integrally molded body using a normal molding method such as the cation method. In the above, in order to improve the adhesiveness etc. between each film, it is preferable to laminate | stack via an adhesive agent. Examples of the adhesive include (meth) acrylic resins, olefinic resins, vinyl resins, and other heat melting adhesives, solvent-based adhesives, photo-curing adhesives, etc. whose main component is a vehicle. It is done.
ここで、高耐久防湿フィルムとは耐候性を向上させる目的で積層されるものであり、高耐久防湿フィルムとしては、例えばポリテトラフロロエチレン(PTFE)、4−フッ化エチレン−パークロロアルコキシ共重合体(PFA)、4−フッ化エチレン−6−フッ化プロピレン共重合体(FEP)、2−エチレン−4フッ化エチレン共重合体(ETFE)、ポリ3−フッ化エチレン(PCTFE)、ポリフッ化ビニデン(PVDF)、もしくはポリフッカビニル(PVF)等のフッ素樹脂フィルム、あるいはポリカーボネート、ポリメチルメタクリレート、ポリアクリレート、ポリエチレンテレフタレート(PET)、ポリエチレンナフタレート(PEN)、アクリル等の樹脂に紫外線吸収剤を練り混んだ樹脂組成物からなるフィルムが挙げられる。 Here, the high durability moisture-proof film is laminated for the purpose of improving the weather resistance. Examples of the high durability moisture-proof film include polytetrafluoroethylene (PTFE), 4-fluoroethylene-perchloroalkoxy copolymer. Polymer (PFA), 4-Fluoroethylene-6-fluoropropylene copolymer (FEP), 2-Ethylene-4 fluoroethylene copolymer (ETFE), Poly-3-fluoroethylene (PCTFE), Polyfluoride Fluorine resin film such as vinylidene (PVDF) or polyfuca vinyl (PVF), or UV absorber for resin such as polycarbonate, polymethyl methacrylate, polyacrylate, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), acrylic A film made of a kneaded resin composition It is.
(太陽電池モジュール)
太陽電池モジュールは、例えば、ガラス基板と、配線を配設した光起電力素子としての太陽電池素子と、太陽電池素子を挟むように介在する封止材と、本発明の太陽電池バックシートを用いて構成される。封止剤としては、エチレン・酢酸ビニル共重合体やポリビニルブチラール樹脂などのオレフィン樹脂が好適に用いられる。特に、本発明の塗布層は上記のような柔軟性を有しているためエチレン・酢酸ビニル共重合体やポリビニルブチラール樹脂といった封止材と良好な接着性を奏することができる。
(Solar cell module)
The solar cell module uses, for example, a glass substrate, a solar cell element as a photovoltaic element provided with wiring, a sealing material interposed so as to sandwich the solar cell element, and the solar cell backsheet of the present invention. Configured. As the sealant, an olefin resin such as an ethylene / vinyl acetate copolymer or a polyvinyl butyral resin is preferably used. In particular, since the coating layer of the present invention has such flexibility, it can exhibit good adhesiveness with a sealing material such as an ethylene / vinyl acetate copolymer or a polyvinyl butyral resin.
封止材としては、ラミネート工程による加熱圧着後に別ラインに設けたオーブンでのキュア工程により硬化反応をさせるスタンダードキュアタイプと、ラミネート工程でのラミネーター内部で硬化反応をさせるファストキュアタイプとに分類されるが、いずれも適用しうる。特に、本発明の塗布層はこれらいずれのタイプにおいても好適な密着性を奏するこができ、高い汎用性を有する。 Sealing materials are classified into a standard cure type that cures by a curing process in an oven provided in a separate line after thermocompression bonding in the laminating process, and a fast cure type that cures inside the laminator in the laminating process. However, either can be applied. In particular, the coating layer of the present invention can exhibit suitable adhesion in any of these types and has high versatility.
封止材の主成分としては、エチレン・酢酸ビニル共重合体やポリビニルブチラール樹脂などのオレフィン樹脂が用いられる。なお、ここで、「主成分」とは、封止剤のうち50質量%以上、より好ましくは70質量%以上含有することを意味する。例えば、架橋反応を進行させるための架橋剤や反応開始材などが添加される。例えば、熱架橋を行う場合は、2,5−ジメチルヘキサン−2,5−ジハイドロキシパーオキサイド、2,5−ジメチル−2,5−ジ(t−ブチルパーオキシ)ヘキシン−3、ジ−t−ブチルパーオキサイド、t−ブチルクミルパーオキサイド、2,5−ジメチル−2,5−ジ(t−ブチルパーオキシ)ヘキサンなどの有機過酸化物が用いられる。また、光硬化を行う場合には、ベンゾフェノン、オルソベンゾイル安息香酸メチルやベンゾインエーテルなどの光増感剤が用いられる。さらに、ガラス基板との接着を考慮してシランカップリング剤も配合しても良い。接着性及び硬化を促進する目的でを配合されている場合もあり、エポキシ基含有化合物としては、トリグリシジルトリス(2−ヒドロキシエチル)イソシアヌレート、ネオペンチルグリコールジグリシジルエーテル、1,6−ヘキサンジオールジグリシジルエーテル、アクリルグリシジルエーテル、2−エチルヘキシルグリシジルエーテルなどのエポキシ基含有化合物が用いられる。 As the main component of the sealing material, an olefin resin such as an ethylene / vinyl acetate copolymer or a polyvinyl butyral resin is used. Here, the “main component” means that 50% by mass or more, more preferably 70% by mass or more of the sealant is contained. For example, a crosslinking agent or a reaction initiator for causing the crosslinking reaction to proceed is added. For example, when thermal crosslinking is performed, 2,5-dimethylhexane-2,5-dihydroxyperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, di-t Organic peroxides such as -butyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane are used. When photocuring is performed, a photosensitizer such as benzophenone, methyl orthobenzoylbenzoate or benzoin ether is used. Furthermore, a silane coupling agent may be blended in consideration of adhesion to the glass substrate. It may be blended for the purpose of accelerating adhesion and curing. Examples of the epoxy group-containing compound include triglycidyl tris (2-hydroxyethyl) isocyanurate, neopentyl glycol diglycidyl ether, 1,6-hexanediol. Epoxy group-containing compounds such as diglycidyl ether, acrylic glycidyl ether, and 2-ethylhexyl glycidyl ether are used.
次に、実施例および比較例を用いて本発明を詳細に説明するが、本発明は当然以下の実施例に限定されるものではない。また、本発明で用いた評価方法は以下の通りである。 EXAMPLES Next, although this invention is demonstrated in detail using an Example and a comparative example, naturally this invention is not limited to a following example. The evaluation method used in the present invention is as follows.
(1)固有粘度
JIS K 7367−5に準拠し、溶媒としてフェノール(60質量%)と1,1,2,2−テトラクロロエタン(40質量%)の混合溶媒を用い、30℃で測定した。
(1) Intrinsic viscosity Based on JIS K7367-5, it measured at 30 degreeC, using the mixed solvent of phenol (60 mass%) and 1,1,2,2-tetrachloroethane (40 mass%) as a solvent.
(2)ガラス転移点温度
JIS K7121に準拠し、示差走査熱量計(セイコーインスツルメンツ株式会社製、DSC6200)を使用して、DSC曲線からガラス転移開始温度を求めた。
(2) Glass transition temperature Based on JIS K7121, the glass transition start temperature was calculated | required from the DSC curve using the differential scanning calorimeter (The Seiko Instruments Inc. make, DSC6200).
(3)赤外分光法による吸光度測定
得られた太陽電池用易接着性ポリエステルフィルムについて塗布層を削り取り、約1mgの試料を採取した。採取した試料に圧力をかけ、厚み約1μmのフィルム状に成型した塗布層試料片(大きさ:約50μm×約50μm)を作成した。さらに、ブランク試料として基材フィルムと同質のPET樹脂についても前記手順と同様にして試料片(ブランク試料片)を作成した。
作成した試料片をKBr板上に載せ、下記条件の顕微透過法により赤外吸収スペクトルを測定した。塗布層の赤外分光スペクトルは、塗布層試料片から得た赤外分光スペクトルとブランク試料片のスペクトルとの差スペクトルとして求めた。
脂肪族系ポリカーボネート成分由来の1460cm−1付近の吸光度(A1460)は1460±10cm−1の領域に吸収極大をもつ吸収ピーク高さの値とし、ウレタン成分由来の1530cm−1付近の吸光度(A1530)は1530±10cm−1の領域に吸収極大をもつ吸収ピーク高さの値とした。なお、ベースラインはそれぞれの極大吸収のピークの両側の裾を結ぶ線とした。得られた吸光度から下記式により吸光度比率を求めた。
(吸光度比率)=A1460/A1530
(3) Absorbance measurement by infrared spectroscopy About the obtained easily adhesive polyester film for solar cells, the coating layer was scraped off and about 1 mg of a sample was collected. A pressure was applied to the collected sample to prepare a coating layer sample piece (size: about 50 μm × about 50 μm) molded into a film having a thickness of about 1 μm. Further, a sample piece (blank sample piece) was prepared in the same manner as described above for a PET resin having the same quality as the base film as a blank sample.
The prepared sample piece was placed on a KBr plate, and an infrared absorption spectrum was measured by a microscopic transmission method under the following conditions. The infrared spectrum of the coating layer was determined as the difference spectrum between the infrared spectrum obtained from the coating layer sample piece and the spectrum of the blank sample piece.
Absorbance around 1460 cm -1 derived from an aliphatic polycarbonate component (A 1460) is 1460 and the value of the absorption peak height having an absorption maximum in the region of ± 10 cm -1, the absorbance in the vicinity of 1530 cm -1 derived from urethane component (A 1530 ) is the value of the absorption peak height having an absorption maximum in the region of 1530 ± 10 cm −1 . The baseline was a line connecting the hems on both sides of each maximum absorption peak. The absorbance ratio was determined from the obtained absorbance by the following formula.
(Absorbance ratio) = A 1460 / A 1530
(測定条件)
装置:FT−IR分析装置SPECTRA TECH社製 IRμs/SIRM
検出器:MCT
分解能:4cm−1
積算回数:128回
(Measurement condition)
Apparatus: FT-IR analyzer SPECTRA TECH IRμs / SIRM
Detector: MCT
Resolution: 4cm -1
Integration count: 128 times
(4)接着性
得られた太陽電池用易接着性ポリエステルフィルムを100mm幅×100mm長、EVAシートを70mm幅×90mm長に切り出したもの用意し、フィルム(塗布層面)/下記記載のEVA/(塗布層面)フィルムの構成で重ね、真空ラミネーターで下記記載の接着条件で加熱圧着し、サンプルを作成した。作成したサンプルを20mm幅×100mm長に切り出した後、SUS板に貼りつけ、下記記載の条件で引張り試験機でフィルム層とEVA層の剥離強度を測定した。剥離強度は極大点を越えた後に安定して剥離している部分の平均値として求めた。下記の基準でランク分けした。
◎:100N/20mm以上、または、フィルムの材破
○:75N/20mm以上、100N/20mm未満
△:50N/20mm以上、75N/20mm未満
×:50N/20mm未満
(4) Adhesiveness The prepared easy-adhesive polyester film for solar cells was cut into 100 mm width × 100 mm length, and the EVA sheet was cut into 70 mm width × 90 mm length, and the film (coating layer surface) / EVA / (described below) Coating layer surface) A sample was prepared by stacking with a film configuration and thermocompression bonding with a vacuum laminator under the adhesion conditions described below. The prepared sample was cut out into a width of 20 mm and a length of 100 mm, attached to a SUS plate, and the peel strength between the film layer and the EVA layer was measured with a tensile tester under the conditions described below. The peel strength was determined as the average value of the portions that peeled stably after exceeding the maximum point. The ranking was based on the following criteria.
◎: 100 N / 20 mm or more, or film breakage of film ○: 75 N / 20 mm or more, less than 100 N / 20 mm Δ: 50 N / 20 mm or more, less than 75 N / 20 mm ×: less than 50 N / 20 mm
(サンプル作成条件)
装置:真空ラミネーター エヌ・ピー・シー社製 LM−30×30型
加圧:1気圧
EVA:
A.スタンダードキュアタイプ
I.サンビック製 Urtla Pearl PV(0.4μm)
ラミネート工程:100℃(真空5分、真空加圧5分)
キュア工程:熱処理150℃(常圧45分)
II.三井ファブロ製 ソーラーエバ SC4(0.4μm)
ラミネート工程:130℃(真空5分、真空加圧5分)
キュア工程:150℃(常圧45分)
B.ファストキュアタイプ
I.サンビック製 Urtla Pearl PV(0.45μm)
ラミネート工程:135℃(真空5分、真空加圧15分)
II.三井ファブロ製 ソーラーエバ RC02B(0.45μm)
ラミネート工程:150℃(真空5分、真空加圧15分)
(Sample creation conditions)
Apparatus: Vacuum laminator NP-30 type LM-30x30 pressurization: 1 atmosphere EVA:
A. Standard cure type Sunvik Ultra Pearl PV (0.4μm)
Lamination process: 100 ° C. (vacuum 5 minutes, vacuum pressurization 5 minutes)
Cure process: Heat treatment 150 ° C (normal pressure 45 minutes)
II. Mitsui Fabro Solar EVA SC4 (0.4μm)
Lamination process: 130 ° C (vacuum 5 minutes, vacuum pressurization 5 minutes)
Cure process: 150 ° C (45 minutes at normal pressure)
B. Fast cure type Sunvik Ultra Pearl PV (0.45μm)
Lamination process: 135 ° C (vacuum 5 minutes, vacuum pressure 15 minutes)
II. Mitsui Fabro Solar Eva RC02B (0.45μm)
Lamination process: 150 ° C. (vacuum 5 minutes, vacuum pressure 15 minutes)
(測定条件)
装置:テンシロン 東洋BALDWIN社製 RTM−100
剥離速度:200mm/分
剥離角度:180度
(Measurement condition)
Apparatus: Tensilon RTM-100 manufactured by Toyo BALDWIN
Peeling speed: 200 mm / min Peeling angle: 180 degrees
(5)耐湿熱性
得られた太陽電池用易接着性ポリエステルフィルムを、高温高湿槽中で85℃、85%RHの環境下1000時間放置した。次いで、太陽電池用ポリエステルフィルムを取りだし、室温常湿で24時間放置した。その後、は、前記(4)と同様の方法で剥離強度を測定し、下記の基準でランク分けをした。
◎:100N/20mm以上、または、フィルムの材破
○:75N/20mm以上、100N/20mm未満
△:50N/20mm以上、75N/20mm未満
×:50N/20mm未満
(5) Moisture and heat resistance The obtained easily adhesive polyester film for solar cells was left in an environment of 85 ° C. and 85% RH for 1000 hours in a high-temperature and high-humidity tank. Next, the polyester film for solar cells was taken out and allowed to stand at room temperature and humidity for 24 hours. Thereafter, the peel strength was measured by the same method as in (4) above, and ranked according to the following criteria.
◎: 100 N / 20 mm or more, or film breakage of film ○: 75 N / 20 mm or more, less than 100 N / 20 mm Δ: 50 N / 20 mm or more, less than 75 N / 20 mm ×: less than 50 N / 20 mm
(脂肪族系ポリカーボネートポリオールを構成成分とするウレタン樹脂A−1の重合)
撹拌機、ジムロート冷却器、窒素導入管、シリカゲル乾燥管、及び温度計を備えた4つ口フラスコに、4,4−ジフェニルメタンジイソシアネート43.75質量部、ジメチロールブタン酸12.85質量部、数平均分子量2000のポリヘキサメチレンカーボネートジオール153.41質量部、ジブチルスズジラウレート0.03質量部、及び溶剤としてアセトン84.00質量部を投入し、窒素雰囲気下、75℃において3時間撹拌し、反応液が所定のアミン当量に達したことを確認した。次に、この反応液を40℃にまで降温した後、トリエチルアミン8.77質量部を添加し、ポリウレタンプレポリマー溶液を得た。次に、高速攪拌可能なホモディスパーを備えた反応容器に、水450gを添加して、25℃に調整して、2000min−1で攪拌混合しながら、イソシアネート基末端プレポリマーを添加して水分散した。その後、減圧下で、アセトンおよび水の一部を除去することにより、固形分35%の水溶性ポリウレタン樹脂溶液(A−1)を調製した。得られたポリウレタン樹脂(A−1)のガラス転移点温度は−30℃であった。
(Polymerization of urethane resin A-1 containing aliphatic polycarbonate polyol)
In a four-necked flask equipped with a stirrer, Dimroth cooler, nitrogen inlet tube, silica gel drying tube, and thermometer, 43.75 parts by mass of 4,4-diphenylmethane diisocyanate, 12.85 parts by mass of dimethylolbutanoic acid, several 153.41 parts by mass of polyhexamethylene carbonate diol having an average molecular weight of 2000, 0.03 parts by mass of dibutyltin dilaurate, and 84.00 parts by mass of acetone as a solvent were added and stirred at 75 ° C. for 3 hours in a nitrogen atmosphere. It was confirmed that had reached the predetermined amine equivalent. Next, after the temperature of this reaction liquid was lowered to 40 ° C., 8.77 parts by mass of triethylamine was added to obtain a polyurethane prepolymer solution. Next, 450 g of water was added to a reaction vessel equipped with a homodisper capable of high-speed stirring, adjusted to 25 ° C., and added with an isocyanate group-terminated prepolymer while stirring and mixing at 2000 min −1 to disperse in water. did. Thereafter, a part of acetone and water was removed under reduced pressure to prepare a water-soluble polyurethane resin solution (A-1) having a solid content of 35%. The obtained polyurethane resin (A-1) had a glass transition temperature of -30 ° C.
(脂肪族系ポリカーボネートポリオールを構成成分とするウレタン樹脂A−2の重合)
撹拌機、ジムロート冷却器、窒素導入管、シリカゲル乾燥管、及び温度計を備えた4つ口フラスコに、4,4−ジフェニルメタンジイソシアネート29.14質量部、ジメチロールブタン酸7.57質量部、数平均分子量3000のポリヘキサメチレンカーボネートジオール173.29質量部、ジブチルスズジラウレート0.03質量部、及び溶剤としてアセトン84.00質量部を投入し、窒素雰囲気下、75℃において3時間撹拌し、反応液が所定のアミン当量に達したことを確認した。次に、この反応液を40℃にまで降温した後、トリエチルアミン5.17質量部を添加し、ポリウレタンプレポリマー溶液を得た。次に、高速攪拌可能なホモディスパーを備えた反応容器に、水450gを添加して、25℃に調整して、2000min−1で攪拌混合しながら、イソシアネート基末端プレポリマーを添加して水分散した。その後、減圧下で、アセトンおよび水の一部を除去することにより、固形分35%の水溶性ポリウレタン樹脂溶液(A−2)を調製した。
(Polymerization of urethane resin A-2 containing aliphatic polycarbonate polyol)
In a four-necked flask equipped with a stirrer, a Dimroth cooler, a nitrogen inlet tube, a silica gel drying tube, and a thermometer, 29.14 parts by mass of 4,4-diphenylmethane diisocyanate, 7.57 parts by mass of dimethylolbutanoic acid, several An average molecular weight of 3000 polyhexamethylene carbonate diol 173.29 parts by mass, dibutyltin dilaurate 0.03 parts by mass, and 84.00 parts by mass of acetone as a solvent were added, and the mixture was stirred at 75 ° C. for 3 hours in a nitrogen atmosphere. It was confirmed that had reached the predetermined amine equivalent. Next, after the temperature of this reaction liquid was lowered to 40 ° C., 5.17 parts by mass of triethylamine was added to obtain a polyurethane prepolymer solution. Next, 450 g of water was added to a reaction vessel equipped with a homodisper capable of high-speed stirring, adjusted to 25 ° C., and added with an isocyanate group-terminated prepolymer while stirring and mixing at 2000 min −1 to disperse in water. did. Thereafter, a part of acetone and water was removed under reduced pressure to prepare a water-soluble polyurethane resin solution (A-2) having a solid content of 35%.
(脂肪族系ポリカーボネートポリオールを構成成分とするウレタン樹脂A−3の重合)
撹拌機、ジムロート冷却器、窒素導入管、シリカゲル乾燥管、及び温度計を備えた4つ口フラスコに、4,4−ジフェニルメタンジイソシアネート43.75質量部、ジメチロールブタン酸11.12質量部、ヘキサンジオール1.97質量部、数平均分子量2000のポリヘキサメチレンカーボネートジオール143.40質量部、ジブチルスズジラウレート0.03質量部、及び溶剤としてアセトン84.00質量部を投入し、窒素雰囲気下、75℃において3時間撹拌し、反応液が所定のアミン当量に達したことを確認した。次に、この反応液を40℃にまで降温した後、トリエチルアミン8.77質量部を添加し、ポリウレタンプレポリマー溶液を得た。次に、高速攪拌可能なホモディスパーを備えた反応容器に、水450gを添加して、25℃に調整して、2000min−1で攪拌混合しながら、ポリウレタンプレポリマー溶液を添加して水分散した。その後、減圧下で、アセトンおよび水の一部を除去することにより、固形分35%の水溶性ポリウレタン樹脂溶液(A−3)を調製した。
(Polymerization of urethane resin A-3 containing aliphatic polycarbonate polyol as a constituent)
In a four-necked flask equipped with a stirrer, Dimroth cooler, nitrogen inlet tube, silica gel drying tube, and thermometer, 43.75 parts by mass of 4,4-diphenylmethane diisocyanate, 11.12 parts by mass of dimethylolbutanoic acid, hexane 1.97 parts by mass of diol, 143.40 parts by mass of polyhexamethylene carbonate diol having a number average molecular weight of 2000, 0.03 parts by mass of dibutyltin dilaurate, and 84.00 parts by mass of acetone as a solvent were added, and 75 ° C. in a nitrogen atmosphere. The mixture was stirred for 3 hours to confirm that the reaction solution reached a predetermined amine equivalent. Next, after the temperature of this reaction liquid was lowered to 40 ° C., 8.77 parts by mass of triethylamine was added to obtain a polyurethane prepolymer solution. Next, 450 g of water was added to a reaction vessel equipped with a homodisper capable of high-speed stirring and adjusted to 25 ° C., while stirring and mixing at 2000 min −1 , the polyurethane prepolymer solution was added and dispersed in water. . Thereafter, a part of acetone and water was removed under reduced pressure to prepare a water-soluble polyurethane resin solution (A-3) having a solid content of 35%.
(脂肪族系ポリカーボネートポリオールを構成成分とするシラノール基含有ウレタン樹脂A−4の重合)
撹拌機、ジムロート冷却器、窒素導入管、シリカゲル乾燥管、及び温度計を備えた4つ口フラスコに、イソホロンジイソシアネート38.41質量部、ジメチロールプロパン酸6.95質量部、数平均分子量2000のポリヘキサメチレンカーボネートジオール158.99質量部、ジブチルスズジラウレート0.03質量部、及び溶剤としてアセトン84.00質量部を投入し、窒素雰囲気下、75℃において3時間撹拌し、反応液が所定のアミン当量に達したことを確認した。次に、この反応液を40℃にまで降温した後、トリエチルアミン4.37質量部を添加し、ポリウレタンプレポリマー溶液を得た。次にγ―(アミノエチル)アミノプロピルトリエトキシシラン3.84質量部、2−[(2−アミノエチル)アミノ]エタノール1.80質量部を水450gを添加して、ポリウレタンプレポリマー溶液を滴下して水分散した。その後、減圧下で、アセトンおよび水の一部を除去することにより、固形分30%の水溶性シラノール基含有ポリウレタン樹脂溶液(A−4)を調製した。
(Polymerization of silanol group-containing urethane resin A-4 containing aliphatic polycarbonate polyol as a constituent)
In a four-necked flask equipped with a stirrer, a Dimroth cooler, a nitrogen inlet tube, a silica gel drying tube, and a thermometer, 38.41 parts by mass of isophorone diisocyanate, 6.95 parts by mass of dimethylolpropanoic acid, and a number average molecular weight of 2000 Polyhexamethylene carbonate diol 158.999 parts by mass, dibutyltin dilaurate 0.03 parts by mass, and acetone 84.00 parts by mass as a solvent were added and stirred at 75 ° C. for 3 hours in a nitrogen atmosphere. It was confirmed that the equivalent amount was reached. Next, after cooling this reaction liquid to 40 degreeC, 4.37 mass parts of triethylamine was added, and the polyurethane prepolymer solution was obtained. Next, 3.84 parts by mass of γ- (aminoethyl) aminopropyltriethoxysilane and 1.80 parts by mass of 2-[(2-aminoethyl) amino] ethanol were added to 450 g of water, and the polyurethane prepolymer solution was added dropwise. And dispersed in water. Thereafter, a part of acetone and water was removed under reduced pressure to prepare a water-soluble silanol group-containing polyurethane resin solution (A-4) having a solid content of 30%.
(脂肪族系ポリカーボネートポリオールを構成成分とするウレタン樹脂A−5の重合)
水溶性ポリウレタン樹脂(A−1)の数平均分子量2000のポリヘキサメチレンカーボネートジオールを数平均分子量1000のポリヘキサメチレンカーボネートジオールに変更した以外は、同様の方法で固形分35%の水溶性ポリウレタン樹脂溶液(A−5)を得た。
(Polymerization of urethane resin A-5 containing aliphatic polycarbonate polyol as a constituent)
A water-soluble polyurethane resin having a solid content of 35% was obtained in the same manner except that the polyhexamethylene carbonate diol having a number average molecular weight of 2000 in the water-soluble polyurethane resin (A-1) was changed to a polyhexamethylene carbonate diol having a number average molecular weight of 1000. A solution (A-5) was obtained.
(脂肪族系ポリカーボネートポリオールを構成成分とするウレタン樹脂A−6の重合)
水溶性ポリウレタン樹脂(A−1)の数平均分子量2000のポリヘキサメチレンカーボネートジオールを数平均分子量5000のポリヘキサメチレンカーボネートジオールに変更した以外は、同様の方法で固形分35%の水溶性ポリウレタン樹脂溶液(A−6)を得た。
(Polymerization of urethane resin A-6 containing aliphatic polycarbonate polyol as a constituent)
A water-soluble polyurethane resin having a solid content of 35% was obtained in the same manner except that the polyhexamethylene carbonate diol having a number average molecular weight of 2000 in the water-soluble polyurethane resin (A-1) was changed to a polyhexamethylene carbonate diol having a number average molecular weight of 5000. A solution (A-6) was obtained.
(ポリエステルポリオールを構成成分とするウレタン樹脂の重合A−7)
水溶性ポリウレタン樹脂(A−1)の数平均分子量2000のポリヘキサメチレンカーボネートジオールを数平均分子量2000のポリエステルジオールに変更した以外は、同様の方法で固形分35%の水溶性ポリウレタン樹脂溶液(A−7)を得た。
(Polymerization A-7 of Polyurethane Resin Containing Polyester Polyol)
A water-soluble polyurethane resin solution (A) having a solid content of 35% was obtained in the same manner except that the polyhexamethylene carbonate diol having a number average molecular weight of 2000 of the water-soluble polyurethane resin (A-1) was changed to a polyester diol having a number average molecular weight of 2000. -7) was obtained.
(ポリエーテルポリオールを構成成分とするウレタン樹脂の重合A−8)
水溶性ポリウレタン樹脂(A−1)の数平均分子量2000のポリヘキサメチレンカーボネートジオールを数平均分子量2000のポリエーテルジオールに変更した以外は、同様の方法で固形分35%の水溶性ポリウレタン樹脂溶液(A−8)を得た。
(Polymerization A-8 of Polyurethane Resin Containing Polyether Polyol)
A water-soluble polyurethane resin solution having a solid content of 35% (with a solid content of 35%), except that the polyhexamethylene carbonate diol having a number average molecular weight of 2000 in the water-soluble polyurethane resin (A-1) was changed to a polyether diol having a number average molecular weight of 2000. A-8) was obtained.
(脂肪族系ポリカーボネートポリオールを構成成分とするウレタン樹脂A−9の重合)
撹拌機、ジムロート冷却器、窒素導入管、シリカゲル乾燥管、及び温度計を備えた4つ口フラスコに、1,3-ビス(イソシアナトメチル)シクロヘキサン32.39質量部、ジメチロールブタン酸13.09質量部、数平均分子量2000のポリヘキサメチレンカーボネートジオール156.74質量部、ジブチルスズジラウレート0.03質量部、及び溶剤としてアセトン80.89質量部を投入し、窒素雰囲気下、75℃において3時間撹拌し、反応液が所定のアミン当量に達したことを確認した。次に、この反応液を40℃にまで降温した後、トリエチルアミン8.77質量部を添加し、ポリウレタンプレポリマー溶液を得た。次に、高速攪拌可能なホモディスパーを備えた反応容器に、水450gを添加して、25℃に調整して、2000min−1で攪拌混合しながら、ポリウレタンプレポリマー溶液を添加して水分散した。その後、減圧下で、アセトンおよび水の一部を除去することにより、固形分35%の水溶性ポリウレタン樹脂溶液(A−9)を調製した。得られたポリウレタン樹脂(A−9)のガラス転移点温度は−30℃であった。
(Polymerization of urethane resin A-9 containing aliphatic polycarbonate polyol as a constituent)
In a four-necked flask equipped with a stirrer, a Dimroth condenser, a nitrogen inlet tube, a silica gel drying tube, and a thermometer, 32.39 parts by mass of 1,3-bis (isocyanatomethyl) cyclohexane, dimethylolbutanoic acid 13. 09 parts by mass, 156.74 parts by mass of polyhexamethylene carbonate diol having a number average molecular weight of 2000, 0.03 parts by mass of dibutyltin dilaurate, and 80.89 parts by mass of acetone as a solvent, and 3 hours at 75 ° C. in a nitrogen atmosphere The mixture was stirred and it was confirmed that the reaction solution reached a predetermined amine equivalent. Next, after the temperature of this reaction liquid was lowered to 40 ° C., 8.77 parts by mass of triethylamine was added to obtain a polyurethane prepolymer solution. Next, 450 g of water was added to a reaction vessel equipped with a homodisper capable of high-speed stirring and adjusted to 25 ° C., while stirring and mixing at 2000 min −1 , the polyurethane prepolymer solution was added and dispersed in water. . Thereafter, a part of acetone and water was removed under reduced pressure to prepare a water-soluble polyurethane resin solution (A-9) having a solid content of 35%. The obtained polyurethane resin (A-9) had a glass transition temperature of -30 ° C.
(脂肪族系ポリカーボネートポリオールを構成成分とするウレタン樹脂A−10の重合)
撹拌機、ジムロート冷却器、窒素導入管、シリカゲル乾燥管、及び温度計を備えた4つ口フラスコに、4,4-ジシクロヘキシルジイソシアネート45.93質量部、ジメチロールブタン酸13.09質量部、数平均分子量3000のポリヘキサメチレンカーボネートジオール235.11質量部、ジブチルスズジラウレート0.03質量部、及び溶剤としてアセトン117.66質量部を投入し、窒素雰囲気下、75℃において3時間撹拌し、反応液が所定のアミン当量に達したことを確認した。次に、この反応液を40℃にまで降温した後、トリエチルアミン8.77質量部を添加し、ポリウレタンプレポリマー溶液を得た。次に、高速攪拌可能なホモディスパーを備えた反応容器に、水450gを添加して、25℃に調整して、2000min−1で攪拌混合しながら、ポリウレタンプレポリマー溶液を添加して水分散した。その後、減圧下で、アセトンおよび水の一部を除去することにより、固形分35%の水溶性ポリウレタン樹脂溶液(A−10)を調製した。得られたポリウレタン樹脂(A−10)のガラス転移点温度は−40℃であった。
(Polymerization of urethane resin A-10 containing aliphatic polycarbonate polyol)
In a four-necked flask equipped with a stirrer, a Dimroth condenser, a nitrogen inlet tube, a silica gel drying tube, and a thermometer, 45.93 parts by mass of 4,4-dicyclohexyl diisocyanate, 13.09 parts by mass of dimethylolbutanoic acid, several An average molecular weight of 3000 polyhexamethylene carbonate diol (235.11 parts by mass), dibutyltin dilaurate (0.03 parts by mass), and acetone (117.66 parts by mass) as a solvent were added, and the mixture was stirred at 75 ° C. for 3 hours in a nitrogen atmosphere. It was confirmed that had reached the predetermined amine equivalent. Next, after the temperature of this reaction liquid was lowered to 40 ° C., 8.77 parts by mass of triethylamine was added to obtain a polyurethane prepolymer solution. Next, 450 g of water was added to a reaction vessel equipped with a homodisper capable of high-speed stirring and adjusted to 25 ° C., while stirring and mixing at 2000 min −1 , the polyurethane prepolymer solution was added and dispersed in water. . Thereafter, a part of acetone and water was removed under reduced pressure to prepare a water-soluble polyurethane resin solution (A-10) having a solid content of 35%. The obtained polyurethane resin (A-10) had a glass transition temperature of -40 ° C.
(ブロックポリイソシアネート架橋剤の重合)
撹拌機、温度計、還流冷却管を備えたフラスコにヘキサメチレンジイソシアネートを原料としたイソシアヌレート構造を有するポリイソシアネート化合物(旭化成ケミカルズ製、デュラネートTPA)100質量部、プロピレングリコールモノメチルエーテルアセテート55質量部、ポリエチレングリコールモノメチルエーテル(平均分子量 750)30質量部を仕込み、窒素雰囲気下、70℃で4時間保持した。その後、反応液温度を50℃に下げ、メチルエチルケトオキシム47質量部を滴下した。反応液の赤外スペクトルを測定し、イソシアネート基の吸収が消失したことを確認し、固形分75質量%のブロックポリイソシアネート水分散液(B)を得た。
(Polymerization of block polyisocyanate crosslinking agent)
100 parts by mass of a polyisocyanate compound having an isocyanurate structure using hexamethylene diisocyanate as a raw material (manufactured by Asahi Kasei Chemicals, Duranate TPA) in a flask equipped with a stirrer, a thermometer and a reflux condenser, 55 parts by mass of propylene glycol monomethyl ether acetate, 30 parts by mass of polyethylene glycol monomethyl ether (average molecular weight 750) was charged and held at 70 ° C. for 4 hours in a nitrogen atmosphere. Thereafter, the reaction solution temperature was lowered to 50 ° C., and 47 parts by mass of methyl ethyl ketoxime was added dropwise. The infrared spectrum of the reaction solution was measured to confirm that the absorption of the isocyanate group had disappeared, and a block polyisocyanate aqueous dispersion (B) having a solid content of 75% by mass was obtained.
(オキサゾリン系架橋剤の重合)
温度計、窒素ガス導入管、還流冷却器、滴下ロート、および攪拌機を備えたフラスコに水性媒体としてのイオン交換水58質量部とイソプロパノール58質量部との混合物、および、重合開始剤(2,2’−アゾビス(2−アミジノプロパン)・二塩酸塩)4質量部を投入した。一方、滴下ロートに、オキサゾリン基を有する重合性不飽和単量体としての2−イソプロペニル−2−オキサゾリン16質量部、メトキシポリエチレングリコールアクリレート(エチレングリコールの平均付加モル数・9モル、新中村化学製)32質量部、およびメタクリル酸メチル32質量部の混合物を投入し、窒素雰囲気下、70℃において1時間にわたり滴下した。滴下終了後、反応溶液を9時間攪拌し、冷却することで固形分濃度40質量%のオキサゾリン基を有する水溶性樹脂溶液(C)を得た。
(Polymerization of oxazoline crosslinking agent)
A mixture of 58 parts by mass of ion-exchanged water and 58 parts by mass of isopropanol as an aqueous medium in a flask equipped with a thermometer, a nitrogen gas introduction tube, a reflux condenser, a dropping funnel, and a stirrer, and a polymerization initiator (2, 2 4 parts by mass of '-azobis (2-amidinopropane) dihydrochloride) was added. On the other hand, in a dropping funnel, 16 parts by mass of 2-isopropenyl-2-oxazoline as a polymerizable unsaturated monomer having an oxazoline group, methoxypolyethylene glycol acrylate (average number of moles of ethylene glycol added: 9 moles, Shin Nakamura Chemical) A mixture of 32 parts by mass and 32 parts by mass of methyl methacrylate was added, and the mixture was added dropwise at 70 ° C. for 1 hour in a nitrogen atmosphere. After completion of dropping, the reaction solution was stirred for 9 hours and cooled to obtain a water-soluble resin solution (C) having an oxazoline group having a solid content concentration of 40% by mass.
(カルボジイミド系架橋剤の重合)
撹拌機、温度計、還流冷却管を備えたフラスコにヘキサメチレンジイソシアネート168質量部とポリエチレングリコールモノメチルエーテル(M400、平均分子量400)220質量部を仕込み、120℃で1時間、撹拌し、更に4,4’−ジシクロヘキシルメタンジイソシアネート26質量部とカルボジイミド化触媒として3−メチル−1−フェニル−2−フォスフォレン−1−オキシド3.8質量部(全イソシイアネートに対し2重量%)を加え、窒素気流下185℃で更に5時間撹拌した。反応液の赤外スペクトルを測定し、波長2200〜2300cm−1の吸収が消失したことを確認した。60℃まで放冷し、イオン交換水を567質量部加え、固形分40質量%のカルボジイミド水溶性樹脂溶液(D)を得た。
(Polymerization of carbodiimide crosslinking agent)
A flask equipped with a stirrer, thermometer and reflux condenser was charged with 168 parts by mass of hexamethylene diisocyanate and 220 parts by mass of polyethylene glycol monomethyl ether (M400, average molecular weight 400), stirred at 120 ° C. for 1 hour, 26 parts by mass of 4′-dicyclohexylmethane diisocyanate and 3.8 parts by mass of 3-methyl-1-phenyl-2-phospholene-1-oxide (2% by weight based on the total isocyanate) were added as a carbodiimidization catalyst, and 185 under a nitrogen stream. Stir at 5 ° C. for a further 5 hours. The infrared spectrum of the reaction solution was measured, and it was confirmed that absorption at a wavelength of 2200 to 2300 cm −1 disappeared. It stood to cool to 60 degreeC, 567 mass parts of ion-exchange water was added, and the carbodiimide water-soluble resin solution (D) of 40 mass% of solid content was obtained.
実施例1
(1)塗布液の調整
下記の塗剤を混合し、塗布液を作成した。
水 55.62質量%
イソプロパノール 30.00質量%
ポリウレタン樹脂溶液(A−1) 11.29質量%
ブロックポリイソシアネート水分散液(B) 2.26質量%
粒子 0.71質量%
(平均粒径40nmのシリカゾル、固形分濃度40質量%)
粒子 0.07質量%
(平均粒径450nmのシリカゾル、固形分濃度40質量%)
界面活性剤 0.05質量%
(シリコン系、固形分濃度100質量%)
Example 1
(1) Adjustment of coating liquid The following coating agent was mixed and the coating liquid was created.
Water 55.62% by mass
Isopropanol 30.00% by mass
Polyurethane resin solution (A-1) 11.29% by mass
Block polyisocyanate aqueous dispersion (B) 2.26% by mass
Particles 0.71% by mass
(Silica sol with an average particle size of 40 nm, solid content concentration of 40% by mass)
0.07% by mass of particles
(Silica sol with an average particle size of 450 nm, solid content concentration of 40% by mass)
Surfactant 0.05% by mass
(Silicon, solid content concentration of 100% by mass)
(2)太陽電池用易接着性ポリエステルフィルムの製造
フィルム原料ポリマーとして平均粒径2.5μmのシリカ粒子を0.03質量%含有するPET樹脂ペレット(固有粘度が0.62dl/g)を、133Paの減圧下、135℃で6時間乾燥した。その後、押し出し機に供給し、約285℃で溶解した。このPET樹脂を、それぞれステンレス焼結体の濾材(公称濾過精度10μm粒子95%カット)で濾過し、シート状に溶融押し出した。表面温度30℃に保った回転冷却金属ロール上で急冷密着固化させ、未延伸PETシートを得た。
(2) Manufacture of easy-adhesive polyester film for solar cell A PET resin pellet (inherent viscosity is 0.62 dl / g) containing 0.03% by mass of silica particles having an average particle diameter of 2.5 μm as a film raw material polymer is 133 Pa. For 6 hours at 135 ° C. under reduced pressure. Then, it supplied to the extruder and melt | dissolved at about 285 degreeC. Each of the PET resins was filtered through a stainless steel filter medium (nominal filtration accuracy: 10 μm particle 95% cut) and melt extruded into a sheet. It was quenched and solidified on a rotating cooling metal roll maintained at a surface temperature of 30 ° C. to obtain an unstretched PET sheet.
この未延伸PETシートを加熱されたロール群及び赤外線ヒーターで100℃に加熱し、その後周速差のあるロール群で長手方向に3.5倍延伸して、一軸延伸PETフィルムを得た。 This unstretched PET sheet was heated to 100 ° C. with a heated roll group and an infrared heater, and then stretched 3.5 times in the longitudinal direction with a roll group having a difference in peripheral speed to obtain a uniaxially stretched PET film.
次いで、前記塗布液をロールコート法でPETフィルムの片面に塗布した後、80℃で20秒間乾燥した。なお、最終(二軸延伸後)の乾燥後の塗布量が0.15g/m2(乾燥後の塗布層厚み150nm)になるように調整した。引続いてテンターで、120℃で幅方向に4.0倍に延伸し、フィルムの幅方向の長さを固定した状態で、230℃で0.5秒間加熱し、さらに100℃で10秒間3%の幅方向の弛緩処理を行ない、250μmの太陽電池用易接着性ポリエステルフィルムを得た。評価結果を表1に示す。 Subsequently, after apply | coating the said coating liquid on the single side | surface of PET film by the roll coat method, it dried at 80 degreeC for 20 second. The final coating amount after drying (after biaxial stretching) was adjusted to 0.15 g / m 2 (the coating layer thickness after drying was 150 nm). Subsequently, the film was stretched 4.0 times in the width direction at 120 ° C. with a tenter, and heated at 230 ° C. for 0.5 seconds with the length in the width direction fixed, and further at 100 ° C. for 10 seconds for 3 seconds. % Relaxation treatment in the width direction was performed to obtain a 250 μm easily adhesive polyester film for solar cells. The evaluation results are shown in Table 1.
比較例1
ポリウレタン樹脂をポリウレタン樹脂(A−5)に変更した以外は実施例1と同様にして太陽電池用易接着性ポリエステルフィルムを得た。
Comparative Example 1
An easily adhesive polyester film for solar cells was obtained in the same manner as in Example 1 except that the polyurethane resin was changed to the polyurethane resin (A-5).
比較例2
ポリウレタン樹脂をポリウレタン樹脂(A−6)に変更した以外は実施例1と同様にして太陽電池用リエステルフィルムを得た。
Comparative Example 2
A solar cell reester film was obtained in the same manner as in Example 1 except that the polyurethane resin was changed to the polyurethane resin (A-6).
比較例3
ポリウレタン樹脂をポリウレタン樹脂(A−7)に変更した以外は実施例1と同様にして太陽電池用易接着性ポリエステルフィルムを得た。
Comparative Example 3
Except having changed the polyurethane resin into the polyurethane resin (A-7), it carried out similarly to Example 1, and obtained the easily adhesive polyester film for solar cells.
比較例4
ポリウレタン樹脂をポリウレタン樹脂(A−8)に変更した以外は実施例1と同様にして太陽電池用易接着性ポリエステルフィルムを得た。
Comparative Example 4
Except having changed the polyurethane resin into the polyurethane resin (A-8), it carried out similarly to Example 1, and obtained the easily adhesive polyester film for solar cells.
比較例5
太陽電池用易接着性ポリエステルフィルムの基材厚みを5μmに変更した以外は実施例1と同様にして太陽電池用易接着性ポリエステルフィルムを得た。
Comparative Example 5
A solar cell easy-adhesive polyester film was obtained in the same manner as in Example 1 except that the substrate thickness of the solar cell easy-adhesive polyester film was changed to 5 μm.
実施例2
塗布液を下記に変更したこと以外は実施例1と同様にして太陽電池用易接着性ポリエステルフィルムを得た。
水 58.02質量%
イソプロパノール 30.00質量%
ポリウレタン樹脂溶液(A−1) 9.47質量%
ブロックポリイソシアネート水分散液(B) 1.89質量%
粒子 0.59質量%
(平均粒径40nmのシリカゾル、固形分濃度40質量%)
界面活性剤 0.03質量%
(シリコン系、固形分濃度100質量%)
Example 2
Except having changed the coating liquid into the following, it carried out similarly to Example 1, and obtained the easily adhesive polyester film for solar cells.
Water 58.02% by mass
Isopropanol 30.00% by mass
Polyurethane resin solution (A-1) 9.47% by mass
Block polyisocyanate aqueous dispersion (B) 1.89 mass%
0.59% by mass of particles
(Silica sol with an average particle size of 40 nm, solid content concentration of 40% by mass)
Surfactant 0.03 mass%
(Silicon, solid content concentration of 100% by mass)
実施例3
塗布液を下記に変更したこと以外は実施例1と同様にして太陽電池用易接着性ポリエステルフィルムを得た。
水 54.75質量%
イソプロパノール 30.00質量%
ポリウレタン樹脂溶液(A−1) 12.99質量%
ブロックポリイソシアネート水分散液(B) 1.52質量%
粒子 0.71質量%
(平均粒径40nmのシリカゾル、固形分濃度40質量%)
界面活性剤 0.03質量%
(シリコン系、固形分濃度100質量%)
Example 3
Except having changed the coating liquid into the following, it carried out similarly to Example 1, and obtained the easily adhesive polyester film for solar cells.
54.75% by mass of water
Isopropanol 30.00% by mass
Polyurethane resin solution (A-1) 12.99% by mass
Block polyisocyanate aqueous dispersion (B) 1.52% by mass
Particles 0.71% by mass
(Silica sol with an average particle size of 40 nm, solid content concentration of 40% by mass)
Surfactant 0.03 mass%
(Silicon, solid content concentration of 100% by mass)
実施例4
塗布液を下記に変更したこと以外は実施例1と同様にして太陽電池用易接着性ポリエステルフィルムを得た。
水 57.35質量%
イソプロパノール 30.00質量%
ポリウレタン樹脂溶液(A−1) 8.12質量%
ブロックポリイソシアネート水分散液(B) 3.79質量%
粒子 0.71質量%
(平均粒径40nmのシリカゾル、固形分濃度40質量%)
界面活性剤 0.03質量%
(シリコン系、固形分濃度100質量%)
Example 4
Except having changed the coating liquid into the following, it carried out similarly to Example 1, and obtained the easily adhesive polyester film for solar cells.
Water 57.35% by mass
Isopropanol 30.00% by mass
Polyurethane resin solution (A-1) 8.12% by mass
Block polyisocyanate aqueous dispersion (B) 3.79% by mass
Particles 0.71% by mass
(Silica sol with an average particle size of 40 nm, solid content concentration of 40% by mass)
Surfactant 0.03 mass%
(Silicon, solid content concentration of 100% by mass)
実施例5
塗布液を下記に変更したこと以外は実施例1と同様にして太陽電池用易接着性ポリエステルフィルムを得た。
水 59.95質量%
イソプロパノール 30.00質量%
ポリウレタン樹脂溶液(A−1) 3.25質量%
ブロックポリイソシアネート水分散液(B) 6.06質量%
粒子 0.71質量%
(平均粒径40nmのシリカゾル、固形分濃度40質量%)
界面活性剤 0.03質量%
(シリコン系、固形分濃度100質量%)
Example 5
Except having changed the coating liquid into the following, it carried out similarly to Example 1, and obtained the easily adhesive polyester film for solar cells.
Water 59.95% by mass
Isopropanol 30.00% by mass
Polyurethane resin solution (A-1) 3.25% by mass
Block polyisocyanate aqueous dispersion (B) 6.06% by mass
Particles 0.71% by mass
(Silica sol with an average particle size of 40 nm, solid content concentration of 40% by mass)
Surfactant 0.03 mass%
(Silicon, solid content concentration of 100% by mass)
実施例6
塗布液を下記に変更したこと以外は実施例1と同様にして太陽電池用易接着性ポリエステルフィルムを得た。
水 60.82質量%
イソプロパノール 30.00質量%
ポリウレタン樹脂溶液(A−1) 1.62質量%
ブロックポリイソシアネート水分散液(B) 6.82質量%
粒子 0.71質量%
(平均粒径40nmのシリカゾル、固形分濃度40質量%)
界面活性剤 0.03質量%
(シリコン系、固形分濃度100質量%)
Example 6
Except having changed the coating liquid into the following, it carried out similarly to Example 1, and obtained the easily adhesive polyester film for solar cells.
60.82% by mass of water
Isopropanol 30.00% by mass
Polyurethane resin solution (A-1) 1.62% by mass
Block polyisocyanate aqueous dispersion (B) 6.82 mass%
Particles 0.71% by mass
(Silica sol with an average particle size of 40 nm, solid content concentration of 40% by mass)
Surfactant 0.03 mass%
(Silicon, solid content concentration of 100% by mass)
実施例7
ポリウレタン樹脂をポリウレタン樹脂(A−2)に変更した以外は実施例1と同様にして太陽電池用易接着性ポリエステルフィルムを得た。
Example 7
Except having changed the polyurethane resin into the polyurethane resin (A-2), it carried out similarly to Example 1, and obtained the easily adhesive polyester film for solar cells.
実施例8
ポリウレタン樹脂をポリウレタン樹脂(A−3)に変更した以外は実施例1と同様にして太陽電池用易接着性ポリエステルフィルムを得た。
Example 8
Except having changed the polyurethane resin into the polyurethane resin (A-3), it carried out similarly to Example 1, and obtained the easily adhesive polyester film for solar cells.
実施例9
ポリウレタン樹脂をシラノール基含有ポリウレタン樹脂(A−4)に変更した以外は実施例1と同様にして太陽電池用易接着性ポリエステルフィルムを得た。
Example 9
An easily adhesive polyester film for solar cells was obtained in the same manner as in Example 1 except that the polyurethane resin was changed to a silanol group-containing polyurethane resin (A-4).
実施例10
ブロックポリイソシアネート水分散液(B)をオキサゾリン基を有する水溶性樹脂(C)に変更した以外は実施例1と同様にして太陽電池用易接着性ポリエステルフィルムを得た。
Example 10
An easily adhesive polyester film for solar cells was obtained in the same manner as in Example 1 except that the block polyisocyanate aqueous dispersion (B) was changed to a water-soluble resin (C) having an oxazoline group.
実施例11
ブロックポリイソシアネート水分散液(C)をカルボジイミド水溶性樹脂(D)に変更した以外は実施例1と同様にして太陽電池用易接着性ポリエステルフィルムを得た。
Example 11
An easily adhesive polyester film for solar cells was obtained in the same manner as in Example 1 except that the block polyisocyanate aqueous dispersion (C) was changed to the carbodiimide water-soluble resin (D).
実施例12
ブロックポリイソシアネート水分散液(C)をイミノ・メチロールメラミン(固形分濃度70質量%)に変更した以外は実施例1と同様にして太陽電池用易接着性ポリエステルフィルムを得た。
Example 12
An easy-adhesive polyester film for solar cells was obtained in the same manner as in Example 1 except that the block polyisocyanate aqueous dispersion (C) was changed to imino / methylolmelamine (solid content concentration: 70% by mass).
実施例13
太陽電池用易接着性ポリエステルフィルムの基材厚みを50μmに変更した以外は実施例1と同様にして太陽電池用易接着性ポリエステルフィルムを得た。
Example 13
An easy-adhesive polyester film for solar cells was obtained in the same manner as in Example 1 except that the substrate thickness of the easy-adhesive polyester film for solar cells was changed to 50 μm.
実施例14
太陽電池用易接着性ポリエステルフィルムの基材厚みを100μmに変更した以外は実施例1と同様にして太陽電池用易接着性ポリエステルフィルムを得た。
Example 14
An easy-adhesive polyester film for solar cells was obtained in the same manner as in Example 1 except that the substrate thickness of the easy-adhesive polyester film for solar cells was changed to 100 μm.
実施例15
太陽電池用易接着性ポリエステルフィルムの基材厚みを350μmに変更した以外は実施例1と同様にして太陽電池用易接着性ポリエステルフィルムを得た。
Example 15
An easy-adhesive polyester film for solar cells was obtained in the same manner as in Example 1 except that the substrate thickness of the easy-adhesive polyester film for solar cells was changed to 350 μm.
実施例16
塗布液を下記に変更したこと以外は実施例1と同様にして太陽電池用易接着性ポリエステルフィルムを得た。
水 62.82質量%
イソプロパノール 30.00質量%
ポリウレタン樹脂溶液(A−1) 5.67質量%
ブロックポリイソシアネート水分散液(B) 1.13質量%
粒子 0.35質量%
(平均粒径40nmのシリカゾル、固形分濃度40質量%)
界面活性剤 0.03質量%
(シリコン系、固形分濃度100質量%)
Example 16
Except having changed the coating liquid into the following, it carried out similarly to Example 1, and obtained the easily adhesive polyester film for solar cells.
62.82% by mass of water
Isopropanol 30.00% by mass
Polyurethane resin solution (A-1) 5.67% by mass
Block polyisocyanate aqueous dispersion (B) 1.13% by mass
0.35% by mass of particles
(Silica sol with an average particle size of 40 nm, solid content concentration of 40% by mass)
Surfactant 0.03 mass%
(Silicon, solid content concentration of 100% by mass)
実施例17
塗布液を下記に変更したこと以外は実施例1と同様にして太陽電池用易接着性ポリエステルフィルムを得た。
水 45.99質量%
イソプロパノール 30.00質量%
ポリウレタン樹脂溶液(A−1) 18.99質量%
ブロックポリイソシアネート水分散液(B) 3.80質量%
粒子 1.19質量%
(平均粒径40nmのシリカゾル、固形分濃度40質量%)
界面活性剤 0.03質量%
(シリコン系、固形分濃度100質量%)
Example 17
Except having changed the coating liquid into the following, it carried out similarly to Example 1, and obtained the easily adhesive polyester film for solar cells.
Water 45.9 mass%
Isopropanol 30.00% by mass
Polyurethane resin solution (A-1) 18.99% by mass
Block polyisocyanate aqueous dispersion (B) 3.80% by mass
1.19% by mass of particles
(Silica sol with an average particle size of 40 nm, solid content concentration of 40% by mass)
Surfactant 0.03 mass%
(Silicon, solid content concentration of 100% by mass)
実施例18
(3)太陽電池用バックシートの製造
実施例1の太陽電池用易接着性ポリエステルフィルム/黒色ポリエステルフィルム(50μm)/アルミ箔(30μm)/ポリフッ化ビニルフィルム(38μm)の構成でドライラミネート法で接着し、太陽電池用バックシートを得た。
ドライラミネート用接着剤
タケラックA−315(三井化学製)/タケネートA−10(三井化学製)=9/1(固形分比)
Example 18
(3) Manufacture of back sheet for solar cell By the dry lamination method with the structure of the easily adhesive polyester film for solar cells / black polyester film (50 μm) / aluminum foil (30 μm) / polyvinyl fluoride film (38 μm) of Example 1. The solar cell back sheet was obtained by bonding.
Adhesive for dry laminate Takelac A-315 (Mitsui Chemicals) / Takenate A-10 (Mitsui Chemicals) = 9/1 (solid content ratio)
実施例19
ポリウレタン樹脂をポリウレタン樹脂(A−9)に変更した以外は実施例1と同様にして太陽電池用易接着性ポリエステルフィルムを得た。
Example 19
An easily adhesive polyester film for solar cells was obtained in the same manner as in Example 1 except that the polyurethane resin was changed to the polyurethane resin (A-9).
実施例20
ポリウレタン樹脂をポリウレタン樹脂(A−10)に変更した以外は実施例1と同様にして太陽電池用易接着性ポリエステルフィルムを得た。
Example 20
Except having changed the polyurethane resin into the polyurethane resin (A-10), it carried out similarly to Example 1, and obtained the easily adhesive polyester film for solar cells.
実施例21
(3)太陽電池用バックシートの製造
実施例19の太陽電池用易接着性ポリエステルフィルム/黒色ポリエステルフィルム(50μm)/アルミ箔(30μm)/ポリフッ化ビニルフィルム(38μm)の構成でドライラミネート法で接着し、太陽電池用バックシートを得た。
ドライラミネート用接着剤
タケラックA−315(三井化学製)/タケネートA−10(三井化学製)=9/1(固形分比)
Example 21
(3) Manufacture of solar cell backsheet A dry laminate method with a configuration of easy-adhesive polyester film for solar cell / black polyester film (50 μm) / aluminum foil (30 μm) / polyvinyl fluoride film (38 μm) in Example 19. The solar cell back sheet was obtained by bonding.
Adhesive for dry laminate Takelac A-315 (Mitsui Chemicals) / Takenate A-10 (Mitsui Chemicals) = 9/1 (solid content ratio)
実施例22、23
実施例18および実施例21において、黒色ポリエステルフィルム(50μm)の代わりに白色ポリエステルフィルム(50μm)を用いた以外は同様の方法で太陽電池バックシートを作製し、実施例1の太陽電池用易接着性ポリエステルフィルムを用いた実施例22、および実施例19の太陽電池用易接着性ポリエステルフィルムを用いた実施例23を作製した。得られた太陽電池用バックシートについて太陽電池用易接着性ポリエステルフィルム面を照射面として岩崎電気株式会社製アイ スーパーUVテスターSUV−W151を用い、63℃、50%Rh、照射強度100mW/cm2で100時間の連続UV照射処理を行った。UV照射後の太陽電池バックシートを蛍光灯下で目視確認した結果、実施例22の太陽電池用バックシートでは僅かに黄変が認められたものの、実施例23の太陽電池用バックシートでは全面において色の変化がなく、良好な外観を保持していた。
Examples 22 and 23
In Example 18 and Example 21, a solar cell back sheet was prepared in the same manner except that a white polyester film (50 μm) was used instead of the black polyester film (50 μm). Example 22 using the easily adhesive polyester film for solar cells of Example 22 and Example 19 using the conductive polyester film was produced. About the obtained back sheet for solar cells, an I-super UV tester SUV-W151 manufactured by Iwasaki Electric Co., Ltd. was used with the easily adhesive polyester film surface for solar cells as an irradiation surface, and 63 ° C., 50% Rh, irradiation intensity 100 mW / cm 2. And 100 hours of continuous UV irradiation treatment. As a result of visually confirming the solar cell backsheet after UV irradiation under a fluorescent lamp, the solar cell backsheet of Example 22 was slightly yellowed, but the solar cell backsheet of Example 23 was entirely exposed. There was no change in color, and a good appearance was maintained.
本発明の太陽電池用易接着性ポリエステルフィルムは、多様な封止材・接着条件での接着性及び高温高湿下での接着性(耐湿熱性)に優れるため、太陽電池用バックシートの最内装の基材フィルムとして好適である。 The easily adhesive polyester film for solar cells of the present invention is excellent in adhesiveness under various sealing materials and adhesive conditions and adhesiveness under high temperature and high humidity (humidity heat resistance), so that it is the innermost interior of the backsheet for solar cells. It is suitable as a substrate film.
Claims (10)
前記塗布層が、脂肪族系ポリカーボネートポリオールを構成成分とするウレタン樹脂と架橋剤を主成分とし、
前記塗布層の赤外分光スペクトルにおいて脂肪族系ポリカーボネート成分由来の1460cm−1付近の吸光度(A1460)とウレタン成分由来の1530cm−1付近の吸光度(A1530)との比率(A1460/A1530)が0.50〜1.55であることを特徴とする太陽電池用易接着性ポリエステルフィルム。 It is a polyester film having a substrate thickness of 20 to 500 μm and having a coating layer on at least one side,
The coating layer is mainly composed of a urethane resin and a cross-linking agent having aliphatic polycarbonate polyol as constituent components,
The ratio (A 1460 / A 1530 ) of the absorbance (A 1460 ) near 1460 cm −1 derived from the aliphatic polycarbonate component and the absorbance (A 1530 ) near 1530 cm −1 derived from the urethane component in the infrared spectrum of the coating layer. ) Is 0.50 to 1.55, an easily adhesive polyester film for solar cells.
鎖延長剤が炭素数4〜10の脂肪族系ジオールもしくは炭素数4〜10の脂肪族系ジアミンである、請求項1〜4のいずれかに記載の太陽電池用易接着性ポリエステルフィルム。 The urethane resin contains aliphatic polycarbonate polyol, polyisocyanate, and chain extender as constituent components,
The easily adhesive polyester film for solar cells according to any one of claims 1 to 4, wherein the chain extender is an aliphatic diol having 4 to 10 carbon atoms or an aliphatic diamine having 4 to 10 carbon atoms.
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