WO2012081500A1 - Polyester film, method of manufacturing polyester film, back sheet for solar cell, and solar cell module - Google Patents
Polyester film, method of manufacturing polyester film, back sheet for solar cell, and solar cell module Download PDFInfo
- Publication number
- WO2012081500A1 WO2012081500A1 PCT/JP2011/078457 JP2011078457W WO2012081500A1 WO 2012081500 A1 WO2012081500 A1 WO 2012081500A1 JP 2011078457 W JP2011078457 W JP 2011078457W WO 2012081500 A1 WO2012081500 A1 WO 2012081500A1
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- WO
- WIPO (PCT)
- Prior art keywords
- polyester film
- polyester
- stretching
- film
- heat
- Prior art date
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- 229920006267 polyester film Polymers 0.000 title claims abstract description 455
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 59
- 229920000728 polyester Polymers 0.000 claims abstract description 216
- 238000001816 cooling Methods 0.000 claims abstract description 78
- 238000010438 heat treatment Methods 0.000 claims abstract description 29
- 239000002994 raw material Substances 0.000 claims description 85
- -1 carbodiimide compound Chemical class 0.000 claims description 81
- 239000000178 monomer Substances 0.000 claims description 45
- 238000006116 polymerization reaction Methods 0.000 claims description 31
- 239000003795 chemical substances by application Substances 0.000 claims description 29
- 150000001875 compounds Chemical class 0.000 claims description 24
- 230000032258 transport Effects 0.000 claims description 21
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 19
- 239000000758 substrate Substances 0.000 claims description 17
- 239000007790 solid phase Substances 0.000 claims description 16
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 14
- 238000001125 extrusion Methods 0.000 claims description 12
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- 239000003566 sealing material Substances 0.000 claims description 7
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 55
- 230000008569 process Effects 0.000 abstract description 28
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- 238000000465 moulding Methods 0.000 abstract 1
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 42
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- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 32
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
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- GCAIEATUVJFSMC-UHFFFAOYSA-N benzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1C(O)=O GCAIEATUVJFSMC-UHFFFAOYSA-N 0.000 description 4
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- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 4
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- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
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- 229910052726 zirconium Inorganic materials 0.000 description 4
- JJTUDXZGHPGLLC-QWWZWVQMSA-N (3r,6r)-3,6-dimethyl-1,4-dioxane-2,5-dione Chemical compound C[C@H]1OC(=O)[C@@H](C)OC1=O JJTUDXZGHPGLLC-QWWZWVQMSA-N 0.000 description 3
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 3
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
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- BDNKZNFMNDZQMI-UHFFFAOYSA-N 1,3-diisopropylcarbodiimide Chemical compound CC(C)N=C=NC(C)C BDNKZNFMNDZQMI-UHFFFAOYSA-N 0.000 description 2
- KKKKCPPTESQGQH-UHFFFAOYSA-N 2-(4,5-dihydro-1,3-oxazol-2-yl)-4,5-dihydro-1,3-oxazole Chemical compound O1CCN=C1C1=NCCO1 KKKKCPPTESQGQH-UHFFFAOYSA-N 0.000 description 2
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- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 description 2
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- 238000005336 cracking Methods 0.000 description 1
- 238000005520 cutting process Methods 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
- STZIXLPVKZUAMV-UHFFFAOYSA-N cyclopentane-1,1,2,2-tetracarboxylic acid Chemical compound OC(=O)C1(C(O)=O)CCCC1(C(O)=O)C(O)=O STZIXLPVKZUAMV-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002708 enhancing 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
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000005338 heat storage Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 1
- 238000005347 high resolution inductively coupled plasma mass spectrometry (HR-ICP-MS) Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical class [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 230000005606 hygroscopic expansion Effects 0.000 description 1
- 230000006872 improvement 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
- 230000009878 intermolecular interaction Effects 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
- 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
- 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
- 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
- YSMULDKSBPCDFH-UHFFFAOYSA-N naphthalene-1,2,3,4,5,6,7-heptacarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(O)=O)=C2C(C(O)=O)=C(C(O)=O)C(C(=O)O)=CC2=C1C(O)=O YSMULDKSBPCDFH-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
- 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
- QQWAKSKPSOFJFF-UHFFFAOYSA-N oxiran-2-ylmethyl 2,2-dimethyloctanoate Chemical compound CCCCCCC(C)(C)C(=O)OCC1CO1 QQWAKSKPSOFJFF-UHFFFAOYSA-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
- 229960003531 phenolsulfonphthalein Drugs 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
- 230000000704 physical effect Effects 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920005672 polyolefin resin 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
- 239000012495 reaction gas Substances 0.000 description 1
- 239000012088 reference solution Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 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
- 239000007858 starting material Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000002834 transmittance Methods 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
- 238000004383 yellowing Methods 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
Images
Classifications
-
- 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
- B29C55/143—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively firstly parallel to the direction of feed and then transversely thereto
-
- 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
- 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
-
- 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 polyester film, a method for producing the polyester film, a solar cell backsheet, and a solar cell module.
- Polyester is used in various applications such as electrical insulation and optical applications.
- solar cell applications such as solar cell backsheets have attracted attention as electrical insulation applications.
- polyester usually has many carboxy groups and hydroxyl groups on its surface, and tends to be hydrolyzed in an environment where moisture exists, and tends to deteriorate over time.
- the 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 an environment that is prone to hydrolysis. Therefore, in solar cell applications, it is important to suppress hydrolysis of polyester. one of.
- a polyester excellent in hydrolysis resistance contains at least one selected from aluminum and its compound as a first metal-containing component, and is represented by chemical formulas (Chemical Formula 1) and (Chemical Formula 2).
- a polyester film produced by using a polyester polymerization catalyst characterized by coexisting at least one selected from phosphorous compounds is disclosed (for example, see International Publication No. 2002/022707).
- polyester films used for solar cell applications are required to have a film with excellent dimensional stability that is difficult to thermally shrink. For example, after the polyester film is stretched, the stretching tension is relaxed to reduce the thermal shrinkage rate. It is known (see, for example, JP-A-2004-130594 and JP-A-2001-212909).
- the present invention provides a polyester film excellent in hydrolysis resistance and dimensional stability, a method for producing the polyester film, a solar cell backsheet, and a solar cell module whose power generation performance is stable for a long period of time. It is an object to achieve this purpose.
- the transverse stretching step is performed after the longitudinal stretching step, and the transverse stretching step further includes transporting the polyester film to a cooling unit that cools the polyester film that has passed through the thermal relaxation portion.
- the width L1 of the polyester film when the width of the polyester film in the transverse stretching step is maximized, and the width L2 of the polyester film at the end of the cooling part where the polyester film is separated from the cooling part are as follows. Satisfies formula (1), and The polyester film production method according to ⁇ 1>, wherein the polyester film conveyance speed S1 in the preheating section and the polyester film conveyance speed S2 in the end of the cooling section satisfy the following formula (2). It is.
- the stretching portion has the stretching angle ⁇ [°] as an angle formed by the transport direction of the polyester film to be transported and the traveling direction of the width direction end of the polyester film.
- the transverse stretching step includes the preheating portion, the stretching portion, the heat fixing portion, the heat relaxation portion, and the cooling portion, and both end portions in the width direction of the polyester film are arranged at one end in the preheating portion.
- a biaxial stretching device that grips using at least two gripping members and transports the polyester film from the preheating unit to the cooling unit, More than the interval between one gripping member of the two gripping members that grips one end of the polyester film in the width direction in the preheating portion and the other gripping member adjacent to the gripping member, in the cooling unit.
- the conveyance speed of the polyester film is reduced by narrowing the interval between one gripping member of the two gripping members gripping one end in the width direction of the polyester film and the other gripping member adjacent to the gripping member. It is a manufacturing method of the polyester film as described in said ⁇ 2> or said ⁇ 3> which makes small.
- ⁇ 5> At least a part of the heat fixing part, the heat relaxation part, and the cooling part, one gripping member of the two gripping members gripping one end part in the width direction of the polyester film, It is a manufacturing method of the polyester film as described in said ⁇ 4> which narrows the space
- ⁇ 6> The method for producing a polyester film according to any one of ⁇ 1> to ⁇ 5>, wherein the raw material polyester is subjected to solid phase polymerization.
- the polyester film obtained through the longitudinal stretching step and the transverse stretching step has a thermal shrinkage rate of 2.0% or less under heating conditions of heating at 150 ° C. for 30 minutes, ⁇ 1> to ⁇ 6 It is a manufacturing method of the polyester film as described in any one of>.
- the film forming step includes a step of adding and melt-extruding at least one kind of end-capping agent of an oxazoline compound, a carbodiimide compound, or an epoxy compound together with the raw material polyester ⁇ 1> to ⁇ 9>
- the manufacturing method of the polyester film as described in any one of 9>.
- the polyester film according to ⁇ 12> including a structural unit derived from a polyfunctional monomer having a total number of carboxylic acid groups and hydroxyl groups of 3 or more.
- polyester film according to any one of ⁇ 1> to ⁇ 14>, wherein the polyester film includes a structural portion derived from at least one end-capping agent of an oxazoline compound, a carbodiimide compound, or an epoxy compound. .
- a solar cell backsheet comprising the polyester film according to any one of ⁇ 12> to ⁇ 16>.
- ⁇ 18> a transparent front substrate on which sunlight is incident;
- a cell structure portion provided on the front substrate and having a solar cell element and a sealing material for sealing the solar cell element;
- the present invention it is possible to provide a polyester film excellent in hydrolysis resistance and dimensional stability, a method for producing the polyester film, and a solar cell backsheet. In addition, it is possible to provide a solar cell module whose power generation performance is stable for a long time.
- the method for producing a polyester film of the present invention includes a film forming step of melt-extruding a raw material polyester and further cooling to form a polyester film having an intrinsic viscosity of 0.75 or more, and a longitudinal direction in which the polyester film is longitudinally stretched in the longitudinal direction A stretching step, a preheating portion for preheating the polyester film, a stretching portion for laterally stretching the preheated polyester film by applying tension in a direction perpendicular to the longitudinal direction of the polyester film, and a polyester film subjected to tension.
- a heat fixing part that heat-fixes the polyester film surface so that the maximum film surface temperature on the surface of the polyester film is 160 ° C.
- a heat-stretching part that heats the heat-fixed polyester film so as to be at a temperature and transports the polyester film in this order to a heat-relaxing part that relaxes the tension, and at least a transverse stretching step that transversely stretches. Is.
- a raw material polyester is melt-extruded to form a polyester film having an intrinsic viscosity of 0.75 or more, and the obtained polyester film is subjected to water resistance by passing through the longitudinal stretching step and the lateral stretching step having the above-described configuration.
- a polyester film excellent in both degradability and dimensional stability can be produced. The reason why hydrolysis resistance and dimensional stability can be simultaneously achieved by the method for producing a polyester of the present invention is not clear, but is presumed to be as follows.
- the hydrolysis resistance of a polyester film (hereinafter also simply referred to as “film”) is good if tension is applied to the film and the polyester molecules are stretched in the length direction of the molecules.
- the dimensional stability of the film is good if the distance between the molecular chains of the polyester molecules is reduced. This is thought to be because when the distance between the molecular chains of the polyester molecules is large, the molecular chains are contracted by the intermolecular interaction, so that the dimensional stability of the film is deteriorated (the thermal shrinkage rate is increased). . Therefore, in order to achieve both the hydrolysis resistance and dimensional stability of the polyester film, for example, it is conceivable to apply tension to the film so that the distance between the molecular chains of the polyester molecules is not shortened.
- the stretching of the film will be described in detail later, but in general, the film is transported using an apparatus equipped with a roll, a clip and the like, and the film is stretched in the transport direction (longitudinal stretching) and orthogonal to the transport direction. Stretching in the direction (transverse stretching) is performed.
- the film is pre-heated for pre-heating the film in preparation for stretching, a stretching section for tensioning the film to stretch the film, and heat setting for heating the film while tension is applied.
- the film is successively conveyed and stretched to the part and the heat relaxation part for relaxing the tension of the film.
- the transverse stretching step tension is given to the film by stretching the film at the stretched portion, so that the polyester molecules are stretched and the hydrolysis resistance of the film is improved.
- the dimensional stability of the film is poor (heat shrinkage rate is large). This is presumably because the molecular chain between the polyester molecules becomes larger due to the stretching of the film.
- the dimensional stability of the film can be improved by releasing the tension on the film in the heat relaxation section. This is probably because the film shrinks and the molecular chain between the polyester molecules narrows.
- hydrolysis resistance deteriorates by releasing tension on the film. This is presumably because the polyester molecules that have been stretched in the length direction of the molecules shrink. Therefore, in the conventional transverse stretching process, it has been difficult to achieve both hydrolysis resistance and dimensional stability.
- a polyester film having an intrinsic viscosity of 0.75 or more obtained by melt-extruding a raw material polyester is drawn. It is considered that the greater the intrinsic viscosity of the polyester, the larger the polyester molecule and the slower the movement of the polyester molecule. Therefore, it is considered that the polyester molecules stretched in the length direction of the molecule by applying tension to the film in the stretched portion are difficult to shrink because the movement of the molecule is slow even when the tension of the film is released. Therefore, it is considered that the hydrolysis resistance does not decrease even if the tension is released and relaxed after stretching a polyester film having an intrinsic viscosity of 0.75 or more. On the other hand, it has been found that the distance between the molecular chains of the polyester molecules does not significantly affect the movement of the polyester molecules themselves, and the dimensional stability can be improved by releasing the tension on the film.
- the tensioned film is heat-set by heating so that the maximum surface temperature of the film surface reaches 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. Further, after the heat setting, the heat-fixed film is heated so that the maximum film surface temperature on the surface of the film is 5 ° C. or lower than the maximum film surface temperature of the film in the heat fixing part.
- the film forming step is a step in which a raw material polyester is melt-extruded and further cooled to form a polyester film having an intrinsic viscosity of 0.75 or more.
- a film formation process includes the process of adding and melt-extruding at least 1 type of terminal blocker of an oxazoline type compound, a carbodiimide compound, or an epoxy compound with respect to raw material polyester. Details of the end sealant will be described later.
- the method of melt-extruding the raw material polyester, and the raw material polyester is not particularly limited as long as it is a method or polyester in which the intrinsic viscosity of the polyester film obtained by melt-extruding the raw material polyester and further cooling is 0.75 or more.
- the intrinsic viscosity can be set to a desired intrinsic viscosity by a catalyst used in the synthesis of the polymer, a polymerization method, or the like. First, raw material polyester is demonstrated.
- the raw material polyester 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.
- the raw material polyester may contain a titanium element derived from the catalyst.
- the kind of polyester contained in the raw material polyester is not particularly limited. You may synthesize
- the polyester when the polyester is 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 known method.
- the dicarboxylic acid component 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
- 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.
- the “main component” means that the proportion of aromatic dicarboxylic acid in the dicarboxylic acid component is 80% by mass or more.
- 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.
- at least one aliphatic diol is used as the (B) diol component.
- 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 aliphatic diol (for example, ethylene glycol) used is in the range of 1.015 to 1.50 mol with respect to 1 mol of the aromatic dicarboxylic acid (for example, terephthalic acid) and, if necessary, its ester derivative. Is preferred.
- 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.
- -Multifunctional monomer- Polyester which is a raw material used in the method for producing a polyester film of the present invention, is a polyfunctional monomer (hereinafter referred to as “3”) 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. It is preferable to include a “functional or higher functional monomer” or simply “polyfunctional monomer”. By including a polyfunctional monomer in polyester, it is excellent in adhesiveness with the coating material adjacent to the polyester film. Examples of the coating material adjacent to the polyester film include a coating layer formed by coating on the polyester film.
- the adhesion between the polyester film and the adjacent coating material is improved because the functional groups not used for the polycondensation of the polyester are not bonded to the components in the coating layer of the coating material adjacent to the polyester film. This is considered to form a covalent bond.
- the raw material polyester preferably contains a polyfunctional monomer as a copolymerization component (a trifunctional or higher functional component).
- a polyfunctional monomer as a copolymerization component a trifunctional or higher functional component
- Containing a polyfunctional monomer as a copolymerization component (a trifunctional or higher functional component) means containing a structural unit derived from a polyfunctional monomer.
- the polyester can be obtained, for example, by subjecting (A) a dicarboxylic acid component and (B) a diol component to an esterification reaction and / or transesterification by a known method, and more preferably It is obtained by copolymerizing a trifunctional or higher polyfunctional monomer.
- the trifunctional aromatic carboxylic acid includes, for example, trimesic acid, trimellitic
- trimesic acid trimellitic
- trifunctional aliphatic carboxylic acids such as methanetricarboxylic acid, ethanetricarboxylic acid, propanetricarboxylic acid, and butanetricarboxylic acid are tetrafunctional aromatics such as acid, pyromellitic acid, naphthalenetricarboxylic acid, and anthracentricarboxylic acid.
- Examples of the group carboxylic acid include benzenetetracarboxylic acid, benzophenonetetracarboxylic acid, naphthalenetetracarboxylic acid, anthracenetetracarboxylic acid, and perylenetetracarboxylic acid.
- Examples of the tetrafunctional aliphatic carboxylic acid include ethanetetracarboxylic acid.
- 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 oxy acids 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 polyfunctional monomer is preferably 0.005 mol% to 2.5 mol% with respect to the total number of moles in the polyester.
- the content ratio of the polyfunctional monomer is more preferably 0.020 mol% or more and 1 mol% or less, further preferably 0.025 mol% or more and 1 mol% or less, and further preferably 0.035 mol% or more and 0 or less.
- 0.5 mol% or less particularly preferably 0.05 mol% or more and 0.5 mol% or less, and most preferably 0.1 mol% or more and 0.25 mol% or less.
- polyester film is finally formed as a constituent unit derived from a trifunctional or higher polyfunctional monomer in the polyester, from a structural unit derived from a trifunctional or higher polyfunctional monomer.
- a structure in which polyester molecular chains are branched can be obtained, and entanglement between polyester molecules can be promoted.
- the polyfunctional monomer may be added during the polymerization of the polyester, that is, during the esterification reaction step of the dicarboxylic acid component and the diol component.
- 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 polyester When the polyester is polymerized, it is preferable to perform the polymerization using a titanium (Ti) compound as a catalyst in the range of 1 ppm to 50 ppm, more preferably 2 ppm to 30 ppm, and even more preferably 3 ppm to 15 ppm.
- the raw material polyester contains 1 ppm or more and 50 ppm or less of titanium element. If the amount of titanium element contained in the raw material polyester is less than 1 ppm, the weight average molecular weight (Mw) of the polyester cannot be increased, and thermal decomposition tends to occur. If the amount of titanium element contained in the raw material polyester exceeds 50 ppm, the Ti-based catalyst becomes a foreign substance and causes uneven stretching when the polyester film is stretched.
- titanium compounds As the titanium compound as the catalyst component, at least one kind of organic chelate titanium complex having an organic acid as a ligand is used.
- organic acid include citric acid, lactic acid, trimellitic acid, malic acid and the like.
- an organic chelate complex having citric acid or citrate as a ligand is preferable.
- the titanium catalyst also has a catalytic effect on 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.
- the complex with citric acid as a ligand is more resistant to hydrolysis than titanium alkoxide, etc., and does not hydrolyze in the esterification reaction process, and maintains the original activity while maintaining the original activity. 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.
- a Ti catalyst is used and the amount of Ti added is 1 ppm to 30 ppm, more preferably 3 ppm to 20 ppm, more preferably 5 ppm to 15 ppm in terms of Ti element. . If the amount of titanium added is 1 ppm or more, it is advantageous in that the polymerization rate is increased, and if it is 30 ppm or less, it is advantageous in that a good color tone is obtained.
- 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 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 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 polyester is produced by a method for producing a polyester comprising a polycondensation step in which a polycondensation product is produced by subjecting a polycondensation reaction product to a polycondensation reaction.
- polyesters that have a color tone and transparency that are inferior to those of other polyesters and that have excellent heat resistance. Moreover, polyester which has high transparency and few yellowishness is obtained, without using color tone adjusting materials, such as a cobalt compound and a pigment
- 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 a process of adding an organic chelate titanium complex which is a titanium compound and a magnesium compound and a pentavalent phosphorus compound as additives in this order is provided. At this time, the esterification reaction proceeds in the presence of the organic chelate titanium complex, and thereafter, the addition of the magnesium compound is 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.
- a chelate titanium complex having 1 ppm or more and 30 ppm or less of citric acid or citrate as a ligand to the aromatic dicarboxylic acid and the aliphatic diol
- a magnesium salt of weak acid of 60 ppm to 90 ppm (more preferably 70 ppm to 80 ppm) is added, and after the addition, 60 ppm to 80 ppm (more preferably 65 ppm to 75 ppm).
- 60 ppm to 80 ppm more preferably 65 ppm to 75 ppm.
- a pentavalent phosphate having no aromatic ring as a substituent is added.
- 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 film is preferably a solid-phase polymerized pellet.
- the polyester film is further subjected to solid phase polymerization, whereby the water 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) [equivalent / ton Intrinsic Viscosity (IV) [dL / g] can be controlled.
- “equivalent / ton” represents a molar equivalent per ton.
- the intrinsic viscosity (IV) of the polyester is set to 0.75 or more from the viewpoint of achieving both hydrolysis resistance and dimensional stability of the polyester film.
- the intrinsic viscosity (IV) of the polyester is preferably 0.75 to 0.9.
- the intrinsic viscosity is 0.75 or more, the molecular motion of the polyester is hindered and it is difficult to crystallize, and when it is 0.9 or less, the thermal decomposition of the polyester due to shear heat generation in the extruder does not occur too much, Crystallization can be suppressed and the acid value (AV) can be kept low.
- IV is more preferably 0.75 or more and 0.85 or less.
- the polyester as a raw material of the polyester film applied to the longitudinal stretching and the transverse stretching preferably has an intrinsic viscosity of 0.75 or more and 0.9 or less, and further contains a titanium atom derived from a catalyst (Ti catalyst). Is preferred.
- Solid phase polymerization of polyester a polyester obtained by the esterification reaction described above or a commercially available polyester in the form of a small piece such as a pellet 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).
- Solid phase polymerization of polyester is 150 ° C. or more and 250 ° C. or less, more preferably 170 ° C. or more and 240 ° C. or less, more preferably 180 ° C.
- the solid phase polymerization is preferably performed in a vacuum or a nitrogen stream.
- 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 acid value (AV) of the polyester is further reduced.
- the solid phase polymerization time is preferably 5 hours to 100 hours, more preferably 10 hours to 75 hours, and still more preferably 15 hours to 50 hours. It is preferable that the time is within the above range in that the acid value (AV) and intrinsic viscosity (IV) of the polyester can be easily controlled within the preferable ranges of the present invention.
- the solid phase polymerization is preferably performed in a vacuum or in a nitrogen atmosphere.
- the raw material polyester obtained as described above is melt-extruded and further cooled to form a polyester film.
- the raw material polyester is melt-extruded by, for example, using an extruder equipped with one or two or more screws, heating to a temperature not lower than the melting point of the raw material polyester, and rotating the screw.
- the raw material polyester is melted into a melt in the extruder by heating and kneading with a screw. Further, from the viewpoint of suppressing thermal decomposition (polyester hydrolysis) in the extruder, it is preferable to perform melt extrusion of the raw material polyester by replacing the inside of the extruder with nitrogen.
- the melted raw material polyester (melt) is extruded from an extrusion die through a gear pump, a filter or the like.
- the extrusion die is also simply referred to as “die” (see JIS B 8650: 2006, a) extrusion molding machine, number 134).
- the melt may be extruded as a single layer or may be extruded as a multilayer.
- 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 more preferably 0.8 mm to 4.6 mm. More preferably.
- 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 film 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 film forming step includes 0.1% by mass or more and 5% by mass or less of at least one terminal blocker of an oxazoline compound, a carbodiimide compound, or an epoxy compound together with the raw material polyester. It is preferable to include the process of adding and melt-extruding. That is, in the melt extrusion of the raw material polyester, it is preferable to use the terminal blocking agent in combination.
- the end-capping agent By using the end-capping agent together, the end of the polyester molecule reacts with the capping agent, the end of the molecular chain becomes bulky, the amount of fine irregularities on the surface of the resulting polyester film increases, and the anchor effect is easily expressed. Excellent adhesion to the material adjacent to the polyester film.
- the end-capping agent is not particularly limited as long as it is from the introduction of the polyester film raw material into the extruder to the extrusion, but the end-capping agent is used after the raw material polyester is dried. Is introduced into the extruder, sent by screw, added before being extruded from the extruder, and is preferably subjected to melt kneading together with the raw material polyester. For example, after the raw material polyester is dried, the end-capping agent may be put into the extruder together with the raw material polyester.
- a supply port for supplying an end-capping agent is provided between the raw material inlet of the extruder that performs melt-kneading and the outlet of the molten polyester (melt), and the end-capping is directly performed on the raw material polyester in the extruder. Stopper may be added. At this time, the end-capping agent may be added to the polyester that has been heated and kneaded but has not completely reached the molten state, or may be added to the molten polyester (melt).
- 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.
- the 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, 1,4-phenylene diisocyanate, 2 , 4-Tolylenecarbodiimide, 2,6-Tolylenecarbodiimide, Mixture of 2,4-Tolylenecarbodiimide and 2,6-Tolylenecarbodiimide, Hexamethylenecarbodiimide, Cyclohexane-1,4-carbodiimide, Xylylenecarbodiimide, Isophorone Carbodiimide, isophorone carbodiimide, dicyclohexylmethane-4,4'-carbodiimide, methylcyclohexanecarbodiimide, tetramethylxylylene carbodiimide, 2,6-diisopropyl phen
- 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 the carbodiimide compound preferably has an amount of isocyanate gas generated of 0 to 0.02% by mass when held at a temperature of 300 ° C. for 30 minutes. If the amount of isocyanate 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 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 among them, a bisoxazoline compound is preferable.
- a bisoxazoline compound examples 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 amount of the terminal blocking agent relative to the polyester is preferably 0.1% by mass or more and 5% by mass or less with respect to the total mass of the raw material polyester.
- a preferable amount of the terminal blocking agent with respect to the raw material polyester 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 addition ratio of the end-capping agent is 5% by mass or less, a decrease in the glass transition temperature (Tg) of the polyester due to the addition of the end-capping agent is suppressed, resulting in a decrease in weather resistance and an increase in heat shrinkage. Can be suppressed.
- Tg glass transition temperature
- 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 longitudinal stretching step of the present invention is a step of longitudinally stretching a polyester film having an intrinsic viscosity of 0.75 or more obtained by the film forming step in the longitudinal direction of the polyester film.
- the longitudinal stretching of the film can be performed, for example, by using the film with 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. it can.
- the rotational speed of the nip roll B on the downstream side is By making it faster than the rotational speed of the nip roll A on the upstream side, the film is stretched in the transport direction (MD).
- MD transport direction
- Two or more pairs of nip rolls may be installed independently on the upstream side and the downstream side, respectively.
- the area stretch ratio of the polyester film is preferably 6 to 18 times, more preferably 8 to 17.5 times the area of the polyester film before stretching, More preferably, it is 10 to 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 or higher and Tg + 30 ° C. or lower.
- the polyester film when extending
- a heat source such as a heater
- the polyester film is at least biaxial in the longitudinal direction (conveying direction, MD) of the polyester film and the direction (TD; Transverse Direction) perpendicular to the longitudinal direction of the polyester film.
- the stretching in the MD direction and the TD direction may be performed at least once each.
- the direction (TD) orthogonal to the longitudinal direction (conveyance direction, MD) of a polyester film intends the direction of an angle (90 degrees) perpendicular to the longitudinal direction (conveyance direction, MD) of a polyester film.
- it may be in the direction of the range of machine error.
- the range of mechanical error refers to the direction of an angle (90 ° ⁇ 5 °) that can be regarded as perpendicular to the longitudinal direction (conveying direction, MD) of polyester.
- 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 process in the present invention will be described in detail.
- a preheating portion for preheating a polyester film having an intrinsic viscosity of 0.75 or more obtained by the film forming step, and tension is applied to the preheated polyester film at least in a direction perpendicular to the longitudinal direction of the polyester film.
- a stretching part for transversely stretching the polyester film a heat fixing part for heating and fixing the tensioned polyester film so that the highest surface temperature of the polyester film reaches 160 ° C. to 210 ° C., And the heat-fixed polyester film is heated to relax the tension so that the maximum film surface temperature on the surface of the polyester film is 5 ° C. or more lower than the maximum film surface temperature of the polyester film in the heat-fixed part.
- the polyester film is conveyed in this order to the heat relaxation part and at least laterally stretched. It is a degree.
- the means for realizing the transverse stretching step is not limited as long as the polyester film is at least transversely stretched in the above configuration, but is preferably performed using a lateral stretching apparatus or a biaxial stretching machine that enables processing of the above configuration. In the transverse stretching step, it is further preferable to cool the polyester film that has passed through the thermal relaxation portion.
- the details of the transverse stretching step will be described in accordance with the description of the biaxial stretching machine.
- FIG. 1 shows an example (top view) of a biaxial stretching machine.
- FIG. 1 shows a biaxial stretching machine 100 and a polyester film 200 attached to the biaxial stretching machine 100.
- the biaxial stretching machine 100 includes a pair of annular rails 60a and 60b, and is arranged symmetrically with the polyester film 200 in between.
- 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. And a cooling unit 50 for cooling the polyester film.
- the annular rail 60a includes at least gripping members 2a, 2b, 2e, 2f, 2i, and 2j that can move the edge of the annular rail 60a.
- the annular rail 60b is a gripping member 2c that can move the edge of the annular rail 60b. 2d, 2g, 2h, 2k, and 2l.
- 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 polyester The other end of the film 200 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 edge of the annular rail 60a, and the gripping members 2c, 2d, 2g, 2h, 2k, and 2l are annular It moves clockwise along the edge of the rail 60b.
- the holding members 2a to 2d hold the end portion of the polyester film 200 in the preheating unit 10 and move the edge of the annular rail 60a or 60b as it is, so that the extending portion 20 and the heat relaxation unit in which the holding members 2e to 2h are shown
- the process proceeds to the cooling unit 50 where the gripping members 2i to 2l are shown.
- 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 the annular rail 60a or 60b is left as it is. Proceed along the edge and return to the preheating section 10.
- the polyester film 200 moves in the direction of the arrow MD in FIG. 1 and is sequentially conveyed to the preheating unit 10, the stretching unit 20, the heat fixing unit 30, the heat relaxation unit 40, and the cooling unit 50. .
- the moving speed of the gripping members 2a to 2l becomes the transport speed at the gripping portion of the polyester film 200.
- the gripping members 2a to 2l can change the moving speed independently of each other. Accordingly, the biaxial stretching machine 100 enables the transverse stretching in which the polyester film 200 is stretched in the TD direction in the stretching section 20, but the polyester film can be changed by changing the moving speed of the gripping members 2a to 2l. 200 can also be stretched in the MD direction. That is, simultaneous biaxial stretching can be performed using the biaxial stretching machine 100.
- gripping members 2a to 2l are shown as gripping members for gripping the end portion of the polyester film 200 in the TD direction. In addition to 2l, it has a gripping member (not shown). Hereinafter, the gripping members 2a to 2l may be collectively referred to as “grip member 2”.
- the polyester film 200 is preheated. Before the polyester film 200 is stretched, it is heated in advance to facilitate the lateral stretching of the polyester film 200.
- 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., where Tg is the glass transition temperature of the polyester film 200, and Tg ° C. to Tg + 50. It is more preferable that the temperature is C.
- 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 preheated polyester film 200 is laterally stretched at least in the direction (TD) perpendicular to the longitudinal direction (conveying direction, MD) of the polyester film 200 to give tension to the polyester film 200.
- Stretching (transverse stretching) in the direction (TD) perpendicular to the longitudinal direction (conveying direction, MD) of the polyester film 200 is perpendicular to the longitudinal direction (conveying direction, MD) of the polyester film 200 (90) as described above. Is intended to be stretched in the direction of the angle (°), but may be in the direction of a range of mechanical errors.
- the range of the mechanical error is a direction at an angle (90 ° ⁇ 5 °) that can be regarded as perpendicular to the longitudinal direction (conveying direction, MD) of the polyester.
- the tension (stretching tension) for lateral stretching applied to the polyester film 200 is 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 of the polyester film 200 during transverse stretching (hereinafter also referred to as “lateral stretching temperature”) is Tg ⁇ 10 ° C. or higher and Tg + 100 ° C. or lower when the glass transition temperature of the polyester film 200 is Tg. More preferably, it is Tg ° C. or more and Tg + 90 ° C. or less, and further preferably Tg + 10 ° C. or more and Tg + 80 ° C. or less.
- the gripping member 2 can independently change the moving speed.
- the extending portion 20 By increasing the moving speed of the gripping member 2 on the downstream side in the MD 20 MD direction such as the heat fixing unit 30, it is also possible to perform longitudinal stretching for stretching the polyester film 200 in the transport direction (MD).
- 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.
- Heat fixing part In the heat fixing unit 30, the tensioned polyester film 200 is heated and fixed so that the maximum film surface temperature on the surface of the polyester film 200 is 160 ° C. to 210 ° C.
- Heat setting refers to heating at a specific temperature while tension is applied to the polyester film 200 in the stretched portion 20. Heat until By heating the tensioned polyester film 200 so that the maximum surface temperature of the surface reaches 160 ° C. to 210 ° C., the polyester molecules can be oriented to impart hydrolysis resistance. .
- heat setting temperature When the maximum film surface temperature of the surface of the polyester film 200 during heat setting (hereinafter also referred to as “heat setting temperature” or “T heat setting ”) is lower than 160 ° C., the polyester hardly crystallizes. Cannot be fixed in the stretched state, and the hydrolysis resistance cannot be sufficiently improved. On the other hand, if the heat setting temperature is higher than 210 ° C., slippage occurs at the entangled portions of the polyester molecules, the polyester molecules shrink, and the hydrolysis resistance cannot be sufficiently improved.
- the heat setting temperature is preferably 170 ° C. to 200 ° C., more preferably 175 ° C. to 195 ° C. The heat setting temperature can be measured by bringing a thermocouple into contact with the surface of the polyester film 200.
- the highest ultimate film surface temperature of the surface of the polyester film 200 is 5 ° C. or lower than the highest ultimate film surface temperature (T heat fixation ) of the polyester film 200 in the heat fixing part 30.
- the polyester film 200 is heated to relax the tension applied to the polyester film 200.
- the highest reached film surface temperature of the surface of the polyester film 200 during thermal relaxation is also referred to as “thermal relaxation temperature” (T thermal relaxation ).
- 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.
- thermal relaxation temperature T thermal relaxation
- T heat relaxation the heat relaxation temperature
- T heat relaxation is equal to or 100 ° C. or less, hardly reduced the inter-molecular chains of the polyester molecules are, for hardly improved dimensional stability
- thermal relaxation temperature (T heat relaxation) is 100 ° C. or higher
- Thermal relaxation temperature (T heat relaxation) is, 100 ° C. or higher, and to be thermally fixed temperature (T heat-) 15 ° C. or higher than the lower temperature (100 ° C.
- the temperature is 110 ° C. or more and 25 ° C. or more lower than the heat setting temperature (T heat setting ) (110 ° C ⁇ T heat relaxation ⁇ T heat setting ⁇ 25 ° C.), more preferably 120 ° C. or more. Further, it is more preferable that the temperature is 120 ° C. or more lower than the heat setting temperature (T heat setting ) (120 ° C. ⁇ T heat relaxation ⁇ T heat setting ⁇ 30 ° C.).
- the thermal relaxation temperature can be 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 200 which passed through the heat relaxation part 40 is cooled.
- the film surface temperature (hereinafter also referred to as “cooling temperature”) of the cooling part outlet of the polyester 200 in the cooling part 50 is preferably lower than the glass transition temperature Tg + 50 ° C. of the polyester film 200.
- the temperature is preferably 25 ° C to 110 ° C, more preferably 25 ° C to 95 ° C, and further preferably 25 ° C to 80 ° C.
- 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, thermal 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 cooled polyester film 200 is cut into grips at both ends in the TD direction and 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 transverse stretching step is preferably performed after the longitudinal stretching step.
- 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) (one gripping member of the two gripping members) that grips one end of the polyester film 200 in the width direction (TD direction) in the preheating unit 10
- a gripping member 2a ( 2c) A grip that grips one end portion of the polyester film 200 in the width direction in the cooling unit 50, rather than a distance from another gripping member 2b (2d) (the other gripping member of the two gripping members) adjacent to 2c).
- the member 2a (2c) (one of the two gripping members) and another gripping member 2b (2d) adjacent to the gripping member 2a (2c) (the other gripping of the two gripping members)
- the conveyance speed of the polyester film 200 is reduced by narrowing the distance between the member and the member. 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. Therefore, when relaxation in the MD direction is performed by the heat fixing unit 30 or the heat relaxation unit 40, the moving speed of the gripping members 2a to 2d when the gripping members 2a to 2d reach the heat fixing unit 30 or the heat relaxation unit 40.
- the conveyance speed of the polyester film 200 is reduced, and the distance between the gripping members 2a-2b and the distance between the gripping members 2c-2d may be narrower than the distance in the preheating portion.
- the polyester film 200 is stretched in the TD direction (lateral stretching) and relaxed in the TD direction, and also stretched in the MD direction (longitudinal stretching) and relaxed in the MD direction.
- the dimensional stability can be improved while improving the decomposability.
- the relaxation of the polyester film 200 in the TD direction and the relaxation in the MD direction are preferably performed by controlling the transport speed of the polyester film 200 and the width (length in the TD direction) of the polyester film 200 as follows.
- the transverse stretching step is performed after the longitudinal stretching step, the width L1 of the polyester film 200 when the width of the polyester film 200 in the transverse stretching step is maximized, and the cooling unit 50 from which the polyester film 200 is separated from the cooling unit 50.
- the width L2 of the polyester film 200 at the end portion satisfies the following formula (1), and the transport speed S1 of the polyester film 200 in the preheating portion 10 and the transport speed S2 of the polyester film 200 at the end portion of the cooling portion 50.
- the width L1 of the polyester film 200 when the width of the polyester film 200 in the transverse stretching step is maximized is the TD of the polyester film 200 after the polyester film 200 is widened in the TD direction at the stretching portion 20.
- the maximum length of the direction In FIG. 1, the width L0 of the polyester film 200 before stretching in the preheating portion 10 is widened in the TD direction by the stretching portion 20 to become the width L1, and the tension is released in the heat relaxation portion 40, and the polyester It is shown that when the film 200 leaves the cooling unit 50, the width L2 is obtained. In FIG. 1, the width increases in the order of L0 ⁇ L2 ⁇ L1.
- L1 is the maximum width of the polyester film 200 in the transverse stretching process from the preheating part 10 to the cooling part 50.
- the polyester film 200 that has passed through the stretched portion 20 is then heated in the heat fixing portion 30 while being tensioned. Therefore, the width L1 is usually the polyester in the heat fixing portion 30. It can also be said to be the width of the film 200 (length in the TD direction).
- the “width L2 of the polyester film 200 at the end of the cooling unit 50 from which the polyester film 200 is separated” is positioned in the cooling unit 50 and holds the polyester film 200 (the holding members 2j and 2l in FIG. 1). ) Is the width of the polyester film 200 when the polyester film 200 is released.
- the polyester film 200 leaves the region of the cooling unit 50.
- the gripping member 2j is at the point P and the gripping member 21 is at the point Q
- the end of the cooling unit 50 is the point P and the point Q. It is represented by a straight line connecting
- the “conveying speed S1 of the polyester film 200 in the preheating unit 10” corresponds to the moving speed of the gripping member 2 (2a to 2d in FIG. 1) that grips the polyester film 200 and moves the edge of the annular rail 60. Further, the “conveying speed S2 of the polyester film 200 at the end of the cooling unit 50” is determined by the gripping member 2 (the gripping members 2j and 2l in FIG. 1) that is positioned in the cooling unit 50 and grips the polyester film 200. It is the conveyance speed of the polyester film 200 when releasing the polyester film 200.
- the “conveying speed S2 of the polyester film 200 at the end of the cooling unit 50” is This corresponds to the conveyance speed when the polyester film 200 exceeds the straight line connecting the P point and the Q point.
- the “conveying speed S2 of the polyester film 200 at the end of the cooling unit 50” corresponds to the moving speed of the gripping members 2j and 2l immediately before the gripping members 2j and 2l release the polyester film 200.
- Formula (1) indicates that when the polyester film 200 is stretched and then relaxed in the TD direction, the maximum width (length in the TD direction) L1 of the polyester film 200 is reduced by 2% to 15% in the cooling unit 50. It is preferable to relax.
- the transport speed S1 in the preheating portion 10 of the polyester film 200 is relaxed so as to be reduced by 2% to 15% in the cooling portion 50. Means.
- ⁇ L indicates the relaxation rate in the TD direction (lateral direction) of the polyester film, and therefore ⁇ L is also referred to as “lateral relaxation rate”. Moreover, since ⁇ S indicates the relaxation rate in the MD direction (longitudinal direction) of the polyester film, ⁇ S is also referred to as “longitudinal relaxation rate”.
- ⁇ L is preferably 2% to 10% (2% ⁇ ⁇ L ⁇ 10%), preferably 3% to More preferably, it is 8% (3% ⁇ ⁇ L ⁇ 8%).
- ⁇ S is preferably 2% to 10% (2% ⁇ ⁇ S ⁇ 10%), more preferably 3% to 8% (3% ⁇ ⁇ S ⁇ 8%).
- the transverse stretching apparatus has the same structure as the biaxial stretching machine except that it does not stretch in the MD direction (longitudinal stretching), and a gripping member for gripping the polyester film, and a gripping member A rail having The transverse stretching apparatus is composed of at least a preheating section, a stretching section, a heat fixing section, and a thermal relaxation section, and the function thereof is the same as that of the biaxial stretching machine described above.
- the polyester film 200 to be subjected to transverse stretching is a thick film (for example, 700 ⁇ m or more) such that the thickness of the polyester film obtained by transverse stretching is 200 ⁇ m or more, a large stretching tension is required. Therefore, a large load is applied in the transverse stretching, and the biaxial stretching machine and the transverse stretching apparatus sometimes break down.
- the polyester film 200 is stretched laterally, it is preferably performed as follows.
- an angle formed by the conveying direction (MD) of the polyester film 200 in the stretching portion 20 and the traveling direction of the end portion in the width direction (TD) of the polyester film 200 in the stretching portion 20 is defined as a stretching angle ⁇ [°].
- a stretching angle ⁇ y [°] at an intermediate position Y between the position X and the position Z in the stretched portion 20 satisfies the following formula (3), and a polyester film having a thickness after the transverse stretching of 200 ⁇ m or more is obtained. It is preferable to stretch the polyester 200 so that the 0 ⁇ x ⁇ ⁇ z ⁇ y ⁇ 10 (3)
- FIG. 2 is a schematic diagram showing a stretching mode of the polyester film in the transverse stretching step.
- 202a and 202b shown in FIG. 2 show the trajectories of the end portions in the TD direction of the polyester film that is laterally stretched in the lateral stretching step.
- point A is the position of one end portion in the width direction (TD) of the polyester film in a state where the polyester film is located in the preheating portion and is not laterally stretched.
- Point B is the position of one end portion in the width direction (TD) of the polyester film in a state where the polyester film is located at the heat fixing portion and the transverse stretching is completed.
- the point X, the point Y, and the point Z are positions at one end in the width direction (TD) of the polyester film in which the polyester film is positioned in the stretched portion and the polyester film is widened in the width direction (TD). is there.
- the width direction (TD) end part of the polyester film reaches point B from point A through point X, point Y, and point Z.
- the positions of the point X, the point Y, and the point Z will be described in more detail.
- the point X is a position where the lateral stretching of the polyester film in the stretched part is started
- the point Z is a position where the lateral stretching of the polyester film in the stretched part is finished.
- “the position at which the lateral stretching of the polyester film in the stretched portion starts” is specifically, from the end on the upstream side in the MD direction of the stretched portion, where M is the length of the stretched portion in the MD direction.
- the 10% position of M refers to a position of 10% of M from the downstream end of the stretched portion in the MD direction.
- Point Y is an intermediate position between the position of point X and the position of point Z.
- the traveling direction at the point X (position X) at the end portion in the width direction of the polyester film is the tangential arrow direction at the point X ( ⁇ x). Therefore, when the angle formed by the conveyance direction (MD) of the polyester film in the stretching portion and the traveling direction of the end portion in the width direction of the polyester film in the stretching portion is the stretching angle ⁇ [°], the position X (point X ) Is expressed as an angle formed by MD and ⁇ x.
- the traveling direction at the point Y (position Y) at the end portion in the width direction of the polyester film is the point Y (position Y).
- the traveling direction at the point Y (position Y) at the end portion in the width direction of the polyester film is the point Y (position Y).
- the traveling direction at the point Y (position Y) at the end portion in the width direction of the polyester film is the point Y (position Y).
- the advancing direction in the point Z (position Z) of the edge part of the width direction of a polyester film is the point Z (position Z). It is represented by the arrow direction ( ⁇ z) of the tangent line.
- the stretching angle ⁇ y [°] at the position Y (point Y) is expressed as an angle formed by the MD and ⁇ y
- the stretching angle ⁇ z [°] at the position Z (point Z) is the difference between the MD and ⁇ z. Expressed as the angle to make.
- ⁇ x [°], ⁇ y [°], and ⁇ z [°] satisfy Expression (3).
- Formula (3) is preferably represented by the following formula (3-1), and more preferably represented by the following formula (3-2).
- the polyester film of this invention will not be restrict
- the polyester film contains a structural unit derived from a trifunctional or higher polyfunctional monomer
- the polyester film is excellent in adhesion to a material adjacent to the polyester film. Moreover, it is excellent in the adhesive force with the material adjacent to a polyester film also when a polyester film contains the structure part originating in a terminal blocker.
- the polyester (raw material polyester) as the raw material of the polyester film of the present invention is, for example, an esterification reaction and / or a (A) dicarboxylic acid component and (B) diol component by a well-known method. It can be obtained by transesterification, and more preferably obtained by copolymerizing a trifunctional or higher polyfunctional monomer. Details of examples and preferred embodiments of the dicarboxylic acid component, the diol component, and the polyfunctional monomer are as described above.
- -Structural units derived from polyfunctional monomers As a structural unit derived from a polyfunctional monomer in which the sum (a + b) of the number of carboxylic acid groups (a) and the number of hydroxyl groups (b) is 3 or more, a structural unit derived from a polyfunctional monomer having 3 or more carboxylic acid groups (a) Polyfunctional monomers having a hydroxyl number (b) of 3 or more, such as acids and ester derivatives or acid anhydrides thereof, and “the number of carboxylic acid groups (a) having both a hydroxyl group and a carboxylic acid group in one molecule; And the total number (a + b) of the number of hydroxyl groups (b) is 3 or more ”.
- oxyacids such as l-lactide, d-lactide, and hydroxybenzoic acid
- a derivative thereof or a combination of a plurality of such oxyacids 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 when exposed to high temperature and high humidity environment, polyester molecules are hydrolyzed and the molecular weight is reduced, so that entanglement is formed between the polyester molecules, so that the embrittlement of the polyester film is suppressed and more excellent. Weather resistance is obtained. Further, such entanglement is also effective in suppressing heat shrinkage.
- the motility of the polyester molecules decreases due to the entanglement of the polyester molecules, so that even if the molecules try to contract due to heat, they cannot contract and the thermal contraction of the polyester film is suppressed. 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 and the low heat shrinkability are easily improved. Moreover, since 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 functional monomer is bulky, so that it is difficult to form a crystal. It is suppressed.
- 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 When the end-capping agent is included in the polyester film, 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. Furthermore, the end-capping agent is bulky and suppresses the movement of the polyester molecules through the free volume. As a result, it also has an effect of suppressing heat shrinkage accompanied by molecular movement.
- the terminal blocking agent constituting the “structural portion derived from the terminal blocking agent” may be a single type or a combination of two or more types.
- the structural portion derived from the end-capping agent is preferably contained in the range of 0.1% by mass or more and 5% by mass or less, more preferably 0.3% by mass or more and 4% by mass with respect to the polyester film. Or less, more preferably 0.5% by mass or more and 2% by mass or less.
- the content ratio of the structural portion derived from 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 can be imparted.
- the fall of the glass transition temperature (Tg) of polyester by addition of terminal blocker is suppressed as the content rate of the structure part originating in terminal blocker is 5 mass% or less, and the weather resistance fall by this And increase in heat shrinkage can be suppressed.
- Tg glass transition temperature
- the preferred embodiment of the terminal blocking agent is as described above.
- polyester film obtained through the above-described stretching step and transverse stretching step in the method for producing a polyester film of the present invention has a heat shrinkage of 2.0% or less under heating conditions of heating at 150 ° C. for 30 minutes. preferable.
- polyester has a higher coefficient of thermal expansion and hygroscopic expansion than glass, so it tends to be stressed by changes in temperature and humidity, and tends to cause cracking and peeling of the layer, but the thermal shrinkage rate is within the above range. By being, it can prevent the peeling of the functional member sheet affixed on the polyester film, the crack of the layer apply
- the heat shrinkage rate can be realized, and in particular, the heating temperature (T heat setting and T heat relaxation in the transverse stretching step). It is possible to adjust to the above range by controlling at least one of the above.
- the heat shrinkage rate under heating conditions of heating at 150 ° C. for 30 minutes is more preferably 1.0% or less, and further preferably 0.5% or less.
- polyester film having a thickness of 30 ⁇ m to 400 ⁇ m by the method for producing a polyester film of the present invention described above.
- the thickness of the polyester film is preferably 40 ⁇ m to 350 ⁇ m, more preferably 50 ⁇ m to 300 ⁇ m, from the viewpoint of electrical insulation.
- the obtained polyester film is suitable for uses such as a back surface protective sheet (so-called back sheet) and a barrier film substrate disposed on the back surface opposite to the sunlight incident side of the solar cell power generation module.
- the solar cell backsheet of the present invention comprises the polyester film of the present invention.
- the solar cell backsheet of this invention can be preferably used as a member which comprises a solar cell module.
- a solar cell module includes a transparent front substrate on which sunlight is incident, a cell structure portion provided on the front substrate and including a solar cell element and a sealing material for sealing the solar cell element, and a cell structure.
- the solar cell backsheet of the present invention is provided on the side opposite to the side where the front substrate is located and is disposed adjacent to the sealing material.
- the transparent substrate only needs to have a light-transmitting property through which sunlight can be transmitted, and can be appropriately selected from base materials that transmit light. From the viewpoint of power generation efficiency, the higher the light transmittance, the better.
- a transparent resin such as an acrylic resin, or the like can be suitably used.
- Solar cell elements include silicon-based materials such as single crystal silicon, polycrystalline silicon, and amorphous silicon, III-V groups such as copper-indium-gallium-selenium, copper-indium-selenium, cadmium-tellurium, gallium-arsenic, and II Various known solar cell elements such as a group VI compound semiconductor can be applied.
- 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 was performed on the polyester pellets obtained as described above by a batch method. Specifically, after putting polyester pellets into a container, solid-state polymerization was performed under the following conditions while stirring under vacuum. After precrystallization at 150 ° C., a solid state polymerization reaction was performed at 190 ° C. for 30 hours.
- the obtained polyester was formed into pellets in the same manner as the raw material polyester 1, and further raw material polyesters 4 to 7 were obtained under the same solid phase polymerization conditions as the raw material polyester 1.
- TMA Trifunctional carboxylic acid type
- BTC Tetrafunctional carboxylic acid type
- Example 1 ⁇ Manufacture of unstretched polyester film> -Film forming process- After the raw material polyester 1 was dried to a water content of 20 ppm or less, it was put into a hopper of a uniaxial kneading extruder having a diameter of 50 mm. The raw material polyester 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 molten resin was extruded from the die under the conditions that the pressure fluctuation was 1% and the temperature distribution of the molten resin was 2%. Specifically, the back pressure was increased by 1% with respect to the average pressure in the barrel of the extruder, and the piping temperature of the extruder was heated at a temperature 2% higher than the average temperature in the barrel of the extruder.
- the molten resin extruded from the die was extruded onto a cooling cast drum and adhered to the cooling cast drum using an electrostatic application method.
- the temperature of the cooling cast drum was set to 25 ° C., and cold air of 25 ° C. was blown from a cold air generator installed facing the cooling cast drum and applied to the molten resin.
- An unstretched polyester film (unstretched polyester film 1) having a thickness of 3.5 mm was peeled from the cooling cast drum using a peeling roll disposed opposite to the cooling cast drum.
- the stretched polyester film 1 (longitudinal stretched polyester film 1) was stretched under the following conditions using a tenter (biaxial stretching machine) having the structure shown in FIG.
- Stretching temperature transverse stretching temperature: 120 ° C
- Stretch ratio transverse stretch ratio: 4.4 times Stretch stress (transverse stretch stress): 18 MPa
- Stretching angle ⁇ z at the position Z where the lateral stretching is finished Angle shown in Table 1 [°]
- Heat fixing part Heat setting temperature (T heat setting ): Temperature shown in Table 1 [° C]
- Thermal relaxation part Thermal relaxation temperature
- T thermal relaxation temperature shown in Table 1 [° C.]
- the thickness of the obtained biaxially stretched polyester film 1 is measured using a contact-type film thickness meter (manufactured by Anritsu). 50 points are sampled at equal intervals (points equally divided into 50 in the width direction) over the entire width of the film in the direction, and the thicknesses of these 100 points are measured. The average thickness of these 100 points was calculated
- the thickness of the biaxially stretched polyester film 1 is shown in Table 1.
- Example 2 Comparative Example 1
- the unstretched polyester film 2 and the unstretched polyester film 3 were used instead of the unstretched polyester film 1, respectively.
- the biaxially stretched polyester film 2 and the biaxially stretched polyester film 101 of Comparative Example 1 were produced.
- Examples 3 to 9, Example 12, and Comparative Examples 2 to 4 In the production of the biaxially stretched polyester film 1 of Example 1, the stretching angle of the tenter in the transverse stretching step, the heat setting temperature (T heat setting ), the heat relaxation temperature (T heat relaxation ), and the heat in the transverse and longitudinal directions Except for changing the relaxation rate ( ⁇ L and ⁇ S) to the conditions shown in Table 1, the biaxially stretched polyester film 3 to the biaxially stretched polyester film 9 of Example 3 to Example 9 and 2 of Example 12 The axially stretched polyester film 12 and the biaxially stretched polyester film 102 to the biaxially stretched polyester film 104 of Comparative Examples 2 to 4 were produced.
- Example 10 In the production of the biaxially stretched polyester film 1 of Example 1, the same procedure was performed except that the unstretched polyester film 4 having a thickness of 2.6 mm was used instead of the unstretched polyester film 1 having a thickness of 3.5 mm. The biaxially stretched polyester film 10 of Example 10 was produced. Further, in the production of the biaxially stretched polyester film 12 of Example 12, the same procedure was performed except that the unstretched polyester film 4 having a thickness of 2.6 mm was used instead of the unstretched polyester film 1 having a thickness of 3.5 mm. Thus, a biaxially stretched polyester film 11 of Example 11 was produced.
- Examples 13 to 19 In the production of the biaxially stretched polyester film 1 of Example 1, the biaxially stretched polyester film of Examples 13 to 19 was similarly used except that unstretched polyester films 5 to 11 were used instead of the unstretched polyester film 1. 13-19 were produced.
- the dimensional stability of the biaxially stretched polyester film was evaluated by the heat shrinkage rate.
- the thermal contraction rate of the biaxially stretched polyester film was measured in the length direction (MD direction) and the width direction (TD direction) of the biaxially stretched polyester film.
- the thermal shrinkage rate was determined by the following method.
- the biaxially stretched polyester film was cut to obtain a sample piece M having a size of 30 mm in the TD direction and 120 mm in the MD direction.
- Two reference lines were inserted into the sample piece M so as to have an interval of 100 mm in the MD direction, and left in a heating oven at 150 ° C. for 30 minutes under no tension. After this standing, the sample piece M is cooled to room temperature, the distance between the two reference lines is measured, this value is set as A (unit: mm), and the equation of 100 ⁇ (100 ⁇ A) / 100
- the heat shrinkage rate in the MD direction was used.
- size of MD direction 30mm and TD direction 120mm was obtained from the base film. Measurement and calculation were performed on the sample piece L in the same manner as the sample piece M, and the heat shrinkage rate in the TD direction was obtained.
- Both MD direction and TD direction are 1% or less.
- ⁇ Either MD direction or TD direction exceeds 1%, and both MD direction and TD direction are 2% or less.
- ⁇ Either MD direction or TD direction exceeds 2%, and both MD direction and TD direction are 3% or less.
- X Either MD direction or TD direction exceeds 3%.
- the breaking elongation (%) of the biaxially stretched polyester film was obtained by cutting the biaxially stretched polyester film to obtain a sample piece P having a size of 1 cm ⁇ 20 cm. Asked by pulling in minutes. The longer the half elongation time at break, the better the hydrolysis resistance of the biaxially stretched polyester film.
- -Criteria- A Half elongation at break exceeds 90 hr.
- ⁇ Half elongation at break exceeds 85 hr and is 90 hr or less.
- ⁇ Half elongation at break exceeds 80 hr and is 85 hr or less.
- X Half elongation at break is 80 hr or less.
- polyester film base materials polyester film base materials
- coating layer was formed by coating the coating solution by a bar coating method so that the dry thickness was 0.5 ⁇ m.
- the coating layer formed on the substrate was formed as follows. The following (i) reflective layer and (ii) easy-adhesion layer were coated in this order on one side of the substrate.
- the reflective layer-forming coating solution obtained above is applied to a sample film with a bar coater and dried at 180 ° C. for 1 minute to form a reflective layer (white layer) with a titanium dioxide coating amount of 6.5 g / m 2. did.
- the polyester film is provided with the following (iii) undercoat layer, (iv) barrier layer, and (v) antifouling layer on the side opposite to the side where the reflective layer and the easy-adhesion layer of the polyester film are formed. Coated sequentially from the side.
- Undercoat layer Various components having the following composition are mixed to prepare a coating solution for an undercoat layer, this coating solution is applied to a polyester film, dried at 180 ° C. for 1 minute, and an undercoat layer (dry coating amount: about 0.1 g / m 2 ) was formed.
- Polyester resin 1.7 parts (Vaironal MD-1200, manufactured by Toyobo Co., Ltd., solid content: 17% by mass) Polyester resin: 3.8 parts (Pesresin A-520, manufactured by Takamatsu Yushi Co., Ltd., solid content: 30% by mass) ⁇ Polyoxyalkylene alkyl ether: 1.5 parts (Naroacty CL95, manufactured by Sanyo Chemical Industries, solid content: 1% by mass) Carbodiimide compound: 1.3 parts (Carbodilite V-02-L2, manufactured by Nisshinbo Co., Ltd., solid content: 10% by mass) ⁇ Distilled water: 91.7 parts
- (V) Antifouling Layer As shown below, a coating solution for forming the first and second antifouling layers is prepared, and the first antifouling layer coating solution and the second antifouling layer are formed on the barrier layer. The coating solution was applied in the order, and a two-layer antifouling layer was applied.
- ⁇ First antifouling layer> -Preparation of coating solution for first antifouling layer- Components in the following composition were mixed to prepare a first antifouling layer coating solution.
- ⁇ Composition of coating solution> ⁇ Ceranate WSA1070 (manufactured by DIC Corporation) 45.9 parts ⁇ Oxazoline compound (crosslinking agent) 7.7 parts (Epocross WS-700, manufactured by Nippon Shokubai Co., Ltd., solid content: 25% by mass) ) Polyoxyalkylene alkyl ether 2.0 parts (Naroacty CL95, manufactured by Sanyo Chemical Industries, solid content: 1% by mass) -Pigment dispersion used in the reflective layer ... 33.0 parts distilled water ... 11.4 parts
- the obtained coating solution was coated on the barrier layer so that the binder coating amount was 3.0 g / m 2 and dried at 180 ° C. for 1 minute to form a first antifouling layer.
- composition of coating solution Fluorine-based binder: Obligard (manufactured by AGC Co-Tech Co., Ltd.) 45.9 parts Oxazoline compound 7.7 parts (Epocross WS-700, manufactured by Nippon Shokubai Co., Ltd., solid content: 25 mass) %: Crosslinker) Polyoxyalkylene alkyl ether 2.0 parts (Naroacty CL95, manufactured by Sanyo Chemical Industries, solid content: 1% by mass) -The pigment dispersion prepared for the reflective layer ... 33.0 parts-Distilled water ... 11.4 parts
- Second antifouling layer The prepared coating solution for the second antifouling layer was applied on the first antifouling layer formed on the barrier layer so that the binder coating amount was 2.0 g / m 2 , and the mixture was applied at 180 ° C. for 1 minute. A second antifouling layer was formed by drying.
- the adhesion between the substrate and the coating layer of the substrate (sample) on which the coating layer was formed was evaluated by the following method, and the results are shown in Table 1.
- the adhesion evaluation 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 to count the number of meshes from which the coating layer was peeled off, and this was taken as the “peeling rate”.
- the evaluation criteria are as follows.
- Peeling rate is less than 1%
- B Peeling rate is 1% or more and less than 5%
- B Peeling rate is 5% or more and less than 10%
- X Peeling rate is 10% or more
- the biaxially stretched polyester film of the example was excellent in both dimensional stability and hydrolysis resistance.
- the tenter can be prevented from being damaged by adjusting the stretching angle to satisfy 0 ⁇ x ⁇ ⁇ z ⁇ y ⁇ 10.
- the raw material polyester contains a polyfunctional monomer, or is end-capped together with the raw material polyester during melt extrusion. It turned out that it is excellent in the adhesiveness of a base material and an application layer by adding a stopper.
- Example 20 to 38 ⁇ Preparation of solar cell backsheet and solar cell power generation module>
- the biaxially stretched polyester ester films 1 to 19 of Examples 1 to 19 produced as described above were used as the solar cell back sheets 1 to 19, and the solar cell back sheets 1 to 19 were obtained. Further, using solar cell back sheets 1 to 19, the solar cell power generation modules 1 to 19 were bonded to a transparent filler (sealing material) so as to have the structure shown in FIG. 1 of JP-A-2009-158952. Produced. At this time, it stuck so that the easily-adhesive layer of a backsheet might contact the transparent filler which embeds a solar cell element.
- the solar cell backsheets 1 to 19 are produced using the biaxially stretched polyester ester films 1 to 19 of Examples 1 to 19 which are excellent in hydrolysis resistance and dimensional stability, they are resistant to hydrolysis. Excellent in stability and dimensional stability.
- the solar cell power generation modules 1 to 19 of Examples 20 to 38 are configured using the back sheets 1 to 19, power generation performance could be stably obtained over a long period of time.
- the disclosures of Japanese Patent Application 2010-282297, Japanese Patent Application 2011-163382 and Japanese Patent Application 2011-189992 are incorporated herein by reference. All documents, patent applications, and technical standards mentioned in this specification are to the same extent as if each individual document, patent application, and technical standard were specifically and individually described to be incorporated by reference, Incorporated herein by reference.
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Abstract
A method of manufacturing a polyester film comprises: a process for molding a polyester film with an intrinsic viscosity of 0.75 or more by melt extruding and cooling raw polyester; a longitudinal direction stretching process for stretching the polyester film in the longitudinal direction; and a transverse direction stretching process for stretching the polyester film at least in the transverse direction, by conveying the polyester film in the sequence of: a preheating unit for preheating the polyester film; a stretching unit for stretching the preheated polyester film in the transverse direction by applying tension to the film; a heat fixation part for heat fixing the tensed polyester film by heating the polyester film to the range 160°C to 210°C; and a heat relaxation unit for relaxing the tension of the heat fixed polyester film by heating the polyester film to the temperature at least 5°C lower than the temperature of the polyester film in the heat fixation unit.
Description
本発明は、ポリエステルフィルムおよびポリエステルフィルムの製造方法、太陽電池用バックシート、ならびに太陽電池モジュールに関する。
The present invention relates to a polyester film, a method for producing the polyester film, a solar cell backsheet, and a solar cell module.
ポリエステルは、電気絶縁用途や、光学用途等、種々の用途で用いられている。電気絶縁用途としては、近年、特に、太陽電池バックシート等の太陽電池用途が注目されている。
Polyester is used in various applications such as electrical insulation and optical applications. In recent years, solar cell applications such as solar cell backsheets have attracted attention as electrical insulation applications.
ところで、ポリエステルは、通常は、その表面にカルボキシ基や水酸基が多く存在しており、水分が存在する環境では加水分解を起こしやすく、経時で劣化する傾向がある。太陽電池モジュールが一般に用いられる環境は、屋外等の常に風雨に曝されるような環境であり、加水分解を起こし易い環境であるため、太陽電池用途においては、ポリエステルの加水分解抑制は重要な課題の一つである。
By the way, polyester usually has many carboxy groups and hydroxyl groups on its surface, and tends to be hydrolyzed in an environment where moisture exists, and tends to deteriorate over time. The 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 an environment that is prone to hydrolysis. Therefore, in solar cell applications, it is important to suppress hydrolysis of polyester. one of.
そのため、例えば、耐加水分解性にも優れたポリエステルを得るため、アルミニウム及びその化合物から選ばれる少なくとも1種を第1金属含有成分として含み、かつ化学式(化1)、(化2)で表されるリン化合物から選択される少なくとも1種を共存させることを特徴とするポリエステル重合触媒を用いて製造したポリエステルフィルムが開示されている(例えば、国際公開第2002/022707号参照)。
Therefore, for example, in order to obtain a polyester excellent in hydrolysis resistance, it contains at least one selected from aluminum and its compound as a first metal-containing component, and is represented by chemical formulas (Chemical Formula 1) and (Chemical Formula 2). A polyester film produced by using a polyester polymerization catalyst characterized by coexisting at least one selected from phosphorous compounds is disclosed (for example, see International Publication No. 2002/022707).
また、太陽電池用途に用いられるポリエステルフィルムは、熱収縮しにくい寸法安定性に優れたフィルムが求められており、例えば、ポリエステルフィルムの延伸処理後、延伸張力を緩めることで熱収縮率を小さくすることが知られている(例えば、特開2004-130594号公報および特開2001-212909号公報参照)。
In addition, polyester films used for solar cell applications are required to have a film with excellent dimensional stability that is difficult to thermally shrink. For example, after the polyester film is stretched, the stretching tension is relaxed to reduce the thermal shrinkage rate. It is known (see, for example, JP-A-2004-130594 and JP-A-2001-212909).
しかし、国際公開第2002/022707号、特開2004-130594号公報および特開2001-212909号公報に記載の方法では、耐加水分解性と寸法安定性とのいずれか一方のみを解決し得るに過ぎず、耐加水分解性と寸法安定性とを、同時に満足することができなかった。
However, the methods described in International Publication No. 2002/022707, JP-A-2004-130594, and JP-A-2001-212909 can solve only one of hydrolysis resistance and dimensional stability. However, hydrolysis resistance and dimensional stability could not be satisfied at the same time.
本発明は、耐加水分解性および寸法安定性に優れたポリエステルフィルムおよびポリエステルフィルムの製造方法、ならびに太陽電池用バックシートを提供すること、また、発電性能が長期間安定な太陽電池モジュールを提供することを目的とし、該目的を達成することを課題とする。
The present invention provides a polyester film excellent in hydrolysis resistance and dimensional stability, a method for producing the polyester film, a solar cell backsheet, and a solar cell module whose power generation performance is stable for a long period of time. It is an object to achieve this purpose.
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。
<1> 原料ポリエステルを溶融押出し、さらに冷却して、固有粘度が0.75以上のポリエステルフィルムを成形するフィルム成形工程と、
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、
前記ポリエステルフィルムを予熱する予熱部、予熱されたポリエステルフィルムを少なくとも前記ポリエステルフィルムの長手方向と直交する方向に緊張を与えて横延伸する延伸部、緊張が与えられたポリエステルフィルムを該ポリエステルフィルムの表面の最高到達膜面温度が160℃~210℃となるように加熱して熱固定する熱固定部、及び、前記ポリエステルフィルムの表面の最高到達膜面温度が、前記熱固定部における前記ポリエステルフィルムの最高到達膜面温度よりも5℃以上低い温度となるように、前記熱固定されたポリエステルフィルムを加熱し、前記緊張を緩める熱緩和部に、前記ポリエステルフィルムをこの順に搬送して、少なくとも横延伸する横延伸工程と、
を含むポリエステルフィルムの製造方法である。 Specific means for achieving the above object are as follows.
<1> A film forming step of melt-extruding the raw material polyester, further cooling, and forming a polyester film having an intrinsic viscosity of 0.75 or more,
A longitudinal stretching step of longitudinally stretching the polyester film in the longitudinal direction;
A preheating portion for preheating the polyester film; a stretching portion for stretching the preheated polyester film in a direction orthogonal to the longitudinal direction of the polyester film; A heat fixing part that is heat-set by heating so that the maximum film surface temperature of the polyester film is 160 ° C. to 210 ° C., and the highest film surface temperature of the surface of the polyester film is the temperature of the polyester film in the heat fixing part Heat the heat-fixed polyester film so that the temperature reaches 5 ° C. or more lower than the highest film surface temperature, and transport the polyester film in this order to a heat relaxation part that relaxes the tension, and at least laterally stretches. A transverse stretching step,
It is a manufacturing method of the polyester film containing this.
<1> 原料ポリエステルを溶融押出し、さらに冷却して、固有粘度が0.75以上のポリエステルフィルムを成形するフィルム成形工程と、
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、
前記ポリエステルフィルムを予熱する予熱部、予熱されたポリエステルフィルムを少なくとも前記ポリエステルフィルムの長手方向と直交する方向に緊張を与えて横延伸する延伸部、緊張が与えられたポリエステルフィルムを該ポリエステルフィルムの表面の最高到達膜面温度が160℃~210℃となるように加熱して熱固定する熱固定部、及び、前記ポリエステルフィルムの表面の最高到達膜面温度が、前記熱固定部における前記ポリエステルフィルムの最高到達膜面温度よりも5℃以上低い温度となるように、前記熱固定されたポリエステルフィルムを加熱し、前記緊張を緩める熱緩和部に、前記ポリエステルフィルムをこの順に搬送して、少なくとも横延伸する横延伸工程と、
を含むポリエステルフィルムの製造方法である。 Specific means for achieving the above object are as follows.
<1> A film forming step of melt-extruding the raw material polyester, further cooling, and forming a polyester film having an intrinsic viscosity of 0.75 or more,
A longitudinal stretching step of longitudinally stretching the polyester film in the longitudinal direction;
A preheating portion for preheating the polyester film; a stretching portion for stretching the preheated polyester film in a direction orthogonal to the longitudinal direction of the polyester film; A heat fixing part that is heat-set by heating so that the maximum film surface temperature of the polyester film is 160 ° C. to 210 ° C., and the highest film surface temperature of the surface of the polyester film is the temperature of the polyester film in the heat fixing part Heat the heat-fixed polyester film so that the temperature reaches 5 ° C. or more lower than the highest film surface temperature, and transport the polyester film in this order to a heat relaxation part that relaxes the tension, and at least laterally stretches. A transverse stretching step,
It is a manufacturing method of the polyester film containing this.
<2> 前記横延伸工程が、前記縦延伸工程の後に行なわれ、前記横延伸工程が、熱緩和部を経たポリエステルフィルムを冷却する冷却部に前記ポリエステルフィルムを搬送することを更に有し、
前記横延伸工程における前記ポリエステルフィルムの幅が最大になるときの前記ポリエステルフィルムの幅L1と、前記冷却部から前記ポリエステルフィルムが離れる前記冷却部の端部における前記ポリエステルフィルムの幅L2とが、下記式(1)を満たし、かつ、
前記予熱部における前記ポリエステルフィルムの搬送速度S1と、前記冷却部の前記端部における前記ポリエステルフィルムの搬送速度S2とが、下記式(2)を満たす前記<1>に記載のポリエステルフィルムの製造方法である。 <2> The transverse stretching step is performed after the longitudinal stretching step, and the transverse stretching step further includes transporting the polyester film to a cooling unit that cools the polyester film that has passed through the thermal relaxation portion.
The width L1 of the polyester film when the width of the polyester film in the transverse stretching step is maximized, and the width L2 of the polyester film at the end of the cooling part where the polyester film is separated from the cooling part are as follows. Satisfies formula (1), and
The polyester film production method according to <1>, wherein the polyester film conveyance speed S1 in the preheating section and the polyester film conveyance speed S2 in the end of the cooling section satisfy the following formula (2). It is.
前記横延伸工程における前記ポリエステルフィルムの幅が最大になるときの前記ポリエステルフィルムの幅L1と、前記冷却部から前記ポリエステルフィルムが離れる前記冷却部の端部における前記ポリエステルフィルムの幅L2とが、下記式(1)を満たし、かつ、
前記予熱部における前記ポリエステルフィルムの搬送速度S1と、前記冷却部の前記端部における前記ポリエステルフィルムの搬送速度S2とが、下記式(2)を満たす前記<1>に記載のポリエステルフィルムの製造方法である。 <2> The transverse stretching step is performed after the longitudinal stretching step, and the transverse stretching step further includes transporting the polyester film to a cooling unit that cools the polyester film that has passed through the thermal relaxation portion.
The width L1 of the polyester film when the width of the polyester film in the transverse stretching step is maximized, and the width L2 of the polyester film at the end of the cooling part where the polyester film is separated from the cooling part are as follows. Satisfies formula (1), and
The polyester film production method according to <1>, wherein the polyester film conveyance speed S1 in the preheating section and the polyester film conveyance speed S2 in the end of the cooling section satisfy the following formula (2). It is.
<3> 前記延伸部は、搬送される前記ポリエステルフィルムの搬送方向と、該ポリエステルフィルムの幅方向端部の進行方向とがなす角度を延伸角度θ〔°〕とするとき、前記延伸部における前記ポリエステルフィルムの横延伸を開始する位置Xでの延伸角度θx〔°〕と、前記延伸部における前記ポリエステルフィルムの横延伸を終了する位置Zでの延伸角度θz〔°〕と、前記延伸部における前記位置Xと前記位置Zとの中間の位置Yでの延伸角度θy〔°〕とが、下記式(3)を満たし、横延伸終了後の厚みが200μm以上のポリエステルフィルムを得る前記<1>または前記<2>に記載のポリエステルフィルムの製造方法である。
0<θx≦θz<θy<10 (3) <3> The stretching portion has the stretching angle θ [°] as an angle formed by the transport direction of the polyester film to be transported and the traveling direction of the width direction end of the polyester film. The stretching angle θx [°] at the position X at which the lateral stretching of the polyester film is started, the stretching angle θz [°] at the position Z at which the lateral stretching of the polyester film in the stretched part is terminated, and the above-mentioned in the stretched part <1> or above, wherein the stretching angle θy [°] at a position Y intermediate between the position X and the position Z satisfies the following formula (3), and a polyester film having a thickness of 200 μm or more after the transverse stretching is completed: It is a manufacturing method of the polyester film as described in said <2>.
0 <θx ≦ θz <θy <10 (3)
0<θx≦θz<θy<10 (3) <3> The stretching portion has the stretching angle θ [°] as an angle formed by the transport direction of the polyester film to be transported and the traveling direction of the width direction end of the polyester film. The stretching angle θx [°] at the position X at which the lateral stretching of the polyester film is started, the stretching angle θz [°] at the position Z at which the lateral stretching of the polyester film in the stretched part is terminated, and the above-mentioned in the stretched part <1> or above, wherein the stretching angle θy [°] at a position Y intermediate between the position X and the position Z satisfies the following formula (3), and a polyester film having a thickness of 200 μm or more after the transverse stretching is completed: It is a manufacturing method of the polyester film as described in said <2>.
0 <θx ≦ θz <θy <10 (3)
<4> 前記横延伸工程は、前記予熱部、前記延伸部、前記熱固定部、前記熱緩和部、及び前記冷却部を備え、前記予熱部において前記ポリエステルフィルムの幅方向の両端部を、片端部につき、少なくとも2つの把持部材を用いて把持して、前記予熱部から前記冷却部まで前記ポリエステルフィルムを搬送する2軸延伸装置を用い、
前記予熱部における前記ポリエステルフィルムの幅方向の片端部を把持する前記2つの把持部材のうちの一方の把持部材と、該把持部材に隣接する他方の把持部材との間隔よりも、前記冷却部における前記ポリエステルフィルムの幅方向の片端部を把持する前記2つの把持部材のうちの一方の把持部材と、該把持部材に隣接する他方の把持部材との間隔を狭めることで、前記ポリエステルフィルムの搬送速度を小さくする前記<2>または前記<3>に記載のポリエステルフィルムの製造方法である。 <4> The transverse stretching step includes the preheating portion, the stretching portion, the heat fixing portion, the heat relaxation portion, and the cooling portion, and both end portions in the width direction of the polyester film are arranged at one end in the preheating portion. For each part, using a biaxial stretching device that grips using at least two gripping members and transports the polyester film from the preheating unit to the cooling unit,
More than the interval between one gripping member of the two gripping members that grips one end of the polyester film in the width direction in the preheating portion and the other gripping member adjacent to the gripping member, in the cooling unit. The conveyance speed of the polyester film is reduced by narrowing the interval between one gripping member of the two gripping members gripping one end in the width direction of the polyester film and the other gripping member adjacent to the gripping member. It is a manufacturing method of the polyester film as described in said <2> or said <3> which makes small.
前記予熱部における前記ポリエステルフィルムの幅方向の片端部を把持する前記2つの把持部材のうちの一方の把持部材と、該把持部材に隣接する他方の把持部材との間隔よりも、前記冷却部における前記ポリエステルフィルムの幅方向の片端部を把持する前記2つの把持部材のうちの一方の把持部材と、該把持部材に隣接する他方の把持部材との間隔を狭めることで、前記ポリエステルフィルムの搬送速度を小さくする前記<2>または前記<3>に記載のポリエステルフィルムの製造方法である。 <4> The transverse stretching step includes the preheating portion, the stretching portion, the heat fixing portion, the heat relaxation portion, and the cooling portion, and both end portions in the width direction of the polyester film are arranged at one end in the preheating portion. For each part, using a biaxial stretching device that grips using at least two gripping members and transports the polyester film from the preheating unit to the cooling unit,
More than the interval between one gripping member of the two gripping members that grips one end of the polyester film in the width direction in the preheating portion and the other gripping member adjacent to the gripping member, in the cooling unit. The conveyance speed of the polyester film is reduced by narrowing the interval between one gripping member of the two gripping members gripping one end in the width direction of the polyester film and the other gripping member adjacent to the gripping member. It is a manufacturing method of the polyester film as described in said <2> or said <3> which makes small.
<5> 前記熱固定部、前記熱緩和部、及び前記冷却部の少なくとも一部において、前記ポリエステルフィルムの幅方向の片端部を把持する前記2つの把持部材のうちの一方の把持部材と、該把持部材に隣接する他方の把持部材との間隔を狭める前記<4>に記載のポリエステルフィルムの製造方法である。
<5> At least a part of the heat fixing part, the heat relaxation part, and the cooling part, one gripping member of the two gripping members gripping one end part in the width direction of the polyester film, It is a manufacturing method of the polyester film as described in said <4> which narrows the space | interval with the other holding member adjacent to a holding member.
<6> 前記原料ポリエステルは、固相重合処理されている前記<1>~前記<5のいずれか1つに記載のポリエステルフィルムの製造方法である。
<6> The method for producing a polyester film according to any one of <1> to <5>, wherein the raw material polyester is subjected to solid phase polymerization.
<7> 前記縦延伸工程および前記横延伸工程を経て得られたポリエステルフィルムは、30分間150℃で加熱する加熱条件における熱収縮率が2.0%以下である前記<1>~前記<6>のいずれか1つに記載のポリエステルフィルムの製造方法である。
<7> The polyester film obtained through the longitudinal stretching step and the transverse stretching step has a thermal shrinkage rate of 2.0% or less under heating conditions of heating at 150 ° C. for 30 minutes, <1> to <6 It is a manufacturing method of the polyester film as described in any one of>.
<8> 前記原料ポリエステルが、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含む前記<1>~前記<7>のいずれか1つに記載のポリエステルフィルムの製造方法である。
<8> The polyester film according to any one of <1> to <7>, wherein the raw material polyester includes a polyfunctional monomer in which the total of the number of carboxylic acid groups and the number of hydroxyl groups is 3 or more. It is a manufacturing method.
<9> 前記多官能モノマーの含有量は、前記原料ポリエステルの全モル量に対して、0.005モル%以上2.5モル%以下である前記<8>に記載のポリエステルフィルムの製造方法である。
<9> The method for producing a polyester film according to <8>, wherein the content of the polyfunctional monomer is 0.005 mol% to 2.5 mol% with respect to the total molar amount of the raw material polyester. is there.
<10> 前記フィルム成形工程は、前記原料ポリエステルと共に、オキサゾリン系化合物、カルボジイミド化合物、又はエポキシ化合物の少なくとも1種類の末端封止剤を添加して溶融押出する工程を含む前記<1>~前記<9>のいずれか1つに記載のポリエステルフィルムの製造方法である。
<10> The film forming step includes a step of adding and melt-extruding at least one kind of end-capping agent of an oxazoline compound, a carbodiimide compound, or an epoxy compound together with the raw material polyester <1> to < 9> The manufacturing method of the polyester film as described in any one of 9>.
<11> 前記末端封止剤の添加量は、前記原料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<10>に記載のポリエステルフィルムの製造方法である。
<11> The method for producing a polyester film according to <10>, wherein the addition amount 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 raw material polyester.
<12> 前記<1>~前記<11>のいずれか1つに記載のポリエステルフィルムの製造方法により得られたポリエステルフィルムである。
<12> A polyester film obtained by the method for producing a polyester film according to any one of <1> to <11>.
<13> 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前記<12>に記載のポリエステルフィルムである。
<13> The polyester film according to <12>, including a structural unit derived from a polyfunctional monomer having a total number of carboxylic acid groups and hydroxyl groups of 3 or more.
<14> 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<13>に記載のポリエステルフィルムである。
<14> The polyester film according to <13>, wherein the content ratio of the structural unit derived from the polyfunctional monomer is 0.005 mol% to 2.5 mol% with respect to all the structural units in the polyester. It is.
<15> オキサゾリン系化合物、カルボジイミド化合物、又はエポキシ化合物の少なくとも1種類の末端封止剤に由来する構造部分を含む前記<1>~前記<14>のいずれか1つに記載のポリエステルフィルムである。
<15> The polyester film according to any one of <1> to <14>, wherein the polyester film includes a structural portion derived from at least one end-capping agent of an oxazoline compound, a carbodiimide compound, or an epoxy compound. .
<16> 前記末端封止剤に由来する構造部分を0.1質量%以上5質量%以下含む前記<15>に記載のポリエステルフィルムである。
<16> The polyester film according to <15>, wherein the structural portion derived from the terminal blocking agent includes 0.1% by mass or more and 5% by mass or less.
<17> 前記<12>~前記<16>のいずれか1つに記載のポリエステルフィルムを含む太陽電池用バックシートである。
<17> A solar cell backsheet comprising the polyester film according to any one of <12> to <16>.
<18> 太陽光が入射する透明性のフロント基板と、
前記フロント基板の上に設けられ、太陽電池素子及び前記太陽電池素子を封止する封止材を有するセル構造部分と、
前記セル構造部分の前記フロント基板が位置する側と反対側に設けられ、前記封止材と隣接して配置された、前記<17>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。 <18> a transparent front substrate on which sunlight is incident;
A cell structure portion provided on the front substrate and having a solar cell element and a sealing material for sealing the solar cell element;
The solar cell backsheet according to <17>, provided on the opposite side of the cell structure portion from the side on which the front substrate is located and disposed adjacent to the sealing material,
It is a solar cell module provided with.
前記フロント基板の上に設けられ、太陽電池素子及び前記太陽電池素子を封止する封止材を有するセル構造部分と、
前記セル構造部分の前記フロント基板が位置する側と反対側に設けられ、前記封止材と隣接して配置された、前記<17>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。 <18> a transparent front substrate on which sunlight is incident;
A cell structure portion provided on the front substrate and having a solar cell element and a sealing material for sealing the solar cell element;
The solar cell backsheet according to <17>, provided on the opposite side of the cell structure portion from the side on which the front substrate is located and disposed adjacent to the sealing material,
It is a solar cell module provided with.
本発明によれば、耐加水分解性および寸法安定性に優れたポリエステルフィルムおよびポリエステルフィルムの製造方法、ならびに太陽電池用バックシートを提供することができる。また、発電性能が長期間安定な太陽電池モジュールを提供することができる
According to the present invention, it is possible to provide a polyester film excellent in hydrolysis resistance and dimensional stability, a method for producing the polyester film, and a solar cell backsheet. In addition, it is possible to provide a solar cell module whose power generation performance is stable for a long time.
<ポリエステルフィルムの製造方法>
本発明のポリエステルフィルムの製造方法は、原料ポリエステルを溶融押出し、さらに冷却して、固有粘度が0.75以上のポリエステルフィルムを成形するフィルム成形工程と、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、前記ポリエステルフィルムを予熱する予熱部、予熱されたポリエステルフィルムを少なくとも前記ポリエステルフィルムの長手方向と直交する方向に緊張を与えて横延伸する延伸部、緊張が与えられたポリエステルフィルムを該ポリエステルフィルムの表面の最高到達膜面温度が160℃~210℃となるように加熱して熱固定する熱固定部、及び、前記ポリエステルフィルムの表面の最高到達膜面温度が、前記熱固定部における前記ポリエステルフィルムの最高到達膜面温度よりも5℃以上低い温度となるように、前記熱固定されたポリエステルフィルムを加熱し、前記緊張を緩める熱緩和部に、前記ポリエステルフィルムをこの順に搬送して、少なくとも横延伸する横延伸工程と、を含む構成としたものである。 <Production method of polyester film>
The method for producing a polyester film of the present invention includes a film forming step of melt-extruding a raw material polyester and further cooling to form a polyester film having an intrinsic viscosity of 0.75 or more, and a longitudinal direction in which the polyester film is longitudinally stretched in the longitudinal direction A stretching step, a preheating portion for preheating the polyester film, a stretching portion for laterally stretching the preheated polyester film by applying tension in a direction perpendicular to the longitudinal direction of the polyester film, and a polyester film subjected to tension. A heat fixing part that heat-fixes the polyester film surface so that the maximum film surface temperature on the surface of the polyester film is 160 ° C. to 210 ° C., and the maximum film surface temperature of the surface of the polyester film is 5 ° C or more lower than the highest film surface temperature of the polyester film A heat-stretching part that heats the heat-fixed polyester film so as to be at a temperature and transports the polyester film in this order to a heat-relaxing part that relaxes the tension, and at least a transverse stretching step that transversely stretches. Is.
本発明のポリエステルフィルムの製造方法は、原料ポリエステルを溶融押出し、さらに冷却して、固有粘度が0.75以上のポリエステルフィルムを成形するフィルム成形工程と、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、前記ポリエステルフィルムを予熱する予熱部、予熱されたポリエステルフィルムを少なくとも前記ポリエステルフィルムの長手方向と直交する方向に緊張を与えて横延伸する延伸部、緊張が与えられたポリエステルフィルムを該ポリエステルフィルムの表面の最高到達膜面温度が160℃~210℃となるように加熱して熱固定する熱固定部、及び、前記ポリエステルフィルムの表面の最高到達膜面温度が、前記熱固定部における前記ポリエステルフィルムの最高到達膜面温度よりも5℃以上低い温度となるように、前記熱固定されたポリエステルフィルムを加熱し、前記緊張を緩める熱緩和部に、前記ポリエステルフィルムをこの順に搬送して、少なくとも横延伸する横延伸工程と、を含む構成としたものである。 <Production method of polyester film>
The method for producing a polyester film of the present invention includes a film forming step of melt-extruding a raw material polyester and further cooling to form a polyester film having an intrinsic viscosity of 0.75 or more, and a longitudinal direction in which the polyester film is longitudinally stretched in the longitudinal direction A stretching step, a preheating portion for preheating the polyester film, a stretching portion for laterally stretching the preheated polyester film by applying tension in a direction perpendicular to the longitudinal direction of the polyester film, and a polyester film subjected to tension. A heat fixing part that heat-fixes the polyester film surface so that the maximum film surface temperature on the surface of the polyester film is 160 ° C. to 210 ° C., and the maximum film surface temperature of the surface of the polyester film is 5 ° C or more lower than the highest film surface temperature of the polyester film A heat-stretching part that heats the heat-fixed polyester film so as to be at a temperature and transports the polyester film in this order to a heat-relaxing part that relaxes the tension, and at least a transverse stretching step that transversely stretches. Is.
本発明では、原料ポリエステルを溶融押出して固有粘度が0.75以上のポリエステルフィルムを成形するとともに、得られたポリエステルフィルムについて、上記構成の縦延伸工程と横延伸工程とを経ることで、耐加水分解性および寸法安定性の両方に優れたポリエステルフィルムを製造することができる。
本発明のポリエステルの製造方法により耐加水分解性と寸法安定性を同時に達成することができる理由は明らかではないが、次の理由によるものと推察される。 In the present invention, a raw material polyester is melt-extruded to form a polyester film having an intrinsic viscosity of 0.75 or more, and the obtained polyester film is subjected to water resistance by passing through the longitudinal stretching step and the lateral stretching step having the above-described configuration. A polyester film excellent in both degradability and dimensional stability can be produced.
The reason why hydrolysis resistance and dimensional stability can be simultaneously achieved by the method for producing a polyester of the present invention is not clear, but is presumed to be as follows.
本発明のポリエステルの製造方法により耐加水分解性と寸法安定性を同時に達成することができる理由は明らかではないが、次の理由によるものと推察される。 In the present invention, a raw material polyester is melt-extruded to form a polyester film having an intrinsic viscosity of 0.75 or more, and the obtained polyester film is subjected to water resistance by passing through the longitudinal stretching step and the lateral stretching step having the above-described configuration. A polyester film excellent in both degradability and dimensional stability can be produced.
The reason why hydrolysis resistance and dimensional stability can be simultaneously achieved by the method for producing a polyester of the present invention is not clear, but is presumed to be as follows.
本発明者は、ポリエステルフィルム(以下、単に「フィルム」とも称する)の耐加水分解性は、フィルムに緊張を与え、ポリエステル分子を、分子の長さ方向に伸びた状態にすると良いことを見出した。一方、フィルムの寸法安定性は、ポリエステル分子同士の分子鎖間の間隔が縮まっていると良いことも見出した。これは、ポリエステル分子同士の分子鎖間の間隔が空いていると、分子間相互作用により分子鎖間が縮まるため、フィルムの寸法安定性が悪くなる(熱収縮率が大きくなる)ものと考えられる。
従って、ポリエステルフィルムの耐加水分解性と寸法安定性とを両立するには、例えば、フィルムに緊張を与え、ポリエステル分子の分子鎖間の距離は縮めないようにすることが考えられる。 The present inventor has found that the hydrolysis resistance of a polyester film (hereinafter also simply referred to as “film”) is good if tension is applied to the film and the polyester molecules are stretched in the length direction of the molecules. . On the other hand, it has also been found that the dimensional stability of the film is good if the distance between the molecular chains of the polyester molecules is reduced. This is thought to be because when the distance between the molecular chains of the polyester molecules is large, the molecular chains are contracted by the intermolecular interaction, so that the dimensional stability of the film is deteriorated (the thermal shrinkage rate is increased). .
Therefore, in order to achieve both the hydrolysis resistance and dimensional stability of the polyester film, for example, it is conceivable to apply tension to the film so that the distance between the molecular chains of the polyester molecules is not shortened.
従って、ポリエステルフィルムの耐加水分解性と寸法安定性とを両立するには、例えば、フィルムに緊張を与え、ポリエステル分子の分子鎖間の距離は縮めないようにすることが考えられる。 The present inventor has found that the hydrolysis resistance of a polyester film (hereinafter also simply referred to as “film”) is good if tension is applied to the film and the polyester molecules are stretched in the length direction of the molecules. . On the other hand, it has also been found that the dimensional stability of the film is good if the distance between the molecular chains of the polyester molecules is reduced. This is thought to be because when the distance between the molecular chains of the polyester molecules is large, the molecular chains are contracted by the intermolecular interaction, so that the dimensional stability of the film is deteriorated (the thermal shrinkage rate is increased). .
Therefore, in order to achieve both the hydrolysis resistance and dimensional stability of the polyester film, for example, it is conceivable to apply tension to the film so that the distance between the molecular chains of the polyester molecules is not shortened.
ここで、フィルムの延伸は、詳細は後述するが、一般に、ロールやクリップ等を備えた装置を用いて、フィルムを搬送すると共に、フィルムの搬送方向の延伸(縦延伸)および搬送方向と直交する方向の延伸(横延伸)を行なう。フィルムの横延伸を行なう工程では、フィルムを、延伸に備えフィルムを予め加熱する予熱部と、フィルムを延伸するためにフィルムに緊張を与える延伸部と、フィルムに緊張を与えたまま加熱する熱固定部と、フィルムの緊張を緩める熱緩和部と、に順次搬送して延伸する。
Here, the stretching of the film will be described in detail later, but in general, the film is transported using an apparatus equipped with a roll, a clip and the like, and the film is stretched in the transport direction (longitudinal stretching) and orthogonal to the transport direction. Stretching in the direction (transverse stretching) is performed. In the process of transverse stretching of the film, the film is pre-heated for pre-heating the film in preparation for stretching, a stretching section for tensioning the film to stretch the film, and heat setting for heating the film while tension is applied. The film is successively conveyed and stretched to the part and the heat relaxation part for relaxing the tension of the film.
横延伸の工程においては、延伸部でのフィルムの延伸によりフィルムに緊張が与えられるため、ポリエステル分子が伸びて、フィルムの耐加水分解性が向上する。一方で、フィルムの寸法安定性は悪く(熱収縮率が大きく)なる。これは、フィルムの延伸により、ポリエステル分子同士の分子鎖間も大きくなるためであると考えられる。
延伸部での延伸後に、熱緩和部でフィルムへの緊張を解くことで、フィルムの寸法安定性を向上することができる。フィルムが縮み、ポリエステル分子同士の分子鎖間が狭まるためと考えられる。一方で、フィルムへの緊張を解くことにより、耐加水分解性は悪くなる。これは、分子の長さ方向に伸びていたポリエステル分子が縮まるためと考えられる。
従って、従来の横延伸工程では、耐加水分解性と、寸法安定性との両立を図ることが困難であった。 In the transverse stretching step, tension is given to the film by stretching the film at the stretched portion, so that the polyester molecules are stretched and the hydrolysis resistance of the film is improved. On the other hand, the dimensional stability of the film is poor (heat shrinkage rate is large). This is presumably because the molecular chain between the polyester molecules becomes larger due to the stretching of the film.
After stretching in the stretching section, the dimensional stability of the film can be improved by releasing the tension on the film in the heat relaxation section. This is probably because the film shrinks and the molecular chain between the polyester molecules narrows. On the other hand, hydrolysis resistance deteriorates by releasing tension on the film. This is presumably because the polyester molecules that have been stretched in the length direction of the molecules shrink.
Therefore, in the conventional transverse stretching process, it has been difficult to achieve both hydrolysis resistance and dimensional stability.
延伸部での延伸後に、熱緩和部でフィルムへの緊張を解くことで、フィルムの寸法安定性を向上することができる。フィルムが縮み、ポリエステル分子同士の分子鎖間が狭まるためと考えられる。一方で、フィルムへの緊張を解くことにより、耐加水分解性は悪くなる。これは、分子の長さ方向に伸びていたポリエステル分子が縮まるためと考えられる。
従って、従来の横延伸工程では、耐加水分解性と、寸法安定性との両立を図ることが困難であった。 In the transverse stretching step, tension is given to the film by stretching the film at the stretched portion, so that the polyester molecules are stretched and the hydrolysis resistance of the film is improved. On the other hand, the dimensional stability of the film is poor (heat shrinkage rate is large). This is presumably because the molecular chain between the polyester molecules becomes larger due to the stretching of the film.
After stretching in the stretching section, the dimensional stability of the film can be improved by releasing the tension on the film in the heat relaxation section. This is probably because the film shrinks and the molecular chain between the polyester molecules narrows. On the other hand, hydrolysis resistance deteriorates by releasing tension on the film. This is presumably because the polyester molecules that have been stretched in the length direction of the molecules shrink.
Therefore, in the conventional transverse stretching process, it has been difficult to achieve both hydrolysis resistance and dimensional stability.
しかし、本発明のポリエステルフィルムの製造方法においては、まず、第一に、原料ポリエステルを溶融押出することにより得た固有粘度が0.75以上のポリエステルフィルムを延伸とする。
ポリエステルの固有粘度が大きいほど、ポリエステル分子は大きくなり、ポリエステル分子の動きも鈍くなると考えられる。従って、延伸部においてフィルムに緊張を与えることにより分子の長さ方向に伸びたポリエステル分子は、フィルムの緊張が解かれても、分子の動きが鈍いために縮まり難いと考えられる。そのため、固有粘度が0.75以上のポリエステルフィルムを延伸した後に、緊張を解いて緩和しても耐加水分解性が低下しないと考えられる。
一方、ポリエステル分子同士の分子鎖間の距離は、ポリエステル分子自体の動きにはあまり影響なく、フィルムへの緊張を解くことで寸法安定性を向上し得ることが分かった。 However, in the method for producing a polyester film of the present invention, first, a polyester film having an intrinsic viscosity of 0.75 or more obtained by melt-extruding a raw material polyester is drawn.
It is considered that the greater the intrinsic viscosity of the polyester, the larger the polyester molecule and the slower the movement of the polyester molecule. Therefore, it is considered that the polyester molecules stretched in the length direction of the molecule by applying tension to the film in the stretched portion are difficult to shrink because the movement of the molecule is slow even when the tension of the film is released. Therefore, it is considered that the hydrolysis resistance does not decrease even if the tension is released and relaxed after stretching a polyester film having an intrinsic viscosity of 0.75 or more.
On the other hand, it has been found that the distance between the molecular chains of the polyester molecules does not significantly affect the movement of the polyester molecules themselves, and the dimensional stability can be improved by releasing the tension on the film.
ポリエステルの固有粘度が大きいほど、ポリエステル分子は大きくなり、ポリエステル分子の動きも鈍くなると考えられる。従って、延伸部においてフィルムに緊張を与えることにより分子の長さ方向に伸びたポリエステル分子は、フィルムの緊張が解かれても、分子の動きが鈍いために縮まり難いと考えられる。そのため、固有粘度が0.75以上のポリエステルフィルムを延伸した後に、緊張を解いて緩和しても耐加水分解性が低下しないと考えられる。
一方、ポリエステル分子同士の分子鎖間の距離は、ポリエステル分子自体の動きにはあまり影響なく、フィルムへの緊張を解くことで寸法安定性を向上し得ることが分かった。 However, in the method for producing a polyester film of the present invention, first, a polyester film having an intrinsic viscosity of 0.75 or more obtained by melt-extruding a raw material polyester is drawn.
It is considered that the greater the intrinsic viscosity of the polyester, the larger the polyester molecule and the slower the movement of the polyester molecule. Therefore, it is considered that the polyester molecules stretched in the length direction of the molecule by applying tension to the film in the stretched portion are difficult to shrink because the movement of the molecule is slow even when the tension of the film is released. Therefore, it is considered that the hydrolysis resistance does not decrease even if the tension is released and relaxed after stretching a polyester film having an intrinsic viscosity of 0.75 or more.
On the other hand, it has been found that the distance between the molecular chains of the polyester molecules does not significantly affect the movement of the polyester molecules themselves, and the dimensional stability can be improved by releasing the tension on the film.
本発明では、緊張が与えられたフィルムを、フィルムの表面の最高到達膜面温度が160℃~210℃となるように加熱して熱固定する。すなわち、フィルムに緊張を与えたまま、160℃~210℃で加熱しておくことで、ポリエステル分子を縮ませることなく結晶化させ、ポリエステル分子を伸びた状態である程度固定化することができ、フィルムの耐加水分解性を向上することができる。さらに、熱固定後に、フィルムの表面の最高到達膜面温度が、熱固定部におけるフィルムの最高到達膜面温度よりも5℃以上低い温度となるように、熱固定したフィルムを加熱して、フィルムの前記緊張を緩めることで、ポリエステル分子を縮ませることなくポリエステル分子同士の分子鎖間を狭めることができ、フィルムの寸法安定性を向上することができると考えられる。
以下、本発明のポリエステルフィルムの製造方法の詳細を、フィルム成形工程、原料ポリエステル、縦延伸工程、および、横延伸工程の各項目に分けて説明する。 In the present invention, the tensioned film is heat-set by heating so that the maximum surface temperature of the film surface reaches 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. Further, after the heat setting, the heat-fixed film is heated so that the maximum film surface temperature on the surface of the film is 5 ° C. or lower than the maximum film surface temperature of the film in the heat fixing part. It is considered that by relaxing the tension, the molecular chain between the polyester molecules can be narrowed without shrinking the polyester molecules, and the dimensional stability of the film can be improved.
Hereafter, the detail of the manufacturing method of the polyester film of this invention is divided and demonstrated to each item of a film formation process, raw material polyester, a longitudinal stretch process, and a horizontal stretch process.
以下、本発明のポリエステルフィルムの製造方法の詳細を、フィルム成形工程、原料ポリエステル、縦延伸工程、および、横延伸工程の各項目に分けて説明する。 In the present invention, the tensioned film is heat-set by heating so that the maximum surface temperature of the film surface reaches 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. Further, after the heat setting, the heat-fixed film is heated so that the maximum film surface temperature on the surface of the film is 5 ° C. or lower than the maximum film surface temperature of the film in the heat fixing part. It is considered that by relaxing the tension, the molecular chain between the polyester molecules can be narrowed without shrinking the polyester molecules, and the dimensional stability of the film can be improved.
Hereafter, the detail of the manufacturing method of the polyester film of this invention is divided and demonstrated to each item of a film formation process, raw material polyester, a longitudinal stretch process, and a horizontal stretch process.
〔フィルム成形工程〕
フィルム成形工程は、原料ポリエステルを溶融押出し、さらに冷却して、固有粘度が0.75以上のポリエステルフィルムを成形する工程である。
また、フィルム成形工程は、原料ポリエステルに対して、オキサゾリン系化合物、カルボジイミド化合物、又はエポキシ化合物の少なくとも1種類の末端封止剤を添加して溶融押出する工程を含むことが好ましい。末端封止剤の詳細は後述する。
原料ポリエステルを溶融押出する方法、及び原料ポリエステルは、原料ポリエステルを溶融押出し、さらに冷却して得られるポリエステルフィルムの固有粘度が0.75以上となる方法ないしポリエステルであれば特に限定されないが、原料ポリエステルの合成に用いる触媒や、重合方法等により固有粘度を所望の固有粘度とすることができる。
まず、原料ポリエステルについて説明する。 [Film forming process]
The film forming step is a step in which a raw material polyester is melt-extruded and further cooled to form a polyester film having an intrinsic viscosity of 0.75 or more.
Moreover, it is preferable that a film formation process includes the process of adding and melt-extruding at least 1 type of terminal blocker of an oxazoline type compound, a carbodiimide compound, or an epoxy compound with respect to raw material polyester. Details of the end sealant will be described later.
The method of melt-extruding the raw material polyester, and the raw material polyester is not particularly limited as long as it is a method or polyester in which the intrinsic viscosity of the polyester film obtained by melt-extruding the raw material polyester and further cooling is 0.75 or more. The intrinsic viscosity can be set to a desired intrinsic viscosity by a catalyst used in the synthesis of the polymer, a polymerization method, or the like.
First, raw material polyester is demonstrated.
フィルム成形工程は、原料ポリエステルを溶融押出し、さらに冷却して、固有粘度が0.75以上のポリエステルフィルムを成形する工程である。
また、フィルム成形工程は、原料ポリエステルに対して、オキサゾリン系化合物、カルボジイミド化合物、又はエポキシ化合物の少なくとも1種類の末端封止剤を添加して溶融押出する工程を含むことが好ましい。末端封止剤の詳細は後述する。
原料ポリエステルを溶融押出する方法、及び原料ポリエステルは、原料ポリエステルを溶融押出し、さらに冷却して得られるポリエステルフィルムの固有粘度が0.75以上となる方法ないしポリエステルであれば特に限定されないが、原料ポリエステルの合成に用いる触媒や、重合方法等により固有粘度を所望の固有粘度とすることができる。
まず、原料ポリエステルについて説明する。 [Film forming process]
The film forming step is a step in which a raw material polyester is melt-extruded and further cooled to form a polyester film having an intrinsic viscosity of 0.75 or more.
Moreover, it is preferable that a film formation process includes the process of adding and melt-extruding at least 1 type of terminal blocker of an oxazoline type compound, a carbodiimide compound, or an epoxy compound with respect to raw material polyester. Details of the end sealant will be described later.
The method of melt-extruding the raw material polyester, and the raw material polyester is not particularly limited as long as it is a method or polyester in which the intrinsic viscosity of the polyester film obtained by melt-extruding the raw material polyester and further cooling is 0.75 or more. The intrinsic viscosity can be set to a desired intrinsic viscosity by a catalyst used in the synthesis of the polymer, a polymerization method, or the like.
First, raw material polyester is demonstrated.
(原料ポリエステル)
原料ポリエステルは、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、原料ポリエステルは、触媒由来のチタン元素を含んでいてもよい。
原料ポリエステルに含まれるポリエステルの種類は特に制限されない。
多価カルボン酸(例えば、ジカルボン酸)成分と、多価アルコール(例えば、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。 (Raw material polyester)
The raw material polyester 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. The raw material polyester may contain a titanium element derived from the catalyst.
The kind of polyester contained in the raw material polyester is not particularly limited.
You may synthesize | combine using a polyhydric carboxylic acid (for example, dicarboxylic acid) component and a polyhydric alcohol (for example, diol) component, and you may use commercially available polyester.
原料ポリエステルは、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、原料ポリエステルは、触媒由来のチタン元素を含んでいてもよい。
原料ポリエステルに含まれるポリエステルの種類は特に制限されない。
多価カルボン酸(例えば、ジカルボン酸)成分と、多価アルコール(例えば、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。 (Raw material polyester)
The raw material polyester 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. The raw material polyester may contain a titanium element derived from the catalyst.
The kind of polyester contained in the raw material polyester is not particularly limited.
You may synthesize | combine using a polyhydric carboxylic acid (for example, dicarboxylic acid) component and a polyhydric alcohol (for example, diol) component, and you may use commercially available polyester.
ポリエステルを合成する場合は、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る。
(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、フェニルエ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。 When the polyester is 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 known method.
(A) Examples of the dicarboxylic acid component 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′-diphenyl ether dicarboxylic acid, 5-sodium sulfo Isophthalic acid, phenyl ether Boy carboxylic acid, anthracene dicarboxylic acid, phenanthrene carboxylic acid, 9,9'-bis (4-carboxyphenyl) a dicarboxylic acid or its ester derivatives such as aromatic dicarboxylic acids such as fluorene acid.
(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、フェニルエ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。 When the polyester is 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 known method.
(A) Examples of the dicarboxylic acid component 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′-diphenyl ether dicarboxylic acid, 5-sodium sulfo Isophthalic acid, phenyl ether Boy carboxylic acid, anthracene dicarboxylic acid, phenanthrene carboxylic acid, 9,9'-bis (4-carboxyphenyl) a dicarboxylic acid or its ester derivatives such as aromatic dicarboxylic acids such as fluorene acid.
(B)ジオール成分としては、例えば、エチレングリコール、1,2-プロパンジオール、1,3-プロパンジオール、1,4-ブタンジオール、1,2-ブタンジオール、1,3-ブタンジオール等の脂肪族ジオール類、シクロヘキサンジメタノール、スピログリコール、イソソルビドなどの脂環式ジオール類、ビスフェノールA、1,3―ベンゼンジメタノール,1,4-ベンセンジメタノール、9,9’-ビス(4-ヒドロキシフェニル)フルオレン、などの芳香族ジオール類等のジオール化合物が挙げられる。
(B) Examples of the diol component 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.
(A)ジカルボン酸成分として、芳香族ジカルボン酸の少なくとも1種が用いられる場合が好ましい。より好ましくは、ジカルボン酸成分のうち、芳香族ジカルボン酸を主成分として含有する。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。芳香族ジカルボン酸以外のジカルボン酸成分を含んでもよい。このようなジカルボン酸成分としては、芳香族ジカルボン酸などのエステル誘導体等である。
また、(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。 (A) As a dicarboxylic acid component, the case where at least 1 sort of aromatic dicarboxylic acid is used is preferable. More preferably, the dicarboxylic acid component contains an aromatic dicarboxylic acid as a main component. The “main component” means that the proportion of aromatic dicarboxylic acid in the dicarboxylic acid component is 80% by mass or more. 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.
Moreover, it is preferable that at least one aliphatic diol is used as the (B) diol component. 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.
また、(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。 (A) As a dicarboxylic acid component, the case where at least 1 sort of aromatic dicarboxylic acid is used is preferable. More preferably, the dicarboxylic acid component contains an aromatic dicarboxylic acid as a main component. The “main component” means that the proportion of aromatic dicarboxylic acid in the dicarboxylic acid component is 80% by mass or more. 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.
Moreover, it is preferable that at least one aliphatic diol is used as the (B) diol component. 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.
脂肪族ジオール(例えばエチレングリコール)の使用量は、前記芳香族ジカルボン酸(例えばテレフタル酸)及び必要に応じそのエステル誘導体の1モルに対して、1.015~1.50モルの範囲であるのが好ましい。該使用量は、より好ましくは1.02~1.30モルの範囲であり、更に好ましくは1.025~1.10モルの範囲である。該使用量は、1.015以上の範囲であると、エステル化反応が良好に進行し、1.50モル以下の範囲であると、例えばエチレングリコールの2量化によるジエチレングリコールの副生が抑えられ、融点やガラス転移温度、結晶性、耐熱性、耐加水分解性、耐候性など多くの特性を良好に保つことができる。
The amount of the aliphatic diol (for example, ethylene glycol) used is in the range of 1.015 to 1.50 mol with respect to 1 mol of the aromatic dicarboxylic acid (for example, terephthalic acid) and, if necessary, its ester derivative. Is preferred. 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. If the amount used is in the range of 1.015 or more, 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.
-多官能モノマー-
本発明のポリエステルフィルムの製造方法に用いる原料であるポリエステルは、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(以下、「3官能以上の多官能モノマー」又は単に「多官能モノマー」ともいう)を含むことが好ましい。ポリエステルに、多官能モノマーを含めることで、ポリエステルフィルムに隣接する塗布材料との密着力に優れる。ポリエステルフィルムに隣接する塗布材料としては、ポリエステルフィルム上に塗布形成する塗布層が挙げられる。
このようにポリエステルフィルムと隣接する塗布材料との密着性が向上するのは、ポリエステルの重縮合に使用されなかった官能基が、ポリエステルフィルムに隣接する塗布材料の塗布層中の成分と水素結合ないし共有結合を形成するためと考えられる。 -Multifunctional monomer-
Polyester, which is a raw material used in the method for producing a polyester film of the present invention, is a polyfunctional monomer (hereinafter referred to as “3”) 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. It is preferable to include a “functional or higher functional monomer” or simply “polyfunctional monomer”. By including a polyfunctional monomer in polyester, it is excellent in adhesiveness with the coating material adjacent to the polyester film. Examples of the coating material adjacent to the polyester film include a coating layer formed by coating on the polyester film.
Thus, the adhesion between the polyester film and the adjacent coating material is improved because the functional groups not used for the polycondensation of the polyester are not bonded to the components in the coating layer of the coating material adjacent to the polyester film. This is considered to form a covalent bond.
本発明のポリエステルフィルムの製造方法に用いる原料であるポリエステルは、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(以下、「3官能以上の多官能モノマー」又は単に「多官能モノマー」ともいう)を含むことが好ましい。ポリエステルに、多官能モノマーを含めることで、ポリエステルフィルムに隣接する塗布材料との密着力に優れる。ポリエステルフィルムに隣接する塗布材料としては、ポリエステルフィルム上に塗布形成する塗布層が挙げられる。
このようにポリエステルフィルムと隣接する塗布材料との密着性が向上するのは、ポリエステルの重縮合に使用されなかった官能基が、ポリエステルフィルムに隣接する塗布材料の塗布層中の成分と水素結合ないし共有結合を形成するためと考えられる。 -Multifunctional monomer-
Polyester, which is a raw material used in the method for producing a polyester film of the present invention, is a polyfunctional monomer (hereinafter referred to as “3”) 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. It is preferable to include a “functional or higher functional monomer” or simply “polyfunctional monomer”. By including a polyfunctional monomer in polyester, it is excellent in adhesiveness with the coating material adjacent to the polyester film. Examples of the coating material adjacent to the polyester film include a coating layer formed by coating on the polyester film.
Thus, the adhesion between the polyester film and the adjacent coating material is improved because the functional groups not used for the polycondensation of the polyester are not bonded to the components in the coating layer of the coating material adjacent to the polyester film. This is considered to form a covalent bond.
原料ポリエステルは、多官能モノマーを共重合成分(3官能以上の構成成分)として含むことが好ましい。「多官能モノマーを共重合成分(3官能以上の構成成分)として含む」とは、多官能モノマーに由来の構成単位を含むことを意味する。
ポリエステルは、既述のように、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。 The raw material polyester preferably contains a polyfunctional monomer as a copolymerization component (a trifunctional or higher functional component). "Containing a polyfunctional monomer as a copolymerization component (a trifunctional or higher functional component)" means containing a structural unit derived from a polyfunctional monomer.
As described above, the polyester can be obtained, for example, by subjecting (A) a dicarboxylic acid component and (B) a diol component to an esterification reaction and / or transesterification by a known method, and more preferably It is obtained by copolymerizing a trifunctional or higher polyfunctional monomer.
ポリエステルは、既述のように、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。 The raw material polyester preferably contains a polyfunctional monomer as a copolymerization component (a trifunctional or higher functional component). "Containing a polyfunctional monomer as a copolymerization component (a trifunctional or higher functional component)" means containing a structural unit derived from a polyfunctional monomer.
As described above, the polyester can be obtained, for example, by subjecting (A) a dicarboxylic acid component and (B) a diol component to an esterification reaction and / or transesterification by a known method, and more preferably It is obtained by copolymerizing a trifunctional or higher polyfunctional monomer.
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。 As an example of 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, the trifunctional aromatic carboxylic acid includes, for example, trimesic acid, trimellitic Examples of trifunctional aliphatic carboxylic acids such as methanetricarboxylic acid, ethanetricarboxylic acid, propanetricarboxylic acid, and butanetricarboxylic acid are tetrafunctional aromatics such as acid, pyromellitic acid, naphthalenetricarboxylic acid, and anthracentricarboxylic acid. Examples of the group carboxylic acid include benzenetetracarboxylic acid, benzophenonetetracarboxylic acid, naphthalenetetracarboxylic acid, anthracenetetracarboxylic acid, and perylenetetracarboxylic acid. Examples of the tetrafunctional aliphatic carboxylic acid include ethanetetracarboxylic acid. , Ethylenetetracarboxylic acid, butante Lacarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, adamantanetetracarboxylic acid and the like are pentafunctional or more aromatic carboxylic acids such as benzenepentacarboxylic acid, benzenehexacarboxylic acid, naphthalenepentacarboxylic acid, naphthalenehexa Carboxylic 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, ethaneheptacarboxylic acid, butanepentacarboxylic acid, butaneheptacarboxylic acid, cyclopentanepentacarboxylic acid, cyclohexanepentacarboxylic acid, cyclohexane Sakarubon acid, adamantane penta carboxylic acid, and adamantane hexa acid.
In the present invention, these ester derivatives, acid anhydrides and the like are mentioned as examples, but are not limited thereto.
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。 As an example of 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, the trifunctional aromatic carboxylic acid includes, for example, trimesic acid, trimellitic Examples of trifunctional aliphatic carboxylic acids such as methanetricarboxylic acid, ethanetricarboxylic acid, propanetricarboxylic acid, and butanetricarboxylic acid are tetrafunctional aromatics such as acid, pyromellitic acid, naphthalenetricarboxylic acid, and anthracentricarboxylic acid. Examples of the group carboxylic acid include benzenetetracarboxylic acid, benzophenonetetracarboxylic acid, naphthalenetetracarboxylic acid, anthracenetetracarboxylic acid, and perylenetetracarboxylic acid. Examples of the tetrafunctional aliphatic carboxylic acid include ethanetetracarboxylic acid. , Ethylenetetracarboxylic acid, butante Lacarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, adamantanetetracarboxylic acid and the like are pentafunctional or more aromatic carboxylic acids such as benzenepentacarboxylic acid, benzenehexacarboxylic acid, naphthalenepentacarboxylic acid, naphthalenehexa Carboxylic 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, ethaneheptacarboxylic acid, butanepentacarboxylic acid, butaneheptacarboxylic acid, cyclopentanepentacarboxylic acid, cyclohexanepentacarboxylic acid, cyclohexane Sakarubon acid, adamantane penta carboxylic acid, and adamantane hexa acid.
In the present invention, these ester derivatives, acid anhydrides and the like are mentioned as examples, but are not limited thereto.
また、上述のカルボン酸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。 Further, those obtained by adding 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.
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。 Further, those obtained by adding 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.
水酸基数(b)が3以上の多官能モノマーの例として、3官能の芳香族化合物としては、例えば、トリヒドロキシベンゼン、トリヒドロキシナフタレン、トリヒドロキシアントラセン、トリヒドロキシカルコン、トリヒドロキシフラボン、トリヒドロキシクマリンが、3官能の脂肪族アルコールとしては、例えば、グリセリン、トリメチロールプロパン、プロパントリオールが、4官能の脂肪族アルコールとしては、例えば、ペンタエリスリトール等が挙げられる。また、上述の化合物の水酸基末端にジオール類を付加させた化合物も好ましく用いられる。
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。 Examples of polyfunctional monomers having a hydroxyl number (b) of 3 or more include trifunctional aromatic compounds such as trihydroxybenzene, trihydroxynaphthalene, trihydroxyanthracene, trihydroxychalcone, trihydroxyflavone, and trihydroxycoumarin. However, examples of the trifunctional aliphatic alcohol include glycerin, trimethylolpropane, and propanetriol, and examples of the tetrafunctional aliphatic alcohol include pentaerythritol. Further, 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.
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。 Examples of polyfunctional monomers having a hydroxyl number (b) of 3 or more include trifunctional aromatic compounds such as trihydroxybenzene, trihydroxynaphthalene, trihydroxyanthracene, trihydroxychalcone, trihydroxyflavone, and trihydroxycoumarin. However, examples of the trifunctional aliphatic alcohol include glycerin, trimethylolpropane, and propanetriol, and examples of the tetrafunctional aliphatic alcohol include pentaerythritol. Further, 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.
また、上記以外の他の多官能モノマーとして、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も挙げられる。このようなオキシ酸類の例としては、ヒドロキシイソフタル酸、ヒドロキシテレフタル酸、ジヒドロキシテレフタル酸、トリヒドロキシテレフタル酸などを挙げることができる。
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。 Moreover, as other polyfunctional monomers other than the above, 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 oxy acids which are the above are also mentioned. Examples of such oxyacids include hydroxyisophthalic acid, hydroxyterephthalic acid, dihydroxyterephthalic acid, and trihydroxyterephthalic acid.
In addition, 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.
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。 Moreover, as other polyfunctional monomers other than the above, 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 oxy acids which are the above are also mentioned. Examples of such oxyacids include hydroxyisophthalic acid, hydroxyterephthalic acid, dihydroxyterephthalic acid, and trihydroxyterephthalic acid.
In addition, 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.
原料ポリエステルは、前記多官能モノマーの含有比率が、ポリエステル中の全モル数に対して、0.005モル%以上2.5モル%以下であることが好ましい。多官能モノマーの含有比率は、より好ましくは0.020モル%以上1モル%以下であり、更に好ましくは0.025モル%以上1モル%以下であり、更に好ましくは0.035モル%以上0.5モル%以下であり、特に好ましくは0.05モル%以上0.5モル%以下であり、最も好ましくは0.1モル%以上0.25モル%以下である。
In the raw material polyester, the content ratio of the polyfunctional monomer is preferably 0.005 mol% to 2.5 mol% with respect to the total number of moles in the polyester. The content ratio of the polyfunctional monomer is more preferably 0.020 mol% or more and 1 mol% or less, further preferably 0.025 mol% or more and 1 mol% or less, and further preferably 0.035 mol% or more and 0 or less. 0.5 mol% or less, particularly preferably 0.05 mol% or more and 0.5 mol% or less, and most preferably 0.1 mol% or more and 0.25 mol% or less.
ポリエステル中に3官能以上の多官能モノマーに由来の構成単位が存在することで、上記したように、最終的にポリエステルフィルムを成形した場合において、3官能以上の多官能モノマーに由来の構成単位からポリエステル分子鎖を枝分かれされた構造が得られ、ポリエステル分子間の絡み合いを促すことができる。
As described above, when a polyester film is finally formed as a constituent unit derived from a trifunctional or higher polyfunctional monomer in the polyester, from a structural unit derived from a trifunctional or higher polyfunctional monomer. A structure in which polyester molecular chains are branched can be obtained, and entanglement between polyester molecules can be promoted.
多官能モノマーは、ポリエステルの重合中、すなわち、ジカルボン酸成分とジオール成分とのエステル化反応工程中に添加すればよい。
The polyfunctional monomer may be added during the polymerization of the polyester, that is, during the esterification reaction step of the dicarboxylic acid component and the diol component.
エステル化反応及び/又はエステル交換反応には、従来から公知の反応触媒を用いることができる。該反応触媒としては、アルカリ金属化合物、アルカリ土類金属化合物、亜鉛化合物、鉛化合物、マンガン化合物、コバルト化合物、アルミニウム化合物、アンチモン化合物、チタン化合物、リン化合物などを挙げることができる。通常、ポリエステルの製造方法が完結する以前の任意の段階において、重合触媒としてアンチモン化合物、ゲルマニウム化合物、チタン化合物を添加することが好ましい。このような方法としては、例えば、ゲルマニウム化合物を例に取ると、ゲルマニウム化合物粉体をそのまま添加することが好ましい。
A conventionally known reaction catalyst can be used for the esterification reaction and / or transesterification reaction. Examples of 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. Usually, it is preferable to add 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. As such a method, for example, when a germanium compound is taken as an example, it is preferable to add the germanium compound powder as it is.
例えば、エステル化反応工程は、芳香族ジカルボン酸と脂肪族ジオールとを、チタン化合物を含有する触媒の存在下で重合する。このエステル化反応工程では、触媒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を用いると共に、工程中に少なくとも、有機キレートチタン錯体と、マグネシウム化合物と、置換基として芳香環を有しない5価のリン酸エステルとをこの順序で添加する過程を設けて構成される。
For example, in the esterification reaction step, an aromatic dicarboxylic acid and an aliphatic diol are polymerized in the presence of a catalyst containing a titanium compound. In this esterification reaction step, 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. And a process of adding a pentavalent phosphate ester having no sulfite in this order.
まず初めに、芳香族ジカルボン酸及び脂肪族ジオールを、マグネシウム化合物及びリン化合物の添加に先立って、チタン化合物である有機キレートチタン錯体を含有する触媒と混合する。有機キレートチタン錯体等のチタン化合物は、エステル化反応に対しても高い触媒活性を持つので、エステル化反応を良好に行なわせることができる。このとき、ジカルボン酸成分及びジオール成分を混合した中にチタン化合物を加えてもよいし、ジカルボン酸成分(又はジオール成分)とチタン化合物を混合してからジオール成分(又はジカルボン酸成分)を混合してもよい。また、ジカルボン酸成分とジオール成分とチタン化合物とを同時に混合するようにしてもよい。混合は、その方法に特に制限はなく、従来公知の方法により行なうことが可能である。
First, 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. At this time, 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.
より好ましいポリエステルは、ポリエチレンテレフタレート(PET)、ポリエチレン-2,6-ナフタレート(PEN)であり、さらに好ましいのはPETである。さらに、PETは、ゲルマニウム(Ge)系触媒、アンチモン(Sb)系触媒、アルミニウム(Al)系触媒、及びチタン(Ti)系触媒から選ばれる1種又は2種以上を用いて重合されるものが好ましく、より好ましくはTi系触媒である。
More preferred polyesters are polyethylene terephthalate (PET) and polyethylene-2,6-naphthalate (PEN), and more preferred is PET. Further, 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. A Ti-based catalyst is more preferable.
前記Ti系触媒は、反応活性が高く、重合温度を低くすることができる。そのため、特に重合反応中にポリエステルが熱分解し、COOHが発生するのを抑制することが可能である。すなわち、Ti系触媒を用いることで、熱分解の原因となるポリエステルの末端カルボン酸の量を低減することができ、異物形成を抑制することができる。ポリエステルの末端カルボン酸の量を低減しておくことで、ポリエステルフィルムを製造した後に、ポリエステルフィルムが熱分解することを抑制することもできる。
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.
前記Ti系触媒としては、酸化物、水酸化物、アルコキシド、カルボン酸塩、炭酸塩、蓚酸塩、有機キレートチタン錯体、及びハロゲン化物等が挙げられる。Ti系触媒は、本発明の効果を損なわない範囲であれば、二種以上のチタン化合物を併用してもよい。
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。 Examples of the Ti-based catalyst 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.
Examples of 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 chelate titanium complex having an organic acid as a ligand, and the like.
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。 Examples of the Ti-based catalyst 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.
Examples of 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 chelate titanium complex having an organic acid as a ligand, and the like.
ポリエステルを重合する際において、触媒としてチタン(Ti)化合物を、1ppm以上50ppm以下、より好ましくは2ppm以上30ppm以下、さらに好ましくは3ppm以上15ppm以下の範囲で用いて重合を行なうことが好ましい。この場合、原料ポリエステルには、1ppm以上50ppm以下のチタン元素が含まれる。
原料ポリエステルに含まれるチタン元素の量が1ppmよりも少ないと、ポリエステルの重量平均分子量(Mw)を上げることができず、熱分解し易いため、押出機内で異物が増加し易く、好ましくない。原料ポリエステルに含まれるチタン元素の量が50ppmを超えると、Ti系触媒が異物となり、ポリエステルフィルムの延伸の際に、延伸むらを引き起こすため、好ましくない。 When the polyester is polymerized, it is preferable to perform the polymerization using a titanium (Ti) compound as a catalyst in the range of 1 ppm to 50 ppm, more preferably 2 ppm to 30 ppm, and even more preferably 3 ppm to 15 ppm. In this case, the raw material polyester contains 1 ppm or more and 50 ppm or less of titanium element.
If the amount of titanium element contained in the raw material polyester is less than 1 ppm, the weight average molecular weight (Mw) of the polyester cannot be increased, and thermal decomposition tends to occur. If the amount of titanium element contained in the raw material polyester exceeds 50 ppm, the Ti-based catalyst becomes a foreign substance and causes uneven stretching when the polyester film is stretched.
原料ポリエステルに含まれるチタン元素の量が1ppmよりも少ないと、ポリエステルの重量平均分子量(Mw)を上げることができず、熱分解し易いため、押出機内で異物が増加し易く、好ましくない。原料ポリエステルに含まれるチタン元素の量が50ppmを超えると、Ti系触媒が異物となり、ポリエステルフィルムの延伸の際に、延伸むらを引き起こすため、好ましくない。 When the polyester is polymerized, it is preferable to perform the polymerization using a titanium (Ti) compound as a catalyst in the range of 1 ppm to 50 ppm, more preferably 2 ppm to 30 ppm, and even more preferably 3 ppm to 15 ppm. In this case, the raw material polyester contains 1 ppm or more and 50 ppm or less of titanium element.
If the amount of titanium element contained in the raw material polyester is less than 1 ppm, the weight average molecular weight (Mw) of the polyester cannot be increased, and thermal decomposition tends to occur. If the amount of titanium element contained in the raw material polyester exceeds 50 ppm, the Ti-based catalyst becomes a foreign substance and causes uneven stretching when the polyester film is stretched.
[チタン化合物]
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。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。 [Titanium compounds]
As the titanium compound as the catalyst component, at least one kind of organic chelate titanium complex having an organic acid as a ligand is used. Examples of 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.
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。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。 [Titanium compounds]
As the titanium compound as the catalyst component, at least one kind of organic chelate titanium complex having an organic acid as a ligand is used. Examples of 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.
例えばクエン酸を配位子とするキレートチタン錯体を用いた場合、微細粒子等の異物の発生が少なく、他のチタン化合物に比べ、重合活性と色調の良好なポリエステルが得られる。更に、クエン酸キレートチタン錯体を用いる場合でも、エステル化反応の段階で添加する方法により、エステル化反応後に添加する場合に比べ、重合活性と色調が良好で、末端カルボキシ基の少ないポリエステルが得られる。この点については、チタン触媒はエステル化反応の触媒効果もあり、エステル化段階で添加することでエステル化反応終了時におけるオリゴマー酸価が低くなり、以降の重縮合反応がより効率的に行なわれること、またクエン酸を配位子とする錯体はチタンアルコキシド等に比べて加水分解耐性が高く、エステル化反応過程において加水分解せず、本来の活性を維持したままエステル化及び重縮合反応の触媒として効果的に機能するものと推定される。
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。 For example, when a chelate titanium complex having citric acid as a ligand is used, there is little generation of foreign matters such as fine particles, and a polyester having good polymerization activity and color tone can be obtained as compared with other titanium compounds. Furthermore, even when a citric acid chelate titanium complex is used, a method of adding at the stage of esterification reaction gives a polyester having better polymerization activity and color tone and less terminal carboxy groups than when added after the esterification reaction. . In this regard, the titanium catalyst also has a catalytic effect on 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. In addition, the complex with citric acid as a ligand is more resistant to hydrolysis than titanium alkoxide, etc., and does not hydrolyze in the esterification reaction process, and maintains the original activity while maintaining the original activity. 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. .
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。 For example, when a chelate titanium complex having citric acid as a ligand is used, there is little generation of foreign matters such as fine particles, and a polyester having good polymerization activity and color tone can be obtained as compared with other titanium compounds. Furthermore, even when a citric acid chelate titanium complex is used, a method of adding at the stage of esterification reaction gives a polyester having better polymerization activity and color tone and less terminal carboxy groups than when added after the esterification reaction. . In this regard, the titanium catalyst also has a catalytic effect on 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. In addition, the complex with citric acid as a ligand is more resistant to hydrolysis than titanium alkoxide, etc., and does not hydrolyze in the esterification reaction process, and maintains the original activity while maintaining the original activity. 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. .
前記クエン酸キレートチタン錯体としては、例えば、ジョンソン・マッセイ社製のVERTEC AC-420など市販品として容易に入手可能である。
As the citrate chelate titanium complex, for example, VERTEC® AC-420 manufactured by Johnson Matthey can be easily obtained as a commercial product.
芳香族ジカルボン酸と脂肪族ジオールは、これらが含まれたスラリーを調製し、これをエステル化反応工程に連続的に供給することにより導入することができる。
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.
エステル化反応させる際において、Ti触媒を用い、Ti添加量がTi元素換算値で1ppm以上30ppm以下、より好ましくは3ppm以上20ppm以下、さらに好ましくは5ppm以上15ppm以下の範囲で重合反応させる態様が好ましい。チタン添加量は、1ppm以上であると、重合速度が速くなる点で有利であり、30ppm以下であると、良好な色調が得られる点で有利である。
In the esterification reaction, an embodiment is preferred in which a Ti catalyst is used and the amount of Ti added is 1 ppm to 30 ppm, more preferably 3 ppm to 20 ppm, more preferably 5 ppm to 15 ppm in terms of Ti element. . If the amount of titanium added is 1 ppm or more, it is advantageous in that the polymerization rate is increased, and if it is 30 ppm or less, it is advantageous in that a good color tone is obtained.
また、チタン化合物としては、有機キレートチタン錯体以外には一般に、酸化物、水酸化物、アルコキシド、カルボン酸塩、炭酸塩、蓚酸塩、及びハロゲン化物等が挙げられる。本発明の効果を損なわない範囲であれば、有機キレートチタン錯体に加えて、他のチタン化合物を併用してもよい。
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。 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.
Examples of such titanium compounds 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 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 titanium oxalate, potassium titanate, sodium titanate, titanium titanate-aluminum hydroxide mixture, titanium chloride, titanium chloride Down - aluminum chloride mixture, and titanium acetylacetonate.
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。 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.
Examples of such titanium compounds 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 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 titanium oxalate, potassium titanate, sodium titanate, titanium titanate-aluminum hydroxide mixture, titanium chloride, titanium chloride Down - aluminum chloride mixture, and titanium acetylacetonate.
本発明においては、芳香族ジカルボン酸と脂肪族ジオールとを、チタン化合物を含有する触媒の存在下で重合するとともに、チタン化合物の少なくとも一種が有機酸を配位子とする有機キレートチタン錯体であって、有機キレートチタン錯体とマグネシウム化合物と置換基として芳香環を有しない5価のリン酸エステルとをこの順序で添加する過程を少なくとも含むエステル化反応工程と、エステル化反応工程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工程と、を設けて構成されているポリエステルの製造方法によりポリエステルが作製されるのが好ましい。
In the present invention, 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 It is preferable that a polyester is produced by a method for producing a polyester comprising a polycondensation step in which a polycondensation product is produced by subjecting a polycondensation reaction product to a polycondensation reaction.
この場合、エステル化反応の過程において、チタン化合物として有機キレートチタン錯体を存在させた中に、マグネシウム化合物を添加し、次いで特定の5価のリン化合物を添加する添加順とすることで、チタン触媒の反応活性を適度に高く保ち、マグネシウムによる静電印加特性を付与しつつ、かつ重縮合における分解反応を効果的に抑制することができるため、結果として着色が少なく、高い静電印加特性を有するとともに高温下に曝された際の黄変色が改善されたポリエステルが得られる。
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。 In this case, in the course of the esterification reaction, the addition of a magnesium compound to the presence of an organic chelate titanium complex as a titanium compound, followed by the addition order of adding a specific pentavalent phosphorus compound, thereby providing a titanium catalyst. As the result, the coloring reaction is less and the electrostatic application property is high. At the same time, a polyester having improved yellow discoloration when exposed to high temperatures is obtained.
As a result, coloring during polymerization and subsequent coloring during melt film formation are reduced, yellowness is reduced as compared with conventional antimony (Sb) catalyst-based polyester, and germanium catalyst system with relatively high transparency. Compared with other polyesters, it is possible to provide polyesters that have a color tone and transparency that are inferior to those of other polyesters and that have excellent heat resistance. Moreover, polyester which has high transparency and few yellowishness is obtained, without using color tone adjusting materials, such as a cobalt compound and a pigment | dye.
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。 In this case, in the course of the esterification reaction, the addition of a magnesium compound to the presence of an organic chelate titanium complex as a titanium compound, followed by the addition order of adding a specific pentavalent phosphorus compound, thereby providing a titanium catalyst. As the result, the coloring reaction is less and the electrostatic application property is high. At the same time, a polyester having improved yellow discoloration when exposed to high temperatures is obtained.
As a result, coloring during polymerization and subsequent coloring during melt film formation are reduced, yellowness is reduced as compared with conventional antimony (Sb) catalyst-based polyester, and germanium catalyst system with relatively high transparency. Compared with other polyesters, it is possible to provide polyesters that have a color tone and transparency that are inferior to those of other polyesters and that have excellent heat resistance. Moreover, polyester which has high transparency and few yellowishness is obtained, without using color tone adjusting materials, such as a cobalt compound and a pigment | dye.
このポリエステルは、透明性に関する要求の高い用途(例えば、光学用フィルム、工業用リス等)に利用が可能であり、高価なゲルマニウム系触媒を用いる必要がないため、大幅なコスト低減が図れる。加えて、Sb触媒系で生じやすい触媒起因の異物の混入も回避されるため、製膜過程での故障の発生や品質不良が軽減され、得率向上による低コスト化も図ることができる。
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. In addition, since foreign matters caused by the catalyst that are likely to occur in the Sb catalyst system are also avoided, 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.
エステル化反応させるにあたり、チタン化合物である有機キレートチタン錯体と添加剤としてマグネシウム化合物と5価のリン化合物とをこの順に添加する過程を設ける。このとき、有機キレートチタン錯体の存在下、エステル化反応を進め、その後はマグネシウム化合物の添加を、リン化合物の添加前に開始する。
In the esterification reaction, a process of adding an organic chelate titanium complex which is a titanium compound and a magnesium compound and a pentavalent phosphorus compound as additives in this order is provided. At this time, the esterification reaction proceeds in the presence of the organic chelate titanium complex, and thereafter, the addition of the magnesium compound is started before the addition of the phosphorus compound.
[リン化合物]
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。 [Phosphorus compounds]
As the pentavalent phosphorus compound, at least one pentavalent phosphate having no aromatic ring as a substituent is used. For example, 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], specifically, phosphoric acid Trimethyl and triethyl phosphate are particularly preferable.
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。 [Phosphorus compounds]
As the pentavalent phosphorus compound, at least one pentavalent phosphate having no aromatic ring as a substituent is used. For example, 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], specifically, phosphoric acid Trimethyl and triethyl phosphate are particularly preferable.
リン化合物の添加量としては、P元素換算値が50ppm以上90ppm以下の範囲となる量が好ましい。リン化合物の量は、より好ましくは60ppm以上80ppm以下となる量であり、さらに好ましくは60ppm以上75ppm以下となる量である。
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.
[マグネシウム化合物]
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。 [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.
Examples of 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.
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。 [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.
Examples of 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.
マグネシウム化合物の添加量としては、高い静電印加性を付与するためには、Mg元素換算値が50ppm以上となる量が好ましく、50ppm以上100ppm以下の範囲となる量がより好ましい。マグネシウム化合物の添加量は、静電印加性の付与の点で、好ましくは60ppm以上90ppm以下の範囲となる量であり、さらに好ましくは70ppm以上80ppm以下の範囲となる量である。
As the addition amount of the magnesium compound, in order to impart high electrostatic applicability, 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.
エステル化反応工程においては、触媒成分である前記チタン化合物と、添加剤である前記マグネシウム化合物及びリン化合物とを、下記式(i)から算出される値Zが下記の関係式(ii)を満たすように、添加して溶融重合させる場合が特に好ましい。ここで、P含有量は芳香環を有しない5価のリン酸エステルを含むリン化合物全体に由来するリン量であり、Ti含有量は、有機キレートチタン錯体を含むTi化合物全体に由来するチタン量である。このように、チタン化合物を含む触媒系でのマグネシウム化合物及びリン化合物の併用を選択し、その添加タイミング及び添加割合を制御することによって、チタン化合物の触媒活性を適度に高く維持しつつも、黄色味の少ない色調が得られ、重合反応時やその後の製膜時(溶融時)などで高温下に曝されても黄着色を生じ難い耐熱性を付与することができる。
(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。 In the esterification reaction step, 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). Thus, the case where it is added and melt polymerized is particularly preferred. Here, the P content is the amount of phosphorus derived from the entire phosphorus compound including the pentavalent phosphate ester having no aromatic ring, and the Ti content is the amount of titanium derived from the entire Ti compound including the organic chelate titanium complex. It is. As described above, by selecting the combined use of the magnesium compound and the phosphorus compound in the catalyst system containing the titanium compound and controlling the addition timing and the addition ratio, while maintaining the catalyst activity of the titanium compound moderately high, yellow A color tone with less taste can be obtained, and heat resistance that hardly causes yellowing can be imparted even when exposed to high temperatures during polymerization reaction or subsequent film formation (during melting).
(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
This is an index for quantitatively expressing the balance between the three because the phosphorus compound not only acts on titanium but also interacts with the magnesium compound.
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. When the value Z is positive, it can be said that there is an excess of phosphorus that inhibits titanium, and conversely, when it is negative, there is a shortage of phosphorus necessary to inhibit titanium. In the reaction, since each atom of Ti, Mg, and P is not equivalent, each mole number in the formula is weighted by multiplying by a valence.
(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。 In the esterification reaction step, 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). Thus, the case where it is added and melt polymerized is particularly preferred. Here, the P content is the amount of phosphorus derived from the entire phosphorus compound including the pentavalent phosphate ester having no aromatic ring, and the Ti content is the amount of titanium derived from the entire Ti compound including the organic chelate titanium complex. It is. As described above, by selecting the combined use of the magnesium compound and the phosphorus compound in the catalyst system containing the titanium compound and controlling the addition timing and the addition ratio, while maintaining the catalyst activity of the titanium compound moderately high, yellow A color tone with less taste can be obtained, and heat resistance that hardly causes yellowing can be imparted even when exposed to high temperatures during polymerization reaction or subsequent film formation (during melting).
(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
This is an index for quantitatively expressing the balance between the three because the phosphorus compound not only acts on titanium but also interacts with the magnesium compound.
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. When the value Z is positive, it can be said that there is an excess of phosphorus that inhibits titanium, and conversely, when it is negative, there is a shortage of phosphorus necessary to inhibit titanium. In the reaction, since each atom of Ti, Mg, and P is not equivalent, each mole number in the formula is weighted by multiplying by a valence.
本発明においては、特殊な合成等が不要であり、安価でかつ容易に入手可能なチタン化合物、リン化合物、マグネシウム化合物を用いて、反応に必要とされる反応活性を持ちながら、色調及び熱に対する着色耐性に優れたポリエステルを得ることができる。
In the present invention, no special synthesis or the like is required, and 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.
前記式(ii)において、重合反応性を保った状態で、色調及び熱に対する着色耐性をより高める観点から、+1.0≦Z≦+4.0を満たす場合が好ましく、+1.5≦Z≦+3.0を満たす場合がより好ましい。
In the formula (ii), from the viewpoint of further enhancing the color tone and the coloration resistance to heat while maintaining the polymerization reactivity, it is preferable to satisfy + 1.0 ≦ Z ≦ + 4.0, and + 1.5 ≦ Z ≦ + 3 Is more preferable.
本発明における好ましい態様として、エステル化反応が終了する前に、芳香族ジカルボン酸及び脂肪族ジオールに、1ppm以上30ppm以下のクエン酸又はクエン酸塩を配位子とするキレートチタン錯体を添加後、該キレートチタン錯体の存在下に、60ppm以上90ppm以下(より好ましくは70ppm以上80ppm以下)の弱酸のマグネシウム塩を添加し、該添加後にさらに、60ppm以上80ppm以下(より好ましくは65ppm以上75ppm以下)の、芳香環を置換基として有しない5価のリン酸エステルを添加する態様が挙げられる。
As a preferred embodiment in the present invention, before the esterification reaction is completed, after adding a chelate titanium complex having 1 ppm or more and 30 ppm or less of citric acid or citrate as a ligand to the aromatic dicarboxylic acid and the aliphatic diol, In the presence of the chelate titanium complex, a magnesium salt of weak acid of 60 ppm to 90 ppm (more preferably 70 ppm to 80 ppm) is added, and after the addition, 60 ppm to 80 ppm (more preferably 65 ppm to 75 ppm). And an embodiment in which a pentavalent phosphate having no aromatic ring as a substituent is added.
エステル化反応は、少なくとも2個の反応器を直列に連結した多段式装置を用いて、エチレングリコールが還流する条件下で、反応によって生成した水又はアルコールを系外に除去しながら実施することができる。
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.
また、上記したエステル化反応は、一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。 The esterification reaction described above may be performed in one stage or may be performed in multiple stages.
When the esterification reaction is carried out in one stage, the esterification reaction temperature is preferably 230 to 260 ° C, more preferably 240 to 250 ° C.
When the esterification reaction is carried out in multiple stages, 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.
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。 The esterification reaction described above may be performed in one stage or may be performed in multiple stages.
When the esterification reaction is carried out in one stage, the esterification reaction temperature is preferably 230 to 260 ° C, more preferably 240 to 250 ° C.
When the esterification reaction is carried out in multiple stages, 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.
-重縮合-
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。 -Polycondensation-
In polycondensation, 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.
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。 -Polycondensation-
In polycondensation, 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.
エステル化反応で生成したオリゴマー等のエステル化反応生成物は、引き続いて重縮合反応に供される。この重縮合反応は、多段階の重縮合反応槽に供給することにより好適に行なうことが可能である。
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.
例えば、3段階の反応槽で行なう場合の重縮合反応条件は、第一反応槽は、反応温度が255~280℃、より好ましくは265~275℃であり、圧力が100~10torr(13.3×10-3~1.3×10-3MPa)、より好ましくは50~20torr(6.67×10-3~2.67×10-3MPa)であって、第二反応槽は、反応温度が265~285℃、より好ましくは270~280℃であり、圧力が20~1torr(2.67×10-3~1.33×10-4MPa)、より好ましくは10~3torr(1.33×10-3~4.0×10-4MPa)であって、最終反応槽内における第三反応槽は、反応温度が270~290℃、より好ましくは275~285℃であり、圧力が10~0.1torr(1.33×10-3~1.33×10-5MPa)、より好ましくは5~0.5torr(6.67×10-4~6.67×10-5MPa)である態様が好ましい。
For example, 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. 33 × 10 −3 to 4.0 × 10 −4 MPa), and 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) .
上記のようにして合成されたポリエステルには、光安定化剤、酸化防止剤、紫外線吸収剤、難燃剤、易滑剤(微粒子)、核剤(結晶化剤)、結晶化阻害剤などの添加剤を更に含有させてもよい。
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.
ポリエステルフィルムの原料であるポリエステルは、固相重合したペレットであることが好ましい。
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)〔当量/トン〕、固有粘度(Interisic Viscosity;IV)〔dL/g〕を制御することができる。なお、本明細書中において、「当量/トン」は1トンあたりのモル当量を表す。 The polyester that is the raw material of the polyester film is preferably a solid-phase polymerized pellet.
After the polymerization by the esterification reaction, the polyester film is further subjected to solid phase polymerization, whereby the water 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) [equivalent / ton Intrinsic Viscosity (IV) [dL / g] can be controlled. In the present specification, “equivalent / ton” represents a molar equivalent per ton.
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)〔当量/トン〕、固有粘度(Interisic Viscosity;IV)〔dL/g〕を制御することができる。なお、本明細書中において、「当量/トン」は1トンあたりのモル当量を表す。 The polyester that is the raw material of the polyester film is preferably a solid-phase polymerized pellet.
After the polymerization by the esterification reaction, the polyester film is further subjected to solid phase polymerization, whereby the water 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) [equivalent / ton Intrinsic Viscosity (IV) [dL / g] can be controlled. In the present specification, “equivalent / ton” represents a molar equivalent per ton.
本発明においては、ポリエステルフィルムの耐加水分解性と寸法安定性との両立の観点から、ポリエステルの固有粘度(IV)は、0.75以上とする。
ポリエステルの固有粘度(IV)は、0.75~0.9であることが好ましい。
固有粘度が0.75以上であると、ポリエステルの分子運動が阻害されて結晶化しにくくすることができ、0.9以下であると、押出機内の剪断発熱によるポリエステルの熱分解が起こり過ぎず、結晶化を抑制し、また、酸価(AV)を低く抑えることができる。
IVは、0.75以上0.85以下であることがより好ましい。 In the present invention, the intrinsic viscosity (IV) of the polyester is set to 0.75 or more from the viewpoint of achieving both hydrolysis resistance and dimensional stability of the polyester film.
The intrinsic viscosity (IV) of the polyester is preferably 0.75 to 0.9.
When the intrinsic viscosity is 0.75 or more, the molecular motion of the polyester is hindered and it is difficult to crystallize, and when it is 0.9 or less, the thermal decomposition of the polyester due to shear heat generation in the extruder does not occur too much, Crystallization can be suppressed and the acid value (AV) can be kept low.
IV is more preferably 0.75 or more and 0.85 or less.
ポリエステルの固有粘度(IV)は、0.75~0.9であることが好ましい。
固有粘度が0.75以上であると、ポリエステルの分子運動が阻害されて結晶化しにくくすることができ、0.9以下であると、押出機内の剪断発熱によるポリエステルの熱分解が起こり過ぎず、結晶化を抑制し、また、酸価(AV)を低く抑えることができる。
IVは、0.75以上0.85以下であることがより好ましい。 In the present invention, the intrinsic viscosity (IV) of the polyester is set to 0.75 or more from the viewpoint of achieving both hydrolysis resistance and dimensional stability of the polyester film.
The intrinsic viscosity (IV) of the polyester is preferably 0.75 to 0.9.
When the intrinsic viscosity is 0.75 or more, the molecular motion of the polyester is hindered and it is difficult to crystallize, and when it is 0.9 or less, the thermal decomposition of the polyester due to shear heat generation in the extruder does not occur too much, Crystallization can be suppressed and the acid value (AV) can be kept low.
IV is more preferably 0.75 or more and 0.85 or less.
特に、エステル化反応において、Ti触媒を使用し、さらに固相重合して、ポリエステルの固有粘度(IV)を、0.75以上0.9以下とすることで、ポリエステルフィルムの製造工程における溶融樹脂の冷却工程において、ポリエステルが結晶化することを抑制し易い。
従って、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0.75以上0.9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。 In particular, in the esterification reaction, a Ti catalyst is used, and further solid phase polymerization is performed so that the intrinsic viscosity (IV) of the polyester is 0.75 or more and 0.9 or less. In the cooling step, it is easy to suppress the crystallization of the polyester.
Accordingly, the polyester as a raw material of the polyester film applied to the longitudinal stretching and the transverse stretching preferably has an intrinsic viscosity of 0.75 or more and 0.9 or less, and further contains a titanium atom derived from a catalyst (Ti catalyst). Is preferred.
従って、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0.75以上0.9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。 In particular, in the esterification reaction, a Ti catalyst is used, and further solid phase polymerization is performed so that the intrinsic viscosity (IV) of the polyester is 0.75 or more and 0.9 or less. In the cooling step, it is easy to suppress the crystallization of the polyester.
Accordingly, the polyester as a raw material of the polyester film applied to the longitudinal stretching and the transverse stretching preferably has an intrinsic viscosity of 0.75 or more and 0.9 or less, and further contains a titanium atom derived from a catalyst (Ti catalyst). Is preferred.
固有粘度(IV)は、溶液粘度(η)と溶媒粘度(η0)の比ηr(=η/η0;相対粘度)から1を引いた比粘度(ηsp=ηr-1)を濃度で割った値を濃度がゼロの状態に外挿した値である。IVは、ウベローデ型粘度計を用い、ポリエステルを1,1,2,2-テトラクロルエタン/フェノール(=2/3[質量比])混合溶媒に溶解させ、25℃の溶液粘度から求められる。
The intrinsic viscosity (IV) is obtained by subtracting 1 from the ratio η r (= η / η 0 ; relative viscosity) of the solution viscosity (η) and the solvent viscosity (η 0 ) (η sp = η r −1). It is a value obtained by extrapolating the value divided by the density to a state where the density is zero. IV is obtained from a solution viscosity at 25 ° C. by using a Ubbelohde viscometer, dissolving polyester in a 1,1,2,2-tetrachloroethane / phenol (= 2/3 [mass ratio]) mixed solvent.
ポリエステルの固相重合には、既述のエステル化反応により重合したポリエステル又は市販のポリエステルを、ペレット状などの小片形状にしたものを、出発物質として用いればよい。
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。
ポリエステルの固相重合は、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1時間以上50時間以下、より好ましくは5時間以上40時間以下、さらに好ましくは10時間以上30時間以下の条件で行なうのが好ましい。また、固相重合は、真空中あるいは窒素気流中で行なうことが好ましい。 In the solid phase polymerization of polyester, a polyester obtained by the esterification reaction described above or a commercially available polyester in the form of a small piece such as a pellet 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).
Solid phase polymerization of polyester is 150 ° C. or more and 250 ° C. or less, more preferably 170 ° C. or more and 240 ° C. or less, more preferably 180 ° C. or more and 230 ° C. or less and 1 hour or more and 50 hours or less, more preferably 5 hours or more and 40 hours or less. More preferably, it is carried out under conditions of 10 hours or more and 30 hours or less. The solid phase polymerization is preferably performed in a vacuum or a nitrogen stream.
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。
ポリエステルの固相重合は、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1時間以上50時間以下、より好ましくは5時間以上40時間以下、さらに好ましくは10時間以上30時間以下の条件で行なうのが好ましい。また、固相重合は、真空中あるいは窒素気流中で行なうことが好ましい。 In the solid phase polymerization of polyester, a polyester obtained by the esterification reaction described above or a commercially available polyester in the form of a small piece such as a pellet 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).
Solid phase polymerization of polyester is 150 ° C. or more and 250 ° C. or less, more preferably 170 ° C. or more and 240 ° C. or less, more preferably 180 ° C. or more and 230 ° C. or less and 1 hour or more and 50 hours or less, more preferably 5 hours or more and 40 hours or less. More preferably, it is carried out under conditions of 10 hours or more and 30 hours or less. The solid phase polymerization is preferably performed in a vacuum or a nitrogen stream.
固相重合の温度は、170℃以上240℃以下が好ましく、より好ましくは180℃以上230℃以下であり、さらに好ましくは190℃以上220℃以下である。温度が上記範囲内であると、ポリエステルの酸価(AV)がより大きく低減することの点で好ましい。また、固相重合時間は、5時間以上100時間以下が好ましく、より好ましくは10時間以上75時間以下であり、さらに好ましくは15時間以上50時間以下である。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)の本発明の好ましい範囲に容易に制御できる点で好ましい。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。
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. When the temperature is within the above range, it is preferable in that the acid value (AV) of the polyester is further reduced. The solid phase polymerization time is preferably 5 hours to 100 hours, more preferably 10 hours to 75 hours, and still more preferably 15 hours to 50 hours. It is preferable that the time is within the above range in that the acid value (AV) and intrinsic viscosity (IV) of the polyester can be easily controlled within the preferable ranges of the present invention. The solid phase polymerization is preferably performed in a vacuum or in a nitrogen atmosphere.
(溶融押出)
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原料ポリエステルを溶融押出し、さらに冷却してポリエステルフィルムを成形する。
原料ポリエステルの溶融押出は、例えば、1本または2本以上のスクリューを備えた押出機を用い、原料ポリエステルの融点以上の温度に加熱し、スクリューを回転させて行なう。原料ポリエステルは、加熱およびスクリューによる混練により、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、原料ポリエステルの溶融押出しを行なうことが好ましい。
溶融された原料ポリエステル(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。 (Melting extrusion)
In the film forming step in the present invention, the raw material polyester obtained as described above is melt-extruded and further cooled to form a polyester film.
The raw material polyester is melt-extruded by, for example, using an extruder equipped with one or two or more screws, heating to a temperature not lower than the melting point of the raw material polyester, and rotating the screw. The raw material polyester is melted into a melt in the extruder by heating and kneading with a screw. Further, from the viewpoint of suppressing thermal decomposition (polyester hydrolysis) in the extruder, it is preferable to perform melt extrusion of the raw material polyester by replacing the inside of the extruder with nitrogen.
The melted raw material polyester (melt) is extruded from an extrusion die through a gear pump, a filter or 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.
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原料ポリエステルを溶融押出し、さらに冷却してポリエステルフィルムを成形する。
原料ポリエステルの溶融押出は、例えば、1本または2本以上のスクリューを備えた押出機を用い、原料ポリエステルの融点以上の温度に加熱し、スクリューを回転させて行なう。原料ポリエステルは、加熱およびスクリューによる混練により、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、原料ポリエステルの溶融押出しを行なうことが好ましい。
溶融された原料ポリエステル(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。 (Melting extrusion)
In the film forming step in the present invention, the raw material polyester obtained as described above is melt-extruded and further cooled to form a polyester film.
The raw material polyester is melt-extruded by, for example, using an extruder equipped with one or two or more screws, heating to a temperature not lower than the melting point of the raw material polyester, and rotating the screw. The raw material polyester is melted into a melt in the extruder by heating and kneading with a screw. Further, from the viewpoint of suppressing thermal decomposition (polyester hydrolysis) in the extruder, it is preferable to perform melt extrusion of the raw material polyester by replacing the inside of the extruder with nitrogen.
The melted raw material polyester (melt) is extruded from an extrusion die through a gear pump, a filter or 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.
ダイからメルト(ポリエステル)をキャスティングドラム上に押出すことで、フィルム状に成形(キャスト処理)することができる。
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は、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。 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 more preferably 0.8 mm to 4.6 mm. More preferably.
By setting the thickness of the film-like polyester molded body to 5 mm or less, a cooling delay due to heat storage of the melt is avoided, and by setting the thickness to 0.5 mm or more, the OH group in the polyester between extrusion and cooling is reduced. And COOH groups are diffused into the polyester to prevent the OH groups and COOH groups that cause hydrolysis from being exposed to the polyester surface.
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は、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。 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 more preferably 0.8 mm to 4.6 mm. More preferably.
By setting the thickness of the film-like polyester molded body to 5 mm or less, a cooling delay due to heat storage of the melt is avoided, and by setting the thickness to 0.5 mm or more, the OH group in the polyester between extrusion and cooling is reduced. And COOH groups are diffused into the polyester to prevent the OH groups and COOH groups that cause hydrolysis from being exposed to the polyester surface.
押出ダイから押出されたメルトを冷却する手段は、特に制限されず、メルトに冷風を当てたり、キャストドラム(冷却キャストドラム)に接触させたり、水を霧吹きすればよい。冷却手段は、1つのみ行なってもよいし、2つ以上を組み合わせて行なってもよい。
冷却手段は、上記の中でも、連続運転時のフィルム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。 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 film 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.
冷却手段は、上記の中でも、連続運転時のフィルム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。 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 film 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.
また、キャストドラム等を用いて冷却されたポリエステル成形体は、剥ぎ取りロール等の剥ぎ取り部材を用いて、キャストドラム等の冷却部材から剥ぎ取られる。
Also, 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.
-末端封止剤-
本発明のポリエステルフィルムの製造方法においては、フィルム成形工程が、原料ポリエステルと共に、オキサゾリン系化合物、カルボジイミド化合物、又はエポキシ化合物の少なくとも1種類の末端封止剤を0.1質量%以上5質量%以下添加して溶融押出する工程を含むことが好ましい。つまり、原料ポリエステルの溶融押出にあたり、前記末端封止剤を併用することが好ましい。末端封止剤を併用することで、ポリエステル分子の末端が封止剤と反応し分子鎖の末端部分が嵩高くなり、得られるポリエステルフィルム表面の微細凹凸量が増えて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に隣接する材料との密着力に優れる。 -End sealant-
In the method for producing a polyester film of the present invention, the film forming step includes 0.1% by mass or more and 5% by mass or less of at least one terminal blocker of an oxazoline compound, a carbodiimide compound, or an epoxy compound together with the raw material polyester. It is preferable to include the process of adding and melt-extruding. That is, in the melt extrusion of the raw material polyester, it is preferable to use the terminal blocking agent in combination. By using the end-capping agent together, the end of the polyester molecule reacts with the capping agent, the end of the molecular chain becomes bulky, the amount of fine irregularities on the surface of the resulting polyester film increases, and the anchor effect is easily expressed. Excellent adhesion to the material adjacent to the polyester film.
本発明のポリエステルフィルムの製造方法においては、フィルム成形工程が、原料ポリエステルと共に、オキサゾリン系化合物、カルボジイミド化合物、又はエポキシ化合物の少なくとも1種類の末端封止剤を0.1質量%以上5質量%以下添加して溶融押出する工程を含むことが好ましい。つまり、原料ポリエステルの溶融押出にあたり、前記末端封止剤を併用することが好ましい。末端封止剤を併用することで、ポリエステル分子の末端が封止剤と反応し分子鎖の末端部分が嵩高くなり、得られるポリエステルフィルム表面の微細凹凸量が増えて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に隣接する材料との密着力に優れる。 -End sealant-
In the method for producing a polyester film of the present invention, the film forming step includes 0.1% by mass or more and 5% by mass or less of at least one terminal blocker of an oxazoline compound, a carbodiimide compound, or an epoxy compound together with the raw material polyester. It is preferable to include the process of adding and melt-extruding. That is, in the melt extrusion of the raw material polyester, it is preferable to use the terminal blocking agent in combination. By using the end-capping agent together, the end of the polyester molecule reacts with the capping agent, the end of the molecular chain becomes bulky, the amount of fine irregularities on the surface of the resulting polyester film increases, and the anchor effect is easily expressed. Excellent adhesion to the material adjacent to the polyester film.
末端封止剤の添加時期は、ポリエステルフィルムの原料の押出機への投入から押出までの段階であれば、特に制限はないが、末端封止剤は、原料ポリエステルを乾燥した後から、原料ポリエステルを押出機に投入し、スクリューで送られ、押出機から押出される前までの間に加えられ、原料ポリエステルと共に溶融混練に供されることが好ましい。
例えば、原料ポリエステルを乾燥した後、原料ポリエステルと共に、末端封止剤を押出機に投入してもよい。また、溶融混練を行なう押出機の原料投入口と、溶融状態のポリエステル(メルト)の排出口との間に末端封止剤を供給する供給口を設け、押出機内の原料ポリエステルに直接、末端封止剤を加えてもよい。このとき、末端封止剤は、加熱混練が開始されているが完全に溶融状態に達していないポリエステルに加えられてもよいし、溶融状態のポリエステル(メルト)に加えられてもよい。 The end-capping agent is not particularly limited as long as it is from the introduction of the polyester film raw material into the extruder to the extrusion, but the end-capping agent is used after the raw material polyester is dried. Is introduced into the extruder, sent by screw, added before being extruded from the extruder, and is preferably subjected to melt kneading together with the raw material polyester.
For example, after the raw material polyester is dried, the end-capping agent may be put into the extruder together with the raw material polyester. In addition, a supply port for supplying an end-capping agent is provided between the raw material inlet of the extruder that performs melt-kneading and the outlet of the molten polyester (melt), and the end-capping is directly performed on the raw material polyester in the extruder. Stopper may be added. At this time, the end-capping agent may be added to the polyester that has been heated and kneaded but has not completely reached the molten state, or may be added to the molten polyester (melt).
例えば、原料ポリエステルを乾燥した後、原料ポリエステルと共に、末端封止剤を押出機に投入してもよい。また、溶融混練を行なう押出機の原料投入口と、溶融状態のポリエステル(メルト)の排出口との間に末端封止剤を供給する供給口を設け、押出機内の原料ポリエステルに直接、末端封止剤を加えてもよい。このとき、末端封止剤は、加熱混練が開始されているが完全に溶融状態に達していないポリエステルに加えられてもよいし、溶融状態のポリエステル(メルト)に加えられてもよい。 The end-capping agent is not particularly limited as long as it is from the introduction of the polyester film raw material into the extruder to the extrusion, but the end-capping agent is used after the raw material polyester is dried. Is introduced into the extruder, sent by screw, added before being extruded from the extruder, and is preferably subjected to melt kneading together with the raw material polyester.
For example, after the raw material polyester is dried, the end-capping agent may be put into the extruder together with the raw material polyester. In addition, a supply port for supplying an end-capping agent is provided between the raw material inlet of the extruder that performs melt-kneading and the outlet of the molten polyester (melt), and the end-capping is directly performed on the raw material polyester in the extruder. Stopper may be added. At this time, the end-capping agent may be added to the polyester that has been heated and kneaded but has not completely reached the molten state, or may be added to the molten polyester (melt).
本発明における末端封止剤としては、カルボジイミド基、エポキシ基、又はオキサゾリン基を有する化合物が好ましい。末端封止剤の具体例としては、カルボジイミド化合物、エポキシ化合物、オキサゾリン系化合物などを好適に挙げることができる。
As the end-capping agent in the present invention, 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.
カルボジイミド基を有する前記カルボジイミド化合物は、1官能性カルボジイミドと多官能性カルボジイミドがある。1官能性カルボジイミドとしては、例えば、ジシクロヘキシルカルボジイミド、ジイソプロピルカルボジイミド、ジメチルカルボジイミド、ジイソブチルカルボジイミド、ジオクチルカルボジイミド、t-ブチルイソプロピルカルボジイミド、ジフェニルカルボジイミド、ジ-t-ブチルカルボジイミド及びジ-β-ナフチルカルボジイミドなどが挙げられ、好ましくはジシクロヘキシルカルボジイミドやジイソプロピルカルボジイミドである。
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、1,4-フェニレンジイソシアネート、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、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。 The carbodiimide compound having a carbodiimide group includes a monofunctional carbodiimide and a polyfunctional carbodiimide. Examples of monofunctional carbodiimides include dicyclohexylcarbodiimide, diisopropylcarbodiimide, dimethylcarbodiimide, diisobutylcarbodiimide, dioctylcarbodiimide, t-butylisopropylcarbodiimide, diphenylcarbodiimide, di-t-butylcarbodiimide and di-β-naphthylcarbodiimide. Of these, dicyclohexylcarbodiimide and diisopropylcarbodiimide are preferable.
The polyfunctional carbodiimide is preferably a polycarbodiimide having a polymerization degree of 3 to 15. The 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. Examples of such repeating units include 1,5-naphthalene carbodiimide, 4,4′-diphenylmethane carbodiimide, 4,4′-diphenyldimethylmethane carbodiimide, 1,3-phenylene carbodiimide, 1,4-phenylene diisocyanate, 2 , 4-Tolylenecarbodiimide, 2,6-Tolylenecarbodiimide, Mixture of 2,4-Tolylenecarbodiimide and 2,6-Tolylenecarbodiimide, Hexamethylenecarbodiimide, Cyclohexane-1,4-carbodiimide, Xylylenecarbodiimide, Isophorone Carbodiimide, isophorone carbodiimide, dicyclohexylmethane-4,4'-carbodiimide, methylcyclohexanecarbodiimide, tetramethylxylylene carbodiimide, 2,6-diisopropyl phen Such as Le carbodiimide and 1,3,5-triisopropylbenzene-2,4-carbodiimide.
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、1,4-フェニレンジイソシアネート、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、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。 The carbodiimide compound having a carbodiimide group includes a monofunctional carbodiimide and a polyfunctional carbodiimide. Examples of monofunctional carbodiimides include dicyclohexylcarbodiimide, diisopropylcarbodiimide, dimethylcarbodiimide, diisobutylcarbodiimide, dioctylcarbodiimide, t-butylisopropylcarbodiimide, diphenylcarbodiimide, di-t-butylcarbodiimide and di-β-naphthylcarbodiimide. Of these, dicyclohexylcarbodiimide and diisopropylcarbodiimide are preferable.
The polyfunctional carbodiimide is preferably a polycarbodiimide having a polymerization degree of 3 to 15. The 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. Examples of such repeating units include 1,5-naphthalene carbodiimide, 4,4′-diphenylmethane carbodiimide, 4,4′-diphenyldimethylmethane carbodiimide, 1,3-phenylene carbodiimide, 1,4-phenylene diisocyanate, 2 , 4-Tolylenecarbodiimide, 2,6-Tolylenecarbodiimide, Mixture of 2,4-Tolylenecarbodiimide and 2,6-Tolylenecarbodiimide, Hexamethylenecarbodiimide, Cyclohexane-1,4-carbodiimide, Xylylenecarbodiimide, Isophorone Carbodiimide, isophorone carbodiimide, dicyclohexylmethane-4,4'-carbodiimide, methylcyclohexanecarbodiimide, tetramethylxylylene carbodiimide, 2,6-diisopropyl phen Such as Le carbodiimide and 1,3,5-triisopropylbenzene-2,4-carbodiimide.
カルボジイミド化合物は、熱分解によるイソシアネート系ガスの発生が抑えられる点で、耐熱性の高いカルボジイミド化合物が好ましい。耐熱性を高めるためには、分子量(重合度)が高いほど好ましく、より好ましくは、カルボジイミド化合物の末端を耐熱性の高い構造にすることが好ましい。また、原料ポリエステルを溶融押出する温度を下げることで、カルボジイミド化合物による耐候性の向上効果及び熱収縮の低減効果がより効果的に得られる。
The carbodiimide compound is preferably a carbodiimide compound having high heat resistance in that generation of isocyanate gas due to thermal decomposition is suppressed. In order to improve heat resistance, it is preferable that the molecular weight (degree of polymerization) is high, and it is more preferable that the terminal of the carbodiimide compound has a structure having high heat resistance. Further, by lowering the temperature at which the raw material polyester is melt-extruded, the effect of improving weather resistance and the effect of reducing thermal shrinkage by the carbodiimide compound can be obtained more effectively.
カルボジイミド化合物を用いたポリエステルフィルムは、温度300℃で30分間保持した際のイソシアネート系ガスの発生量が0~0.02質量%であることが好ましい。イソシアネート系ガスの発生量が0.02質量%以下であると、ポリエステルフィルム中に気泡(ボイド)が生成され難く、したがって応力集中する部位が形成されにくいため、ポリエステルフィルム内に生じやすい破壊や剥離を防ぐことができる。これにより、隣接する材料との間の密着が良好になる。
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。 The polyester film using the carbodiimide compound preferably has an amount of isocyanate gas generated of 0 to 0.02% by mass when held at a temperature of 300 ° C. for 30 minutes. If the amount of isocyanate 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 contact | adherence between adjacent materials becomes favorable.
Here, 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.
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。 The polyester film using the carbodiimide compound preferably has an amount of isocyanate gas generated of 0 to 0.02% by mass when held at a temperature of 300 ° C. for 30 minutes. If the amount of isocyanate 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 contact | adherence between adjacent materials becomes favorable.
Here, 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.
エポキシ基を有する前記エポキシ化合物としては、好ましい例として、グリシジルエステル化合物やグリシジルエーテル化合物などが挙げられる。
Preferred examples of the epoxy compound having an epoxy group include glycidyl ester compounds and glycidyl ether compounds.
グリシジルエステル化合物の具体例としては、安息香酸グリシジルエステル、t-Bu-安息香酸グリシジルエステル、P-トルイル酸グリシジルエステル、シクロヘキサンカルボン酸グリシジルエステル、ペラルゴン酸グリシジルエステル、ステアリン酸グリシジルエステル、ラウリン酸グリシジルエステル、パルミチン酸グリシジルエステル、ベヘン酸グリシジルエステル、バーサティク酸グリシジルエステル、オレイン酸グリシジルエステル、リノール酸グリシジルエステル、リノレイン酸グリシジルエステル、ベヘノール酸グリシジルエステル、ステアロール酸グリシジルエステル、テレフタル酸ジグリシジルエステル、イソフタル酸ジグリシジルエステル、フタル酸ジグリシジルエステル、ナフタレンジカルボン酸ジグリシジルエステル、メチルテレフタル酸ジグリシジルエステル、ヘキサヒドロフタル酸ジグリシジルエステル、テトラヒドロフタル酸ジグリシジルエステル、シクロヘキサンジカルボン酸ジグリシジルエステル、アジピン酸ジグリシジルエステル、コハク酸ジグリシジルエステル、セバシン酸ジグリシジルエステル、ドデカンジオン酸ジグリシジルエステル、オクタデカンジカルボン酸ジグリシジルエステル、トリメリット酸トリグリシジルエステル及びピロメリット酸テトラグリシジルエステル等を挙げられる。
Specific examples of 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 dicarboxylate Stell, methyl terephthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, cyclohexanedicarboxylic acid diglycidyl ester, adipic acid diglycidyl ester, succinic acid diglycidyl ester, sebacic acid diglycidyl ester, dodecane Examples include diionic acid diglycidyl ester, octadecanedicarboxylic acid diglycidyl ester, trimellitic acid triglycidyl ester, and pyromellitic acid tetraglycidyl ester.
また、グリシジルエーテル化合物の具体例としては、フェニルグリシジルエ-テル、O-フェニルグリシジルエ-テル、1,4-ビス(β,γ-エポキシプロポキシ)ブタン、1,6-ビス(β,γ-エポキシプロポキシ)ヘキサン、1,4-ビス(β,γ-エポキシプロポキシ)ベンゼン、1-(β,γ-エポキシプロポキシ)-2-エトキシエタン、1-(β,γ-エポキシプロポキシ)-2-ベンジルオキシエタン、2,2-ビス-[р-(β,γ-エポキシプロポキシ)フェニル]プロパン及び2,2-ビス-(4-ヒドロキシフェニル)プロパンや2,2-ビス-(4-ヒドロキシフェニル)メタンなどのビスフェノールとエピクロルヒドリンの反応で得られるビスグリシジルポリエーテルなどが挙げられる。
Specific examples of the glycidyl ether compound include phenyl glycidyl ether, O-phenyl glycidyl ether, 1,4-bis (β, γ-epoxypropoxy) butane, 1,6-bis (β, γ- Epoxypropoxy) hexane, 1,4-bis (β, γ-epoxypropoxy) benzene, 1- (β, γ-epoxypropoxy) -2-ethoxyethane, 1- (β, γ-epoxypropoxy) -2-benzyl Oxyethane, 2,2-bis- [р- (β, γ-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.
前記オキサゾリン化合物としては、オキサゾリン基を有する化合物の中から適宜選択して用いることができるが、その中ではビスオキサゾリン化合物が好ましい。
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。 The oxazoline compound can be appropriately selected from compounds having an oxazoline group, and among them, a bisoxazoline compound is preferable.
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). -Oxazoline), 2,2'-bis (4-ethyl-2-oxazoline), 2,2'-bis (4,4'-diethyl-2-oxazoline), 2,2'-bis (4-propyl- 2-oxazoline), 2,2′-bis (4-butyl-2-oxazoline), 2,2′-bis (4-hexyl-2-oxazoline), 2,2′-bis (4-phenyl-2-) Oxazoline), 2,2′-bis (4-cyclohexyl-2-oxazoline), 2,2′-bis (4-benzyl-2-oxazoline), 2,2′-p-phenylenebis (2-oxazoline), 2,2'-m-phenylenebis (2-oxazoline) 2,2'-o-phenylenebis (2-oxazoline), 2,2'-p-phenylenebis (4-methyl-2-oxazoline), 2,2'-p-phenylenebis (4,4-dimethyl- 2-oxazoline), 2,2'-m-phenylenebis (4-methyl-2-oxazoline), 2,2'-m-phenylenebis (4,4-dimethyl-2-oxazoline), 2,2'- Ethylenebis (2-oxazoline), 2,2'-tetramethylenebis (2-oxazoline), 2,2'-hexamethylenebis (2-oxazoline), 2,2'-octamethylenebis (2-oxazoline), 2,2'-Decamethylenebis (2-oxazoline), 2,2'-ethylenebis (4-methyl-2-oxazoline), 2,2'-tetramethylenebis (4,4-dimethyl-2-oxazoline) , 2, 2 Examples include '-9,9'-diphenoxyethanebis (2-oxazoline), 2,2'-cyclohexylenebis (2-oxazoline), 2,2'-diphenylenebis (2-oxazoline), and the like. it can. Among these, 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.
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。 The oxazoline compound can be appropriately selected from compounds having an oxazoline group, and among them, a bisoxazoline compound is preferable.
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). -Oxazoline), 2,2'-bis (4-ethyl-2-oxazoline), 2,2'-bis (4,4'-diethyl-2-oxazoline), 2,2'-bis (4-propyl- 2-oxazoline), 2,2′-bis (4-butyl-2-oxazoline), 2,2′-bis (4-hexyl-2-oxazoline), 2,2′-bis (4-phenyl-2-) Oxazoline), 2,2′-bis (4-cyclohexyl-2-oxazoline), 2,2′-bis (4-benzyl-2-oxazoline), 2,2′-p-phenylenebis (2-oxazoline), 2,2'-m-phenylenebis (2-oxazoline) 2,2'-o-phenylenebis (2-oxazoline), 2,2'-p-phenylenebis (4-methyl-2-oxazoline), 2,2'-p-phenylenebis (4,4-dimethyl- 2-oxazoline), 2,2'-m-phenylenebis (4-methyl-2-oxazoline), 2,2'-m-phenylenebis (4,4-dimethyl-2-oxazoline), 2,2'- Ethylenebis (2-oxazoline), 2,2'-tetramethylenebis (2-oxazoline), 2,2'-hexamethylenebis (2-oxazoline), 2,2'-octamethylenebis (2-oxazoline), 2,2'-Decamethylenebis (2-oxazoline), 2,2'-ethylenebis (4-methyl-2-oxazoline), 2,2'-tetramethylenebis (4,4-dimethyl-2-oxazoline) , 2, 2 Examples include '-9,9'-diphenoxyethanebis (2-oxazoline), 2,2'-cyclohexylenebis (2-oxazoline), 2,2'-diphenylenebis (2-oxazoline), and the like. it can. Among these, 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.
末端封止剤のポリエステルに対する量としては、原料ポリエステルの全質量に対して、0.1質量%以上5質量%以下が好ましい。末端封止剤の原料ポリエステルに対する好ましい量は、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。
末端封止剤の添加比率が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、低熱収縮性も付与することができる。また、末端封止剤の添加比率が5質量%以下であると、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。 The amount of the terminal blocking agent relative to the polyester is preferably 0.1% by mass or more and 5% by mass or less with respect to the total mass of the raw material polyester. A preferable amount of the terminal blocking agent with respect to the raw material polyester 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.
When the addition ratio of the terminal blocking agent is 0.1% by mass or more, weather resistance can be improved due to the AV lowering effect, and low heat shrinkability can be imparted. Moreover, when the addition ratio of the end-capping agent is 5% by mass or less, a decrease in the glass transition temperature (Tg) of the polyester due to the addition of the end-capping agent is suppressed, resulting in a decrease in weather resistance and an 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.
末端封止剤の添加比率が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、低熱収縮性も付与することができる。また、末端封止剤の添加比率が5質量%以下であると、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。 The amount of the terminal blocking agent relative to the polyester is preferably 0.1% by mass or more and 5% by mass or less with respect to the total mass of the raw material polyester. A preferable amount of the terminal blocking agent with respect to the raw material polyester 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.
When the addition ratio of the terminal blocking agent is 0.1% by mass or more, weather resistance can be improved due to the AV lowering effect, and low heat shrinkability can be imparted. Moreover, when the addition ratio of the end-capping agent is 5% by mass or less, a decrease in the glass transition temperature (Tg) of the polyester due to the addition of the end-capping agent is suppressed, resulting in a decrease in weather resistance and an 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.
〔縦延伸工程〕
本発明の縦延伸工程は、フィルム成形工程により得られた固有粘度0.75以上のポリエステルフィルムを、ポリエステルフィルムの長手方向に縦延伸する工程である。
フィルムの縦延伸は、例えば、フィルムを挟む1対のニップロールにフィルムを通して、フィルムの長手方向にフィルムを搬送しながら、フィルムの搬送方向に並べた2対以上のニップロールでフィルムを用いて行なうことができる。
具体的には、例えば、フィルムの搬送方向上流側に1対のニップロールA、下流側に1対のニップロールBを設置したとき、フィルムを搬送する際に、下流側のニップロールBの回転速度を、上流側のニップロールAの回転速度より速くすることで、フィルムが搬送方向(MD;Machine Direction)に延伸される。
なお、上流側、下流側、それぞれに、各々独立に、2対以上のニップロールを設置してもよい。
また、ポリエステルフィルムの縦延伸は、上記ニップロールを備えた縦延伸装置を用いて行なってもよい。 [Vertical stretching process]
The longitudinal stretching step of the present invention is a step of longitudinally stretching a polyester film having an intrinsic viscosity of 0.75 or more obtained by the film forming step in the longitudinal direction of the polyester film.
The longitudinal stretching of the film can be performed, for example, by using the film with 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. it can.
Specifically, for example, when a pair of nip rolls A is installed on the upstream side in the film transport direction and a pair of nip rolls B is installed on the downstream side, when the film is transported, the rotational speed of the nip roll B on the downstream side is By making it faster than the rotational speed of the nip roll A on the upstream side, the film is stretched in the transport direction (MD).
Two or more pairs of nip rolls may be installed independently on the upstream side and the downstream side, respectively.
Moreover, you may perform the longitudinal stretch of a polyester film using the longitudinal stretch apparatus provided with the said nip roll.
本発明の縦延伸工程は、フィルム成形工程により得られた固有粘度0.75以上のポリエステルフィルムを、ポリエステルフィルムの長手方向に縦延伸する工程である。
フィルムの縦延伸は、例えば、フィルムを挟む1対のニップロールにフィルムを通して、フィルムの長手方向にフィルムを搬送しながら、フィルムの搬送方向に並べた2対以上のニップロールでフィルムを用いて行なうことができる。
具体的には、例えば、フィルムの搬送方向上流側に1対のニップロールA、下流側に1対のニップロールBを設置したとき、フィルムを搬送する際に、下流側のニップロールBの回転速度を、上流側のニップロールAの回転速度より速くすることで、フィルムが搬送方向(MD;Machine Direction)に延伸される。
なお、上流側、下流側、それぞれに、各々独立に、2対以上のニップロールを設置してもよい。
また、ポリエステルフィルムの縦延伸は、上記ニップロールを備えた縦延伸装置を用いて行なってもよい。 [Vertical stretching process]
The longitudinal stretching step of the present invention is a step of longitudinally stretching a polyester film having an intrinsic viscosity of 0.75 or more obtained by the film forming step in the longitudinal direction of the polyester film.
The longitudinal stretching of the film can be performed, for example, by using the film with 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. it can.
Specifically, for example, when a pair of nip rolls A is installed on the upstream side in the film transport direction and a pair of nip rolls B is installed on the downstream side, when the film is transported, the rotational speed of the nip roll B on the downstream side is By making it faster than the rotational speed of the nip roll A on the upstream side, the film is stretched in the transport direction (MD).
Two or more pairs of nip rolls may be installed independently on the upstream side and the downstream side, respectively.
Moreover, you may perform the longitudinal stretch of a polyester film using the longitudinal stretch apparatus provided with the said nip roll.
縦延伸工程において、ポリエステルフィルムの面積延伸倍率(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。 In the longitudinal stretching step, the area stretch ratio of the polyester film (product of each stretch ratio) is preferably 6 to 18 times, more preferably 8 to 17.5 times the area of the polyester film before stretching, More preferably, it is 10 to 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 or higher and Tg + 30 ° C. or lower.
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。 In the longitudinal stretching step, the area stretch ratio of the polyester film (product of each stretch ratio) is preferably 6 to 18 times, more preferably 8 to 17.5 times the area of the polyester film before stretching, More preferably, it is 10 to 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 or higher and Tg + 30 ° C. or lower.
なお、ポリエステルフィルムを加熱する手段としては、ニップロール等のロールを用いて延伸する場合は、ロール内部にヒーターや温溶媒を流すことのできる配管を設けることで、ロールに接するポリエステルフィルムを加熱することができる。また、ロールを用いない場合においても、ポリエステルフィルムに温風を吹きかけたり、ヒーター等の熱源に接触させ、又は熱源の近傍を通過させることにより、ポリエステルフィルムを加熱することができる。
In addition, as a means to heat a polyester film, when extending | stretching using rolls, such as a nip roll, heating the polyester film which touches a roll by providing piping which can flow a heater and a warm solvent inside a roll. Can do. Even when a roll is not used, the polyester film can be heated by spraying warm air on the polyester film, contacting the polyester film with a heat source such as a heater, or passing the vicinity of the heat source.
本発明のポリエステルフィルムの製造方法では、縦延伸工程とは別に、後述する横延伸工程を含む。従って、本発明のポリエステルフィルムの製造方法では、ポリエステルフィルムを、ポリエステルフィルムの長手方向(搬送方向、MD)と、ポリエステルフィルムの長手方向と直交する方向(TD;Transverse Direction)との少なくとも2軸に延伸する。また、MD方向およびTD方向への延伸は、各々、少なくとも1回ずつ行なえばよい。
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°)の角度の方向を意図するものであるが、機械誤差の範囲の方向であってもよい。機械誤差の範囲とは、ポリエステルの長手方向(搬送方向、MD)と垂直とみなせる角度(90°±5°)の方向をいう。 In the manufacturing method of the polyester film of this invention, the horizontal stretch process mentioned later is included separately from a vertical stretch process. Therefore, in the method for producing a polyester film of the present invention, the polyester film is at least biaxial in the longitudinal direction (conveying direction, MD) of the polyester film and the direction (TD; Transverse Direction) perpendicular to the longitudinal direction of the polyester film. Stretch. The stretching in the MD direction and the TD direction may be performed at least once each.
In addition, "the direction (TD) orthogonal to the longitudinal direction (conveyance direction, MD) of a polyester film" intends the direction of an angle (90 degrees) perpendicular to the longitudinal direction (conveyance direction, MD) of a polyester film. However, it may be in the direction of the range of machine error. The range of mechanical error refers to the direction of an angle (90 ° ± 5 °) that can be regarded as perpendicular to the longitudinal direction (conveying direction, MD) of polyester.
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°)の角度の方向を意図するものであるが、機械誤差の範囲の方向であってもよい。機械誤差の範囲とは、ポリエステルの長手方向(搬送方向、MD)と垂直とみなせる角度(90°±5°)の方向をいう。 In the manufacturing method of the polyester film of this invention, the horizontal stretch process mentioned later is included separately from a vertical stretch process. Therefore, in the method for producing a polyester film of the present invention, the polyester film is at least biaxial in the longitudinal direction (conveying direction, MD) of the polyester film and the direction (TD; Transverse Direction) perpendicular to the longitudinal direction of the polyester film. Stretch. The stretching in the MD direction and the TD direction may be performed at least once each.
In addition, "the direction (TD) orthogonal to the longitudinal direction (conveyance direction, MD) of a polyester film" intends the direction of an angle (90 degrees) perpendicular to the longitudinal direction (conveyance direction, MD) of a polyester film. However, it may be in the direction of the range of machine error. The range of mechanical error refers to the direction of an angle (90 ° ± 5 °) that can be regarded as perpendicular to the longitudinal direction (conveying direction, MD) of polyester.
2軸延伸する方法としては、縦延伸と横延伸とを分離して行なう逐次2軸延伸方法のほか、縦延伸と横延伸を同時に行なう同時2軸延伸方法のいずれであってもよい。
縦延伸と横延伸とは、各々独立に2回以上行なってもよく、縦延伸と横延伸の順序は問わない。例えば、縦延伸→横延伸、縦延伸→横延伸→縦延伸、縦延伸→縦延伸→横延伸、横延伸→縦延伸などの延伸態様が挙げられる。中でも縦延伸→横延伸が好ましい。
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。 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. For example, 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.
Next, the transverse stretching process in the present invention will be described in detail.
縦延伸と横延伸とは、各々独立に2回以上行なってもよく、縦延伸と横延伸の順序は問わない。例えば、縦延伸→横延伸、縦延伸→横延伸→縦延伸、縦延伸→縦延伸→横延伸、横延伸→縦延伸などの延伸態様が挙げられる。中でも縦延伸→横延伸が好ましい。
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。 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. For example, 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.
Next, the transverse stretching process in the present invention will be described in detail.
〔横延伸工程〕
本発明の横延伸工程は、フィルム成形工程により得られた固有粘度0.75以上のポリエステルフィルムを予熱する予熱部、予熱されたポリエステルフィルムを少なくともポリエステルフィルムの長手方向と直交する方向に緊張を与えて、ポリエステルフィルムを横延伸する延伸部、緊張が与えられたポリエステルフィルムを該ポリエステルフィルムの表面の最高到達膜面温度が160℃~210℃となるように加熱して熱固定する熱固定部、及び、ポリエステルフィルムの表面の最高到達膜面温度が、熱固定部におけるポリエステルフィルムの最高到達膜面温度よりも5℃以上低い温度となるように、熱固定したポリエステルフィルムを加熱し、緊張を緩める熱緩和部に、ポリエステルフィルムをこの順に搬送して、少なくとも横延伸する工程である。
横延伸工程は、上記構成でポリエステルフィルムが少なくとも横延伸されれば、その実現手段は制限されないが、上記構成の処理を可能とする横延伸装置または2軸延伸機を用いて行なうことが好ましい。
また、横延伸工程では、更に、熱緩和部を経たポリエステルフィルムを冷却することが好ましい。
以下、2軸延伸機の説明に即して横延伸工程の詳細を説明する。 [Horizontal stretching process]
In the transverse stretching step of the present invention, a preheating portion for preheating a polyester film having an intrinsic viscosity of 0.75 or more obtained by the film forming step, and tension is applied to the preheated polyester film at least in a direction perpendicular to the longitudinal direction of the polyester film. A stretching part for transversely stretching the polyester film, a heat fixing part for heating and fixing the tensioned polyester film so that the highest surface temperature of the polyester film reaches 160 ° C. to 210 ° C., And the heat-fixed polyester film is heated to relax the tension so that the maximum film surface temperature on the surface of the polyester film is 5 ° C. or more lower than the maximum film surface temperature of the polyester film in the heat-fixed part. The polyester film is conveyed in this order to the heat relaxation part and at least laterally stretched. It is a degree.
The means for realizing the transverse stretching step is not limited as long as the polyester film is at least transversely stretched in the above configuration, but is preferably performed using a lateral stretching apparatus or a biaxial stretching machine that enables processing of the above configuration.
In the transverse stretching step, it is further preferable to cool the polyester film that has passed through the thermal relaxation portion.
Hereinafter, the details of the transverse stretching step will be described in accordance with the description of the biaxial stretching machine.
本発明の横延伸工程は、フィルム成形工程により得られた固有粘度0.75以上のポリエステルフィルムを予熱する予熱部、予熱されたポリエステルフィルムを少なくともポリエステルフィルムの長手方向と直交する方向に緊張を与えて、ポリエステルフィルムを横延伸する延伸部、緊張が与えられたポリエステルフィルムを該ポリエステルフィルムの表面の最高到達膜面温度が160℃~210℃となるように加熱して熱固定する熱固定部、及び、ポリエステルフィルムの表面の最高到達膜面温度が、熱固定部におけるポリエステルフィルムの最高到達膜面温度よりも5℃以上低い温度となるように、熱固定したポリエステルフィルムを加熱し、緊張を緩める熱緩和部に、ポリエステルフィルムをこの順に搬送して、少なくとも横延伸する工程である。
横延伸工程は、上記構成でポリエステルフィルムが少なくとも横延伸されれば、その実現手段は制限されないが、上記構成の処理を可能とする横延伸装置または2軸延伸機を用いて行なうことが好ましい。
また、横延伸工程では、更に、熱緩和部を経たポリエステルフィルムを冷却することが好ましい。
以下、2軸延伸機の説明に即して横延伸工程の詳細を説明する。 [Horizontal stretching process]
In the transverse stretching step of the present invention, a preheating portion for preheating a polyester film having an intrinsic viscosity of 0.75 or more obtained by the film forming step, and tension is applied to the preheated polyester film at least in a direction perpendicular to the longitudinal direction of the polyester film. A stretching part for transversely stretching the polyester film, a heat fixing part for heating and fixing the tensioned polyester film so that the highest surface temperature of the polyester film reaches 160 ° C. to 210 ° C., And the heat-fixed polyester film is heated to relax the tension so that the maximum film surface temperature on the surface of the polyester film is 5 ° C. or more lower than the maximum film surface temperature of the polyester film in the heat-fixed part. The polyester film is conveyed in this order to the heat relaxation part and at least laterally stretched. It is a degree.
The means for realizing the transverse stretching step is not limited as long as the polyester film is at least transversely stretched in the above configuration, but is preferably performed using a lateral stretching apparatus or a biaxial stretching machine that enables processing of the above configuration.
In the transverse stretching step, it is further preferable to cool the polyester film that has passed through the thermal relaxation portion.
Hereinafter, the details of the transverse stretching step will be described in accordance with the description of the biaxial stretching machine.
(2軸延伸機)
図1に、2軸延伸機の一例(上面図)を示す。
図1には、2軸延伸機100と、2軸延伸機100に装着されたポリエステルフィルム200とが示されている。2軸延伸機100は、1対の環状レール60aおよび60bを備え、ポリエステルフィルム200を挟んで対称に並んでいる。 (Biaxial stretching machine)
FIG. 1 shows an example (top view) of a biaxial stretching machine.
FIG. 1 shows abiaxial stretching machine 100 and a polyester film 200 attached to the biaxial stretching machine 100. The biaxial stretching machine 100 includes a pair of annular rails 60a and 60b, and is arranged symmetrically with the polyester film 200 in between.
図1に、2軸延伸機の一例(上面図)を示す。
図1には、2軸延伸機100と、2軸延伸機100に装着されたポリエステルフィルム200とが示されている。2軸延伸機100は、1対の環状レール60aおよび60bを備え、ポリエステルフィルム200を挟んで対称に並んでいる。 (Biaxial stretching machine)
FIG. 1 shows an example (top view) of a biaxial stretching machine.
FIG. 1 shows a
2軸延伸機100は、ポリエステルフィルム200を予熱する予熱部10と、ポリエステルフィルム200を、矢印MD方向と直交する方向である矢印TD方向に延伸してポリエステルフィルムに緊張を与える延伸部20と、緊張が与えられたポリエステルフィルムに緊張を与えたまま加熱する熱固定部30と、熱固定したポリエステルフィルムを加熱して熱固定したポリエステルフィルムの緊張を緩める熱緩和部40と、熱緩和部を経たポリエステルフィルムを冷却する冷却部50と、に分けられる。
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. And a cooling unit 50 for cooling the polyester film.
環状レール60aは、環状レール60aの縁を移動可能な把持部材2a、2b、2e、2f、2i、及び、2jを少なくとも備え、環状レール60bは、環状レール60bの縁を移動可能な把持部材2c、2d、2g、2h、2k、及び、2lを少なくとも備えている。把持部材2a、2b、2e、2f、2i、及び、2jは、ポリエステルフィルム200のTD方向の一方の端部を把持し、把持部材2c、2d、2g、2h、2k、及び、2lは、ポリエステルフィルム200のTD方向の他方の端部を把持している。把持部材2a~2lは、一般に、チャック、クリップ等と称される。
把持部材2a、2b、2e、2f、2i、及び、2jは、環状レール60aの縁に沿って反時計回りに移動し、把持部材2c、2d、2g、2h、2k、及び、2lは、環状レール60bの縁に沿って時計回りに移動する。 Theannular rail 60a includes at least gripping members 2a, 2b, 2e, 2f, 2i, and 2j that can move the edge of the annular rail 60a. The annular rail 60b is a gripping member 2c that can move the edge of the annular rail 60b. 2d, 2g, 2h, 2k, and 2l. 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 polyester The other end of the film 200 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 edge of the annular rail 60a, and the gripping members 2c, 2d, 2g, 2h, 2k, and 2l are annular It moves clockwise along the edge of the rail 60b.
把持部材2a、2b、2e、2f、2i、及び、2jは、環状レール60aの縁に沿って反時計回りに移動し、把持部材2c、2d、2g、2h、2k、及び、2lは、環状レール60bの縁に沿って時計回りに移動する。 The
The gripping
把持部材2a~2dは、予熱部10においてポリエステルフィルム200の端部を把持し、そのまま、環状レール60aまたは60bの縁を移動し、延伸部20や、把持部材2e~2hが示される熱緩和部40を経て、把持部材2i~2lが示される冷却部50まで進む。その後、把持部材2aおよび2bと、把持部材2cおよび2dとは、搬送方向順に、冷却部50のMD方向下流側の端部でポリエステルフィルム200の端部を離し、そのまま、環状レール60aまたは60bの縁に沿って進行し、予熱部10に戻る。
その結果、ポリエステルフィルム200は、図1における矢印MD方向に移動し、予熱部10と、延伸部20と、熱固定部30と、熱緩和部40と、冷却部50とに、順に搬送される。
把持部材2a~2lの移動速度が、ポリエステルフィルム200の把持部分における搬送速度となる。 The holdingmembers 2a to 2d hold the end portion of the polyester film 200 in the preheating unit 10 and move the edge of the annular rail 60a or 60b as it is, so that the extending portion 20 and the heat relaxation unit in which the holding members 2e to 2h are shown After 40, the process proceeds to the cooling unit 50 where the gripping members 2i to 2l are shown. Thereafter, 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 the annular rail 60a or 60b is left as it is. Proceed along the edge and return to the preheating section 10.
As a result, thepolyester film 200 moves in the direction of the arrow MD in FIG. 1 and is sequentially conveyed to the preheating unit 10, the stretching unit 20, the heat fixing unit 30, the heat relaxation unit 40, and the cooling unit 50. .
The moving speed of thegripping members 2a to 2l becomes the transport speed at the gripping portion of the polyester film 200.
その結果、ポリエステルフィルム200は、図1における矢印MD方向に移動し、予熱部10と、延伸部20と、熱固定部30と、熱緩和部40と、冷却部50とに、順に搬送される。
把持部材2a~2lの移動速度が、ポリエステルフィルム200の把持部分における搬送速度となる。 The holding
As a result, the
The moving speed of the
把持部材2a~2lは、各々独立に、移動速度を変化することができる。
従って、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。 The grippingmembers 2a to 2l can change the moving speed independently of each other.
Accordingly, thebiaxial stretching machine 100 enables the transverse stretching in which the polyester film 200 is stretched in the TD direction in the stretching section 20, but the polyester film can be changed by changing the moving speed of the gripping members 2a to 2l. 200 can also be stretched in the MD direction.
That is, simultaneous biaxial stretching can be performed using thebiaxial stretching machine 100.
従って、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。 The gripping
Accordingly, the
That is, simultaneous biaxial stretching can be performed using the
ポリエステルフィルム200のTD方向の端部を把持する把持部材は、図1では、2a~2lの12個のみを図示しているが、ポリエステルフィルム200を支えるため、2軸延伸機100は、2a~2lのほかにも、図示しない把持部材を有する。
なお、以下、把持部材2a~2lを、「把持部材2」と総称することもある。 In FIG. 1, only twelvegripping members 2a to 2l are shown as gripping members for gripping the end portion of the polyester film 200 in the TD direction. In addition to 2l, it has a gripping member (not shown).
Hereinafter, the grippingmembers 2a to 2l may be collectively referred to as “grip member 2”.
なお、以下、把持部材2a~2lを、「把持部材2」と総称することもある。 In FIG. 1, only twelve
Hereinafter, the gripping
(予熱部)
予熱部10では、ポリエステルフィルム200を予熱する。ポリエステルフィルム200を延伸する前に予め加熱して、ポリエステルフィルム200の横延伸を容易にする。
予熱部終了点における膜面温度(以下、「予熱温度」とも称する)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℃~Tg+60℃であることが好ましく、Tg℃~Tg+50℃であることがより好ましい。
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。 (Preheating part)
In the preheatingunit 10, the polyester film 200 is preheated. Before the polyester film 200 is stretched, it is heated in advance to facilitate the lateral stretching of the polyester film 200.
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., where Tg is the glass transition temperature of thepolyester film 200, and Tg ° C. to Tg + 50. It is more preferable that the temperature is C.
The end point of the preheating portion refers to the time when the preheating of thepolyester film 200 is finished, that is, the position where the polyester film 200 is separated from the region of the preheating portion 10.
予熱部10では、ポリエステルフィルム200を予熱する。ポリエステルフィルム200を延伸する前に予め加熱して、ポリエステルフィルム200の横延伸を容易にする。
予熱部終了点における膜面温度(以下、「予熱温度」とも称する)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℃~Tg+60℃であることが好ましく、Tg℃~Tg+50℃であることがより好ましい。
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。 (Preheating part)
In the preheating
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., where Tg is the glass transition temperature of the
The end point of the preheating portion refers to the time when the preheating of the
(延伸部)
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(搬送方向、MD)と直交する方向(TD)に横延伸してポリエステルフィルム200に緊張を与える。
ポリエステルフィルム200の長手方向(搬送方向、MD)と直交する方向(TD)への延伸(横延伸)は、既述のように、ポリエステルフィルム200の長手方向(搬送方向、MD)と垂直(90°)の角度の方向に延伸することを意図するものであるが、機械誤差の範囲の方向であってもよい。機械誤差の範囲とは、ポリエステルの長手方向(搬送方向、MD)と垂直とみなせる角度(90°±5°)の方向である。 (Extension part)
In the stretchingunit 20, the preheated polyester film 200 is laterally stretched at least in the direction (TD) perpendicular to the longitudinal direction (conveying direction, MD) of the polyester film 200 to give tension to the polyester film 200.
Stretching (transverse stretching) in the direction (TD) perpendicular to the longitudinal direction (conveying direction, MD) of thepolyester film 200 is perpendicular to the longitudinal direction (conveying direction, MD) of the polyester film 200 (90) as described above. Is intended to be stretched in the direction of the angle (°), but may be in the direction of a range of mechanical errors. The range of the mechanical error is a direction at an angle (90 ° ± 5 °) that can be regarded as perpendicular to the longitudinal direction (conveying direction, MD) of the polyester.
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(搬送方向、MD)と直交する方向(TD)に横延伸してポリエステルフィルム200に緊張を与える。
ポリエステルフィルム200の長手方向(搬送方向、MD)と直交する方向(TD)への延伸(横延伸)は、既述のように、ポリエステルフィルム200の長手方向(搬送方向、MD)と垂直(90°)の角度の方向に延伸することを意図するものであるが、機械誤差の範囲の方向であってもよい。機械誤差の範囲とは、ポリエステルの長手方向(搬送方向、MD)と垂直とみなせる角度(90°±5°)の方向である。 (Extension part)
In the stretching
Stretching (transverse stretching) in the direction (TD) perpendicular to the longitudinal direction (conveying direction, MD) of the
延伸部20において、ポリエステルフィルム200に与える横延伸のための緊張(延伸張力)は、0.1t/m~6.0t/mである。
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」とも称する)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。 In the stretchingportion 20, the tension (stretching tension) for lateral stretching applied to the polyester film 200 is 0.1 t / m to 6.0 t / m.
Further, the area stretch ratio (product of each stretch ratio) of thepolyester 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.
Further, the film surface temperature of thepolyester film 200 during transverse stretching (hereinafter also referred to as “lateral stretching temperature”) is Tg−10 ° C. or higher and Tg + 100 ° C. or lower when the glass transition temperature of the polyester film 200 is Tg. More preferably, it is Tg ° C. or more and Tg + 90 ° C. or less, and further preferably Tg + 10 ° C. or more and Tg + 80 ° C. or less.
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」とも称する)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。 In the stretching
Further, the area stretch ratio (product of each stretch ratio) of the
Further, the film surface temperature of the
既述のように、把持部材2(把持部材2a~2l)は、各々独立に、移動速度を変化することができ、例えば、予熱部10における把持部材2の移動速度よりも、延伸部20、熱固定部30等の延伸部20MD方向下流側における把持部材2の移動速度を速めることで、ポリエステルフィルム200を、搬送方向(MD)に延伸する縦延伸を併せて行なうことも可能である。
横延伸工程におけるポリエステルフィルム200の縦延伸は、延伸部20のみで行なってもよいし、後述する熱固定部30、熱緩和部40、または、冷却部50で行なってもよい。複数の箇所で縦延伸を行なってもよい。 As described above, the gripping member 2 (grip members 2a to 2l) can independently change the moving speed. For example, the extending portion 20, By increasing the moving speed of the gripping member 2 on the downstream side in the MD 20 MD direction such as the heat fixing unit 30, it is also possible to perform longitudinal stretching for stretching the polyester film 200 in the transport direction (MD).
The longitudinal stretching of thepolyester 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.
横延伸工程におけるポリエステルフィルム200の縦延伸は、延伸部20のみで行なってもよいし、後述する熱固定部30、熱緩和部40、または、冷却部50で行なってもよい。複数の箇所で縦延伸を行なってもよい。 As described above, the gripping member 2 (
The longitudinal stretching of the
(熱固定部)
熱固定部30では、緊張が与えられたポリエステルフィルム200を、ポリエステルフィルム200の表面の最高到達膜面温度が160℃~210℃となるように加熱して熱固定する。
熱固定とは、延伸部20においてポリエステルフィルム200に緊張を与えたまま、特定の温度で加熱することをいい、本発明では、ポリエステルフィルム200の表面の最高到達膜面温度が160℃~210℃となるように加熱する。
緊張の与えられたポリエステルフィルム200を表面の最高到達膜面温度が160℃~210℃となるように加熱することで、ポリエステル分子の結晶を配向させて、耐加水分解性を付与することができる。 (Heat fixing part)
In theheat fixing unit 30, the tensioned polyester film 200 is heated and fixed so that the maximum film surface temperature on the surface of the polyester film 200 is 160 ° C. to 210 ° C.
Heat setting refers to heating at a specific temperature while tension is applied to thepolyester film 200 in the stretched portion 20. Heat until
By heating the tensionedpolyester film 200 so that the maximum surface temperature of the surface reaches 160 ° C. to 210 ° C., the polyester molecules can be oriented to impart hydrolysis resistance. .
熱固定部30では、緊張が与えられたポリエステルフィルム200を、ポリエステルフィルム200の表面の最高到達膜面温度が160℃~210℃となるように加熱して熱固定する。
熱固定とは、延伸部20においてポリエステルフィルム200に緊張を与えたまま、特定の温度で加熱することをいい、本発明では、ポリエステルフィルム200の表面の最高到達膜面温度が160℃~210℃となるように加熱する。
緊張の与えられたポリエステルフィルム200を表面の最高到達膜面温度が160℃~210℃となるように加熱することで、ポリエステル分子の結晶を配向させて、耐加水分解性を付与することができる。 (Heat fixing part)
In the
Heat setting refers to heating at a specific temperature while tension is applied to the
By heating the tensioned
熱固定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(以下、「熱固定温度」、「T熱固定」とも称する)が160℃よりも低いと、ポリエステルがほとんど結晶化しないため、ポリエステル分子を伸びた状態で固定化することができず、耐加水分解性を十分向上することができない。また、熱固定温度が210℃よりも高いと、ポリエステル分子同士の絡み合い箇所で滑りが生じ、ポリエステル分子が縮んでしまい、耐加水分解性を十分向上することができない。
熱固定温度は、170℃~200℃であることが好ましく、175℃~195℃であることがより好ましい。
なお、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ることで測定することができる。 When the maximum film surface temperature of the surface of thepolyester film 200 during heat setting (hereinafter also referred to as “heat setting temperature” or “T heat setting ”) is lower than 160 ° C., the polyester hardly crystallizes. Cannot be fixed in the stretched state, and the hydrolysis resistance cannot be sufficiently improved. On the other hand, if the heat setting temperature is higher than 210 ° C., slippage occurs at the entangled portions of the polyester molecules, the polyester molecules shrink, and the hydrolysis resistance cannot be sufficiently improved.
The heat setting temperature is preferably 170 ° C. to 200 ° C., more preferably 175 ° C. to 195 ° C.
The heat setting temperature can be measured by bringing a thermocouple into contact with the surface of thepolyester film 200.
熱固定温度は、170℃~200℃であることが好ましく、175℃~195℃であることがより好ましい。
なお、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ることで測定することができる。 When the maximum film surface temperature of the surface of the
The heat setting temperature is preferably 170 ° C. to 200 ° C., more preferably 175 ° C. to 195 ° C.
The heat setting temperature can be measured by bringing a thermocouple into contact with the surface of the
(熱緩和部)
熱緩和部40では、ポリエステルフィルム200の表面の最高到達膜面温度が、熱固定部30におけるポリエステルフィルム200の最高到達膜面温度(T熱固定)よりも5℃以上低い温度となるように、ポリエステルフィルム200を加熱して、ポリエステルフィルム200に与えられている緊張を緩める。
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)とも称する。
熱緩和部40において、熱緩和温度(T熱緩和)を、熱固定温度(T熱固定)よりも5℃以上低い温度(T熱緩和≦T熱固定-5℃)で加熱して緊張を解く(延伸張力を小さくする)ことで、ポリエステルフィルムの寸法安定性を向上することができる。 (Heat relaxation part)
In theheat relaxation part 40, the highest ultimate film surface temperature of the surface of the polyester film 200 is 5 ° C. or lower than the highest ultimate film surface temperature (T heat fixation ) of the polyester film 200 in the heat fixing part 30. The polyester film 200 is heated to relax the tension applied to the polyester film 200.
Hereinafter, the highest reached film surface temperature of the surface of thepolyester film 200 during thermal relaxation is also referred to as “thermal relaxation temperature” (T thermal relaxation ).
In thethermal relaxation section 40, 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. By reducing the stretching tension, the dimensional stability of the polyester film can be improved.
熱緩和部40では、ポリエステルフィルム200の表面の最高到達膜面温度が、熱固定部30におけるポリエステルフィルム200の最高到達膜面温度(T熱固定)よりも5℃以上低い温度となるように、ポリエステルフィルム200を加熱して、ポリエステルフィルム200に与えられている緊張を緩める。
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)とも称する。
熱緩和部40において、熱緩和温度(T熱緩和)を、熱固定温度(T熱固定)よりも5℃以上低い温度(T熱緩和≦T熱固定-5℃)で加熱して緊張を解く(延伸張力を小さくする)ことで、ポリエステルフィルムの寸法安定性を向上することができる。 (Heat relaxation part)
In the
Hereinafter, the highest reached film surface temperature of the surface of the
In the
熱緩和温度(T熱緩和)が、「T熱固定-5℃」よりも高い温度であると、緩和工程でポリエステル分子の伸びが縮んでしまい、ポリエステルフィルムの耐加水分解性が低下する。
一方、熱緩和温度(T熱緩和)が、100℃以下になると、ポリエステル分子同士の分子鎖間を縮めにくく、寸法安定性を良化しにくいため、熱緩和温度(T熱緩和)は100℃以上であることが好ましい。
熱緩和温度(T熱緩和)は、100℃以上、かつ、熱固定温度(T熱固定)よりも15℃以上低い温度(100℃≦T熱緩和≦T熱固定-15℃)であることがより好ましく、110℃以上、かつ、熱固定温度(T熱固定)よりも25℃以上低い温度(110℃≦T熱緩和≦T熱固定-25℃)であることがさらに好ましく、120℃以上、かつ、熱固定温度(T熱固定)よりも30℃以上低い温度(120℃≦T熱緩和≦T熱固定-30℃)であることがより好ましい。
なお、熱緩和温度は、ポリエステルフィルム200の表面に熱電対を接触させることで測定することができる。 When the thermal relaxation temperature (T thermal relaxation ) is higher than “T heat fixation— 5 ° C.”, the elongation of the polyester molecules is shrunk in the relaxation step, and the hydrolysis resistance of the polyester film is lowered.
On the other hand, the heat relaxation temperature (T heat relaxation) is equal to or 100 ° C. or less, hardly reduced the inter-molecular chains of the polyester molecules are, for hardly improved dimensional stability, thermal relaxation temperature (T heat relaxation) is 100 ° C. or higher It is preferable that
Thermal relaxation temperature (T heat relaxation) is, 100 ° C. or higher, and to be thermally fixed temperature (T heat-) 15 ° C. or higher than the lower temperature (100 ° C. ≦ T heat relaxation ≦ T heat--15 ° C.) More preferably, the temperature is 110 ° C. or more and 25 ° C. or more lower than the heat setting temperature (T heat setting ) (110 ° C ≦ T heat relaxation ≦ T heat setting−25 ° C.), more preferably 120 ° C. or more. Further, it is more preferable that the temperature is 120 ° C. or more lower than the heat setting temperature (T heat setting ) (120 ° C. ≦ T heat relaxation ≦ T heat setting−30 ° C.).
The thermal relaxation temperature can be measured by bringing a thermocouple into contact with the surface of thepolyester film 200.
一方、熱緩和温度(T熱緩和)が、100℃以下になると、ポリエステル分子同士の分子鎖間を縮めにくく、寸法安定性を良化しにくいため、熱緩和温度(T熱緩和)は100℃以上であることが好ましい。
熱緩和温度(T熱緩和)は、100℃以上、かつ、熱固定温度(T熱固定)よりも15℃以上低い温度(100℃≦T熱緩和≦T熱固定-15℃)であることがより好ましく、110℃以上、かつ、熱固定温度(T熱固定)よりも25℃以上低い温度(110℃≦T熱緩和≦T熱固定-25℃)であることがさらに好ましく、120℃以上、かつ、熱固定温度(T熱固定)よりも30℃以上低い温度(120℃≦T熱緩和≦T熱固定-30℃)であることがより好ましい。
なお、熱緩和温度は、ポリエステルフィルム200の表面に熱電対を接触させることで測定することができる。 When the thermal relaxation temperature (T thermal relaxation ) is higher than “T heat fixation— 5 ° C.”, the elongation of the polyester molecules is shrunk in the relaxation step, and the hydrolysis resistance of the polyester film is lowered.
On the other hand, the heat relaxation temperature (T heat relaxation) is equal to or 100 ° C. or less, hardly reduced the inter-molecular chains of the polyester molecules are, for hardly improved dimensional stability, thermal relaxation temperature (T heat relaxation) is 100 ° C. or higher It is preferable that
Thermal relaxation temperature (T heat relaxation) is, 100 ° C. or higher, and to be thermally fixed temperature (T heat-) 15 ° C. or higher than the lower temperature (100 ° C. ≦ T heat relaxation ≦ T heat--15 ° C.) More preferably, the temperature is 110 ° C. or more and 25 ° C. or more lower than the heat setting temperature (T heat setting ) (110 ° C ≦ T heat relaxation ≦ T heat setting−25 ° C.), more preferably 120 ° C. or more. Further, it is more preferable that the temperature is 120 ° C. or more lower than the heat setting temperature (T heat setting ) (120 ° C. ≦ T heat relaxation ≦ T heat setting−30 ° C.).
The thermal relaxation temperature can be measured by bringing a thermocouple into contact with the surface of the
また、熱緩和部40においては、少なくともポリエステルフィルム200のTD方向における緩和を行なう。かかる処理により、緊張が与えられたポリエステルフィルム200は、TD方向に縮む。
TD方向の緩和は、延伸部20においてポリエステルフィルム200に与えた延伸張力を2%~90%弱めればよい。本発明においては、40%とすることが好ましい。 Moreover, in thethermal relaxation part 40, the polyester film 200 is relaxed at least in the TD direction. By this treatment, the tensioned polyester film 200 shrinks in the TD direction.
For relaxation in the TD direction, the stretching tension applied to thepolyester film 200 at the stretching portion 20 may be reduced by 2% to 90%. In the present invention, it is preferably 40%.
TD方向の緩和は、延伸部20においてポリエステルフィルム200に与えた延伸張力を2%~90%弱めればよい。本発明においては、40%とすることが好ましい。 Moreover, in the
For relaxation in the TD direction, the stretching tension applied to the
(冷却部)
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を冷却する。
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の形状を固定化することができる。
冷却部50におけるポリエステル200の冷却部出口の膜面温度(以下、「冷却温度」ともいう)は、ポリエステルフィルム200のガラス転移温度Tg+50℃よりも低いことが好ましい。具体的には、25℃~110℃であることが好ましく、より好ましくは25℃~95℃、さらに好ましくは25℃~80℃である。
上記範囲であることで、クリップ把持を解いたあとフィルムが不均一に縮むことを防止することができる。
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および2l)が、ポリエステルフィルム200を離すときの位置をいう。 (Cooling section)
In the coolingpart 50, the polyester film 200 which passed through the heat relaxation part 40 is cooled.
By cooling thepolyester film 200 heated by the heat fixing unit 30 or the heat relaxation unit 40, the shape of the polyester film 200 can be fixed.
The film surface temperature (hereinafter also referred to as “cooling temperature”) of the cooling part outlet of thepolyester 200 in the cooling part 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.
By being in the above range, it is possible to prevent the film from shrinking unevenly after releasing the clip.
Here, the cooling unit outlet refers to an end portion of the coolingunit 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.
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を冷却する。
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の形状を固定化することができる。
冷却部50におけるポリエステル200の冷却部出口の膜面温度(以下、「冷却温度」ともいう)は、ポリエステルフィルム200のガラス転移温度Tg+50℃よりも低いことが好ましい。具体的には、25℃~110℃であることが好ましく、より好ましくは25℃~95℃、さらに好ましくは25℃~80℃である。
上記範囲であることで、クリップ把持を解いたあとフィルムが不均一に縮むことを防止することができる。
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および2l)が、ポリエステルフィルム200を離すときの位置をいう。 (Cooling section)
In the cooling
By cooling the
The film surface temperature (hereinafter also referred to as “cooling temperature”) of the cooling part outlet of the
By being in the above range, it is possible to prevent the film from shrinking unevenly after releasing the clip.
Here, the cooling unit outlet refers to an end portion of the cooling
なお、横延伸工程における予熱、延伸、熱固定、熱緩和、及び冷却において、ポリエステルフィルム200を加熱し、または冷却する温度制御手段としては、ポリエステルフィルム200に温風や冷風を吹きかけたり、ポリエステルフィルム200を、温度制御可能な金属板の表面に接触させ、又は前記金属板の近傍を通過させることが挙げられる
In addition, as the temperature control means for heating or cooling the polyester film 200 in preheating, stretching, heat setting, thermal 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.
(フィルムの回収)
冷却されたポリエステルフィルム200は、TD方向両端の把持部分をカットし、ロール状に巻き取られる。 (Recovery of film)
The cooledpolyester film 200 is cut into grips at both ends in the TD direction and wound up in a roll shape.
冷却されたポリエステルフィルム200は、TD方向両端の把持部分をカットし、ロール状に巻き取られる。 (Recovery of film)
The cooled
横延伸工程においては、製造されるポリエステルフィルムの耐加水分解性及び寸法安定性を、より高めるために、次の手法により、延伸したポリエステルフィルムの緩和を行なうことが好ましい。
In the transverse stretching step, 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.
既述のように、横延伸工程は、縦延伸工程の後に行なうことが好ましい。
このように、横延伸工程を縦延伸工程の後に行なった後、冷却部50でMD方向の緩和を行なう場合、次のようにして行なうことができる。
まず、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および2bで把持し、他方を把持部材2cおよび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。 As described above, the transverse stretching step is preferably performed after the longitudinal stretching step.
As described above, after the transverse stretching process is performed after the longitudinal stretching process, when the coolingunit 50 performs relaxation in the MD direction, it can be performed as follows.
First, in the preheatingpart 10, the both ends of the width direction (TD) of the polyester film 200 are hold | gripped using at least 2 holding member per one end part. For example, 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. Next, the polyester film 200 is conveyed from the preheating unit 10 to the cooling unit 50 by moving the gripping members 2a to 2d.
このように、横延伸工程を縦延伸工程の後に行なった後、冷却部50でMD方向の緩和を行なう場合、次のようにして行なうことができる。
まず、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および2bで把持し、他方を把持部材2cおよび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。 As described above, the transverse stretching step is preferably performed after the longitudinal stretching step.
As described above, after the transverse stretching process is performed after the longitudinal stretching process, when the cooling
First, in the preheating
かかる搬送において、予熱部10におけるポリエステルフィルム200の幅方向(TD方向)の片端部を把持する把持部材2a(2c)(前記2つの把持部材のうちの一方の把持部材)と、把持部材2a(2c)に隣接する他の把持部材2b(2d)(前記2つの把持部材のうちの他方の把持部材)との間隔よりも、冷却部50におけるポリエステルフィルム200の幅方向の片端部を把持する把持部材2a(2c)(前記2つの把持部材のうちの一方の把持部材)と、把持部材2a(2c)に隣接する他の把持部材2b(2d)(前記2つの把持部材のうちの他方の把持部材)との間隔を狭めることで、ポリエステルフィルム200の搬送速度を小さくする。かかる手法によって、冷却部50でMD方向の緩和を行なうことができる。
In this conveyance, a gripping member 2a (2c) (one gripping member of the two gripping members) that grips one end of the polyester film 200 in the width direction (TD direction) in the preheating unit 10, and a gripping member 2a ( 2c) A grip that grips one end portion of the polyester film 200 in the width direction in the cooling unit 50, rather than a distance from another gripping member 2b (2d) (the other gripping member of the two gripping members) adjacent to 2c). The member 2a (2c) (one of the two gripping members) and another gripping member 2b (2d) adjacent to the gripping member 2a (2c) (the other gripping of the two gripping members) The conveyance speed of the polyester film 200 is reduced by narrowing the distance between the member and the member. With this method, the cooling unit 50 can relax the MD direction.
ポリエステルフィルム200のMD方向の緩和は、熱固定部30、熱緩和部40、及び冷却部50の少なくとも一部において行なうことができる。
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。従って、MD方向の緩和を熱固定部30または熱緩和部40で行なう場合は、把持部材2a~2dが熱固定部30または熱緩和部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。 The relaxation of thepolyester 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.
As described above, thepolyester 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. Therefore, when relaxation in the MD direction is performed by the heat fixing unit 30 or the heat relaxation unit 40, the moving speed of the gripping members 2a to 2d when the gripping members 2a to 2d reach the heat fixing unit 30 or the heat relaxation unit 40. The conveyance speed of the polyester film 200 is reduced, and the distance between the gripping members 2a-2b and the distance between the gripping members 2c-2d may be narrower than the distance in the preheating portion.
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。従って、MD方向の緩和を熱固定部30または熱緩和部40で行なう場合は、把持部材2a~2dが熱固定部30または熱緩和部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。 The relaxation of the
As described above, the
このように、横延伸工程において、ポリエステルフィルム200のTD方向の延伸(横延伸)およびTD方向の緩和をすると共に、MD方向の延伸(縦延伸)およびMD方向の緩和をすることで、耐加水分解性を向上しつつ、寸法安定性を改良することができる。
ポリエステルフィルム200のTD方向の緩和およびMD方向の緩和は、ポリエステルフィルム200の搬送速度と、ポリエステルフィルム200の幅(TD方向の長さ)を次のように制御することによって行なうことが好ましい。 As described above, in the transverse stretching step, thepolyester film 200 is stretched in the TD direction (lateral stretching) and relaxed in the TD direction, and also stretched in the MD direction (longitudinal stretching) and relaxed in the MD direction. The dimensional stability can be improved while improving the decomposability.
The relaxation of thepolyester film 200 in the TD direction and the relaxation in the MD direction are preferably performed by controlling the transport speed of the polyester film 200 and the width (length in the TD direction) of the polyester film 200 as follows.
ポリエステルフィルム200のTD方向の緩和およびMD方向の緩和は、ポリエステルフィルム200の搬送速度と、ポリエステルフィルム200の幅(TD方向の長さ)を次のように制御することによって行なうことが好ましい。 As described above, in the transverse stretching step, the
The relaxation of the
すなわち、横延伸工程を、縦延伸工程の後に行い、横延伸工程におけるポリエステルフィルム200の幅が最大になるときのポリエステルフィルム200の幅L1と、冷却部50からポリエステルフィルム200が離れる冷却部50の端部におけるポリエステルフィルム200の幅L2とが、下記式(1)を満たし、かつ、予熱部10におけるポリエステルフィルム200の搬送速度S1と、冷却部50の前記端部におけるポリエステルフィルム200の搬送速度S2とが、下記式(2)を満たすことが好ましい。
That is, the transverse stretching step is performed after the longitudinal stretching step, the width L1 of the polyester film 200 when the width of the polyester film 200 in the transverse stretching step is maximized, and the cooling unit 50 from which the polyester film 200 is separated from the cooling unit 50. The width L2 of the polyester film 200 at the end portion satisfies the following formula (1), and the transport speed S1 of the polyester film 200 in the preheating portion 10 and the transport speed S2 of the polyester film 200 at the end portion of the cooling portion 50. Preferably satisfies the following formula (2).
ここで、「横延伸工程におけるポリエステルフィルム200の幅が最大になるときのポリエステルフィルム200の幅L1」は、ポリエステルフィルム200が延伸部20でTD方向に拡幅された後の、ポリエステルフィルム200のTD方向の最大の長さである。
図1においては、予熱部10における延伸前のポリエステルフィルム200の幅L0が、延伸部20によりポリエステルフィルム200がTD方向に拡幅されて幅L1となり、熱緩和部40で緊張が解かれて、ポリエステルフィルム200が冷却部50から離れるときに幅L2となっていることが示されている。図1においては、L0<L2<L1の順に幅が大きい。すなわち、L1は、予熱部10~冷却部50に至る横延伸工程におけるポリエステルフィルム200の最大の幅である。
図1に示すように、延伸部20を過ぎたポリエステルフィルム200は、その後、熱固定部30にて、緊張が与えられたまま加熱されるため、通常、幅L1は、熱固定部30におけるポリエステルフィルム200の幅(TD方向の長さ)ともいえる。
また、「ポリエステルフィルム200が離れる冷却部50の端部におけるポリエステルフィルム200の幅L2」は、冷却部50に位置し、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および2l)が、ポリエステルフィルム200を離すときにおけるポリエステルフィルム200の幅である。
ポリエステルフィルム200を把持する把持部材2が、ポリエステルフィルム200を離すことで、ポリエステルフィルム200は、冷却部50の領域から離れる。例えば、把持部材2jがP点において、また、把持部材2lがQ点において、それぞれ、ポリエステルフィルム200を離すとき、冷却部50の端部(MD方向の端部)は、P点とQ点とを結んだ直線で表される。 Here, “the width L1 of thepolyester film 200 when the width of the polyester film 200 in the transverse stretching step is maximized” is the TD of the polyester film 200 after the polyester film 200 is widened in the TD direction at the stretching portion 20. The maximum length of the direction.
In FIG. 1, the width L0 of thepolyester film 200 before stretching in the preheating portion 10 is widened in the TD direction by the stretching portion 20 to become the width L1, and the tension is released in the heat relaxation portion 40, and the polyester It is shown that when the film 200 leaves the cooling unit 50, the width L2 is obtained. In FIG. 1, the width increases in the order of L0 <L2 <L1. That is, L1 is the maximum width of the polyester film 200 in the transverse stretching process from the preheating part 10 to the cooling part 50.
As shown in FIG. 1, thepolyester film 200 that has passed through the stretched portion 20 is then heated in the heat fixing portion 30 while being tensioned. Therefore, the width L1 is usually the polyester in the heat fixing portion 30. It can also be said to be the width of the film 200 (length in the TD direction).
The “width L2 of thepolyester film 200 at the end of the cooling unit 50 from which the polyester film 200 is separated” is positioned in the cooling unit 50 and holds the polyester film 200 (the holding members 2j and 2l in FIG. 1). ) Is the width of the polyester film 200 when the polyester film 200 is released.
When the holdingmember 2 that holds the polyester film 200 releases the polyester film 200, the polyester film 200 leaves the region of the cooling unit 50. For example, when the gripping member 2j is at the point P and the gripping member 21 is at the point Q, when the polyester film 200 is released, the end of the cooling unit 50 (the end in the MD direction) is the point P and the point Q. It is represented by a straight line connecting
図1においては、予熱部10における延伸前のポリエステルフィルム200の幅L0が、延伸部20によりポリエステルフィルム200がTD方向に拡幅されて幅L1となり、熱緩和部40で緊張が解かれて、ポリエステルフィルム200が冷却部50から離れるときに幅L2となっていることが示されている。図1においては、L0<L2<L1の順に幅が大きい。すなわち、L1は、予熱部10~冷却部50に至る横延伸工程におけるポリエステルフィルム200の最大の幅である。
図1に示すように、延伸部20を過ぎたポリエステルフィルム200は、その後、熱固定部30にて、緊張が与えられたまま加熱されるため、通常、幅L1は、熱固定部30におけるポリエステルフィルム200の幅(TD方向の長さ)ともいえる。
また、「ポリエステルフィルム200が離れる冷却部50の端部におけるポリエステルフィルム200の幅L2」は、冷却部50に位置し、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および2l)が、ポリエステルフィルム200を離すときにおけるポリエステルフィルム200の幅である。
ポリエステルフィルム200を把持する把持部材2が、ポリエステルフィルム200を離すことで、ポリエステルフィルム200は、冷却部50の領域から離れる。例えば、把持部材2jがP点において、また、把持部材2lがQ点において、それぞれ、ポリエステルフィルム200を離すとき、冷却部50の端部(MD方向の端部)は、P点とQ点とを結んだ直線で表される。 Here, “the width L1 of the
In FIG. 1, the width L0 of the
As shown in FIG. 1, the
The “width L2 of the
When the holding
「予熱部10におけるポリエステルフィルム200の搬送速度S1」は、ポリエステルフィルム200を把持して環状レール60の縁を移動する把持部材2(図1では、2a~2d)の移動速度に相当する。
また、「冷却部50の前記端部におけるポリエステルフィルム200の搬送速度S2」は、冷却部50に位置し、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および2l)が、ポリエステルフィルム200を離すときにおけるポリエステルフィルム200の搬送速度である。換言すると、例えば、把持部材2jがP点において、また、把持部材2lがQ点において、それぞれ、ポリエステルフィルム200を離すとき、「冷却部50の前記端部におけるポリエステルフィルム200の搬送速度S2」は、ポリエステルフィルム200がP点とQ点とを結んだ直線を超えるときの搬送速度に相当する。さらに換言すると、「冷却部50の前記端部におけるポリエステルフィルム200の搬送速度S2」は、把持部材2jおよび2lが、ポリエステルフィルム200を離す直前の把持部材2jおよび2lの移動速度に相当する。 The “conveying speed S1 of thepolyester film 200 in the preheating unit 10” corresponds to the moving speed of the gripping member 2 (2a to 2d in FIG. 1) that grips the polyester film 200 and moves the edge of the annular rail 60.
Further, the “conveying speed S2 of thepolyester film 200 at the end of the cooling unit 50” is determined by the gripping member 2 (the gripping members 2j and 2l in FIG. 1) that is positioned in the cooling unit 50 and grips the polyester film 200. It is the conveyance speed of the polyester film 200 when releasing the polyester film 200. In other words, for example, when the polyester film 200 is released at the gripping member 2j at the point P and the gripping member 21 at the point Q, the "conveying speed S2 of the polyester film 200 at the end of the cooling unit 50" is This corresponds to the conveyance speed when the polyester film 200 exceeds the straight line connecting the P point and the Q point. In other words, the “conveying speed S2 of the polyester film 200 at the end of the cooling unit 50” corresponds to the moving speed of the gripping members 2j and 2l immediately before the gripping members 2j and 2l release the polyester film 200.
また、「冷却部50の前記端部におけるポリエステルフィルム200の搬送速度S2」は、冷却部50に位置し、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および2l)が、ポリエステルフィルム200を離すときにおけるポリエステルフィルム200の搬送速度である。換言すると、例えば、把持部材2jがP点において、また、把持部材2lがQ点において、それぞれ、ポリエステルフィルム200を離すとき、「冷却部50の前記端部におけるポリエステルフィルム200の搬送速度S2」は、ポリエステルフィルム200がP点とQ点とを結んだ直線を超えるときの搬送速度に相当する。さらに換言すると、「冷却部50の前記端部におけるポリエステルフィルム200の搬送速度S2」は、把持部材2jおよび2lが、ポリエステルフィルム200を離す直前の把持部材2jおよび2lの移動速度に相当する。 The “conveying speed S1 of the
Further, the “conveying speed S2 of the
式(1)は、ポリエステルフィルム200を延伸した後、TD方向に緩和するときは、ポリエステルフィルム200の最大の幅(TD方向の長さ)L1が、冷却部50において2%~15%縮まるように緩和することが好ましいことを意味する。
式(2)は、ポリエステルフィルム200をMD方向に緩和するときは、ポリエステルフィルム200の予熱部10における搬送速度S1が、冷却部50において2%~15%減速するように緩和することが好ましいことを意味する。
横延伸工程を、上記構成とすることで、耐加水分解性を向上しつつ、寸法安定性を改良することができる。 Formula (1) indicates that when thepolyester film 200 is stretched and then relaxed in the TD direction, the maximum width (length in the TD direction) L1 of the polyester film 200 is reduced by 2% to 15% in the cooling unit 50. It is preferable to relax.
In the formula (2), when thepolyester film 200 is relaxed in the MD direction, it is preferable that the transport speed S1 in the preheating portion 10 of the polyester film 200 is relaxed so as to be reduced by 2% to 15% in the cooling portion 50. Means.
By setting the lateral stretching step as described above, the dimensional stability can be improved while improving the hydrolysis resistance.
式(2)は、ポリエステルフィルム200をMD方向に緩和するときは、ポリエステルフィルム200の予熱部10における搬送速度S1が、冷却部50において2%~15%減速するように緩和することが好ましいことを意味する。
横延伸工程を、上記構成とすることで、耐加水分解性を向上しつつ、寸法安定性を改良することができる。 Formula (1) indicates that when the
In the formula (2), when the
By setting the lateral stretching step as described above, the dimensional stability can be improved while improving the hydrolysis resistance.
ΔLは、ポリエステルフィルムのTD方向(横方向)の緩和率を示すことから、ΔLを「横方向の緩和率」とも称する。また、ΔSは、ポリエステルフィルムのMD方向(縦方向)の緩和率を示すことから、ΔSを「縦方向の緩和率」とも称する。
ΔL indicates the relaxation rate in the TD direction (lateral direction) of the polyester film, and therefore ΔL is also referred to as “lateral relaxation rate”. Moreover, since ΔS indicates the relaxation rate in the MD direction (longitudinal direction) of the polyester film, ΔS is also referred to as “longitudinal relaxation rate”.
L1とL2との関係、及び、S1とS2との関係を、上記のように示す場合、ΔLは、2%~10%(2%≦ΔL≦10%)であることが好ましく、3%~8%(3%≦ΔL≦8%)であることがより好ましい。また、ΔSは、2%~10%(2%≦ΔS≦10%)であることが好ましく、3%~8%(3%≦ΔS≦8%)であることがより好ましい。
When the relationship between L1 and L2 and the relationship between S1 and S2 is shown as described above, ΔL is preferably 2% to 10% (2% ≦ ΔL ≦ 10%), preferably 3% to More preferably, it is 8% (3% ≦ ΔL ≦ 8%). ΔS is preferably 2% to 10% (2% ≦ ΔS ≦ 10%), more preferably 3% to 8% (3% ≦ ΔS ≦ 8%).
なお、横延伸工程は、既述のように、ポリエステルフィルムの横延伸に特化した横延伸装置を用いて行なってもよい。横延伸装置は、図示していないが、MD方向の延伸(縦延伸)をしない他は、2軸延伸機と同様の構造を有しており、ポリエステルフィルムを把持する把持部材、及び、把持部材を有するレールを備える。横延伸装置が少なくとも予熱部、延伸部、熱固定部、及び熱緩和部で構成されていること、及びその機能についても、既述の2軸延伸機と同様である。
In addition, you may perform a horizontal stretch process using the horizontal stretch apparatus specialized in the horizontal stretch of the polyester film as stated above. Although the transverse stretching apparatus is not shown, it has the same structure as the biaxial stretching machine except that it does not stretch in the MD direction (longitudinal stretching), and a gripping member for gripping the polyester film, and a gripping member A rail having The transverse stretching apparatus is composed of at least a preheating section, a stretching section, a heat fixing section, and a thermal relaxation section, and the function thereof is the same as that of the biaxial stretching machine described above.
ところで、横延伸の対象となるポリエステルフィルム200が、横延伸により得られるポリエステルフィルムの厚みが200μm以上となるような、厚手のフィルム(例えば、700μm以上)である場合、大きな延伸張力を必要とするため、横延伸において、大きな負荷がかかり、2軸延伸機や横延伸装置が故障することがあった。
かかる問題を解決すべく、ポリエステルフィルム200について横延伸を行なう場合は、次のようにして行なうことが好ましい。 By the way, when thepolyester film 200 to be subjected to transverse stretching is a thick film (for example, 700 μm or more) such that the thickness of the polyester film obtained by transverse stretching is 200 μm or more, a large stretching tension is required. Therefore, a large load is applied in the transverse stretching, and the biaxial stretching machine and the transverse stretching apparatus sometimes break down.
In order to solve such a problem, when thepolyester film 200 is stretched laterally, it is preferably performed as follows.
かかる問題を解決すべく、ポリエステルフィルム200について横延伸を行なう場合は、次のようにして行なうことが好ましい。 By the way, when the
In order to solve such a problem, when the
すなわち、延伸部20におけるポリエステルフィルム200の搬送方向(MD)と、延伸部20におけるポリエステルフィルム200の幅方向(TD)の端部の進行方向と、がなす角度を延伸角度θ〔°〕とするとき、延伸部20におけるポリエステルフィルム200の横延伸を開始する位置Xでの延伸角度θx〔°〕と、延伸部20におけるポリエステルフィルム200の横延伸を終了する位置Zでの延伸角度θz〔°〕と、延伸部20における位置Xと位置Zとの中間の位置Yでの延伸角度θy〔°〕とが、下記式(3)を満たし、横延伸終了後の厚みが200μm以上のポリエステルフィルムが得られるように、ポリエステル200を延伸することが好ましい。
0<θx≦θz<θy<10 (3) That is, an angle formed by the conveying direction (MD) of thepolyester film 200 in the stretching portion 20 and the traveling direction of the end portion in the width direction (TD) of the polyester film 200 in the stretching portion 20 is defined as a stretching angle θ [°]. When, the stretching angle θx [°] at the position X where the lateral stretching of the polyester film 200 in the stretching part 20 starts, and the stretching angle θz [°] at the position Z where the lateral stretching of the polyester film 200 in the stretching part 20 ends. And a stretching angle θy [°] at an intermediate position Y between the position X and the position Z in the stretched portion 20 satisfies the following formula (3), and a polyester film having a thickness after the transverse stretching of 200 μm or more is obtained. It is preferable to stretch the polyester 200 so that the
0 <θx ≦ θz <θy <10 (3)
0<θx≦θz<θy<10 (3) That is, an angle formed by the conveying direction (MD) of the
0 <θx ≦ θz <θy <10 (3)
上記横延伸の詳細を、図2を用いて説明する。
図2は、横延伸工程におけるポリエステルフィルムの延伸態様を示す模式図である。
図2に示す202a及び、202bは、横延伸工程において横延伸されているポリエステルフィルムのTD方向端部の軌跡を示す。 The detail of the said horizontal extending | stretching is demonstrated using FIG.
FIG. 2 is a schematic diagram showing a stretching mode of the polyester film in the transverse stretching step.
202a and 202b shown in FIG. 2 show the trajectories of the end portions in the TD direction of the polyester film that is laterally stretched in the lateral stretching step.
図2は、横延伸工程におけるポリエステルフィルムの延伸態様を示す模式図である。
図2に示す202a及び、202bは、横延伸工程において横延伸されているポリエステルフィルムのTD方向端部の軌跡を示す。 The detail of the said horizontal extending | stretching is demonstrated using FIG.
FIG. 2 is a schematic diagram showing a stretching mode of the polyester film in the transverse stretching step.
202a and 202b shown in FIG. 2 show the trajectories of the end portions in the TD direction of the polyester film that is laterally stretched in the lateral stretching step.
図2において、点Aは、ポリエステルフィルムが予熱部に位置し、横延伸されていない状態におけるポリエステルフィルムの幅方向(TD)の片端部の位置である。点Bは、ポリエステルフィルムが熱固定部に位置し、横延伸が完了した状態におけるポリエステルフィルムの幅方向(TD)の片端部の位置である。
点X、点Y、及び点Zは、ポリエステルフィルムが延伸部に位置し、ポリエステルフィルムが幅方向(TD)に拡幅されている最中のポリエステルフィルムの幅方向(TD)の片端部の位置である。
ポリエステルフィルムの幅方向(TD)端部は、点Aから、点X、点Y、点Z、を経て点Bに到達する。 In FIG. 2, point A is the position of one end portion in the width direction (TD) of the polyester film in a state where the polyester film is located in the preheating portion and is not laterally stretched. Point B is the position of one end portion in the width direction (TD) of the polyester film in a state where the polyester film is located at the heat fixing portion and the transverse stretching is completed.
The point X, the point Y, and the point Z are positions at one end in the width direction (TD) of the polyester film in which the polyester film is positioned in the stretched portion and the polyester film is widened in the width direction (TD). is there.
The width direction (TD) end part of the polyester film reaches point B from point A through point X, point Y, and point Z.
点X、点Y、及び点Zは、ポリエステルフィルムが延伸部に位置し、ポリエステルフィルムが幅方向(TD)に拡幅されている最中のポリエステルフィルムの幅方向(TD)の片端部の位置である。
ポリエステルフィルムの幅方向(TD)端部は、点Aから、点X、点Y、点Z、を経て点Bに到達する。 In FIG. 2, point A is the position of one end portion in the width direction (TD) of the polyester film in a state where the polyester film is located in the preheating portion and is not laterally stretched. Point B is the position of one end portion in the width direction (TD) of the polyester film in a state where the polyester film is located at the heat fixing portion and the transverse stretching is completed.
The point X, the point Y, and the point Z are positions at one end in the width direction (TD) of the polyester film in which the polyester film is positioned in the stretched portion and the polyester film is widened in the width direction (TD). is there.
The width direction (TD) end part of the polyester film reaches point B from point A through point X, point Y, and point Z.
点X、点Y、及び点Zの位置について、より詳しく説明する。
点Xは、延伸部におけるポリエステルフィルムの横延伸を開始する位置であり、点Zは、延伸部におけるポリエステルフィルムの横延伸を終了する位置である。
ここで、「延伸部におけるポリエステルフィルムの横延伸を開始する位置」は、具体的には、延伸部のMD方向の長さをMとしたとき、延伸部のMD方向の上流側の端部からMの10%の位置をいう。また、「延伸部におけるポリエステルフィルムの横延伸を終了する位置」とは、延伸部のMD方向の下流側の端部からMの10%の位置をいう。
点Yは、点Xの位置と、点Zの位置との中間の位置である。 The positions of the point X, the point Y, and the point Z will be described in more detail.
The point X is a position where the lateral stretching of the polyester film in the stretched part is started, and the point Z is a position where the lateral stretching of the polyester film in the stretched part is finished.
Here, “the position at which the lateral stretching of the polyester film in the stretched portion starts” is specifically, from the end on the upstream side in the MD direction of the stretched portion, where M is the length of the stretched portion in the MD direction. The 10% position of M. In addition, “the position at which the lateral stretching of the polyester film in the stretched portion is finished” refers to a position of 10% of M from the downstream end of the stretched portion in the MD direction.
Point Y is an intermediate position between the position of point X and the position of point Z.
点Xは、延伸部におけるポリエステルフィルムの横延伸を開始する位置であり、点Zは、延伸部におけるポリエステルフィルムの横延伸を終了する位置である。
ここで、「延伸部におけるポリエステルフィルムの横延伸を開始する位置」は、具体的には、延伸部のMD方向の長さをMとしたとき、延伸部のMD方向の上流側の端部からMの10%の位置をいう。また、「延伸部におけるポリエステルフィルムの横延伸を終了する位置」とは、延伸部のMD方向の下流側の端部からMの10%の位置をいう。
点Yは、点Xの位置と、点Zの位置との中間の位置である。 The positions of the point X, the point Y, and the point Z will be described in more detail.
The point X is a position where the lateral stretching of the polyester film in the stretched part is started, and the point Z is a position where the lateral stretching of the polyester film in the stretched part is finished.
Here, “the position at which the lateral stretching of the polyester film in the stretched portion starts” is specifically, from the end on the upstream side in the MD direction of the stretched portion, where M is the length of the stretched portion in the MD direction. The 10% position of M. In addition, “the position at which the lateral stretching of the polyester film in the stretched portion is finished” refers to a position of 10% of M from the downstream end of the stretched portion in the MD direction.
Point Y is an intermediate position between the position of point X and the position of point Z.
ポリエステルフィルムの幅方向(TD)の片端部が点X(位置X)にある場合、ポリエステルフィルムの幅方向の端部の点X(位置X)における進行方向は、点Xにおける接線の矢印方向(γx)で表される。
従って、延伸部におけるポリエステルフィルムの搬送方向(MD)と、延伸部におけるポリエステルフィルムの幅方向の端部の進行方向と、がなす角度を延伸角度θ〔°〕とするとき、位置X(点X)での延伸角度θx〔°〕は、MDとγxとのなす角度として表される。 When one end portion in the width direction (TD) of the polyester film is at the point X (position X), the traveling direction at the point X (position X) at the end portion in the width direction of the polyester film is the tangential arrow direction at the point X ( γx).
Therefore, when the angle formed by the conveyance direction (MD) of the polyester film in the stretching portion and the traveling direction of the end portion in the width direction of the polyester film in the stretching portion is the stretching angle θ [°], the position X (point X ) Is expressed as an angle formed by MD and γx.
従って、延伸部におけるポリエステルフィルムの搬送方向(MD)と、延伸部におけるポリエステルフィルムの幅方向の端部の進行方向と、がなす角度を延伸角度θ〔°〕とするとき、位置X(点X)での延伸角度θx〔°〕は、MDとγxとのなす角度として表される。 When one end portion in the width direction (TD) of the polyester film is at the point X (position X), the traveling direction at the point X (position X) at the end portion in the width direction of the polyester film is the tangential arrow direction at the point X ( γx).
Therefore, when the angle formed by the conveyance direction (MD) of the polyester film in the stretching portion and the traveling direction of the end portion in the width direction of the polyester film in the stretching portion is the stretching angle θ [°], the position X (point X ) Is expressed as an angle formed by MD and γx.
同様に、ポリエステルフィルムの幅方向(TD)の片端部が点Y(位置Y)にある場合、ポリエステルフィルムの幅方向の端部の点Y(位置Y)における進行方向は、点Y(位置Y)における接線の矢印方向(γy)で表される。また、ポリエステルフィルムの幅方向(TD)の片端部が点Z(位置Z)にある場合、ポリエステルフィルムの幅方向の端部の点Z(位置Z)における進行方向は、点Z(位置Z)における接線の矢印方向(γz)で表される。
Similarly, when the one end portion in the width direction (TD) of the polyester film is at the point Y (position Y), the traveling direction at the point Y (position Y) at the end portion in the width direction of the polyester film is the point Y (position Y). ) In the direction of the tangent arrow (γy). Moreover, when the one end part of the width direction (TD) of a polyester film exists in the point Z (position Z), the advancing direction in the point Z (position Z) of the edge part of the width direction of a polyester film is the point Z (position Z). It is represented by the arrow direction (γz) of the tangent line.
従って、位置Y(点Y)での延伸角度θy〔°〕は、MDとγyとのなす角度として表され、位置Z(点Z)での延伸角度θz〔°〕は、MDとγzとのなす角度として表される。
Therefore, the stretching angle θy [°] at the position Y (point Y) is expressed as an angle formed by the MD and γy, and the stretching angle θz [°] at the position Z (point Z) is the difference between the MD and γz. Expressed as the angle to make.
さらに、θx〔°〕と、θy〔°〕と、θz〔°〕とが式(3)を満たすことが好ましい。
ポリエステルフィルムの横延伸を上記構成で行なって、厚みが200μm以上のポリエステルフィルムを得ることで、2軸延伸機や横延伸装置に生じ得る大きな負荷を低減することができる。 Furthermore, it is preferable that θx [°], θy [°], and θz [°] satisfy Expression (3).
By carrying out the transverse stretching of the polyester film with the above-described configuration to obtain a polyester film having a thickness of 200 μm or more, it is possible to reduce a large load that may occur in a biaxial stretching machine or a transverse stretching apparatus.
ポリエステルフィルムの横延伸を上記構成で行なって、厚みが200μm以上のポリエステルフィルムを得ることで、2軸延伸機や横延伸装置に生じ得る大きな負荷を低減することができる。 Furthermore, it is preferable that θx [°], θy [°], and θz [°] satisfy Expression (3).
By carrying out the transverse stretching of the polyester film with the above-described configuration to obtain a polyester film having a thickness of 200 μm or more, it is possible to reduce a large load that may occur in a biaxial stretching machine or a transverse stretching apparatus.
式(3)は、下記式(3-1)で表されることが好ましく、下記式(3-2)で表されることがより好ましい。
0.5≦θx≦θz<θy≦8.0 (3-1)
1.0≦θx≦θz<θy≦7.0 (3-2) Formula (3) is preferably represented by the following formula (3-1), and more preferably represented by the following formula (3-2).
0.5 ≦ θx ≦ θz <θy ≦ 8.0 (3-1)
1.0 ≦ θx ≦ θz <θy ≦ 7.0 (3-2)
0.5≦θx≦θz<θy≦8.0 (3-1)
1.0≦θx≦θz<θy≦7.0 (3-2) Formula (3) is preferably represented by the following formula (3-1), and more preferably represented by the following formula (3-2).
0.5 ≦ θx ≦ θz <θy ≦ 8.0 (3-1)
1.0 ≦ θx ≦ θz <θy ≦ 7.0 (3-2)
<ポリエステルフィルム>
本発明のポリエステルフィルムは、既述の本発明のポリエステルフィルムの製造方法により製造されたポリエステルフィルムであれば特に制限されないが、次の構成を有することが好ましい。
すなわち、本発明のポリエステルフィルムは、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する構成単位を含むことが好ましい。また、本発明のポリエステルフィルムは、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の少なくとも1種類の末端封止剤に由来する構造部分を含むことが好ましい。
ポリエステルフィルムが、3官能以上の多官能モノマーに由来の構成単位を含むことで、ポリエステルフィルムに隣接する材料との密着力に優れる。また、ポリエステルフィルムが、末端封止剤に由来する構造部分を含むことによっても、ポリエステルフィルムに隣接する材料との密着力に優れる。 <Polyester film>
Although the polyester film of this invention will not be restrict | limited especially if it is the polyester film manufactured by the manufacturing method of the polyester film of this invention as stated above, it is preferable to have the following structure.
That is, the polyester film of the present invention preferably contains a structural unit derived from 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. Moreover, it is preferable that the polyester film of this invention contains the structure part originating in the at least 1 sort (s) of terminal blocker of an oxazoline type compound, a carbodiimide compound, and an epoxy compound.
When the polyester film contains a structural unit derived from a trifunctional or higher polyfunctional monomer, the polyester film is excellent in adhesion to a material adjacent to the polyester film. Moreover, it is excellent in the adhesive force with the material adjacent to a polyester film also when a polyester film contains the structure part originating in a terminal blocker.
本発明のポリエステルフィルムは、既述の本発明のポリエステルフィルムの製造方法により製造されたポリエステルフィルムであれば特に制限されないが、次の構成を有することが好ましい。
すなわち、本発明のポリエステルフィルムは、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する構成単位を含むことが好ましい。また、本発明のポリエステルフィルムは、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の少なくとも1種類の末端封止剤に由来する構造部分を含むことが好ましい。
ポリエステルフィルムが、3官能以上の多官能モノマーに由来の構成単位を含むことで、ポリエステルフィルムに隣接する材料との密着力に優れる。また、ポリエステルフィルムが、末端封止剤に由来する構造部分を含むことによっても、ポリエステルフィルムに隣接する材料との密着力に優れる。 <Polyester film>
Although the polyester film of this invention will not be restrict | limited especially if it is the polyester film manufactured by the manufacturing method of the polyester film of this invention as stated above, it is preferable to have the following structure.
That is, the polyester film of the present invention preferably contains a structural unit derived from 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. Moreover, it is preferable that the polyester film of this invention contains the structure part originating in the at least 1 sort (s) of terminal blocker of an oxazoline type compound, a carbodiimide compound, and an epoxy compound.
When the polyester film contains a structural unit derived from a trifunctional or higher polyfunctional monomer, the polyester film is excellent in adhesion to a material adjacent to the polyester film. Moreover, it is excellent in the adhesive force with the material adjacent to a polyester film also when a polyester film contains the structure part originating in a terminal blocker.
既述のように、本発明のポリエステルフィルムの原料としてのポリエステル(原料ポリエステル)は、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たものであることが好ましい。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、既述のとおりである。
As described above, the polyester (raw material polyester) as the raw material of the polyester film of the present invention is, for example, an esterification reaction and / or a (A) dicarboxylic acid component and (B) diol component by a well-known method. It can be obtained by transesterification, and more preferably obtained by copolymerizing a trifunctional or higher polyfunctional monomer. Details of examples and preferred embodiments of the dicarboxylic acid component, the diol component, and the polyfunctional monomer are as described above.
-多官能モノマーに由来の構成単位-
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、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、既述のとおりである。
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。 -Structural units derived from polyfunctional monomers-
As a structural unit derived from a polyfunctional monomer in which the sum (a + b) of the number of carboxylic acid groups (a) and the number of hydroxyl groups (b) is 3 or more, a structural unit derived from a polyfunctional monomer having 3 or more carboxylic acid groups (a) Polyfunctional monomers having a hydroxyl number (b) of 3 or more, such as acids and ester derivatives or acid anhydrides thereof, and “the number of carboxylic acid groups (a) having both a hydroxyl group and a carboxylic acid group in one molecule; And the total number (a + b) of the number of hydroxyl groups (b) is 3 or more ”. Details of these examples and preferred embodiments are as described above.
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, and It is also preferable to add a derivative thereof or a combination of a plurality of such oxyacids.
These may be used individually by 1 type, or may use multiple types together as needed.
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、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、既述のとおりである。
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。 -Structural units derived from polyfunctional monomers-
As a structural unit derived from a polyfunctional monomer in which the sum (a + b) of the number of carboxylic acid groups (a) and the number of hydroxyl groups (b) is 3 or more, a structural unit derived from a polyfunctional monomer having 3 or more carboxylic acid groups (a) Polyfunctional monomers having a hydroxyl number (b) of 3 or more, such as acids and ester derivatives or acid anhydrides thereof, and “the number of carboxylic acid groups (a) having both a hydroxyl group and a carboxylic acid group in one molecule; And the total number (a + b) of the number of hydroxyl groups (b) is 3 or more ”. Details of these examples and preferred embodiments are as described above.
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, and It is also preferable to add a derivative thereof or a combination of a plurality of such oxyacids.
These may be used individually by 1 type, or may use multiple types together as needed.
本発明のポリエステルフィルムにおいて、前記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、ポリエステルフィルム中の全構成単位に対して、0.005モル%以上2.5モル%以下であることが好ましい。多官能モノマーに由来の構成単位の含有比率は、より好ましくは0.020モル%以上1モル%以下であり、更に好ましくは0.025モル%以上1モル%以下であり、更に好ましくは0.035モル%以上0.5モル%以下であり、特に好ましくは0.05モル%以上0.5モル%以下であり、最も好ましくは0.1モル%以上0.25モル%以下である。
In the polyester film of the present invention, 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.
ポリエステルフィルム中に3官能以上の多官能モノマーに由来の構成単位が存在することで、3官能以上の多官能モノマーに由来の構成単位からポリエステル分子鎖を枝分かれされた構造が得られ、ポリエステル分子間の絡み合いを促すことができる。その結果、高温高湿環境下に曝されてポリエステル分子が加水分解し分子量が低下しても、ポリエステル分子間に絡み合いが形成されていることにより、ポリエステルフィルムの脆化が抑制され、より優れた耐候性が得られる。さらに、このような絡み合いは、熱収縮の抑制にも有効である。これは、上記のポリエステル分子の絡み合いによりポリエステル分子の運動性が低下するため、熱で分子が収縮しようとしても収縮できず、ポリエステルフィルムの熱収縮が抑制されたものと推定される。
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、低熱収縮性がさらに向上し易い。また、3官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、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。 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 when exposed to high temperature and high humidity environment, polyester molecules are hydrolyzed and the molecular weight is reduced, so that entanglement is formed between the polyester molecules, so that the embrittlement of the polyester film is suppressed and more excellent. Weather resistance is obtained. Further, such entanglement is also effective in suppressing heat shrinkage. This is presumably because the motility of the polyester molecules decreases due to the entanglement of the polyester molecules, so that even if the molecules try to contract due to heat, they cannot contract and the thermal contraction of the polyester film is suppressed.
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 and the low heat shrinkability are easily improved. Moreover, since 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 functional 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 structural units derived from trifunctional or higher polyfunctional monomers, increasing free volume (gap between molecules) is suppressed, and thermal shrinkage that occurs when polyester molecules slip through a large free volume is suppressed. can do. In addition, 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.
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、低熱収縮性がさらに向上し易い。また、3官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、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。 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 when exposed to high temperature and high humidity environment, polyester molecules are hydrolyzed and the molecular weight is reduced, so that entanglement is formed between the polyester molecules, so that the embrittlement of the polyester film is suppressed and more excellent. Weather resistance is obtained. Further, such entanglement is also effective in suppressing heat shrinkage. This is presumably because the motility of the polyester molecules decreases due to the entanglement of the polyester molecules, so that even if the molecules try to contract due to heat, they cannot contract and the thermal contraction of the polyester film is suppressed.
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 and the low heat shrinkability are easily improved. Moreover, since 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 functional 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 structural units derived from trifunctional or higher polyfunctional monomers, increasing free volume (gap between molecules) is suppressed, and thermal shrinkage that occurs when polyester molecules slip through a large free volume is suppressed. can do. In addition, 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.
-末端封止剤に由来する構造部分-
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。 -Structural part derived from end-capping agent-
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.
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。 -Structural part derived from end-capping agent-
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.
末端封止剤がポリエステルフィルム中に含められると、末端封止剤はポリエステル末端のカルボン酸と反応し、ポリエステル末端に結合して存在するため、末端COOH量(AV値)を、既述の好ましい範囲など所望とする値に安定的に維持し易くなる。すなわち、末端カルボン酸により促進されるポリエステルの加水分解が抑制され、耐候性を高く保つことができる。さらに、末端封止剤は嵩高く、ポリエステル分子が自由体積中をすり抜けて移動するのを抑制する。その結果、分子の移動を伴なう熱収縮を抑制する効果も有する。
When the end-capping agent is included in the polyester film, 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. Furthermore, the end-capping agent is bulky and suppresses the movement of the polyester molecules through the free volume. As a result, it also has an effect of suppressing heat shrinkage accompanied by molecular movement.
「末端封止剤に由来する構造部分」を構成する末端封止剤は、1種単独であってもよく、2種以上の組合せでもよい。
末端封止剤に由来する構造部分は、ポリエステルフィルムに対して、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。
末端封止剤に由来する構造部分の含有比率が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、低熱収縮性も付与することができる。また、末端封止剤に由来する構造部分の含有比率が5質量%以下であると、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。
末端封止剤の好ましい態様については既述のとおりである。 The terminal blocking agent constituting the “structural portion derived from the terminal blocking agent” may be a single type or a combination of two or more types.
The structural portion derived from the end-capping agent is preferably contained in the range of 0.1% by mass or more and 5% by mass or less, more preferably 0.3% by mass or more and 4% by mass with respect to the polyester film. Or less, more preferably 0.5% by mass or more and 2% by mass or less.
When the content ratio of the structural portion derived from 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 can be imparted. Moreover, the fall of the glass transition temperature (Tg) of polyester by addition of terminal blocker is suppressed as the content rate of the structure part originating in terminal blocker is 5 mass% or less, and the weather resistance fall by this 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 preferred embodiment of the terminal blocking agent is as described above.
末端封止剤に由来する構造部分は、ポリエステルフィルムに対して、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。
末端封止剤に由来する構造部分の含有比率が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、低熱収縮性も付与することができる。また、末端封止剤に由来する構造部分の含有比率が5質量%以下であると、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。
末端封止剤の好ましい態様については既述のとおりである。 The terminal blocking agent constituting the “structural portion derived from the terminal blocking agent” may be a single type or a combination of two or more types.
The structural portion derived from the end-capping agent is preferably contained in the range of 0.1% by mass or more and 5% by mass or less, more preferably 0.3% by mass or more and 4% by mass with respect to the polyester film. Or less, more preferably 0.5% by mass or more and 2% by mass or less.
When the content ratio of the structural portion derived from 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 can be imparted. Moreover, the fall of the glass transition temperature (Tg) of polyester by addition of terminal blocker is suppressed as the content rate of the structure part originating in terminal blocker is 5 mass% or less, and the weather resistance fall by this 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 preferred embodiment of the terminal blocking agent is as described above.
(ポリエステルフィルムの物性)
本発明のポリエステルフィルムの製造方法における既述の延伸工程および横延伸工程を経て得られたポリエステルフィルムは、30分間150℃で加熱する加熱条件における熱収縮率が2.0%以下であることが好ましい。
一般にポリエステルは、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に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により、ポリエステルフィルムに貼り付けられた機能性の部材シートの剥離や、ポリエステルフィルムに塗布形成した層のひび割れ等を防止することができる。
既述の本発明のポリエステルフィルムの製造方法を実施することにより、上記熱収縮率を実現することができ、特に、横延伸工程における熱固定および熱緩和における加熱温度(T熱固定およびT熱緩和の少なくとも一方)を制御するによって、上記範囲に調整することができる。
30分間150℃で加熱する加熱条件における熱収縮率は、1.0%以下であることがより好ましく、0.5%以下であることがさらに好ましい。 (Physical properties of polyester film)
The polyester film obtained through the above-described stretching step and transverse stretching step in the method for producing a polyester film of the present invention has a heat shrinkage of 2.0% or less under heating conditions of heating at 150 ° C. for 30 minutes. preferable.
In general, polyester has a higher coefficient of thermal expansion and hygroscopic expansion than glass, so it tends to be stressed by changes in temperature and humidity, and tends to cause cracking and peeling of the layer, but the thermal shrinkage rate is within the above range. By being, it can prevent the peeling of the functional member sheet affixed on the polyester film, the crack of the layer apply | coated and formed on the polyester film, etc.
By carrying out the above-described method for producing a polyester film of the present invention, the heat shrinkage rate can be realized, and in particular, the heating temperature (T heat setting and T heat relaxation in the transverse stretching step). It is possible to adjust to the above range by controlling at least one of the above.
The heat shrinkage rate under heating conditions of heating at 150 ° C. for 30 minutes is more preferably 1.0% or less, and further preferably 0.5% or less.
本発明のポリエステルフィルムの製造方法における既述の延伸工程および横延伸工程を経て得られたポリエステルフィルムは、30分間150℃で加熱する加熱条件における熱収縮率が2.0%以下であることが好ましい。
一般にポリエステルは、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に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により、ポリエステルフィルムに貼り付けられた機能性の部材シートの剥離や、ポリエステルフィルムに塗布形成した層のひび割れ等を防止することができる。
既述の本発明のポリエステルフィルムの製造方法を実施することにより、上記熱収縮率を実現することができ、特に、横延伸工程における熱固定および熱緩和における加熱温度(T熱固定およびT熱緩和の少なくとも一方)を制御するによって、上記範囲に調整することができる。
30分間150℃で加熱する加熱条件における熱収縮率は、1.0%以下であることがより好ましく、0.5%以下であることがさらに好ましい。 (Physical properties of polyester film)
The polyester film obtained through the above-described stretching step and transverse stretching step in the method for producing a polyester film of the present invention has a heat shrinkage of 2.0% or less under heating conditions of heating at 150 ° C. for 30 minutes. preferable.
In general, polyester has a higher coefficient of thermal expansion and hygroscopic expansion than glass, so it tends to be stressed by changes in temperature and humidity, and tends to cause cracking and peeling of the layer, but the thermal shrinkage rate is within the above range. By being, it can prevent the peeling of the functional member sheet affixed on the polyester film, the crack of the layer apply | coated and formed on the polyester film, etc.
By carrying out the above-described method for producing a polyester film of the present invention, the heat shrinkage rate can be realized, and in particular, the heating temperature (T heat setting and T heat relaxation in the transverse stretching step). It is possible to adjust to the above range by controlling at least one of the above.
The heat shrinkage rate under heating conditions of heating at 150 ° C. for 30 minutes is more preferably 1.0% or less, and further preferably 0.5% or less.
既述の本発明のポリエステルフィルムの製造方法により、厚さ30μm~400μmのポリエステルフィルムを製造することが好ましい。
ポリエステルフィルムの厚みは、電気絶縁性の観点から、40μm~350μmであることが好ましく、50μm~300μmであることがより好ましい。
得られたポリエステルフィルムは、太陽電池発電モジュールの太陽光入射側とは反対側の裏面に配置される裏面保護シート(いわゆるバックシート)、バリアフィルム基材等の用途に好適である。 It is preferable to produce a polyester film having a thickness of 30 μm to 400 μm by the method for producing a polyester film of the present invention described above.
The thickness of the polyester film is preferably 40 μm to 350 μm, more preferably 50 μm to 300 μm, from the viewpoint of electrical insulation.
The obtained polyester film is suitable for uses such as a back surface protective sheet (so-called back sheet) and a barrier film substrate disposed on the back surface opposite to the sunlight incident side of the solar cell power generation module.
ポリエステルフィルムの厚みは、電気絶縁性の観点から、40μm~350μmであることが好ましく、50μm~300μmであることがより好ましい。
得られたポリエステルフィルムは、太陽電池発電モジュールの太陽光入射側とは反対側の裏面に配置される裏面保護シート(いわゆるバックシート)、バリアフィルム基材等の用途に好適である。 It is preferable to produce a polyester film having a thickness of 30 μm to 400 μm by the method for producing a polyester film of the present invention described above.
The thickness of the polyester film is preferably 40 μm to 350 μm, more preferably 50 μm to 300 μm, from the viewpoint of electrical insulation.
The obtained polyester film is suitable for uses such as a back surface protective sheet (so-called back sheet) and a barrier film substrate disposed on the back surface opposite to the sunlight incident side of the solar cell power generation module.
<太陽電池用バックシート、及び、太陽電池モジュール>
本発明の太陽電池用バックシートは、本発明のポリエステルフィルムを含んで構成される。
本発明の太陽電池用バックシートは、太陽電池モジュールを構成する部材として好ましく用いることができる。
例えば、太陽電池モジュールは、太陽光が入射する透明性のフロント基板と、フロント基板の上に設けられ、太陽電池素子及び太陽電池素子を封止する封止材を有するセル構造部分と、セル構造部分のフロント基板が位置する側と反対側に設けられ、封止材と隣接して配置された、本発明の太陽電池用バックシートと、を備えて構成することができる。 <Back sheet for solar cell and solar cell module>
The solar cell backsheet of the present invention comprises the polyester film of the present invention.
The solar cell backsheet of this invention can be preferably used as a member which comprises a solar cell module.
For example, a solar cell module includes a transparent front substrate on which sunlight is incident, a cell structure portion provided on the front substrate and including a solar cell element and a sealing material for sealing the solar cell element, and a cell structure. The solar cell backsheet of the present invention is provided on the side opposite to the side where the front substrate is located and is disposed adjacent to the sealing material.
本発明の太陽電池用バックシートは、本発明のポリエステルフィルムを含んで構成される。
本発明の太陽電池用バックシートは、太陽電池モジュールを構成する部材として好ましく用いることができる。
例えば、太陽電池モジュールは、太陽光が入射する透明性のフロント基板と、フロント基板の上に設けられ、太陽電池素子及び太陽電池素子を封止する封止材を有するセル構造部分と、セル構造部分のフロント基板が位置する側と反対側に設けられ、封止材と隣接して配置された、本発明の太陽電池用バックシートと、を備えて構成することができる。 <Back sheet for solar cell and solar cell module>
The solar cell backsheet of the present invention comprises the polyester film of the present invention.
The solar cell backsheet of this invention can be preferably used as a member which comprises a solar cell module.
For example, a solar cell module includes a transparent front substrate on which sunlight is incident, a cell structure portion provided on the front substrate and including a solar cell element and a sealing material for sealing the solar cell element, and a cell structure. The solar cell backsheet of the present invention is provided on the side opposite to the side where the front substrate is located and is disposed adjacent to the sealing material.
太陽電池モジュール、太陽電池セル、バックシート以外の部材については、例えば、「太陽光発電システム構成材料」(杉本栄一監修、(株)工業調査会、2008年発行)に詳細に記載されている。
Components other than solar cell modules, solar cells, and backsheets are described in detail in, for example, “Solar Power Generation System Constituent Materials” (supervised by Eiichi Sugimoto, Industrial Research Committee, Inc., issued in 2008).
透明性の基板は、太陽光が透過し得る光透過性を有していればよく、光を透過する基材から適宜選択することができる。発電効率の観点からは、光の透過率が高いものほど好ましく、このような基板として、例えば、ガラス基板、アクリル樹脂などの透明樹脂などを好適に用いることができる。
The transparent substrate only needs to have a light-transmitting property through which sunlight can be transmitted, and can be appropriately selected from base materials that transmit light. From the viewpoint of power generation efficiency, the higher the light transmittance, the better. For such a substrate, for example, a glass substrate, a transparent resin such as an acrylic resin, or the like can be suitably used.
太陽電池素子としては、単結晶シリコン、多結晶シリコン、アモルファスシリコンなどのシリコン系、銅-インジウム-ガリウム-セレン、銅-インジウム-セレン、カドミウム-テルル、ガリウム-砒素などのIII-V族やII-VI族化合物半導体系など、各種公知の太陽電池素子を適用することができる。
Solar cell elements include silicon-based materials such as single crystal silicon, polycrystalline silicon, and amorphous silicon, III-V groups such as copper-indium-gallium-selenium, copper-indium-selenium, cadmium-tellurium, gallium-arsenic, and II Various known solar cell elements such as a group VI compound semiconductor can be applied.
以下、本発明を実施例により更に具体的に説明するが、本発明はその主旨を越えない限り、以下の実施例に限定されるものではない。なお、「部」、「%」はとくに記載しない限り、質量基準である。
Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples as long as the gist thereof is not exceeded. “Parts” and “%” are based on mass unless otherwise specified.
<原料ポリエステルの合成>
(原料ポリエステル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。 <Synthesis of raw material polyester>
(Raw material polyester 1)
As shown below, 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.
(原料ポリエステル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。 <Synthesis of raw material polyester>
(Raw material polyester 1)
As shown below, 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.
(1)エステル化反応
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。 (1) Esterification reaction In a first esterification reactor, 4.7 tons of high-purity terephthalic acid and 1.8 tons of ethylene glycol are mixed over 90 minutes to form a slurry, and continuously at a flow rate of 3800 kg / h. It supplied to the 1st esterification reaction tank. Furthermore, an ethylene glycol solution of a citrate chelate titanium complex (VERTEC AC-420, manufactured by Johnson Matthey) in which citric acid is coordinated to Ti metal is continuously supplied, and the average residence time is maintained at 250 ° C. with stirring in the reaction vessel. The reaction was carried out for about 4.3 hours. At this time, the citric acid chelate titanium complex was continuously added so that the amount of Ti added was 9 ppm in terms of element. At this time, the acid value of the obtained oligomer was 600 equivalent / ton.
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。 (1) Esterification reaction In a first esterification reactor, 4.7 tons of high-purity terephthalic acid and 1.8 tons of ethylene glycol are mixed over 90 minutes to form a slurry, and continuously at a flow rate of 3800 kg / h. It supplied to the 1st esterification reaction tank. Furthermore, an ethylene glycol solution of a citrate chelate titanium complex (VERTEC AC-420, manufactured by Johnson Matthey) in which citric acid is coordinated to Ti metal is continuously supplied, and the average residence time is maintained at 250 ° C. with stirring in the reaction vessel. The reaction was carried out for about 4.3 hours. At this time, the citric acid chelate titanium complex was continuously added so that the amount of Ti added was 9 ppm in terms of element. At this time, the acid value of the obtained oligomer was 600 equivalent / ton.
この反応物を第二エステル化反応槽に移送し、攪拌下、反応槽内温度250℃で、平均滞留時間で1.2時間反応させ、酸価が200当量/トンのオリゴマーを得た。第二エステル化反応槽は内部が3ゾーンに仕切られており、第2ゾーンから酢酸マグネシウムのエチレングリコール溶液を、Mg添加量が元素換算値で75ppmになるように連続的に供給し、続いて第3ゾーンから、リン酸トリメチルのエチレングリコール溶液を、P添加量が元素換算値で65ppmになるように連続的に供給した。
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.
(2)重縮合反応
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。 (2) the polycondensation reaction above-obtained esterification reaction product supplied to the first polycondensation reaction vessel continuously stirring, the reaction temperature 270 ° C., thereaction vessel pressure 20 torr (2.67 × 10 - 3 MPa) and polycondensation with an average residence time of about 1.8 hours.
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。 (2) the polycondensation reaction above-obtained esterification reaction product supplied to the first polycondensation reaction vessel continuously stirring, the reaction temperature 270 ° C., the
更に、第二重縮合反応槽に移送し、この反応槽において攪拌下、反応槽内温度276℃、反応槽内圧力5torr(6.67×10-4MPa)で滞留時間約1.2時間の条件で反応(重縮合)させた。
Further, it was transferred to the second double condensation reaction tank, and while stirring in this reaction tank, the reaction tank temperature was 276 ° C., the reaction tank pressure was 5 torr (6.67 × 10 −4 MPa), and the residence time was about 1.2 hours. The reaction (polycondensation) was performed under the conditions.
次いで、更に第三重縮合反応槽に移送し、この反応槽では、反応槽内温度278℃、反応槽内圧力1.5torr(2.0×10-4MPa)で、滞留時間1.5時間の条件で反応(重縮合)させ、反応物(ポリエチレンテレフタレート(PET))を得た。
Subsequently, it was further transferred to the third triple condensation reaction tank, in which the temperature in the reaction tank was 278 ° C., the pressure in the reaction tank was 1.5 torr (2.0 × 10 −4 MPa), and the residence time was 1.5 hours. The reaction product (polyethylene terephthalate (PET)) was obtained by reaction (polycondensation) under the following conditions.
次に、得られた反応物を、冷水にストランド状に吐出し、直ちにカッティングしてポリエステルのペレット<断面:長径約4mm、短径約2mm、長さ:約3mm>を作製した。
Next, the obtained reaction product was discharged into cold water in a strand shape and immediately cut to prepare polyester pellets (cross section: major axis: about 4 mm, minor axis: about 2 mm, length: about 3 mm).
得られたポリエステルについて、高分解能型高周波誘導結合プラズマ-質量分析(HR-ICP-MS;SIIナノテクノロジー社製AttoM)を用いて以下に示すように測定した結果、Ti=9ppm、Mg=75ppm、P=60ppmであった。Pは当初の添加量に対して僅かに減少しているが、重合過程において揮発したものと推定される。
得られたポリマーは、IV=0.65、末端カルボキシ基濃度AV=22当量/トン、融点=257℃、溶液ヘイズ=0.3%であった。 The obtained polyester was measured as shown below using high resolution high frequency inductively coupled plasma-mass spectrometry (HR-ICP-MS; AttoM, manufactured by SII Nanotechnology). As a result, Ti = 9 ppm, Mg = 75 ppm, P = 60 ppm. P is slightly reduced with respect to the initial addition amount, but is estimated to have volatilized during the polymerization process.
The obtained polymer had IV = 0.65, terminal carboxy group concentration AV = 22 eq / ton, melting point = 257 ° C., and solution haze = 0.3%.
得られたポリマーは、IV=0.65、末端カルボキシ基濃度AV=22当量/トン、融点=257℃、溶液ヘイズ=0.3%であった。 The obtained polyester was measured as shown below using high resolution high frequency inductively coupled plasma-mass spectrometry (HR-ICP-MS; AttoM, manufactured by SII Nanotechnology). As a result, Ti = 9 ppm, Mg = 75 ppm, P = 60 ppm. P is slightly reduced with respect to the initial addition amount, but is estimated to have volatilized during the polymerization process.
The obtained polymer had IV = 0.65, terminal carboxy group concentration AV = 22 eq / ton, melting point = 257 ° C., and solution haze = 0.3%.
-固相重合-
また、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、以下の条件で固相重合した。
150℃で予備結晶化処理した後、190℃で30時間の固相重合反応を行った。 -Solid state polymerization-
In addition, solid phase polymerization was performed on the polyester pellets obtained as described above by a batch method. Specifically, after putting polyester pellets into a container, solid-state polymerization was performed under the following conditions while stirring under vacuum.
After precrystallization at 150 ° C., a solid state polymerization reaction was performed at 190 ° C. for 30 hours.
また、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、以下の条件で固相重合した。
150℃で予備結晶化処理した後、190℃で30時間の固相重合反応を行った。 -Solid state polymerization-
In addition, solid phase polymerization was performed on the polyester pellets obtained as described above by a batch method. Specifically, after putting polyester pellets into a container, solid-state polymerization was performed under the following conditions while stirring under vacuum.
After precrystallization at 150 ° C., a solid state polymerization reaction was performed at 190 ° C. for 30 hours.
(原料ポリエステル2)
原料ポリエステル1の合成において、固相重合時間を12時間に変更したほかは同様にして、原料ポリエステル2を得た。 (Raw material polyester 2)
In the synthesis of the raw material polyester 1, theraw material polyester 2 was obtained in the same manner except that the solid phase polymerization time was changed to 12 hours.
原料ポリエステル1の合成において、固相重合時間を12時間に変更したほかは同様にして、原料ポリエステル2を得た。 (Raw material polyester 2)
In the synthesis of the raw material polyester 1, the
(原料ポリエステル3)
原料ポリエステル1の合成において、固相重合時間を10時間に変更したほかは同様にして、原料ポリエステル3を得た。 (Raw material polyester 3)
The raw material polyester 3 was obtained in the same manner except that the solid phase polymerization time was changed to 10 hours in the synthesis of the raw material polyester 1.
原料ポリエステル1の合成において、固相重合時間を10時間に変更したほかは同様にして、原料ポリエステル3を得た。 (Raw material polyester 3)
The raw material polyester 3 was obtained in the same manner except that the solid phase polymerization time was changed to 10 hours in the synthesis of the raw material polyester 1.
(原料ポリエステル4~7)
原料ポリエステル1の合成における(1)エステル化反応において、原料組成中のジカルボン酸成分(テレフタル酸)およびジオール成分(エチレングリコール)に加えて、表1の「材料・添加剤」、「多官能成分」欄に記載の種類の多官能モノマーを、当該欄に示す量だけ添加した。なお、ここでいう添加量とは、ジカルボン酸成分およびジオール成分の和(全モル量)に対するモル%で示した。 (Raw material polyester 4-7)
(1) In the esterification reaction in the synthesis of the raw material polyester 1, in addition to the dicarboxylic acid component (terephthalic acid) and the diol component (ethylene glycol) in the raw material composition, the “materials / additives” and “multifunctional components” in Table 1 The polyfunctional monomer of the type described in the “column” was added in the amount shown in the column. In addition, the addition amount here was shown by mol% with respect to the sum (total molar amount) of a dicarboxylic acid component and a diol component.
原料ポリエステル1の合成における(1)エステル化反応において、原料組成中のジカルボン酸成分(テレフタル酸)およびジオール成分(エチレングリコール)に加えて、表1の「材料・添加剤」、「多官能成分」欄に記載の種類の多官能モノマーを、当該欄に示す量だけ添加した。なお、ここでいう添加量とは、ジカルボン酸成分およびジオール成分の和(全モル量)に対するモル%で示した。 (Raw material polyester 4-7)
(1) In the esterification reaction in the synthesis of the raw material polyester 1, in addition to the dicarboxylic acid component (terephthalic acid) and the diol component (ethylene glycol) in the raw material composition, the “materials / additives” and “multifunctional components” in Table 1 The polyfunctional monomer of the type described in the “column” was added in the amount shown in the column. In addition, the addition amount here was shown by mol% with respect to the sum (total molar amount) of a dicarboxylic acid component and a diol component.
この後、得られたポリエステルを、原料ポリエステル1と同様にしてペレットとし、さらに、原料ポリエステル1と同様の固相重合条件にて原料ポリエステル4~7を得た。
得られたポリエステルは、IV=0.65、末端カルボキシ基濃度AV=22当量/トン、融点=257℃、溶液ヘイズ=0.3%であった。 Thereafter, the obtained polyester was formed into pellets in the same manner as the raw material polyester 1, and further raw material polyesters 4 to 7 were obtained under the same solid phase polymerization conditions as the raw material polyester 1.
The obtained polyester had IV = 0.65, terminal carboxy group concentration AV = 22 eq / ton, melting point = 257 ° C., and solution haze = 0.3%.
得られたポリエステルは、IV=0.65、末端カルボキシ基濃度AV=22当量/トン、融点=257℃、溶液ヘイズ=0.3%であった。 Thereafter, the obtained polyester was formed into pellets in the same manner as the raw material polyester 1, and further raw material polyesters 4 to 7 were obtained under the same solid phase polymerization conditions as the raw material polyester 1.
The obtained polyester had IV = 0.65, terminal carboxy group concentration AV = 22 eq / ton, melting point = 257 ° C., and solution haze = 0.3%.
なお、表1の「材料・添加剤」、「多官能成分」、「種」欄に「TMA」、「BTC」として示す多官能モノマーの詳細は、次のとおりである。
TMA:3官能カルボン酸型、トリメリット酸
BTC:4官能カルボン酸型、ベンゼンテトラカルボン酸 The details of the polyfunctional monomers shown as “TMA” and “BTC” in the “Materials / Additives”, “Polyfunctional Component”, and “Species” columns in Table 1 are as follows.
TMA: Trifunctional carboxylic acid type, trimellitic acid BTC: Tetrafunctional carboxylic acid type, benzenetetracarboxylic acid
TMA:3官能カルボン酸型、トリメリット酸
BTC:4官能カルボン酸型、ベンゼンテトラカルボン酸 The details of the polyfunctional monomers shown as “TMA” and “BTC” in the “Materials / Additives”, “Polyfunctional Component”, and “Species” columns in Table 1 are as follows.
TMA: Trifunctional carboxylic acid type, trimellitic acid BTC: Tetrafunctional carboxylic acid type, benzenetetracarboxylic acid
〔実施例1〕
<未延伸ポリエステルフィルムの製造>
-フィルム成形工程-
原料ポリエステル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。原料ポリエステル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。
溶融樹脂の押出条件は、圧力変動を1%、溶融樹脂の温度分布を2%として、溶融樹脂をダイから押出した。具体的には、背圧を、押出機のバレル内平均圧力に対して1%加圧し、押出機の配管温度を、押出機のバレル内平均温度に対して2%高い温度で加熱した。
ダイから押出した溶融樹脂は、冷却キャストドラム上に押出し、静電印加法を用い冷却キャストドラムに密着させた。
溶融樹脂の冷却は、冷却キャストドラムの温度を25℃に設定し、冷却キャストドラムに対面して設置された冷風発生装置から、25℃の冷風を吹き出し、溶融樹脂に当てた。冷却キャストドラムに対向配置された剥ぎ取りロールを用いて、冷却キャストドラムから厚さ3.5mmの未延伸ポリエステルフィルム(未延伸ポリエステルフィルム1)を剥離した。 [Example 1]
<Manufacture of unstretched polyester film>
-Film forming process-
After the raw material polyester 1 was dried to a water content of 20 ppm or less, it was put into a hopper of a uniaxial kneading extruder having a diameter of 50 mm. The raw material polyester 1 was melted at 300 ° C. and extruded from a die through a gear pump and a filter (pore diameter: 20 μm) 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 molten resin was extruded from the die under the conditions that the pressure fluctuation was 1% and the temperature distribution of the molten resin was 2%. Specifically, the back pressure was increased by 1% with respect to the average pressure in the barrel of the extruder, and the piping temperature of the extruder was heated at atemperature 2% higher than the average temperature in the barrel of the extruder.
The molten resin extruded from the die was extruded onto a cooling cast drum and adhered to the cooling cast drum using an electrostatic application method.
For cooling the molten resin, the temperature of the cooling cast drum was set to 25 ° C., and cold air of 25 ° C. was blown from a cold air generator installed facing the cooling cast drum and applied to the molten resin. An unstretched polyester film (unstretched polyester film 1) having a thickness of 3.5 mm was peeled from the cooling cast drum using a peeling roll disposed opposite to the cooling cast drum.
<未延伸ポリエステルフィルムの製造>
-フィルム成形工程-
原料ポリエステル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。原料ポリエステル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。
溶融樹脂の押出条件は、圧力変動を1%、溶融樹脂の温度分布を2%として、溶融樹脂をダイから押出した。具体的には、背圧を、押出機のバレル内平均圧力に対して1%加圧し、押出機の配管温度を、押出機のバレル内平均温度に対して2%高い温度で加熱した。
ダイから押出した溶融樹脂は、冷却キャストドラム上に押出し、静電印加法を用い冷却キャストドラムに密着させた。
溶融樹脂の冷却は、冷却キャストドラムの温度を25℃に設定し、冷却キャストドラムに対面して設置された冷風発生装置から、25℃の冷風を吹き出し、溶融樹脂に当てた。冷却キャストドラムに対向配置された剥ぎ取りロールを用いて、冷却キャストドラムから厚さ3.5mmの未延伸ポリエステルフィルム(未延伸ポリエステルフィルム1)を剥離した。 [Example 1]
<Manufacture of unstretched polyester film>
-Film forming process-
After the raw material polyester 1 was dried to a water content of 20 ppm or less, it was put into a hopper of a uniaxial kneading extruder having a diameter of 50 mm. The raw material polyester 1 was melted at 300 ° C. and extruded from a die through a gear pump and a filter (pore diameter: 20 μm) 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 molten resin was extruded from the die under the conditions that the pressure fluctuation was 1% and the temperature distribution of the molten resin was 2%. Specifically, the back pressure was increased by 1% with respect to the average pressure in the barrel of the extruder, and the piping temperature of the extruder was heated at a
The molten resin extruded from the die was extruded onto a cooling cast drum and adhered to the cooling cast drum using an electrostatic application method.
For cooling the molten resin, the temperature of the cooling cast drum was set to 25 ° C., and cold air of 25 ° C. was blown from a cold air generator installed facing the cooling cast drum and applied to the molten resin. An unstretched polyester film (unstretched polyester film 1) having a thickness of 3.5 mm was peeled from the cooling cast drum using a peeling roll disposed opposite to the cooling cast drum.
得られた未延伸ポリエステルフィルム1は、固有粘度IV=0.80、末端カルボキシ基濃度AV=15当量/トン、ガラス転移温度Tg=72℃であった。
The obtained unstretched polyester film 1 had an intrinsic viscosity IV = 0.80, a terminal carboxy group concentration AV = 15 eq / ton, and a glass transition temperature Tg = 72 ° C.
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。
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、これを基準液(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
Tgは、JIS K 7121に準じた測定により求めた。 In IV, the unstretched polyester film 1 is dissolved in a 1,1,2,2-tetrachloroethane / phenol (= 2/3 [mass ratio]) mixed solvent, and the solution viscosity at 25 ° C. in the mixed solvent is as follows. I asked for it.
In AV, unstretched polyester film 1 is completely dissolved in a mixed solution of benzyl alcohol / chloroform (= 2/3; volume ratio), phenol red is used as an indicator, and this is used as a reference solution (0.025N KOH-methanol mixed solution). Tg calculated from the appropriate amount was determined by measurement according to JIS K7121.
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、これを基準液(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
Tgは、JIS K 7121に準じた測定により求めた。 In IV, the unstretched polyester film 1 is dissolved in a 1,1,2,2-tetrachloroethane / phenol (= 2/3 [mass ratio]) mixed solvent, and the solution viscosity at 25 ° C. in the mixed solvent is as follows. I asked for it.
In AV, unstretched polyester film 1 is completely dissolved in a mixed solution of benzyl alcohol / chloroform (= 2/3; volume ratio), phenol red is used as an indicator, and this is used as a reference solution (0.025N KOH-methanol mixed solution). Tg calculated from the appropriate amount was determined by measurement according to JIS K7121.
<2軸延伸ポリエステルフィルムの製造>
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軸延伸を施し、次のように延伸して、250μmの2軸延伸ポリエステルフィルム1を得た。 <Production of biaxially stretched polyester film>
The obtained unstretched polyester film 1 was sequentially biaxially stretched by the following method and stretched as follows to obtain a 250 μm biaxially stretched polyester film 1.
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軸延伸を施し、次のように延伸して、250μmの2軸延伸ポリエステルフィルム1を得た。 <Production of biaxially stretched polyester film>
The obtained unstretched polyester film 1 was sequentially biaxially stretched by the following method and stretched as follows to obtain a 250 μm biaxially stretched polyester film 1.
-縦延伸工程-
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 -Longitudinal drawing process-
The unstretched polyester film 1 was passed between two pairs of nip rolls having different peripheral speeds, and stretched in the longitudinal direction (conveying direction) under the following conditions.
Preheating temperature: 80 ° C
Longitudinal stretching temperature: 90 ° C
Longitudinal stretching ratio: 3.6 times Longitudinal stretching stress: 12 MPa
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 -Longitudinal drawing process-
The unstretched polyester film 1 was passed between two pairs of nip rolls having different peripheral speeds, and stretched in the longitudinal direction (conveying direction) under the following conditions.
Preheating temperature: 80 ° C
Longitudinal stretching temperature: 90 ° C
Longitudinal stretching ratio: 3.6 times Longitudinal stretching stress: 12 MPa
-横延伸工程-
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、下記条件にて延伸した。 -Transverse stretching process-
The stretched polyester film 1 (longitudinal stretched polyester film 1) was stretched under the following conditions using a tenter (biaxial stretching machine) having the structure shown in FIG.
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、下記条件にて延伸した。 -Transverse stretching process-
The stretched polyester film 1 (longitudinal stretched polyester film 1) was stretched under the following conditions using a tenter (biaxial stretching machine) having the structure shown in FIG.
(予熱部)
予熱温度:110℃とした。 (Preheating part)
Preheating temperature: 110 ° C.
予熱温度:110℃とした。 (Preheating part)
Preheating temperature: 110 ° C.
(延伸部)
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
延伸角度
横延伸を開始する位置Xでの延伸角度θx:表1に示す角度〔°〕
XとZとの中間の位置Yでの延伸角度θy:表1に示す角度〔°〕
横延伸を終了する位置Zでの延伸角度θz:表1に示す角度〔°〕 (Extension part)
Stretching temperature (transverse stretching temperature): 120 ° C
Stretch ratio (transverse stretch ratio): 4.4 times Stretch stress (transverse stretch stress): 18 MPa
Stretching angle Stretching angle θx at the position X at which lateral stretching is started: angle shown in Table 1 [°]
Stretching angle θy at an intermediate position Y between X and Z: angle shown in Table 1 [°]
Stretching angle θz at the position Z where the lateral stretching is finished: Angle shown in Table 1 [°]
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
延伸角度
横延伸を開始する位置Xでの延伸角度θx:表1に示す角度〔°〕
XとZとの中間の位置Yでの延伸角度θy:表1に示す角度〔°〕
横延伸を終了する位置Zでの延伸角度θz:表1に示す角度〔°〕 (Extension part)
Stretching temperature (transverse stretching temperature): 120 ° C
Stretch ratio (transverse stretch ratio): 4.4 times Stretch stress (transverse stretch stress): 18 MPa
Stretching angle Stretching angle θx at the position X at which lateral stretching is started: angle shown in Table 1 [°]
Stretching angle θy at an intermediate position Y between X and Z: angle shown in Table 1 [°]
Stretching angle θz at the position Z where the lateral stretching is finished: Angle shown in Table 1 [°]
(熱固定部)
熱固定温度(T熱固定):表1に示す温度〔℃〕 (Heat fixing part)
Heat setting temperature (T heat setting ): Temperature shown in Table 1 [° C]
熱固定温度(T熱固定):表1に示す温度〔℃〕 (Heat fixing part)
Heat setting temperature (T heat setting ): Temperature shown in Table 1 [° C]
(熱緩和部)
熱緩和温度(T熱緩和):表1に示す温度〔℃〕
緩和率
横方向(ΔL):表1に示す大きさ〔%〕
縦方向(ΔS):表1に示す大きさ〔%〕 (Heat relaxation part)
Thermal relaxation temperature (T thermal relaxation ): temperature shown in Table 1 [° C.]
Relaxation rate lateral direction (ΔL): size shown in Table 1 [%]
Longitudinal direction (ΔS): size shown in Table 1 [%]
熱緩和温度(T熱緩和):表1に示す温度〔℃〕
緩和率
横方向(ΔL):表1に示す大きさ〔%〕
縦方向(ΔS):表1に示す大きさ〔%〕 (Heat relaxation part)
Thermal relaxation temperature (T thermal relaxation ): temperature shown in Table 1 [° C.]
Relaxation rate lateral direction (ΔL): size shown in Table 1 [%]
Longitudinal direction (ΔS): size shown in Table 1 [%]
(冷却部)
冷却温度:65〔℃〕 (Cooling section)
Cooling temperature: 65 [° C]
冷却温度:65〔℃〕 (Cooling section)
Cooling temperature: 65 [° C]
(フィルムの回収)
熱緩和の後、ポリエステルフィルム1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。
以上のようにして、厚さ250μmの実施例1の2軸延伸ポリエステルフィルム(PETフィルム)1を製造した。 (Recovery of film)
After heat relaxation, both ends of the polyester film 1 were trimmed by 20 cm. Then, after extruding (knurling) with a width of 10 mm at both ends, it was wound up with a tension of 25 kg / m.
As described above, a biaxially stretched polyester film (PET film) 1 of Example 1 having a thickness of 250 μm was produced.
熱緩和の後、ポリエステルフィルム1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。
以上のようにして、厚さ250μmの実施例1の2軸延伸ポリエステルフィルム(PETフィルム)1を製造した。 (Recovery of film)
After heat relaxation, both ends of the polyester film 1 were trimmed by 20 cm. Then, after extruding (knurling) with a width of 10 mm at both ends, it was wound up with a tension of 25 kg / m.
As described above, a biaxially stretched polyester film (PET film) 1 of Example 1 having a thickness of 250 μm was produced.
得られた2軸延伸ポリエステルフィルム1の厚さの測定は、接触式膜厚測定計(アンリツ社製)を用いて行い、長手方向に0.5mに渡り等間隔に50点をサンプリングし、幅方向に製膜全幅にわたり等間隔(幅方向に50等分した点)に50点をサンプリングし、これらの100点の厚みを測定する。これら100点の平均厚みを求め、フィルムの平均厚みとした。
2軸延伸ポリエステルフィルム1の厚みを、表1に示した。 The thickness of the obtained biaxially stretched polyester film 1 is measured using a contact-type film thickness meter (manufactured by Anritsu). 50 points are sampled at equal intervals (points equally divided into 50 in the width direction) over the entire width of the film in the direction, and the thicknesses of these 100 points are measured. The average thickness of these 100 points was calculated | required and it was set as the average thickness of the film.
The thickness of the biaxially stretched polyester film 1 is shown in Table 1.
2軸延伸ポリエステルフィルム1の厚みを、表1に示した。 The thickness of the obtained biaxially stretched polyester film 1 is measured using a contact-type film thickness meter (manufactured by Anritsu). 50 points are sampled at equal intervals (points equally divided into 50 in the width direction) over the entire width of the film in the direction, and the thicknesses of these 100 points are measured. The average thickness of these 100 points was calculated | required and it was set as the average thickness of the film.
The thickness of the biaxially stretched polyester film 1 is shown in Table 1.
〔実施例2、比較例1〕
実施例1の2軸延伸ポリエステルフィルム1の製造において、未延伸ポリエステルフィルム1に代えて、それぞれ、未延伸ポリエステルフィルム2、及び未延伸ポリエステルフィルム3を用いた他は同様にして、実施例2の2軸延伸ポリエステルフィルム2、及び比較例1の2軸延伸ポリエステルフィルム101を製造した。 [Example 2, Comparative Example 1]
In the production of the biaxially stretched polyester film 1 of Example 1, theunstretched polyester film 2 and the unstretched polyester film 3 were used instead of the unstretched polyester film 1, respectively. The biaxially stretched polyester film 2 and the biaxially stretched polyester film 101 of Comparative Example 1 were produced.
実施例1の2軸延伸ポリエステルフィルム1の製造において、未延伸ポリエステルフィルム1に代えて、それぞれ、未延伸ポリエステルフィルム2、及び未延伸ポリエステルフィルム3を用いた他は同様にして、実施例2の2軸延伸ポリエステルフィルム2、及び比較例1の2軸延伸ポリエステルフィルム101を製造した。 [Example 2, Comparative Example 1]
In the production of the biaxially stretched polyester film 1 of Example 1, the
<未延伸ポリエステルフィルム2、及び未延伸ポリエステルフィルム3の製造>
未延伸ポリエステルフィルム1の製造において、原料ポリエステル1を、それぞれ、原料ポリエステル2及び原料ポリエステル3に代えた他は、同様にして、未延伸ポリエステルフィルム2、及び未延伸ポリエステルフィルム3を製造した。
得られた未延伸ポリエステルフィルム2は、固有粘度IV=0.75、末端カルボキシ基濃度AV=19当量/トン、ガラス転移温度Tg=72℃であった。
得られた未延伸ポリエステルフィルム3は、固有粘度IV=0.72、末端カルボキシ基濃度AV=10当量/トン、ガラス転移温度Tg=72℃であった。 <Manufacture ofunstretched polyester film 2 and unstretched polyester film 3>
In the production of the unstretched polyester film 1, theunstretched polyester film 2 and the unstretched polyester film 3 were produced in the same manner except that the raw material polyester 1 was replaced with the raw material polyester 2 and the raw material polyester 3, respectively.
The obtainedunstretched polyester film 2 had an intrinsic viscosity IV = 0.75, a terminal carboxy group concentration AV = 19 eq / ton, and a glass transition temperature Tg = 72 ° C.
The obtained unstretched polyester film 3 had an intrinsic viscosity IV = 0.72, a terminal carboxy group concentration AV = 10 equivalents / ton, and a glass transition temperature Tg = 72 ° C.
未延伸ポリエステルフィルム1の製造において、原料ポリエステル1を、それぞれ、原料ポリエステル2及び原料ポリエステル3に代えた他は、同様にして、未延伸ポリエステルフィルム2、及び未延伸ポリエステルフィルム3を製造した。
得られた未延伸ポリエステルフィルム2は、固有粘度IV=0.75、末端カルボキシ基濃度AV=19当量/トン、ガラス転移温度Tg=72℃であった。
得られた未延伸ポリエステルフィルム3は、固有粘度IV=0.72、末端カルボキシ基濃度AV=10当量/トン、ガラス転移温度Tg=72℃であった。 <Manufacture of
In the production of the unstretched polyester film 1, the
The obtained
The obtained unstretched polyester film 3 had an intrinsic viscosity IV = 0.72, a terminal carboxy group concentration AV = 10 equivalents / ton, and a glass transition temperature Tg = 72 ° C.
なお、表1中、「未延伸フィルム」「原料」欄における「原料1」~「原料3」は、原料ポリエステルとして、それぞれ、原料ポリエステル1~原料ポリエステル3を用いていることを示す。
In Table 1, “Raw material 1” to “Raw material 3” in the “Unstretched film” and “Raw material” columns indicate that raw material polyester 1 to raw material polyester 3 are used as the raw material polyester, respectively.
〔実施例3~実施例9、実施例12、及び比較例2~比較例4〕
実施例1の2軸延伸ポリエステルフィルム1の製造において、横延伸工程におけるテンターの延伸角度、熱固定温度(T熱固定)、熱緩和温度(T熱緩和)、並びに、横方向及び縦方向の熱緩和率(ΔL及びΔS)を、表1に示す条件に変更したほかは同様にして、実施例3~実施例9の2軸延伸ポリエステルフィルム3~2軸延伸ポリエステルフィルム9、実施例12の2軸延伸ポリエステルフィルム12、及び比較例2~比較例4の2軸延伸ポリエステルフィルム102~2軸延伸ポリエステルフィルム104を製造した。 [Examples 3 to 9, Example 12, and Comparative Examples 2 to 4]
In the production of the biaxially stretched polyester film 1 of Example 1, the stretching angle of the tenter in the transverse stretching step, the heat setting temperature (T heat setting ), the heat relaxation temperature (T heat relaxation ), and the heat in the transverse and longitudinal directions Except for changing the relaxation rate (ΔL and ΔS) to the conditions shown in Table 1, the biaxially stretched polyester film 3 to the biaxially stretched polyester film 9 of Example 3 to Example 9 and 2 of Example 12 The axially stretched polyester film 12 and the biaxially stretched polyester film 102 to the biaxially stretched polyester film 104 of Comparative Examples 2 to 4 were produced.
実施例1の2軸延伸ポリエステルフィルム1の製造において、横延伸工程におけるテンターの延伸角度、熱固定温度(T熱固定)、熱緩和温度(T熱緩和)、並びに、横方向及び縦方向の熱緩和率(ΔL及びΔS)を、表1に示す条件に変更したほかは同様にして、実施例3~実施例9の2軸延伸ポリエステルフィルム3~2軸延伸ポリエステルフィルム9、実施例12の2軸延伸ポリエステルフィルム12、及び比較例2~比較例4の2軸延伸ポリエステルフィルム102~2軸延伸ポリエステルフィルム104を製造した。 [Examples 3 to 9, Example 12, and Comparative Examples 2 to 4]
In the production of the biaxially stretched polyester film 1 of Example 1, the stretching angle of the tenter in the transverse stretching step, the heat setting temperature (T heat setting ), the heat relaxation temperature (T heat relaxation ), and the heat in the transverse and longitudinal directions Except for changing the relaxation rate (ΔL and ΔS) to the conditions shown in Table 1, the biaxially stretched polyester film 3 to the biaxially stretched polyester film 9 of Example 3 to Example 9 and 2 of Example 12 The axially stretched polyester film 12 and the biaxially stretched polyester film 102 to the biaxially stretched polyester film 104 of Comparative Examples 2 to 4 were produced.
〔実施例10、実施例11〕
実施例1の2軸延伸ポリエステルフィルム1の製造において、厚さが3.5mmの未延伸ポリエステルフィルム1に代えて、厚さが2.6mmの未延伸ポリエステルフィルム4を用いた他は同様にして、実施例10の2軸延伸ポリエステルフィルム10を製造した。
また、実施例12の2軸延伸ポリエステルフィルム12の製造において、厚さが3.5mmの未延伸ポリエステルフィルム1に代えて、厚さが2.6mmの未延伸ポリエステルフィルム4を用いた他は同様にして、実施例11の2軸延伸ポリエステルフィルム11を製造した。 [Example 10, Example 11]
In the production of the biaxially stretched polyester film 1 of Example 1, the same procedure was performed except that the unstretched polyester film 4 having a thickness of 2.6 mm was used instead of the unstretched polyester film 1 having a thickness of 3.5 mm. The biaxially stretchedpolyester film 10 of Example 10 was produced.
Further, in the production of the biaxially stretched polyester film 12 of Example 12, the same procedure was performed except that the unstretched polyester film 4 having a thickness of 2.6 mm was used instead of the unstretched polyester film 1 having a thickness of 3.5 mm. Thus, a biaxially stretched polyester film 11 of Example 11 was produced.
実施例1の2軸延伸ポリエステルフィルム1の製造において、厚さが3.5mmの未延伸ポリエステルフィルム1に代えて、厚さが2.6mmの未延伸ポリエステルフィルム4を用いた他は同様にして、実施例10の2軸延伸ポリエステルフィルム10を製造した。
また、実施例12の2軸延伸ポリエステルフィルム12の製造において、厚さが3.5mmの未延伸ポリエステルフィルム1に代えて、厚さが2.6mmの未延伸ポリエステルフィルム4を用いた他は同様にして、実施例11の2軸延伸ポリエステルフィルム11を製造した。 [Example 10, Example 11]
In the production of the biaxially stretched polyester film 1 of Example 1, the same procedure was performed except that the unstretched polyester film 4 having a thickness of 2.6 mm was used instead of the unstretched polyester film 1 having a thickness of 3.5 mm. The biaxially stretched
Further, in the production of the biaxially stretched polyester film 12 of Example 12, the same procedure was performed except that the unstretched polyester film 4 having a thickness of 2.6 mm was used instead of the unstretched polyester film 1 having a thickness of 3.5 mm. Thus, a biaxially stretched polyester film 11 of Example 11 was produced.
<未延伸ポリエステルフィルム4の製造>
未延伸ポリエステルフィルム1の製造におけるフィルム成形工程において、ダイから押出す溶融樹脂の量を調整して、厚さが2.6mmの未延伸ポリエステルフィルム4を製造した。
得られた未延伸ポリエステルフィルム4は、固有粘度IV=0.80、末端カルボキシ基濃度AV=15当量/トン、ガラス転移温度Tg=72℃であった。 <Manufacture of unstretched polyester film 4>
In the film forming step in the production of the unstretched polyester film 1, the amount of the molten resin extruded from the die was adjusted to produce a non-stretched polyester film 4 having a thickness of 2.6 mm.
The obtained unstretched polyester film 4 had an intrinsic viscosity IV = 0.80, a terminal carboxy group concentration AV = 15 eq / ton, and a glass transition temperature Tg = 72 ° C.
未延伸ポリエステルフィルム1の製造におけるフィルム成形工程において、ダイから押出す溶融樹脂の量を調整して、厚さが2.6mmの未延伸ポリエステルフィルム4を製造した。
得られた未延伸ポリエステルフィルム4は、固有粘度IV=0.80、末端カルボキシ基濃度AV=15当量/トン、ガラス転移温度Tg=72℃であった。 <Manufacture of unstretched polyester film 4>
In the film forming step in the production of the unstretched polyester film 1, the amount of the molten resin extruded from the die was adjusted to produce a non-stretched polyester film 4 having a thickness of 2.6 mm.
The obtained unstretched polyester film 4 had an intrinsic viscosity IV = 0.80, a terminal carboxy group concentration AV = 15 eq / ton, and a glass transition temperature Tg = 72 ° C.
〔実施例13~実施例19〕
実施例1の2軸延伸ポリエステルフィルム1の製造において、未延伸ポリエステルフィルム1に代えて、未延伸ポリエステルフィルム5~11を用いたほかは同様にして、実施例13~19の2軸延伸ポリエステルフィルム13~19を製造した。 [Examples 13 to 19]
In the production of the biaxially stretched polyester film 1 of Example 1, the biaxially stretched polyester film of Examples 13 to 19 was similarly used except that unstretched polyester films 5 to 11 were used instead of the unstretched polyester film 1. 13-19 were produced.
実施例1の2軸延伸ポリエステルフィルム1の製造において、未延伸ポリエステルフィルム1に代えて、未延伸ポリエステルフィルム5~11を用いたほかは同様にして、実施例13~19の2軸延伸ポリエステルフィルム13~19を製造した。 [Examples 13 to 19]
In the production of the biaxially stretched polyester film 1 of Example 1, the biaxially stretched polyester film of Examples 13 to 19 was similarly used except that unstretched polyester films 5 to 11 were used instead of the unstretched polyester film 1. 13-19 were produced.
<未延伸ポリエステルフィルム5~11の製造>
未延伸ポリエステルフィルム1の製造において、原料ポリエステル1に代えて、表1に示す原料ポリエステルを用い、フィルム成形工程における原料ポリエステルの1軸混練押出機のホッパーへの投入時に、原料ポリエステルと共に、表1の「材料・添加剤」、「末端封止剤」欄に示す種類・量の末端封止剤を添加したほかは、同様にして、実施例13~19のポリエステルフィルム13~19を製造した。
得られた未延伸ポリエステルフィルム5~11は、固有粘度IV=0.80、末端カルボキシ基濃度AV=15当量/トン、ガラス転移温度Tg=72℃であった。 <Manufacture of unstretched polyester films 5 to 11>
In the production of the unstretched polyester film 1, in place of the raw material polyester 1, the raw material polyester shown in Table 1 was used. Polyester films 13 to 19 of Examples 13 to 19 were produced in the same manner except that the types and amounts of the end capping agents shown in “Materials and additives” and “End capping agents” were added.
The obtained unstretched polyester films 5 to 11 had an intrinsic viscosity IV = 0.80, a terminal carboxy group concentration AV = 15 eq / ton, and a glass transition temperature Tg = 72 ° C.
未延伸ポリエステルフィルム1の製造において、原料ポリエステル1に代えて、表1に示す原料ポリエステルを用い、フィルム成形工程における原料ポリエステルの1軸混練押出機のホッパーへの投入時に、原料ポリエステルと共に、表1の「材料・添加剤」、「末端封止剤」欄に示す種類・量の末端封止剤を添加したほかは、同様にして、実施例13~19のポリエステルフィルム13~19を製造した。
得られた未延伸ポリエステルフィルム5~11は、固有粘度IV=0.80、末端カルボキシ基濃度AV=15当量/トン、ガラス転移温度Tg=72℃であった。 <Manufacture of unstretched polyester films 5 to 11>
In the production of the unstretched polyester film 1, in place of the raw material polyester 1, the raw material polyester shown in Table 1 was used. Polyester films 13 to 19 of Examples 13 to 19 were produced in the same manner except that the types and amounts of the end capping agents shown in “Materials and additives” and “End capping agents” were added.
The obtained unstretched polyester films 5 to 11 had an intrinsic viscosity IV = 0.80, a terminal carboxy group concentration AV = 15 eq / ton, and a glass transition temperature Tg = 72 ° C.
表1の「材料・添加剤」、「末端封止剤」、「種」欄に「CI」、「EP」、「OX」として示す末端封止剤の詳細は、次のとおりである。なお、ここでいう添加量とは原料ポリエステルの全質量に対する割合(質量%)を指す。
・CI:カルボジイミド系化合物、ラインケミー社製スタバクゾールP100
・EP:エポキシ系化合物:Hexion Speciality Cnemicals社製「カージュラE10P」
・OX:オキサゾリン系化合物:日本触媒社製「エポクロスRPS-1005」 The details of the end capping agents shown as “CI”, “EP”, and “OX” in the “Materials / Additives”, “End Capping Agent”, and “Species” columns in Table 1 are as follows. In addition, the addition amount here refers to the ratio (mass%) with respect to the total mass of raw material polyester.
CI: Carbodiimide compound, Stabaxol P100 manufactured by Rhein Chemie
・ EP: Epoxy compound: “Cardura E10P” manufactured by Hexion Specialty Cnemicals
OX: Oxazoline compound: “Epocross RPS-1005” manufactured by Nippon Shokubai Co., Ltd.
・CI:カルボジイミド系化合物、ラインケミー社製スタバクゾールP100
・EP:エポキシ系化合物:Hexion Speciality Cnemicals社製「カージュラE10P」
・OX:オキサゾリン系化合物:日本触媒社製「エポクロスRPS-1005」 The details of the end capping agents shown as “CI”, “EP”, and “OX” in the “Materials / Additives”, “End Capping Agent”, and “Species” columns in Table 1 are as follows. In addition, the addition amount here refers to the ratio (mass%) with respect to the total mass of raw material polyester.
CI: Carbodiimide compound, Stabaxol P100 manufactured by Rhein Chemie
・ EP: Epoxy compound: “Cardura E10P” manufactured by Hexion Specialty Cnemicals
OX: Oxazoline compound: “Epocross RPS-1005” manufactured by Nippon Shokubai Co., Ltd.
<評価>
得られた2軸延伸ポリエステルフィルム1~19及び101~104について、下記評価を行なった。結果は表1に示す。 <Evaluation>
The obtained biaxially stretched polyester films 1 to 19 and 101 to 104 were evaluated as follows. The results are shown in Table 1.
得られた2軸延伸ポリエステルフィルム1~19及び101~104について、下記評価を行なった。結果は表1に示す。 <Evaluation>
The obtained biaxially stretched polyester films 1 to 19 and 101 to 104 were evaluated as follows. The results are shown in Table 1.
1.寸法安定性(熱収縮率)
2軸延伸ポリエステルフィルムの寸法安定性を、熱収縮率により評価した。
2軸延伸ポリエステルフィルムの熱収縮率は、2軸延伸ポリエステルフィルムの長さ方向(MD方向)と幅方向(TD方向)とでそれぞれ測定した。 1. Dimensional stability (heat shrinkage)
The dimensional stability of the biaxially stretched polyester film was evaluated by the heat shrinkage rate.
The thermal contraction rate of the biaxially stretched polyester film was measured in the length direction (MD direction) and the width direction (TD direction) of the biaxially stretched polyester film.
2軸延伸ポリエステルフィルムの寸法安定性を、熱収縮率により評価した。
2軸延伸ポリエステルフィルムの熱収縮率は、2軸延伸ポリエステルフィルムの長さ方向(MD方向)と幅方向(TD方向)とでそれぞれ測定した。 1. Dimensional stability (heat shrinkage)
The dimensional stability of the biaxially stretched polyester film was evaluated by the heat shrinkage rate.
The thermal contraction rate of the biaxially stretched polyester film was measured in the length direction (MD direction) and the width direction (TD direction) of the biaxially stretched polyester film.
熱収縮率は、以下の方法で求めた。
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の大きさの試料片Mを得た。試料片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。この放置の後、試料片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A(単位;mm)とおき、100×(100-A)/100の式をもってMD方向での加熱収縮率とした。
また、基材フィルムからMD方向30mm、TD方向120mmの大きさの試料片Lを得た。試料片Lに対し、試料片Mと同様に測定と計算とを行い、TD方向での加熱収縮率とした。 The thermal shrinkage rate was determined by the following method.
The biaxially stretched polyester film was cut to obtain a sample piece M having a size of 30 mm in the TD direction and 120 mm in the MD direction. Two reference lines were inserted into the sample piece M so as to have an interval of 100 mm in the MD direction, and left in a heating oven at 150 ° C. for 30 minutes under no tension. After this standing, the sample piece M is cooled to room temperature, the distance between the two reference lines is measured, this value is set as A (unit: mm), and the equation of 100 × (100−A) / 100 The heat shrinkage rate in the MD direction was used.
Moreover, the sample piece L of the magnitude | size of MD direction 30mm and TD direction 120mm was obtained from the base film. Measurement and calculation were performed on the sample piece L in the same manner as the sample piece M, and the heat shrinkage rate in the TD direction was obtained.
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の大きさの試料片Mを得た。試料片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。この放置の後、試料片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A(単位;mm)とおき、100×(100-A)/100の式をもってMD方向での加熱収縮率とした。
また、基材フィルムからMD方向30mm、TD方向120mmの大きさの試料片Lを得た。試料片Lに対し、試料片Mと同様に測定と計算とを行い、TD方向での加熱収縮率とした。 The thermal shrinkage rate was determined by the following method.
The biaxially stretched polyester film was cut to obtain a sample piece M having a size of 30 mm in the TD direction and 120 mm in the MD direction. Two reference lines were inserted into the sample piece M so as to have an interval of 100 mm in the MD direction, and left in a heating oven at 150 ° C. for 30 minutes under no tension. After this standing, the sample piece M is cooled to room temperature, the distance between the two reference lines is measured, this value is set as A (unit: mm), and the equation of 100 × (100−A) / 100 The heat shrinkage rate in the MD direction was used.
Moreover, the sample piece L of the magnitude | size of MD direction 30mm and TD direction 120mm was obtained from the base film. Measurement and calculation were performed on the sample piece L in the same manner as the sample piece M, and the heat shrinkage rate in the TD direction was obtained.
-判定基準-
◎:MD方向とTD方向のいずれもが1%以下。
○:MD方向とTD方向のいずれか一方が1%を超え、MD方向とTD方向のいずれもが2%以下。
△:MD方向とTD方向のいずれか一方が2%を超え、MD方向とTD方向のいずれもが3%以下。
×:MD方向とTD方向のいずれか一方が3%を超える。 -Criteria-
(Double-circle): Both MD direction and TD direction are 1% or less.
○: Either MD direction or TD direction exceeds 1%, and both MD direction and TD direction are 2% or less.
Δ: Either MD direction or TD direction exceeds 2%, and both MD direction and TD direction are 3% or less.
X: Either MD direction or TD direction exceeds 3%.
◎:MD方向とTD方向のいずれもが1%以下。
○:MD方向とTD方向のいずれか一方が1%を超え、MD方向とTD方向のいずれもが2%以下。
△:MD方向とTD方向のいずれか一方が2%を超え、MD方向とTD方向のいずれもが3%以下。
×:MD方向とTD方向のいずれか一方が3%を超える。 -Criteria-
(Double-circle): Both MD direction and TD direction are 1% or less.
○: Either MD direction or TD direction exceeds 1%, and both MD direction and TD direction are 2% or less.
Δ: Either MD direction or TD direction exceeds 2%, and both MD direction and TD direction are 3% or less.
X: Either MD direction or TD direction exceeds 3%.
2.耐加水分解性(破断伸度半減時間)
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によって評価した。
2軸延伸ポリエステルフィルムを、120℃、相対湿度100%の条件で保存した後の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。 2. Hydrolysis resistance (half elongation time at break)
The hydrolysis resistance of the biaxially stretched polyester film was evaluated by the half elongation time at break of the biaxially stretched polyester film.
The breaking elongation (%) exhibited by the biaxially stretched polyester film after storing the biaxially stretched polyester film under the conditions of 120 ° C. and 100% relative humidity is the breaking elongation (%) exhibited by the biaxially stretched polyester film before storage ( %), The storage time at 50% was defined as the half elongation at break.
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によって評価した。
2軸延伸ポリエステルフィルムを、120℃、相対湿度100%の条件で保存した後の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。 2. Hydrolysis resistance (half elongation time at break)
The hydrolysis resistance of the biaxially stretched polyester film was evaluated by the half elongation time at break of the biaxially stretched polyester film.
The breaking elongation (%) exhibited by the biaxially stretched polyester film after storing the biaxially stretched polyester film under the conditions of 120 ° C. and 100% relative humidity is the breaking elongation (%) exhibited by the biaxially stretched polyester film before storage ( %), The storage time at 50% was defined as the half elongation at break.
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、1cm×20cmの大きさの試料片Pを得て、試料片Pを、チャック間5cm、20%/分にて引っ張って求めた。
破断伸度半減時間が長い程、2軸延伸ポリエステルフィルムの耐加水分解性が優れていることを示す The breaking elongation (%) of the biaxially stretched polyester film was obtained by cutting the biaxially stretched polyester film to obtain a sample piece P having a size of 1 cm × 20 cm. Asked by pulling in minutes.
The longer the half elongation time at break, the better the hydrolysis resistance of the biaxially stretched polyester film.
破断伸度半減時間が長い程、2軸延伸ポリエステルフィルムの耐加水分解性が優れていることを示す The breaking elongation (%) of the biaxially stretched polyester film was obtained by cutting the biaxially stretched polyester film to obtain a sample piece P having a size of 1 cm × 20 cm. Asked by pulling in minutes.
The longer the half elongation time at break, the better the hydrolysis resistance of the biaxially stretched polyester film.
-判定基準-
◎:破断伸度半減時間が90hrを超える。
○:破断伸度半減時間が85hrを超え、90hr以下。
△:破断伸度半減時間が80hrを超え、85hr以下。
×:破断伸度半減時間が80hr以下。 -Criteria-
A: Half elongation at break exceeds 90 hr.
○: Half elongation at break exceeds 85 hr and is 90 hr or less.
Δ: Half elongation at break exceeds 80 hr and is 85 hr or less.
X: Half elongation at break is 80 hr or less.
◎:破断伸度半減時間が90hrを超える。
○:破断伸度半減時間が85hrを超え、90hr以下。
△:破断伸度半減時間が80hrを超え、85hr以下。
×:破断伸度半減時間が80hr以下。 -Criteria-
A: Half elongation at break exceeds 90 hr.
○: Half elongation at break exceeds 85 hr and is 90 hr or less.
Δ: Half elongation at break exceeds 80 hr and is 85 hr or less.
X: Half elongation at break is 80 hr or less.
3.テンター破損度
未延伸ポリエステルフィルム1~19及び101~104を用いて、横延伸を行なった際におけるテンターの破損の有無から、テンター破損度を判定した。
-判定基準-
○:テンターの破損なし
△:テンターの破損あり 3. Degree of Tenter Breakage Using the unstretched polyester films 1-19 and 101-104, the degree of tenter breakage was determined from the presence or absence of breakage of the tenter during transverse stretching.
-Criteria-
○: Tenter is not damaged △: Tenter is damaged
未延伸ポリエステルフィルム1~19及び101~104を用いて、横延伸を行なった際におけるテンターの破損の有無から、テンター破損度を判定した。
-判定基準-
○:テンターの破損なし
△:テンターの破損あり 3. Degree of Tenter Breakage Using the unstretched polyester films 1-19 and 101-104, the degree of tenter breakage was determined from the presence or absence of breakage of the tenter during transverse stretching.
-Criteria-
○: Tenter is not damaged △: Tenter is damaged
4.総合判定
上記1~3の各評価結果から、下記判定基準に基づき、判定した。
-判定基準-
◎:極めて良好(熱収縮率と耐加水分解性のいずれも◎以上の評価)
○:良好(熱収縮率と耐加水分解性のいずれも○以上の評価)
△:問題なし(熱収縮率と耐加水分解性のいずれも△以上の評価)
×:問題あり(熱収縮率と耐加水分解性のいずれか、もしくは両方が×の評価) 4). Comprehensive judgment Based on the evaluation results 1 to 3 above, judgment was made based on the following judgment criteria.
-Criteria-
◎: Extremely good (Evaluation of ◎ or higher for both thermal shrinkage and hydrolysis resistance)
○: Good (Evaluation of ○ or higher for both heat shrinkage and hydrolysis resistance)
△: No problem (Evaluation of △ or higher for both heat shrinkage and hydrolysis resistance)
×: There is a problem (Evaluation of either heat shrinkage and hydrolysis resistance or both are ×)
上記1~3の各評価結果から、下記判定基準に基づき、判定した。
-判定基準-
◎:極めて良好(熱収縮率と耐加水分解性のいずれも◎以上の評価)
○:良好(熱収縮率と耐加水分解性のいずれも○以上の評価)
△:問題なし(熱収縮率と耐加水分解性のいずれも△以上の評価)
×:問題あり(熱収縮率と耐加水分解性のいずれか、もしくは両方が×の評価) 4). Comprehensive judgment Based on the evaluation results 1 to 3 above, judgment was made based on the following judgment criteria.
-Criteria-
◎: Extremely good (Evaluation of ◎ or higher for both thermal shrinkage and hydrolysis resistance)
○: Good (Evaluation of ○ or higher for both heat shrinkage and hydrolysis resistance)
△: No problem (Evaluation of △ or higher for both heat shrinkage and hydrolysis resistance)
×: There is a problem (Evaluation of either heat shrinkage and hydrolysis resistance or both are ×)
5.密着性
さらに、得られた2軸延伸ポリエステルフィルム1~19及び101~104を、それぞれ、基材(ポリエステルフィルム基材)とし、各基材の表面に下記塗布層を形成して、基材と、塗布層との密着性を評価した。
塗布層は、乾燥厚みが0.5μmとなるように、塗布液をバー塗布法によって塗布して形成した。 5. Further, the obtained biaxially stretched polyester films 1 to 19 and 101 to 104 were used as base materials (polyester film base materials), and the following coating layers were formed on the surfaces of the respective base materials. The adhesion with the coating layer was evaluated.
The coating layer was formed by coating the coating solution by a bar coating method so that the dry thickness was 0.5 μm.
さらに、得られた2軸延伸ポリエステルフィルム1~19及び101~104を、それぞれ、基材(ポリエステルフィルム基材)とし、各基材の表面に下記塗布層を形成して、基材と、塗布層との密着性を評価した。
塗布層は、乾燥厚みが0.5μmとなるように、塗布液をバー塗布法によって塗布して形成した。 5. Further, the obtained biaxially stretched polyester films 1 to 19 and 101 to 104 were used as base materials (polyester film base materials), and the following coating layers were formed on the surfaces of the respective base materials. The adhesion with the coating layer was evaluated.
The coating layer was formed by coating the coating solution by a bar coating method so that the dry thickness was 0.5 μm.
基材に形成した塗布層は、具体的には、次のようにして形成した。
基材の片面に、下記の(i)反射層と(ii)易接着性層をこの順で塗設した。 Specifically, the coating layer formed on the substrate was formed as follows.
The following (i) reflective layer and (ii) easy-adhesion layer were coated in this order on one side of the substrate.
基材の片面に、下記の(i)反射層と(ii)易接着性層をこの順で塗設した。 Specifically, the coating layer formed on the substrate was formed as follows.
The following (i) reflective layer and (ii) easy-adhesion layer were coated in this order on one side of the substrate.
(i)反射層(着色層)
まず初めに、下記組成の諸成分を混合し、ダイノミル型分散機により1時間分散処理して顔料分散物を調製した。
<顔料分散物の処方>
・二酸化チタン・・・39.9部
(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部
(PVA-105、(株)クラレ製、固形分10%)
・界面活性剤(デモールEP、花王(株)製、固形分:25%)・・・0.5部
・蒸留水・・・51.6部 (I) Reflective layer (colored layer)
First, various components having the following composition were mixed, and a pigment dispersion was prepared by dispersing for 1 hour using a dynomill type disperser.
<Prescription of pigment dispersion>
・ Titanium dioxide: 39.9 parts (Taipek R-780-2, manufactured by Ishihara Sangyo Co., Ltd., solid content: 100% by mass)
・ Polyvinyl alcohol: 8.0 parts (PVA-105, manufactured by Kuraray Co., Ltd., solid content: 10%)
・ Surfactant (Demol EP, manufactured by Kao Corporation, solid content: 25%) 0.5 part ・ Distilled water 51.6 parts
まず初めに、下記組成の諸成分を混合し、ダイノミル型分散機により1時間分散処理して顔料分散物を調製した。
<顔料分散物の処方>
・二酸化チタン・・・39.9部
(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部
(PVA-105、(株)クラレ製、固形分10%)
・界面活性剤(デモールEP、花王(株)製、固形分:25%)・・・0.5部
・蒸留水・・・51.6部 (I) Reflective layer (colored layer)
First, various components having the following composition were mixed, and a pigment dispersion was prepared by dispersing for 1 hour using a dynomill type disperser.
<Prescription of pigment dispersion>
・ Titanium dioxide: 39.9 parts (Taipek R-780-2, manufactured by Ishihara Sangyo Co., Ltd., solid content: 100% by mass)
・ Polyvinyl alcohol: 8.0 parts (PVA-105, manufactured by Kuraray Co., Ltd., solid content: 10%)
・ Surfactant (Demol EP, manufactured by Kao Corporation, solid content: 25%) 0.5 part ・ Distilled water 51.6 parts
次いで、得られた顔料分散物を用い、下記組成の諸成分を混合することにより反射層形成用塗布液を調製した。
<反射層形成用塗布液の処方>
・上記の顔料分散物・・・71.4部
・ポリアクリル樹脂水分散液・・・17.1部
(バインダー:ジュリマーET410、日本純薬工業(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・・・2.7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)・・・1.8部
(エポクロスWS-700、日本触媒(株)製、固形分:25質量%)
・蒸留水・・・7.0部 Next, using the obtained pigment dispersion, various components having the following composition were mixed to prepare a coating solution for forming a reflective layer.
<Prescription of reflection layer forming coating solution>
・ The above pigment dispersion: 71.4 parts ・ Polyacrylic resin aqueous dispersion: 17.1 parts (Binder: Jurimer ET410, manufactured by Nippon Pure Chemical Industries, Ltd., solid content: 30% by mass)
Polyoxyalkylene alkyl ether 2.7 parts (Naroacty CL95, manufactured by Sanyo Chemical Industries, solid content: 1% by mass)
・ Oxazoline compound (crosslinking agent): 1.8 parts (Epocross WS-700, manufactured by Nippon Shokubai Co., Ltd., solid content: 25% by mass)
・ Distilled water: 7.0 parts
<反射層形成用塗布液の処方>
・上記の顔料分散物・・・71.4部
・ポリアクリル樹脂水分散液・・・17.1部
(バインダー:ジュリマーET410、日本純薬工業(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・・・2.7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)・・・1.8部
(エポクロスWS-700、日本触媒(株)製、固形分:25質量%)
・蒸留水・・・7.0部 Next, using the obtained pigment dispersion, various components having the following composition were mixed to prepare a coating solution for forming a reflective layer.
<Prescription of reflection layer forming coating solution>
・ The above pigment dispersion: 71.4 parts ・ Polyacrylic resin aqueous dispersion: 17.1 parts (Binder: Jurimer ET410, manufactured by Nippon Pure Chemical Industries, Ltd., solid content: 30% by mass)
Polyoxyalkylene alkyl ether 2.7 parts (Naroacty CL95, manufactured by Sanyo Chemical Industries, solid content: 1% by mass)
・ Oxazoline compound (crosslinking agent): 1.8 parts (Epocross WS-700, manufactured by Nippon Shokubai Co., Ltd., solid content: 25% by mass)
・ Distilled water: 7.0 parts
上記より得られた反射層形成用塗布液をサンプルフィルムにバーコーターにより塗布し、180℃で1分間乾燥して、二酸化チタン塗布量が6.5g/m2の反射層(白色層)を形成した。
The reflective layer-forming coating solution obtained above is applied to a sample film with a bar coater and dried at 180 ° C. for 1 minute to form a reflective layer (white layer) with a titanium dioxide coating amount of 6.5 g / m 2. did.
(ii)易接着性層
下記組成の諸成分を混合して易接着性層用塗布液を調製し、これをバインダー塗布量が0.09g/m2になるように反射層の上に塗布した。その後、180℃で1分間乾燥させ、易接着性層を形成した。
<易接着性層用塗布液の組成>
・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S75N、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・・・0.8部
(エポクロスWS-700、日本触媒(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、固形分:10質量%)
・蒸留水・・・83.3部 (Ii) Easy-adhesive layer Various components having the following composition were mixed to prepare an easy-adhesive layer coating solution, which was applied onto the reflective layer so that the binder coating amount was 0.09 g / m 2 . . Then, it was made to dry at 180 degreeC for 1 minute, and the easily bonding layer was formed.
<Composition of coating solution for easy adhesion layer>
-Polyolefin resin aqueous dispersion: 5.2 parts (Binder: Chemipearl S75N, manufactured by Mitsui Chemicals, solid content: 24% by mass)
Polyoxyalkylene alkyl ether: 7.8 parts (Naroacty CL95, manufactured by Sanyo Chemical Industries, solid content: 1% by mass)
Oxazoline compound: 0.8 parts (Epocross WS-700, manufactured by Nippon Shokubai Co., Ltd., solid content: 25% by mass)
Silica fine particle aqueous dispersion: 2.9 parts (Aerosil OX-50, manufactured by Nippon Aerosil Co., Ltd., solid content: 10% by mass)
・ Distilled water: 83.3 parts
下記組成の諸成分を混合して易接着性層用塗布液を調製し、これをバインダー塗布量が0.09g/m2になるように反射層の上に塗布した。その後、180℃で1分間乾燥させ、易接着性層を形成した。
<易接着性層用塗布液の組成>
・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S75N、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・・・0.8部
(エポクロスWS-700、日本触媒(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、固形分:10質量%)
・蒸留水・・・83.3部 (Ii) Easy-adhesive layer Various components having the following composition were mixed to prepare an easy-adhesive layer coating solution, which was applied onto the reflective layer so that the binder coating amount was 0.09 g / m 2 . . Then, it was made to dry at 180 degreeC for 1 minute, and the easily bonding layer was formed.
<Composition of coating solution for easy adhesion layer>
-Polyolefin resin aqueous dispersion: 5.2 parts (Binder: Chemipearl S75N, manufactured by Mitsui Chemicals, solid content: 24% by mass)
Polyoxyalkylene alkyl ether: 7.8 parts (Naroacty CL95, manufactured by Sanyo Chemical Industries, solid content: 1% by mass)
Oxazoline compound: 0.8 parts (Epocross WS-700, manufactured by Nippon Shokubai Co., Ltd., solid content: 25% by mass)
Silica fine particle aqueous dispersion: 2.9 parts (Aerosil OX-50, manufactured by Nippon Aerosil Co., Ltd., solid content: 10% by mass)
・ Distilled water: 83.3 parts
次に、ポリエステルフィルムの反射層及び易接着性層が形成されている側と反対側の面に、下記の(iii)下塗り層、(iv)バリア層、及び(v)防汚層をポリエステルフィルム側から順次、塗設した。
Next, the polyester film is provided with the following (iii) undercoat layer, (iv) barrier layer, and (v) antifouling layer on the side opposite to the side where the reflective layer and the easy-adhesion layer of the polyester film are formed. Coated sequentially from the side.
(iii)下塗り層
下記組成の諸成分を混合して下塗り層用塗布液を調製し、この塗布液をポリエステルフィルムに塗布し、180℃で1分間乾燥させ、下塗り層(乾燥塗設量:約0.1g/m2)を形成した。
<下塗り層用塗布液の組成>
・ポリエステル樹脂・・・1.7部
(バイロナールMD-1200、東洋紡(株)製、固形分:17質量%)
・ポリエステル樹脂・・・3.8部
(ペスレジンA-520、高松油脂(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・・・1.5部
(ナロアクティーCL95、三洋化成工業(株)製、固形分:1質量%)
・カルボジイミド化合物・・・1.3部
(カルボジライトV-02-L2、日清紡(株)製、固形分:10質量%)
・蒸留水・・・91.7部 (Iii) Undercoat layer Various components having the following composition are mixed to prepare a coating solution for an undercoat layer, this coating solution is applied to a polyester film, dried at 180 ° C. for 1 minute, and an undercoat layer (dry coating amount: about 0.1 g / m 2 ) was formed.
<Composition of coating solution for undercoat layer>
Polyester resin: 1.7 parts (Vaironal MD-1200, manufactured by Toyobo Co., Ltd., solid content: 17% by mass)
Polyester resin: 3.8 parts (Pesresin A-520, manufactured by Takamatsu Yushi Co., Ltd., solid content: 30% by mass)
・ Polyoxyalkylene alkyl ether: 1.5 parts (Naroacty CL95, manufactured by Sanyo Chemical Industries, solid content: 1% by mass)
Carbodiimide compound: 1.3 parts (Carbodilite V-02-L2, manufactured by Nisshinbo Co., Ltd., solid content: 10% by mass)
・ Distilled water: 91.7 parts
下記組成の諸成分を混合して下塗り層用塗布液を調製し、この塗布液をポリエステルフィルムに塗布し、180℃で1分間乾燥させ、下塗り層(乾燥塗設量:約0.1g/m2)を形成した。
<下塗り層用塗布液の組成>
・ポリエステル樹脂・・・1.7部
(バイロナールMD-1200、東洋紡(株)製、固形分:17質量%)
・ポリエステル樹脂・・・3.8部
(ペスレジンA-520、高松油脂(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・・・1.5部
(ナロアクティーCL95、三洋化成工業(株)製、固形分:1質量%)
・カルボジイミド化合物・・・1.3部
(カルボジライトV-02-L2、日清紡(株)製、固形分:10質量%)
・蒸留水・・・91.7部 (Iii) Undercoat layer Various components having the following composition are mixed to prepare a coating solution for an undercoat layer, this coating solution is applied to a polyester film, dried at 180 ° C. for 1 minute, and an undercoat layer (dry coating amount: about 0.1 g / m 2 ) was formed.
<Composition of coating solution for undercoat layer>
Polyester resin: 1.7 parts (Vaironal MD-1200, manufactured by Toyobo Co., Ltd., solid content: 17% by mass)
Polyester resin: 3.8 parts (Pesresin A-520, manufactured by Takamatsu Yushi Co., Ltd., solid content: 30% by mass)
・ Polyoxyalkylene alkyl ether: 1.5 parts (Naroacty CL95, manufactured by Sanyo Chemical Industries, solid content: 1% by mass)
Carbodiimide compound: 1.3 parts (Carbodilite V-02-L2, manufactured by Nisshinbo Co., Ltd., solid content: 10% by mass)
・ Distilled water: 91.7 parts
(iv)バリア層
続いて、形成された下塗り層の表面に下記の蒸着条件にて厚み800Åの酸化珪素の蒸着膜を形成し、バリア層とした。
<蒸着条件>
・反応ガス混合比(単位:slm):ヘキサメチルジシロキサン/酸素ガス/ヘリウム=1/10/10
・真空チャンバー内の真空度:5.0×10-6mbar
・蒸着チャンバー内の真空度:6.0×10-2mbar
・冷却・電極ドラム供給電力:20kW
・フィルムの搬送速度 :80m/分 (Iv) Barrier layer Subsequently, a vapor deposition film of silicon oxide having a thickness of 800 mm was formed on the surface of the formed undercoat layer under the following vapor deposition conditions to obtain a barrier layer.
<Deposition conditions>
Reaction gas mixture ratio (unit: slm): hexamethyldisiloxane / oxygen gas / helium = 1/10/10
・ Vacuum degree in the vacuum chamber: 5.0 × 10 −6 mbar
・ Vacuum degree in the deposition chamber: 6.0 × 10 −2 mbar
・ Cooling ・ Electrode drum power supply: 20kW
-Film transport speed: 80 m / min
続いて、形成された下塗り層の表面に下記の蒸着条件にて厚み800Åの酸化珪素の蒸着膜を形成し、バリア層とした。
<蒸着条件>
・反応ガス混合比(単位:slm):ヘキサメチルジシロキサン/酸素ガス/ヘリウム=1/10/10
・真空チャンバー内の真空度:5.0×10-6mbar
・蒸着チャンバー内の真空度:6.0×10-2mbar
・冷却・電極ドラム供給電力:20kW
・フィルムの搬送速度 :80m/分 (Iv) Barrier layer Subsequently, a vapor deposition film of silicon oxide having a thickness of 800 mm was formed on the surface of the formed undercoat layer under the following vapor deposition conditions to obtain a barrier layer.
<Deposition conditions>
Reaction gas mixture ratio (unit: slm): hexamethyldisiloxane / oxygen gas / helium = 1/10/10
・ Vacuum degree in the vacuum chamber: 5.0 × 10 −6 mbar
・ Vacuum degree in the deposition chamber: 6.0 × 10 −2 mbar
・ Cooling ・ Electrode drum power supply: 20kW
-Film transport speed: 80 m / min
(v)防汚層
以下に示すように、第1及び第2防汚層を形成するための塗布液を調製し、バリア層の上に第1防汚層用塗布液、第2防汚層用塗布液の順に塗布し、2層構造の防汚層を塗設した。 (V) Antifouling Layer As shown below, a coating solution for forming the first and second antifouling layers is prepared, and the first antifouling layer coating solution and the second antifouling layer are formed on the barrier layer. The coating solution was applied in the order, and a two-layer antifouling layer was applied.
以下に示すように、第1及び第2防汚層を形成するための塗布液を調製し、バリア層の上に第1防汚層用塗布液、第2防汚層用塗布液の順に塗布し、2層構造の防汚層を塗設した。 (V) Antifouling Layer As shown below, a coating solution for forming the first and second antifouling layers is prepared, and the first antifouling layer coating solution and the second antifouling layer are formed on the barrier layer. The coating solution was applied in the order, and a two-layer antifouling layer was applied.
<第1防汚層>
-第1防汚層用塗布液の調製-
下記組成中の成分を混合し、第1防汚層用塗布液を調製した。
<塗布液の組成>
・セラネートWSA1070(DIC(株)製)・・・45.9部
・オキサゾリン化合物(架橋剤)・・・7.7部
(エポクロスWS-700、日本触媒(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・・・2.0部
(ナロアクティーCL95、三洋化成工業(株)製、固形分:1質量%)
・反射層で用いた顔料分散物・・・33.0部
蒸留水・・・11.4部 <First antifouling layer>
-Preparation of coating solution for first antifouling layer-
Components in the following composition were mixed to prepare a first antifouling layer coating solution.
<Composition of coating solution>
・ Ceranate WSA1070 (manufactured by DIC Corporation) 45.9 parts ・ Oxazoline compound (crosslinking agent) 7.7 parts (Epocross WS-700, manufactured by Nippon Shokubai Co., Ltd., solid content: 25% by mass) )
Polyoxyalkylene alkyl ether 2.0 parts (Naroacty CL95, manufactured by Sanyo Chemical Industries, solid content: 1% by mass)
-Pigment dispersion used in the reflective layer ... 33.0 parts distilled water ... 11.4 parts
-第1防汚層用塗布液の調製-
下記組成中の成分を混合し、第1防汚層用塗布液を調製した。
<塗布液の組成>
・セラネートWSA1070(DIC(株)製)・・・45.9部
・オキサゾリン化合物(架橋剤)・・・7.7部
(エポクロスWS-700、日本触媒(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・・・2.0部
(ナロアクティーCL95、三洋化成工業(株)製、固形分:1質量%)
・反射層で用いた顔料分散物・・・33.0部
蒸留水・・・11.4部 <First antifouling layer>
-Preparation of coating solution for first antifouling layer-
Components in the following composition were mixed to prepare a first antifouling layer coating solution.
<Composition of coating solution>
・ Ceranate WSA1070 (manufactured by DIC Corporation) 45.9 parts ・ Oxazoline compound (crosslinking agent) 7.7 parts (Epocross WS-700, manufactured by Nippon Shokubai Co., Ltd., solid content: 25% by mass) )
Polyoxyalkylene alkyl ether 2.0 parts (Naroacty CL95, manufactured by Sanyo Chemical Industries, solid content: 1% by mass)
-Pigment dispersion used in the reflective layer ... 33.0 parts distilled water ... 11.4 parts
-第1防汚層の形成-
得られた塗布液を、バインダー塗布量が3.0g/m2になるように、バリア層の上に塗布し、180℃で1分間乾燥させて第1防汚層を形成した。 -Formation of the first antifouling layer-
The obtained coating solution was coated on the barrier layer so that the binder coating amount was 3.0 g / m 2 and dried at 180 ° C. for 1 minute to form a first antifouling layer.
得られた塗布液を、バインダー塗布量が3.0g/m2になるように、バリア層の上に塗布し、180℃で1分間乾燥させて第1防汚層を形成した。 -Formation of the first antifouling layer-
The obtained coating solution was coated on the barrier layer so that the binder coating amount was 3.0 g / m 2 and dried at 180 ° C. for 1 minute to form a first antifouling layer.
-第2防汚層用塗布液の調製-
下記組成中の成分を混合し、第2防汚層用塗布液を調製した。
<塗布液の組成>
・フッ素系バインダー:オブリガード(AGCコーテック(株)製)・・・45.9部
・オキサゾリン化合物・・・7.7部
(エポクロスWS-700、日本触媒(株)製、固形分:25質量%;架橋剤)
・ポリオキシアルキレンアルキルエーテル・・・2.0部
(ナロアクティーCL95、三洋化成工業(株)製、固形分:1質量%)
・前記反射層用に調製した前記顔料分散物・・・33.0部
・蒸留水・・・11.4部 -Preparation of coating solution for second antifouling layer-
Components in the following composition were mixed to prepare a second antifouling layer coating solution.
<Composition of coating solution>
Fluorine-based binder: Obligard (manufactured by AGC Co-Tech Co., Ltd.) 45.9 parts Oxazoline compound 7.7 parts (Epocross WS-700, manufactured by Nippon Shokubai Co., Ltd., solid content: 25 mass) %: Crosslinker)
Polyoxyalkylene alkyl ether 2.0 parts (Naroacty CL95, manufactured by Sanyo Chemical Industries, solid content: 1% by mass)
-The pigment dispersion prepared for the reflective layer ... 33.0 parts-Distilled water ... 11.4 parts
下記組成中の成分を混合し、第2防汚層用塗布液を調製した。
<塗布液の組成>
・フッ素系バインダー:オブリガード(AGCコーテック(株)製)・・・45.9部
・オキサゾリン化合物・・・7.7部
(エポクロスWS-700、日本触媒(株)製、固形分:25質量%;架橋剤)
・ポリオキシアルキレンアルキルエーテル・・・2.0部
(ナロアクティーCL95、三洋化成工業(株)製、固形分:1質量%)
・前記反射層用に調製した前記顔料分散物・・・33.0部
・蒸留水・・・11.4部 -Preparation of coating solution for second antifouling layer-
Components in the following composition were mixed to prepare a second antifouling layer coating solution.
<Composition of coating solution>
Fluorine-based binder: Obligard (manufactured by AGC Co-Tech Co., Ltd.) 45.9 parts Oxazoline compound 7.7 parts (Epocross WS-700, manufactured by Nippon Shokubai Co., Ltd., solid content: 25 mass) %: Crosslinker)
Polyoxyalkylene alkyl ether 2.0 parts (Naroacty CL95, manufactured by Sanyo Chemical Industries, solid content: 1% by mass)
-The pigment dispersion prepared for the reflective layer ... 33.0 parts-Distilled water ... 11.4 parts
-第2防汚層の形成-
調製した第2防汚層用塗布液を、バインダー塗布量が2.0g/m2になるように、バリア層上に形成された第1防汚層の上に塗布し、180℃で1分間乾燥させて第2防汚層を形成した。 -Formation of second antifouling layer-
The prepared coating solution for the second antifouling layer was applied on the first antifouling layer formed on the barrier layer so that the binder coating amount was 2.0 g / m 2 , and the mixture was applied at 180 ° C. for 1 minute. A second antifouling layer was formed by drying.
調製した第2防汚層用塗布液を、バインダー塗布量が2.0g/m2になるように、バリア層上に形成された第1防汚層の上に塗布し、180℃で1分間乾燥させて第2防汚層を形成した。 -Formation of second antifouling layer-
The prepared coating solution for the second antifouling layer was applied on the first antifouling layer formed on the barrier layer so that the binder coating amount was 2.0 g / m 2 , and the mixture was applied at 180 ° C. for 1 minute. A second antifouling layer was formed by drying.
(密着性評価)
塗布層が形成された基材(試料)の、基材と塗布層との密着性を、下記方法で評価し、結果を表1に記載した。
(1)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。
(2)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。
(3)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〔日東電工社製ポリエステル粘着テープ(No.31B)〕を貼り付け、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。
(4)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」とした。評価基準は下記のとおりである。 (Adhesion evaluation)
The adhesion between the substrate and the coating layer of the substrate (sample) on which the coating layer was formed was evaluated by the following method, and the results are shown in Table 1.
(1) Wet heat treatment was performed by allowing the sample to stand in an environment of 85 ° C. and 80% RH for 100 hours.
(2) The sample after the wet heat treatment was taken out, and 10 vertical and horizontal cuts were made with a cutter knife at intervals of 3 mm on the surface of the easy adhesion layer side of the sample to make 100 squares.
(3) After immersing the sample in which the cells were made in 50 ° C. warm water for 1 hour, the sample was taken out into a room at 25 ° C. and 60% RH, and the moisture on the surface of the sample was wiped off with a cloth. Thereafter, an adhesive tape [Nitto Denko's polyester adhesive tape (No. 31B)] was applied to the surface of the sample with the meshes, and then the adhesive tape was peeled off in a 180 ° direction at once. The time from taking out the hot water to peeling off the adhesive tape was within 5 minutes. That is, the adhesion evaluation is an evaluation of the adhesion when the coating layer of the sample is in a wet state.
(4) The surface of the sample containing the meshes was visually observed to count the number of meshes from which the coating layer was peeled off, and this was taken as the “peeling rate”. The evaluation criteria are as follows.
塗布層が形成された基材(試料)の、基材と塗布層との密着性を、下記方法で評価し、結果を表1に記載した。
(1)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。
(2)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。
(3)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〔日東電工社製ポリエステル粘着テープ(No.31B)〕を貼り付け、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。
(4)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」とした。評価基準は下記のとおりである。 (Adhesion evaluation)
The adhesion between the substrate and the coating layer of the substrate (sample) on which the coating layer was formed was evaluated by the following method, and the results are shown in Table 1.
(1) Wet heat treatment was performed by allowing the sample to stand in an environment of 85 ° C. and 80% RH for 100 hours.
(2) The sample after the wet heat treatment was taken out, and 10 vertical and horizontal cuts were made with a cutter knife at intervals of 3 mm on the surface of the easy adhesion layer side of the sample to make 100 squares.
(3) After immersing the sample in which the cells were made in 50 ° C. warm water for 1 hour, the sample was taken out into a room at 25 ° C. and 60% RH, and the moisture on the surface of the sample was wiped off with a cloth. Thereafter, an adhesive tape [Nitto Denko's polyester adhesive tape (No. 31B)] was applied to the surface of the sample with the meshes, and then the adhesive tape was peeled off in a 180 ° direction at once. The time from taking out the hot water to peeling off the adhesive tape was within 5 minutes. That is, the adhesion evaluation is an evaluation of the adhesion when the coating layer of the sample is in a wet state.
(4) The surface of the sample containing the meshes was visually observed to count the number of meshes from which the coating layer was peeled off, and this was taken as the “peeling rate”. The evaluation criteria are as follows.
-評価基準-
◎:剥離率が1%未満
○:剥離率が1%以上5%未満
△:剥離率が5%以上10%未満
×:剥離率が10%以上 -Evaluation criteria-
A: Peeling rate is less than 1% B: Peeling rate is 1% or more and less than 5% B: Peeling rate is 5% or more and less than 10% X: Peeling rate is 10% or more
◎:剥離率が1%未満
○:剥離率が1%以上5%未満
△:剥離率が5%以上10%未満
×:剥離率が10%以上 -Evaluation criteria-
A: Peeling rate is less than 1% B: Peeling rate is 1% or more and less than 5% B: Peeling rate is 5% or more and less than 10% X: Peeling rate is 10% or more
表1より、実施例の2軸延伸ポリエスエステルフィルムは、寸法安定性および耐加水分解性の両方に優れた。また、横延伸工程では、延伸角度を調節して、0<θx≦θz<θy<10とすることにより、テンターの破損を抑制することができた。
From Table 1, the biaxially stretched polyester film of the example was excellent in both dimensional stability and hydrolysis resistance. In the transverse stretching step, the tenter can be prevented from being damaged by adjusting the stretching angle to satisfy 0 <θx ≦ θz <θy <10.
また、実施例1~12および実施例13~実施例19の2軸延伸ポリエスエステルフィルムに関する密着性評価から、原料ポリエステルに多官能モノマーを含有させ、または、溶融押出の際に原料ポリエステルと共に末端封止剤を添加することで、基材と塗布層との密着性に優れることがわかった。
In addition, from the evaluation of adhesion regarding the biaxially stretched polyester ester films of Examples 1 to 12 and Examples 13 to 19, the raw material polyester contains a polyfunctional monomer, or is end-capped together with the raw material polyester during melt extrusion. It turned out that it is excellent in the adhesiveness of a base material and an application layer by adding a stopper.
〔実施例20~実施例38〕
<太陽電池用バックシートおよび太陽電池発電モジュールの作製>
上記のようにして作製した実施例1~実施例19の2軸延伸ポリエスエステルフィルム1~19を太陽電池用バックシート1~19として用い、太陽電池用バックシート1~19とした。
さらに、太陽電池用バックシート1~19を用い、特開2009-158952号公報の図1に示す構造になるように透明充填剤(封止材)に貼り合わせ、太陽電池発電モジュール1~19を作製した。このとき、バックシートの易接着性層が、太陽電池素子を包埋する透明充填剤に接するように貼り付けた。 [Examples 20 to 38]
<Preparation of solar cell backsheet and solar cell power generation module>
The biaxially stretched polyester ester films 1 to 19 of Examples 1 to 19 produced as described above were used as the solar cell back sheets 1 to 19, and the solar cell back sheets 1 to 19 were obtained.
Further, using solar cell back sheets 1 to 19, the solar cell power generation modules 1 to 19 were bonded to a transparent filler (sealing material) so as to have the structure shown in FIG. 1 of JP-A-2009-158952. Produced. At this time, it stuck so that the easily-adhesive layer of a backsheet might contact the transparent filler which embeds a solar cell element.
<太陽電池用バックシートおよび太陽電池発電モジュールの作製>
上記のようにして作製した実施例1~実施例19の2軸延伸ポリエスエステルフィルム1~19を太陽電池用バックシート1~19として用い、太陽電池用バックシート1~19とした。
さらに、太陽電池用バックシート1~19を用い、特開2009-158952号公報の図1に示す構造になるように透明充填剤(封止材)に貼り合わせ、太陽電池発電モジュール1~19を作製した。このとき、バックシートの易接着性層が、太陽電池素子を包埋する透明充填剤に接するように貼り付けた。 [Examples 20 to 38]
<Preparation of solar cell backsheet and solar cell power generation module>
The biaxially stretched polyester ester films 1 to 19 of Examples 1 to 19 produced as described above were used as the solar cell back sheets 1 to 19, and the solar cell back sheets 1 to 19 were obtained.
Further, using solar cell back sheets 1 to 19, the solar cell power generation modules 1 to 19 were bonded to a transparent filler (sealing material) so as to have the structure shown in FIG. 1 of JP-A-2009-158952. Produced. At this time, it stuck so that the easily-adhesive layer of a backsheet might contact the transparent filler which embeds a solar cell element.
太陽電池用バックシート1~19は、耐加水分解性および寸法安定性に優れた実施例1~実施例19の2軸延伸ポリエスエステルフィルム1~19を用いて製造しているため、耐加水分解性および寸法安定性に優れる。また、実施例20~38の太陽電池発電モジュール1~19は、かかるバックシート1~19を用いて構成されているため、発電性能を長期に亘って安定的に得ることができた。
日本特許出願2010-282297、日本特許出願2011-163382および日本特許出願2011-189992の開示は、参照により本明細書に取り込まれる。
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。 Since the solar cell backsheets 1 to 19 are produced using the biaxially stretched polyester ester films 1 to 19 of Examples 1 to 19 which are excellent in hydrolysis resistance and dimensional stability, they are resistant to hydrolysis. Excellent in stability and dimensional stability. In addition, since the solar cell power generation modules 1 to 19 of Examples 20 to 38 are configured using the back sheets 1 to 19, power generation performance could be stably obtained over a long period of time.
The disclosures of Japanese Patent Application 2010-282297, Japanese Patent Application 2011-163382 and Japanese Patent Application 2011-189992 are incorporated herein by reference.
All documents, patent applications, and technical standards mentioned in this specification are to the same extent as if each individual document, patent application, and technical standard were specifically and individually described to be incorporated by reference, Incorporated herein by reference.
日本特許出願2010-282297、日本特許出願2011-163382および日本特許出願2011-189992の開示は、参照により本明細書に取り込まれる。
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。 Since the solar cell backsheets 1 to 19 are produced using the biaxially stretched polyester ester films 1 to 19 of Examples 1 to 19 which are excellent in hydrolysis resistance and dimensional stability, they are resistant to hydrolysis. Excellent in stability and dimensional stability. In addition, since the solar cell power generation modules 1 to 19 of Examples 20 to 38 are configured using the back sheets 1 to 19, power generation performance could be stably obtained over a long period of time.
The disclosures of Japanese Patent Application 2010-282297, Japanese Patent Application 2011-163382 and Japanese Patent Application 2011-189992 are incorporated herein by reference.
All documents, patent applications, and technical standards mentioned in this specification are to the same extent as if each individual document, patent application, and technical standard were specifically and individually described to be incorporated by reference, Incorporated herein by reference.
Claims (18)
- 原料ポリエステルを溶融押出し、さらに冷却して、固有粘度が0.75以上のポリエステルフィルムを成形するフィルム成形工程と、
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、
前記ポリエステルフィルムを予熱する予熱部、予熱されたポリエステルフィルムを少なくとも前記ポリエステルフィルムの長手方向と直交する方向に緊張を与えて横延伸する延伸部、緊張が与えられたポリエステルフィルムを該ポリエステルフィルムの表面の最高到達膜面温度が160℃~210℃となるように加熱して熱固定する熱固定部、及び、前記ポリエステルフィルムの表面の最高到達膜面温度が、前記熱固定部における前記ポリエステルフィルムの最高到達膜面温度よりも5℃以上低い温度となるように、前記熱固定されたポリエステルフィルムを加熱し、前記緊張を緩める熱緩和部に、前記ポリエステルフィルムをこの順に搬送して、少なくとも横延伸する横延伸工程と、
を含むポリエステルフィルムの製造方法。 A film forming step of melt-extruding the raw material polyester, further cooling, and forming a polyester film having an intrinsic viscosity of 0.75 or more,
A longitudinal stretching step of longitudinally stretching the polyester film in the longitudinal direction;
A preheating portion for preheating the polyester film; a stretching portion for stretching the preheated polyester film in a direction orthogonal to the longitudinal direction of the polyester film; A heat fixing part that is heat-set by heating so that the maximum film surface temperature of the polyester film is 160 ° C. to 210 ° C., and the highest film surface temperature of the surface of the polyester film is the temperature of the polyester film in the heat fixing part Heat the heat-fixed polyester film so that the temperature reaches 5 ° C. or more lower than the highest film surface temperature, and transport the polyester film in this order to a heat relaxation part that relaxes the tension, and at least laterally stretches. A transverse stretching step,
The manufacturing method of the polyester film containing this. - 前記横延伸工程が、前記縦延伸工程の後に行なわれ、前記横延伸工程が、熱緩和部を経たポリエステルフィルムを冷却する冷却部に前記ポリエステルフィルムを搬送することを更に有し、
前記横延伸工程における前記ポリエステルフィルムの幅が最大になるときの前記ポリエステルフィルムの幅L1と、前記冷却部から前記ポリエステルフィルムが離れる前記冷却部の端部における前記ポリエステルフィルムの幅L2とが、下記式(1)を満たし、かつ、
前記予熱部における前記ポリエステルフィルムの搬送速度S1と、前記冷却部の前記端部における前記ポリエステルフィルムの搬送速度S2とが、下記式(2)を満たす請求項1に記載のポリエステルフィルムの製造方法。
The transverse stretching step is performed after the longitudinal stretching step, and the transverse stretching step further includes transporting the polyester film to a cooling unit that cools the polyester film that has passed through the heat relaxation unit,
The width L1 of the polyester film when the width of the polyester film in the transverse stretching step is maximized, and the width L2 of the polyester film at the end of the cooling part where the polyester film is separated from the cooling part are as follows. Satisfies formula (1), and
2. The method for producing a polyester film according to claim 1, wherein a transport speed S <b> 1 of the polyester film in the preheating section and a transport speed S <b> 2 of the polyester film at the end of the cooling section satisfy the following formula (2).
- 前記延伸部は、搬送される前記ポリエステルフィルムの搬送方向と、該ポリエステルフィルムの幅方向端部の進行方向とがなす角度を延伸角度θ〔°〕とするとき、前記延伸部における前記ポリエステルフィルムの横延伸を開始する位置Xでの延伸角度θx〔°〕と、前記延伸部における前記ポリエステルフィルムの横延伸を終了する位置Zでの延伸角度θz〔°〕と、前記延伸部における前記位置Xと前記位置Zとの中間の位置Yでの延伸角度θy〔°〕とが、下記式(3)を満たし、横延伸終了後の厚みが200μm以上のポリエステルフィルムを得る請求項1または請求項2に記載のポリエステルフィルムの製造方法。
0<θx≦θz<θy<10 (3) The stretching portion has a stretching angle θ [°] as an angle formed between a transport direction of the polyester film to be transported and a traveling direction of the width direction end portion of the polyester film. The stretching angle θx [°] at the position X where the lateral stretching is started, the stretching angle θz [°] at the position Z where the lateral stretching of the polyester film in the stretched portion is terminated, and the position X in the stretched portion The stretching angle θy [°] at a position Y intermediate from the position Z satisfies the following formula (3), and a polyester film having a thickness of 200 μm or more after transverse stretching is obtained: The manufacturing method of the polyester film of description.
0 <θx ≦ θz <θy <10 (3) - 前記横延伸工程は、前記予熱部、前記延伸部、前記熱固定部、前記熱緩和部、及び前記冷却部を備え、前記予熱部において前記ポリエステルフィルムの幅方向の両端部を、片端部につき、少なくとも2つの把持部材を用いて把持して、前記予熱部から前記冷却部まで前記ポリエステルフィルムを搬送する2軸延伸装置を用い、
前記予熱部における前記ポリエステルフィルムの幅方向の片端部を把持する前記2つの把持部材のうちの一方の把持部材と、該把持部材に隣接する他方の把持部材との間隔よりも、前記冷却部における前記ポリエステルフィルムの幅方向の片端部を把持する前記2つの把持部材のうちの一方の把持部材と、該把持部材に隣接する他方の把持部材との間隔を狭めることで、前記ポリエステルフィルムの搬送速度を小さくする請求項2または請求項3に記載のポリエステルフィルムの製造方法。 The transverse stretching step includes the preheating part, the stretching part, the heat fixing part, the heat relaxation part, and the cooling part, and both end parts in the width direction of the polyester film in the preheating part, Using a biaxial stretching device that grips using at least two gripping members and transports the polyester film from the preheating unit to the cooling unit,
More than the interval between one gripping member of the two gripping members that grips one end of the polyester film in the width direction in the preheating portion and the other gripping member adjacent to the gripping member, in the cooling unit. The conveyance speed of the polyester film is reduced by narrowing the interval between one gripping member of the two gripping members that grips one end in the width direction of the polyester film and the other gripping member adjacent to the gripping member. The manufacturing method of the polyester film of Claim 2 or Claim 3 which makes small. - 前記熱固定部、前記熱緩和部、及び前記冷却部の少なくとも一部において、前記ポリエステルフィルムの幅方向の片端部を把持する前記2つの把持部材のうちの一方の把持部材と、該把持部材に隣接する他方の把持部材との間隔を狭める請求項4に記載のポリエステルフィルムの製造方法。 At least a part of the heat fixing part, the heat relaxation part, and the cooling part, one gripping member of the two gripping members that grips one end of the polyester film in the width direction, and the gripping member The manufacturing method of the polyester film of Claim 4 which narrows the space | interval with the other adjacent holding member.
- 前記原料ポリエステルは、固相重合処理されている請求項1~請求項5のいずれか1項に記載のポリエステルフィルムの製造方法。 6. The method for producing a polyester film according to claim 1, wherein the raw material polyester is subjected to solid phase polymerization treatment.
- 前記縦延伸工程および前記横延伸工程を経て得られたポリエステルフィルムは、30分間150℃で加熱する加熱条件における熱収縮率が2.0%以下である請求項1~請求項6のいずれか1に記載のポリエステルフィルムの製造方法。 The polyester film obtained through the longitudinal stretching step and the lateral stretching step has a heat shrinkage rate of 2.0% or less under heating conditions of heating at 150 ° C for 30 minutes. The manufacturing method of the polyester film of description.
- 前記原料ポリエステルが、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含む請求項1~請求項7のいずれか1項に記載のポリエステルフィルムの製造方法。 The method for producing a polyester film according to any one of claims 1 to 7, wherein the raw material polyester includes a polyfunctional monomer having a total of three or more carboxylic acid groups and hydroxyl groups.
- 前記多官能モノマーの含有量は、前記原料ポリエステルの全モル量に対して、0.005モル%以上2.5モル%以下である請求項8に記載のポリエステルフィルムの製造方法。 The method for producing a polyester film according to claim 8, wherein the content of the polyfunctional monomer is 0.005 mol% to 2.5 mol% with respect to the total molar amount of the raw material polyester.
- 前記フィルム成形工程は、前記原料ポリエステルと共に、オキサゾリン系化合物、カルボジイミド化合物、又はエポキシ化合物の少なくとも1種類の末端封止剤を添加して溶融押出する工程を含む請求項1~請求項9のいずれか1項に記載のポリエステルフィルムの製造方法。 The film forming step includes a step of adding at least one end-capping agent of an oxazoline-based compound, a carbodiimide compound, or an epoxy compound together with the raw material polyester and performing melt extrusion. 2. A method for producing a polyester film according to item 1.
- 前記末端封止剤の添加量は、前記原料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10に記載のポリエステルフィルムの製造方法。 The method for producing a polyester film according to claim 10, wherein the amount of the end-capping agent added is 0.1% by mass or more and 5% by mass or less based on the total mass of the raw material polyester.
- 請求項1~請求項11のいずれか1項に記載のポリエステルフィルムの製造方法により得られたポリエステルフィルム。 A polyester film obtained by the method for producing a polyester film according to any one of claims 1 to 11.
- 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12に記載のポリエステルフィルム。 The polyester film according to claim 12, comprising a structural unit derived from a polyfunctional monomer having a total of 3 or more carboxylic acid groups and hydroxyl groups.
- 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13に記載のポリエステルフィルム。 The polyester film according to claim 13, wherein the content ratio of the structural unit derived from the polyfunctional monomer is 0.005 mol% or more and 2.5 mol% or less with respect to all the structural units in the polyester.
- オキサゾリン系化合物、カルボジイミド化合物、又はエポキシ化合物の少なくとも1種類の末端封止剤に由来する構造部分を含む請求項12~請求項14のいずれか1項に記載のポリエステルフィルム。 The polyester film according to any one of claims 12 to 14, comprising a structural portion derived from at least one kind of end-capping agent of an oxazoline compound, a carbodiimide compound, or an epoxy compound.
- 前記末端封止剤に由来する構造部分を0.1質量%以上5質量%以下含む請求項15に記載のポリエステルフィルム。 The polyester film according to claim 15, comprising a structural portion derived from the end-capping agent in an amount of 0.1% by mass to 5% by mass.
- 請求項12~請求項16のいずれか1項に記載のポリエステルフィルムを含む太陽電池用バックシート。 A solar cell backsheet comprising the polyester film according to any one of claims 12 to 16.
- 太陽光が入射する透明性のフロント基板と、
前記フロント基板の上に設けられ、太陽電池素子及び前記太陽電池素子を封止する封止材を有するセル構造部分と、
前記セル構造部分の前記フロント基板が位置する側と反対側に設けられ、前記封止材と隣接して配置された、請求項17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。 A transparent front substrate on which sunlight is incident;
A cell structure portion provided on the front substrate and having a solar cell element and a sealing material for sealing the solar cell element;
The solar cell backsheet according to claim 17, provided on the side opposite to the side where the front substrate is positioned of the cell structure portion, and disposed adjacent to the sealing material.
Solar cell module with
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