WO2012111531A1 - 2軸延伸ポリエステルフィルム及びその製造方法、太陽電池用バックシート、並びに太陽電池モジュール - Google Patents
2軸延伸ポリエステルフィルム及びその製造方法、太陽電池用バックシート、並びに太陽電池モジュール Download PDFInfo
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- WO2012111531A1 WO2012111531A1 PCT/JP2012/053012 JP2012053012W WO2012111531A1 WO 2012111531 A1 WO2012111531 A1 WO 2012111531A1 JP 2012053012 W JP2012053012 W JP 2012053012W WO 2012111531 A1 WO2012111531 A1 WO 2012111531A1
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- WIPO (PCT)
- Prior art keywords
- polyester film
- film
- polyester
- stretching
- biaxially stretched
- Prior art date
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- UIPVMGDJUWUZEI-UHFFFAOYSA-N copper;selanylideneindium Chemical compound [Cu].[In]=[Se] UIPVMGDJUWUZEI-UHFFFAOYSA-N 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- WLWKIJKUDWYINL-UHFFFAOYSA-N cyclohexane-1,1,2,2,3,3-hexacarboxylic acid Chemical compound OC(=O)C1(C(O)=O)CCCC(C(O)=O)(C(O)=O)C1(C(O)=O)C(O)=O WLWKIJKUDWYINL-UHFFFAOYSA-N 0.000 description 1
- DTLWQZBOAYMHTO-UHFFFAOYSA-N cyclohexane-1,1,2,2,3-pentacarboxylic acid Chemical compound OC(=O)C1CCCC(C(O)=O)(C(O)=O)C1(C(O)=O)C(O)=O DTLWQZBOAYMHTO-UHFFFAOYSA-N 0.000 description 1
- RZIPTXDCNDIINL-UHFFFAOYSA-N cyclohexane-1,1,2,2-tetracarboxylic acid Chemical compound OC(=O)C1(C(O)=O)CCCCC1(C(O)=O)C(O)=O RZIPTXDCNDIINL-UHFFFAOYSA-N 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- KQWGXHWJMSMDJJ-UHFFFAOYSA-N cyclohexyl isocyanate Chemical compound O=C=NC1CCCCC1 KQWGXHWJMSMDJJ-UHFFFAOYSA-N 0.000 description 1
- MTGGGUZRAGKYEM-UHFFFAOYSA-N cyclopentane-1,1,2,2,3-pentacarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)(C(O)=O)C1(C(O)=O)C(O)=O MTGGGUZRAGKYEM-UHFFFAOYSA-N 0.000 description 1
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- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
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- 230000005611 electricity Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- DIZMSOQXELWOLG-UHFFFAOYSA-N ethane-1,1,1,2,2-pentacarboxylic acid Chemical compound OC(=O)C(C(O)=O)C(C(O)=O)(C(O)=O)C(O)=O DIZMSOQXELWOLG-UHFFFAOYSA-N 0.000 description 1
- HFKBPAKZRASAGX-UHFFFAOYSA-N ethane-1,1,1,2-tetracarboxylic acid Chemical compound OC(=O)CC(C(O)=O)(C(O)=O)C(O)=O HFKBPAKZRASAGX-UHFFFAOYSA-N 0.000 description 1
- MCOFCVVDZHTYIX-UHFFFAOYSA-N ethane-1,1,1-tricarboxylic acid Chemical compound OC(=O)C(C)(C(O)=O)C(O)=O MCOFCVVDZHTYIX-UHFFFAOYSA-N 0.000 description 1
- AIJZIRPGCQPZSL-UHFFFAOYSA-N ethylenetetracarboxylic acid Chemical compound OC(=O)C(C(O)=O)=C(C(O)=O)C(O)=O AIJZIRPGCQPZSL-UHFFFAOYSA-N 0.000 description 1
- UKFXDFUAPNAMPJ-UHFFFAOYSA-N ethylmalonic acid Chemical compound CCC(C(O)=O)C(O)=O UKFXDFUAPNAMPJ-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
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- 230000005484 gravity Effects 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000005338 heat storage Methods 0.000 description 1
- 238000005347 high resolution inductively coupled plasma mass spectrometry (HR-ICP-MS) Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 230000005606 hygroscopic expansion Effects 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- DXDRHHKMWQZJHT-FPYGCLRLSA-N isoliquiritigenin Chemical compound C1=CC(O)=CC=C1\C=C\C(=O)C1=CC=C(O)C=C1O DXDRHHKMWQZJHT-FPYGCLRLSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 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
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 150000002697 manganese compounds Chemical class 0.000 description 1
- FRVOOSTVCDXSRG-UHFFFAOYSA-N methanediimine;3,5,5-trimethylcyclohex-2-en-1-one Chemical compound N=C=N.CC1=CC(=O)CC(C)(C)C1 FRVOOSTVCDXSRG-UHFFFAOYSA-N 0.000 description 1
- RKGQUTNLMXNUME-UHFFFAOYSA-N methanetricarboxylic acid Chemical compound OC(=O)C(C(O)=O)C(O)=O RKGQUTNLMXNUME-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- 230000004899 motility Effects 0.000 description 1
- KMBWMZQYDLDUQQ-UHFFFAOYSA-N n'-[2,6-di(propan-2-yl)phenyl]methanediimine Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N=C=N KMBWMZQYDLDUQQ-UHFFFAOYSA-N 0.000 description 1
- SQEHYBILZVXINP-UHFFFAOYSA-N n'-tert-butyl-n-propan-2-ylmethanediimine Chemical compound CC(C)N=C=NC(C)(C)C SQEHYBILZVXINP-UHFFFAOYSA-N 0.000 description 1
- JEQPWXGHMRFTRF-UHFFFAOYSA-N n,n'-bis(2-methylpropyl)methanediimine Chemical compound CC(C)CN=C=NCC(C)C JEQPWXGHMRFTRF-UHFFFAOYSA-N 0.000 description 1
- NASVTBDJHWPMOO-UHFFFAOYSA-N n,n'-dimethylmethanediimine Chemical compound CN=C=NC NASVTBDJHWPMOO-UHFFFAOYSA-N 0.000 description 1
- ATYQZACNIHLXIS-UHFFFAOYSA-N n,n'-dinaphthalen-2-ylmethanediimine Chemical compound C1=CC=CC2=CC(N=C=NC3=CC4=CC=CC=C4C=C3)=CC=C21 ATYQZACNIHLXIS-UHFFFAOYSA-N 0.000 description 1
- NWBVGPKHJHHPTA-UHFFFAOYSA-N n,n'-dioctylmethanediimine Chemical compound CCCCCCCCN=C=NCCCCCCCC NWBVGPKHJHHPTA-UHFFFAOYSA-N 0.000 description 1
- CMESPBFFDMPSIY-UHFFFAOYSA-N n,n'-diphenylmethanediimine Chemical compound C1=CC=CC=C1N=C=NC1=CC=CC=C1 CMESPBFFDMPSIY-UHFFFAOYSA-N 0.000 description 1
- 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
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- GHHOKORHSWHMCC-UHFFFAOYSA-N naphthalene-1,2,3,4,5,6,7,8-octacarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(O)=O)=C(C(O)=O)C2=C(C(O)=O)C(C(=O)O)=C(C(O)=O)C(C(O)=O)=C21 GHHOKORHSWHMCC-UHFFFAOYSA-N 0.000 description 1
- NMIOQQFCVOLKMH-UHFFFAOYSA-N naphthalene-1,2,3,4,5,6-hexacarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(O)=O)=C(C(O)=O)C2=C(C(O)=O)C(C(=O)O)=CC=C21 NMIOQQFCVOLKMH-UHFFFAOYSA-N 0.000 description 1
- UAKKJHRECUCKMN-UHFFFAOYSA-N naphthalene-1,2,3,4,5-pentacarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(O)=O)=C2C(C(=O)O)=CC=CC2=C1C(O)=O UAKKJHRECUCKMN-UHFFFAOYSA-N 0.000 description 1
- MZYHMUONCNKCHE-UHFFFAOYSA-N naphthalene-1,2,3,4-tetracarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=C(C(O)=O)C(C(O)=O)=C21 MZYHMUONCNKCHE-UHFFFAOYSA-N 0.000 description 1
- KVQQRFDIKYXJTJ-UHFFFAOYSA-N naphthalene-1,2,3-tricarboxylic acid Chemical compound C1=CC=C2C(C(O)=O)=C(C(O)=O)C(C(=O)O)=CC2=C1 KVQQRFDIKYXJTJ-UHFFFAOYSA-N 0.000 description 1
- NCIAGQNZQHYKGR-UHFFFAOYSA-N naphthalene-1,2,3-triol Chemical compound C1=CC=C2C(O)=C(O)C(O)=CC2=C1 NCIAGQNZQHYKGR-UHFFFAOYSA-N 0.000 description 1
- ABMFBCRYHDZLRD-UHFFFAOYSA-N naphthalene-1,4-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1 ABMFBCRYHDZLRD-UHFFFAOYSA-N 0.000 description 1
- DFFZOPXDTCDZDP-UHFFFAOYSA-N naphthalene-1,5-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1C(O)=O DFFZOPXDTCDZDP-UHFFFAOYSA-N 0.000 description 1
- HRRDCWDFRIJIQZ-UHFFFAOYSA-N naphthalene-1,8-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=C2C(C(=O)O)=CC=CC2=C1 HRRDCWDFRIJIQZ-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
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012788 optical film Substances 0.000 description 1
- 239000011146 organic particle Substances 0.000 description 1
- LOGTZDQTPQYKEN-HZJYTTRNSA-N oxiran-2-ylmethyl (9z,12z)-octadeca-9,12-dienoate Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(=O)OCC1CO1 LOGTZDQTPQYKEN-HZJYTTRNSA-N 0.000 description 1
- XRQKARZTFMEBBY-UHFFFAOYSA-N oxiran-2-ylmethyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCC1CO1 XRQKARZTFMEBBY-UHFFFAOYSA-N 0.000 description 1
- BEJZOPYRAQVYHS-UHFFFAOYSA-N oxiran-2-ylmethyl cyclohexanecarboxylate Chemical compound C1CCCCC1C(=O)OCC1CO1 BEJZOPYRAQVYHS-UHFFFAOYSA-N 0.000 description 1
- PGXFPHPLDLNGQY-UHFFFAOYSA-N oxiran-2-ylmethyl docosanoate Chemical compound CCCCCCCCCCCCCCCCCCCCCC(=O)OCC1CO1 PGXFPHPLDLNGQY-UHFFFAOYSA-N 0.000 description 1
- PTLZMJYQEBOHHM-UHFFFAOYSA-N oxiran-2-ylmethyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OCC1CO1 PTLZMJYQEBOHHM-UHFFFAOYSA-N 0.000 description 1
- KYVUJPJYTYQNGJ-UHFFFAOYSA-N oxiran-2-ylmethyl hexadecanoate Chemical compound CCCCCCCCCCCCCCCC(=O)OCC1CO1 KYVUJPJYTYQNGJ-UHFFFAOYSA-N 0.000 description 1
- DJTYNOVDSWHTJM-UHFFFAOYSA-N oxiran-2-ylmethyl nonanoate Chemical compound CCCCCCCCC(=O)OCC1CO1 DJTYNOVDSWHTJM-UHFFFAOYSA-N 0.000 description 1
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluenecarboxylic acid Natural products CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 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
- FVDOBFPYBSDRKH-UHFFFAOYSA-N perylene-3,4,9,10-tetracarboxylic acid Chemical compound C=12C3=CC=C(C(O)=O)C2=C(C(O)=O)C=CC=1C1=CC=C(C(O)=O)C2=C1C3=CC=C2C(=O)O FVDOBFPYBSDRKH-UHFFFAOYSA-N 0.000 description 1
- KFDKNTQGTAEZGC-UHFFFAOYSA-N phenanthrene-1-carboxylic acid Chemical compound C1=CC2=CC=CC=C2C2=C1C(C(=O)O)=CC=C2 KFDKNTQGTAEZGC-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- CASUWPDYGGAUQV-UHFFFAOYSA-M potassium;methanol;hydroxide Chemical compound [OH-].[K+].OC CASUWPDYGGAUQV-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 1
- 229940039790 sodium oxalate Drugs 0.000 description 1
- HZJQZHXRILHFBL-UHFFFAOYSA-L sodium oxalate titanium(4+) Chemical compound C(C(=O)[O-])(=O)[O-].[Na+].[Ti+4] HZJQZHXRILHFBL-UHFFFAOYSA-L 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 239000005341 toughened glass Substances 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/048—Encapsulation of modules
- H01L31/049—Protective back sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
- B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
- B29C55/14—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
- B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
- B29C55/16—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial simultaneously
- B29C55/165—Apparatus therefor
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Definitions
- the present invention relates to a biaxially stretched polyester film and a method for producing the same, a solar cell backsheet, and a solar cell module.
- Polyester is applied to various applications such as electrical insulation and optical applications.
- solar cell applications such as a sheet for protecting the back surface of a solar cell (so-called back sheet) have attracted attention as electrical insulation applications in recent years.
- polyester usually has many carboxy groups and hydroxyl groups on its surface, and tends to undergo a hydrolysis reaction under environmental conditions where moisture exists and tends to deteriorate over time.
- the installation environment in which solar cell modules are generally used is an environment that is constantly exposed to wind and rain, such as outdoors, and is exposed to conditions where hydrolysis reaction is likely to proceed. Therefore, polyester is applied to solar cell applications. Sometimes, it is an important property that the hydrolyzability of polyester is suppressed.
- heat setting in which crystallization is performed by applying heat at a somewhat high temperature after stretching.
- This heat setting is usually performed in a temperature range of about 230 to 240 ° C. from the viewpoint of increasing the crystallinity and removing residual strain.
- it is desirable that the temperature during heat setting is low.
- a wrinkle, a crack, etc. tend to arise for various reasons at the time of heating conveyance.
- a laminate in which a layer containing a metal or a metal-based oxide is provided on a polyester film is disclosed from the viewpoint of dimensional stabilization (see, for example, JP 2010-52416 A). .
- a stretched polyester film in which the maximum value of the specific gravity change amount in the film width direction is 0.13% or less, and the thermal shrinkage rate in the longitudinal direction and the width direction is 3% or less (for example, Japanese Patent Laid-Open No. 2004-2004). No. -18784), it is said that the bowing phenomenon that deforms in a bow shape in the longitudinal direction of the film when the film stretched in the longitudinal direction is stretched in the width direction and heat-set is suppressed.
- the bowing phenomenon is one factor that disturbs uniformity in the film width direction.
- the heating temperature at the time of heat setting works effectively.
- the temperature at the time of heat setting (heat setting temperature) is lowered to, for example, 210 ° C. or less.
- the polyester film tends to loosen at the center compared to the edge in the film width direction when drying and laminating the film during the process, and the wrinkles and scratches during transportation due to the difference in slack between the edge and the center. Etc. are likely to occur.
- the wrinkles and scratches formed on the polyester tend to impair hydrolysis resistance, and in order to achieve longer-term durability than before, it is indispensable to establish a method that is less likely to cause wrinkles and scratches during transportation. .
- the present invention has been made in view of the above, and a biaxially stretched polyester film excellent in hydrolysis resistance with less generation of scratches than in the past, a method for producing the same, and a solar cell excellent in long-term durability performance.
- An object is to provide a back sheet and a solar cell module capable of obtaining stable power generation performance over a long period of time, and to achieve the object.
- the present invention has obtained the knowledge that the cause that the central part is more likely to be slack than the edge part in the width direction of the film is the variation in the thermal shrinkage rate in the width direction accompanying the variation in the crystallinity in the film width direction, This has been achieved based on such knowledge.
- Specific means for achieving the above object are as follows.
- ⁇ 1> It has a film width of 1 m or more, an intrinsic viscosity (IV) of 0.70 dL / g or more, and a pre-peak temperature measured by differential scanning calorimetry (DSC) of 160 ° C. or more and 210 ° C. or less, the variation in crystallinity in the film width direction is the biaxially oriented polyester film is 5.0% or less than 0.3%.
- DSC differential scanning calorimetry
- the variation in the thermal shrinkage rate in the direction orthogonal to the film width direction and the variation in the thermal shrinkage rate in the direction parallel to the film width direction are both 0.03% or more and 0.50%.
- ⁇ 5> The biaxial stretching according to any one of ⁇ 1> to ⁇ 4>, including a structural unit derived from a polyfunctional monomer in which the total number of carboxylic acid groups and hydroxyl groups is 3 or more. It is a polyester film.
- ⁇ 6> A constitutional unit derived from a polyfunctional monomer in which the total of the number of carboxylic acid groups and the number of hydroxyl groups is 3 or more, and the content ratio of the constitutional unit derived from the polyfunctional monomer is the total constitution in the polyester.
- ⁇ 7> The biaxially stretched polyester according to any one of ⁇ 1> to ⁇ 6>, further including a structural portion derived from an end-capping agent selected from an oxazoline compound, a carbodiimide compound, and an epoxy compound It is a film.
- ⁇ 8> The biaxially stretched polyester film according to ⁇ 7>, wherein the content ratio of the structural portion derived from the end-capping agent is 0.1% by mass or more and 5% by mass or less with respect to the total mass of the polyester. It is.
- a polyester raw material resin is melt-extruded into a sheet, cooled on a casting drum to form a polyester film, a longitudinal stretching step of longitudinally stretching the formed polyester film in a longitudinal direction, and the longitudinal A transverse stretching step of transversely stretching the stretched polyester film in the width direction perpendicular to the longitudinal direction, and
- the transverse stretching step includes a preheating step of preheating the polyester film after longitudinal stretching to a temperature at which the polyester film can be stretched, and a stretching step of stretching the preheated polyester film laterally by applying tension in the width direction orthogonal to the longitudinal direction. While the maximum reachable film surface temperature of the polyester film after the longitudinal stretching and the transverse stretch is controlled in a range of 160 ° C. or more and 210 ° C.
- the variation in the maximum reachable film surface temperature in the width direction is set to 0.
- the heat setting step is a method for producing a biaxially stretched polyester film according to ⁇ 9>, wherein the widthwise end of the polyester film is selectively heated from at least one side of the polyester film.
- the thickness of the polyester film after passing through the cooling step is 180 ⁇ m or more and 350 ⁇ m or less, and in the heat setting step, the heating surface of the polyester film to be heated is brought into contact with the casting drum in the film forming step. And heating so that the surface temperature of the heating surface immediately after the heating is higher in the range of 0.5 ° C. or more and 5.0 ° C. or less than the surface temperature of the non-heating surface opposite to the heating surface.
- the heat setting step is the method for producing a biaxially stretched polyester film according to any one of ⁇ 9> to ⁇ 11>, wherein the widthwise end of the polyester film is radiatively heated by a heater.
- At least one of the preheating step, the stretching step, and the thermal relaxation step may be any one of the items ⁇ 9> to ⁇ 13>, in which a width direction end of the polyester film is radiatively heated by a heater. It is a manufacturing method of the biaxially stretched polyester film of description.
- the polyester raw material resin includes any one of the above ⁇ 9> to ⁇ 14>, which contains a polyfunctional monomer having a total of 3 or more carboxylic acid groups and hydroxyl groups as a copolymerization component. It is a manufacturing method of the biaxially stretched polyester film of description.
- the polyester raw material resin includes a polyfunctional monomer having a total number of carboxylic acid groups and hydroxyl groups of 3 or more as a copolymerization component, and is a structural unit derived from the polyfunctional monomer.
- the content ratio in is any one of ⁇ 9> to ⁇ 15> above, wherein the content ratio in the polyester raw material resin is 0.005 mol% or more and 2.5 mol% or less.
- the film forming step includes a step of including, in the polyester raw material resin, an end-capping agent selected from an oxazoline-based compound, a carbodiimide compound, and an epoxy compound, and reacted with the end-capping agent by melt kneading.
- ⁇ 18> The production of the biaxially stretched polyester film according to ⁇ 17>, wherein the content of the terminal blocking agent is 0.1% by mass or more and 5% by mass or less with respect to the total mass of the polyester raw material resin. Is the method.
- a solar cell backsheet comprising the biaxially stretched polyester film according to any one of ⁇ 1> to ⁇ 8>.
- ⁇ 20> A transparent substrate on which sunlight is incident, a solar cell element disposed on one side of the substrate, and the ⁇ 19>.
- the solar cell module provided with the solar cell backsheet as described in 19>.
- the solar cell module which can obtain the stable power generation performance over the long term and the solar cell backsheet excellent in the long-term durability performance can be provided.
- polyester film of the present invention and the production method thereof will be described in detail, and the solar cell backsheet and the solar cell module of the present invention will also be described based on the description.
- the polyester film of the present invention has a film width of 1 m or more, an intrinsic viscosity (IV) value of 0.70 dL / g or more, and differential scanning calorimetry (DSC), hereinafter abbreviated as “DSC”.
- the pre-peak temperature measured in (1) is 160 ° C. or higher and 210 ° C. or lower, and the variation in crystallinity in the film width direction is in the range of 0.3% or higher and 5.0% or lower. It is.
- the hydrolysis resistance of the polyester film was insufficient because the heat setting temperature in the case of crystallization after stretching and heat setting was generally high at about 230 ° C to 240 ° C. From the viewpoint of improving hydrolysis resistance Therefore, it is effective that the heat fixing temperature at the time of heat fixing is controlled to 160 to 210 ° C. at the film temperature. However, if the heat fixing temperature is set to 210 ° C. or lower, the center portion of the polyester film is more likely to be loosened during the manufacturing process than the widthwise end portion. There is a problem in that scratches are easily generated.
- the variation in crystallinity in the width direction that is, the crystallinity at the edge is lower than the crystallinity at the center of the film. It is estimated that there is variation in the heat shrinkage rate in the width direction due to. Specifically, the thermal contraction rate of the central portion is smaller than that of the end portion of the film. Thus, when a difference arises in the thermal shrinkage rate in the film width direction, the film center portion is less likely to shrink than the end portion, and therefore the film center portion is loosened compared to the end portion.
- the IV 0.3% or more and 5.0% or less
- crystallization is delayed when the IV is increased, and variation in crystallinity can be suppressed to a small level.
- said manufacturing process it heats to predetermined temperature, for example, the drying process after film forming, or 2 or more types of films to bond together to a metal roll, and apply
- the heat setting temperature is usually 230 to 240 ° C., but the horizontal axis indicates the heat setting temperature, and the vertical axis indicates the crystallinity (the crystallinity reached when the temperature is held for 20 seconds).
- the change in crystallinity when the heat setting temperature is 160 to 210 ° C is larger than the change in crystallinity when the heat setting temperature is 230 to 240 ° C, and the temperature dependence is large.
- the film temperature at the end tends to be lower than the center of the film due to the effect of heat escaping from the clip. As a result, the heat setting temperature is lower at the film edge than at the center in the film width direction.
- the influence of the difference in the heat setting temperature between the center portion and the end portion in the film width direction is likely to appear as a difference in crystallinity.
- the variation in crystallinity tends to be large (the crystallinity at the end is smaller than that at the center). That is, when the heat setting temperature is lowered to increase the hydrolysis resistance, the change in crystallinity in the film plane increases.
- the IV value is 0.70 or more, the molecular chain of the polyester moves. Since it becomes difficult, crystallization can be made difficult to occur. As a result, variation in crystallinity in the film width direction is suppressed while forming a relatively thick film, scratches such as scratches are prevented, and the hydrolysis resistance is excellent.
- the intrinsic viscosity (IV) is set to a relatively high range of 0.70 dL / g or more. As described above, when IV is less than 0.70 dL / g, crystallization is relatively easy to proceed, and the film surface is easily scratched. Therefore, even if the heating temperature at the time of heat setting is lowered to, for example, 210 ° C. or lower in order to improve hydrolysis resistance, good hydrolysis resistance cannot be obtained. From the viewpoint of further improving the hydrolysis resistance and improving the weather resistance, the IV value is preferably 0.75 dL / g or more, more preferably 0.78 dL / g or more, and further preferably 0.80 dL / g or more.
- the IV value is preferably 0.70 dL / g or more and 0.90 dL / g or less, more preferably 0.75 dL / g or more and 0.90 dL / g or less, and 0.75 dL / g or less.
- g or more and 0.85 dL / g or less is more preferable, and 0.78 dL / g or more and 0.85 dL / g or less is most preferable.
- the pre-peak temperature when measured by differential scanning calorimetry is in the range of 160 ° C. or higher and 210 ° C. or lower.
- the “pre-peak temperature” of DSC here is the temperature of the peak that appears first when DSC measurement is performed, and generally corresponds to the highest film surface temperature (heat setting temperature) of the polyester film during heat setting.
- the heat setting temperature is too low to sufficiently perform heat setting, resulting in a large variation in crystallinity and consequently a large heat shrinkage difference. That is, the slack at the center of the film becomes large and scratches occur.
- the DSC pre-peak temperature is more preferably 170 ° C. or more and 200 ° C. or less, and still more preferably 175 ° C. or more and 195 ° C. or less for the same reason as described above.
- the pre-peak temperature of the DSC is a value obtained by a conventional method by differential scanning calorimetry.
- the variation in crystallinity in the film width direction is in the range of 0.3% to 5.0%.
- the change in crystallinity changes the heat shrinkage rate, and the crystallinity tends to be higher at the center of the film than at the edge of the film. Smaller than the part. Therefore, if the variation in crystallinity is less than 0.3%, the film center portion is almost free from slack, so that the film center portion is too tensioned and wrinkles are likely to occur during conveyance. Further, if the variation in crystallinity exceeds 5.0%, the film is greatly loosened at the central part in the film width direction, and wrinkles, scratches, etc. are likely to occur at the time of conveyance due to the slack difference between the edge part in the width direction and the central part. When scratches or the like occur on the film surface, the weather resistance is impaired.
- the variation in crystallinity is preferably from 0.5% to 3.0%, more preferably from 0.6% to 1.5%, and more preferably from 0.7% to 1.3% for the same reason as above. % Or less is more preferable.
- Dispersion of crystallinity in the film width direction is obtained by cutting out a total of three points, one at the center and two at both ends, with respect to the total width of the film in the width direction perpendicular to the film longitudinal direction. It is calculated by subtracting the crystallinity of the smaller value of the crystallinity at both ends from the crystallinity of the two.
- the degree of crystallinity is a value calculated from the density of the film. That is, the density X (g / cm 3) of the film density at a crystallinity of 0% Y (g / cm 3 ), using density Z (g / cm 3) at 100% crystalline, following The crystallinity Xc (%) derived from the calculation formula.
- the density can be measured according to JIS K7112.
- Xc ⁇ Z ⁇ (XY) ⁇ / ⁇ X ⁇ (ZY) ⁇ ⁇ 100
- the above variation in crystallinity tends to occur remarkably when the film width is 1 m or more.
- the film width is larger than 1m, the temperature change at the end gripped by clips etc. is large, but the temperature change hardly occurs near the center, so crystallization occurs near the center and at the end.
- the difference in degree widens, the degree of crystallinity near the center increases, and it becomes easier to loosen.
- the thermal shrinkage rate (heating condition: heating at 150 ° C. for 30 minutes) of the polyester film of the present invention is preferably 2.0% or less.
- the heat shrinkage rate is adjusted to the above range by controlling the heating temperature (T heat setting and / or T heat relaxation ) in each step of heat setting and / or heat relaxation in the transverse stretching step.
- T heat setting and / or T heat relaxation the heating temperature
- polyester generally has a larger thermal expansion coefficient and hygroscopic expansion coefficient than glass, so it tends to be stressed by changes in temperature and humidity and tends to cause cracks and peeling of the layer, but the thermal contraction rate is within the above range.
- the heat shrinkage rate is more preferably 1.0% or less, and further preferably 0.5% or less.
- the polyester film of the present invention is formed in the film width direction [in the case of producing by stretching and the like while transporting a long film, the direction (TD direction) perpendicular to the transport direction (MD direction)].
- the variation in the heat shrinkage rate in the direction perpendicular to the width direction (MD direction during production) and the variation in the heat shrinkage rate in the direction parallel to the film width direction (TD direction during production) are both 0.03%.
- the content is preferably in the range of 0.50% or more. If the variation in thermal shrinkage is 0.03% or more, it is advantageous in terms of wrinkles during conveyance.
- the variation in the thermal shrinkage rate is 0.50% or less, the difference in slackness in the film width direction is suppressed, and the occurrence of wrinkles, scratches, etc. during conveyance accompanying the difference in slackness can be prevented.
- the variation in the thermal shrinkage rate can be adjusted by adjusting the variation in the crystallinity in the range of 0.3% to 5.0%.
- the variation in the thermal shrinkage rate is more preferably in the range of 0.04% to 0.30%, more preferably in the range of 0.04% to 0.10%, for the same reason as described above.
- the range of 04% or more and 0.08% or less is most preferable.
- the thermal shrinkage rate has two values in the film width direction depending on whether the MD direction expansion or contraction is observed as the amount of contraction (stretching length) at the measurement point.
- the variation in the heat shrinkage rate in the film width direction is obtained by cutting out a total of three points, one at the center and two at both ends, with respect to the entire film width in the width direction orthogonal to the film longitudinal direction (MD direction at the time of manufacture).
- the rate is measured, and the absolute value is calculated by subtracting the thermal contraction rate of the center portion from the thermal contraction rate at both ends and subtracting the thermal contraction rate having the larger difference from the thermal contraction rate of the central portion.
- two types of the MD direction and the TD direction can be respectively obtained according to the direction in which the contraction amount is measured.
- the thickness of the polyester film of the present invention is preferably in the range of 180 ⁇ m or more and 350 ⁇ m or less.
- temperature distribution is likely to occur in the film thickness direction, and variations in crystallinity are likely to occur.In the present invention, variations in crystallinity are suppressed. The occurrence of scratches can be prevented and the hydrolysis resistance can be improved more effectively.
- the thickness is more preferably in the range of 200 ⁇ m to 320 ⁇ m, and still more preferably in the range of 200 ⁇ m to 290 ⁇ m.
- the amount of terminal carboxyl groups (terminal COOH amount; AV) of the polyester film of the present invention is preferably 5 eq / ton or more and 21 eq / ton or less.
- the amount of terminal COOH is more preferably 6 eq / ton to 20 eq / ton, and further preferably 7 eq / ton to 19 eq / ton.
- “eq / ton” represents a molar equivalent per ton.
- the polyester film of the present invention is synthesized by copolymerizing a dicarboxylic acid component and a diol component. Details of the dicarboxylic acid component and the diol component will be described later.
- the polyester film of the present invention is a polyfunctional monomer having a total (a + b) of the number of carboxylic acid groups (a) and the number of hydroxyl groups (b) of 3 or more (hereinafter referred to as “a trifunctional or more polyfunctional monomer”). Alternatively, it is preferable to include a structural unit derived simply from “polyfunctional monomer”).
- the polyester film of the present invention can be obtained, for example, by subjecting (A) a dicarboxylic acid component and (B) a diol component to an esterification reaction and / or transesterification reaction by a well-known method. Is obtained by copolymerizing a trifunctional or higher polyfunctional monomer. Details such as examples and preferred embodiments of the dicarboxylic acid component, the diol component, and the polyfunctional monomer are as described below.
- -Constituent units derived from polyfunctional monomers As a structural unit derived from a polyfunctional monomer in which the total (a + b) of the number of carboxylic acid groups (a) and the number of hydroxyl groups (b) is 3 or more, as described later, the number of carboxylic acid groups (a) Is a carboxylic acid having 3 or more and a polyfunctional monomer having a hydroxyl number (b) of 3 or more, such as an ester derivative or an acid anhydride thereof, and “a carboxylic acid group having both a hydroxyl group and a carboxylic acid group in one molecule.
- Oxyacids in which the total (a + b) of the number (a) of hydroxyl groups and the number (b) of hydroxyl groups is 3 or more. Details of these examples and preferred embodiments are as described later. Further, at the carboxy terminus of the carboxylic acid or the carboxy terminus of the “polyfunctional monomer having both a hydroxyl group and a carboxylic acid group in one molecule”, oxyacids such as l-lactide, d-lactide, and hydroxybenzoic acid, Those obtained by adding a derivative thereof or a combination of a plurality of such oxyacids are also suitable. These may be used individually by 1 type, or may use multiple types together as needed.
- the content ratio of the structural unit derived from the trifunctional or higher polyfunctional monomer is 0.005 mol% to 2.5 mol% with respect to all the structural units in the polyester film. It is preferable.
- the content ratio of the structural unit derived from the polyfunctional monomer is more preferably 0.020 mol% to 1 mol%, still more preferably 0.025 mol% to 1 mol%, still more preferably 0.8. It is 035 mol% or more and 0.5 mol% or less, Especially preferably, it is 0.05 mol% or more and 0.5 mol% or less, Most preferably, it is 0.1 mol% or more and 0.25 mol% or less.
- a structure in which a polyester molecular chain is branched from a structural unit derived from a trifunctional or higher polyfunctional monomer is obtained by the presence of a structural unit derived from a trifunctional or higher polyfunctional monomer in the polyester film. Can be entangled. As a result, even if the polyester molecules are hydrolyzed and the molecular weight decreases due to exposure to a high temperature and high humidity environment, entanglement is formed between the polyester molecules, so that the embrittlement of the polyester film is suppressed and more excellent. Weather resistance is obtained. Furthermore, such entanglement is also effective in suppressing heat shrinkage.
- the polyester film used for the back sheet for solar cell is in close contact with a sealing agent such as EVA after an application layer such as an easy-adhesion layer is applied and formed, but in an environment where it is exposed to wind and rain such as outdoors. Even when left for a long time, good adhesion that hardly peels off can be obtained. Therefore, when the content ratio of the structural unit derived from the trifunctional or higher polyfunctional monomer is 0.005 mol% or more, the weather resistance, low heat shrinkage, and adhesion with the coating layer formed on the polyester film are adhered. The power is likely to improve further.
- the content ratio of the structural unit derived from the trifunctional or higher polyfunctional monomer is 2.5 mol% or less, the structural unit derived from the trifunctional or higher polyfunctional monomer is bulky, so that it is difficult to form a crystal. It is suppressed. As a result, it is possible to promote the formation of a low migration component formed through the crystal and suppress the decrease in hydrolyzability. Furthermore, due to the bulkiness of the structural unit derived from a trifunctional or higher polyfunctional monomer, the amount of fine irregularities on the film surface increases, so that an anchor effect is easily manifested, and the polyester film and the coating layer formed on the film Adhesion improves.
- the increase in free volume is suppressed by the bulkiness, and heat shrinkage that occurs when polyester molecules slip through the large free volume can be suppressed.
- a decrease in glass transition temperature (Tg) due to excessive addition of structural units derived from a trifunctional or higher polyfunctional monomer is also suppressed, which is effective in preventing a decrease in weather resistance.
- the polyester film of the present invention preferably further has a structural portion derived from an end-capping agent selected from an oxazoline-based compound, a carbodiimide compound, and an epoxy compound.
- the “structural portion derived from the end-capping agent” refers to a structure in which the end-capping agent reacts with the carboxylic acid at the polyester end and is bonded to the end.
- the end-capping agent reacts with the carboxylic acid at the end of the polyester and is bonded to the end of the polyester. It becomes easy to stably maintain a desired value such as a range. That is, the hydrolysis of the polyester promoted by the terminal carboxylic acid is suppressed, and the weather resistance can be kept high.
- the end portion of the molecular chain becomes bulky by binding to the polyester terminal, and the amount of fine irregularities on the film surface increases, so that the anchor effect is easily developed, and the polyester film and a coating layer formed on the film by coating Improved adhesion.
- the end-capping agent is bulky and the polyester molecules are prevented from moving through the free volume. As a result, it also has an effect of suppressing heat shrinkage accompanied by molecular movement.
- the end-capping agent is an additive that reacts with the carboxyl group at the end of the polyester to reduce the amount of carboxyl end of the polyester.
- a terminal blocker may be used individually by 1 type, and may be used in combination of 2 or more type.
- the end-capping agent is preferably contained in the range of 0.1% by mass to 5% by mass, more preferably 0.3% by mass to 4% by mass with respect to the mass of the polyester film. More preferably, it is 0.5 mass% or more and 2 mass% or less.
- the content ratio of the end-capping agent in the polyester film is 0.1% by mass or more, the adhesion with the coating layer is improved and the weather resistance can be improved due to the AV lowering effect, and the low heat shrinkage is also achieved. Can be granted.
- the content ratio of the terminal sealing agent in the polyester film is 5% by mass or less, the adhesion with the coating layer is improved and the glass transition temperature (Tg) of the polyester is decreased by the addition of the terminal sealing agent. Is suppressed, and a decrease in weather resistance and an increase in heat shrinkage due to this can be suppressed. This is due to the fact that the increase in hydrolyzability caused by the relatively increased polyester reactivity is suppressed by the decrease in Tg, or the mobility of the polyester molecules that increase due to the decrease in Tg is likely to increase. This is because heat shrinkage is suppressed.
- a compound having a carbodiimide group, an epoxy group, or an oxazoline group is preferable.
- Specific examples of the terminal blocking agent include carbodiimide compounds, epoxy compounds, oxazoline compounds, and the like.
- the carbodiimide compound having a carbodiimide group includes a monofunctional carbodiimide and a polyfunctional carbodiimide.
- monofunctional carbodiimides include dicyclohexylcarbodiimide, diisopropylcarbodiimide, dimethylcarbodiimide, diisobutylcarbodiimide, dioctylcarbodiimide, t-butylisopropylcarbodiimide, diphenylcarbodiimide, di-t-butylcarbodiimide and di- ⁇ -naphthylcarbodiimide. Of these, dicyclohexylcarbodiimide and diisopropylcarbodiimide are preferable.
- the polyfunctional carbodiimide is preferably a polycarbodiimide having a polymerization degree of 3 to 15.
- Polycarbodiimide generally has a repeating unit represented by “—R—N ⁇ C ⁇ N—” or the like, and R represents a divalent linking group such as alkylene or arylene.
- repeating units examples include 1,5-naphthalene carbodiimide, 4,4′-diphenylmethane carbodiimide, 4,4′-diphenyldimethylmethane carbodiimide, 1,3-phenylene carbodiimide, 2,4-tolylene carbodiimide, 2,6-tolylenecarbodiimide, a mixture of 2,4-tolylenecarbodiimide and 2,6-tolylenecarbodiimide, hexamethylenecarbodiimide, cyclohexane-1,4-carbodiimide, xylylenecarbodiimide, isophoronecarbodiimide, dicyclohexylmethane-4, 4'-carbodiimide, methylcyclohexanecarbodiimide, tetramethylxylylene carbodiimide, 2,6-diisopropylphenylcarbodiimide and 1,3,5-triisopropylbenzene-2 Such as
- the carbodiimide compound is preferably a carbodiimide compound having high heat resistance in that generation of isocyanate gas due to thermal decomposition is suppressed.
- the molecular weight degree of polymerization
- the terminal of the carbodiimide compound has a structure having high heat resistance.
- the polyester film using a carbodiimide compound preferably has an isocyanate gas generation amount of 0 to 0.02 mass% when held at a temperature of 300 ° C. for 30 minutes. If the amount of isocyanate-based gas generated is 0.02% by mass or less, bubbles (voids) are not easily generated in the polyester film, and therefore stress-concentrated sites are not easily formed. Can be prevented. Thereby, the close_contact
- the isocyanate-based gas is a gas having an isocyanate group, such as diisopropylphenyl isocyanate, 1,3,5-triisopropylphenyl diisocyanate, 2-amino-1,3,5-triisopropylphenyl-6-isocyanate. 4,4′-dicyclohexylmethane diisocyanate, isophorone diisocyanate, and cyclohexyl isocyanate.
- an isocyanate group such as diisopropylphenyl isocyanate, 1,3,5-triisopropylphenyl diisocyanate, 2-amino-1,3,5-triisopropylphenyl-6-isocyanate.
- 4,4′-dicyclohexylmethane diisocyanate, isophorone diisocyanate, and cyclohexyl isocyanate such as diisopropylphenyl isocyanate, 1,3,5
- Preferred examples of the epoxy compound having an epoxy group include glycidyl ester compounds and glycidyl ether compounds.
- glycidyl ester compounds include benzoic acid glycidyl ester, t-Bu-benzoic acid glycidyl ester, P-toluic acid glycidyl ester, cyclohexanecarboxylic acid glycidyl ester, pelargonic acid glycidyl ester, stearic acid glycidyl ester, lauric acid glycidyl ester , Glycidyl palmitate, glycidyl behenate, glycidyl versatate, glycidyl oleate, glycidyl linoleate, glycidyl linolein, glycidyl behenol, glycidyl stearol, diglycidyl terephthalate, isophthalic acid Diglycidyl ester, diglycidyl phthalate, diglycidyl naphthalene dicar
- the glycidyl ether compound examples include phenyl glycidyl ether, O-phenyl glycidyl ether, 1,4-bis ( ⁇ , ⁇ -epoxypropoxy) butane, 1,6-bis ( ⁇ , ⁇ - Epoxypropoxy) hexane, 1,4-bis ( ⁇ , ⁇ -epoxypropoxy) benzene, 1- ( ⁇ , ⁇ -epoxypropoxy) -2-ethoxyethane, 1- ( ⁇ , ⁇ -epoxypropoxy) -2-benzyl Oxyethane, 2,2-bis- [ politician- ( ⁇ , ⁇ -epoxypropoxy) phenyl] propane, 2,2-bis- (4-hydroxyphenyl) propane and 2,2-bis- (4-hydroxyphenyl) Examples thereof include bisglycidyl polyether obtained by the reaction of bisphenol such as methane and epichlorohydrin.
- the oxazoline compound can be appropriately selected from compounds having an oxazoline group and is preferably a bisoxazoline compound.
- Examples of the bisoxazoline compound include 2,2′-bis (2-oxazoline), 2,2′-bis (4-methyl-2-oxazoline), and 2,2′-bis (4,4-dimethyl-2).
- 2,2′-bis (2-oxazoline) is most preferable from the viewpoint of good reactivity with polyester and high weather resistance improvement effect.
- Bisoxazoline compounds may be used singly or in combination of two or more unless the effects of the present invention are impaired.
- the trifunctional or higher polyfunctional monomer and the terminal blocking agent described above or below may be used singly or in combination.
- the polyester film of the present invention may be produced by any method as long as it can satisfy the variations in the IV value, the pre-peak temperature, and the crystallinity.
- it can be most suitably produced by the method for producing a polyester film of the present invention shown below.
- the manufacturing method of the polyester film of this invention is demonstrated concretely.
- the method for producing a polyester film of the present invention includes a film forming step of melt-extruding a polyester raw material resin into a sheet shape, cooling on a casting drum to form a polyester film, and longitudinally stretching the formed polyester film in the longitudinal direction. While comprising at least a longitudinal stretching step and a lateral stretching step of laterally stretching the polyester film after the longitudinal stretching in the width direction perpendicular to the longitudinal direction,
- the transverse stretching step includes a preheating step of preheating the polyester film after longitudinal stretching to a temperature at which the polyester film can be stretched, and a stretching step of stretching the preheated polyester film laterally by applying tension in the width direction orthogonal to the longitudinal direction.
- the variation in the maximum reachable film surface temperature in the width direction is set to 0.
- a heat setting step for heating and crystallizing by heating at 5 ° C. or more and 5.0 ° C. or less, a heat relaxation step for heating the heat-fixed polyester film, and relaxing the tension of the polyester film, and after heat relaxation And a cooling step for cooling the polyester film.
- the polyester after longitudinal stretching is preheated in advance.
- the maximum temperature in the width direction is achieved while controlling the maximum film surface temperature of the polyester film subjected to the longitudinal stretching and the lateral stretching in the range of 160 ° C. to 210 ° C. Heating so that the variation in the film surface temperature is 0.5 ° C. or more and 5.0 ° C.
- the hydrolysis resistance of a polyester film is preferably when a tension is applied to the film to stretch the polyester molecules in the length direction of the molecules.
- stretching is generally performed using a device equipped with a roll, a clip, and the like, and the film is stretched in the transport direction (longitudinal stretching) and stretched in the direction perpendicular to the transport direction (lateral stretching).
- the film is preheated for heating the film in advance during stretching, a stretching section for tensioning the film to stretch the film, a heat fixing section for heating the film while tensioning the film, and the film Stretching is performed by sequentially transporting the heat relaxation part for relaxing the tension and the cooling part for cooling the film.
- the polyester molecules When the film is stretched by stretching in the transverse direction, the polyester molecules are stretched and the hydrolysis resistance of the film is improved. On the other hand, since the molecular chain between the polyester molecules also increases during stretching, the thermal shrinkage rate in the width direction of the film tends to increase. However, when the film has a relatively large size of 1 m or more in width, Because of the decomposability, when the maximum film surface temperature at the time of heat setting is in the range of 160 ° C. or higher and 210 ° C. or lower, the degree of crystallinity changes greatly, the thermal shrinkage rate further increases, and the fluctuation variation increases.
- the dimensional stability of the film can be improved by releasing the tension on the film in the heat relaxation part. This is probably because the film shrinks and the molecular chain between the polyester molecules narrows. At this time, the hydrolysis resistance tends to be deteriorated by relaxing the heat and releasing the tension.
- the intrinsic viscosity (IV) of the obtained polyester film is 0.70 dL / g or more, the polyester molecule becomes large and the molecule It is presumed that the movement of is also dull, and as a result, it can be excellent in hydrolysis resistance.
- the tensioned film is heat-fixed by heating so that the maximum film surface temperature on the surface of the film is 160 ° C. to 210 ° C. That is, by heating at 160 ° C. to 210 ° C. with tension applied to the film, the polyester molecules can be crystallized without shrinking, and the polyester molecules can be fixed to some extent in the stretched state.
- the hydrolysis resistance of can be improved.
- the maximum film surface temperature is relatively low at 210 ° C. or lower, although it is good in terms of hydrolysis resistance, the temperature dependence of crystallinity is large in this temperature range, and the crystallinity in the film The variability tends to increase.
- the crystallization is delayed by increasing the IV value of the finally obtained film to 0.70 or more, and the variation in the crystallinity in the film width direction is suppressed to a small value.
- a polyester raw material resin is melt-extruded into a sheet and cooled on a casting drum to form a polyester film.
- a polyester film having an intrinsic viscosity (IV) of 0.70 dL / g or more is suitably formed.
- the polyester film obtained has an intrinsic viscosity of 0.70 dL / g or more.
- the intrinsic viscosity can be set to a desired intrinsic viscosity by a catalyst used for synthesis of the polyester raw material resin, a polymerization method, or the like.
- polyester raw material resin is not particularly limited as long as it is a raw material for the polyester film and contains polyester, and may contain a slurry of inorganic particles or organic particles in addition to the polyester. Moreover, the polyester raw material resin may contain a titanium element derived from a catalyst.
- the kind of polyester contained in the polyester raw material resin is not particularly limited. It may be synthesized using a dicarboxylic acid component and a diol component, or a commercially available polyester may be used.
- the polyester when synthesized, for example, it can be obtained by subjecting (A) a dicarboxylic acid component and (B) a diol component to an esterification reaction and / or a transesterification reaction by a well-known method.
- dicarboxylic acid component examples include malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, dodecanedioic acid, dimer acid, eicosandioic acid, pimelic acid, azelaic acid, methylmalonic acid Aliphatic dicarboxylic acids such as ethylmalonic acid, adamantane dicarboxylic acid, norbornene dicarboxylic acid, isosorbide, cyclohexanedicarboxylic acid, decalin dicarboxylic acid, and the like, terephthalic acid, isophthalic acid, phthalic acid, 1,4- Naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 1,8-naphthalene dicarboxylic acid, 4,4′-diphenyl dicarboxylic acid, 4,4
- diol component examples include fats such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,2-butanediol, and 1,3-butanediol.
- Diols cycloaliphatic dimethanol, spiroglycol, isosorbide and other alicyclic diols, bisphenol A, 1,3-benzenedimethanol, 1,4-benzenedimethanol, 9,9'-bis (4-hydroxyphenyl)
- Diol compounds such as aromatic diols such as fluorene.
- the dicarboxylic acid component contains an aromatic dicarboxylic acid as a main component.
- a dicarboxylic acid component other than the aromatic dicarboxylic acid may be included. Examples of such a dicarboxylic acid component include ester derivatives such as aromatic dicarboxylic acids.
- the “main component” means that the proportion of aromatic dicarboxylic acid in the dicarboxylic acid component is 80% by mass or more.
- it is preferable that at least one kind of aliphatic diol is used as the diol component (B).
- the aliphatic diol can contain ethylene glycol, and preferably contains ethylene glycol as a main component.
- the main component means that the proportion of ethylene glycol in the diol component is 80% by mass or more.
- the amount of the diol component (for example, ethylene glycol) is 1.015 to 1.50 mol per 1 mol of the dicarboxylic acid component (particularly the aromatic dicarboxylic acid (for example, terephthalic acid)) and, if necessary, its ester derivative. It is preferable that it is the range of these.
- the amount used is more preferably in the range of 1.02 to 1.30 mol, and still more preferably in the range of 1.025 to 1.10 mol.
- the esterification reaction proceeds favorably, and if it is in the range of 1.50 mol or less, for example, by-production of diethylene glycol due to dimerization of ethylene glycol is suppressed, Many characteristics such as melting point, glass transition temperature, crystallinity, heat resistance, hydrolysis resistance, and weather resistance can be kept good.
- a polyfunctional monomer in which the total (a + b) of the number of carboxylic acid groups (a) and the number of hydroxyl groups (b) is 3 or more is used as a copolymerization component (a trifunctional or more functional component). It is preferable to include. "Containing a polyfunctional monomer as a copolymerization component (a trifunctional or higher functional component)" means containing a structural unit derived from a polyfunctional monomer.
- Examples of the structural unit derived from the polyfunctional monomer in which the total (a + b) of the number of carboxylic acid groups (a) and the number of hydroxyl groups (b) is 3 or more include the structural units derived from carboxylic acids shown below. .
- examples of the trifunctional aromatic carboxylic acid include trimesic acid, trimellitic acid, pyromellitic acid, naphthalenetricarboxylic acid, Anthracentricarboxylic acid and the like are trifunctional aliphatic carboxylic acids such as methanetricarboxylic acid, ethanetricarboxylic acid, propanetricarboxylic acid, and butanetricarboxylic acid, and tetrafunctional aromatic carboxylic acids are exemplified by benzenetetracarboxylic acid.
- Carboxylic acid benzophenone tetracarboxylic acid, naphthalene tetracarboxylic acid, anthracene tetracarboxylic acid, perylene tetracarboxylic acid, etc. are tetrafunctional aliphatic carboxylic acids such as ethane tetracarboxylic acid, ethylene tetracarboxylic acid, butane tetracarboxylic acid. , Cyclopen Tetracarboxylic acid, cyclohexanetetracarboxylic acid, adamantanetetracarboxylic acid, etc.
- aromatic carboxylic acids such as benzenepentacarboxylic acid, benzenehexacarboxylic acid, naphthalenepentacarboxylic acid, naphthalenehexacarboxylic acid, naphthalene.
- Heptacarboxylic acid, naphthalene octacarboxylic acid, anthracene pentacarboxylic acid, anthracene hexacarboxylic acid, anthracene heptacarboxylic acid, anthracene octacarboxylic acid and the like are pentafunctional or higher aliphatic carboxylic acids such as ethanepentacarboxylic acid, ethanehepta Carboxylic acid, butanepentacarboxylic acid, butaneheptacarboxylic acid, cyclopentanepentacarboxylic acid, cyclohexanepentacarboxylic acid, cyclohexanehexacarboxylic acid, adamanta Penta carboxylic acid, and adamantane hexa acid.
- these ester derivatives, acid anhydrides and the like are mentioned as examples, but are not limited
- oxyacids and derivatives thereof such as l-lactide, d-lactide, hydroxybenzoic acid, and a combination of a plurality of oxyacids to the carboxy terminus of the carboxylic acid described above are also preferably used. . These may be used individually by 1 type, or may use multiple types together as needed.
- polyfunctional monomers having a hydroxyl number (b) of 3 or more include trifunctional aromatic compounds such as trihydroxybenzene, trihydroxynaphthalene, trihydroxyanthracene, trihydroxychalcone, trihydroxyflavone, and trihydroxycoumarin.
- trifunctional aromatic compounds such as trihydroxybenzene, trihydroxynaphthalene, trihydroxyanthracene, trihydroxychalcone, trihydroxyflavone, and trihydroxycoumarin.
- examples of the trifunctional aliphatic alcohol include glycerin, trimethylolpropane, and propanetriol
- examples of the tetrafunctional aliphatic alcohol include pentaerythritol.
- a compound obtained by adding a diol to the hydroxyl terminal of the above compound is also preferably used. These may be used individually by 1 type, or may use multiple types together as needed.
- one molecule has both a hydroxyl group and a carboxylic acid group, and the total (a + b) of the number of carboxylic acid groups (a) and the number of hydroxyl groups (b) is 3
- the oxyacids which are the above are also mentioned. Examples of such oxyacids include hydroxyisophthalic acid, hydroxyterephthalic acid, dihydroxyterephthalic acid, and trihydroxyterephthalic acid.
- those obtained by adding oxyacids and derivatives thereof such as l-lactide, d-lactide, hydroxybenzoic acid, or a combination of a plurality of such oxyacids to the carboxy terminus of these polyfunctional monomers are also preferably used. It is done. These may be used individually by 1 type, or may use multiple types together as needed.
- the content ratio of the structural unit derived from the polyfunctional monomer in the polyester raw material resin is 0.005 mol% or more and 2.5 mol based on all the structural units in the polyester raw resin. % Or less is preferable.
- the content ratio of the structural unit derived from the polyfunctional monomer is more preferably 0.020 mol% to 1 mol%, still more preferably 0.025 mol% to 1 mol%, still more preferably 0.8. It is 035 mol% or more and 0.5 mol% or less, Especially preferably, it is 0.05 mol% or more and 0.5 mol% or less, Most preferably, it is 0.1 mol% or more and 0.25 mol% or less.
- the functional group that is not used for polycondensation is polyester.
- the adhesion between the coating layer and the polyester film can be kept better, and the occurrence of peeling can be effectively prevented.
- a structure in which a polyester molecular chain is branched from a structural unit derived from a trifunctional or higher polyfunctional monomer can be obtained, and entanglement between polyester molecules can be promoted.
- a conventionally known reaction catalyst can be used for the esterification reaction and / or transesterification reaction.
- the reaction catalyst include alkali metal compounds, alkaline earth metal compounds, zinc compounds, lead compounds, manganese compounds, cobalt compounds, aluminum compounds, antimony compounds, titanium compounds, and phosphorus compounds.
- an antimony compound, a germanium compound, or a titanium compound as a polymerization catalyst at an arbitrary stage before the polyester production method is completed.
- a germanium compound is taken as an example, it is preferable to add the germanium compound powder as it is.
- an aromatic dicarboxylic acid and an aliphatic diol are polymerized in the presence of a catalyst containing a titanium compound.
- an organic chelate titanium complex having an organic acid as a ligand is used as a catalyst titanium compound, and at least an organic chelate titanium complex, a magnesium compound, and an aromatic ring as a substituent in the step.
- a process of adding a pentavalent phosphate ester having no sulfite in this order is
- an aromatic dicarboxylic acid and an aliphatic diol are mixed with a catalyst containing an organic chelate titanium complex, which is a titanium compound, prior to addition of a magnesium compound and a phosphorus compound.
- Titanium compounds such as organic chelate titanium complexes have high catalytic activity for esterification reactions, so that esterification reactions can be performed satisfactorily.
- the titanium compound may be added to the mixture of the dicarboxylic acid component and the diol component, or after mixing the dicarboxylic acid component (or diol component) and the titanium compound, the diol component (or dicarboxylic acid component) is mixed. May be. Further, the dicarboxylic acid component, the diol component, and the titanium compound may be mixed at the same time.
- the mixing is not particularly limited, and can be performed by a conventionally known method.
- PET polyethylene terephthalate
- PEN polyethylene-2,6-naphthalate
- PET is polymerized using one or more selected from a germanium (Ge) -based catalyst, an antimony (Sb) -based catalyst, an aluminum (Al) -based catalyst, and a titanium (Ti) -based catalyst.
- Ge germanium
- Sb antimony
- Al aluminum
- Ti titanium
- the Ti catalyst has a high reaction activity and can lower the polymerization temperature. Therefore, it is possible to suppress the polyester from being thermally decomposed during the polymerization reaction and generating COOH. That is, by using a Ti-based catalyst, it is possible to reduce the amount of terminal carboxylic acid of polyester that causes thermal decomposition, and it is possible to suppress foreign matter formation. By reducing the amount of the terminal carboxylic acid of the polyester, it is possible to suppress thermal decomposition of the polyester film after the production of the polyester film.
- Ti-based catalyst examples include oxides, hydroxides, alkoxides, carboxylates, carbonates, oxalates, organic chelate titanium complexes, and halides.
- the Ti-based catalyst may be used in combination of two or more titanium compounds as long as the effects of the present invention are not impaired.
- Ti-based catalysts include tetra-n-propyl titanate, tetra-i-propyl titanate, tetra-n-butyl titanate, tetra-n-butyl titanate tetramer, tetra-t-butyl titanate, tetracyclohexyl titanate, tetraphenyl Titanium alkoxide such as titanate and tetrabenzyl titanate, titanium oxide obtained by hydrolysis of titanium alkoxide, titanium-silicon or zirconium composite oxide obtained by hydrolysis of a mixture of titanium alkoxide and silicon alkoxide or zirconium alkoxide, titanium acetate , Titanium oxalate, potassium potassium oxalate, sodium oxalate, potassium titanate, sodium titanate, titanium titanate-aluminum hydroxide mixture, titanium chloride, titanium chloride-aluminum chloride Miniumu mixture, titanium acetylacetonate, an organic
- the polymerization is performed using a titanium (Ti) compound as a catalyst in the range of 1 ppm to 50 ppm, more preferably 2 ppm to 30 ppm, more preferably 3 ppm to 15 ppm in terms of titanium element. Is preferred.
- the polyester raw material resin contains 1 ppm or more and 50 ppm or less of titanium element.
- Mw weight average molecular weight
- the amount of the titanium element contained in the polyester raw material resin is 1 ppm or more, the weight average molecular weight (Mw) of the polyester is increased, and thermal decomposition is difficult. For this reason, foreign matters are reduced in the extruder.
- the amount of the titanium element contained in the polyester raw material resin is 50 ppm or less, the Ti-based catalyst is unlikely to become a foreign substance, and stretching unevenness is reduced when the polyester sheet is stretched.
- titanium compounds As the titanium compound as the catalyst component, at least one organic chelate titanium complex having an organic acid as a ligand is preferably used.
- the organic acid include citric acid, lactic acid, trimellitic acid, malic acid and the like. Among them, an organic chelate complex having citric acid or citrate as a ligand is preferable.
- the titanium catalyst also has a catalytic effect of the esterification reaction. By adding it at the esterification stage, the oligomer acid value at the end of the esterification reaction is lowered, and the subsequent polycondensation reaction is performed more efficiently.
- complexes with citric acid as a ligand are more resistant to hydrolysis than titanium alkoxides, etc., and do not hydrolyze in the esterification reaction process, while maintaining the original activity and catalyzing the esterification and polycondensation reactions It is estimated to function effectively as In general, it is known that the hydrolysis resistance deteriorates as the amount of terminal carboxy groups increases, and the hydrolysis resistance is expected to be improved by decreasing the amount of terminal carboxy groups by the above addition method. .
- citrate chelate titanium complex for example, VERTEC® AC-420 manufactured by Johnson Matthey can be easily obtained as a commercial product.
- the aromatic dicarboxylic acid and the aliphatic diol can be introduced by preparing a slurry containing them and continuously supplying it to the esterification reaction step.
- titanium compounds In addition to the organic chelate titanium complex, titanium compounds generally include oxides, hydroxides, alkoxides, carboxylates, carbonates, oxalates, and halides. Other titanium compounds may be used in combination with the organic chelate titanium complex as long as the effects of the present invention are not impaired.
- titanium compounds examples include tetra-n-propyl titanate, tetra-i-propyl titanate, tetra-n-butyl titanate, tetra-n-butyl titanate tetramer, tetra-t-butyl titanate, tetracyclohexyl titanate, Titanium alkoxide such as tetraphenyl titanate, tetrabenzyl titanate, titanium oxide obtained by hydrolysis of titanium alkoxide, titanium-silicon or zirconium composite oxide obtained by hydrolysis of a mixture of titanium alkoxide and silicon alkoxide or zirconium alkoxide, Titanium acetate, titanium oxalate, potassium potassium oxalate, sodium titanium oxalate, potassium titanate, sodium titanate, titanium titanate-aluminum hydroxide mixture, titanium chloride, titanium chloride Down - aluminum chloride mixture, and titanium acetylacetonate.
- Titanium alkoxide such
- an aromatic dicarboxylic acid and an aliphatic diol are polymerized in the presence of a catalyst containing a titanium compound, and at least one of the titanium compounds is an organic chelate titanium complex having an organic acid as a ligand.
- An esterification reaction step including at least a step of adding an organic chelate titanium complex, a magnesium compound, and a pentavalent phosphate ester having no aromatic ring as a substituent in this order, and an ester formed in the esterification reaction step
- a polycondensation step in which a polycondensation product is produced by a polycondensation reaction of the chemical reaction product, and is preferably produced by a polyester production method.
- This polyester can be used for applications requiring high transparency (for example, optical film, industrial squirrel, etc.), and it is not necessary to use an expensive germanium-based catalyst, so that the cost can be greatly reduced.
- the occurrence of failures and quality defects in the film forming process can be reduced, and the cost can be reduced by improving the yield.
- esterification reaction it is preferable to provide a process in which an organic chelate titanium complex which is a titanium compound and a magnesium compound and a pentavalent phosphorus compound as additives are added in this order. At this time, the esterification reaction proceeds in the presence of the organic chelate titanium complex, and thereafter, the addition of the magnesium compound can be started before the addition of the phosphorus compound.
- pentavalent phosphorus compound at least one pentavalent phosphate having no aromatic ring as a substituent is used.
- pentavalent phosphate having no aromatic ring as a substituent
- phosphoric acid esters having a lower alkyl group having 2 or less carbon atoms as a substituent [(OR) 3 —P ⁇ O; R an alkyl group having 1 or 2 carbon atoms]
- phosphoric acid Trimethyl and triethyl phosphate are particularly preferable.
- the amount of phosphorus compound added is preferably such that the P element conversion value is in the range of 50 ppm to 90 ppm.
- the amount of the phosphorus compound is more preferably 60 ppm or more and 80 ppm or less, and still more preferably 60 ppm or more and 75 ppm or less.
- magnesium compound By including a magnesium compound in the polyester, the electrostatic applicability of the polyester is improved. In this case, although it is easy to color, in this invention, coloring is suppressed and the outstanding color tone and heat resistance are obtained.
- the magnesium compound include magnesium salts such as magnesium oxide, magnesium hydroxide, magnesium alkoxide, magnesium acetate, and magnesium carbonate. Among these, magnesium acetate is most preferable from the viewpoint of solubility in ethylene glycol.
- the Mg element conversion value is preferably 50 ppm or more, and more preferably 50 ppm or more and 100 ppm or less.
- the addition amount of the magnesium compound is preferably an amount that is in the range of 60 ppm to 90 ppm, more preferably 70 ppm to 80 ppm in terms of imparting electrostatic applicability.
- the value Z calculated from the following formula (i) for the titanium compound as the catalyst component and the magnesium compound and phosphorus compound as the additive satisfies the following relational expression (ii).
- the P content is the amount of phosphorus derived from the entire phosphorus compound including the pentavalent phosphate ester having no aromatic ring
- the Ti content is the amount of titanium derived from the entire Ti compound including the organic chelate titanium complex. It is.
- (I) Z 5 ⁇ (P content [ppm] / P atomic weight) ⁇ 2 ⁇ (Mg content [ppm] / Mg atomic weight) ⁇ 4 ⁇ (Ti content [ppm] / Ti atomic weight) (Ii) 0 ⁇ Z ⁇ + 5.0
- the formula (i) expresses the amount of phosphorus that can act on titanium by excluding the phosphorus content that acts on magnesium from the total amount of phosphorus that can be reacted.
- the titanium compound, phosphorus compound, and magnesium compound which are inexpensive and easily available, are used for color tone and heat while having the reaction activity required for the reaction.
- a polyester excellent in coloring resistance can be obtained.
- chelating titanium having aromatic dicarboxylic acid and aliphatic diol as a ligand with citric acid or citrate of 1 ppm or more and 30 ppm or less in terms of Ti element.
- a magnesium salt of weak acid of 60 ppm or more and 90 ppm or less (more preferably 70 ppm or more and 80 ppm or less) in terms of Mg element is added.
- chelate titanium complex organic chelate titanium complex
- magnesium salt magnesium compound
- pentavalent phosphate 70% by mass or more of the total addition amount is added in the above order. preferable.
- the esterification reaction may be carried out using a multistage apparatus in which at least two reactors are connected in series under conditions where ethylene glycol is refluxed while removing water or alcohol produced by the reaction from the system. it can.
- the esterification reaction described above may be performed in one stage or may be performed in multiple stages.
- the esterification reaction temperature is preferably 230 to 260 ° C, more preferably 240 to 250 ° C.
- the temperature of the esterification reaction in the first reaction tank is preferably 230 to 260 ° C, more preferably 240 to 250 ° C, and the pressure is 1.0 to 5.0 kg / cm 2 is preferable, and 2.0 to 3.0 kg / cm 2 is more preferable.
- the temperature of the esterification reaction in the second reaction tank is preferably 230 to 260 ° C., more preferably 245 to 255 ° C., and the pressure is 0.5 to 5.0 kg / cm 2 , more preferably 1.0 to 3. 0 kg / cm 2 . Furthermore, when carrying out by dividing into three or more stages, it is preferable to set the conditions for the esterification reaction in the intermediate stage to the conditions between the first reaction tank and the final reaction tank.
- a polycondensation product is produced by subjecting an esterification reaction product produced by the esterification reaction to a polycondensation reaction.
- the polycondensation reaction may be performed in one stage or may be performed in multiple stages.
- the esterification reaction product such as an oligomer generated by the esterification reaction is subsequently subjected to a polycondensation reaction.
- This polycondensation reaction can be suitably performed by supplying it to a multistage polycondensation reaction tank.
- the polycondensation reaction conditions in a three-stage reaction tank are as follows: the first reaction tank has a reaction temperature of 255 to 280 ° C., more preferably 265 to 275 ° C., and a pressure of 100 to 10 torr (13.3). ⁇ 10 ⁇ 3 to 1.3 ⁇ 10 ⁇ 3 MPa), more preferably 50 to 20 torr (6.67 ⁇ 10 ⁇ 3 to 2.67 ⁇ 10 ⁇ 3 MPa). The temperature is 265 to 285 ° C., more preferably 270 to 280 ° C., and the pressure is 20 to 1 torr (2.67 ⁇ 10 ⁇ 3 to 1.33 ⁇ 10 ⁇ 4 MPa), more preferably 10 to 3 torr (1.
- the third reaction vessel in the final reaction vessel has a reaction temperature of 270 to 290 ° C., more preferably 275 to 285 ° C., and a pressure of 10-0.1tor (1.33 ⁇ 10 -3 ⁇ 1.33 ⁇ 10 -5 MPa), aspect is preferably more preferably 5 ⁇ 0.5torr (6.67 ⁇ 10 -4 ⁇ 6.67 ⁇ 10 -5 MPa) .
- Additives such as light stabilizers, antioxidants, UV absorbers, flame retardants, lubricants (fine particles), nucleating agents (crystallization agents), crystallization inhibitors, etc. to the polyester synthesized as described above May further be included.
- the polyester that is the raw material of the polyester sheet is preferably a solid-phase polymerized pellet. After polymerization by the esterification reaction, solid phase polymerization is further performed, whereby the moisture content of the polyester film, the crystallinity, the acid value of the polyester, that is, the concentration of the terminal carboxy group of the polyester (Acid Value; AV), the intrinsic viscosity ( Interstitial Visibility (IV) can be controlled.
- the intrinsic viscosity (IV) of the polyester is set to 0.70 dL / g or more.
- the intrinsic viscosity (IV) of the polyester is preferably 0.70 dL / g or more and 0.9 dL / g or less. If the IV is less than 0.70 dL / g, the molecular motion of the polyester is not hindered, so that crystallization is likely to proceed. Moreover, when IV is 0.9 dL / g or less, thermal decomposition of the polyester due to shear heat generation in the extruder does not occur excessively, crystallization is suppressed, and the acid value (AV) can be suppressed low.
- IV is more preferably 0.75 dL / g or more and 0.90 dL / g or less, more preferably 0.75 dL / g or more and 0.85 dL / g or less, and 0.78 dL / g or more and 0 or less. .85 dL / g or less is more preferable.
- the polyester intrinsic viscosity (IV) is adjusted to 0.70 dL / g or more and 0.9 dL / g or less to produce a polyester sheet.
- the polyester as a raw material of the polyester film applied to the longitudinal stretching and the lateral stretching has an intrinsic viscosity of 0.70 dL / g or more and 0.9 dL / g or less, and further a titanium atom derived from the catalyst (Ti catalyst). It is preferable to contain.
- a polyester obtained by the esterification reaction described above or a commercially available polyester in the form of small pieces such as pellets may be used as a starting material.
- the solid phase polymerization of polyester may be a continuous method (a method in which a tower is filled with a resin, and this is slowly heated for a predetermined period of time while being heated and then sequentially fed out), or a batch method (a resin is placed in a container). Or a method of heating for a predetermined time).
- the solid phase polymerization is preferably performed in a vacuum or in a nitrogen atmosphere.
- the solid phase polymerization temperature of the polyester is preferably 150 ° C. or higher and 250 ° C. or lower, more preferably 170 ° C.
- the solid phase polymerization time is preferably from 1 hour to 100 hours, more preferably from 5 hours to 100 hours, further preferably from 10 hours to 75 hours, and particularly preferably from 15 hours to 50 hours.
- the acid value (AV) and intrinsic viscosity (IV) of the polyester can be easily controlled within a preferable range.
- the temperature of the solid phase polymerization is preferably 170 ° C. or higher and 240 ° C. or lower, more preferably 180 ° C. or higher and 230 ° C. or lower, and further preferably 190 ° C. or higher and 220 ° C. or lower.
- the polyester raw material resin obtained as described above is melt-extruded and further cooled to form a polyester film.
- the melt extrusion of the polyester raw material resin is performed, for example, using an extruder equipped with one or two or more screws, heated to a temperature equal to or higher than the melting point of the polyester raw resin, rotating the screw, and melt-kneading.
- the polyester raw material resin is melted into a melt in the extruder by heating and kneading with a screw.
- the extruder is preferably a twin screw extruder because the kneading temperature can be kept low.
- the melted polyester raw resin (melt) is extruded from an extrusion die through a gear pump, a filter and the like.
- the extrusion die is also simply referred to as “die” (see JIS B 8650: 2006, a) extrusion molding machine, number 134). At this time, the melt may be extruded as a single layer or may be extruded as a multilayer.
- the polyester raw material resin preferably contains an end-capping agent selected from an oxazoline compound, a carbodiimide compound, and an epoxy compound.
- an end-capping agent selected from an oxazoline compound, a carbodiimide compound, and an epoxy compound.
- the polyester raw material resin to which the end-capping agent is added is melt-kneaded, and the polyester raw material resin that has reacted with the end-capping agent during the melt-kneading is melt-extruded.
- the end-capping agent is not particularly limited as long as it is melt-kneaded with the polyester raw material resin in the process from the raw material charging to the extrusion. It is preferably added until it is fed to the vent port and is used for melt kneading together with the raw material resin.
- a supply port for supplying the end sealant can be provided between the raw material charging port and the vent port of the cylinder for performing melt kneading, and can be directly added to the raw material resin in the cylinder.
- the end-capping agent may be added to the polyester raw material resin that has been heated and kneaded but has not completely reached the molten state, or may be added to the molten polyester raw material resin (melt). Good.
- 0.1 to 5 mass% is preferable with respect to the total mass of the polyester raw resin.
- a preferable amount of the terminal blocking agent with respect to the polyester raw material resin is 0.3% by mass or more and 4% by mass or less, and more preferably 0.5% by mass or more and 2% by mass or less.
- the content ratio of the end-capping agent is 0.1% by mass or more, weather resistance can be improved due to the AV lowering effect, and low heat shrinkability and adhesion can be imparted.
- the content ratio of the end-capping agent is 5% by mass or less, the adhesion is improved, and the decrease in the glass transition temperature (Tg) of the polyester due to the addition of the end-capping agent is suppressed.
- Tg glass transition temperature
- Decrease and increase in heat shrinkage can be suppressed. This is due to the fact that the increase in hydrolyzability caused by the relatively increased polyester reactivity is suppressed by the decrease in Tg, or the mobility of the polyester molecules that increase due to the decrease in Tg is likely to increase. This is because heat shrinkage is suppressed.
- the compound which has a carbodiimide group, an epoxy group, or an oxazoline group is preferable.
- Specific examples of the terminal blocking agent include carbodiimide compounds, epoxy compounds, oxazoline compounds, and the like. Details of the carbodiimide compound, the epoxy compound, and the oxazoline-based compound, such as examples and preferred embodiments, are as described above in the section “Polyester film”.
- the melt (polyester) can be extruded from a die onto a casting drum to be formed into a film (cast process).
- the thickness of the film-like polyester molded body obtained by the cast treatment is preferably 0.5 mm to 5 mm, more preferably 0.7 mm to 4.7 mm, and 0.8 mm to 4.6 mm. Is more preferable.
- the means for cooling the melt extruded from the extrusion die is not particularly limited, and it is sufficient to apply cold air to the melt, bring it into contact with a cast drum (cooled cast drum), or spray water. Only one cooling means may be performed, or two or more cooling means may be combined. Among the above, the cooling means is preferably at least one of cooling by cold air and cooling using a cast drum from the viewpoint of preventing oligomer adhesion to the sheet surface during continuous operation. Furthermore, it is particularly preferable that the melt extruded from the extruder is cooled with cold air, and the melt is brought into contact with the cast drum and cooled.
- the polyester molded body cooled using a cast drum or the like is peeled off from a cooling member such as a cast drum using a peeling member such as a peeling roll.
- the polyester film formed in the film forming step is longitudinally stretched in the longitudinal direction.
- the longitudinal stretching of the film is performed, for example, by applying tension between two or more pairs of nip rolls arranged in the film conveyance direction while passing the film through a pair of nip rolls sandwiching the film and conveying the film in the longitudinal direction of the film.
- tension between two or more pairs of nip rolls arranged in the film conveyance direction while passing the film through a pair of nip rolls sandwiching the film and conveying the film in the longitudinal direction of the film.
- the longitudinal stretching ratio of the polyester film is preferably 2 to 5 times, more preferably 2.5 to 4.5 times, and even more preferably 2.8 to 4 times.
- the area stretch ratio represented by the product of the longitudinal and lateral stretch ratios is preferably 6 to 18 times, more preferably 8 to 17.5 times the area of the polyester film before stretching, more preferably 10 to More preferably, it is 17 times.
- the temperature during the longitudinal stretching of the polyester film (hereinafter also referred to as “longitudinal stretching temperature”) is preferably Tg ⁇ 20 ° C. or more and Tg + 50 ° C. or less, more preferably Tg as the glass transition temperature of the polyester film. Tg ⁇ 10 ° C. or higher and Tg + 40 ° C. or lower, more preferably Tg ° C. or higher and Tg + 30 ° C. or lower.
- the polyester film when extending
- a heat source such as a heater
- a polyester film is made into at least 2 axis
- the direction (TD) orthogonal to the longitudinal direction (conveyance direction, MD) of a polyester film intends the direction which makes a perpendicular
- a direction in which the angle with respect to the longitudinal direction (that is, the conveyance direction) can be regarded as 90 ° due to mechanical error or the like (for example, a direction of 90 ° ⁇ 5 ° with respect to the MD direction) is included.
- the biaxial stretching method may be any of a sequential biaxial stretching method in which longitudinal stretching and lateral stretching are separated and a simultaneous biaxial stretching method in which longitudinal stretching and lateral stretching are simultaneously performed.
- the longitudinal stretching and the lateral stretching may be independently performed twice or more, and the order of the longitudinal stretching and the lateral stretching is not limited.
- stretching modes such as longitudinal stretching ⁇ transverse stretching, longitudinal stretching ⁇ transverse stretching ⁇ longitudinal stretching, longitudinal stretching ⁇ longitudinal stretching ⁇ transverse stretching, transverse stretching ⁇ longitudinal stretching can be mentioned. Of these, longitudinal stretching ⁇ transverse stretching is preferred.
- the transverse stretching step in the present invention is a step of transversely stretching the longitudinally stretched polyester film in the width direction perpendicular to the longitudinal direction. This lateral stretching is preheated to a temperature at which the longitudinally stretched polyester film can be stretched.
- a preheating step, a stretching step in which the preheated polyester film is stretched in the width direction perpendicular to the longitudinal direction and stretched in the transverse direction, and a maximum reachable film of the polyester film after the longitudinal stretching and the transverse stretching are performed. Heat fixing that heats and crystallizes by varying the maximum reachable film surface temperature in the width direction from 0.5 ° C. to 5.0 ° C.
- the specific means is not limited as long as the polyester film is transversely stretched in the above configuration, but a lateral stretching apparatus or biaxial stretching capable of processing each step constituting the above configuration. It is preferable to use a machine.
- the biaxial stretching machine 100 includes a pair of annular rails 60a and 60b, and gripping members 2a to 2l attached to each annular rail and movable along the rails.
- the annular rails 60a and 60b are arranged symmetrically with respect to the polyester film 200.
- the annular rails 60a and 60b can be stretched in the film width direction by gripping the polyester film 200 with the gripping members 2a to 21 and moving along the rail. It has become.
- FIG. 1 is a top view showing an example of a biaxial stretching machine from the top.
- the biaxial stretching machine 100 includes a preheating unit 10 that preheats the polyester film 200, a stretching unit 20 that stretches the polyester film 200 in an arrow TD direction that is a direction orthogonal to the arrow MD direction, and applies tension to the polyester film,
- the heat fixing part 30 that heats the polyester film to which the tension is applied is heated
- the heat relaxation part 40 that relaxes the tension of the polyester film that is heat-fixed by heating the heat-fixed polyester film, and the heat relaxation part. It is comprised in the area
- Grip members 2a, 2b, 2e, 2f, 2i, and 2j that are movable along the annular rail 60a are attached to the annular rail 60a, and the annular rail 60b is movable along the annular rail 60b.
- Gripping members 2c, 2d, 2g, 2h, 2k, and 2l are attached.
- the grip members 2a, 2b, 2e, 2f, 2i, and 2j grip one end of the polyester film 200 in the TD direction, and the grip members 2c, 2d, 2g, 2h, 2k, and 2l are the polyester film 200. The other end in the TD direction is gripped.
- the gripping members 2a to 2l are generally called chucks, clips, and the like.
- the gripping members 2a, 2b, 2e, 2f, 2i, and 2j move counterclockwise along the annular rail 60a, and the gripping members 2c, 2d, 2g, 2h, 2k, and 2l move along the annular rail 60b. To move clockwise.
- the gripping members 2a to 2d grip the end portion of the polyester film 200 in the preheating unit 10 and move along the annular rail 60a or 60b while gripping, so that the heat at which the extending unit 20 and the gripping members 2e to 2h are located
- the process proceeds through the relaxation part 40 to the cooling part 50 where the gripping members 2i to 2l are located.
- the gripping members 2a and 2b and the gripping members 2c and 2d are separated from the end of the polyester film 200 at the end of the cooling unit 50 on the downstream side in the MD direction in the transport direction, and then the annular rail 60a or 60b. , And return to the preheating unit 10.
- the polyester film 200 moves in the direction of the arrow MD and sequentially heats in the preheating process in the preheating unit 10, the stretching process in the stretching unit 20, the heat fixing process in the heat fixing unit 30, and the heat in the heat relaxation unit 40. It is subjected to a relaxation process and a cooling process in the cooling unit 50, and transverse stretching is performed.
- the moving speed of the gripping members 2a to 2l in each region such as the preheating portion becomes the conveying speed of the polyester film 200.
- the gripping members 2a to 2l can change the moving speed independently of each other.
- the biaxial stretching machine 100 is capable of lateral stretching in which the polyester film 200 is stretched in the TD direction in the stretching unit 20, but by changing the moving speed of the gripping members 2a to 2l, It can also extend in the MD direction. That is, simultaneous biaxial stretching can be performed using the biaxial stretching machine 100.
- gripping members 2a to 21 may be collectively referred to as “grip member 2”.
- the polyester film that has been longitudinally stretched in the longitudinal stretching step is preheated to a temperature at which it can be stretched.
- the polyester film 200 is preheated in the preheating unit 10.
- the polyester film 200 is preheated before being stretched so that the polyester film 200 can be easily stretched in the transverse direction.
- the film surface temperature at the end point of the preheating part (hereinafter also referred to as “preheating temperature”) is preferably Tg ⁇ 10 ° C. to Tg + 60 ° C. when the glass transition temperature of the polyester film 200 is Tg, It is more preferable that it is Tg + 50 degreeC.
- the end point of the preheating portion refers to the time when the preheating of the polyester film 200 is finished, that is, the position where the polyester film 200 is separated from the region of the preheating portion 10.
- the polyester film preheated in the preheating step is stretched laterally by applying tension in the width direction (TD direction) perpendicular to the longitudinal direction (MD direction).
- TD direction width direction
- MD direction longitudinal direction
- the preheated polyester film 200 is laterally stretched at least in the TD direction orthogonal to the longitudinal direction of the polyester film 200 to give tension to the polyester film 200.
- the tension (stretching tension) for transverse stretching applied to the polyester film 200 is preferably 0.1 t / m to 6.0 t / m.
- the area stretch ratio (product of each stretch ratio) of the polyester film 200 is preferably 6 to 18 times, more preferably 8 to 17.5 times the area of the polyester film 200 before stretching. More preferably, it is from 1 to 17 times.
- the film surface temperature (hereinafter also referred to as “lateral stretching temperature”) of the polyester film 200 during transverse stretching is Tg ⁇ 10 ° C. or higher and Tg + 100 ° C. or lower when the glass transition temperature of the polyester film 200 is Tg. It is preferably Tg ° C. or more and Tg + 90 ° C. or less, and more preferably Tg + 10 ° C. or more and Tg + 80 ° C. or less.
- the gripping members 2a to 2l can change their moving speeds independently. Therefore, for example, the polyester film 200 is transported by increasing the moving speed of the gripping member 2 on the downstream side in the extending portion 20MD direction of the extending portion 20 and the heat fixing portion 30 rather than the moving speed of the holding member 2 in the preheating portion 10. It is also possible to perform longitudinal stretching that stretches in the direction (MD direction).
- the longitudinal stretching of the polyester film 200 in the transverse stretching step may be performed only by the stretching unit 20 or may be performed by the heat fixing unit 30, the heat relaxation unit 40, or the cooling unit 50 described later. You may longitudinally stretch in several places.
- the polyester film after having been subjected to the longitudinal stretching and the transverse stretching has a maximum ultimate film surface temperature in the width direction while controlling the maximum ultimate film surface temperature in the range of 160 ° C to 210 ° C. It heat-fixes by heating and crystallizing variation as 0.5 to 5.0 degreeC.
- Heat setting refers to heating and crystallizing at a specific temperature while applying tension to the polyester film 200 in the stretching section 20.
- the maximum film surface temperature (also referred to as “heat setting temperature” in the present specification) of the surface of the polyester film 200 is 160 with respect to the polyester film 200 to which tension is applied. Heating is performed while being controlled within the range of from °C to 210 °C.
- the maximum film surface temperature is lower than 160 ° C.
- the polyester hardly crystallizes, so that the polyester molecules cannot be fixed in the stretched state, and the hydrolysis resistance cannot be improved.
- the heat setting temperature is higher than 210 ° C., slippage occurs at the portion where the polyester molecules are entangled with each other, and the polyester molecules shrink, so that the hydrolysis resistance cannot be improved.
- the polyester molecules are oriented, and the hydrolysis resistance is improved.
- the heat setting temperature is preferably in the range of 170 ° C. to 200 ° C. for the same reason as described above, and more preferably in the range of 175 ° C. to 195 ° C.
- the maximum film surface temperature is a value measured by bringing a thermocouple into contact with the surface of the polyester film 200.
- the variation in the maximum film surface temperature in the film width direction is set to 0.5 ° C. or more and 5.0 ° C. or less.
- the variation in the maximum film surface temperature of the film is 0.5 ° C or more, which is advantageous in terms of wrinkles during conveyance in the subsequent process, and is suppressed to 5.0 ° C or less.
- Variation in crystallinity in the width direction is suppressed. Thereby, the difference in slackness in the film width direction is reduced, the generation of scratches on the film surface during the production process is prevented, and the hydrolysis resistance is enhanced.
- the variation in the maximum reached film surface temperature is more preferably 0.7 ° C. or higher and 3.0 ° C. or lower, further preferably 0.8 ° C. or higher and 2.0 ° C. or lower, for the same reason as described above. It is particularly preferably from 8 to 1.5 ° C.
- the heating of the film during heat setting may be performed only from one side of the film or from both sides.
- the molded polyester film is different in how it is cooled on one side and the opposite side, so that the film tends to curl. It has become. Therefore, it is preferable to perform the heating in the heat setting step on the surface brought into contact with the casting drum in the film forming step. Curling can be eliminated by setting the heating surface in the heat setting step to the surface in contact with the casting drum, that is, the cooling surface. At this time, the heating is performed in such a manner that the surface temperature immediately after heating on the heating surface in the heat setting step is higher in the range of 0.5 ° C.
- the temperature difference between the heated surface and the non-heated surface on the opposite side is more preferably in the range of 0.7 to 3.0 ° C, and 0.8 ° C or higher and 2.0 ° C. The following is more preferable.
- the curl eliminating effect is great.
- the film thickness is thick, if a temperature change is applied to the film from one side of the film, a temperature distribution is easily formed in the film thickness direction, and curling is likely to occur.
- polyester melt-extruded in the film forming process is cooled from one side when it comes into contact with the cast drum, while the opposite side is in contact with the atmosphere, for example, and there is heat dissipation, but one side and the opposite side Since different cooling advances, temperature differences are likely to occur. Therefore, if the thickness of the polyester film is 180 ⁇ m or more, a temperature difference is likely to occur, so that a curling elimination effect is expected, and if it is 350 ⁇ m or less, the hydrolysis resistance is favorably maintained.
- the temperature of the film end tends to decrease due to the attachment of a clip or the like as described above, and the temperature variation in the width direction, and hence the variation in crystallinity tends to occur. Therefore, it is preferable to heat the width direction end part of the polyester film at the time of heat setting.
- a mode in which radiation heating is performed by a radiation heater such as an infrared heater is more preferable.
- radiant heating it is preferable to narrow the temperature variation in the film width direction to a range of 0.7 ° C. or more and 3.0 ° C. or less, and thereby the crystallinity variation in the film width direction is 0.5% to 3%. It can be reduced to a range of 0.0% or less. If it does in this way, the slack difference in the width direction will reduce, generation
- the residence time in a heat setting part shall be 5 to 50 second.
- the residence time is the time during which the state in which the film is heated in the heat fixing part is continued. If the residence time is 5 seconds or longer, the change in crystallinity with respect to the heating time is small, and this is advantageous in that unevenness in the crystallinity in the width direction is relatively less likely to occur. This is advantageous in terms of productivity because it is not necessary to extremely reduce the line speed.
- the residence time is preferably 8 seconds or longer and 40 seconds or shorter, and more preferably 10 seconds or longer and 30 seconds or shorter, for the same reason as described above.
- the width direction end of the polyester film is radiantly heated by a radiant heater such as an infrared heater. It may be configured.
- the heating to the end in the width direction is to reduce the temperature variation in the width direction, and hence the variation in crystallinity, and not only at the time of heat fixation but also any one or more of preheating, stretching and thermal relaxation. A further improvement effect can be expected by further heating in this step.
- Heat relaxation process In the heat relaxation step, the polyester film fixed in the heat setting step is heated, the tension of the polyester film is relaxed, and the residual strain is removed. While improving the dimensional stability of a film, the hydrolysis resistance can be made compatible as the IV value of the obtained polyester film is 0.70 or more.
- the maximum ultimate film surface temperature of the surface of the polyester film 200 is 5 ° C. or more lower than the maximum ultimate film surface temperature (T heat fixation ) of the polyester film 200 in the heat fixing part 30.
- T heat fixation maximum ultimate film surface temperature
- the highest reached film surface temperature of the surface of the polyester film 200 at the time of thermal relaxation is also referred to as “thermal relaxation temperature (T thermal relaxation )”.
- the thermal relaxation temperature (T thermal relaxation ) is heated at a temperature 5 ° C. lower than the thermal fixing temperature (T thermal fixing ) (T thermal relaxation ⁇ T thermal fixing ⁇ 5 ° C.) to release the tension.
- T thermal fixing the thermal fixing temperature
- T thermal relaxation ⁇ T thermal fixing ⁇ 5 ° C. the thermal fixing temperature
- T heat relaxation ⁇ T heat--15 ° C.
- 110 ° C. or higher and more preferably than T heat setting temperature is lower region 25 ° C. or higher (110 ° C. ⁇ T heat relaxation ⁇ T heat--25 ° C.), at 120 ° C. or higher, and lower 30 ° C. or higher than T heat set
- a temperature range 120 ° C. ⁇ T thermal relaxation ⁇ T heat setting ⁇ 30 ° C. is particularly preferable.
- the T heat relaxation is a value measured by bringing a thermocouple into contact with the surface of the polyester film 200.
- the polyester film 200 is relaxed at least in the TD direction.
- the tensioned polyester film 200 shrinks in the TD direction.
- the stretching tension applied to the polyester film 200 at the stretching portion 20 may be reduced by 2% to 90%. In the present invention, it is preferably 40%.
- the polyester film after the thermal relaxation in the thermal relaxation step is cooled.
- the polyester film 200 which passed through the heat relaxation part 40 is cooled.
- the shape of the polyester film 200 is fixed.
- the film surface temperature (hereinafter also referred to as “cooling temperature”) of the cooling unit outlet of the polyester 200 in the cooling unit 50 is preferably lower than the glass transition temperature Tg + 50 ° C. of the polyester film 200. Specifically, the temperature is preferably 25 ° C to 110 ° C, more preferably 25 ° C to 95 ° C, and further preferably 25 ° C to 80 ° C. When the cooling temperature is in the above range, it is possible to prevent the film from shrinking unevenly after releasing the clip.
- the cooling unit outlet refers to an end portion of the cooling unit 50 when the polyester 200 is separated from the cooling unit 50, and the gripping member 2 (the gripping members 2j and 2l in FIG. 1) grips the polyester film 200. The position when releasing the polyester film 200 is said.
- the temperature control means for heating or cooling the polyester film 200 in preheating, stretching, heat setting, heat relaxation, and cooling in the transverse stretching step hot or cold air is blown on the polyester film 200, or the polyester film 200 is brought into contact with the surface of a metal plate whose temperature can be controlled, or is passed through the vicinity of the metal plate.
- the polyester film 200 cooled in the cooling step cuts the gripped portion held by the clips at both ends in the TD direction, and is wound up in a roll shape.
- the stretched polyester film is preferably relaxed by the following method in order to further improve the hydrolysis resistance and dimensional stability of the produced polyester film.
- the both ends of the width direction (TD) of the polyester film 200 are hold
- one end of the polyester film 200 in the width direction (TD) is held by the holding members 2a and 2b, and the other is held by the holding members 2c and 2d.
- the polyester film 200 is conveyed from the preheating unit 10 to the cooling unit 50 by moving the gripping members 2a to 2d.
- a gripping member 2a (2c) that grips one end of the polyester film 200 in the width direction (TD direction) in the preheating unit 10 and another gripping member 2b (2d) adjacent to the gripping member 2a (2c)
- the distance between the gripping member 2a (2c) that grips one end of the polyester film 200 in the width direction in the cooling unit 50 and the other gripping member 2b (2d) adjacent to the gripping member 2a (2c) By narrowing, the conveyance speed of the polyester film 200 is reduced. With this method, the cooling unit 50 can relax the MD direction.
- the relaxation of the polyester film 200 in the MD direction can be performed in at least a part of the heat fixing unit 30, the heat relaxation unit 40, and the cooling unit 50.
- the polyester film 200 can be relaxed in the MD direction by narrowing the gap between the gripping members 2a-2b and the gap between the gripping members 2c-2d more downstream than the upstream side in the MD direction. it can.
- the polyester film 200 is stretched in the TD direction (lateral stretching) and relaxed in the TD direction, and stretched in the MD direction (longitudinal stretching) and relaxed in the MD direction.
- the dimensional stability can be improved while improving the decomposability.
- a solar cell module generally includes a solar cell element that converts light energy of sunlight into electric energy, a transparent substrate on which sunlight is incident, and the polyester film of the present invention described above (back sheet for solar cell). It is arranged between them.
- a power generating element solar cell element
- a lead wiring not shown
- a sealing agent such as ethylene / vinyl acetate copolymer system (EVA system) resin
- EVA system ethylene / vinyl acetate copolymer system
- solar cell elements examples include silicon-based materials such as single crystal silicon, polycrystalline silicon, and amorphous silicon, and group III-V such as copper-indium-gallium-selenium, copper-indium-selenium, cadmium-tellurium, and gallium-arsenic.
- group III-V such as copper-indium-gallium-selenium, copper-indium-selenium, cadmium-tellurium, and gallium-arsenic.
- group III-V such as copper-indium-gallium-selenium, copper-indium-selenium, cadmium-tellurium, and gallium-arsenic.
- group III-V such as copper-indium-gallium-selenium, copper-indium-selenium, cadmium-tellurium, and gallium-arsenic.
- II-VI group compound semiconductor systems can be applied.
- the substrate and the polyester film can be formed by sealing with a
- polyester raw resin 1 Polyethylene glycol
- terephthalic acid and ethylene glycol are directly reacted to distill off water, esterify, and then use a direct esterification method in which polycondensation is performed under reduced pressure, and polyester (Ti catalyst) by a continuous polymerization apparatus. System PET) was obtained.
- the reaction product was transferred to a second esterification reaction vessel and reacted with stirring at a temperature in the reaction vessel of 250 ° C. and an average residence time of 1.2 hours to obtain an oligomer having an acid value of 200 equivalents / ton.
- the inside of the second esterification reaction tank is partitioned into three zones, and an ethylene glycol solution of magnesium acetate is continuously supplied from the second zone so that the amount of Mg added is 75 ppm in terms of element, From the third zone, an ethylene glycol solution of trimethyl phosphate was continuously supplied so that the added amount of P was 65 ppm in terms of element.
- reaction tank temperature was 276 ° C.
- reaction tank pressure was 5 torr (6.67 ⁇ 10 ⁇ 4 MPa)
- residence time was about 1.2 hours.
- the reaction (polycondensation) was performed under the conditions.
- the reaction product (polyethylene terephthalate (PET)) was obtained by reaction (polycondensation) under the following conditions.
- polyester pellets cross section: major axis: about 4 mm, minor axis: about 2 mm, length: about 3 mm).
- Solid phase Polymerization Reaction Solid phase polymerization was carried out by a batch method on the polyester pellets obtained as described above. That is, polyester pellets were put into a container, preliminarily crystallized at 150 ° C. while stirring under vacuum, and then a solid-state polymerization reaction was performed at 190 ° C. for 30 hours. Polyester raw material resin 1 was synthesized as described above.
- Polyester raw material resin 2 was obtained in the same manner except that the solid phase polymerization time was changed from 30 hours to 12 hours in the synthesis of polyester raw material resin 1.
- Polyester raw material resin 3 was obtained in the same manner except that the solid phase polymerization time was changed from 30 hours to 10 hours in the synthesis of polyester raw material resin 1.
- Example 1 Preparation of unstretched polyester film> -Film forming process-
- the polyester raw material resin 1 was dried to a moisture content of 20 ppm or less and then charged into a hopper of a single-screw kneading extruder having a diameter of 50 mm.
- the polyester raw material resin 1 was melted at 300 ° C. and extruded from a die through a gear pump and a filter (pore diameter: 20 ⁇ m) under the following extrusion conditions. Note that the dimensions of the die slit were adjusted so that the thickness of the polyester sheet was 4 mm.
- the thickness of the polyester sheet was measured by an automatic thickness meter installed at the exit of the cast drum.
- the extrusion of the molten resin was performed under the condition that the pressure fluctuation was 1% and the temperature distribution of the molten resin was 2%. Specifically, the back pressure in the barrel of the extruder is 1% higher than the average pressure in the barrel of the extruder, and the piping temperature of the extruder is 2% higher than the average temperature in the barrel of the extruder. Heated as temperature.
- the molten resin was extruded onto a cooling cast drum and brought into close contact with the cast drum using an electrostatic application method. For cooling the molten resin, the temperature of the cast drum was set to 25 ° C., and cold air of 25 ° C.
- An unstretched polyester film (unstretched polyester film 1) having a thickness of 3.5 mm and a film width of 0.7 m was peeled off from the cast drum by a peeling roll disposed opposite to the cast drum.
- IV Intrinsic viscosity
- AV Intrinsic viscosity
- the obtained unstretched polyester film 1 was stretched by sequentially biaxially stretching by the following method to produce a biaxially stretched polyester film 1 having a thickness of 250 ⁇ m and a film width of 1.5 m.
- the preheating temperature was 110 ° C., and heating was performed so that stretching was possible.
- Extension part The preheated longitudinally stretched polyester film 1 was stretched laterally by applying tension to the film width direction perpendicular to the longitudinally stretched direction (longitudinal direction) under the following conditions.
- -Stretching temperature transverse stretching temperature: 120 ° C -Stretch ratio (lateral stretch ratio): 4.4 times-Stretch stress (lateral stretch stress): 18 MPa
- PET film biaxially stretched polyester film having a thickness of 250 ⁇ m was produced.
- a sample piece L having a size of 30 mm in the MD direction and 120 mm in the TD direction is obtained, and two reference lines are inserted into the sample piece L so as to have an interval of 100 mm in the TD direction. Then, measurement and calculation were performed, and the obtained value was defined as the heat shrinkage rate in the TD direction.
- the above operation is performed by cutting out a total of three points, one at the center and two at both ends, with respect to the total film width in the TD direction of the biaxially stretched polyester film.
- the absolute value was obtained by subtracting the heat shrinkage rate with the larger difference from the heat shrinkage rate at the center, and it was defined as the variation in the heat shrinkage rate in each of the MD direction and the TD direction.
- the thickness of the obtained biaxially stretched polyester film was determined as follows. Using a contact-type film thickness meter (manufactured by Anritsu Co., Ltd.) for biaxially stretched polyester film, 50 points were sampled at equal intervals over 0.5 m in the longitudinally stretched direction (longitudinal direction), and the film width direction ( After sampling 50 points at equal intervals (50 equal parts in the width direction) over the entire width of the film in the direction perpendicular to the longitudinal direction, the thicknesses of these 100 points were measured. The average thickness of these 100 points was determined and used as the thickness of the polyester film. The obtained thickness is shown in Table 1 below.
- the hydrolysis resistance of the biaxially stretched polyester film was evaluated from the half elongation time at break of the biaxially stretched polyester film.
- the biaxially stretched polyester film is stored under conditions of 120 ° C. and relative humidity 100%, and the breaking elongation (%) exhibited by the biaxially stretched polyester film after storage is the breaking elongation exhibited by the biaxially stretched polyester film before storage.
- the storage time of 50% with respect to (%) was defined as the half elongation time at break. The longer the half elongation time at break, the better the hydrolysis resistance of the biaxially stretched polyester film.
- the break elongation (%) of the biaxially stretched polyester film is determined by cutting the biaxially stretched polyester film.
- the obtained sample piece having a size of 1 cm ⁇ 20 cm was obtained by pulling at a chuck interval of 5 cm and 20% / min.
- X Half elongation at break was less than 80 hours.
- ⁇ Formation of reflective layer> Preparation of pigment dispersion- Components in the following composition were mixed, and the mixture was subjected to a dispersion treatment for 1 hour by a dynomill type disperser to prepare a pigment dispersion.
- composition> The above pigment dispersion: 80.0 parts-Polyacrylic resin aqueous dispersion: 19.2 parts (Binder: Jurimer ET410, manufactured by Nippon Pure Chemicals Co., Ltd., solid content: 30% by mass) Polyoxyalkylene alkyl ether: 3.0 parts (Naroacty CL95, manufactured by Sanyo Chemical Industries, solid content: 1% by mass) Oxazoline compound (crosslinking agent) 2.0 parts (Epocross WS-700, manufactured by Nippon Shokubai Chemical Industry Co., Ltd., solid content: 25% by mass) ⁇ Distilled water: 7.8 parts
- the obtained coating solution for the reflective layer is applied on a biaxially stretched polyester film, dried at 180 ° C. for 1 minute, and as a colored layer, a white layer (light reflecting layer) having an amount of titanium dioxide of 6.5 g / m 2. Formed.
- ⁇ Back layer> Preparation of back layer coating solution- Components in the following composition were mixed to prepare a back layer coating solution.
- ⁇ Composition> Ceranate WSA-1070 (binder) 323 parts (acrylic / silicone binder, manufactured by DIC Corporation, solid content: 40% by mass) Oxazoline compound (crosslinking agent) 52 parts (Epocross WS-700, manufactured by Nippon Shokubai Chemical Industry Co., Ltd., solid content: 25% by mass) ⁇ Polyoxyalkylene alkyl ether (surfactant) 32 parts (Naroacty CL95, manufactured by Sanyo Chemical Industries, solid content: 1% by mass) ⁇ Distilled water ... 594 parts
- back layer coating solution was applied to the side of the biaxially stretched polyester film where the reflective layer and the easy adhesion layer were not formed so that the binder amount was 3.0 g / m 2 in terms of wet coating amount, and 180 Drying was performed at a temperature of 1 ° C. for 1 minute to form a back layer having a dry thickness of 3 ⁇ m.
- a back sheet was produced as described above.
- the adhesive tape [The polyester adhesive tape (No. 31B) by Nitto Denko Corporation] was affixed on the surface where the sample's mesh entered. Subsequently, the adhesive tape was peeled off at a 180 degree direction at a stretch. The time from taking out the hot water to peeling off the adhesive tape was within 5 minutes. That is, the evaluation of the adhesion is an evaluation of the adhesion when the coating layer of the sample is in a wet state.
- the surface of the sample containing the meshes was visually observed, and the number of meshes from which the coating layer was peeled was counted, and this was used as an index for evaluating adhesion as a “peeling rate”.
- the evaluation criteria are as follows. ⁇ Evaluation criteria> A: The peeling rate was less than 1%. ⁇ : The peel rate was 1% or more and less than 5%. (Triangle
- Example 2 In Example 1, by changing the solid phase polymerization time from 30 hours to 12 hours and changing the IV of the polyester film from 0.80 to 0.75, the variation in crystallinity in the film width direction of the polyester film A biaxially stretched polyester film (PET film) having a thickness of 250 ⁇ m was produced in the same manner as in Example 1 except that 0.8 was changed from 0.8% to 2.2%, and a back sheet was further produced. Measurement and evaluation were performed.
- PET film biaxially stretched polyester film having a thickness of 250 ⁇ m
- T heat setting; DSC pre-peak temperature
- PET film biaxially stretched polyester film
- Example 5 In Example 1, except that the variation of crystallinity in the film width direction of the polyester film was changed from 0.8% to 4.8% by not using the infrared heater used in the heat setting zone. In the same manner as in No. 1, a biaxially stretched polyester film (PET film) having a thickness of 250 ⁇ m was produced, and a back sheet was further produced and measured and evaluated.
- PET film biaxially stretched polyester film
- Example 6 Example 7
- the thickness was changed to the thickness shown in Table 1 below, and the rotational speed of the extruder was adjusted, so that the thickness of the polyester film was changed from 250 ⁇ m to 180 ⁇ m and 350 ⁇ m.
- a biaxially stretched polyester film PET film
- PET film back sheet was further prepared, and measurement and evaluation were performed.
- Example 8 In Example 1, except that the residence time in the heat setting part for performing the heat setting step of the transverse stretching step was changed from 25 seconds to 5 seconds and 50 seconds, the same as in Example 1, 2 with a thickness of 250 ⁇ m.
- An axially stretched polyester film (PET film) was prepared, a back sheet was further prepared, and measurement and evaluation were performed.
- Example 10 to 18 In the “film forming step” of Example 1, after the polyester raw resin was dried and charged into the hopper, the melted and kneaded polyester raw resin was added to the cylinder of the uniaxial kneading extruder as shown in Table 1 below.
- a biaxial shaft having a thickness of 250 ⁇ m was obtained in the same manner as in Example 1 except that the polyester raw material resin 1 was changed to the following polyester raw material resins 4 to 9 with or without the addition of the end-capping material described.
- a stretched polyester film (PET film) was produced, a back sheet was further produced, and measurement and evaluation were performed.
- TMA trimellitic acid
- Example 20 a biaxially stretched polyester film (PET film) having a thickness of 250 ⁇ m was produced, and a back sheet was further produced and measured and evaluated.
- Example 10 Other than having changed the variation in the maximum film surface temperature in the film width direction from 0.9 ° C to 0.6 ° C by changing the temperature from °C to 185 ° C and increasing the speed of the hot air from the hot air blowing nozzle of the heat fixing part
- PET film biaxially stretched polyester film having a thickness of 250 ⁇ m was produced, and a back sheet was further produced and measured and evaluated.
- Example 1 In Example 1, the solid phase polymerization time was changed from 30 hours to 10 hours, so that the IV of the polyester film was changed to 0.72, and the biaxial stretching with a thickness of 250 ⁇ m was performed in the same manner as in Example 1. A polyester film (PET film) was produced, a back sheet was further produced, and measurement and evaluation were performed.
- PET film PET film
- T heat setting; DSC pre-peak temperature
- Example 4 In Example 1, the use of the infrared heater used in the heat setting zone was stopped, and further, the variation in the crystallinity in the film width direction of the polyester film was reduced from 0.8% by reducing the wind speed of the hot air coming out of the hot air blowing nozzle.
- a biaxially stretched polyester film (PET film) having a thickness of 250 ⁇ m was prepared in the same manner as in Example 1 except that the content was changed to 5.3%, and a back sheet was further prepared and measured and evaluated. .
- Comparative Example 5 In Example 1, the variation in crystallinity in the film width direction of the polyester film was changed from 0.8% to 0.1% by changing the surface temperature of the infrared heater used in the heat setting zone from 450 ° C.
- T heat setting; DSC pre-peak temperature
- Example 2 Other than having changed the maximum film surface temperature variation in the film width direction from 0.9 ° C to 3.4 ° C by changing the temperature from 200 ° C to 200 ° C and weakening the wind speed of the hot air from the hot air blowing nozzle of the heat fixing part
- PET film biaxially stretched polyester film having a thickness of 250 ⁇ m was produced, and a back sheet was further produced and measured and evaluated.
- TMA Trimellitic acid (trifunctional carboxylic acid)
- BTC benzenetetracarboxylic acid (tetrafunctional carboxylic acid)
- CI Stabaxol P100 (carbodiimide compound) manufactured by Rhein Chemie EP: Khajura E10P (epoxy compound) manufactured by Hexion Specialty Chemicals
- Example 19 A tempered glass having a thickness of 3 mm, an EVA sheet (SC50B manufactured by Mitsui Chemicals Fabro Co., Ltd.), a crystalline solar cell, an EVA sheet (SC50B manufactured by Mitsui Chemicals Fabro Co., Ltd.), and Examples 1 to 18
- the back sheets prepared in Step 1 were superposed and bonded to EVA by hot pressing using a vacuum laminator (manufactured by Nisshinbo Co., Ltd., vacuum laminating machine) to produce a crystalline solar cell module.
- the back sheet was disposed such that the easy-adhesive layer was in contact with the EVA sheet, and adhesion was performed by the method described below.
- ⁇ Adhesion method> Using a vacuum laminator, vacuum was applied at 128 ° C. for 3 minutes, and then pressure was applied for 2 minutes to temporarily bond. Thereafter, the main adhesion treatment was performed in a dry oven at 150 ° C. for 30 minutes.
- the polyester film of the present invention can be suitably used for applications that require excellent weather resistance, such as solar cell protective sheets. Especially, it is suitable for uses, such as a back surface protection sheet (what is called a back sheet) arrange
- a back surface protection sheet what is called a back sheet
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Abstract
Description
前記課題を達成するための具体的手段は以下の通りである。
<2> 固有粘度(IV)が0.75dL/g以上である前記<1>に記載の2軸延伸ポリエステルフィルムである。
<3> 前記フィルム幅方向において、該フィルム幅方向に直交する方向の熱収縮率のバラツキと該フィルム幅方向と平行な方向の熱収縮率のバラツキとが共に0.03%以上0.50%以下である前記<1>又は前記<2>に記載の2軸延伸ポリエステルフィルムである。
<4> 厚みが180μm以上350μm以下である前記<1>~前記<3>のいずれか1つに記載の2軸延伸ポリエステルフィルムである。
<6> カルボン酸基の数と水酸基の数との合計が3以上である多官能モノマーに由来する構成単位を含み、前記多官能モノマーに由来の構成単位の含有比率が、ポリエステル中の全構成単位に対して、0.005モル%以上2.5モル%以下である前記<1>~前記<5>のいずれか1つに記載の2軸延伸ポリエステルフィルムである。
<7> 更に、オキサゾリン系化合物、カルボジイミド化合物、及びエポキシ化合物から選ばれる末端封止剤に由来する構造部分を含む前記<1>~前記<6>のいずれか1つに記載の2軸延伸ポリエステルフィルムである。
<8> 前記末端封止剤に由来する構造部分の含有比率が、ポリエステルの全質量に対して、0.1質量%以上5質量%以下である前記<7>に記載の2軸延伸ポリエステルフィルムである。
前記横延伸工程は、縦延伸後のポリエステルフィルムを延伸可能な温度に予熱する予熱工程と、予熱された前記ポリエステルフィルムを前記長手方向と直交する幅方向に緊張を与えて横延伸する延伸工程と、前記縦延伸及び前記横延伸を行なった後の前記ポリエステルフィルムの最高到達膜面温度を160℃以上210℃以下の範囲に制御しながら、前記幅方向における最高到達膜面温度のバラツキを0.5℃以上5.0℃以下として加熱し結晶化させて熱固定する熱固定工程と、前記熱固定されたポリエステルフィルムを加熱し、ポリエステルフィルムの緊張を緩和する熱緩和工程と、熱緩和後のポリエステルフィルムを冷却する冷却工程と、を含む、2軸延伸ポリエステルフィルムの製造方法である。
<11> 前記冷却工程通過後のポリエステルフィルムの厚みが180μm以上350μm以下であって、前記熱固定工程は、加熱されるポリエステルフィルムの加熱面を、前記フィルム成形工程でのキャスティングドラムに接触させた面とし、前記加熱直後における前記加熱面の表面温度が、前記加熱面と反対側の非加熱面の表面温度に比べて、0.5℃以上5.0℃以下の範囲で高くなるように加熱する前記<9>又は前記<10>に記載の2軸延伸ポリエステルフィルムの製造方法である。
<12> 前記熱固定工程は、ポリエステルフィルムの幅方向端部をヒーターにより輻射加熱する前記<9>~前記<11>のいずれか1つに記載の2軸延伸ポリエステルフィルムの製造方法である。
<13> 前記熱固定工程は、加熱状態での滞留時間を5秒以上50秒以下とする前記<9>~前記<12>のいずれか1つに記載の2軸延伸ポリエステルフィルムの製造方法である。
<14> 前記予熱工程、前記延伸工程、及び前記熱緩和工程の少なくとも1つは、ポリエステルフィルムの幅方向端部をヒーターにより輻射加熱する前記<9>~前記<13>のいずれか1つに記載の2軸延伸ポリエステルフィルムの製造方法である。
<16> 前記ポリエステル原料樹脂は、カルボン酸基の数と水酸基の数との合計が3以上である多官能モノマーを共重合成分として含み、前記多官能モノマーに由来の構成単位の前記ポリエステル原料樹脂中における含有比率が、前記ポリエステル原料樹脂中の全構成単位に対して、0.005モル%以上2.5モル%以下である前記<9>~前記<15>のいずれか1つに記載の2軸延伸ポリエステルフィルムの製造方法である。
<17> 前記フィルム成形工程は、前記ポリエステル原料樹脂に、オキサゾリン系化合物、カルボジイミド化合物、及びエポキシ化合物から選ばれる末端封止剤を含める工程を有し、溶融混練により前記末端封止剤と反応した前記ポリエステル原料樹脂を溶融押出する前記<9>~前記<16>のいずれか1つに記載の2軸延伸ポリエステルフィルムの製造方法である。
<18> 前記末端封止剤の含有量が、前記ポリエステル原料樹脂の全質量に対して、0.1質量%以上5質量%以下である前記<17>に記載の2軸延伸ポリエステルフィルムの製造方法である。
<20> 太陽光が入射する透明性の基板と、前記基板の一方の側に配された太陽電池素子と、該太陽電池素子の前記基板が配された側と反対側に配された前記<19>に記載の太陽電池用バックシートと、を備えた太陽電池モジュールである。
本発明によれば、長期での耐久性能に優れた太陽電池用バックシート、及び長期に亘り安定的な発電性能が得られる太陽電池モジュールを提供することができる。
本発明のポリエステルフィルムは、1m以上のフィルム幅を有すると共に、固有粘度(IV)値が0.70dL/g以上であり、示差走査熱量測定(DSC;Differential scanning calorimetry、以下、「DSC」と略記することがある。)で測定されるプレピーク温度が160℃以上210℃以下であり、前記フィルム幅方向における結晶化度のバラツキを0.3%以上5.0%以下の範囲として構成されたものである。
製造工程において、フィルムの中央部が幅方向端部に比べて弛みやすい要因として、幅方向における結晶化度のバラツキ、すなわちフィルム中央部の結晶化度に比べて端部の結晶化度が低いことによる幅方向の熱収縮率のバラツキにあると推定される。具体的には、フィルムの端部に比べて中央部の熱収縮率が小さくなる。このようにフィルム幅方向に熱収縮率に差が生じる場合、フィルム中央部の方が端部に比べて収縮し難いため、フィルム中央部が端部に比べて弛んでしまう。そこで、本発明においては、ポリエステルの固有粘度(IV)を0.70dL/g以上とし、ポリエステルフィルムの幅方向における結晶化度のバラツキ(=フィルム中央部の結晶化度-フィルム端部の結晶化度)を0.3%以上5.0%以下にすることで、IVを高くすると結晶化を遅らせられ、結晶化度のバラツキが小さく抑えられるので、耐加水分解性が向上し、製造工程中にフィルムの幅方向端部と中央部との弛みに差が生じ難くなる。これにより、搬送中でのポリエステルフィルムにおける皺や擦り傷の発生が抑えられる。
なお、上記の製造工程としては、例えば、製膜後の乾燥工程や、貼り合せたい2種以上のフィルムを金属ロールに搬送しながら所定の温度まで加熱し、接着剤や粘着剤等を塗布してフィルム同士を貼り合わせる貼合工程などである。
耐加水分解性をより高めて耐候性を向上させる観点から、IV値としては、0.75dL/g以上が好ましく、0.78dL/g以上がより好ましく、0.80dL/g以上が更に好ましい。具体的には、IV値は、0.70dL/g以上0.90dL/g以下であることが好ましく、0.75dL/g以上0.90dL/g以下であることがより好ましく、0.75dL/g以上0.85dL/g以下であることが更に好ましく、0.78dL/g以上0.85dL/g以下であることが最も好ましい。
DSCのプレピーク温度が160℃未満であると、熱固定温度が低過ぎて熱固定が充分に行なえず、結晶化度のバラツキが大きくなり、ひいては熱収縮率差が大きくなる。すなわち、フィルム中央部の弛みが大きくなりキズが発生する。また、DSCのプレピーク温度が210℃を超えると、IV値は高まるものの、耐加水分解性が低下し、長期に亘る耐久性能の点で劣る。
DSCのプレピーク温度としては、上記同様の理由から、170℃以上200℃以下がより好ましく、175℃以上195℃以下が更に好ましい。
前記DSCのプレピーク温度は、示差走査熱量測定 (Differential scanning calorimetry)で常法により求められる値である。
結晶化度は、フィルムの密度から算出される値である。すなわち、フィルムの密度X(g/cm3)、結晶化度0%での密度Y(g/cm3)、結晶化度100%での密度Z(g/cm3)を用いて、下記の計算式により導出される結晶化度Xc(%)である。密度の測定は、JIS K7112に準じて行なうことができる。
Xc={Z×(X-Y)}/{X×(Z-Y)}×100
ポリエステルは一般に、ガラスに比べて熱膨張係数や吸湿膨張係数が大きいため、温湿度変化で応力がかかりやすくひび割れや層の剥がれを招来しやすい傾向があるが、熱収縮率が上記範囲内であることで、ポリエステルフィルムに貼り付けられた機能性の層やシートの剥離やポリエステルフィルムに塗布形成された層のひび割れ等を防止することができる。
その中では、熱収縮率は、1.0%以下がより好ましく、0.5%以下がさらに好ましい。
前記熱収縮率のバラツキは、上記の結晶化度のバラツキを0.3%以上5.0%以下の範囲に調節することによって調整することができる。
上記と同様の理由から、厚みは、200μm以上320μm以下の範囲がより好ましく、200μm以上290μm以下の範囲が更に好ましい。
なお、本明細書中において、「eq/トン」は1トンあたりのモル当量を表す。
AVは、ポリエステルをベンジルアルコール/クロロホルム(=2/3;体積比)の混合溶液に完全溶解させ、指示薬としてフェノールレッドを用い、基準液(0.025N KOH-メタノール混合溶液)で滴定し、その適定量から算出される値である。
本発明のポリエステルフィルムは、後述のように、例えば(A)ジカルボン酸成分と(B)ジオール成分とを周知の方法でエステル化反応及び/又はエステル交換反応させることによって得ることができ、更に好ましくは、これに3官能以上の多官能モノマーを共重合させて得られる。ジカルボン酸成分、ジオール成分、及び多官能モノマー等の例示や好ましい態様などの詳細については、後述する通りである。
カルボン酸基の数(a)と水酸基の数(b)との合計(a+b)が3以上である多官能モノマーに由来の構成単位としては、後述するように、カルボン酸基の数(a)が3以上のカルボン酸並びにこれらのエステル誘導体や酸無水物等、水酸基数(b)が3以上の多官能モノマー、並びに「一分子中に水酸基とカルボン酸基の両方を有し、カルボン酸基の数(a)と水酸基の数(b)との合計(a+b)が3以上であるオキシ酸類」などを挙げることができる。これらの例示及び好ましい態様などの詳細については、後述する通りである。
また、前記カルボン酸のカルボキシ末端、又は前記「一分子中に水酸基とカルボン酸基の両方を有する多官能モノマー」のカルボキシ末端に、l-ラクチド、d-ラクチド、ヒドロキシ安息香酸などのオキシ酸類及びその誘導体、そのオキシ酸類が複数個連なったもの等を付加させたものも好適である。
これらは、一種単独で用いても、必要に応じて、複数種を併用してもよい。
また、3官能以上の多官能モノマーを構成単位として含むことにより、エステル化反応後の重縮合において用いられなかった官能基がポリエステルフィルム上に塗布形成される塗布層中の成分と水素結合、共有結合することで、塗布層とポリエステルフィルムとの密着性がより良好に保たれ、剥離の発生を効果的に防ぐことができる。太陽電池用バックシートに用いられるポリエステルフィルムは、易接着層などの塗布層が塗布形成された後にEVA等の封止剤と密着されるが、屋外等の風雨に曝されるような環境下に長時間置かれた場合においても、剥がれ難い良好な密着性が得られる。
したがって、3官能以上の多官能モノマーに由来の構成単位の含有比率が0.005モル%以上であることで、耐候性、低熱収縮性、及びポリエステルフィルム上に塗布形成される塗布層との密着力がさらに向上し易い。また、3官能以上の多官能モノマーに由来の構成単位の含有比率が2.5モル%以下であることで、3官能以上の多官能モノマーに由来の構成単位は嵩高いため、結晶形成し難くなるのが抑制される。その結果として、結晶を介して形成される低移動成分の形成を促し、加水分解性が低下するのを抑制することができる。さらに、3官能以上の多官能モノマーに由来の構成単位の嵩高さにより、フィルム表面の微細凹凸量が増えるためアンカー効果が発現しやすく、ポリエステルフィルムと該フィルム上に塗布形成される塗布層との密着が向上する。また、当該嵩高さにより、増加する自由体積(分子間の隙間)が抑制され、大きな自由体積中をポリエステル分子がすり抜けることで発生する熱収縮を抑制することができる。また、3官能以上の多官能モノマーに由来の構成単位の添加過剰に伴なうガラス転移温度(Tg)の低下も抑制され、耐候性の低下防止にも有効である。
本発明のポリエステルフィルムは、更に、オキサゾリン系化合物、カルボジイミド化合物、及びエポキシ化合物から選ばれる末端封止剤に由来する構造部分を有していることが好ましい。なお、「末端封止剤に由来する構造部分」とは、末端封止剤がポリエステル末端のカルボン酸と反応して末端に結合している構造をさす。
末端封止剤は、ポリエステルフィルムの質量に対して、0.1質量%以上5質量%以下の範囲で含有されていることが好ましく、より好ましくは0.3質量%以上4質量%以下であり、さらに好ましくは0.5質量%以上2質量%以下である。
ポリエステルフィルム中における末端封止剤の含有比率が0.1質量%以上であることで、塗布層との密着が良好になると共に、AV低下効果による耐候性向上を達成できる上、低熱収縮性も付与することができる。また、ポリエステルフィルム中における末端封止剤の含有比率が5質量%以下であると、塗布層との密着が良好になると共に、末端封止剤の添加によるポリエステルのガラス転移温度(Tg)の低下が抑制され、これによる耐候性の低下や熱収縮の増加を抑制することができる。これは、Tgが低下した分、相対的にポリエステルの反応性が増加することで生じる加水分解性の増加を抑制したり、Tg低下で増加するポリエステル分子の運動性が増加し易くなることで生じる熱収縮が抑制されるためである。
また、多官能性カルボジイミドとしては、重合度3~15のポリカルボジイミドが好ましい。ポリカルボジイミドは、一般に「-R-N=C=N-」等で表される繰り返し単位を有し、前記Rは、アルキレン、アリーレン等の2価の連結基を表す。このような繰り返し単位としては、例えば、1,5-ナフタレンカルボジイミド、4,4'-ジフェニルメタンカルボジイミド、4,4'-ジフェニルジメチルメタンカルボジイミド、1,3-フェニレンカルボジイミド、2,4-トリレンカルボジイミド、2,6-トリレンカルボジイミド、2,4-トリレンカルボジイミドと2,6-トリレンカルボジイミドの混合物、ヘキサメチレンカルボジイミド、シクロヘキサン-1,4-カルボジイミド、キシリレンカルボジイミド、イソホロンカルボジイミド、ジシクロヘキシルメタン-4,4'-カルボジイミド、メチルシクロヘキサンカルボジイミド、テトラメチルキシリレンカルボジイミド、2,6-ジイソプロピルフェニルカルボジイミド及び1,3,5-トリイソプロピルベンゼン-2,4-カルボジイミドなどが挙げられる。
ここで、イソシアネート系ガスは、イソシアネート基をもつガスであり、例えば、ジイソプロピルフェニルイソシアネート、1,3,5-トリイソプロピルフェニルジイソシアネート、2-アミノ-1,3,5-トリイソプロピルフェニル-6-イソシアネート、4,4’-ジシクロヘキシルメタンジイソシアネート、イソホロンジイソシアネート、及びシクロヘキシルイソシアネートなどが挙げられる。
ビスオキサゾリン化合物としては、例えば、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-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-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'-テトラメチレンビス(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)等を例示することができる。これらの中では、ポリエステルとの反応性が良好で耐候性の向上効果が高い観点から、2,2'-ビス(2-オキサゾリン)が最も好ましい。
ビスオキサゾリン化合物は、本発明の効果を損なわない限り、1種単独で用いてもよいし、2種以上を組み合わせて用いてもよい。
以下、本発明のポリエステルフィルムの製造方法について具体的に説明する。
本発明のポリエステルフィルムの製造方法は、ポリエステル原料樹脂をシート状に溶融押出し、キャスティングドラム上で冷却してポリエステルフィルムを成形するフィルム成形工程と、成形された前記ポリエステルフィルムを長手方向に縦延伸する縦延伸工程と、前記縦延伸後のポリエステルフィルムを前記長手方向に直交する幅方向に横延伸する横延伸工程とを少なくとも設けて構成されると共に、
前記横延伸工程は、縦延伸後のポリエステルフィルムを延伸可能な温度に予熱する予熱工程と、予熱された前記ポリエステルフィルムを前記長手方向と直交する幅方向に緊張を与えて横延伸する延伸工程と、前記縦延伸及び前記横延伸を行なった後の前記ポリエステルフィルムの最高到達膜面温度を160℃以上210℃以下の範囲に制御しながら、前記幅方向における最高到達膜面温度のバラツキを0.5℃以上5.0℃以下として加熱し結晶化させて熱固定する熱固定工程と、前記熱固定されたポリエステルフィルムを加熱し、ポリエステルフィルムの緊張を緩和する熱緩和工程と、熱緩和後のポリエステルフィルムを冷却する冷却工程とを設けて構成されたものである。
フィルム成形工程では、ポリエステル原料樹脂をシート状に溶融押出し、キャスティングドラム上で冷却してポリエステルフィルムを成形する。本発明においては、固有粘度(IV)が0.70dL/g以上のポリエステルフィルムが好適に成形される。
(ポリエステル原料樹脂)
ポリエステル原料樹脂は、ポリエステルフィルムの原料となり、ポリエステルを含んでいる材料であれば、特に制限されず、ポリエステルのほかに、無機粒子や有機粒子のスラリーを含んでいてもよい。また、ポリエステル原料樹脂は、触媒由来のチタン元素を含んでいてもよい。
ポリエステル原料樹脂に含まれるポリエステルの種類は特に制限されない。
ジカルボン酸成分と、ジオール成分とを用いて合成してもよいし、市販のポリエステルを用いてもよい。
(A)ジカルボン酸成分としては、例えば、マロン酸、コハク酸、グルタル酸、アジピン酸、スベリン酸、セバシン酸、ドデカンジオン酸、ダイマー酸、エイコサンジオン酸、ピメリン酸、アゼライン酸、メチルマロン酸、エチルマロン酸等の脂肪族ジカルボン酸類、アダマンタンジカルボン酸、ノルボルネンジカルボン酸、イソソルビド、シクロヘキサンジカルボン酸、デカリンジカルボン酸、などの脂環族ジカルボン酸、テレフタル酸、イソフタル酸、フタル酸、1,4-ナフタレンジカルボン酸、1,5-ナフタレンジカルボン酸、2,6-ナフタレンジカルボン酸、1,8-ナフタレンジカルボン酸、4,4’-ジフェニルジカルボン酸、4,4’-ジフェニルエーテルジカルボン酸、5-ナトリウムスルホイソフタル酸、フェニルインダンジカルボン酸、アントラセンジカルボン酸、フェナントレンジカルボン酸、9,9’-ビス(4-カルボキシフェニル)フルオレン酸等の芳香族ジカルボン酸などのジカルボン酸もしくはそのエステル誘導体が挙げられる。
なお、「主成分」とは、ジカルボン酸成分に占める芳香族ジカルボン酸の割合が80質量%以上であることをいう。
また、前記(B)ジオール成分として、脂肪族ジオールの少なくとも1種が用いられる場合が好ましい。脂肪族ジオールとして、エチレングリコールを含むことができ、好ましくはエチレングリコールを主成分として含有する。
なお、主成分とは、ジオール成分に占めるエチレングリコールの割合が80質量%以上であることをいう。
カルボン酸基の数(a)が3以上のカルボン酸(多官能モノマー)の例として、3官能の芳香族カルボン酸としては、例えば、トリメシン酸、トリメリット酸、ピロメリット酸、ナフタレントリカルボン酸、アントラセントリカルボン酸等が、3官能の脂肪族カルボン酸としては、例えば、メタントリカルボン酸、エタントリカルボン酸、プロパントリカルボン酸、ブタントリカルボン酸等が、4官能の芳香族カルボン酸としては、例えば、ベンゼンテトラカルボン酸、ベンゾフェノンテトラカルボン酸、ナフタレンテトラカルボン酸、アントラセンテトラカルボン酸、ペリレンテトラカルボン酸等が、4官能の脂肪族カルボン酸として、例えば、エタンテトラカルボン酸、エチレンテトラカルボン酸、ブタンテトラカルボン酸、シクロペンタンテトラカルボン酸、シクロヘキサンテトラカルボン酸、アダマンタンテトラカルボン酸等が、5官能以上の芳香族カルボン酸として、例えば、ベンゼンペンタカルボン酸、ベンゼンヘキサカルボン酸、ナフタレンペンタカルボン酸、ナフタレンヘキサカルボン酸、ナフタレンヘプタカルボン酸、ナフタレンオクタカルボン酸、アントラセンペンタカルボン酸、アントラセンヘキサカルボン酸、アントラセンヘプタカルボン酸、アントラセンオクタカルボン酸等が、5官能以上の脂肪族カルボン酸として、例えば、エタンペンタカルボン酸、エタンヘプタカルボン酸、ブタンペンタカルボン酸、ブタンヘプタカルボン酸、シクロペンタンペンタカルボン酸、シクロヘキサンペンタカルボン酸、シクロヘキサンヘキサカルボン酸、アダマンタンペンタカルボン酸、アダマンタンヘキサカルボン酸等が挙げられる。
本発明においては、これらのエステル誘導体や酸無水物等が例として挙げられるが、これらに限定されるものではない。
これらは、1種単独で用いても、必要に応じて、複数種を併用してもよい。
これらは、1種単独で用いても、必要に応じて、複数種を併用してもよい。
また、これらの多官能モノマーのカルボキシ末端に、l-ラクチド、d-ラクチド、ヒドロキシ安息香酸などのオキシ酸類及びその誘導体、そのオキシ酸類が複数個連なったもの等を付加させたものも好適に用いられる。
これらは、1種単独で用いても、必要に応じて、複数種を併用してもよい。
Ti系触媒の例としては、テトラ-n-プロピルチタネート、テトラ-i-プロピルチタネート、テトラ-n-ブチルチタネート、テトラ-n-ブチルチタネートテトラマー、テトラ-t-ブチルチタネート、テトラシクロヘキシルチタネート、テトラフェニルチタネート、テトラベンジルチタネート等のチタンアルコキシド、チタンアルコキシドの加水分解により得られるチタン酸化物、チタンアルコキシドと珪素アルコキシドもしくはジルコニウムアルコキシドとの混合物の加水分解により得られるチタン-珪素もしくはジルコニウム複合酸化物、酢酸チタン、蓚酸チタン、蓚酸チタンカリウム、蓚酸チタンナトリウム、チタン酸カリウム、チタン酸ナトリウム、チタン酸-水酸化アルミニウム混合物、塩化チタン、塩化チタン-塩化アルミニウム混合物、チタンアセチルアセトナート、有機酸を配位子とする有機キレートチタン錯体、等が挙げられる。
ポリエステル原料樹脂に含まれるチタン元素の量が1ppm以上であると、ポリエステルの重量平均分子量(Mw)が上がり、熱分解しにくい。そのため、押出機内で異物が軽減される。ポリエステル原料樹脂に含まれるチタン元素の量が50ppm以下であると、Ti系触媒が異物となり難く、ポリエステルシートの延伸の際に延伸ムラが軽減される。
触媒成分であるチタン化合物として、有機酸を配位子とする有機キレートチタン錯体の少なくとも1種が用いられることが好ましい。有機酸としては、例えば、クエン酸、乳酸、トリメリット酸、リンゴ酸等を挙げることができる。中でも、クエン酸又はクエン酸塩を配位子とする有機キレート錯体が好ましい。
また、一般に、末端カルボキシ基量が多いほど耐加水分解性が悪化することが知られており、上記の添加方法によって末端カルボキシ基量が少なくなることで、耐加水分解性の向上が期待される。
このようなチタン化合物の例としては、テトラ-n-プロピルチタネート、テトラ-i-プロピルチタネート、テトラ-n-ブチルチタネート、テトラ-n-ブチルチタネートテトラマー、テトラ-t-ブチルチタネート、テトラシクロヘキシルチタネート、テトラフェニルチタネート、テトラベンジルチタネート等のチタンアルコキシド、チタンアルコキシドの加水分解により得られるチタン酸化物、チタンアルコキシドと珪素アルコキシドもしくはジルコニウムアルコキシドとの混合物の加水分解により得られるチタン-珪素もしくはジルコニウム複合酸化物、酢酸チタン、蓚酸チタン、蓚酸チタンカリウム、蓚酸チタンナトリウム、チタン酸カリウム、チタン酸ナトリウム、チタン酸-水酸化アルミニウム混合物、塩化チタン、塩化チタン-塩化アルミニウム混合物、チタンアセチルアセトナート等が挙げられる。
これにより、重合時の着色及びその後の溶融製膜時における着色が少なくなり、従来のアンチモン(Sb)触媒系のポリエステルに比べて黄色味が軽減され、また、透明性の比較的高いゲルマニウム触媒系のポリエステルに比べて遜色のない色調、透明性を持ち、しかも耐熱性に優れたポリエステルを提供できる。また、コバルト化合物や色素などの色調調整材を用いずに高い透明性を有し、黄色味の少ないポリエステルが得られる。
5価のリン化合物として、置換基として芳香環を有しない5価のリン酸エステルの少なくとも一種が用いられる。例えば、炭素数2以下の低級アルキル基を置換基として有するリン酸エステル〔(OR)3-P=O;R=炭素数1又は2のアルキル基〕が挙げられ、具体的には、リン酸トリメチル、リン酸トリエチルが特に好ましい。
ポリエステルにマグネシウム化合物を含めることにより、ポリエステルの静電印加性が向上する。この場合に着色がおきやすいが、本発明においては、着色を抑え、優れた色調、耐熱性が得られる。
マグネシウム化合物としては、例えば、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、炭酸マグネシウム等のマグネシウム塩が挙げられる。中でも、エチレングリコールへの溶解性の観点から、酢酸マグネシウムが最も好ましい。
(i)Z=5×(P含有量[ppm]/P原子量)-2×(Mg含有量[ppm]/Mg原子量)-4×(Ti含有量[ppm]/Ti原子量)
(ii)0≦Z≦+5.0
これは、リン化合物はチタンに作用するのみならずマグネシウム化合物とも相互作用することから、3者のバランスを定量的に表現する指標となるものである。
前記式(i)は、反応可能な全リン量から、マグネシウムに作用するリン分を除き、チタンに作用可能なリンの量を表現したものである。値Zが正の場合は、チタンを阻害するリンが余剰な状況にあり、逆に負の場合はチタンを阻害するために必要なリンが不足する状況にあるといえる。反応においては、Ti、Mg、Pの各原子1個は等価ではないことから、式中の各々のモル数に価数を乗じて重み付けを施してある。
エステル化反応を一段階で行なう場合、エステル化反応温度は230~260℃が好ましく、240~250℃がより好ましい。
エステル化反応を多段階に分けて行なう場合、第一反応槽のエステル化反応の温度は230~260℃が好ましく、より好ましくは240~250℃であり、圧力は1.0~5.0kg/cm2が好ましく、より好ましくは2.0~3.0kg/cm2である。第二反応槽のエステル化反応の温度は230~260℃が好ましく、より好ましくは245~255℃であり、圧力は0.5~5.0kg/cm2、より好ましくは1.0~3.0kg/cm2である。さらに3段階以上に分けて実施する場合は、中間段階のエステル化反応の条件は、前記第一反応槽と最終反応槽の間の条件に設定するのが好ましい。
重縮合は、エステル化反応で生成されたエステル化反応生成物を重縮合反応させて重縮合物を生成する。重縮合反応は、1段階で行なってもよいし、多段階に分けて行なうようにしてもよい。
エステル化反応により重合した後に、さらに固相重合することにより、ポリエステルフィルムの含水率、結晶化度、ポリエステルの酸価、すなわち、ポリエステルの末端カルボキシ基の濃度(Acid Value;AV)、固有粘度(Interisic Viscosity;IV)を制御することができる。
したがって、縦延伸及び横延伸に適用するポリエステルフィルムの原料であるポリエステルは、固有粘度が0.70dL/g以上0.9dL/g以下であることが好ましく、さらに触媒(Ti触媒)由来のチタン原子を含有することが好ましい。
ポリエステルの固相重合は、連続法(タワーの中に樹脂を充満させ、これを加熱しながらゆっくり所定の時間滞流させた後、順次送り出す方法)でもよく、バッチ法(容器の中に樹脂を投入し、所定の時間加熱する方法)でもよい。
固相重合は、真空中あるいは窒素雰囲気下で行なうことが好ましい。
ポリエステルの固相重合温度は、150℃以上250℃以下、より好ましくは170℃以上240℃以下、さらに好ましくは180℃以上230℃以下であることが好ましい。温度が上記範囲内であると、ポリエステルの酸価(AV)がより低減する点で好ましい。
また、固相重合時間は、1時間以上100時間以下が好ましく、より好ましくは5時間以上100時間以下、さらに好ましくは10時間以上75時間以下、特に好ましくは15時間以上50時間以下である。固相重合時間が上記範囲内であると、ポリエステルの酸価(AV)と固有粘度(IV)とを好ましい範囲に容易に制御できる。
本発明におけるフィルム成形工程では、上記のようにして得られるポリエステル原料樹脂を溶融押出し、さらに冷却してポリエステルフィルムを成形する。
ポリエステル原料樹脂の溶融押出は、例えば、1本又は2本以上のスクリュを備えた押出機を用い、ポリエステル原料樹脂の融点以上の温度に加熱し、スクリュを回転させて溶融混練しながら行なわれる。ポリエステル原料樹脂は、加熱及びスクリュによる混練により、押出機内で溶融してメルトとなる。また、押出機内での熱分解(ポリエステルの加水分解)を抑制する観点から、押出機内を窒素置換して、ポリエステル原料樹脂の溶融押出しを行なうことが好ましい。押出機は、混練温度が低く抑えられる点で二軸押出機が好ましい。
溶融されたポリエステル原料樹脂(メルト)は、ギアポンプ、濾過器等を通して、押出ダイから押出す。押出ダイは、単に「ダイ」とも称する〔JIS B8650:2006、a)押出成形機、番号134参照〕。
このとき、メルトは、単層で押出してもよいし、多層で押出してもよい。
ポリエステル原料樹脂に末端封止剤を含める工程を設けることで、耐候性が向上する上、熱収縮を低く抑えることができる。また、ポリエステルフィルムを成形した場合において、ポリエステル末端に結合して分子鎖の末端部分が嵩高くなり、フィルム表面の微細凹凸量が増えるため、アンカー効果が発現しやすくなり、ポリエステルフィルムと該フィルム上に塗布形成される塗布層との密着が向上する。
末端封止剤の含有比率が0.1質量%以上であることで、AV低下効果による耐候性向上を達成できる上、低熱収縮性及び密着性を付与することができる。また、末端封止剤の含有比率が5質量%以下であると、密着性が向上するほか、末端封止剤の添加によるポリエステルのガラス転移温度(Tg)の低下が抑制され、これによる耐候性の低下や熱収縮の増加を抑制することができる。これは、Tgが低下した分、相対的にポリエステルの反応性が増加することで生じる加水分解性の増加を抑制したり、Tg低下で増加するポリエステル分子の運動性が増加し易くなることで生じる熱収縮が抑制されるためである。
カルボジイミド化合物、エポキシ化合物、及びオキサゾリン系化合物の例示及び好ましい態様等の詳細は、前記「ポリエステルフィルム」の項において既述した通りである。
キャスト処理により得られるフィルム状のポリエステル成形体の厚みは、0.5mm~5mmであることが好ましく、0.7mm~4.7mmであることがより好ましく、0.8mm~4.6mmであることがさらに好ましい。
フィルム状のポリエステル成形体の厚みを5mm以下とすることで、メルトの蓄熱による冷却遅延を回避し、また、0.5mm以上とすることで、押出しから冷却までの間に、ポリエステル中のOH基やCOOH基がポリエステル内部に拡散され、加水分解発生の要因となるOH基及びCOOH基がポリエステル表面に露出することを抑制する。
冷却手段は、上記の中でも、連続運転時のシート表面へのオリゴマー付着防止の観点から、冷風による冷却及びキャストドラムを用いた冷却の少なくとも一方が好ましい。さらには、押出機から押出されたメルトを冷風で冷却すると共に、メルトをキャストドラムに接触させて冷却することが特に好ましい。
本発明の縦延伸工程では、前記フィルム成形工程で成形されたポリエステルフィルムを長手方向に縦延伸する。
また、縦横の延伸倍率の積で表される面積延伸倍率は、延伸前のポリエステルフィルムの面積の6倍~18倍が好ましく、8倍~17.5倍であることがより好ましく、10倍~17倍であることがさらに好ましい。
ポリエステルフィルムの縦延伸時の温度(以下、「縦延伸温度」とも称する)は、ポリエステルフィルムのガラス転移温度をTgとするとき、Tg-20℃以上Tg+50℃以下であることが好ましく、より好ましくはTg-10℃以上Tg+40℃以下、さらに好ましくはTg℃以上Tg+30℃以下である。
なお、「ポリエステルフィルムの長手方向(搬送方向、MD)と直交する方向(TD)」とは、ポリエステルフィルムの長手方向(搬送方向、MD)と垂直(90°)をなす方向を意図するものであるが、機械的な誤差などから実質的に長手方向(すなわち搬送方向)に対する角度が90°とみなせる方向(例えば、MD方向に対し90°±5°の方向)が含まれる。
次に、本発明における横延伸工程について詳細に説明する。
本発明における横延伸工程は、縦延伸後のポリエステルフィルムを長手方向に直交する幅方向に横延伸する工程であるが、この横延伸を、縦延伸後のポリエステルフィルムを延伸可能な温度に予熱する予熱工程と、予熱された前記ポリエステルフィルムを前記長手方向と直交する幅方向に緊張を与えて横延伸する延伸工程と、前記縦延伸及び前記横延伸を行なった後の前記ポリエステルフィルムの最高到達膜面温度を160℃以上210℃以下の範囲に制御しながら、前記幅方向における最高到達膜面温度のバラツキを0.5℃以上5.0℃以下として加熱し結晶化させて熱固定する熱固定工程と、前記熱固定されたポリエステルフィルムを加熱し、ポリエステルフィルムの緊張を緩和する熱緩和工程と、熱緩和後のポリエステルフィルムを冷却する冷却工程と、を設けて行なう。
本発明における横延伸工程では、上記構成でポリエステルフィルムが横延伸される態様であればその具体的な手段は制限されないが、上記構成をなす各工程の処理が可能な横延伸装置又は2軸延伸機を用いて行なうことが好ましい。
図1に示すように、2軸延伸機100は、1対の環状レール60a及び60bと、各環状レールに取り付けられ、レールに沿って移動可能な把持部材2a~2lとを備えている。環状レール60a及び60bは、ポリエステルフィルム200を挟んで互いに対称配置されており、把持部材2a~2lでポリエステルフィルム200を握持し、レールに沿って移動させることによりフィルム幅方向に延伸可能なようになっている。
図1は、2軸延伸機の一例を上面から示す上面図である。
2軸延伸機100は、延伸部20において、ポリエステルフィルム200をTD方向に延伸する横延伸を可能とするものであるが、把持部材2a~2lの移動速度を変化させることにより、ポリエステルフィルム200をMD方向にも延伸することができる。すなわち、2軸延伸機100を用いて同時2軸延伸を行なうことも可能である。
予熱工程では、前記縦延伸工程で縦延伸した後のポリエステルフィルムを延伸可能な温度に予熱する。
図1に示すように、予熱部10においてポリエステルフィルム200を予熱する。予熱部10では、ポリエステルフィルム200を延伸する前に予め加熱し、ポリエステルフィルム200の横延伸を容易に行なえるようにする。
なお、予熱部終了点は、ポリエステルフィルム200の予熱を終了する時点、すなわち予熱部10の領域からポリエステルフィルム200が離れる位置をいう。
延伸工程では、前記予熱工程で予熱されたポリエステルフィルムを長手方向(MD方向)と直交する幅方向(TD方向)に緊張を与えて横延伸する。
図1に示すように、延伸部20では、予熱されたポリエステルフィルム200を、少なくともポリエステルフィルム200の長手方向と直交するTD方向に横延伸してポリエステルフィルム200に緊張を与える。
また、ポリエステルフィルム200の面積延伸倍率(各延伸倍率の積)は、延伸前のポリエステルフィルム200の面積の6倍~18倍が好ましく、8倍~17.5倍であることがより好ましく、10倍~17倍であることがさらに好ましい。
また、ポリエステルフィルム200の横延伸時の膜面温度(以下、「横延伸温度」ともいう。)は、ポリエステルフィルム200のガラス転移温度をTgとするとき、Tg-10℃以上Tg+100℃以下であることが好ましく、より好ましくはTg℃以上Tg+90℃以下、さらに好ましくはTg+10℃以上Tg+80℃以下である。
熱固定工程では、既に縦延伸及び横延伸が施された後のポリエステルフィルムを、その最高到達膜面温度を160℃以上210℃以下の範囲に制御しながら、幅方向における最高到達膜面温度のバラツキを0.5℃以上5.0℃以下として加熱して結晶化させることで熱固定する。
熱固定温度は、上記同様の理由から、170℃~200℃の範囲が好ましく、175℃~195℃の範囲がより好ましい。
なお、最高到達膜面温度(熱固定温度)は、ポリエステルフィルム200の表面に熱電対を接触させて測定される値である。
上記の中では、最高到達膜面温度のバラツキは、上記と同様の理由から、0.7℃以上3.0℃以下がより好ましく、0.8℃以上2.0℃以下が更に好ましく、0.8℃以上1.5℃以下が特に好ましい。
このとき、加熱は、熱固定工程での加熱面における加熱直後の表面温度が、加熱面と反対側の非加熱面の表面温度に比べて0.5℃以上5.0℃以下の範囲で高くなるように行なわれることが好ましい。熱固定時の加熱面の温度がその反対側の面より高く、その表裏間の温度差が0.5~5.0℃であることで、フィルムのカールがより効果的に解消される。カールの解消効果の観点からは、加熱面とその反対側の非加熱面との間の温度差は、0.7~3.0℃の範囲がより好ましく、0.8℃以上2.0℃以下が更に好ましい。
中でも、滞留時間は、上記同様の理由から、8秒以上40秒以下が好ましく、10秒以上30秒以下がより好ましい。
熱緩和工程は、前記熱固定工程で固定されたポリエステルフィルムを加熱し、ポリエステルフィルムの緊張を緩和し、残留歪みを除去する。フィルムの寸法安定性を向上すると共に、得られるポリエステルフィルムのIV値が0.70以上であると、耐加水分解性を両立することができる。
以下、熱緩和時におけるポリエステルフィルム200の表面の最高到達膜面温度を「熱緩和温度(T熱緩和)」ともいう。
T熱緩和が「T熱固定-5℃」以下であると、ポリエステルフィルムの耐加水分解性により優れる。また、T熱緩和は、寸法安定性が良好になる点で、100℃以上であることが好ましい。
更には、T熱緩和は、100℃以上で、かつT熱固定よりも15℃以上低い温度領域(100℃≦T熱緩和≦T熱固定-15℃)であることが好ましく、110℃以上で、かつT熱固定よりも25℃以上低い温度領域(110℃≦T熱緩和≦T熱固定-25℃)であることがより好ましく、120℃以上で、かつT熱固定よりも30℃以上低い温度領域(120℃≦T熱緩和≦T熱固定-30℃)であることが特に好ましい。
なお、T熱緩和は、ポリエステルフィルム200の表面に熱電対を接触させることで測定される値である。
冷却工程では、前記熱緩和工程で熱緩和した後のポリエステルフィルムを冷却する。
図1に示すように、冷却部50では、熱緩和部40を経たポリエステルフィルム200が冷却される。熱固定部30や熱緩和部40で加熱されたポリエステルフィルム200を冷却することにより、ポリエステルフィルム200の形状が固定化される。
ここで、冷却部出口とは、ポリエステル200が冷却部50から離れるときの、冷却部50の端部をいい、ポリエステルフィルム200を把持する把持部材2(図1では、把持部材2j及び2l)が、ポリエステルフィルム200を離すときの位置をいう。
前記冷却工程で冷却されたポリエステルフィルム200は、TD方向両端のクリップで握持された把持部分をカットし、ロール状に巻き取られる。
予熱部10においてポリエステルフィルム200の幅方向(TD)の両端部を、片端部につき、少なくとも2つの把持部材を用いて把持する。例えば、ポリエステルフィルム200の幅方向(TD)の片端部の一方を把持部材2a及び2bで把持し、他方を把持部材2c及び2dで把持する。次いで、把持部材2a~2dを移動させることにより、予熱部10から冷却部50までポリエステルフィルム200を搬送する。
上記のように、把持部材2a-2b間の間隔、及び把持部材2c-2d間の間隔を、MD方向上流側よりも下流側で狭めることで、ポリエステルフィルム200のMD方向の緩和を行なうことができる。したがって、MD方向の緩和を熱固定部30又は熱緩和部40で行なう場合は、把持部材2a~2dが熱固定部30又は熱緩和部40に到達したときに、把持部材2a~2dの移動速度を遅くして、ポリエステルフィルム200の搬送速度を小さくし、把持部材2a-2b間の間隔、及び把持部材2c-2d間の間隔を、予熱部における間隔よりも狭めればよい。
太陽電池モジュールは、一般に、太陽光の光エネルギーを電気エネルギーに変換する太陽電池素子を、太陽光が入射する透明性の基板と既述の本発明のポリエステルフィルム(太陽電池用バックシート)との間に配置して構成されている。具体的な実施態様として、電気を取り出すリード配線(不図示)で接続された発電素子(太陽電池素子)をエチレン・酢酸ビニル共重合体系(EVA系)樹脂等の封止剤で封止し、これを、ガラス等の透明基板と、本発明のポリエステルフィルム(バックシート)との間に挟んで互いに張り合わせることによって構成される態様に構成されてもよい。
(ポリエステル原料樹脂1)
以下に示すように、テレフタル酸及びエチレングリコールを直接反応させて水を留去し、エステル化した後、減圧下で重縮合を行なう直接エステル化法を用いて、連続重合装置によりポリエステル(Ti触媒系PET)を得た。
第一エステル化反応槽に、高純度テレフタル酸4.7トンとエチレングリコール1.8トンを90分かけて混合してスラリー形成させ、3800kg/hの流量で連続的に第一エステル化反応槽に供給した。更にクエン酸がTi金属に配位したクエン酸キレートチタン錯体(VERTEC AC-420、ジョンソン・マッセイ社製)のエチレングリコール溶液を連続的に供給し、反応槽内温度250℃、攪拌下、平均滞留時間約4.3時間で反応を行なった。このとき、クエン酸キレートチタン錯体は、Ti添加量が元素換算値で9ppmとなるように連続的に添加した。このとき、得られたオリゴマーの酸価は600当量/トンであった。なお、本明細書中において、「当量/t」は1トンあたりのモル当量を表す。
上記で得られたエステル化反応生成物を連続的に第一重縮合反応槽に供給し、攪拌下、反応温度270℃、反応槽内圧力20torr(2.67×10-3MPa)で、平均滞留時間約1.8時間で重縮合させた。
得られたポリマーは、IV=0.65、末端カルボキシ基の量(AV)=22当量/トン、融点=257℃、溶液ヘイズ=0.3%であった。IV及びAVの測定は、以下に示す方法により行なった。
上記のようにして得たポリエステルのペレットに対して、バッチ法で固相重合を実施した。すなわち、ポリエステルのペレットを容器に投入した後、真空にして撹拌しながら、150℃で予備結晶化処理し、その後190℃で30時間の固相重合反応を行なった。
以上のようにして、ポリエステル原料樹脂1を合成した。
ポリエステル原料樹脂1の合成において、固相重合時間を30時間から12時間に変更したほかは同様にして、ポリエステル原料樹脂2を得た。
ポリエステル原料樹脂1の合成において、固相重合時間を30時間から10時間に変更したほかは同様にして、ポリエステル原料樹脂3を得た。
<未延伸ポリエステルフィルムの作製>
-フィルム成形工程-
ポリエステル原料樹脂1を、含水率20ppm以下に乾燥させた後、直径50mmの1軸混練押出機のホッパーに投入した。ポリエステル原料樹脂1は、300℃に溶融し、下記押出条件により、ギアポンプ、濾過器(孔径20μm)を介し、ダイから押出した。なお、ポリエステルシートの厚さが4mmとなるように、ダイのスリットの寸法を調整した。ポリエステルシートの厚さは、キャストドラムの出口に設置した自動厚み計により測定した。
固有粘度(IV)は、未延伸ポリエステルフィルム1を、1,1,2,2-テトラクロルエタン/フェノール(=2/3[質量比])混合溶媒に溶解し、該混合溶媒中の25℃での溶液粘度から求めた。
末端COOH量(AV)は、未延伸ポリエステルフィルム1をベンジルアルコール/クロロホルム(=2/3;体積比)の混合溶液に完全溶解させ、指示薬としてフェノールレッドを用い、基準液(0.025N KOH-メタノール混合溶液)で滴定し、その適定量から算出した。
得られた未延伸ポリエステルフィルム1について、以下の方法で逐次2軸延伸することによって延伸し、厚み250μm、フィルム幅1.5mの2軸延伸ポリエステルフィルム1を作製した。
未延伸ポリエステルフィルム1を周速の異なる2対のニップロールの間に通し、下記条件で縦方向(搬送方向)に延伸した。
予熱温度 :80℃
縦延伸温度:90℃
縦延伸倍率:3.6倍
縦延伸応力:12MPa
縦延伸したポリエステルフィルム1(縦延伸ポリエステルフィルム1)に対し、図1に示す構造を有するテンター(2軸延伸機)を用いて、下記の方法、条件にて延伸した。
予熱温度を110℃とし、延伸可能なように加熱した。
予熱された縦延伸ポリエステルフィルム1を、縦延伸した方向(長手方向)と直交するフィルム幅方向に下記の条件にて緊張を与え、横延伸した。
<条件>
・延伸温度(横延伸温度) :120℃
・延伸倍率(横延伸倍率) :4.4倍
・延伸応力(横延伸応力):18MPa
次いで、ポリエステルフィルムの最高到達膜面温度を下記範囲に制御しながら、熱風吹き出しノズルから出る熱風の風速を微調整することによって、幅方向における最高到達膜面温度のバラツキが下記範囲となるように加熱し、結晶化させた。このとき、フィルム幅方向の両端部を、フィルム成形工程でキャストドラムと接触したキャスト面側から赤外線ヒータ(ヒータ表面温度:450℃)で輻射加熱した。
・最高到達膜面温度(熱固定温度T熱固定):下記表1に示す温度〔℃〕
・最高到達膜面温度(熱固定温度T熱固定)のバラツキ:下記表1に示す温度〔℃〕
ここでの熱固定温度T熱固定が、DSCのプレピーク温度〔℃〕である。
熱固定後のポリエステルフィルムを下記の温度に加熱し、フィルムの緊張を緩和した。このとき、フィルム幅方向の両端部を、前記熱固定工程と同様にキャスト面側から赤外線ヒータ(ヒータ表面温度:350℃)で輻射加熱した。
・熱緩和温度(T熱緩和):150℃
・熱緩和率:TD方向(フィルム幅方向)=5%
MD方向(フィルム幅方向に直交する方向)=5%
次に、熱緩和後のポリエステルフィルムを65℃の冷却温度にて冷却した。
冷却終了後、ポリエステルフィルムの両端を20cmずつトリミングした。その後、両端に幅10mmで押出し加工(ナーリング)を行なった後、張力25kg/mで巻き取った。
上記で作製した2軸延伸ポリエステルフィルムに対し、下記の測定、評価を行なった。測定、評価の結果は下記表1に示す。
2軸延伸ポリエステルフィルムを裁断し、TD方向30mm、MD方向120mmの大きさのサンプル片Mを得た。サンプル片Mに対し、MD方向で100mmの間隔となるように2本の基準線を入れ、無張力下で150℃の加熱オーブン中に30分間放置した。放置後、サンプル片Mを室温まで冷却して2本の基準線の間隔を測定し、この値をAmmとし、「100×(100-A)/100」を計算し、得られた値をMD方向における熱収縮率とした。
また、MD方向30mm、TD方向120mmの大きさのサンプル片Lを得、このサンプル片Lに対して、TD方向で100mmの間隔となるように2本の基準線を入れ、サンプル片Mと同様にして測定と計算とを行ない、得られた値をTD方向における加熱収縮率とした。
上記の操作を、2軸延伸ポリエステルフィルムのTD方向におけるフィルム全幅に対して、中央部1点、両端2点の合計3点を切出して行ない、中央部の熱収縮率から両端の熱収縮率のうち中央部の熱収縮率との差が大きい方の熱収縮率を減算して絶対値を求め、MD方向とTD方向の各々における熱収縮率のバラツキとした。
2軸延伸ポリエステルフィルムのフィルム全幅に対して、中央部1点、両端2点の合計3点を切出し、結晶化度を測定し、中央部の結晶化度から両端の結晶化度のうち値の小さい方の結晶化度を減算することにより算出した。このとき、結晶化度は、フィルムの密度から算出した。すなわち、
フィルムの密度X(g/cm3)、結晶化度0%での密度Y(g/cm3)、結晶化度100%での密度Z(g/cm3)を用いて、下記の計算式により結晶化度Xc(%)を導出した。なお、密度の測定は、JIS K7112に準じて測定を行なった。
Xc={Z×(X-Y)}/{X×(Z-Y)}×100
得られた2軸延伸ポリエステルフィルムの厚さは、以下のようにして求めた。
2軸延伸ポリエステルフィルムに対して、接触式膜厚測定計(アンリツ社製)を用い、縦延伸した方向(長手方向)に0.5mにわたり等間隔に50点をサンプリングし、さらにフィルム幅方向(長手方向に直交する方向)にフィルム全幅にわたり等間隔(幅方向に50等分)に50点をサンプリングした後、これらの100点の厚みを測定した。これら100点の平均の厚みを求め、ポリエステルフィルムの厚みとした。求めた厚みを下記表1に示す。
得られた2軸延伸ポリエステルフィルムについて、目視によりフィルム面のキズ、皺の程度を観察し、下記の評価基準に従って評価した。
<評価基準>
◎:キズ、皺の発生はほとんどみられなかった。
○:キズの発生が僅かにみられたが、フィルム面は良好であった。
△:キズ、皺ともに発生がみられたが、実用上は支障のない程度であった。
×:キズ、皺の発生が顕著にみられた。
2軸延伸ポリエステルフィルムの耐加水分解性を、2軸延伸ポリエステルフィルムの破断伸度半減時間から評価した。具体的には、
2軸延伸ポリエステルフィルムを120℃、相対湿度100%の条件で保存し、保存後の2軸延伸ポリエステルフィルムが示す破断伸度(%)が、保存前の2軸延伸ポリエステルフィルムが示す破断伸度(%)に対して50%となる保存時間を、破断伸度半減時間とした。破断伸度半減時間が長いほど、2軸延伸ポリエステルフィルムの耐加水分解性に優れることを示す
ここで、2軸延伸ポリエステルフィルムの破断伸度(%)は、2軸延伸ポリエステルフィルムを裁断して得たサイズ1cm×20cmのサンプル片を、チャック間5cm、20%/分にて引っ張って求めた。
<評価基準>
◎:破断伸度半減時間が90時間を超えていた。
○:破断伸度半減時間が85時間を超え90時間以下であった。
△:破断伸度半減時間が80時間を超え85時間以下であった。
×:破断伸度半減時間が80時間未満であった。
得られた2軸延伸ポリエステルフィルムをTD方向300mm、MD方向300mmのサンプル片に裁断し、このサンプル片の四隅が浮き上がる向きに机上に載置し、机面から浮き上がった四隅の高さの平均を求め、下記の評価基準に従って評価した。
<評価基準>
◎:平均高さが3mm未満であり、極めて良好であった。
○:平均高さが3mm以上10mm未満であり、良好であった。
△:平均高さが10mm以上20mm未満であり、実用上は支障のない程度であった。
×:平均高さが20mmを超えていた。
前記(3)~(6)の評価結果から、下記の基準に基づいて評価した。
<評価基準>
◎:極めて良好
○:良好
△:必ずしも良好ではないが、実用上の支障を来す程度ではない
×:実用上支障を来す
-顔料分散物の調製-
下記組成中の成分を混合し、その混合物に対してダイノミル型分散機により1時間、分散処理を施し、顔料分散物を調製した。
<組成>
・二酸化チタン(体積平均粒子径=0.42μm・・・39.9質量%
(タイペークR-780-2、石原産業(株)製、固形分100質量%)
・ポリビニルアルコール ・・・8.0質量%
(PVA-105、(株)クラレ製、固形分:10質量%)
・界面活性剤 ・・・0.5質量%
(デモールEP、花王(株)製、固形分:25質量%)
・蒸留水 ・・・51.6質量%
下記組成中の成分を混合し、反射層用塗布液を調製した。
<組成>
・上記の顔料分散物 ・・・80.0部
・ポリアクリル樹脂水分散液 ・・・19.2部
(バインダー:ジュリマーET410、日本純薬(株)製、固形分:30質量%)
・ポリオキシアルキレンアルキルエーテル ・・・3.0部
(ナロアクティーCL95、三洋化成工業(株)製、固形分:1質量%)
・オキサゾリン化合物(架橋剤) ・・・2.0部
(エポクロスWS-700、日本触媒化学工業(株)製、固形分:25質量%)
・蒸留水 ・・・7.8部
得られた反射層用塗布液を2軸延伸ポリエステルフィルム上に塗布し、180℃で1分間乾燥させて、着色層として、二酸化チタン量が6.5g/m2の白色層(光反射層)を形成した。
-易接着性層塗布液の調製-
下記組成中の成分を混合し、易接着性層用塗布液を調製した。
<組成>
・ポリオレフィン樹脂水分散液 ・・・5.2部
(バインダー:ケミパールS-75N、三井化学(株)製、固形分:24質量%)
・ポリオキシアルキレンアルキルエーテル ・・・7.8部
(ナロアクティーCL95、三洋化成工業(株)製、固形分:1質量%)
・オキサゾリン化合物(架橋剤) ・・・0.8部
(エポクロスWS-700、日本触媒化学工業(株)製、固形分:25質量%)
・シリカ微粒子水分散物 ・・・2.9部
(アエロジルOX-50、日本アエロジル(株)製、体積平均粒子径=0.15μm、固形分:10質量%)
・蒸留水 ・・・83.3部
得られた塗布液を前記光反射層の上に、バインダー量が0.09g/m2になるように塗布し、180℃で1分間乾燥させて、易接着性層を形成した。
-バック層塗布液の調製-
下記組成中の成分を混合し、バック層用塗布液を調製した。
<組成>
・セラネートWSA-1070(バインダー) ・・・323部
(アクリル/シリコーン系バインダー、DIC(株)製、固形分:40質量%)
・オキサゾリン化合物(架橋剤) ・・・52部
(エポクロスWS-700、日本触媒化学工業(株)製、固形分:25質量%)
・ポリオキシアルキレンアルキルエーテル(界面活性剤)・・・32部
(ナロアクティーCL95、三洋化成工業(株)製、固形分:1質量%)
・蒸留水 ・・・594部
得られたバック層塗布液を、2軸延伸ポリエステルフィルムの反射層及び易接着層が形成されていない側に、バインダー量がウェット塗布量で3.0g/m2になるように塗布し、180℃で1分間乾燥させて、乾燥厚み3μmのバック層を形成した。
以上のようにして、バックシートを作製した。
上記で作製したバックシートに対し、下記の密着性評価を行なった。評価結果は、下記表1に示す。
(8)密着性
上記で作製したバックシートについて、基材と塗布層との密着性を、下記方法で評価した。
(a)試料を85℃、80%RH環境下で100時間放置する湿熱処理を施した。
(b)湿熱処理後の試料を取り出し、試料の易接着層側の表面に3mm間隔にカッターナイフで縦横10本ずつの切れ込みを入れ、100個の升目を作った。
(c)升目を作った試料を50℃の温水に1時間浸漬した後、25℃、60%RH環境下の室内に取り出し、試料の表面の水分を布で拭き取った。その後、試料の升目が入った表面に、粘着テープ〔日東電工社製のポリエステル粘着テープ(No.31B)〕を貼り付けた。次いで、粘着テープを一気に180度方向に引き剥がした。なお、温水から取り出した後から粘着テープ引き剥がしまでの時間は5分以内で実施した。つまり、密着性の評価は、試料の塗布層が湿潤状態での密着性を評価したものである。
(d)試料の升目が入った表面を目視観察し、塗布層が剥離した升目の数を数え、これを「剥離率」として密着性を評価する指標とした。評価基準は、下記の通りである。
<評価基準>
◎:剥離率が1%未満であった。
○:剥離率が1%以上5%未満であった。
△:剥離率が5%以上10%未満であった。
×:剥離率が10%以上であった。
実施例1において、固相重合時間を30時間から12時間に変更することでポリエステルフィルムのIVを0.80から0.75に変更することで、ポリエステルフィルムのフィルム幅方向における結晶化度のバラツキを0.8%から2.2%に変えたこと以外は、実施例1と同様にして、厚さ250μmの2軸延伸ポリエステルフィルム(PETフィルム)を作製し、更にバックシートを作製すると共に、測定、評価を行なった。
実施例1において、熱固定工程での熱固定温度(T熱固定;=DSCプレピーク温度)を190℃から160℃、210℃にそれぞれ代えたこと以外は、実施例1と同様にして、厚さ250μmの2軸延伸ポリエステルフィルム(PETフィルム)を作製し、更にバックシートを作製すると共に、測定、評価を行なった。
実施例1において、熱固定ゾーンで使用した赤外線ヒーターを使用しないことによって、ポリエステルフィルムのフィルム幅方向における結晶化度のバラツキを0.8%から4.8%に変えたこと以外は、実施例1と同様にして、厚さ250μmの2軸延伸ポリエステルフィルム(PETフィルム)を作製し、更にバックシートを作製すると共に、測定、評価を行なった。
実施例1において、厚みを下記表1に示す厚みに変更し、押出機の回転数を調整することによって、ポリエステルフィルムの厚みを250μmから180μm、350μmとしたこと以外は、実施例1と同様にして、2軸延伸ポリエステルフィルム(PETフィルム)を作製し、更にバックシートを作製すると共に、測定、評価を行なった。
実施例1において、横延伸工程の熱固定工程を行なう熱固定部での滞留時間を25秒から5秒、50秒に変えたこと以外は、実施例1と同様にして、厚さ250μmの2軸延伸ポリエステルフィルム(PETフィルム)を作製し、更にバックシートを作製すると共に、測定、評価を行なった。
実施例1の「フィルム成形工程」において、ポリエステル原料樹脂を乾燥させてホッパーに投入した後に、溶融混練しているポリエステル原料樹脂に1軸混練押出機のシリンダーに取り付けた投入口から下記表1に記載の末端封止材を添加すると共にあるいは添加せずに、ポリエステル原料樹脂1を下記のポリエステル原料樹脂4~9に変更したこと以外は、実施例1と同様にして、厚さ250μmの2軸延伸ポリエステルフィルム(PETフィルム)を作製し、更にバックシートを作製すると共に、測定、評価を行なった。
(A)ポリエステル原料樹脂4~6,8~9の合成
前記ポリエステル原料樹脂1の合成において、「(1)エステル化反応」にて、テレフタル酸及びエチレングリコールに加えて、トリメリット酸(TMA;3官能カルボン酸)を下記表1の割合で添加して共重合させたこと以外は、ポリエステル原料樹脂1の合成と同様にして、多官能モノマーに由来の構成単位を含むポリエステル原料樹脂4~6,8~9を合成した。
(B)ポリエステル原料樹脂7の合成
前記ポリエステル原料樹脂1の合成において、「(1)エステル化反応」にて、テレフタル酸及びエチレングリコールに加えて、ベンゼンテトラカルボン酸(BTC:4官能カルボン酸)を添加して共重合させたこと以外は、ポリエステル原料樹脂1の合成と同様にして、多官能モノマーに由来の構成単位を含むポリエステル原料樹脂7を合成した。
(実施例19)
実施例1において、固相重合時間を30時間から9時間に変更することによってポリエステルフィルムのIVを0.71とし、熱固定工程での熱固定温度(T熱固定;=DSCプレピーク温度)を190℃から185℃に変更し、熱固定部の熱風吹き出しノズルから出る熱風の風速を強めることによってフィルム幅方向における最高到達膜面温度のバラツキを0.9℃から0.6℃に変更したこと以外は、実施例1と同様にして、厚さ250μmの2軸延伸ポリエステルフィルム(PETフィルム)を作製し、更にバックシートを作製すると共に、測定、評価を行なった。
(実施例20)
実施例10において、固相重合時間を30時間から9時間に変更することによってポリエステルフィルムのIVを0.71とし、熱固定工程での熱固定温度(T熱固定;=DSCプレピーク温度)を190℃から185℃に変更し、熱固定部の熱風吹き出しノズルから出る熱風の風速を強めることによってフィルム幅方向における最高到達膜面温度のバラツキを0.9℃から0.6℃に変更したこと以外は、実施例10と同様にして、厚さ250μmの2軸延伸ポリエステルフィルム(PETフィルム)を作製し、更にバックシートを作製すると共に、測定、評価を行なった。
実施例1において、固相重合時間を30時間から10時間に変更することによって、ポリエステルフィルムのIVを0.72としたこと以外は、実施例1と同様にして、厚さ250μmの2軸延伸ポリエステルフィルム(PETフィルム)を作製し、更にバックシートを作製すると共に、測定、評価を行なった。
実施例1において、熱固定工程での熱固定温度(T熱固定;=DSCプレピーク温度)を190℃から155℃、215℃にそれぞれ代えたこと以外は、実施例1と同様にして、厚さ250μmの2軸延伸ポリエステルフィルム(PETフィルム)を作製し、更にバックシートを作製すると共に、測定、評価を行なった。
実施例1において、熱固定ゾーンで使用した赤外線ヒーターの使用をとりやめ、更に熱風吹き出しノズルから出る熱風の風速を弱めることによって、ポリエステルフィルムのフィルム幅方向における結晶化度のバラツキを0.8%から5.3%に変えたこと以外は、実施例1と同様にして、厚さ250μmの2軸延伸ポリエステルフィルム(PETフィルム)を作製し、更にバックシートを作製すると共に、測定、評価を行なった。
(比較例5)
実施例1において、熱固定ゾーンで使用した赤外線ヒーターの表面温度を450℃から600℃に変更することによって、ポリエステルフィルムのフィルム幅方向における結晶化度のバラツキを0.8%から0.1%に変えたこと以外は、実施例1と同様にして、厚さ250μmの2軸延伸ポリエステルフィルム(PETフィルム)を作製し、更にバックシートを作製すると共に、測定、評価を行なった。
(比較例6)
実施例1において、固相重合時間を30時間から7時間に変更することによってポリエステルフィルムのIVを0.67とし、熱固定工程での熱固定温度(T熱固定;=DSCプレピーク温度)を190℃から200℃に変更し、熱固定部の熱風吹き出しノズルから出る熱風の風速を弱めることによってフィルム幅方向における最高到達膜面温度のバラツキを0.9℃から3.4℃に変更したこと以外は、実施例1と同様にして、厚さ250μmの2軸延伸ポリエステルフィルム(PETフィルム)を作製し、更にバックシートを作製すると共に、測定、評価を行なった。
・TMA:トリメリット酸(3官能カルボン酸)
・BTC:ベンゼンテトラカルボン酸(4官能カルボン酸)
・CI:ラインケミー社製のスタバクゾールP100(カルボジイミド系化合物)
・EP:Hexion Speciality Chemicals社製のカジューラE10P(エポキシ系化合物)
厚さ3mmの強化ガラスと、EVAシート(三井化学ファブロ(株)製のSC50B)と、結晶系太陽電池セルと、EVAシート(三井化学ファブロ(株)製のSC50B)と、実施例1~18で作製したバックシートとをこの順に重ね合わせ、真空ラミネータ(日清紡(株)製、真空ラミネート機)を用いてホットプレスすることによりEVAと接着させ、結晶系の太陽電池モジュールを作製した。このとき、バックシートを、その易接着性層がEVAシートと接触するように配置し、接着は以下に示す方法により行なった。
<接着方法>
真空ラミネータを用い、128℃で3分間の真空引きした後、2分間加圧して仮接着した。その後、ドライオーブンにて150℃で30分間、本接着処理を施した。
本明細書に記載された全ての文献、特許出願、および技術規格は、個々の文献、特許出願、および技術規格が参照により取り込まれることが具体的かつ個々に記された場合と同程度に、本明細書中に参照により取り込まれる。
Claims (20)
- 1m以上のフィルム幅を有すると共に、固有粘度(IV)が0.70dL/g以上であり、示差走査熱量測定(DSC)で測定されるプレピーク温度が160℃以上210℃以下であり、前記フィルム幅方向における結晶化度のバラツキが0.3%以上5.0%以下である2軸延伸ポリエステルフィルム。
- 固有粘度(IV)が0.75dL/g以上である請求項1に記載の2軸延伸ポリエステルフィルム。
- 前記フィルム幅方向において、該フィルム幅方向に直交する方向の熱収縮率のバラツキと該フィルム幅方向と平行な方向の熱収縮率のバラツキとが共に0.03%以上0.50%以下である請求項1又は請求項2に記載の2軸延伸ポリエステルフィルム。
- 厚みが180μm以上350μm以下である請求項1~請求項3のいずれか1項に記載の2軸延伸ポリエステルフィルム。
- カルボン酸基の数と水酸基の数との合計が3以上である多官能モノマーに由来する構成単位を含む請求項1~請求項4のいずれか1項に記載の2軸延伸ポリエステルフィルム。
- カルボン酸基の数と水酸基の数との合計が3以上である多官能モノマーに由来する構成単位を含み、前記多官能モノマーに由来の構成単位の含有比率が、ポリエステル中の全構成単位に対して、0.005モル%以上2.5モル%以下である請求項1~請求項5のいずれか1項に記載の2軸延伸ポリエステルフィルム。
- 更に、オキサゾリン系化合物、カルボジイミド化合物、及びエポキシ化合物から選ばれる末端封止剤に由来する構造部分を含む請求項1~請求項6のいずれか1項に記載の2軸延伸ポリエステルフィルム。
- 前記末端封止剤に由来する構造部分の含有比率が、ポリエステルの全質量に対して、0.1質量%以上5質量%以下である請求項7に記載の2軸延伸ポリエステルフィルム。
- ポリエステル原料樹脂をシート状に溶融押出し、キャスティングドラム上で冷却してポリエステルフィルムを成形するフィルム成形工程と、
成形された前記ポリエステルフィルムを長手方向に縦延伸する縦延伸工程と、
前記縦延伸後のポリエステルフィルムを前記長手方向に直交する幅方向に横延伸する横延伸工程と、
を含むと共に、前記横延伸工程は、
縦延伸後のポリエステルフィルムを延伸可能な温度に予熱する予熱工程と、
予熱された前記ポリエステルフィルムを前記長手方向と直交する幅方向に緊張を与えて横延伸する延伸工程と、
前記縦延伸及び前記横延伸を行なった後の前記ポリエステルフィルムの最高到達膜面温度を160℃以上210℃以下の範囲に制御しながら、前記幅方向における最高到達膜面温度のバラツキを0.5℃以上5.0℃以下として加熱し結晶化させて熱固定する熱固定工程と、
前記熱固定されたポリエステルフィルムを加熱し、ポリエステルフィルムの緊張を緩和する熱緩和工程と、
熱緩和後のポリエステルフィルムを冷却する冷却工程と、
を含む、2軸延伸ポリエステルフィルムの製造方法。 - 前記熱固定工程は、ポリエステルフィルムの幅方向端部を選択的に、該ポリエステルフィルムの少なくとも片側から加熱する請求項9に記載の2軸延伸ポリエステルフィルムの製造方法。
- 前記冷却工程通過後のポリエステルフィルムの厚みが180μm以上350μm以下であって、
前記熱固定工程は、加熱されるポリエステルフィルムの加熱面を、前記フィルム成形工程でのキャスティングドラムに接触させた面とし、前記加熱直後における前記加熱面の表面温度が、前記加熱面と反対側の非加熱面の表面温度に比べて、0.5℃以上5.0℃以下の範囲で高くなるように加熱する請求項9又は請求項10に記載の2軸延伸ポリエステルフィルムの製造方法。 - 前記熱固定工程は、ポリエステルフィルムの幅方向端部をヒーターにより輻射加熱する請求項9~請求項11のいずれか1項に記載の2軸延伸ポリエステルフィルムの製造方法。
- 前記熱固定工程は、加熱状態での滞留時間を5秒以上50秒以下とする請求項9~請求項12のいずれか1項に記載の2軸延伸ポリエステルフィルムの製造方法。
- 前記予熱工程、前記延伸工程、及び前記熱緩和工程の少なくとも1つは、ポリエステルフィルムの幅方向端部をヒーターにより輻射加熱する請求項9~請求項13のいずれか1項に記載の2軸延伸ポリエステルフィルムの製造方法。
- 前記ポリエステル原料樹脂は、カルボン酸基の数と水酸基の数との合計が3以上である多官能モノマーを共重合成分として含む請求項9~請求項14のいずれか1項に記載の2軸延伸ポリエステルフィルムの製造方法。
- 前記ポリエステル原料樹脂は、カルボン酸基の数と水酸基の数との合計が3以上である多官能モノマーを共重合成分として含み、前記多官能モノマーに由来の構成単位の前記ポリエステル原料樹脂中における含有比率が、前記ポリエステル原料樹脂中の全構成単位に対して、0.005モル%以上2.5モル%以下である請求項9~請求項15のいずれか1項に記載の2軸延伸ポリエステルフィルムの製造方法。
- 前記フィルム成形工程は、前記ポリエステル原料樹脂に、オキサゾリン系化合物、カルボジイミド化合物、及びエポキシ化合物から選ばれる末端封止剤を含める工程を有し、溶融混練により前記末端封止剤と反応した前記ポリエステル原料樹脂を溶融押出する請求項9~請求項16のいずれか1項に記載の2軸延伸ポリエステルフィルムの製造方法。
- 前記末端封止剤の含有量が、前記ポリエステル原料樹脂の全質量に対して、0.1質量%以上5質量%以下である請求項17に記載の2軸延伸ポリエステルフィルムの製造方法。
- 請求項1~請求項8のいずれか1項に記載の2軸延伸ポリエステルフィルムを含む太陽電池用バックシート。
- 太陽光が入射する透明性の基板と、前記基板の一方の側に配された太陽電池素子と、該太陽電池素子の前記基板が配された側と反対側に配された請求項19に記載の太陽電池用バックシートと、を備えた太陽電池モジュール。
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CN105392839A (zh) * | 2013-07-23 | 2016-03-09 | 富士胶片株式会社 | 双轴拉伸聚酯薄膜及其制造方法、以及光学片 |
US10179844B2 (en) | 2013-07-23 | 2019-01-15 | Fujifilm Corporation | Biaxially stretched polyester film and method for producing same, and optical sheet |
CN107428964A (zh) * | 2015-03-31 | 2017-12-01 | 富士胶片株式会社 | 白色聚酯薄膜及其制造方法、太阳能电池用背板以及太阳能电池模块 |
US20170368736A1 (en) * | 2015-03-31 | 2017-12-28 | Fujifilm Corporation | White polyester film and method for manufacturing same, solar cell back sheet, and solar cell module |
CN107428964B (zh) * | 2015-03-31 | 2020-10-02 | 富士胶片株式会社 | 白色聚酯薄膜及其制造方法、太阳能电池用背板以及太阳能电池模块 |
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KR101630652B1 (ko) | 2016-06-15 |
US20130319525A1 (en) | 2013-12-05 |
JP2013047317A (ja) | 2013-03-07 |
CN103370183A (zh) | 2013-10-23 |
KR20140007379A (ko) | 2014-01-17 |
JP5752617B2 (ja) | 2015-07-22 |
CN103370183B (zh) | 2016-05-04 |
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