JP2019062209A - 太陽電池モジュール用のバックシート - Google Patents
太陽電池モジュール用のバックシート Download PDFInfo
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- JP2019062209A JP2019062209A JP2018217144A JP2018217144A JP2019062209A JP 2019062209 A JP2019062209 A JP 2019062209A JP 2018217144 A JP2018217144 A JP 2018217144A JP 2018217144 A JP2018217144 A JP 2018217144A JP 2019062209 A JP2019062209 A JP 2019062209A
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- group
- water
- polyisocyanate
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- 239000005056 polyisocyanate Substances 0.000 claims abstract description 87
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 87
- 239000010410 layer Substances 0.000 claims abstract description 63
- 239000012790 adhesive layer Substances 0.000 claims abstract description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000000203 mixture Substances 0.000 claims abstract description 23
- 229920000642 polymer Polymers 0.000 claims description 41
- 230000002209 hydrophobic effect Effects 0.000 claims description 39
- 229920000728 polyester Polymers 0.000 claims description 39
- 239000011230 binding agent Substances 0.000 claims description 35
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 19
- 239000004971 Cross linker Substances 0.000 claims description 14
- 239000004811 fluoropolymer Substances 0.000 claims description 14
- 229920002313 fluoropolymer Polymers 0.000 claims description 14
- 239000004814 polyurethane Substances 0.000 claims description 13
- 229920000098 polyolefin Polymers 0.000 claims description 11
- 150000001718 carbodiimides Chemical class 0.000 claims description 10
- 229920002635 polyurethane Polymers 0.000 claims description 9
- 125000001931 aliphatic group Chemical group 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 229920000570 polyether Polymers 0.000 claims description 8
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 claims description 7
- 229920000178 Acrylic resin Polymers 0.000 claims description 7
- 239000004925 Acrylic resin Substances 0.000 claims description 7
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical group O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 7
- 229920000058 polyacrylate Polymers 0.000 claims description 7
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 5
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical group OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 239000013638 trimer Substances 0.000 claims description 3
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims description 2
- 239000007822 coupling agent Substances 0.000 abstract 1
- 238000002845 discoloration Methods 0.000 abstract 1
- -1 polyethylene terephthalate Polymers 0.000 description 63
- 150000001875 compounds Chemical class 0.000 description 46
- 239000000178 monomer Substances 0.000 description 31
- 239000002245 particle Substances 0.000 description 25
- 239000007789 gas Substances 0.000 description 24
- 239000003054 catalyst Substances 0.000 description 22
- 239000012948 isocyanate Substances 0.000 description 22
- 229920002554 vinyl polymer Polymers 0.000 description 22
- 150000002513 isocyanates Chemical class 0.000 description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 20
- 229920006267 polyester film Polymers 0.000 description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 19
- 239000006096 absorbing agent Substances 0.000 description 19
- 229910010413 TiO 2 Inorganic materials 0.000 description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 18
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 17
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 17
- 238000000576 coating method Methods 0.000 description 16
- 238000006068 polycondensation reaction Methods 0.000 description 15
- 239000011248 coating agent Substances 0.000 description 14
- 239000006185 dispersion Substances 0.000 description 14
- 229920000139 polyethylene terephthalate Polymers 0.000 description 13
- 239000005020 polyethylene terephthalate Substances 0.000 description 13
- 238000011282 treatment Methods 0.000 description 13
- 239000012463 white pigment Substances 0.000 description 13
- 239000010936 titanium Substances 0.000 description 12
- 230000032050 esterification Effects 0.000 description 11
- 238000005886 esterification reaction Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
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- 208000028659 discharge Diseases 0.000 description 10
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- 239000004645 polyester resin Substances 0.000 description 10
- 239000004593 Epoxy Substances 0.000 description 9
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 9
- 239000008393 encapsulating agent Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 9
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 8
- 239000000945 filler Substances 0.000 description 8
- 229910052809 inorganic oxide Inorganic materials 0.000 description 8
- 150000002918 oxazolines Chemical class 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 8
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 7
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 7
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 7
- 125000001165 hydrophobic group Chemical group 0.000 description 7
- 239000000155 melt Substances 0.000 description 7
- 229920002620 polyvinyl fluoride Polymers 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 238000004383 yellowing Methods 0.000 description 7
- KHXKESCWFMPTFT-UHFFFAOYSA-N 1,1,1,2,2,3,3-heptafluoro-3-(1,2,2-trifluoroethenoxy)propane Chemical compound FC(F)=C(F)OC(F)(F)C(F)(F)C(F)(F)F KHXKESCWFMPTFT-UHFFFAOYSA-N 0.000 description 6
- BLTXWCKMNMYXEA-UHFFFAOYSA-N 1,1,2-trifluoro-2-(trifluoromethoxy)ethene Chemical compound FC(F)=C(F)OC(F)(F)F BLTXWCKMNMYXEA-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 6
- 239000013036 UV Light Stabilizer Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000003431 cross linking reagent Substances 0.000 description 6
- 125000005442 diisocyanate group Chemical group 0.000 description 6
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical class CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 5
- 239000004970 Chain extender Substances 0.000 description 5
- 239000004594 Masterbatch (MB) Substances 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 239000013522 chelant Substances 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 150000002681 magnesium compounds Chemical class 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 5
- 239000010452 phosphate Substances 0.000 description 5
- 238000009832 plasma treatment Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- YSYRISKCBOPJRG-UHFFFAOYSA-N 4,5-difluoro-2,2-bis(trifluoromethyl)-1,3-dioxole Chemical compound FC1=C(F)OC(C(F)(F)F)(C(F)(F)F)O1 YSYRISKCBOPJRG-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 4
- 239000007864 aqueous solution Substances 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
- 230000008901 benefit Effects 0.000 description 4
- DMSMPAJRVJJAGA-UHFFFAOYSA-N benzo[d]isothiazol-3-one Chemical compound C1=CC=C2C(=O)NSC2=C1 DMSMPAJRVJJAGA-UHFFFAOYSA-N 0.000 description 4
- 229910052797 bismuth Inorganic materials 0.000 description 4
- 230000000903 blocking effect Effects 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000003851 corona treatment Methods 0.000 description 4
- 229910001882 dioxygen Inorganic materials 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 238000009998 heat setting Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000010954 inorganic particle Substances 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 description 3
- YAOJJEJGPZRYJF-UHFFFAOYSA-N 1-ethenoxyhexane Chemical compound CCCCCCOC=C YAOJJEJGPZRYJF-UHFFFAOYSA-N 0.000 description 3
- KKKKCPPTESQGQH-UHFFFAOYSA-N 2-(4,5-dihydro-1,3-oxazol-2-yl)-4,5-dihydro-1,3-oxazole Chemical compound O1CCN=C1C1=NCCO1 KKKKCPPTESQGQH-UHFFFAOYSA-N 0.000 description 3
- QMIWYOZFFSLIAK-UHFFFAOYSA-N 3,3,3-trifluoro-2-(trifluoromethyl)prop-1-ene Chemical group FC(F)(F)C(=C)C(F)(F)F QMIWYOZFFSLIAK-UHFFFAOYSA-N 0.000 description 3
- GVEUEBXMTMZVSD-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,6-nonafluorohex-1-ene Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C=C GVEUEBXMTMZVSD-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical compound O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 description 3
- 229920005692 JONCRYL® Polymers 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000012736 aqueous medium Substances 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 229960002479 isosorbide Drugs 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- 235000012245 magnesium oxide Nutrition 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
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- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 3
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 3
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 2
- PCHXZXKMYCGVFA-UHFFFAOYSA-N 1,3-diazetidine-2,4-dione Chemical group O=C1NC(=O)N1 PCHXZXKMYCGVFA-UHFFFAOYSA-N 0.000 description 2
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidine Chemical compound CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 2
- LEVFXWNQQSSNAC-UHFFFAOYSA-N 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexoxyphenol Chemical compound OC1=CC(OCCCCCC)=CC=C1C1=NC(C=2C=CC=CC=2)=NC(C=2C=CC=CC=2)=N1 LEVFXWNQQSSNAC-UHFFFAOYSA-N 0.000 description 2
- RFJVDJWCXSPUBY-UHFFFAOYSA-N 2-(difluoromethylidene)-4,4,5-trifluoro-5-(trifluoromethyl)-1,3-dioxolane Chemical compound FC(F)=C1OC(F)(F)C(F)(C(F)(F)F)O1 RFJVDJWCXSPUBY-UHFFFAOYSA-N 0.000 description 2
- MUBZACKCHQIRSY-UHFFFAOYSA-N 2-[3-(4,4-Dimethyl-5H-1,3-oxazol-2-yl)phenyl]-4,4-dimethyl-5H-1,3-oxazole Chemical compound CC1(C)COC(C=2C=C(C=CC=2)C=2OCC(C)(C)N=2)=N1 MUBZACKCHQIRSY-UHFFFAOYSA-N 0.000 description 2
- HMOZDINWBHMBSQ-UHFFFAOYSA-N 2-[3-(4,5-dihydro-1,3-oxazol-2-yl)phenyl]-4,5-dihydro-1,3-oxazole Chemical compound O1CCN=C1C1=CC=CC(C=2OCCN=2)=C1 HMOZDINWBHMBSQ-UHFFFAOYSA-N 0.000 description 2
- LDXQWLJXDIZULP-UHFFFAOYSA-N 2-[6-(4,5-dihydro-1,3-oxazol-2-yl)hexyl]-4,5-dihydro-1,3-oxazole Chemical compound N=1CCOC=1CCCCCCC1=NCCO1 LDXQWLJXDIZULP-UHFFFAOYSA-N 0.000 description 2
- MPPNPBNSYXFIBF-UHFFFAOYSA-N 2-[8-(4,5-dihydro-1,3-oxazol-2-yl)octyl]-4,5-dihydro-1,3-oxazole Chemical compound N=1CCOC=1CCCCCCCCC1=NCCO1 MPPNPBNSYXFIBF-UHFFFAOYSA-N 0.000 description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- IFIUFEBEPGGBIJ-UHFFFAOYSA-N 4-methyl-4,5-dihydro-1,3-oxazole Chemical compound CC1COC=N1 IFIUFEBEPGGBIJ-UHFFFAOYSA-N 0.000 description 2
- AIXZBGVLNVRQSS-UHFFFAOYSA-N 5-tert-butyl-2-[5-(5-tert-butyl-1,3-benzoxazol-2-yl)thiophen-2-yl]-1,3-benzoxazole Chemical compound CC(C)(C)C1=CC=C2OC(C3=CC=C(S3)C=3OC4=CC=C(C=C4N=3)C(C)(C)C)=NC2=C1 AIXZBGVLNVRQSS-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
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- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
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- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
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- IDVWLLCLTVBSCS-UHFFFAOYSA-N n,n'-ditert-butylmethanediimine Chemical compound CC(C)(C)N=C=NC(C)(C)C IDVWLLCLTVBSCS-UHFFFAOYSA-N 0.000 description 1
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- 150000003752 zinc compounds Chemical class 0.000 description 1
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Abstract
Description
本発明は太陽光発電モジュール用のバックシート及びそのようなバックシートの製造方法に関する。
エネルギー価格が上昇し、且つ炭化水素燃料の不足及び環境的影響への懸念が増加し、産業は太陽エネルギーのような代替エネルギー源に向きつつある。
おけるそのようなポリイソシアナート化合物の使用は、高温多湿条件下で保存されると層のピンホール、劣った接着性又は黄変の増加を生じ得ることが観察された。
定義
本明細書で用いられる場合、高分子支持体及びシートという用語は自立性のポリマーに基づくシートを意味し、それは1つもしくはそれより多い下塗り層と関連している場合がある。高分子支持体は通常、押出を介して製造される。高分子シートは通常(高分子)支持体上に、場合により接着剤を介して積層される。
本発明に従う太陽光発電モジュール(5)用のバックシート(1)は:
−支持体(300)
−支持体の片面上に与えられる接着層(100)及び
−支持体の他の面上に与えられる外層(200)
を含み、接着層及び外層の少なくとも1つが水性組成物からコーティングされ、水性組成物は水溶性もしくは水分散性結合剤及び水分散性コア/シェルポリイソシアナートを含むことを特徴とする。
重量%かもしくはそれより多くの水を含む組成物又は溶液を意味する。
本発明に従う水に基づく接着層及び/又は外層中で用いられる架橋剤は、水分散性コア/シェルポリイソシアナートである。
ポリイソシアナートのコアは、好ましくは疎水性ポリイソシアナートを含む。
ポリイソシアナート化合物のシェルは、好ましくは親水性分散性基及び疎水性イソシアナート−遮蔽基を含むポリマーを含む。
好ましい水分散性コア/シェルポリイソシアナートは:
a)疎水性ポリイソシアナート及び
b)親水性基及びイソシアナート基と反応する場合がある反応性基を有するポリマー
の反応生成物である。
むポリエーテルを含むコア/シェルポリイソシアナートは欧州特許第A 1788050号明細書[0031]節〜[0037]節に開示されている。
チルアクリレート、2−ヒドロキシエチルメタクリレート又は2−ヒドロキシプロピルメタクリレートである。
−疎水性ポリイソシアナートと親水性基及びシアナート遮蔽基を含むポリマーの重量比。−親水性基及びイソシアナート遮蔽基を含むポリマーの疎水度。
−(疎水性ポリイソシアナートの)イソシアナート基対親水性基及びイソシアナート遮蔽基を含むポリマーの反応性基の量の比。疎水性ポリイソシアナートと親水性基及びシアナート遮蔽基を含む反応性ポリマーの反応によってより多くのNCOが消費されると、利用可能で残るイソシアナート基はより少ない。親水性基及びイソシアナート遮蔽基を含む反応性ポリマーの反応性基の量はシェルの厚さ及び利用可能なイソシアナート基の量の両方を決定する。
−シェルポリマーのガラス転移温度(Tg)の選択(adopting)。Tgが低いポリマーは、周囲温度より低い温度でまだポリマーが可動性であるので、優れた被覆シェル(covering shell)を形成する利点を有し得る。
水性接着層は水溶性もしくは水分散性結合剤及び架橋剤を含み、ここで架橋剤は水分散性コア/シェルポリイソシアナートである。
接着層は水溶性もしくは水分散性結合剤を含む。
2171;BASFから商業的に入手可能なLuhydran S945T、Joncryl OH 8312及びJoncryl OH 8313;DSMから商業的に入手可能なNeocryl XK110;及びNuplexから商業的に入手可能なSetaqua 510である。
Kasei Corporationから商業的に入手可能なH7620、H7630及びH76S0である。
/m2である。
太陽光の反射を最大にし、それにより太陽電池モジュールの効率を向上させるために、接着層は好ましくは白色顔料を含む。
5g/m2、最も好ましくは1.5〜3g/m2である。
接着層は、好ましくはさらに無機酸化物充填剤を含む。
コア/シェルポリイソシアナート架橋性化合物を他の架橋剤と組み合わせる場合がある。
紫外線により引き起こされるバックシートの分解を予防するために、接着層は好ましくはUV吸収剤を含む。UV吸収剤は有機又は無機UV吸収性化合物の場合がある。
水性耐候性層は、水溶性もしくは水分散性結合剤及び架橋剤を含み、ここで架橋剤は水分散性コア/シェルポリイソシアナート化合物である。
耐候性層は水性接着層に関して上記で開示された水溶性又は水分散性結合剤を含む場合がある。
Ofluorine Chemical Technologyから商業的に入手可能なDF−01とである。
支持体を紫外線から保護するために、耐候性層は、好ましくはUV吸収剤を含む。
TiO2粒子は典型的に水性分散系として水性コーティング溶液に加えられる。コーテ
ィング溶液中の水が多すぎるのを避けるために、TiO2分散系は好ましくは分散系の合
計量に対して25重量%に等しいかもしくはそれより多い、より好ましくは40重量%より多い、最も好ましくは50重量%より多いTiO2を含む。
分散剤を用いる場合がある。しかしながら、そのような有機安定剤の存在はTiO2が用
いられる水性層の耐引掻性を低下させ得るか、並びに/あるいは多湿高温条件で保存されると層の黄変を増加させ得る。
調製できることが観察された。
、最も好ましくは0.15〜0.50μmである。
くはアンモニウム安定化されているか、シラン改質(modified)もしくはアルミニウム改質されている。
300F、Levasil 500、Levasil 200A/30、Levasil
100/45、Bindzil CC151 HS、Bindzil 159/500
、Bindzil 15/750、Bindzil CC301及びBindzil CC151 HSである。
結合剤の架橋効率を向上させるために、接着層又は耐候性層に触媒を加える場合がある。
本発明のバックシートにおいて用いられる基材とも呼ばれる支持体は、好ましくは高分子支持体である。封止剤及び/又は耐候性層への接着性を向上させるために、支持体に追加の層を与える場合がある。
典型的なポリエステル樹脂製造法は:ジカルボン酸又はそのエステル誘導体とジオール化合物のエステル化及び/又はエステル交換反応段階と、これに続く重縮合段階との2段階を含む。
わちポリエステル支持体)を形成する。
ジカルボン酸は脂肪族、脂環式及び芳香族ジカルボン酸から選ばれる場合がある。
ジオール化合物は脂肪族ジオール化合物、脂環式ジオール化合物及び芳香族ジオール化合物から選ばれる場合がある。
3個以上のカルボキシル基又はヒドロキシル基を有する化合物の少量を用いる場合、ポ
リエステル分子鎖の分枝が誘導され、従ってポリエステル鎖の絡み合いが促進され得る。結果として、ポリエステル分子が加水分解され、それによりポリエステルの分子量が下がった場合、ポリエステルフィルムの脆化を避ける場合がある。そのような絡み合いは、ポリエステルフィルムの熱収縮も妨げる場合がある。そのような化合物及び好ましいその使用量は、例えば米国特許第2011/0306747号明細書、[0121]節〜[0127]節に開示されている。
芳香族ジカルボン酸及び脂肪族ジオールを含むスラリを調製し、スラリをエステル化段階に供給することにより、芳香族ジカルボン酸及び脂肪族ジオールを製造法に導入する場合がある。直列に連結された少なくとも2個の反応器の多段式装置を用いてエステル化を行うことができ、装置ではエチレングリコールが還流下に保たれ、反応により生成する水とアルコールは系から除去される。
エステル化段階で製造されるエステル化生成物を次いで重縮合させる。重縮合は一段階で、又は複数段階で行われ得る。重縮合は典型的に減圧下で行われる。
ポリエステル製造法において、アルカリ金属化合物、アルカリ土類金属化合物、亜鉛化合物、鉛化合物、マンガン化合物、コバルト化合物、アルミニウム化合物、アンチモン化合物、チタン化合物、ゲルマニウム化合物又はリン化合物のようないずれの既知の通常の触媒も用いる場合がある。好ましくは、アンチモン化合物、ゲルマニウム化合物又はチタン化合物をポリエステル製造において用いる。
好ましくは、置換基として芳香環を有していない5価リン化合物をTi触媒と組み合わせて用いる。
methyl acid phosphate)、リン酸エチル(ethyl acid
phosphate)、リン酸モノブチル、リン酸ジフチル、リン酸ジオクチル及びリン酸トリエチレングリコール(triethylene glycol acid phosphate)から選ばれる場合がある。
マグネシウム化合物(Mg化合物)を加えることは、樹脂フィルムに静電気特性を与える。マグネシウム化合物は、酸化マグネシウム、水酸化マグネシウム、マグネシウムアルコキシド、酢酸マグネシウム及び炭酸マグネシウムから選ばれる場合がある。これらのマグネシウム化合物の中で、酢酸マグネシウムが好ましい。
重縮合段階の後、重縮合生成物を溶融押出機に直接供給するか、あるいは重縮合生成物を最初にペレット化し、次いで押出機において溶融させる。
て、縦延伸(機械方向(MD)又はフィルムの走行方向)及び横延伸(横方向(Cross direction)(CD)又は幅方向)の順序は特に規定されない。好ましくは、縦延伸を最初に行う。
二軸延伸されたポリエステルフィルムの厚さは、好ましくは75μm〜500μm、より好ましくは100μm〜350μm、最も好ましくは125μm〜275μmである。
ポリエステル中に存在するカルボキシル基は、ポリエステル分子の加水分解において酸触媒として働く場合がある。例えばポリエステルをある時間多湿条件に保ったときのそのような加水分解は分子量を低下させ、従ってポリエステルフィルムの機械的強度を低下させる。ポリエステルフィルムの十分な加水分解安定性を得るために、カルボキシル基含有量は好ましくは可能な限り低い。
より好ましくは5〜20meq/kgである。
カルボジイミド化合物は一官能基性及び多官能基性カルボジイミドに分類され得る。一官能基性カルボジイミドの例にはN,N’−ジシクロヘキシルカルボジイミド、1,3−ジイソプロピル−カルボジイミド、N,N’−ジイソプロピルフェニルカルボジイミド、N,N’−ジメチル−カルボジイミド、N,N’−ジイソブチルカルボジイミド、N,N’−ジオクチルカルボジイミド、t−ブチルイソプロピルカルボジイミド、N,N’−ジフェニルカルボジイミド、N,N’−ジ−t−ブチル−カルボジイミド、1−(3−ジメチルアミノプロピル)−3−エチルカルボジイミド及びジナフチルカルボジイミドが含まれる。
エポキシ化合物の好ましい例にはグリシジル化合物が含まれる。好ましい例は国際公開第2012120260号パンフレットに開示されているもの(例えばCardura E10P)である。
ステルと反応してポリエステル鎖を互いに連結させる少なくとも2個の反応性基、好ましくはエポキシ基を有する分子である。典型的にそれらの反応性基は押出の間にすでに実質的に(75%かもっと高い程度まで)枯渇しており、ポリエステルフィルムの製造後のその使用の間の鎖修復のためにはもはや利用できない。
オキサゾリン化合物は、好ましくは、2,2’−ビス(2−オキサゾリン)、2,2’−ビス(4−メチル−2−オキサゾリン)、2,2’−ビス(4,4’−ジメチル−2−オキサゾリン)、2,2’−ビス(4−メチル−2−オキサゾリン)、2,2’−ビス(4−エチル−2−オキサゾリン)、2,2’−ビス(4,4’−ジエチル−2−オキサゾリン)、2,2’−ビス(4−プロピル−2−オキサゾリン)、2,2’−ビス(4−ブチル−2−オキサゾリン)、2,2’−ビス(4−ヘキシル−2−オキサゾリン)、2,2’−ビス(4−フェニル−2−オキサゾリン)、2,2’−ビス(4−シクロヘキシル−2−オキサゾリン)、2,2’−ビス(4−ベンジル−2−オキサゾリン)、2,2’−p−フェニレンビス(2−オキサゾリン)、2,2’−m−フェニレンビス(2−オキサゾリン)、2,2’−o−フェニレンビス(2−オキサゾリン)、2,2’−p−フェニレン−ビス(4−メチル−2−オキサゾリン)、2,2’−p−フェニレンビス(4,4’−ジメチル−2−オキサゾリン)、2,2’−m−フェニレンビス(4,4’−ジメチル−2−オキサゾリン)、2,2’−m−フェニレンビス(4−メチル−2−オキサゾリン)、2,2’−m−フェニレンビス(4,4’−ジメチル−2−オキサゾリン)、2,2’−エチレンビス(2−オキサゾリン)、2,2’−テトラメチレンビス(2−オキサゾリン)、2,2’−ヘキサメチレンビス(2−オキサゾリン)、2,2’オクタメチレンビス(2−オキサゾリン)、2,2’−デカメチレンビス(2−オキサゾリン)、2,2’−エチレンビス(4−メチル−2−オキサゾリン)、2,2’−エチレンビス(4,4’−ジメチル−2−オキサゾリン)、2,2’−9,9’−ジフェノキシエタンビス(2−オキサゾリン)、2,2’−シクロヘキシレンビス(2−オキサゾリン)及び2,2’−ジフェニレンビス(2−オキサゾリン)のようなビスオキサゾリン化合物である。これらの中で、2,2’−ビス(2−オキサゾリン)は、ポリエステルとの反応性の観点から最も好適に用いられる。
UV光により引き起こされる分解を妨げるために、UV光吸収剤及び/又はUV光安定剤をポリエステルフィルムに加える場合がある。UV光吸収剤は、UV光を吸収してそれ
を熱エネルギーに変換するが、UV光安定剤は、ポリエステル樹脂の光分解により生成するラジカルを捕捉し、樹脂のさらなる分解を妨げる。ポリエステル樹脂の分解は、部分放電電圧の低下を生じ得、ポリエステルフィルムの強度の低下を生じ得、且つポリエステルフィルムの色調変化(例えば黄変)を生じ得る。
ポリエステルフィルムの表面の滑り性、耐摩耗性、耐引掻性のような性質を最適化するために、ポリエステルに無機粒子を加えるのが好ましい。無機粒子の例は、例えば粘土、雲母、酸化チタン、炭酸カルシウム、カオリン、タルク、シリカ、リン酸カルシウム、硫酸バリウム、アルミナ及びジルコニアの粒子である。好ましい無機粒子はシリカ及びアルミナである。シリカ及び/又はアルミナの量は、好ましくは0.025〜1.500重量%、より好ましくは0.050〜1.000重量%である。
無機粒子、UV光吸収性化合物、加水分解抵抗性を向上させる添加剤のような添加剤をいわゆるマスターバッチによりポリエステル樹脂に加えるのが好ましい。そのようなマス
ターバッチを調製するために、添加剤を最初に担体材料中に分散させる。担体材料は、好ましくはポリエステルであるが、それはポリエステルと適合性の別のポリマーの場合がある。フィルム形成の前に溶融押出機においてマスターバッチをポリエステルに加え、マスターバッチの成分をポリエステル中に溶解させるか又は微細に分散させる。
典型的に支持体とその上に与えられる層の間の接着を強化するために、高分子支持体を表面処理する場合がある。
図2は、本発明に従う太陽光発電モジュールの態様を略図的に示す。
材料
実施例において用いられるすべての材料は、他に特定しなければAldrich Chemical Co.(Belgium)及びAcros(Belgium)のような標準的な供給源から容易に入手可能であった。
Levasil 500、212.3gの脱塩水(DW)及び5.2gのProxel K dispをDISPERLUXTM ディスペンザーを用いて容器中で混合した。次いで650のRDI−S TiO2を撹拌下で加えた。撹拌を30分間続け、その後107
.5gのDW及び109.2gのKieselsol 500を加えて最終的な濃度を得た。系をさらに5分間撹拌した。得られる濃厚顔料分散系は、MalvernTM nano−Sを用いて測定される289nmの平均粒度及び25℃において且つ10s-1のせん断速度において13mPa.sの粘度を示した。
ピンホール
コーティング層におけるピンホールの発生を、Copex LF505(倍率は2xである)上で見られる約63cm2のコーティング層上のピンホールの数をカウントするこ
とにより視覚的に評価した。さらに、Leica−microsystemsから商業的に入手可能なLeica光学顕微鏡を用い、10x及び50xの倍率を用いてコーティング層の写真を撮った。
クロス−ハッチ試験法(Cross−Hatch test method)を用い、接着性に関してコーティングを試験した。さらに、121℃の温度及び100%の相対湿度(RH)において結露を伴う圧力下に試料を45時間保つ45時間プレッシャークッカーテスト(45 hours Pressure Cooker Test)の後に接着性を試験した。BS/ISO/DINリポーティングシステムを用いて、すなわち0−1が許容され得る接着性と考えられ、2−5が劣った接着性として、接着性を0−5まで等級付けした。
ダンプヒート試験(Damp Heat Test)(DHT)において、試料を85℃及び85%の相対湿度(RH)に1000時間保った。保存の間の色変化をCIE Δ
E(1976)及び黄色度指数YI313(ASTM E313)により評価した。
2715μmの厚さのポリエチレンテレフタレート(PET)シートを最初に縦に延伸し(x3.13)、次いで乾燥組成が表1に示される水性プライマーを片面上にコーティングした(10μmの湿潤コーティング厚さ)。乾燥の後、縦延伸され且つコーティングされたPETを横に延伸し(x3.33)、片面上にプライマーを含む260μmの厚さの二軸延伸されたPET(BOPET)シートを得た。
Claims (15)
- 太陽光発電モジュール(5)用のバックシート(1)であって、
支持体(300)と
支持体の片面上に与えられる接着層(100)と、
支持体の他の面上に与えられる外層(200)と
を含み、接着層及び外層の少なくとも1つが水性組成物からコーティングされ、水性組成物は水溶性又は水分散性結合剤と、水分散性コア/シェルポリイソシアナートとを含むことを特徴とする、バックシート。 - ポリイソシアナートのコアが疎水性ポリイソシアナートを含む、請求項1に記載のバックシート。
- 疎水性ポリイソシアナートが脂肪族ポリイソシアナートである、請求項2に記載のバックシート。
- 脂肪族ポリイソシアナートがヘキサメチレンジ−イソシアナート(HDI)又はそれから誘導されるイソシアヌレート三量体である、請求項3に記載のバックシート。
- ポリイソシアナートのシェルが親水性分散性基及び疎水性イソシアナート−遮蔽基を含むポリマーを含む、請求項1〜4のいずれかに記載のバックシート。
- 親水性分散性基が、ポリオキシアルキレシン基、スルホネート基、サルフェート基、ホスフェート基、ホスホネート基及びカルボキシル基からなる群から選ばれる、請求項5に記載のバックシート。
- 疎水性イソシアナート−遮蔽基が、ポリアクリレート、ポリエステル、ポリエーテル、ポリウレタン、ポリカーボネート、ポリオレフィン及びポリアミドからなる群から選ばれる、請求項5又は6に記載のバックシート。
- 疎水性ポリイソシアナートと、親水性分散性基及び疎水性イソシアナート−遮蔽基を含むポリマーとの重量比が30:70〜85:15の範囲内である、請求項1〜7のいずれかに記載のバックシート。
- 疎水性ポリイソシアナートと、親水性分散性基及び疎水性イソシアナート−遮蔽基を含むポリマーとが互いに共有結合している、請求項1〜8のいずれかに記載のバックシート。
- 接着層の水溶性もしくは水分散性結合剤が、アクリル樹脂と、ポリオレフィンと、ポリウレタンと、ウレタン−アクリルハイブリッドポリマーから選ばれる、請求項1〜9のいずれかに記載のバックシート。
- 外層の水溶性又は水分散性結合剤がアクリル樹脂及びフルオロポリマーから選ばれる、請求項1〜10のいずれかに記載のバックシート。
- アクリル樹脂が架橋可能な基を含む、請求項11に記載のバックシート。
- 水性組成物がさらにオキサゾリン又はカルボジイミド架橋剤を含む、請求項1〜12のいずれかに記載のバックシート。
- 請求項1〜13のいずれかに記載のバックシートを含む、太陽光発電モジュール(5)。
- 太陽光発電モジュール(5)用のバックシート(1)の製造方法であって、
−支持体(300)を用意する段階と、
−支持体の片面上に接着層(100)を適用する段階と、
−支持体の他の面上に外層(200)を適用する段階と
を含み、接着層及び外層の少なくとも1つが水性組成物から適用され、水性組成物は水溶性又は水分散性結合剤と、水分散性コア/シェルポリイソシアナートとを含むことを特徴とする方法。
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-
2015
- 2015-12-23 EP EP18203054.4A patent/EP3506372B1/en active Active
- 2015-12-23 EP EP15202413.9A patent/EP3185310B1/en not_active Not-in-force
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2016
- 2016-12-12 CN CN201811366816.0A patent/CN110071189A/zh active Pending
- 2016-12-12 CN CN201680075645.9A patent/CN108369966B/zh not_active Expired - Fee Related
- 2016-12-12 US US16/063,710 patent/US11121274B2/en active Active
- 2016-12-12 JP JP2018533096A patent/JP6546348B2/ja not_active Expired - Fee Related
- 2016-12-12 WO PCT/EP2016/080590 patent/WO2017108471A1/en active Application Filing
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2018
- 2018-11-20 JP JP2018217144A patent/JP2019062209A/ja active Pending
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JP2019503075A (ja) | 2019-01-31 |
EP3506372B1 (en) | 2020-12-02 |
CN108369966A (zh) | 2018-08-03 |
US20200266312A1 (en) | 2020-08-20 |
EP3185310B1 (en) | 2019-02-20 |
EP3185310A1 (en) | 2017-06-28 |
US11121274B2 (en) | 2021-09-14 |
WO2017108471A1 (en) | 2017-06-29 |
CN108369966B (zh) | 2021-07-09 |
EP3506372A1 (en) | 2019-07-03 |
CN110071189A (zh) | 2019-07-30 |
JP6546348B2 (ja) | 2019-07-17 |
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