JP5979157B2 - Durable polyester film and method for producing the same, solar cell sealing film and solar cell using the same - Google Patents
Durable polyester film and method for producing the same, solar cell sealing film and solar cell using the same Download PDFInfo
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- JP5979157B2 JP5979157B2 JP2013553171A JP2013553171A JP5979157B2 JP 5979157 B2 JP5979157 B2 JP 5979157B2 JP 2013553171 A JP2013553171 A JP 2013553171A JP 2013553171 A JP2013553171 A JP 2013553171A JP 5979157 B2 JP5979157 B2 JP 5979157B2
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- Prior art keywords
- film
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- polyester
- width direction
- polyester resin
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- 229920006267 polyester film Polymers 0.000 title claims description 151
- 238000004519 manufacturing process Methods 0.000 title claims description 31
- 238000007789 sealing Methods 0.000 title claims description 17
- 229920001225 polyester resin Polymers 0.000 claims description 122
- 239000004645 polyester resin Substances 0.000 claims description 122
- 238000000034 method Methods 0.000 claims description 98
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 74
- 238000010438 heat treatment Methods 0.000 claims description 62
- 230000008569 process Effects 0.000 claims description 58
- 229910000318 alkali metal phosphate Inorganic materials 0.000 claims description 53
- 238000006116 polymerization reaction Methods 0.000 claims description 34
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 29
- 150000002009 diols Chemical class 0.000 claims description 21
- 229910052698 phosphorus Inorganic materials 0.000 claims description 20
- 239000011574 phosphorus Substances 0.000 claims description 20
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 16
- 230000014759 maintenance of location Effects 0.000 claims description 15
- 238000002844 melting Methods 0.000 claims description 12
- 230000008018 melting Effects 0.000 claims description 12
- 229910052783 alkali metal Inorganic materials 0.000 claims description 8
- 150000001340 alkali metals Chemical class 0.000 claims description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 6
- 238000000113 differential scanning calorimetry Methods 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 4
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- 230000002194 synthesizing effect Effects 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 71
- 229920000728 polyester Polymers 0.000 description 53
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 42
- 238000006460 hydrolysis reaction Methods 0.000 description 34
- 230000007062 hydrolysis Effects 0.000 description 30
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- 239000002994 raw material Substances 0.000 description 29
- -1 phosphorus compound Chemical class 0.000 description 25
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 24
- 239000000243 solution Substances 0.000 description 22
- 239000002245 particle Substances 0.000 description 21
- 210000004027 cell Anatomy 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 19
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- 238000005259 measurement Methods 0.000 description 17
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- 239000000126 substance Substances 0.000 description 15
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 12
- 230000007423 decrease Effects 0.000 description 12
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- 238000005809 transesterification reaction Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000013067 intermediate product Substances 0.000 description 9
- 230000009257 reactivity Effects 0.000 description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
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- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000006068 polycondensation reaction Methods 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 7
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- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 6
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- 239000010936 titanium Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 150000001463 antimony compounds Chemical class 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
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- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical compound C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000002390 adhesive tape Substances 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 239000003990 capacitor Substances 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
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- 239000012528 membrane Substances 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
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- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- OOSZCNKVJAVHJI-UHFFFAOYSA-N 1-[(4-fluorophenyl)methyl]piperazine Chemical compound C1=CC(F)=CC=C1CN1CCNCC1 OOSZCNKVJAVHJI-UHFFFAOYSA-N 0.000 description 2
- HQQTZCPKNZVLFF-UHFFFAOYSA-N 4h-1,2-benzoxazin-3-one Chemical class C1=CC=C2ONC(=O)CC2=C1 HQQTZCPKNZVLFF-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical compound O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 description 2
- 229910052776 Thorium Inorganic materials 0.000 description 2
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- 150000008366 benzophenones Chemical class 0.000 description 1
- 125000003354 benzotriazolyl group Chemical class N1N=NC2=C1C=CC=C2* 0.000 description 1
- IHWUGQBRUYYZNM-UHFFFAOYSA-N bicyclo[2.2.1]hept-2-ene-3,4-dicarboxylic acid Chemical compound C1CC2(C(O)=O)C(C(=O)O)=CC1C2 IHWUGQBRUYYZNM-UHFFFAOYSA-N 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- ZNFNDZCXTPWRLQ-UHFFFAOYSA-N butane-1,1,1-tricarboxylic acid Chemical compound CCCC(C(O)=O)(C(O)=O)C(O)=O ZNFNDZCXTPWRLQ-UHFFFAOYSA-N 0.000 description 1
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 210000004899 c-terminal region Anatomy 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- NLCKLZIHJQEMCU-UHFFFAOYSA-N cyano prop-2-enoate Chemical class C=CC(=O)OC#N NLCKLZIHJQEMCU-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
- 230000002950 deficient Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 239000012777 electrically insulating material Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000004049 embossing Methods 0.000 description 1
- 238000005516 engineering process Methods 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
- UKFXDFUAPNAMPJ-UHFFFAOYSA-N ethylmalonic acid Chemical compound CCC(C(O)=O)C(O)=O UKFXDFUAPNAMPJ-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 229940119177 germanium dioxide Drugs 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-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
- 239000002346 layers by function Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 description 1
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 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
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 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
- 239000005022 packaging material Substances 0.000 description 1
- AJDJKHROQJQURF-UHFFFAOYSA-N phenanthrene-1,2-dicarboxylic acid Chemical compound C1=CC=C2C3=CC=C(C(=O)O)C(C(O)=O)=C3C=CC2=C1 AJDJKHROQJQURF-UHFFFAOYSA-N 0.000 description 1
- 229960003531 phenolsulfonphthalein Drugs 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 230000002040 relaxant effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical class OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-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
- 230000000007 visual effect Effects 0.000 description 1
- 238000004736 wide-angle X-ray diffraction Methods 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/692—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/053—Polyhydroxylic alcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- 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
- H01L31/0481—Encapsulation of modules characterised by the composition of the encapsulation material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/90—Applications
- C08G2261/91—Photovoltaic applications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
- C08L2203/162—Applications used for films sealable films
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Mechanical Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Materials Engineering (AREA)
- Power Engineering (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Photovoltaic Devices (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
Description
本発明は、耐久性が良好なポリエステルフィルムに関する。さらに詳しくは耐湿熱環境下における特性保持率が高く、かつフィルムの生産性や加工性に優れた、特に太陽電池封止用フィルムを始め、建築材料、自動車材料等、屋外で使用される用途に有用なポリエステルフィルムおよびその製造方法に関する。 The present invention relates to a polyester film having good durability. More specifically, it has a high property retention rate in a moist and heat resistant environment and is excellent in film productivity and workability, especially for applications used outdoors such as solar cell sealing films, building materials, automobile materials, etc. The present invention relates to a useful polyester film and a method for producing the same.
ポリエステル樹脂は機械特性、熱特性、耐薬品性、電気特性、成形性に優れ、様々な用途に用いられている。そのポリエステル樹脂をフィルム化したポリエステルフィルム、中でも二軸配向ポリエステルフィルムは、その機械的特性、電気的特性などから、銅貼り積層板、太陽電池封止フィルム、粘着テープ、フレキシブルプリント基板、メンブレンスイッチ、面状発熱体、もしくはフラットケーブルなどの電気絶縁材料、磁気記録材料や、コンデンサ用材料、包装材料、自動車用材料、建築材料、写真用途、グラフィック用途、感熱転写用途などの各種工業材料として使用されている。 Polyester resins are excellent in mechanical properties, thermal properties, chemical resistance, electrical properties, and moldability, and are used in various applications. The polyester film made from the polyester resin, especially the biaxially oriented polyester film, has its mechanical properties, electrical properties, etc., and has a copper-clad laminate, solar cell sealing film, adhesive tape, flexible printed circuit board, membrane switch, Used as various industrial materials such as sheet heating elements or electrical insulation materials such as flat cables, magnetic recording materials, capacitor materials, packaging materials, automotive materials, building materials, photographic applications, graphic applications, thermal transfer applications, etc. ing.
これらの用途のうち、特に屋外で用いられる電気絶縁材料（例えば太陽電池封止フィルムなど）、自動車用材料、建築材料などでは、長期にわたり過酷な環境下で使用されることが多い。そのような過酷な環境下で長期にわたり使用すると、ポリエステル樹脂は加水分解により分子量が低下し、また、脆化が進行して機械物性などが低下する。そのため、長期にわたり過酷な環境下で使用される場合、或いは湿気のある状態で使用される様な用途では、湿熱に対する耐久性が求められている。たとえば、太陽電池封止用途では太陽電池の耐用年数の向上による発電コストダウンを図るために、ポリエステルフィルムの耐湿熱性向上が求められている。 Among these applications, electrical insulating materials (for example, solar cell sealing films) used outdoors, automotive materials, building materials, and the like are often used in harsh environments for a long period of time. When used in such a harsh environment for a long period of time, the polyester resin has a molecular weight that decreases due to hydrolysis, and the embrittlement progresses, resulting in a decrease in mechanical properties. Therefore, when it is used in a harsh environment for a long period of time or in an application where it is used in a damp state, durability against wet heat is required. For example, in a solar cell sealing application, in order to reduce the power generation cost by improving the service life of the solar cell, it is required to improve the wet heat resistance of the polyester film.
そのため、ポリエステル樹脂の加水分解を抑制すべく様々な検討がなされてきた。例えば、ポリエステル樹脂の重縮合触媒を検討したり（特許文献１）、エポキシ化合物（特許文献２）やポリカルボジイミド（特許文献３）を添加して、ポリエステル樹脂自体の耐湿熱性を向上させる技術が検討されている。また、ポリエステル樹脂に緩衝剤を添加したり（特許文献４）、さらにポリエステル樹脂に３官能成分を導入する事で分子間架橋により耐湿熱性を向上させる方法（特許文献５）が検討されている。 Therefore, various studies have been made to suppress hydrolysis of the polyester resin. For example, a polycondensation catalyst for a polyester resin is studied (Patent Document 1), or an epoxy compound (Patent Document 2) or a polycarbodiimide (Patent Document 3) is added to improve the heat and moisture resistance of the polyester resin itself. Has been. In addition, a method of improving moisture and heat resistance by intermolecular crosslinking by adding a buffering agent to a polyester resin (Patent Document 4) and further introducing a trifunctional component into the polyester resin has been studied (Patent Document 5).
しかしながら、特許文献１の手法では耐加水分解性が不十分であった。特許文献２、３の技術では、フィルム溶融製膜時にゲル化が進行して厚み不良となったり、フィルタ詰まりが発生したり、二軸配向フィルム製造時にフィルム破れが発生しやすく耐加水分解性を向上させるために必要な配向を付与できないといったフィルム製膜プロセスでの問題が発生したり、フィルム中に異物が残り品質不良となったりする問題があった。フィルム中に緩衝剤を含有した特許文献４では、ポリエステル樹脂の耐久性が十分ではなく、また、耐加水分解性を向上させるために必要な分子配向をフィルムに与えるような製膜条件とした場合は、二軸配向フィルム製造時に破れや厚み斑などの問題が発生しやすく、生産性と耐加水分解性の両立は困難であった。さらに、特許文献５のように分子間架橋構造を有した場合は、フィルムの耐加水分解性は向上するが、フィルムの延伸性がさらに低下するため、特許文献４の場合と同様に生産性と耐加水分解性の両立は困難であった。また、特許文献４，５に使用される緩衝剤は、添加時に凝集しやすい問題があり、これら凝集物が濾過工程でのフィルタ寿命を縮めたり、濾過しきれずに残存した微小な凝集物が、異物としてフィルム内部に残存するため、外観不良として歩留まりを悪化させてしまう問題もあった。近年コストダウンのための歩留まり向上検討が進む中、フィルムに対する異物欠陥低減に対する要求レベルも益々高くなっており、耐加水分解性の向上に加えて、異物欠陥低減についての改善も求められてきている。 However, the method of Patent Document 1 has insufficient hydrolysis resistance. In the techniques of Patent Documents 2 and 3, gelation progresses during film melting and film formation, resulting in poor thickness, filter clogging, and film breakage during biaxially oriented film production, which is resistant to hydrolysis. There is a problem in the film forming process that the orientation necessary for improvement cannot be imparted, or there is a problem that foreign matter remains in the film, resulting in poor quality. In Patent Document 4 containing a buffer in the film, the durability of the polyester resin is not sufficient, and the film forming conditions are such that the film is provided with the molecular orientation necessary to improve hydrolysis resistance. However, when producing a biaxially oriented film, problems such as tearing and unevenness in thickness easily occur, and it was difficult to achieve both productivity and hydrolysis resistance. Furthermore, when it has an intermolecular cross-linked structure as in Patent Document 5, the hydrolysis resistance of the film is improved, but the stretchability of the film is further reduced. It was difficult to achieve both hydrolysis resistance. In addition, the buffer used in Patent Documents 4 and 5 has a problem of being easily aggregated at the time of addition, and these aggregates shorten the filter life in the filtration process, or the minute aggregates that remain without being filtered, Since it remains inside the film as a foreign substance, there is also a problem that the yield is deteriorated as an appearance defect. In recent years, with the progress of yield improvement for cost reduction proceeding, the level of demand for reducing foreign material defects on films has been increasing, and in addition to improving resistance to hydrolysis, improvements in reducing foreign material defects have been required. .
本発明の目的は、かかる従来技術の問題点に鑑み、高温高湿下の条件でも耐久性が維持でき、かつ、フィルム製膜工程における厚み不良・破れ、フィルム内部欠陥等の発生を抑制できる、生産性に優れたポリエステルフィルム及びその製造方法を提供することである。 In view of the problems of the prior art, the object of the present invention is to maintain durability even under conditions of high temperature and high humidity, and can suppress the occurrence of defective thickness, tearing, film internal defects, etc. in the film forming process. It is providing the polyester film excellent in productivity, and its manufacturing method.
本発明は、かかる課題を解決するために、次のような手段を用いるものである。
［１］リン酸アルカリ金属塩を０．１モル／ｔ以上５．０モル／ｔ以下含有するポリエステル樹脂を含有するフィルムであって、フィルムを構成するポリエステル樹脂の固有粘度（ＩＶ）が０．６５以上０．８０以下、末端カルボキシル基量が２０当量／ｔ以下、ジエチレングリコール含有量が０．９質量％以上３．０質量％以下であり、かつフィルムの平均超音波伝導速度が２．２０ｋｍ／秒以上である二軸配向ポリエステルフィルム。
［２］フィルムに含まれる長径１００μｍ以上のリン元素を含有する異物が１０ヶ／１０００ｃｍ２以下である［１］に記載の二軸配向ポリエステルフィルム。
［３］フィルムの超音波伝導速度の最大値と最小値の比率が１．００以上１．３０以下である［１］または［２］に記載の二軸配向ポリエステルフィルム。
［４］フィルムの超音波伝導速度が最大値を示す方向とフィルム長手方向とのなす角度（θ）が１０°以上８０°である［３］に記載の二軸配向ポリエステルフィルム。
［５］１５０℃にて３０分処理した時の長手方向収縮率が０．８％以下である［１］〜［４］のいずれかに記載の二軸配向ポリエステルフィルム。
［６］示差走査熱量測定（ＤＳＣ）により求められる微小吸熱ピーク温度Ｔｍｅｔａ（℃）が２２０℃以上である［１］〜［５］のいずれかに記載の二軸配向ポリエステルフィルム。
［７］前記ポリエステル樹脂中のアルカリ金属元素含有量：ＷＡ（ｐｐｍ）とリン元素含有量：ＷＰ（ｐｐｍ）との比ＷＡ／ＷＰが０．３以上０．７以下である［１］〜［６］のいずれかに記載の二軸配向ポリエステルフィルム。
［８］前記ポリエステル樹脂中にマンガン化合物をマンガン元素量として１００ｐｐｍ以上３００ｐｐｍ以下含有する［１］〜［７］のいずれかに記載の二軸配向ポリエステルフィルム。
［９］１２５℃１００％ＲＨ下に７２時間保持したときの伸度保持率が５０％以上である［１］〜［８］のいずれかに記載の二軸配向ポリエステルフィルム。
［１０］リン酸アルカリ金属塩を０．１モル／ｔ以上５．０モル／ｔ以下含有するポリエステル樹脂を溶融し、シート状に成型する工程と、以下（１）〜（３）に記載の長手方向・幅方向の延伸工程および熱処理工程を有し、フィルムを構成するポリエステル樹脂の固有粘度（ＩＶ）が０．６５〜０．８０、末端カルボキシル基量が２０当量／ｔ以下、ジエチレングリコール含有量が０．９質量％以上３．０質量％以下であり、かつフィルムの平均超音波伝導速度が２．２０ｋｍ／秒以上である二軸配向ポリエステルフィルムの製造方法。
（１）長手方向に延伸速度２,０００％／秒〜１０,０００％／秒にて３．０〜４．５倍延伸する工程
（２）幅方向に３．５〜４．５倍延伸し、かつ幅方向延伸工程開始前のフィルム幅をＷ０、幅方向延伸工程の中間点でのフィルム幅をＷ１、幅方向延伸工程終了後でのフィルム幅をＷ２とした場合、以下の式（Ａ）を満たす工程
６０ ≦ １００×（Ｗ１−Ｗ０）／（Ｗ２−Ｗ０）≦ ８０ ・・・ 式（Ａ）
（３）幅方向延伸工程と熱処理工程の間に中間工程を有し、該中間工程の温度が幅方向延伸工程の最終区間の温度：Ｔｓ（℃）と熱処理工程最初の区間にあたる第１の熱処理工程温度：Ｔｈ（℃）との間の温度であり、かつ中間工程をフィルムが通過する時間をＳｍ（秒）とした時に以下式（Ｂ）を満たす工程
（Ｔｈ−Ｔｓ）／Ｓｍ ≦ ５０ ・・・ 式（Ｂ）
［１１］前記リン酸アルカリ金属塩を含有するポリエステル樹脂が以下（４）〜（６）を満たす工程で製造される［１０］に記載の二軸配向ポリエステルフィルムの製造方法。
（４）前記ポリエステル樹脂を合成する重合工程において、リン酸アルカリ金属塩を添加する事
（５）リン酸アルカリ金属塩をジオール成分に溶解または混合し、リン酸アルカリ金属塩の濃度が１質量％以下の溶液またはスラリー状態として添加する事
（６）前記リン酸アルカリ金属塩を添加する時の反応物の温度が２５０℃以下である事。
［１２］ ［１］〜［９］のいずれかに記載の二軸配向ポリエステルフィルムを用いた太陽電池封止用フィルム。
［１３］ ［１２］に記載の太陽電池封止用フィルムを用いた太陽電池。The present invention uses the following means in order to solve this problem.
[1] A film containing a polyester resin containing 0.1 mol / t or more and 5.0 mol / t or less of an alkali metal phosphate, wherein the intrinsic viscosity (IV) of the polyester resin constituting the film is 0.00. 65 to 0.80, terminal carboxyl group content is 20 equivalent / t or less, diethylene glycol content is 0.9 mass% or more and 3.0 mass% or less, and the average ultrasonic conduction velocity of the film is 2.20 km / Biaxially oriented polyester film that is longer than a second.
[2] The biaxially oriented polyester film according to [1], wherein the film contains 10 or 1000 cm 2 of foreign matter containing a phosphorus element having a major axis of 100 μm or more.
[3] The biaxially oriented polyester film according to [1] or [2], wherein the ratio of the maximum value and the minimum value of the ultrasonic conduction velocity of the film is 1.00 or more and 1.30 or less.
[4] The biaxially oriented polyester film according to [3], wherein an angle (θ) between the direction in which the ultrasonic conduction velocity of the film shows a maximum value and the film longitudinal direction is 10 ° or more and 80 °.
[5] The biaxially oriented polyester film according to any one of [1] to [4], which has a longitudinal shrinkage of 0.8% or less when treated at 150 ° C. for 30 minutes.
[6] The biaxially oriented polyester film according to any one of [1] to [5], wherein a minute endothermic peak temperature Tmeta (° C.) determined by differential scanning calorimetry (DSC) is 220 ° C. or higher.
[7] The ratio WA / WP of the alkali metal element content: WA (ppm) and the phosphorus element content: WP (ppm) in the polyester resin is 0.3 or more and 0.7 or less [1] to [ 6] The biaxially oriented polyester film according to any one of [6].
[8] The biaxially oriented polyester film according to any one of [1] to [7], wherein the polyester resin contains a manganese compound in an amount of 100 ppm or more and 300 ppm or less as a manganese element amount.
[9] The biaxially oriented polyester film according to any one of [1] to [8], wherein the elongation retention when held at 125 ° C. and 100% RH for 72 hours is 50% or more.
[10] A step of melting a polyester resin containing an alkali metal phosphate from 0.1 mol / t to 5.0 mol / t and molding it into a sheet, and the following (1) to (3) Having a stretching process and a heat treatment process in the longitudinal direction and the width direction, the intrinsic viscosity (IV) of the polyester resin constituting the film is 0.65 to 0.80, the amount of terminal carboxyl groups is 20 equivalents / t or less, and the diethylene glycol content Is 0.9 mass% or more and 3.0 mass% or less, and the manufacturing method of the biaxially-oriented polyester film whose average ultrasonic conduction velocity of a film is 2.20 km / sec or more.
(1) Step of stretching 3.0 to 4.5 times in the longitudinal direction at a stretching speed of 2,000% / second to 10,000% / second (2) Stretching to 3.5 to 4.5 times in the width direction When the film width before starting the width direction stretching step is W0, the film width at the midpoint of the width direction stretching step is W1, and the film width after the end of the width direction stretching step is W2, the following formula (A) The process which satisfy | fills 60 <= 100 * (W1-W0) / (W2-W0) <= 80 ... Formula (A)
(3) There is an intermediate step between the width direction stretching step and the heat treatment step, and the temperature of the intermediate step is the temperature of the last section of the width direction stretching step: Ts (° C.) and the first heat treatment corresponding to the first section of the heat treatment step Process temperature: a temperature between Th (° C.) and satisfying the following formula (B) when the time for the film to pass through the intermediate process is Sm (seconds) (Th−Ts) / Sm ≦ 50 ..Formula (B)
[11] The method for producing a biaxially oriented polyester film according to [10], wherein the polyester resin containing the alkali metal phosphate is produced in the following steps (4) to (6).
(4) In the polymerization step of synthesizing the polyester resin, adding an alkali metal phosphate (5) dissolving or mixing the alkali metal phosphate in the diol component, the concentration of the alkali metal phosphate being 1% by mass (6) The temperature of the reaction product when adding the alkali metal phosphate is 250 ° C. or lower.
[12] A solar cell sealing film using the biaxially oriented polyester film according to any one of [1] to [9].
[13] A solar cell using the solar cell sealing film according to [12].
中でも、上記［１］、［２］、［３］および［４］の組合せに係る発明、上記［１０］に係る発明、ならびに、上記［１０］および［１１］の組合せに係る発明が、特に顕著な効果を奏する。 Among them, the invention according to the combination of [1], [2], [3] and [4], the invention according to [10], and the invention according to the combination of [10] and [11] Has a remarkable effect.
本発明によれば、高温高湿下での耐久性と生産性を両立することができ、かつ内部欠陥が少ないポリエステルフィルムを提供することができる。かかるポリエステルフィルムは、太陽電池封止シート、銅貼り積層板、粘着テープ、フレキシブルプリント基板、メンブレンスイッチ、面状発熱体、もしくはフラットケーブルなどの電気絶縁材料、コンデンサ用材料、自動車用材料、建築材料を初めとした耐久性が重視されるような用途に好適に使用することができる。 According to the present invention, it is possible to provide a polyester film that can achieve both durability and productivity under high temperature and high humidity and has few internal defects. Such a polyester film is a solar cell encapsulating sheet, a copper-clad laminate, an adhesive tape, a flexible printed circuit board, a membrane switch, a planar heating element, a flat cable, or other electrically insulating material, capacitor material, automotive material, building material. Can be suitably used for applications where durability is important.
本発明のポリエステルフィルムには、リン酸アルカリ金属塩を０．１モル／ｔ以上５．０モル／ｔ以下含有するポリエステル樹脂を含有し、かつフィルムを構成するポリエステル樹脂の末端カルボキシル基量が２０当量／ｔ以下であることが、高温高湿下での耐久性向上のために必要である。 The polyester film of the present invention contains a polyester resin containing 0.1 mol / t or more and 5.0 mol / t or less of an alkali metal phosphate, and the terminal carboxyl group content of the polyester resin constituting the film is 20 It is necessary for the durability improvement under high temperature and high humidity to be equivalent / t or less.
一般的なポリエステルフィルムは結晶性ポリエステルから構成され、フィルム中にはポリエステルの結晶部と非晶部が存在する。また、かかる結晶性ポリエステルを二軸延伸して得られるポリエステルフィルム中には、配向によりポリエステルが結晶化した部分（以下、「配向結晶化部」と称する）と非晶部が存在する。ここで、非晶部は、結晶部、配向結晶部に比べて密度が低く、分子間の平均距離が大きい状態にあると考えられる。ポリエステルフィルムが湿熱雰囲気下に曝された場合、水分（水蒸気）は、密度の低いこの非晶部の分子間を通って内部に進入し、非晶部を可塑化させ分子の運動性を高める。また、水分（水蒸気）は、ポリエステルのカルボキシル基末端のプロトンを反応触媒として、分子運動性の高まった非晶部の加水分解を促進する。加水分解され、低分子量化したポリエステルは、分子運動性が更に高まり、加水分解が進行すると共に結晶化が進む。これが繰り返される結果、フィルムの脆化が進行し、最終的には僅かな衝撃でも破断に至る状態となる。 A general polyester film is composed of crystalline polyester, and there are crystalline and amorphous parts of the polyester in the film. Further, in a polyester film obtained by biaxially stretching such crystalline polyester, there are a portion where the polyester is crystallized by orientation (hereinafter referred to as “oriented crystallized portion”) and an amorphous portion. Here, it is considered that the amorphous part is in a state where the density is lower than that of the crystal part and the oriented crystal part, and the average distance between molecules is large. When the polyester film is exposed to a moist heat atmosphere, moisture (water vapor) enters the inside through the molecules of the amorphous part having a low density, plasticizes the amorphous part, and increases the mobility of the molecule. Further, moisture (water vapor) promotes hydrolysis of an amorphous part having increased molecular mobility using a proton at the carboxyl group terminal of the polyester as a reaction catalyst. Hydrolyzed polyester with a low molecular weight further increases molecular mobility, and progresses in hydrolysis and crystallization. As a result of this being repeated, embrittlement of the film progresses, and finally, even a slight impact results in a state of breaking.
前記の通り、ポリエステルのカルボキシル基末端のプロトンを反応触媒として加水分解反応が進むため、ポリエステルフィルムを構成するポリエステル樹脂中の末端カルボキシル基量が少ないほど耐加水分解性が向上すると考えられる。末端カルボキシル基量は好ましくは１５当量／ｔ以下、さらには１３当量／ｔ以下が好ましい。下限値は特には限定されないが、実質的に１当量／ｔ以下とすることは困難である。 As described above, since the hydrolysis reaction proceeds using the proton at the carboxyl group terminal of the polyester as a reaction catalyst, it is considered that the hydrolysis resistance improves as the amount of terminal carboxyl group in the polyester resin constituting the polyester film decreases. The terminal carboxyl group amount is preferably 15 equivalent / t or less, more preferably 13 equivalent / t or less. Although a lower limit is not specifically limited, It is difficult to make it substantially 1 equivalent / t or less.
また、リン酸アルカリ金属塩はポリエステル中で乖離してイオン性を示すため、加水分解反応の触媒として作用するプロトンを中和する事ができる。この結果、プロトンによる加水分解反応を抑制し、耐湿熱性を向上することが可能となる。このような緩衝作用を示すリン酸アルカリ金属塩の具体例としては、下記化学式（Ｉ）で示される化合物が挙げられるが、ポリエステル樹脂の重合反応性や、溶融成形時の耐熱性、耐湿熱性の観点から、リン酸二水素カリウム、リン酸二水素ナトリウムが特に好ましい例として挙げられる。
ＰＯｘＨｙＭｚ・・・化学式（Ｉ）
（ここで、ｘは２〜４の整数、ｙは１または２、ｚは１または２であり、Ｍはアルカリ金属である）。Moreover, since the alkali metal phosphate is dissociated in the polyester and exhibits ionicity, it can neutralize protons that act as a catalyst for the hydrolysis reaction. As a result, the hydrolysis reaction by protons can be suppressed and the heat and humidity resistance can be improved. Specific examples of such alkali metal phosphates having a buffering action include compounds represented by the following chemical formula (I), but the polyester resin polymerization reactivity, heat resistance during melt molding, and heat and humidity resistance From the viewpoint, potassium dihydrogen phosphate and sodium dihydrogen phosphate are particularly preferable examples.
PO x H y M z Chemical formula (I)
(Where x is an integer from 2 to 4, y is 1 or 2, z is 1 or 2, and M is an alkali metal).
本発明のポリエステルフィルムを構成するポリエステル樹脂のリン酸アルカリ金属塩含有量が０．１モル／ｔ未満である場合は、十分な耐湿熱性が得られず、５．０モル／ｔを越えると過剰なアルカリ金属により分解反応が促進される。リン酸アルカリ金属塩含有量は０．３モル／ｔ以上３．０モル／ｔ以下がより好ましく、更に好ましくは１．０モル／ｔ以上２．０モル／ｔ以下である。また、本発明のポリエステルフィルムは、上記リン酸アルカリ金属塩を０．１〜５．０モル／ｔ含有するポリエステル樹脂を５０質量％以上含有していると、フィルムの耐湿熱性能を維持するため好ましく、さらには７０質量％以上、さらには９０質量％以上、特には９５質量％以上が好ましい。５０質量％未満である場合は、耐湿熱性能に劣る場合がある。なお、本発明においてポリエステル樹脂に含有するリン酸アルカリ金属塩の含有量は、ポリエステル樹脂合成時に添加されるリン酸アルカリ金属塩の添加量とする。 When the content of the alkali metal phosphate of the polyester resin constituting the polyester film of the present invention is less than 0.1 mol / t, sufficient heat and heat resistance cannot be obtained. The decomposition reaction is accelerated by the alkali metal. The alkali metal phosphate content is more preferably 0.3 mol / t or more and 3.0 mol / t or less, and still more preferably 1.0 mol / t or more and 2.0 mol / t or less. Moreover, since the polyester film of this invention contains 50 mass% or more of polyester resins containing 0.1-5.0 mol / t of the said alkali metal phosphate, in order to maintain the heat-and-moisture resistance performance of a film. It is preferably 70% by mass or more, more preferably 90% by mass or more, and particularly preferably 95% by mass or more. When the amount is less than 50% by mass, the heat-and-moisture resistance may be inferior. In the present invention, the content of the alkali metal phosphate contained in the polyester resin is the addition amount of the alkali metal phosphate added during the synthesis of the polyester resin.
本発明のポリエステルフィルムを構成するポリエステル樹脂において、ポリエステル樹脂中のアルカリ金属元素含有量ＷＡ（ｐｐｍ）とリン元素含有量ＷＰ（ｐｐｍ）の比ＷＡ／ＷＰが０．３以上０．７以下であることが好ましい。この範囲に含有量を調整することで、ポリエステルフィルムの加水分解抑制効果が維持しながら、耐熱安定性を付与することができる。また、リン化合物としてリン酸アルカリ金属塩とリン酸を併用すると、加水分解抑制効果をさらに高めることが可能となるため特に好ましい。 In the polyester resin constituting the polyester film of the present invention, the ratio WA / WP of the alkali metal element content WA (ppm) and the phosphorus element content WP (ppm) in the polyester resin is 0.3 or more and 0.7 or less. It is preferable. By adjusting the content within this range, heat resistance stability can be imparted while maintaining the hydrolysis inhibiting effect of the polyester film. In addition, it is particularly preferable to use an alkali metal phosphate and phosphoric acid together as the phosphorus compound because the hydrolysis inhibiting effect can be further enhanced.
本発明において、リン酸アルカリ金属塩はポリエステルの重合時に添加しても、溶融成形時に添加してもいずれも構わないが、リン酸アルカリ金属塩のフィルム中への均一分散の点や重合時における末端カルボキシル基量低減のためには、重合時に添加することが好ましい。重合時に添加する場合、添加時期は、ポリエステルの重合時のエステル化反応、またはエステル交換反応終了後から、重縮合反応初期（固有粘度が０．３未満）までの間であれば任意の時期に添加することができる。しかしながら、リン酸アルカリ金属塩は、添加時にリン酸アルカリ金属塩そのものが凝集したり、反応により高分子化したりする事により、ポリエステル樹脂中にリン化合物を主成分とした異物を発生させることがある。その結果、フィルム製膜工程におけるフィルタを閉塞させ生産性が低下したり、またフィルム中に異物として残り、外観の悪化や絶縁性能の低下などの問題が発生する事がある。このため、本発明のポリエステルフィルムにおいては、フィルムに含まれる長径１００μｍ以上のリン元素を含有する異物が１０ヶ／１０００ｃｍ２以下であることが好ましく、さらに好ましくは５ヶ／１０００ｃｍ２以下、特に好ましくは３ヶ／１０００ｃｍ２である。かかる異物の個数の下限は特に限定されるものではないが、０ヶ／１０００ｃｍ２が実質的な下限となる。In the present invention, the alkali metal phosphate may be added at the time of polymerization of the polyester or at the time of melt molding. However, the alkali metal phosphate may be uniformly dispersed in the film or at the time of polymerization. In order to reduce the amount of terminal carboxyl groups, it is preferable to add at the time of polymerization. When adding at the time of polymerization, the addition time may be any time as long as it is from the end of the esterification reaction or the transesterification reaction at the time of polymerization of the polyester to the beginning of the polycondensation reaction (inherent viscosity is less than 0.3). Can be added. However, alkali metal phosphates may generate foreign substances mainly composed of phosphorus compounds in the polyester resin due to aggregation of the alkali metal phosphates themselves upon addition or polymerisation by reaction. . As a result, the filter in the film forming process may be blocked to reduce productivity, or may remain as a foreign substance in the film, resulting in problems such as deterioration in appearance and deterioration in insulation performance. Therefore, in the polyester film of the present invention, it is preferable that foreign substances containing elemental phosphorus or major axis 100μm is 10 months / 1000 cm 2 or less contained in the film, more preferably 5 months / 1000 cm 2 or less, particularly preferably Is 3/1000 cm 2 . The lower limit of the number of such foreign substances is not particularly limited, but 0/1000 cm 2 is a substantial lower limit.
ポリエステル内部のリン元素を含有する異物量を低減させるためには、リン酸アルカリ金属塩の添加方法として、あらかじめリン酸アルカリ金属塩をエチレングリコール等のジオール成分に溶解または混合し、濃度１質量％以下の溶液またはスラリー状態として添加する事が好ましく、さらには０．５質量％以下の濃度とし、該希釈溶液またはスラリーを２０分以上の時間をかけて徐々に添加する方法が好ましい。また、リン酸アルカリ金属塩添加時のポリエステルの温度が２５０℃を越えると、リン化合物による異物が発生しやすいため、リン酸アルカリ金属塩添加時のポリエステルの温度としては２５０℃以下が好ましく、さらに好ましくは２１０℃〜２４０℃である。リン酸アルカリ金属塩添加時のポリエステルの温度が２１０℃未満となると、リン酸アルカリ金属塩の添加時期がエステル化反応またはエステル交換反応前のときはエステル化反応またはエステル交換反応速度が低下するため生産性が悪化し好ましくなく、リン酸アルカリ金属塩の添加時期がエステル化反応またはエステル交換反応終了後から重縮合反応初期（固有粘度が０．３未満）までの間であるときは、ポリエステル樹脂中のリン酸アルカリ金属塩の分散性が悪化する場合があるため好ましくない。 In order to reduce the amount of foreign matter containing phosphorus element inside the polyester, the alkali metal phosphate is added in advance by dissolving or mixing the alkali metal phosphate in a diol component such as ethylene glycol, and a concentration of 1% by mass. It is preferable to add in the following solution or slurry state, and more preferably, the concentration is 0.5% by mass or less, and the diluted solution or slurry is gradually added over 20 minutes or more. Further, when the temperature of the polyester at the time of addition of the alkali metal phosphate exceeds 250 ° C., foreign matter due to the phosphorus compound is likely to be generated. Therefore, the temperature of the polyester at the time of the addition of the alkali metal phosphate is preferably 250 ° C. or less. Preferably it is 210 to 240 degreeC. If the temperature of the polyester during addition of the alkali metal phosphate is less than 210 ° C., the rate of esterification or transesterification will decrease when the alkali metal phosphate is added before the esterification or transesterification. When the productivity deteriorates and is not preferred, and the addition time of the alkali metal phosphate is between the end of the esterification reaction or transesterification reaction and the beginning of the polycondensation reaction (inherent viscosity is less than 0.3), the polyester resin This is not preferable because the dispersibility of the alkali metal phosphate may deteriorate.
また、ポリエステル樹脂を合成する方法としては、ジカルボン酸成分の原料として、ジカルボン酸化合物を使用する方法と、ジカルボン酸エステル化合物を使用する方法などが挙げられるが、ジカルボン酸化合物（ポリエチレンテレフタレートの場合ではテレフタル酸）を出発原料とした場合は、ジカルボン酸化合物に由来する酸成分によりリン酸アルカリ金属塩の凝集が発生しやすい傾向がある。そのため、ジカルボン酸成分は、ジカルボン酸エステル化合物（ポリエチレンテレフタレートの場合では、例えばテレフタル酸ジメチル等）を原料とする方が好ましい。 Examples of the method for synthesizing the polyester resin include a method using a dicarboxylic acid compound and a method using a dicarboxylic acid ester compound as a raw material of the dicarboxylic acid component, but a dicarboxylic acid compound (in the case of polyethylene terephthalate). When terephthalic acid) is used as a starting material, aggregation of the alkali metal phosphate tends to occur due to the acid component derived from the dicarboxylic acid compound. Therefore, the dicarboxylic acid component is preferably made from a dicarboxylic acid ester compound (in the case of polyethylene terephthalate, for example, dimethyl terephthalate).
なお、ジカルボン酸化合物を原料として用いる場合は、リン酸アルカリ金属塩の濃度を０．５質量％以下とし、ポリエステルの温度が２１０〜２３０℃の範囲にて添加する事で、リン化合物による異物の形成を実用範囲内に抑制することは可能となる。また、ジカルボン酸エステル化合物を原料として用いるエステル交換反応においては、ジオール成分とジカルボン酸成分とのモル比（ジオール成分の物質量（モル）／ジカルボン酸成分の物質量（モル））が１．１〜１．３倍となるように原料が混合され、エステル交換反応の開始温度を２５０〜２７０℃の範囲として初期の反応を促進した後、エステル交換反応終了温度を２２０〜２４０℃の範囲とし、最終的に、ジオール成分とジカルボン酸成分とのモル比（ジオール成分の物質量（モル）／ジカルボン酸成分の物質量（モル））が１．５〜２．０倍となるようにエチレングリコールとジエチンレングリコールの混合物をエステル交換反応中に追添加すると、反応性が良好となりポリエステル樹脂の生産性を向上できるため好ましく、またポリエステル樹脂に含まれるＤＥＧ（ジエチレングリコール）量を制御することが容易になるため好ましい。 In addition, when using a dicarboxylic acid compound as a raw material, the density | concentration of an alkali metal phosphate is 0.5 mass% or less, and the temperature of polyester adds in the range of 210-230 degreeC, The foreign material by a phosphorus compound is added. It is possible to suppress the formation within a practical range. In the transesterification reaction using a dicarboxylic acid ester compound as a raw material, the molar ratio of the diol component to the dicarboxylic acid component (substance amount of diol component (mol) / substance amount of dicarboxylic acid component (mol)) is 1.1. The raw materials are mixed so as to be about -1.3 times, the initial temperature of the transesterification reaction is set in the range of 250 to 270 ° C, and the initial reaction is promoted. Finally, the ethylene glycol and the dicarboxylic acid component have a molar ratio (substance amount of diol component (mol) / substance amount of dicarboxylic acid component (mol)) of 1.5 to 2.0 times. It is preferable to add a mixture of diethylene glycol during the transesterification reaction because the reactivity is improved and the productivity of the polyester resin can be improved. Preferable because it is easy to control the the DEG (diethylene glycol) content in the polyester resin.
本発明のポリエステル樹脂の重縮合触媒としては、従来のアンチモン化合物、ゲルマニウム化合物、チタン化合物を用いることができる。アンチモン化合物および／またはゲルマニウム化合物を用いる場合は、そのアンチモン元素、ゲルマニウム元素の和として５０ｐｐｍ〜５００ｐｐｍであることが重縮合反応性、固相重合反応性の点から好ましく、さらには５０〜３００ｐｐｍであることが耐熱性、耐加水分解性の点から好ましい。５００ｐｐｍを超えると重縮合反応性、固相重合反応性は向上するものの、再溶融時の分解反応も促進されるため、カルボンキシル末端基が増加し、耐熱性、耐加水分解性が低下する原因となることがある。好適に使用されるアンチモン化合物、ゲルマニウム化合物としては、五酸化アンチモン、三酸化アンチモン、二酸化ゲルマニウムを挙げることができ、それぞれ目的に応じて使い分けることができる。例えば、色調が最も良好となるのはゲルマニウム化合物であり、固相重合反応性が良好となるのはアンチモン化合物である。環境面を配慮し、非アンチモン系で製造する場合には、チタン触媒が重縮合反応や固相重合の反応性が良好となる点で好ましい。さらに、マンガン化合物を１００〜３００ｐｐｍの範囲で添加すると耐加水分解性が良好となるため好ましい。これは、マンガンの水和エネルギーが高い事で、ポリエステルフィルム中の水との親和性が低くなり加水分解反応が進行しにくくなるためと考えられる。１００ｐｐｍ未満の場合は、加水分解抑制効果が不十分となり、３００ｐｐｍを越えると逆に耐加水分解性が悪化する傾向が見られる。 As the polycondensation catalyst for the polyester resin of the present invention, conventional antimony compounds, germanium compounds, and titanium compounds can be used. When using an antimony compound and / or a germanium compound, the sum of the antimony element and germanium element is preferably 50 ppm to 500 ppm from the viewpoint of polycondensation reactivity and solid phase polymerization reactivity, and more preferably 50 to 300 ppm. Is preferable from the viewpoint of heat resistance and hydrolysis resistance. If it exceeds 500 ppm, the polycondensation reactivity and solid-phase polymerization reactivity will improve, but the decomposition reaction during remelting will also be accelerated, leading to an increase in carboxyxyl end groups and a decrease in heat resistance and hydrolysis resistance. It may become. Examples of the antimony compound and the germanium compound that are preferably used include antimony pentoxide, antimony trioxide, and germanium dioxide, which can be used according to the purpose. For example, the germanium compound has the best color tone, and the antimony compound has the best solid-phase polymerization reactivity. In consideration of the environment, when producing non-antimony system, a titanium catalyst is preferable in that the reactivity of polycondensation reaction or solid phase polymerization is improved. Furthermore, it is preferable to add a manganese compound in the range of 100 to 300 ppm because hydrolysis resistance is improved. This is presumably because the hydration energy of manganese is high, the affinity with water in the polyester film is lowered, and the hydrolysis reaction is difficult to proceed. When it is less than 100 ppm, the hydrolysis inhibiting effect is insufficient, and when it exceeds 300 ppm, the hydrolysis resistance tends to deteriorate.
したがって、本発明のフィルムにおいては、フィルムを構成するポリエステル樹脂中にマンガン化合物をマンガン元素量として１００ｐｐｍ以上３００ｐｐｍ以下含有することが好ましい。 Therefore, in the film of this invention, it is preferable to contain 100 ppm or more and 300 ppm or less of a manganese compound as a manganese element amount in the polyester resin which comprises a film.
本発明において、ポリエステルフィルムを構成するポリエステル樹脂の固有粘度（ＩＶ）は０．６５以上０．８０以下であり、好ましくは０．６８以上０．７５以下である。固有粘度（ＩＶ）が０．６５未満である場合は、分子鎖が短く耐湿熱環境下での分子運動性が高まり易かったり、末端部分が増える事で耐加水分解性が悪化しやすい。また０．８０を越える場合は、粘度が高くなりすぎるため、フィルム製膜時に破断が増えるなど生産性が悪化したり、厚みムラが悪化したりする事がある。また、ポリエステル樹脂製造時に固相重合を行うと、前述の末端カルボキシル基量を低下させ、かつ固有粘度（ＩＶ）を上記の範囲に調整する事が容易となるため好ましい。なお、ポリエステル樹脂を溶融製膜する際の溶融状態において、残存する水分による加水分解や熱分解が進行するため、フィルム原料として用いるポリエステル樹脂の固有粘度（ＩＶ）は、フィルムを構成するポリエステル樹脂におけるＩＶの目標値よりも高くすることが好ましい。ただし、フィルム原料のポリエステル樹脂の固有粘度（ＩＶ）を上げるためには、ポリエステル樹脂製造時の固相重合の時間を長くしたり、触媒添加量を増やす必要があり、ポリエステル樹脂の着色や特性の悪化につながる場合がある。そのため、フィルム原料のポリエステル樹脂の固有粘度（ＩＶ）は、フィルムを構成するポリエステル樹脂におけるＩＶの目標値よりも高くするとしても、その差は小さい方が好ましい。フィルム原料のポリエステル樹脂の固有粘度（ＩＶ）は、フィルムを構成するポリエステル樹脂におけるＩＶの目標値よりも０．０５〜０．１５高くすることが好ましい。ポリエステル樹脂をフィルムに溶融押出製膜する前に、ポリエステル樹脂を減圧下にて加熱する等の方法にてあらかじめポリエステル樹脂中の水分量を５０ｐｐｍ以下とする事や、フィルムに溶融押出製膜する時のポリエステル樹脂の温度をポリエステル樹脂の融点（Ｔｍ）＋３０℃以下として、さらに押出機先端から口金までの樹脂の溶融時間を５分未満、さらには３分未満とする事によって、ポリエステル樹脂の溶融製膜時の加水分解や熱分解を抑制して固有粘度（ＩＶ）の低下を少なくし、安定して耐加水分解性の良いポリエステルフィルムを得る事が可能となる。 In the present invention, the intrinsic viscosity (IV) of the polyester resin constituting the polyester film is 0.65 or more and 0.80 or less, preferably 0.68 or more and 0.75 or less. When the intrinsic viscosity (IV) is less than 0.65, the molecular chain is short and the molecular mobility in a heat-and-moisture resistant environment is likely to increase, and the hydrolysis resistance is likely to deteriorate due to an increase in the terminal portion. On the other hand, when it exceeds 0.80, the viscosity becomes too high, so that the productivity may be deteriorated such as an increase in breakage during film formation, and the thickness unevenness may be deteriorated. Further, it is preferable to perform solid-state polymerization at the time of producing the polyester resin because the amount of the terminal carboxyl group can be reduced and the intrinsic viscosity (IV) can be easily adjusted to the above range. In addition, in the melted state when the polyester resin is melt-formed, hydrolysis and thermal decomposition with residual water proceed, so the intrinsic viscosity (IV) of the polyester resin used as the film raw material is the polyester resin constituting the film. It is preferable to make it higher than the target value of IV. However, in order to increase the intrinsic viscosity (IV) of the polyester resin of the film raw material, it is necessary to lengthen the solid phase polymerization time during the production of the polyester resin or increase the amount of the catalyst added. It may lead to deterioration. Therefore, even if the intrinsic viscosity (IV) of the polyester resin of the film raw material is higher than the target value of IV in the polyester resin constituting the film, the difference is preferably small. It is preferable that the intrinsic viscosity (IV) of the polyester resin of the film raw material is 0.05 to 0.15 higher than the target value of IV in the polyester resin constituting the film. Before the polyester resin is melt-extruded and formed into a film, when the polyester resin is made to have a moisture content of 50 ppm or less in advance, such as by heating the polyester resin under reduced pressure, or when the film is melt-extruded into a film The temperature of the polyester resin is set to the melting point of the polyester resin (Tm) + 30 ° C. or less, and the melting time of the resin from the extruder tip to the die is set to less than 5 minutes, and further to less than 3 minutes. It is possible to obtain a polyester film having good hydrolysis resistance stably by suppressing hydrolysis and thermal decomposition during filming to reduce the decrease in intrinsic viscosity (IV).
本発明において、ポリエステルフィルムを構成するポリエステル樹脂のジエチレングリコール（ＤＥＧ）の含有量が０．９質量％以上３．０質量％以下であり、好ましくは１．０質量％以上２．０質量％以下である。本発明において、ポリエステル樹脂のジエチレングリコール（ＤＥＧ）の含有量は、後述する測定方法により求められる。また、本発明において、ポリエステル樹脂に含まれるジエチレングリコールとは、ポリエステル鎖に共重合された状態でポリエステル樹脂中に含まれているジエチレングリコール、ポリエステル樹脂中に単独で含有しているジエチレングリコールのどちらも含む。ジエチレングリコール（ＤＥＧ）の含有量が０．９質量％未満である場合は、フィルム製造工程における延伸性が悪化し、フィルム破断による生産性低減の問題が生じたり、加工工程での裁断時のバリや割れが生じやすい等の問題が発生する事がある。特にこれまでの耐加水分解性が高いフィルムは、上述のように固有粘度（ＩＶ）が高いため、それにより延伸張力も高くなり、特に広いフィルム幅を持つフィルムを生産する際における幅方向の延伸工程において、フィルムのエッジ（フィルム幅方向の端部）近傍に応力が集中して、フィルムが破れやすくなる問題があった。また末端カルボキシル基量が低いフィルムでは、分子内での相互作用が弱くなり、特に幅方向中央部と両端部における分子配向の均一性が悪化しやすく、延伸時の破れが増加したり、フィルム幅方向の位置により特性の差が大きくなったりする等の問題があった。ジエチレングリコール（ＤＥＧ）の含有量を上記の範囲とする事で、ポリエステル分子に適度な柔軟性が付与され、フィルムが破断しにくくなり、生産性が向上すると共に、打抜き加工などを行った場合の切断面のバリや破れなどが発生しにくく加工性が良好なフィルムを得ることができる。更に、ポリエステルフィルムを構成するポリエステル樹脂中のＤＥＧ含有量を上記の範囲とした本発明のポリエステルフィルムは、生産性、加工性が良好であるだけでなく、高温高湿下での耐久性（耐湿熱性）も良好となる。本発明のポリエステルフィルムは加工性が良好であるため、従来の耐加水分解性が高いフィルムではフィルム破断が発生するため不可能であった後述する延伸速度が速い延伸条件を取ることが可能となる。この延伸条件を用いて得られるポリエステルフィルムは、特に広幅製膜における幅方向中央部と端部の配向差、および配向差による特性差を低減させることが可能となり、高温高湿下での耐久性（耐湿熱性）の向上と共に、幅方向での特性差を低減する事が可能となる。 In the present invention, the content of diethylene glycol (DEG) of the polyester resin constituting the polyester film is 0.9% by mass or more and 3.0% by mass or less, preferably 1.0% by mass or more and 2.0% by mass or less. is there. In the present invention, the content of diethylene glycol (DEG) in the polyester resin is determined by a measurement method described later. In the present invention, the diethylene glycol contained in the polyester resin includes both diethylene glycol contained in the polyester resin in a state copolymerized with the polyester chain and diethylene glycol contained alone in the polyester resin. When the content of diethylene glycol (DEG) is less than 0.9% by mass, the stretchability in the film production process is deteriorated, resulting in a problem of productivity reduction due to film breakage, Problems such as easy cracking may occur. In particular, films with high hydrolysis resistance so far have high intrinsic viscosity (IV) as described above, so that the stretching tension is also increased, and in particular, stretching in the width direction when producing a film having a wide film width. In the process, there was a problem that stress was concentrated near the edge of the film (the end in the film width direction) and the film was easily broken. In addition, in the film with a low amount of terminal carboxyl groups, the interaction within the molecule becomes weak, and the uniformity of molecular orientation at the center and both ends in the width direction tends to deteriorate, and the tearing during stretching increases, the film width There is a problem that the difference in characteristics increases depending on the position in the direction. By setting the content of diethylene glycol (DEG) within the above range, the polyester molecules are given adequate flexibility, the film is less likely to break, the productivity is improved, and cutting is performed when punching is performed. It is possible to obtain a film that is less prone to burrs and tears and has good processability. Furthermore, the polyester film of the present invention having the DEG content in the polyester resin constituting the polyester film in the above range not only has good productivity and processability, but also has durability (high humidity resistance) under high temperature and high humidity. Thermal properties are also good. Since the polyester film of the present invention has good processability, it becomes possible to take stretching conditions with a high stretching speed described later, which was impossible because a film breakage occurs in a conventional film having high hydrolysis resistance. . The polyester film obtained by using these stretching conditions can reduce the difference in orientation between the center and end in the width direction, and the characteristic difference due to the orientation difference, especially in wide film formation, and durability under high temperature and high humidity conditions. It becomes possible to reduce the difference in characteristics in the width direction as well as (resistance to moist heat).
フィルムを構成するポリエステル樹脂中のジエチレングリコール（ＤＥＧ）量を上記の範囲とするためには、ポリエステル樹脂重合時のジオール成分としてジエチレングリコール（ＤＥＧ）を添加する方法が最も好ましい方法として挙げられる。ただ、ジエチレングリコール成分はエチレングリコール成分の副反応成分としても生じるため、ジエチレングリコール（ＤＥＧ）量を安定して上記範囲とするためには、重合反応中の副反応成分を抑制し、かつ制御する事が必要となる。そのため、ジカルボン酸構成成分としては、例えばテレフタル酸ジメチルの様な末端がエステル化された原料を用いる事が好ましい。例えばテレフタル酸の様な末端がカルボン酸となっている原料を出発原料として用いた場合は、カルボン酸成分によりジオール成分同士が反応する副反応を生じやすい。例えばジオール成分としてエチレングリコールを用いた場合は、副反応としてジエチレングリコール（ＤＥＧ）を生じやすく、ポリエステル樹脂中に一定量のジエチレングリコール（ＤＥＧ）成分が導入される。しかし、副反応生成物として発生するためにその量の制御が難しい事や、上述した通り、本発明で使用されるリン酸アルカリ金属塩添加時に残存するカルボン酸成分の影響により、リン元素を含む異物が発生しやすく、ポリエステルフィルムを製造した際にフィルム中の異物量が増える傾向がある。また、エステル交換反応時においては、ジオール成分がジカルボン酸成分に対して過剰とならないように、ジオール成分を反応に従い徐々に添加する方法を用いたり、ジオール成分追添時の温度を２２０℃〜２４０℃の低温条件下で行う事が、副反応を抑制するための好ましい方法として挙げられる。 In order to make the amount of diethylene glycol (DEG) in the polyester resin constituting the film within the above range, a method of adding diethylene glycol (DEG) as a diol component at the time of polymerization of the polyester resin is the most preferable method. However, since the diethylene glycol component also occurs as a side reaction component of the ethylene glycol component, in order to stabilize the amount of diethylene glycol (DEG) within the above range, the side reaction component during the polymerization reaction can be suppressed and controlled. Necessary. Therefore, as the dicarboxylic acid component, it is preferable to use a raw material in which the terminal is esterified, such as dimethyl terephthalate. For example, when a raw material such as terephthalic acid having a terminal carboxylic acid is used as a starting material, a side reaction in which diol components react with each other easily occurs due to the carboxylic acid component. For example, when ethylene glycol is used as the diol component, diethylene glycol (DEG) is easily generated as a side reaction, and a certain amount of diethylene glycol (DEG) component is introduced into the polyester resin. However, since it is generated as a side reaction product, it is difficult to control its amount, and as described above, it contains phosphorus element due to the influence of the carboxylic acid component remaining when adding the alkali metal phosphate used in the present invention. Foreign matter tends to be generated, and the amount of foreign matter in the film tends to increase when a polyester film is produced. In the transesterification reaction, a method of gradually adding the diol component according to the reaction is used so that the diol component does not become excessive with respect to the dicarboxylic acid component, or the temperature at the time of adding the diol component is 220 ° C. to 240 ° C. Performing under a low temperature condition of ° C. is a preferable method for suppressing side reactions.
本発明のポリエステルフィルムを構成するポリエステル樹脂はジカルボン酸構成成分とジオール構成成分を有してなるポリエステルである。なお、本明細書内において、構成成分とはポリエステルを加水分解することで得ることが可能な最小単位のことを示す。 The polyester resin constituting the polyester film of the present invention is a polyester having a dicarboxylic acid component and a diol component. In addition, in this specification, a structural component shows the minimum unit which can be obtained by hydrolyzing polyester.
かかるポリエステルを構成するジカルボン酸構成成分としては、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がこれらに限定されない。また、上述のカルボン酸構成成分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、およびその誘導体や、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。また、これらは単独で用いても、必要に応じて、複数種類用いても構わない。 Examples of the dicarboxylic acid component constituting the polyester include malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, dodecanedioic acid, dimer acid, eicosandioic acid, pimelic acid, azelaic acid, methylmalon. Aliphatic dicarboxylic acids such as acid, ethylmalonic acid and the like, adamantane dicarboxylic acid, norbornene dicarboxylic acid, isosorbide, cyclohexanedicarboxylic acid, decalin dicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, 1,4 -Naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 4,4'-diphenylether dicarboxylic acid, 5-sodium Sulfoiso Examples include dicarboxylic acids such as taric acid, phenylendanedicarboxylic acid, anthracene dicarboxylic acid, phenanthrene dicarboxylic acid, aromatic dicarboxylic acid such as 9,9′-bis (4-carboxyphenyl) fluorenic acid, or ester derivatives thereof. It is not limited. Also suitable are those obtained by adding oxyacids such as l-lactide, d-lactide, hydroxybenzoic acid, and derivatives thereof, or a combination of a plurality of oxyacids to the carboxy terminus of the carboxylic acid component. Used for. Moreover, these may be used independently or may be used in multiple types as needed.
また、かかるポリエステルを構成するジオール構成成分としては、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、芳香族ジオール類等のジオール、上述のジオールが複数個連なったものなどが例としてあげられるがこれらに限定されない。また、これらは単独で用いても、必要に応じて、複数種類用いても構わない。 Examples of the diol component constituting the polyester include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,2-butanediol, and 1,3-butanediol. Aliphatic diols such as cyclohexanedimethanol, spiroglycol and isosorbide, bisphenol A, 1,3-benzenedimethanol, 1,4-benzenedimethanol, 9,9′-bis (4 -Hydroxyphenyl) fluorene, diols such as aromatic diols, and a series of a plurality of the above-mentioned diols are exemplified, but the invention is not limited thereto. Moreover, these may be used independently or may be used in multiple types as needed.
また、本発明にて用いられるポリエステル樹脂中には、カルボキシル基（カルボン酸成分）の数と水酸基の数の合計が３以上である構成成分や、エポキシ系化合物やカルボジイミド系化合物、オキサゾリン系化合物など末端カルボキシル基の封止剤を本発明の効果を損なわない程度に含有することが可能である。カルボキシル基（カルボン酸成分）の数と水酸基の数の合計が３以上である構成成分の例としては、三官能の芳香族カルボン酸構成成分としては、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、三官能の脂肪族カルボン酸構成成分として、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挙げられ、水酸基数が３以上の構成成分の例としては、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等が挙げられる。ただし上記、カルボキシル基（カルボン酸成分）の数と水酸基の数の合計が３以上である構成成分や末端封止剤を添加すると、ポリエステル樹脂の分子鎖同士を架橋した３次元構造を形成しやすく、結果としてフィルムの延伸性を悪化させたり、ゲル化物によるフィルム中の異物量が増加するため、極力使用しない方が好ましい。 Further, in the polyester resin used in the present invention, a component having a total number of carboxyl groups (carboxylic acid components) and hydroxyl groups of 3 or more, an epoxy compound, a carbodiimide compound, an oxazoline compound, etc. It is possible to contain a terminal carboxyl group sealant to such an extent that the effects of the present invention are not impaired. Examples of components having a total number of carboxyl groups (carboxylic acid components) and hydroxyl groups of 3 or more include trifunctional aromatic carboxylic acid components as trimesic acid, trimellitic acid, pyromellitic acid, Naphthalenetricarboxylic acid, anthracentricarboxylic acid, etc. are trifunctional aliphatic carboxylic acid constituents such as methanetricarboxylic acid, ethanetricarboxylic acid, propanetricarboxylic acid, butanetricarboxylic acid, etc. Examples include trihydroxybenzene, trihydroxynaphthalene, trihydroxyanthracene, trihydroxychalcone, trihydroxyflavone, trihydroxycoumarin and the like. However, when a component having a total number of carboxyl groups (carboxylic acid components) and hydroxyl groups of 3 or more and a terminal blocking agent are added, it is easy to form a three-dimensional structure in which molecular chains of the polyester resin are cross-linked. As a result, the stretchability of the film is deteriorated, or the amount of foreign matter in the film due to the gelled product is increased.
また、本発明のポリエステルフィルムを構成するポリエステル樹脂において、ポリエステル中の全ジカルボン酸構成成分中の芳香族ジカルボン酸構成成分の割合は、９０モル％以上１００モル％以下が好ましい。より好ましくは９５モル％以上１００モル％以下が好ましい。更に好ましくは９８モル％以上１００モル％以下、特に好ましくは９９モル％以上１００モル％以下、最も好ましくは１００モル％、すなわちジカルボン酸構成成分全てが芳香族ジカルボン酸構成成分であるのがよい。９０モル％に満たないと、耐湿熱性、耐熱性が低下したりする場合がある。本発明のポリエステルフィルムにおいて、ポリエステル中の全ジカルボン酸構成成分中の芳香族ジカルボン酸構成成分の割合を９０モル％以上１００モル％以下とすることで、耐湿熱性、耐熱性を両立することが可能となる。 Moreover, the polyester resin which comprises the polyester film of this invention WHEREIN: 90 mol% or more and 100 mol% or less of the ratio of the aromatic dicarboxylic acid structural component in all the dicarboxylic acid structural components in polyester are preferable. More preferably, it is 95 mol% or more and 100 mol% or less. More preferably, it is 98 mol% or more and 100 mol% or less, particularly preferably 99 mol% or more and 100 mol% or less, and most preferably 100 mol%, that is, all dicarboxylic acid components should be aromatic dicarboxylic acid components. If it is less than 90 mol%, the heat and moisture resistance and heat resistance may decrease. In the polyester film of the present invention, by making the ratio of the aromatic dicarboxylic acid constituent component in the total dicarboxylic acid constituent component in the polyester 90 mol% or more and 100 mol% or less, it is possible to achieve both heat and moisture resistance and heat resistance. It becomes.
本発明のポリエステルフィルムを構成するポリエステル樹脂において、ポリエステルが主として構成される、ジカルボン酸構成成分とジオール構成成分からなる主たる繰り返し単位は、エチレンテレフタレート、エチレン−２，６−ナフタレンジカルボキシレート、プロピレンテレフタレート、ブチレンテレフタレート、１，４−シクロヘキシレンジメチレンテレフタレート、エチレン−２，６−ナフタレンジカルボキシレートおよびこれら混合物をからなるものが好適に用いられる。なお、ここでいう主たる繰り返し単位とは、上記繰り返し単位の合計が全繰り返し単位の７０モル％以上、より好ましくは８０モル％以上、更に好ましくは９０モル％以上である。さらには低コストで、より容易に重合が可能で、かつ耐熱性に優れるという点で、エチレンテレフタレート、エチレン−２，６−ナフタレンジカルボキシレート、およびこれらの混合物が主たる繰り返し単位であることが好ましい。この場合、エチレンテレフタレートを繰り返し単位としてより多く用いた場合はより安価で汎用性のある耐湿熱性を有するフィルムを得ることができ、またエチレン−２，６−ナフタレンジカルボキシレートを繰り返し単位としてより多く用いた場合はより耐湿熱性に優れるフィルムとすることができる。 In the polyester resin constituting the polyester film of the present invention, the main repeating unit comprising a dicarboxylic acid component and a diol component, which are mainly composed of polyester, is ethylene terephthalate, ethylene-2,6-naphthalenedicarboxylate, propylene terephthalate. , Butylene terephthalate, 1,4-cyclohexylenedimethylene terephthalate, ethylene-2,6-naphthalenedicarboxylate and mixtures thereof are preferably used. The main repeating unit as used herein means that the total of the above repeating units is 70 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more of all repeating units. Furthermore, it is preferable that ethylene terephthalate, ethylene-2,6-naphthalenedicarboxylate, and a mixture thereof are main repeating units in that they can be easily polymerized at low cost and have excellent heat resistance. . In this case, when ethylene terephthalate is used more as a repeating unit, a cheaper and more versatile film having moisture and heat resistance can be obtained, and more ethylene-2,6-naphthalenedicarboxylate is used as a repeating unit. When used, the film can be made more excellent in heat and moisture resistance.
更に、本発明のポリエステルフィルムを構成するポリエステル樹脂中には、各種添加剤、例えば、酸化防止剤、耐熱安定剤、耐候安定剤、紫外線吸収剤、有機の易滑剤、顔料、染料、有機または無機の微粒子、充填剤、帯電防止剤、核剤、架橋剤などがその特性を悪化させない程度に添加されていてもよい。特に、紫外線カット能を付与するにはポリエステルフィルム中に隠蔽性が高い二酸化チタンなどの無機粒子や紫外線吸収剤を含有させるのが好ましく、特に二酸化チタンはその隠蔽性および反射率の高さから、太陽電池封止フィルムとして使用した場合、内部の配線を見えにくくしたり、背面側の封止フィルムとして使用した場合は、発電に利用されなかった光を反射することで発電効率向上に寄与する事が出来るため好ましい。 Further, in the polyester resin constituting the polyester film of the present invention, various additives such as antioxidants, heat stabilizers, weathering stabilizers, ultraviolet absorbers, organic lubricants, pigments, dyes, organic or inorganic Fine particles, fillers, antistatic agents, nucleating agents, cross-linking agents, etc. may be added to such an extent that the properties are not deteriorated. In particular, it is preferable to contain inorganic particles such as titanium dioxide having a high concealment property or an ultraviolet absorber in the polyester film in order to impart ultraviolet cut ability, and in particular, titanium dioxide has a high concealability and high reflectance. When used as a solar cell sealing film, the internal wiring is less visible, or when used as a back side sealing film, it contributes to improving power generation efficiency by reflecting light that was not used for power generation. Is preferable.
二酸化チタンとしては、アナターゼ型及びルチル型の結晶構造を有する二酸化チタンが存在するが、アナターゼ型と比較してルチル型の方が結晶構造が密であるため屈折率が高い。そのため本発明にて使用される二酸化チタンは、高い反射作用による隠蔽効果を得ることができるという観点から、ルチル型二酸化チタンが好ましい。 Titanium dioxide includes titanium dioxide having anatase and rutile crystal structures, but the rutile type has a higher refractive index because the crystal structure is denser than the anatase type. Therefore, the titanium dioxide used in the present invention is preferably rutile titanium dioxide from the viewpoint that a concealing effect due to high reflection action can be obtained.
二酸化チタン粒子の製造方法としては、主に硫酸法と塩素法が挙げられる。硫酸法プロセスではイルメナイト鉱を濃硫酸に溶解し、鉄分を硫酸鉄として分離した後、この溶液を加水分解することでチタンを水酸化物としてとして沈殿分離する。次いでこの水酸化物を高温のロータリーキールン等で焼くことで、二酸化チタンを得ることができる。一方塩素法プロセスでは、ルチル鉱を原料とし、約１，０００℃の高温で塩素ガスとカーボンに反応させ、四塩化チタンを生成させた後に、四塩化チタンを分離し、高速に噴射しながら酸化することで二酸化チタンを得ることができる。塩素法プロセスで生成された二酸化チタンは、硫酸法プロセスと比較して、気体だけが関与する気相反応で合成されることから、バナジウム、鉄、マンガンといった不純物が少なく、高純度な二酸化チタンを得ることができ、特に好ましい。 As a production method of the titanium dioxide particles, mainly a sulfuric acid method and a chlorine method are exemplified. In the sulfuric acid process, ilmenite ore is dissolved in concentrated sulfuric acid, iron is separated as iron sulfate, and the solution is hydrolyzed to precipitate and separate titanium as a hydroxide. Next, titanium dioxide can be obtained by baking this hydroxide with a high-temperature rotary keeln or the like. On the other hand, in the chlorine process, rutile ore is used as a raw material and reacted with chlorine gas and carbon at a high temperature of about 1,000 ° C. to produce titanium tetrachloride. Then, titanium tetrachloride is separated and oxidized while being injected at high speed. By doing so, titanium dioxide can be obtained. Compared to the sulfuric acid process, titanium dioxide produced by the chlorine process is synthesized by a gas phase reaction involving only gas, so there are few impurities such as vanadium, iron, and manganese, and high purity titanium dioxide is used. It can be obtained and is particularly preferred.
本発明で使用される二酸化チタンは、二酸化チタンの光触媒活性を抑制するため、あるいはポリエステル樹脂中での分散性を向上させるために、表面処理が行われていることが好ましい。光触媒活性を抑制するためには、例えば表面をシリカ、アルミナなどの無機酸化物で被覆処理する方法が挙げられる。また、分散性向上のためには、例えば、シロキサン化合物やポリオールなどで表面処理をする方法が挙げられる。 The titanium dioxide used in the present invention is preferably surface-treated in order to suppress the photocatalytic activity of titanium dioxide or to improve the dispersibility in the polyester resin. In order to suppress the photocatalytic activity, for example, a method of coating the surface with an inorganic oxide such as silica or alumina can be mentioned. In order to improve dispersibility, for example, a method of surface treatment with a siloxane compound or a polyol can be used.
本発明での二酸化チタンの粒径は、０．１μｍ〜０．５μｍであることが好ましい。二酸化チタンの光反射能力が最大発揮される波長は、二酸化チタン粒径の約２倍の波長であるため、二酸化チタンの粒径が上記の範囲であると可視光線領域の反射効率が高くなるため、例えば太陽電池の封止フィルムとして用いられた場合は、発電効率が向上し好ましい。二酸化チタンの粒径は０．２μｍ〜０．４μｍであることが特に好ましい。二酸化チタンの粒径が０．１μｍ未満となると、二酸化チタン粒子が凝集しやすく、分散が難しい傾向があり、また０．５μｍを越えると可視光線領域の反射効率が落ちる傾向がある。なお、ここで言う二酸化チタン粒子の平均粒径とは、フィルムを灰化処理をした後に、走査型電子顕微鏡（ＳＥＭ）にて２０，０００倍の倍率で観察し、観察された粒子５０ヶの数平均粒径を求めた値である。 The particle diameter of titanium dioxide in the present invention is preferably 0.1 μm to 0.5 μm. The wavelength at which the light reflection ability of titanium dioxide is maximized is about twice the wavelength of the titanium dioxide particle size, and if the titanium dioxide particle size is in the above range, the reflection efficiency in the visible light region is increased. For example, when used as a sealing film for solar cells, the power generation efficiency is improved, which is preferable. The particle size of titanium dioxide is particularly preferably 0.2 μm to 0.4 μm. When the particle diameter of titanium dioxide is less than 0.1 μm, the titanium dioxide particles tend to aggregate and tend to be difficult to disperse, and when it exceeds 0.5 μm, the reflection efficiency in the visible light region tends to decrease. The average particle diameter of the titanium dioxide particles referred to here is the ashing treatment of the film, followed by observation with a scanning electron microscope (SEM) at a magnification of 20,000 times, and 50 particles observed. It is the value which calculated | required the number average particle diameter.
本発明のポリエステルフィルムを構成するポリエステル樹脂中に含有される二酸化チタン粒子の量としては、２〜２５質量％が好ましく、さらに好ましくは３〜２０質量％である。２質量％未満である場合は、隠蔽性が不十分となる場合があり、２５質量％を越えると、延伸時にフィルム破断が発生しやすくなったり、耐湿熱性が低下する場合がある。なお、本発明のポリエステルフィルムにおいて、ポリエステルフィルムを厚さ方向に共押出積層を行い、その一方の面側はニ酸化チタン粒子量を１０〜２５重量％含む紫外線を遮断機能層とし、もう一方の面側にはニ酸化チタン粒子量を２〜８質量％とし、湿熱環境下での耐久性維持を目的とした層とする事で、高い紫外線耐久性と高い耐湿熱性能を両立することが出来るため好ましい。この時に、ニ酸化チタン粒子量を１０〜２５重量％含む層とニ酸化チタン粒子量を２〜８質量％含む層の厚みの比率を１：１０〜１：５とすると、紫外線耐久性と高い耐湿熱性能をバランスよく両立する事ができ、さらに好ましい。なお、通常光触媒反応性を有するチタン系化合物をポリエステルフィルム中に含有する場合は、その触媒活性の高さからポリエステルフィルムの加水分解が促進され、湿熱環境下での耐久性が低下する。しかしながら、本発明のポリエステルフィルムは、チタン系化合物（チタン系粒子）を含有した場合でも、高い耐湿熱性を維持する事が可能となる。 As a quantity of the titanium dioxide particle contained in the polyester resin which comprises the polyester film of this invention, 2-25 mass% is preferable, More preferably, it is 3-20 mass%. When the content is less than 2% by mass, the concealing property may be insufficient. When the content exceeds 25% by mass, film breakage may easily occur during stretching, or the heat and moisture resistance may be reduced. In the polyester film of the present invention, the polyester film is coextruded and laminated in the thickness direction, and one surface side thereof has an ultraviolet ray containing 10 to 25% by weight of titanium dioxide particles as a blocking functional layer, and the other side. By making the amount of titanium dioxide particles 2 to 8% by mass on the surface side and making it a layer intended to maintain durability in a humid heat environment, it is possible to achieve both high UV durability and high moisture resistance. Therefore, it is preferable. At this time, when the ratio of the thickness of the layer containing 10 to 25% by weight of the titanium dioxide particles and the layer containing 2 to 8% by weight of the titanium dioxide particles is 1:10 to 1: 5, the ultraviolet durability is high. It is possible to achieve a good balance between moisture and heat resistance, which is more preferable. In addition, when the titanium-type compound which has normal photocatalytic reactivity is contained in a polyester film, the hydrolysis of a polyester film is accelerated | stimulated from the height of the catalytic activity, and durability in a humid heat environment falls. However, even when the polyester film of the present invention contains a titanium-based compound (titanium-based particles), it becomes possible to maintain high moisture and heat resistance.
また、本発明にて使用可能な紫外線吸収剤としては、例えばサリチル酸系化合物、ベンゾフェノン系化合物、ベンゾトリアゾール系化合物、シアノアクリレート系化合物、およびベンゾオキサジノン系化合物、環状イミノエステル系化合物などを好ましく例示することができるが、分散性の点からベンゾオキサジノン系化合物が最も好ましい。これらの化合物は１種単独であるいは２種以上一緒に併用することができる。またＨＡＬＳや酸化防止剤等の安定剤を併用することもでき、特にリン系の酸化防止剤を併用することが好ましい。 Further, preferable examples of the ultraviolet absorber usable in the present invention include salicylic acid compounds, benzophenone compounds, benzotriazole compounds, cyanoacrylate compounds, benzoxazinone compounds, and cyclic imino ester compounds. However, benzoxazinone compounds are most preferable from the viewpoint of dispersibility. These compounds can be used alone or in combination of two or more. In addition, stabilizers such as HALS and antioxidants can be used in combination, and it is particularly preferable to use a phosphorus-based antioxidant in combination.
本発明のポリエステルフィルムは二軸配向ポリエステルフィルムである。ここで言う二軸配向とは、広角Ｘ線回折で二軸配向のパターンを示すものをいう。二軸配向ポリエステルフィルムは、一般に、未延伸状態のポリエステルシートをシート長手方向および幅方向に延伸し、その後熱処理を施し、結晶配向を完了させることにより、得ることができる。 The polyester film of the present invention is a biaxially oriented polyester film. The term “biaxial orientation” as used herein refers to a pattern showing a biaxial orientation pattern by wide-angle X-ray diffraction. In general, a biaxially oriented polyester film can be obtained by stretching an unstretched polyester sheet in the sheet longitudinal direction and width direction, followed by heat treatment to complete crystal orientation.
本発明のポリエステルフィルムは、フィルムの平均超音波伝導速度が２．２０ｋｍ／秒以上である必要がある。また、フィルムの超音波伝導速度の最大値（ｋｍ／秒）と最小値（ｋｍ／秒）の比率（最大値／最小値）が１．００以上１．３０以下である事が好ましい。本発明においてフィルムの平均超音波伝導速度とは、後述の測定方法によって測定される超音波伝導速度を、ポリエステルフィルムの長手方向を基準（０゜）とし５°毎に０°〜１８０°まで測定し、得られた値の平均値のことをあらわす。また、本発明において、フィルムの超音波伝導速度の最大値と最小値の比率とは、上記のフィルムの平均超音波伝導速度の測定結果から算出される超音波伝導速度の最大値を最小値で除した値（最大値／最小値）をあらわす。フィルムの超音波伝導速度はポリエステルフィルムを構成しているポリエステル鎖の配向性と関連がある指標であり、超音波伝導速度が速いほど、その方向におけるポリエステル鎖の配向が強い事を示している。前述の通り、ポリエステルフィルムが湿熱雰囲気下に曝された場合、水分（水蒸気）は密度の低い非晶部の分子間を通って内部に進入し、非晶部を可塑化させ分子の運動性を高めるが、分子配向が強い場合は非晶部の運動性が制限されるため、湿熱環境下での耐久性を向上させることが可能となる。よって、フィルムの平均超音波伝導速度が２．２０ｋｍ／秒未満である場合は、耐湿熱性が悪化する傾向がある。平均超音波伝導速度は、好ましくは２．２５ｋｍ／秒以上、更に好ましくは２．３０ｋｍ／秒以上である。また、超音波伝導速度の最大値と最小値の比率が１．３０を越える場合は、方向による耐湿熱性能の差が大きくなりバランスが悪化し、特に最小値の方向において耐湿熱性が弱くなるため好ましくない。超音波伝導速度の最大値と最小値の比率は１．００以上１．２５以下が更に好ましい。 The polyester film of the present invention needs to have an average ultrasonic conduction velocity of 2.20 km / second or more. Moreover, it is preferable that the ratio (maximum value / minimum value) of the maximum value (km / second) and the minimum value (km / second) of the ultrasonic conduction velocity of the film is 1.00 or more and 1.30 or less. In the present invention, the average ultrasonic conduction velocity of the film is an ultrasonic conduction velocity measured by a measurement method described later, measured from 0 ° to 180 ° every 5 ° with the longitudinal direction of the polyester film as a reference (0 °). It represents the average value of the obtained values. In the present invention, the ratio of the maximum value and the minimum value of the ultrasonic conduction velocity of the film is the minimum value of the ultrasonic conduction velocity calculated from the measurement result of the average ultrasonic conduction velocity of the film. Indicates the divided value (maximum value / minimum value). The ultrasonic conduction velocity of the film is an index related to the orientation of the polyester chain constituting the polyester film, and the higher the ultrasonic conduction velocity, the stronger the orientation of the polyester chain in that direction. As described above, when the polyester film is exposed to a moist heat atmosphere, moisture (water vapor) enters the interior through the molecules of the amorphous part having a low density, plasticizing the amorphous part, and increasing the molecular mobility. However, when the molecular orientation is strong, the mobility of the amorphous part is limited, so that it is possible to improve the durability in a humid heat environment. Therefore, when the average ultrasonic conduction velocity of the film is less than 2.20 km / sec, the moisture and heat resistance tends to deteriorate. The average ultrasonic conduction velocity is preferably 2.25 km / second or more, more preferably 2.30 km / second or more. In addition, when the ratio between the maximum value and the minimum value of the ultrasonic conduction velocity exceeds 1.30, the difference in moisture and heat resistance performance depending on the direction becomes large and the balance deteriorates. In particular, the moisture and heat resistance becomes weak in the direction of the minimum value. It is not preferable. The ratio between the maximum value and the minimum value of the ultrasonic conduction velocity is more preferably 1.00 or more and 1.25 or less.
さらに、従来は、フィルムの幅方向中央部から離れた位置においてはボーイング現象にて面内の配向差が大きくなり耐湿熱性能のバラツキが悪化していた。しかし、例えば後述する製造方法（長手方向延伸方法、幅方向延伸方法、幅方向延工程と熱処理工程の間の中間工程）を適用する事で得られる本発明のフィルムは、フィルムの幅方向中央部から離れた位置（つまり、配向角のズレが１０°以上である位置）においても、面内の方向による耐湿熱性能の差を小さくする事が可能である。 Further, conventionally, in the position away from the central portion in the width direction of the film, the in-plane orientation difference is increased due to the bowing phenomenon, and the variation in the wet heat resistance performance is deteriorated. However, the film of the present invention obtained by applying, for example, a production method (longitudinal direction stretching method, width direction stretching method, intermediate step between the width direction stretching step and the heat treatment step) described below is the center in the width direction of the film. Even at a position away from the position (that is, a position where the deviation of the orientation angle is 10 ° or more), it is possible to reduce the difference in wet heat resistance performance depending on the in-plane direction.
また、二軸配向ポリエステルフィルムは一般に二つの配向軸を有するが、本明細書においては、配向が強い方の配向軸を長軸、配向が弱い方の配向軸を短軸と称する。また、本発明において、超音波伝導速度が最大値を示す方向とは、二軸配向ポリエステルフィルムの面内において配向が最も強い方向（長軸方向）を示す。 In addition, the biaxially oriented polyester film generally has two orientation axes, but in this specification, the orientation axis with the stronger orientation is called the major axis and the orientation axis with the weaker orientation is called the minor axis. In the present invention, the direction in which the ultrasonic conduction velocity has the maximum value indicates the direction (long axis direction) in which the orientation is strongest in the plane of the biaxially oriented polyester film.
また、本発明において、フィルムの超音波伝導速度が最大値を示す方向とフィルム長手方向とのなす角度（θ）とは、長軸方向とフィルムの長手方向のなす角度を示す。 In the present invention, the angle (θ) formed between the direction in which the ultrasonic conduction velocity of the film exhibits the maximum value and the film longitudinal direction indicates the angle formed between the major axis direction and the film longitudinal direction.
なお、製造後に幅方向にカットされていない二軸配向ポリエステルフィルムの中間製品における幅方向中央部においては、フィルムの配向軸は、通常、長手方向および幅方向の２方向となるが、長手方向および幅方向のどちらが長軸となり、どちらが短軸となるかは、フィルムの製造方法によって異なる。フィルムの長手方向の延伸倍率がフィルムの幅方向と比較して高い場合は、配向の長軸が長手方向となり、超音波伝導速度の最大値を示す方向もフィルムの長手方向になる。この場合の角度（θ）はフィルム幅方向中央部では０°となるが、（例えば、フィルム幅方向の中央部以外の部分において）長軸方向がフィルム長手方向に対して１０°ずれた場合、角度（θ）は１０°となる。一方、フィルムの幅方向の延伸倍率がフィルムの長手方向と比較して高い場合は、配向の長軸が幅方向となり、超音波伝導速度の最大値を示す方向もフィルムの幅方向となる。この場合の角度（θ）はフィルム幅方向中央部では９０°となるが、（例えば、フィルム幅方向の中央部以外の部分において）長軸方向がフィルム長手方向に対して１０°ずれた場合、角度（θ）は８０°となる。 In addition, in the center part in the width direction in the intermediate product of the biaxially oriented polyester film that is not cut in the width direction after production, the orientation axes of the film are usually two directions of the longitudinal direction and the width direction. Which in the width direction is the major axis and which is the minor axis depends on the film production method. When the draw ratio in the longitudinal direction of the film is higher than the width direction of the film, the major axis of orientation is the longitudinal direction, and the direction showing the maximum value of the ultrasonic conduction velocity is also the longitudinal direction of the film. In this case, the angle (θ) is 0 ° in the central portion in the film width direction, but when the major axis direction is deviated by 10 ° with respect to the film longitudinal direction (for example, in a portion other than the central portion in the film width direction) The angle (θ) is 10 °. On the other hand, when the draw ratio in the width direction of the film is higher than the longitudinal direction of the film, the major axis of orientation is the width direction, and the direction showing the maximum value of the ultrasonic conduction velocity is also the width direction of the film. In this case, the angle (θ) is 90 ° in the central portion in the film width direction, but when the major axis direction is deviated by 10 ° with respect to the film longitudinal direction (for example, in a portion other than the central portion in the film width direction) The angle (θ) is 80 °.
また、近年では生産性を向上させるために、広いフィルム幅を持つ二軸配向ポリエステルフィルムを一旦製造して中間製品（中間ロール）を得た後、その中間製品（中間ロール）をフィルムの幅方向にスリットして、数本から十数本のロール（最終製品）を得る方法が採用されることがある。中間製品の幅方向中央部では、上述したとおりフィルム長手方向に配向が高い場合の角度（θ）は０°であり、フィルム幅方向に配向が高い場合の角度（θ）は９０°であるが、ポリエステルフィルムの幅方向中央部から離れる（端部に近づく）に従い、一般的にはボーイング現象により配向角のズレが発生する。 In recent years, in order to improve productivity, a biaxially oriented polyester film having a wide film width is once manufactured to obtain an intermediate product (intermediate roll), and then the intermediate product (intermediate roll) is changed in the width direction of the film. In some cases, a method of obtaining several to a dozen or so rolls (final product) is used. At the center in the width direction of the intermediate product, as described above, the angle (θ) when the orientation is high in the film longitudinal direction is 0 °, and the angle (θ) when the orientation is high in the film width direction is 90 °. As the polyester film moves away from the central portion in the width direction (approaching the end portion), a misalignment of the orientation angle generally occurs due to the bowing phenomenon.
なお、フィルム長手方向に配向が高い場合は、角度（θ）が０°から大きくなり、フィルム幅方向に配向が高い場合は、角度（θ）が９０°から小さくなる。この様に配向角のズレが発生すると共に、長軸方向と短軸方向の配向差が大きくなると、一般的には、フィルム面内の方向による特性差も大きくなる傾向があった。しかし、本発明の二軸配向ポリエステルフィルムは、上記のように配向軸のズレが１０°以上、すなわち角度（θ）が１０°以上８０°以下、さらには配向軸のズレが２０°以上、すなわち角度（θ）が２０°以上６０°以下となる幅方向の端部位置においても、上述した様に面内の超音波伝導度の差が小さい、すなわち配向の差が小さい状態を保つ事で、フィルム面内の方向による耐湿熱性能の差を低減する事が可能となる。したがって、フィルムの角度（θ）が１０°以上８０°以下のときに、本発明の効果を最も顕著に認めることができる。なお、角度（θ）が４０°を越えて５０°未満であると片伸びが大きくなる傾向や斜め方向の収縮率の差が大きくなる傾向が見られる事がある。 When the orientation is high in the film longitudinal direction, the angle (θ) increases from 0 °, and when the orientation is high in the film width direction, the angle (θ) decreases from 90 °. As described above, when the orientation angle shift occurs and the orientation difference between the major axis direction and the minor axis direction increases, generally, the characteristic difference depending on the direction in the film plane also tends to increase. However, in the biaxially oriented polyester film of the present invention, as described above, the displacement of the orientation axis is 10 ° or more, that is, the angle (θ) is 10 ° or more and 80 ° or less, and further, the displacement of the orientation axis is 20 ° or more, Even at the end position in the width direction where the angle (θ) is 20 ° or more and 60 ° or less, as described above, the difference in the in-plane ultrasonic conductivity is small, that is, the orientation difference is kept small. It is possible to reduce the difference in wet heat resistance performance depending on the direction in the film plane. Therefore, when the film angle (θ) is 10 ° or more and 80 ° or less, the effect of the present invention can be recognized most remarkably. If the angle (θ) is more than 40 ° and less than 50 °, there may be a tendency that the half-elongation tends to increase or the difference in shrinkage rate in the oblique direction increases.
本発明のポリエステルフィルムを構成するポリエステル樹脂は、示差走査熱量測定（ＤＳＣ）により求められる微小吸熱ピーク温度（Ｔｍｅｔａ）が２２０℃以上である事が熱収縮率を低減する観点から好ましい。Ｔｍｅｔａは熱処理工程においてフィルムに付与した熱量に応じた値であり、高いほど熱処理が高温・長時間実施された事を示している。二軸配向フィルムの製造プロセスにおいて熱処理工程は、二軸配向されたフィルムに熱を与えることにより、フィルム中のポリエステル分子の結晶化度を高め、熱安定性等が付与されると同時にフィルム表面の接着性も向上する事がある。Ｔｍｅｔａは、好ましくは２３５℃以下であり、２３５℃を越える場合は熱処理時のフィルム破れにより安定した生産が出来ない場合があったり、分子配向が緩和しすぎて耐湿熱性能が低下する場合がある。Ｔｍｅｔａを上記範囲にするための方法は特には限定されないが、ポリエステルフィルムを２２５℃以上２４０℃以下の温度にて５秒以上処理する事が好ましい。このような高い熱処理温度で処理を実施した場合やＤＥＧ成分を多く含有する場合は一般的に分子配向の低下に伴い耐湿熱性が低下するが、後述する製造方法を適用することで、フィルムの配向を高くすることができ、平均超音波伝導速度および超音波伝導速度の最大値／最小値を上記の範囲に制御する事が可能となるため好ましい。 The polyester resin constituting the polyester film of the present invention preferably has a minute endothermic peak temperature (Tmeta) obtained by differential scanning calorimetry (DSC) of 220 ° C. or more from the viewpoint of reducing the heat shrinkage rate. Tmeta is a value corresponding to the amount of heat applied to the film in the heat treatment step, and the higher the value, the higher the temperature and the longer the heat treatment. In the production process of the biaxially oriented film, the heat treatment step applies heat to the biaxially oriented film, thereby increasing the crystallinity of the polyester molecules in the film and imparting thermal stability etc. at the same time. Adhesion may also be improved. Tmeta is preferably 235 ° C. or lower, and if it exceeds 235 ° C., stable production may not be possible due to film breakage during heat treatment, or the molecular orientation may be too relaxed and the heat-and-moisture resistance performance may be reduced. . The method for setting Tmeta in the above range is not particularly limited, but it is preferable to treat the polyester film at a temperature of 225 ° C. or higher and 240 ° C. or lower for 5 seconds or longer. When processing is carried out at such a high heat treatment temperature or when a large amount of DEG components are contained, the heat and humidity resistance generally decreases with a decrease in molecular orientation, but by applying the production method described later, the orientation of the film The average ultrasonic conduction velocity and the maximum / minimum value of the ultrasonic conduction velocity can be controlled within the above ranges, which is preferable.
本発明のポリエステルフィルムは、１５０℃にて３０分処理した時の長手方向熱収縮率が、２．０％以下であることが好ましく、０．８％以下であることがさらに好ましく、０．６％以下であると特に好ましい。長手方向熱収縮率が大きすぎる場合は貼り合わせ時にカールが生じたり、寸法差によるズレが生じたりする場合があり、できるだけ小さい方が好ましい。長手方向熱収縮率の下限値は特に規定されないが、０．０％以下とする事は実質的に困難である。また、１５０℃３０分における幅方向熱収縮率は加工時の幅縮み防止の観点から０．０％以上１．０％以下が好ましく、さらに好ましくは０．０％以上０．５％以下である。幅方向のみならず長手方向の熱収縮率は主に熱処理工程において２２５℃以上の高温で処理することと、引き続き熱処理工程〜冷却工程において、弛緩を行う事で上記の好ましい範囲である０．８％以下に調整する事が可能となるが、特に長手方向の収縮率を平面性を良好な状態に維持したまま低減するためには、フィルム両端を保持している走行方向に隣り合うクリップ間の間隙を縮める方法を実施することが好ましい。熱収縮率を適度な値に低減し、かつ平面性を維持するためには、温度１６０℃〜２００℃にて弛緩率１．０％〜２．０％の長手方向弛緩処理を実施することが好ましい。従来の技術では２２５℃以上の高温にて熱処理を実施した場合は、フィルムの配向が緩和し易く耐湿熱性が低下するため、熱寸法安定性と耐湿熱性を両立することが困難であったが、本発明に係る技術を用いる事で、これらを両立することが可能となった。 The polyester film of the present invention preferably has a longitudinal heat shrinkage of 2.0% or less, more preferably 0.8% or less, when treated at 150 ° C. for 30 minutes. % Or less is particularly preferable. When the longitudinal direction thermal contraction rate is too large, curling may occur at the time of bonding, or displacement due to a dimensional difference may occur, and the smaller one is preferable. The lower limit value of the longitudinal heat shrinkage rate is not particularly specified, but it is substantially difficult to make it 0.0% or less. Further, the heat shrinkage in the width direction at 150 ° C. for 30 minutes is preferably 0.0% or more and 1.0% or less, more preferably 0.0% or more and 0.5% or less from the viewpoint of preventing width shrinkage during processing. . The thermal shrinkage rate in the longitudinal direction as well as the width direction is the above-mentioned preferable range by treating at a high temperature of 225 ° C. or higher mainly in the heat treatment step, and subsequently relaxing in the heat treatment step to the cooling step. However, in order to reduce the contraction rate in the longitudinal direction while maintaining the flatness in a good state, the distance between the clips adjacent to each other in the running direction holding both ends of the film can be adjusted. It is preferable to implement a method for reducing the gap. In order to reduce the thermal shrinkage rate to an appropriate value and maintain the flatness, it is necessary to perform a longitudinal direction relaxation treatment with a relaxation rate of 1.0% to 2.0% at a temperature of 160 ° C. to 200 ° C. preferable. In the conventional technique, when heat treatment is performed at a high temperature of 225 ° C. or higher, the orientation of the film is easy to relax, and the heat and humidity resistance is lowered. Therefore, it has been difficult to achieve both thermal dimensional stability and moisture and heat resistance. By using the technique according to the present invention, it has become possible to achieve both.
本発明のポリエステルフィルムにおいて、フィルム幅方向中央部のみではなく特に角度（θ）が１０°以上８０°以下であるフィルム幅方向端部においても、フィルムの平均超音波伝導速度および超音波伝導速度の最大値／最小値を上記の範囲にするための方法としては、好ましくは以下に示す方法を適用することで達成することができる。 In the polyester film of the present invention, the average ultrasonic conduction velocity and the ultrasonic conduction velocity of the film are not only at the central portion in the film width direction but also at the end portion in the film width direction where the angle (θ) is 10 ° or more and 80 ° or less. As a method for setting the maximum value / minimum value in the above range, it can be achieved preferably by applying the following method.
本発明のポリエステルフィルムの製造方法として長手方向に延伸速度２,０００％／秒〜１０,０００％／秒にて３．０〜４．５倍延伸する工程を有することが好ましい。ポリエステル分子鎖を長手方向に効率良く配向するためには延伸倍率のみでなく、延伸速度を上記の範囲とする事が好ましい。長手方向の延伸速度が２，０００％／秒未満の場合や延伸倍率が３．０倍未満では配向が不十分となる事があり、１０,０００％／秒を越える場合や延伸倍率が４．５倍を越える場合では、フィルム製造時の破断が多くなる事がある。また、長手方向の延伸速度は、さらに好ましくは２,５００％／秒〜８,０００％／秒であり、特に好ましくは３，０００％／秒〜６,０００％／秒である。なお、ここで言う延伸速度とは、延伸倍率／延伸時間（秒）×１００で表される。例えばロールの周速差を用いた延伸の場合は、フィルムが延伸開始点のロールを離れる位置から延伸終了点のロールに着地する地点に到達するまでの時間を計測して延伸時間として、上記の式から算出する。長手方向延伸時におけるフィルム温度は、ポリエステル樹脂のガラス転移温度をＴｇとした場合Ｔｇ以上Ｔｇ＋４０℃以下が好ましく、さらに好ましくはＴｇ＋１０℃以上Ｔｇ＋３０℃以下である。上記の条件にて長手方向延伸を実施すれば、長手方向の分子配向が均一化し、さらに後述する幅方向延伸〜熱処理工程における、フィルムのボーイングの影響を低減する事が可能となる。 The method for producing the polyester film of the present invention preferably includes a step of stretching 3.0 to 4.5 times in the longitudinal direction at a stretching speed of 2,000% / second to 10,000% / second. In order to efficiently orient the polyester molecular chain in the longitudinal direction, it is preferable to set not only the draw ratio but also the draw speed in the above range. When the stretching speed in the longitudinal direction is less than 2,000% / second or when the stretching ratio is less than 3.0 times, the orientation may be insufficient. When the stretching speed exceeds 10,000% / second, the stretching ratio is 4. When it exceeds 5 times, the breakage during film production may increase. The stretching speed in the longitudinal direction is more preferably 2500% / second to 8,000% / second, and particularly preferably 3,000% / second to 6,000% / second. The stretching speed referred to here is expressed by stretching ratio / stretching time (seconds) × 100. For example, in the case of stretching using the peripheral speed difference of the roll, the time until the film reaches the point where it reaches the roll at the stretching end point from the position where it leaves the roll at the stretching start point is measured as the stretching time. Calculate from the formula. The film temperature during stretching in the longitudinal direction is preferably Tg or more and Tg + 40 ° C. or less, more preferably Tg + 10 ° C. or more and Tg + 30 ° C. or less when the glass transition temperature of the polyester resin is Tg. If the longitudinal stretching is carried out under the above conditions, the molecular orientation in the longitudinal direction becomes uniform, and the influence of film bowing in the width direction stretching to the heat treatment step described later can be reduced.
本発明のポリエステルフィルムの製造方法として、幅方向に３．５〜４．５倍延伸し、かつ幅方向延伸工程の中間点での延伸量が幅方向延伸工程終了時の延伸量の６０〜８０％とする工程を有する事が好ましい。ここで言う延伸量の６０〜８０％とは、幅方向延伸工程開始前のフィルム幅をＷ０、幅方向延伸工程の中間点でのフィルム幅をＷ１、幅方向延伸工程終了時でのフィルム幅をＷ２とした場合、以下の式（Ａ）を満たす事である。
６０ ≦ １００×（Ｗ１−Ｗ０）／（Ｗ２−Ｗ０）≦ ８０ ・・・ 式（Ａ）。As a method for producing the polyester film of the present invention, the stretch amount is 3.5 to 4.5 times in the width direction, and the stretch amount at the midpoint of the width direction stretch step is 60 to 80 of the stretch amount at the end of the width direction stretch step. % Is preferable. Here, 60 to 80% of the stretching amount means W0 as the film width before the start of the width direction stretching step, W1 as the film width at the midpoint of the width direction stretching step, and the film width at the end of the width direction stretching step. In the case of W2, the following expression (A) is satisfied.
60 <= 100 * (W1-W0) / (W2-W0) <= 80 ... Formula (A).
さらに、幅方向延伸工程と熱処理工程の間に中間工程を有し、該中間工程の雰囲気温度が幅方向延伸工程の最終区間の雰囲気温度：Ｔｓ（℃）と熱処理工程最初の区間にあたる第１の熱処理工程雰囲気温度：Ｔｈ（℃）の間の温度であり、かつ中間工程をフィルムが通過する時間をＳｍ（秒）とした時に以下式（Ｂ）を満たす事が好ましい。なお、中間工程の雰囲気温度は、温度制御のしやすさから、ＴｈとＴｓの中間に近い温度である事が好ましく、（（Ｔｓ＋Ｔｈ）／２）−２０（℃）以上、（（Ｔｓ＋Ｔｈ）／２）＋２０（℃）以下である事が更に好ましい。また、中間工程においては、延伸工程および熱処理工程においてフィルムに吹き付けられる熱風の一部が流れ込み温度が不安定となる事があるため、排気処理を実施する事が温度をより安定に保つことが出来るため好ましい。
（Ｔｈ−Ｔｓ）／Ｓｍ ≦ ５０ ・・・ 式（Ｂ）。Further, there is an intermediate step between the width direction stretching step and the heat treatment step, and the atmosphere temperature of the intermediate step is the first temperature corresponding to the atmospheric temperature: Ts (° C.) in the final section of the width direction stretching step and the first section of the heat treatment step. It is preferable that the following formula (B) is satisfied when the atmosphere temperature of the heat treatment process: Th (° C.) and the time during which the film passes through the intermediate process is Sm (seconds). The atmosphere temperature in the intermediate process is preferably a temperature close to the middle of Th and Ts from the viewpoint of ease of temperature control, ((Ts + Th) / 2) −20 (° C.) or more, ((Ts + Th) / 2) It is still more preferable that it is +20 (degreeC) or less. Also, in the intermediate process, part of hot air blown to the film in the stretching process and heat treatment process may flow in and the temperature may become unstable, so the exhaust process can keep the temperature more stable. Therefore, it is preferable.
(Th-Ts) / Sm <= 50 ... Formula (B).
なお、ここでいう熱処理工程とは、フィルムに加熱された熱風を吹き付ける手段やラジエーションヒーター等の加熱手段を用いてフィルムを加熱することで結晶化を進める工程のことをさす。熱処理工程においては、ポリエステル樹脂の融点をＴｍ（℃）とすると、Ｔｍ−８０（℃）以上Ｔｍ（℃）以下の温度にてフィルムを加熱処理する事が好ましい。 In addition, the heat treatment process here refers to the process which advances crystallization by heating a film using heating means, such as a means to blow the hot air heated to the film, and a radiation heater. In the heat treatment step, when the melting point of the polyester resin is Tm (° C.), the film is preferably heat-treated at a temperature of Tm-80 (° C.) or more and Tm (° C.) or less.
また、本発明における中間工程とは、幅方向延伸工程と熱処理工程の中間に位置し、フィルムを加熱する手段を有さず、長手方向・幅方向共にフィルムの寸法を変えない状態で幅方向両端を保持しながら搬送する工程をさす。中間工程では温度変動を抑制するために、周囲が断熱壁などで囲われていることが好ましい。また中間工程における雰囲気温度はＴｈとＴｓの間の温度である事が好ましく、（（Ｔｓ＋Ｔｈ）／２）−２０（℃）以上、（（Ｔｓ＋Ｔｈ）／２）＋２０（℃）以下が更に好ましい。 The intermediate step in the present invention is located in the middle of the width direction stretching step and the heat treatment step, does not have a means for heating the film, and both ends in the width direction without changing the dimension of the film in the longitudinal direction and the width direction. This refers to the process of conveying while holding. In order to suppress temperature fluctuation in the intermediate process, it is preferable that the periphery is surrounded by a heat insulating wall or the like. The atmospheric temperature in the intermediate step is preferably a temperature between Th and Ts, more preferably ((Ts + Th) / 2) −20 (° C.) or more and ((Ts + Th) / 2) +20 (° C.) or less.
二軸延伸フィルムの製造において、フィルムの幅方向延伸〜熱処理工程にて、幅方向延伸時の延伸張力により、フィルムが保持されていない幅方向中央部分において、熱処理工程側のフィルムが幅方向延伸側へと引き込まれるため、幅方向の端部に行くに従い配向角が斜め方向にずれるボーイング現象が発生する。この現象によりフィルム面内でのポリエステル分子配向の方向による差が幅方向端部ほど大きくなる。前述の通り分子配向のムラは、フィルムの湿熱環境下の耐久性に影響を与えるため好ましくない。上記の幅方向延伸工程および中間工程を有する事で、幅方向延伸時の延伸張力が熱処理工程に伝搬しにくくなり、フィルム配向軸の歪みを抑制することが可能となる。幅方向の延伸倍率が３．５倍未満である場合や、幅方向延伸工程の中間点での延伸量が幅方向延伸工程終了時の延伸量の６０％未満である場合、あるいは（Ｔｈ−Ｔｓ）／Ｓｍの値が５０を越える場合は、フィルム配向軸の歪み改善効果が不十分となり、幅方向端部のフィルムの超音波伝導速度の最大値と最小値の比率が１．３０を越える場合がある。幅方向の延伸倍率が４．５倍を越える場合や、幅方向延伸工程の中間点での延伸量が幅方向延伸工程終了時の延伸量の８０％を越える場合は、延伸時のフィルム破断が発生しやすく生産性が劣る事がある。さらに、（Ｔｈ−Ｔｓ）／Ｓｍの値については４０未満が好ましく、３０未満である事が特に好ましい。また、幅方向延伸工程の温度については、Ｔｇ以上Ｔｇ＋４０℃以下が好ましく、さらに好ましくはＴｇ＋１０℃以上Ｔｇ＋３０℃以下である。熱処理工程については、ポリエステル樹脂の融点をＴｍとした場合、Ｔｍ−８０℃以上Ｔｍ−２０℃以下が好ましく、更にはＴｍ−６０℃以上Ｔｍ−３０℃以下が好ましい。なお、熱処理工程は複数工程に分け、最初の区間にあたる第１工程での温度Ｔｈを下げ、段階的に温度を上げていく方法がボーイングの影響を低減しながら、適切な熱処理温度での処理が実施できるため、特に好ましい。 In the production of a biaxially stretched film, the film on the heat treatment process side is in the width direction stretch side in the width direction center part where the film is not held by the stretching tension at the time of width direction stretching in the film width direction stretching to the heat treatment process. Therefore, a bowing phenomenon occurs in which the orientation angle shifts in an oblique direction as it goes to the end in the width direction. Due to this phenomenon, the difference in the direction of the polyester molecular orientation in the film plane increases toward the end in the width direction. As described above, unevenness in molecular orientation is not preferable because it affects the durability of the film in a moist heat environment. By having the width direction stretching step and the intermediate step, the stretching tension at the time of width direction stretching becomes difficult to propagate to the heat treatment step, and distortion of the film orientation axis can be suppressed. When the stretching ratio in the width direction is less than 3.5 times, when the stretching amount at the midpoint of the width direction stretching step is less than 60% of the stretching amount at the end of the width direction stretching step, or (Th-Ts ) / Sm value exceeding 50, the effect of improving the distortion of the film orientation axis is insufficient, and the ratio of the maximum value and the minimum value of the ultrasonic conduction velocity of the film at the end in the width direction exceeds 1.30. There is. When the stretching ratio in the width direction exceeds 4.5 times, or when the stretching amount at the midpoint of the stretching direction in the width direction exceeds 80% of the stretching amount at the end of the stretching process in the width direction, the film breaks during stretching. It is likely to occur and productivity may be inferior. Furthermore, the value of (Th−Ts) / Sm is preferably less than 40, and particularly preferably less than 30. Moreover, about the temperature of the width direction extending | stretching process, Tg or more and Tg + 40 degrees C or less are preferable, More preferably, they are Tg + 10 degreeC or more and Tg + 30 degrees C or less. Regarding the heat treatment step, when the melting point of the polyester resin is Tm, Tm-80 ° C or higher and Tm-20 ° C or lower is preferable, and Tm-60 ° C or higher and Tm-30 ° C or lower is more preferable. In addition, the heat treatment process is divided into a plurality of processes, and the method of lowering the temperature Th in the first process corresponding to the first section and increasing the temperature step by step reduces the influence of bowing, while allowing the treatment at an appropriate heat treatment temperature. This is particularly preferable because it can be carried out.
フィルムの製造コストを低減するためには、例えばフィルム幅が２ｍを越えるような広幅にて二軸配向ポリエステルフィルムを製造することが必要となってくるが、フィルム幅が広くなる程、幅方向端部位置での配向軸が傾くため、このような広幅のフィルムを製造する場合に、上記の製造方法を用いる事は特に好ましい。なお、上記のような延伸速度が速い条件を適用した場合は、一般的にフィルムへの延伸時の負荷が大きくなり、特に耐久性維持のため固有粘度が高いポリエステル樹脂を使用した場合には、フィルム破断が多くなる問題がある。しかしながら、本発明のポリエステルフィルムにおいては、上述の様にフィルム中のジエチレングリコール（ＤＥＧ）量を適切な量に調整する等の手段を併用することで、生産性を悪化させることなく製造することが可能となる。 In order to reduce the production cost of the film, for example, it is necessary to produce a biaxially oriented polyester film with a wide width such that the film width exceeds 2 m. Since the orientation axis at the part position is inclined, it is particularly preferable to use the above production method when producing such a wide film. In addition, when applying conditions such as the above stretching speed is high, generally the load during stretching to the film is large, especially when using a polyester resin having a high intrinsic viscosity for maintaining durability, There is a problem that film breakage increases. However, the polyester film of the present invention can be produced without deteriorating productivity by using a means such as adjusting the amount of diethylene glycol (DEG) in the film to an appropriate amount as described above. It becomes.
したがって、ポリエステル樹脂を含有するポリエステルフィルムの製造方法であって、フィルムを構成するポリエステル樹脂の固有粘度（ＩＶ）が０．６５〜０．８０、末端カルボキシル基量が２０当量／ｔ以下、ジエチレングリコール含有量が０．９質量％以上３．０質量％以下であり、かつフィルムの平均超音波伝導速度が２．２０ｋｍ／秒以上である二軸配向ポリエステルフィルムの製造方法として、以下の製造方法が特に好ましい。 Accordingly, a method for producing a polyester film containing a polyester resin, wherein the polyester resin constituting the film has an intrinsic viscosity (IV) of 0.65 to 0.80, a terminal carboxyl group content of 20 equivalent / t or less, and diethylene glycol containing As a method for producing a biaxially oriented polyester film having an amount of 0.9 mass% or more and 3.0 mass% or less and an average ultrasonic conduction velocity of the film of 2.20 km / second or more, the following production method is particularly preferred. preferable.
すなわち、リン酸アルカリ金属塩を０．１モル／ｔ以上５．０モル／ｔ以下含有するポリエステル樹脂（原料）を溶融し、シート状に成型する工程と、以下（１）〜（３）に記載の長手方向・幅方向の延伸工程および熱処理工程を有する製造方法が特に好ましい。
（１）長手方向に延伸速度２,０００％／秒〜１０,０００％／秒にて３．０〜４．５倍延伸する工程
（２）幅方向に３．５〜４．５倍延伸し、かつ幅方向延伸工程開始前のフィルム幅をＷ０、幅方向延伸工程の中間点でのフィルム幅をＷ１、幅方向延伸工程終了後でのフィルム幅をＷ２とした場合、以下の式（Ａ）を満たす工程
６０ ≦ １００×（Ｗ１−Ｗ０）／（Ｗ２−Ｗ０）≦ ８０ ・・・ 式（Ａ）
（３）幅方向延伸工程と熱処理工程の間に中間工程を有し、該中間工程の温度が幅方向延伸工程の最終区間の温度：Ｔｓ（℃）と熱処理工程最初の区間にあたる第１の熱処理工程温度：Ｔｈ（℃）との間の温度であり、かつ中間工程をフィルムが通過する時間をＳｍ（秒）とした時に以下式（Ｂ）を満たす工程
（Ｔｈ−Ｔｓ）／Ｓｍ ≦ ５０ ・・・ 式（Ｂ）。That is, a step of melting a polyester resin (raw material) containing an alkali metal phosphate from 0.1 mol / t to 5.0 mol / t and molding it into a sheet, and (1) to (3) below A production method having the drawing step and the heat treatment step in the longitudinal direction and the width direction as described is particularly preferable.
(1) Step of stretching 3.0 to 4.5 times in the longitudinal direction at a stretching speed of 2,000% / second to 10,000% / second (2) Stretching to 3.5 to 4.5 times in the width direction When the film width before starting the width direction stretching step is W0, the film width at the midpoint of the width direction stretching step is W1, and the film width after the end of the width direction stretching step is W2, the following formula (A) The process which satisfy | fills 60 <= 100 * (W1-W0) / (W2-W0) <= 80 ... Formula (A)
(3) There is an intermediate step between the width direction stretching step and the heat treatment step, and the temperature of the intermediate step is the temperature of the last section of the width direction stretching step: Ts (° C.) and the first heat treatment corresponding to the first section of the heat treatment step Process temperature: a temperature between Th (° C.) and satisfying the following formula (B) when the time for the film to pass through the intermediate process is Sm (seconds) (Th−Ts) / Sm ≦ 50 -Formula (B).
さらに、リン酸アルカリ金属塩を０．１モル／ｔ以上５．０モル／ｔ以下含有するポリエステル樹脂（原料）が以下（４）〜（６）を満たす工程で製造されることが好ましい。
（４）前記ポリエステル樹脂を合成する重合工程において、リン酸アルカリ金属塩を添加する事。
（５）リン酸アルカリ金属塩をジオール成分に溶解または混合し、リン酸アルカリ金属塩の濃度が１質量％以下の溶液またはスラリー状態として添加する事。
（６）前記リン酸アルカリ金属塩を添加する時の反応物の温度が２５０℃以下である事。Furthermore, it is preferable that the polyester resin (raw material) containing 0.1 mol / t or more and 5.0 mol / t or less of the alkali metal phosphate is manufactured in a process that satisfies the following (4) to (6).
(4) In the polymerization step for synthesizing the polyester resin, an alkali metal phosphate is added.
(5) An alkali metal phosphate is dissolved or mixed in a diol component and added as a solution or slurry in which the concentration of the alkali metal phosphate is 1% by mass or less.
(6) The temperature of the reaction product when adding the alkali metal phosphate is 250 ° C. or less.
本発明のポリエステルフィルムは、温度１２５℃、湿度１００％ＲＨ下に７２時間保持したときの伸度保持率が５０％以上であることが好ましい。本発明において伸度保持率が５０％以上であるとは、上記超音波伝導速度が最大となる方向および最小となる方向の２つの方向において、どちらも伸度保持率が５０％以上であることを表す。フィルム使用時にはフィルムのあらゆる方向に力が加わる場合が多く、特定の方向に対する耐湿熱性が悪い場合、その方向からフィルムの割れや破れが発生しやすくなる。そのため、超音波伝導速度が最小となるポリエステル分子鎖配向が低い方向、すなわち耐湿熱性に最も不利な方向に対しても上記の伸度保持率を有するフィルムは、高い耐久性を有するため好ましい。さらに好ましくは６０％以上、特に好ましくは７０％以上である。伸度保持率が５０％未満である場合は、使用時にフィルムが劣化し割れたり、破断したりするトラブルが発生する場合がある。 The polyester film of the present invention preferably has an elongation retention of 50% or more when held at a temperature of 125 ° C. and a humidity of 100% RH for 72 hours. In the present invention, the elongation retention rate of 50% or more means that the elongation retention rate is 50% or more in both the directions in which the ultrasonic conduction velocity is maximum and the minimum direction. Represents. When a film is used, a force is often applied in all directions of the film. When the heat and humidity resistance in a specific direction is poor, the film is likely to crack or break from that direction. Therefore, a film having the above-described elongation retention rate in a direction in which the polyester molecular chain orientation is low, that is, the ultrasonic conduction speed is minimum, that is, the direction most disadvantageous in wet heat resistance is preferable because it has high durability. More preferably, it is 60% or more, and particularly preferably 70% or more. When the elongation retention is less than 50%, there may be a problem that the film deteriorates and breaks or breaks during use.
本発明のポリエステルフィルムの厚みは１０μｍ以上５００μｍ以下が好ましく、２０μｍ以上３００μｍ以下がより好ましい。更に好ましくは、２５μｍ以上２００μｍ以下である。厚みが１０μｍ未満の場合、フィルムの耐湿熱性が低下しすぎる場合がある。一方、５００μｍより厚い場合は、フィルム延伸工程で破れやすくなる等、耐湿熱性と生産性の両立が難しくなる傾向がある。 The thickness of the polyester film of the present invention is preferably 10 μm or more and 500 μm or less, and more preferably 20 μm or more and 300 μm or less. More preferably, they are 25 micrometers or more and 200 micrometers or less. When thickness is less than 10 micrometers, the heat-and-moisture resistance of a film may fall too much. On the other hand, when it is thicker than 500 μm, it tends to be difficult to achieve both heat resistance and productivity, such as being easily broken in the film stretching process.
次に、本発明のポリエステルフィルムの製造方法について、その一例を説明するが、本発明は、かかる例によって得られる物のみに限定して解釈されるものではない。 Next, although an example is demonstrated about the manufacturing method of the polyester film of this invention, this invention is limited to only the thing obtained by this example, and is not interpreted.
まず、ポリエステル樹脂の製造方法（重合工程）の一例としては、エステル化反応またはエステル交換反応を行う第一の工程、リン酸アルカリ金属塩などの添加物を添加する第二の工程、重合反応を行う第三の工程を含む製造方法が挙げられ、必要に応じて固相重合反応を行う第四の工程をさらに追加しても良い。 First, as an example of a polyester resin production method (polymerization step), a first step of performing an esterification reaction or a transesterification reaction, a second step of adding an additive such as an alkali metal phosphate, a polymerization reaction The manufacturing method including the 3rd process to perform is mentioned, You may add further the 4th process of performing a solid-phase polymerization reaction as needed.
第一の工程において、ジカルボン酸成分としてテレフタル酸ジメチル、ジオール構成成分としてエチレングリコールとジエチンレングリコールの混合物をジオール成分のモル比がジカルボン酸成分のモル比の１．１〜１．３倍となるように混合した後に、温度２２０〜２７０℃にて三酸化アンチモンなどの公知の重合触媒およびマンガン系の金属触媒を添加し、さらにエチレングリコールとジエチンレングリコールの混合物を最終的なジオール成分とジカルボン酸成分のモル比１：１．５〜１：２．０の範囲となるように追添しながらエステル交換反応を行う。 In the first step, dimethyl terephthalate as the dicarboxylic acid component, a mixture of ethylene glycol and diethylene glycol as the diol constituent component, the molar ratio of the diol component is 1.1 to 1.3 times the molar ratio of the dicarboxylic acid component Then, a known polymerization catalyst such as antimony trioxide and a manganese-based metal catalyst are added at a temperature of 220 to 270 ° C., and a mixture of ethylene glycol and diethylene glycol is added as a final diol component. The ester exchange reaction is carried out while adding so that the molar ratio of the dicarboxylic acid component is in the range of 1: 1.5 to 1: 2.0.
第二の工程は、エステル交換反応が実質的に終了した後から、固有粘度が０．３に達するまでの間にリン酸アルカリ金属塩などの添加物を添加する工程である。リン酸アルカリ金属塩はリン酸とアルカリ金属元素量とリン元素量の比が０．３〜０．７の範囲となるような比率で混合し、さらにエチレングリコールにて濃度１質量％以下に希釈して添加される。なお、このときの混合希釈液のｐＨを４．０以上６．０以下の酸性に調整することが異物生成抑制の点からさらに好ましい。さらに、上記リン酸アルカリ金属塩は、添加時のポリエステルの温度が２４０℃以下であり、添加時間を２０分以上となるように徐々に添加していく事が異物生成抑制の点で好ましい。また、重合により得られるポリエステルのカルボキシル基末端数を低減する手法として、微量の水酸化カリウムなどのアルカリ化合物を添加しても良い。 The second step is a step of adding an additive such as an alkali metal phosphate after the transesterification reaction is substantially completed until the intrinsic viscosity reaches 0.3. The alkali metal phosphate is mixed in such a ratio that the ratio of phosphoric acid, the amount of alkali metal element and the amount of phosphorus element is in the range of 0.3 to 0.7, and further diluted with ethylene glycol to a concentration of 1% by mass or less. Added. It is more preferable to adjust the pH of the mixed dilution at this time to an acidity of 4.0 or more and 6.0 or less from the viewpoint of suppressing the generation of foreign matter. Further, the alkali metal phosphate is preferably added in such a manner that the temperature of the polyester at the time of addition is 240 ° C. or less and the addition time is 20 minutes or more, from the viewpoint of suppressing foreign matter formation. Moreover, you may add a trace amount alkali compounds, such as potassium hydroxide, as a method of reducing the carboxyl group terminal number of polyester obtained by superposition | polymerization.
第三の工程においては、公知の方法で重合反応を行うことができる。重縮合により得られるポリエステルの末端カルボキシル基量を２０当量／ｔ以下の範囲でより低減させ、かつポリエステルの固有粘度を高めるためには、上記重合を行った後、第四工程として、１９０℃以上ポリエステルの融点未満の温度で、減圧または窒素ガスのような不活性気体の流通下で加熱する、いわゆる固相重合を行うことが好ましい。この場合、第三工程で固有粘度を０．５以上０．６以下の範囲ポリエステルを重合した後、第四工程として１９０℃以上ポリエステルの融点未満の温度で、減圧または窒素ガスのような不活性気体の流通下で加熱することによって固相重合することが好ましい。第三工程で得られるポリエステルの固有粘度が０．５未満であると、チップが割れやすく、形態が不均一になる結果、第四工程において固相重合して得られるポリエステルの重合度にムラが生じる場合がある。また第三工程で得られるポリエステルの固有粘度が０．６より大きいと、第三工程における熱劣化が激しくなり、その結果、得られるポリエステルの末端カルボキシル基量が増大して、フィルム化した際に耐加水分解性が低下することがあるため好ましくない。第三工程で得られるポリエステルの固有粘度を０．５以上０．６以下とすることで、固相重合した際に、カルボキシル基末端数を低く維持した状態で、均一な固有粘度を有するポリエステルを得ることが出来る。その結果、フィルム化した際に耐加水分解性をより高めることが可能となる。 In the third step, the polymerization reaction can be performed by a known method. In order to further reduce the amount of terminal carboxyl groups of the polyester obtained by polycondensation in the range of 20 equivalent / t or less and to increase the intrinsic viscosity of the polyester, after the above polymerization, as the fourth step, 190 ° C. or higher It is preferable to perform so-called solid-state polymerization, in which heating is performed under reduced pressure or a flow of an inert gas such as nitrogen gas at a temperature lower than the melting point of the polyester. In this case, after polymerizing the polyester having an intrinsic viscosity of 0.5 or more and 0.6 or less in the third step, the fourth step is performed at a temperature of 190 ° C. or more and lower than the melting point of the polyester, under reduced pressure or inert like nitrogen gas Solid-phase polymerization is preferably performed by heating in a gas flow. If the intrinsic viscosity of the polyester obtained in the third step is less than 0.5, the chip is easily cracked and the shape becomes non-uniform, resulting in unevenness in the degree of polymerization of the polyester obtained by solid phase polymerization in the fourth step. May occur. Moreover, when the intrinsic viscosity of the polyester obtained in the third step is larger than 0.6, the thermal deterioration in the third step becomes severe, and as a result, the amount of terminal carboxyl groups of the obtained polyester is increased and formed into a film. Since hydrolysis resistance may fall, it is not preferable. By setting the intrinsic viscosity of the polyester obtained in the third step to 0.5 or more and 0.6 or less, a polyester having a uniform intrinsic viscosity is maintained in a state where the number of carboxyl group terminals is kept low when solid-phase polymerization is performed. Can be obtained. As a result, it is possible to further improve the hydrolysis resistance when the film is formed.
次に得られたポリエステル樹脂を用いてポリエステルフィルムを製造する方法について例示する。 Next, it illustrates about the method of manufacturing a polyester film using the obtained polyester resin.
上記の方法にて得られたポリエステル樹脂を真空下加熱し内在する水分量が５０ｐｐｍ以下となるように乾燥する。乾燥は、真空度３ｋＰａ以下、温度１６０℃以上で３時間以上乾燥させることが好ましい。次いで乾燥したポリエステル樹脂を押出機で２６０〜３００℃で溶融し、フィルタにて異物を濾過した後にＴ字型口金よりシート状に押し出し、静電印加キャスト法を用いて表面温度１０〜６０℃の鏡面キャスティングドラムに巻き付けて、冷却固化せしめて未延伸フィルムを得る。この工程でのポリエステル樹脂の加水分解を抑制し、固有粘度（ＩＶ）の低下や末端カルボキシル基量の増加を防止するために、押出機に供給されるポリエステル樹脂の水分率をできる限り少なくする事が好ましい。また、押出機から樹脂が押し出されてから、キャスティングドラムに着地するまでの時間は短い程良く、目安としては１０分以下、より好ましくは５分以下、特には３分以下とすることが好ましい。 The polyester resin obtained by the above method is heated under vacuum and dried so that the inherent moisture content is 50 ppm or less. Drying is preferably performed at a vacuum degree of 3 kPa or less and a temperature of 160 ° C. or more for 3 hours or more. Next, the dried polyester resin is melted at 260 to 300 ° C. with an extruder, foreign matter is filtered with a filter, and then extruded into a sheet form from a T-shaped die. The surface temperature is 10 to 60 ° C. using an electrostatic application casting method. It is wound around a mirror casting drum and cooled and solidified to obtain an unstretched film. In order to suppress hydrolysis of the polyester resin in this step and prevent a decrease in intrinsic viscosity (IV) and an increase in the amount of terminal carboxyl groups, the moisture content of the polyester resin supplied to the extruder should be reduced as much as possible. Is preferred. Further, it is preferable that the time from the extrusion of the resin from the extruder to the landing on the casting drum is as short as possible. As a guideline, it is preferably 10 minutes or less, more preferably 5 minutes or less, and particularly preferably 3 minutes or less.
この未延伸フィルムを７０〜１００℃に加熱されたロールにて予熱した後に、ラジエーションヒーター等を用いて温度９０〜１２０℃に加熱しながら長手方向に延伸速度２，０００〜１０，０００％／秒にて３．０〜４．５倍延伸して一軸配向フィルムを得る。さらに、フィルムの両端をクリップにて固定しながらオーブンへ導き７０〜１５０℃の温度で加熱を行い、引き続き連続的に７０〜１５０℃の加熱ゾーンで幅方向に３．５〜４．５倍延伸し、続いて１８０〜２４０℃の加熱ゾーンで５〜４０秒間熱処理を施し、１００〜２００℃の冷却ゾーンを経て結晶配向の完了した二軸配向ポリエステルフィルムを得る。なお、上記熱処理中に必要に応じて３〜１２％の弛緩処理を施してもよい。なお、幅方向の延伸工程においては、幅方向延伸工程の中間点での延伸量が幅方向延伸工程終了時の延伸量の６０〜８０％とする事、および幅方向延伸工程と熱処理工程の間に、フィルムを加熱する手段を有さず、長手方向・幅方向共にフィルムの寸法を変えない状態で幅方向両端を保持しながら搬送する中間工程を有し、中間工程通過時間（秒）あたりの温度変化量（℃）が５０℃／秒以下とすることが、ボーイングによる配向軸の歪みを抑制でき好ましい。 This unstretched film is preheated with a roll heated to 70 to 100 ° C. and then stretched at a stretching speed of 2,000 to 10,000% / second in the longitudinal direction while being heated to a temperature of 90 to 120 ° C. using a radiation heater or the like. To obtain a uniaxially oriented film. Further, the film is guided to an oven while being fixed with clips at both ends and heated at a temperature of 70 to 150 ° C, and continuously stretched 3.5 to 4.5 times in the width direction in a heating zone of 70 to 150 ° C. Subsequently, heat treatment is performed in a heating zone at 180 to 240 ° C. for 5 to 40 seconds, and a biaxially oriented polyester film in which crystal orientation is completed is obtained through a cooling zone at 100 to 200 ° C. In addition, you may perform a 3-12% relaxation process as needed during the said heat processing. In the stretching process in the width direction, the stretching amount at the midpoint of the stretching process in the width direction is 60 to 80% of the stretching amount at the end of the stretching process in the width direction, and between the stretching process in the width direction and the heat treatment process. In addition, there is no means for heating the film, and there is an intermediate process that conveys the film while holding both ends in the width direction without changing the dimension of the film in both the longitudinal direction and the width direction. It is preferable that the temperature change amount (° C.) is 50 ° C./second or less because distortion of the alignment axis due to bowing can be suppressed.
なお、二軸延伸は同時二軸延伸を用いる事も可能である。また長手方向、幅方向延伸後、熱処理工程前に、長手方向・幅方向の両方向、あるいはいずれか片方の方向に再延伸してもよい。得られた二軸配向ポリエステルフィルムの端部をカットした後に巻き取り中間製品とし、その後スリッターを用いて所望の幅にカット後、円筒状のコアに巻き付け所望の長さのポリエステルフィルムロールを得ることができる。なお、巻き取り時に巻姿改善のためにフィルム両端部にエンボス処理を施しても良い。 In addition, simultaneous biaxial stretching can also be used for biaxial stretching. Moreover, after extending | stretching a longitudinal direction and the width direction, you may re-extend to both the direction of a longitudinal direction and the width direction, or any one direction before a heat treatment process. After cutting the end of the obtained biaxially oriented polyester film, it is made into a winding intermediate product, then cut into a desired width using a slitter, and then wound around a cylindrical core to obtain a polyester film roll having a desired length. Can do. In addition, you may give an embossing process to both ends of a film for winding-up improvement at the time of winding.
このようにして得られた本発明のポリエステルフィルムは、高い耐湿熱性を有するため、特に太陽電池封止用フィルムとして好適である。つまり、本発明の太陽電池封止用フィルムとは、本発明の二軸配向ポリエステルを用いた太陽電池封止用フィルムである。また、本発明のポリエステルフィルムを封止フィルムとして使用する事で、従来の太陽電池と比べて高耐久としたり、厚みを薄くすることが可能なる。したがって、本発明の太陽電池とは、本発明の二太陽電池封止用フィルムを用いた太陽電池である。 The polyester film of the present invention thus obtained is particularly suitable as a film for encapsulating solar cells because it has high heat and humidity resistance. That is, the solar cell sealing film of the present invention is a solar cell sealing film using the biaxially oriented polyester of the present invention. In addition, by using the polyester film of the present invention as a sealing film, it is possible to make it more durable and reduce the thickness compared to conventional solar cells. Therefore, the solar cell of the present invention is a solar cell using the film for sealing two solar cells of the present invention.
［物性の測定法］
以下、実施例により本発明の構成、効果をさらに具体的に説明する。なお、本発明は下記実施例に限定されるものではない。各実施例の記述に先立ち、各種物性の測定方法を記載する。[Measurement method of physical properties]
Hereinafter, the configuration and effects of the present invention will be described more specifically with reference to examples. In addition, this invention is not limited to the following Example. Prior to describing each example, a method for measuring various physical properties will be described.
（１）ジエチレングリコール（ＤＥＧ）含有量
測定試料（ポリエステル樹脂（原料）またはポリエステルフィルム）１．０ｇをモノエタノールアミン２．５ｍＬを溶媒として２６０℃で加水分解した。次いでメタノール１０ｍＬを加えて冷却し、テレフタル酸にて中和後、遠心分離した後に上澄みをガスクロマトグラフィー（（株）島津製作所製 ＧＣ−１４Ａ）にてジエチレングリコール（ＤＥＧ）含有量を測定した。なお、無機粒子などの添加成分は不溶物として遠心分離時に沈降するため、沈降成分について濾過、重量測定を行い、その重量を測定試料重量から差し引いて測定試料重量の補正を実施した。また、ポリエステルフィルムを測定試料として用いて得られた値を、ポリエステルフィルムを構成するポリエステル樹脂の値とした。(1) Diethylene glycol (DEG) content 1.0 g of a measurement sample (polyester resin (raw material) or polyester film) was hydrolyzed at 260 ° C. using 2.5 mL of monoethanolamine as a solvent. Next, 10 mL of methanol was added, cooled, neutralized with terephthalic acid, centrifuged, and then the supernatant was measured for diethylene glycol (DEG) content by gas chromatography (GC-14A, manufactured by Shimadzu Corporation). In addition, since additional components, such as inorganic particles, settle as an insoluble substance during centrifugation, the sedimented components were filtered and weighed, and the weight was subtracted from the measured sample weight to correct the measured sample weight. Moreover, the value obtained using a polyester film as a measurement sample was made into the value of the polyester resin which comprises a polyester film.
（２）固有粘度（ＩＶ）
オルトクロロフェノール１００ｍＬに測定試料（ポリエステル樹脂（原料）又はポリエステルフィルム）を溶解させ（溶液濃度Ｃ（測定試料重量／溶液体積）＝１．２ｇ／ｍＬ）、その溶液の２５℃での粘度をオストワルド粘度計を用いて測定した。また、同様に溶媒の粘度を測定した。得られた溶液粘度、溶媒粘度を用いて、下記式（Ｃ）により、［η］を算出し、得られた値でもって固有粘度（ＩＶ）とした。
ηｓｐ／Ｃ＝［η］＋Ｋ［η］２・Ｃ ・・・式（Ｃ）
（ここで、ηｓｐ＝（溶液粘度／溶媒粘度）―１、Ｋはハギンス定数（０．３４３とする）
である。）。(2) Intrinsic viscosity (IV)
A measurement sample (polyester resin (raw material) or polyester film) is dissolved in 100 mL of orthochlorophenol (solution concentration C (measurement sample weight / solution volume) = 1.2 g / mL), and the viscosity of the solution at 25 ° C. is Ostwald. It measured using the viscometer. Similarly, the viscosity of the solvent was measured. Using the obtained solution viscosity and solvent viscosity, [η] was calculated by the following formula (C), and the obtained value was used as the intrinsic viscosity (IV).
ηsp / C = [η] + K [η] 2 · C Formula (C)
(Where ηsp = (solution viscosity / solvent viscosity) −1, K is a Huggins constant (assuming 0.343)
It is. ).
なお、ポリエステル樹脂（原料）又はポリエステルフィルムを溶解させた溶液に無機粒子などの不溶物がある場合は、以下の方法を用いて測定を行った。
ｉ）オルトクロロフェノール１００ｍＬに測定試料（ポリエステル樹脂（原料）又はポリエステルフィルム）を溶解させ、溶液濃度が１．２ｍｇ／ｍＬよりも濃い溶液を作成する。ここで、オルトクロロフェノールに供した測定試料の重量を測定試料重量とする。
ｉｉ）次に、不溶物を含む溶液を濾過し、不溶物の重量測定と、濾過後の濾液の体積測定を行う。
ｉｉｉ）濾過後の濾液にオルトクロロフェノールを追加して、（測定試料重量（ｇ）−不溶物の重量（ｇ））／（濾過後の濾液の体積（ｍＬ）＋追加したオルトクロロフェノールの体積（ｍＬ））が、１．２ｇ／１００ｍＬとなるように調整する。
（例えば、測定試料重量２．０ｇ／溶液体積１００ｍＬの濃厚溶液を作成したときに、該溶液を濾過したときの不溶物の重量が０．２ｇ、濾過後の濾液の体積が９９ｍＬであった場合は、オルトクロロフェノールを５１ｍＬ追加する調整を実施する。（（２．０ｇ−０．２ｇ）／（９９ｍＬ＋５１ｍＬ）＝１．２ｇ／ｍＬ））
ｉｖ）ｉｉｉ）で得られた溶液を用いて、２５℃での粘度をオストワルド粘度計を用いて測定し、得られた溶液粘度、溶媒粘度を用いて、上記式（Ｃ）により、［η］を算出し、得られた値をもって固有粘度（ＩＶ）とする。In addition, when there existed insoluble matters, such as an inorganic particle, in the solution which dissolved the polyester resin (raw material) or the polyester film, it measured using the following method.
i) A measurement sample (polyester resin (raw material) or polyester film) is dissolved in 100 mL of orthochlorophenol to prepare a solution having a solution concentration higher than 1.2 mg / mL. Here, let the weight of the measurement sample used for orthochlorophenol be a measurement sample weight.
ii) Next, the solution containing the insoluble matter is filtered, and the weight of the insoluble matter and the volume of the filtrate after filtration are measured.
iii) Adding orthochlorophenol to the filtrate after filtration, (measurement sample weight (g) −insoluble matter weight (g)) / (volume of filtrate after filtration (mL) + volume of orthochlorophenol added) (ML)) is adjusted to 1.2 g / 100 mL.
(For example, when a concentrated solution having a measurement sample weight of 2.0 g / solution volume of 100 mL was prepared, the weight of insoluble matter when the solution was filtered was 0.2 g, and the filtrate volume after filtration was 99 mL Adjust to add 51 mL of orthochlorophenol ((2.0 g-0.2 g) / (99 mL + 51 mL) = 1.2 g / mL))
iv) Using the solution obtained in iii), the viscosity at 25 ° C. is measured using an Ostwald viscometer, and the obtained solution viscosity and solvent viscosity are used to calculate [η] according to the above formula (C). And the obtained value is taken as the intrinsic viscosity (IV).
（３）末端カルボキシル基量
Ｍａｕｌｉｃｅの方法（文献 Ｍ．Ｊ．Ｍａｕｌｉｃｅ，Ｆ．Ｈｕｉｚｉｎｇａ．Ａｎａｌ．Ｃｈｉｍ．Ａｃｔａ，２２ ３６３（１９６０））に準じて、以下の方法にて測定した。
測定試料（ポリエステル樹脂（原料）またはポリエステルフィルム）２ｇをｏ−クレゾール／クロロホルム（重量比７／３）５０ｍＬに温度８０℃にて溶解し、０．０５ＮのＫＯＨ／メタノール溶液によって滴定し、末端カルボキシル基濃度を測定し、当量／ポリエステル１ｔの値で示した。なお、滴定時の指示薬はフェノールレッドを用いて、黄緑色から淡紅色に変化したところを滴定の終点とした。なお、ポリエステル樹脂（原料）又はポリエステルフィルムを溶解させた溶液に無機粒子などの不溶物がある場合は、溶液を濾過して不溶物の重量測定を行い、不溶物の重量を測定試料重量から差し引いた値を測定試料重量とする補正を実施した。また、ポリエステルフィルムを測定試料として用いて得られた値を、ポリエステルフィルムを構成するポリエステル樹脂の値とした。(3) Terminal carboxyl group amount It was measured by the following method according to the method of Malice (reference MJ Malice, F. Huizinga. Anal. Chim. Acta, 22 363 (1960)).
2 g of a measurement sample (polyester resin (raw material) or polyester film) was dissolved in 50 mL of o-cresol / chloroform (weight ratio 7/3) at a temperature of 80 ° C., and titrated with a 0.05 N KOH / methanol solution to obtain a terminal carboxyl. The base concentration was measured and indicated as equivalent / polyester 1t. In addition, the indicator at the time of titration used phenol red, and the place where it changed from yellowish green to light red was set as the end point of titration. If there is insoluble matter such as inorganic particles in the solution in which the polyester resin (raw material) or polyester film is dissolved, the solution is filtered to measure the weight of the insoluble matter, and the weight of the insoluble matter is subtracted from the measured sample weight. Correction was performed with the measured value as the measured sample weight. Moreover, the value obtained using a polyester film as a measurement sample was made into the value of the polyester resin which comprises a polyester film.
（４）アルカリ金属元素含有量
原子吸光分析法（日立製作所製：偏光ゼーマン原子吸光光度計１８０−８０。フレーム：アセチレン−空気）にて定量を行った。(4) Alkali metal element content Quantification was performed by atomic absorption spectrometry (manufactured by Hitachi, Ltd .: polarized Zeeman atomic absorption photometer 180-80, frame: acetylene-air).
（５）リン元素およびマンガン元素含有量
（株）リガク社製波長分散型蛍光Ｘ線分析装置（型番：ＺＳＸ１００ｅ）を用いて測定した。(5) Phosphorus element and manganese element content Measured using a wavelength dispersive X-ray fluorescence spectrometer (model number: ZSX100e) manufactured by Rigaku Corporation.
（６）リン元素を含有する異物数
三波長蛍光灯を光源としてフィルムを透過光および反射光にて１０００ｃｍ２を検査し観察された異物をマーキングして試料を採取した。なお、この時にフィルム位置での光量が１０００ルクスとなるように光源とフィルム間距離を調整した。得られた異物試料について光学顕微鏡（倍率１００倍）にて観察して異物のサイズが最も大きくなる方向で測定し異物の長径とした。また、異物試料を走査型電子顕微鏡（ＳＥＭ）Ｓ−４３００Ａ形（（株）日立製作所製）にエネルギー分散型Ｘ線分析装置（ＥＤＸ）ＥＭＡＸ−７０００（（株）堀場製作所製）を付属させた装置を用いて異物部分の元素分析を行い、リン元素の含有有無を測定し、長径１００μｍ以上のリン元素を含有する異物の個数をカウントした。(6) Number of foreign substances containing phosphorus element Using a three-wavelength fluorescent lamp as a light source, the film was inspected 1000 cm 2 with transmitted light and reflected light, and the observed foreign substances were marked to collect samples. At this time, the distance between the light source and the film was adjusted so that the amount of light at the film position was 1000 lux. The obtained foreign material sample was observed with an optical microscope (magnification 100 times) and measured in the direction in which the size of the foreign material was the largest, and was taken as the long diameter of the foreign material. In addition, an energy dispersive X-ray analyzer (EDX) EMAX-7000 (manufactured by Horiba, Ltd.) was attached to a scanning electron microscope (SEM) S-4300A (manufactured by Hitachi, Ltd.) as a foreign material sample. Elemental analysis of the foreign matter portion was performed using an apparatus, the presence or absence of phosphorus element was measured, and the number of foreign matters containing phosphorus element having a major axis of 100 μm or more was counted.
（７）フィルムの平均超音波伝導速度、超音波伝導速度の最大値と最小値の比率、および超音波伝導速度が最大値を示す方向とフィルム長手方向とのなす角度（θ）
（７−１）フィルムの平均超音波伝導速度
幅方向３００ｍｍ、長手方向３００ｍｍのフィルム試料を採取し、野村商事（株）製ＳＯＮＩＣ ＳＨＥＥＴ ＴＥＳＴＥＲ ＳＳＴ−２５０にて、ポリエステルフィルムの長手方向を基準（０゜）とし、フィルムの垂線を軸としてこのフィルム試料を回転させ、５°毎に０°〜１８０°まで超音波伝導速度（ｋｍ／秒）を測定し、得られた値の平均値を算出した。(7) The average ultrasonic conduction velocity of the film, the ratio between the maximum value and the minimum value of the ultrasonic conduction velocity, and the angle (θ) between the direction in which the ultrasonic conduction velocity exhibits the maximum value and the film longitudinal direction.
(7-1) Average Ultrasonic Conduction Speed of Film A film sample having a width direction of 300 mm and a longitudinal direction of 300 mm was collected, and the length direction of the polyester film was determined based on the length of the polyester film by Nomura Shoji Co., Ltd. The film sample was rotated about the perpendicular of the film, and the ultrasonic conduction velocity (km / sec) was measured from 0 ° to 180 ° every 5 °, and the average value of the obtained values was calculated. .
（７−２）超音波伝導速度の最大値と最小値の比率
（７−１）によって得られる、０°〜１８０°までの超音波伝導速度（ｋｍ／秒）の測定結果から超音波伝導速度の最大値と最小値を抽出し、超音波伝導速度の最大値を最小値で除した値（最大値／最小値）を、超音波伝導速度の最大値と最小値の比率とした。(7-2) Ratio of the maximum value and the minimum value of the ultrasonic conduction velocity The ultrasonic conduction velocity is obtained from the measurement result of the ultrasonic conduction velocity (km / sec) from 0 ° to 180 ° obtained by (7-1). The maximum value and the minimum value were extracted, and the value obtained by dividing the maximum value of the ultrasonic conduction velocity by the minimum value (maximum value / minimum value) was taken as the ratio of the maximum value and the minimum value of the ultrasonic conduction velocity.
（７−３）超音波伝導速度が最大値を示す方向とフィルム長手方向とのなす角度（θ）
また、超音波伝導速度が最大値を示す方向と、フィルム長手方向とのなす角度（θ）を算出した。なお、角度（θ）は、超音波伝導速度が最大値を示す方向と、フィルム長手方向とのなす角度のうち、鋭角（０°以上９０°以下）となる角度を指す。(7-3) Angle (θ) formed by the direction in which the ultrasonic conduction velocity shows the maximum value and the film longitudinal direction
Moreover, the angle (θ) formed between the direction in which the ultrasonic conduction velocity shows the maximum value and the film longitudinal direction was calculated. Note that the angle (θ) indicates an acute angle (0 ° or more and 90 ° or less) among the angles formed by the direction in which the ultrasonic conduction velocity has the maximum value and the film longitudinal direction.
なお、以下の実施例や比較例においては、ポリエステルフィルムの中間ロールを一旦得た後に、その中間ロールをフィルムの幅方向にスリットして、数本のロール（最終製品）を得る方法が採用されている。そして、以下の実施例や比較例においては、中間ロールのロール（フィルム）幅方向の中央部に対応するロール（最終製品）と、中間ロールのロール（フィルム）幅方向の最端部に対応するロール（最終製品）のそれぞれについて、フィルムの平均超音波伝導速度、超音波伝導速度の最大値と最小値の比率、および超音波伝導速度が最大値を示す方向とフィルム長手方向とのなす角度（θ）が測定されている。また、スリット後のフィルムロール（最終製品）からフィルム試料の採取に際しては、ロール（フィルム）の幅方向の中央部から採取されている。 In the following Examples and Comparative Examples, a method of obtaining several rolls (final product) by once obtaining an intermediate roll of a polyester film and then slitting the intermediate roll in the width direction of the film is adopted. ing. And in the following Examples and Comparative Examples, it corresponds to the roll (final product) corresponding to the center part in the roll (film) width direction of the intermediate roll and the extreme end part in the roll (film) width direction of the intermediate roll. For each roll (final product), the average ultrasonic conduction velocity of the film, the ratio of the maximum and minimum ultrasonic conduction velocity, and the angle between the direction in which the ultrasonic conduction velocity shows the maximum value and the longitudinal direction of the film ( θ) is measured. Further, when a film sample is collected from the film roll (final product) after the slit, the film sample is collected from the center in the width direction of the roll (film).
（８）フィルムの耐湿熱性評価（伸度保持率）
（８−１）超音波伝導速度の最大値の方向における耐湿熱性評価
（７）項にて測定した超音波伝導速度の最大値の方向が長さ方向となるように、幅１０ｍｍ、長さ２５０ｍｍの短冊状に切り出した伸度測定用のフィルム試料を準備した。(8) Evaluation of moisture and heat resistance of film (elongation retention)
(8-1) Humidity and heat resistance evaluation in the direction of the maximum value of the ultrasonic conduction velocity The width of 10 mm and the length of 250 mm so that the direction of the maximum value of the ultrasonic conduction velocity measured in (7) is the length direction. A film sample for measuring elongation was cut out into a strip shape.
準備された試料を高度加速寿命試験装置ＥＨＳ−２２１（エスペック社製）にて、温度１２５℃、湿度１００ＲＨ％の環境下にて７２時間処理を実施した。上記処理前および処理後のフィルムの伸度をテンシロンを用いて、原長（チャック間距離）１００ｍｍ、引っ張り速度２００ｍｍ／分の条件にて測定した。なお、伸度についてはそれぞれＮ＝５で測定した平均値とした。得られたフィルム伸度について処理後の伸度を処理前の伸度で除した値を、耐湿熱評価における超音波伝導速度の最大値の方向の伸度保持率とした。 The prepared sample was processed for 72 hours in an environment with a temperature of 125 ° C. and a humidity of 100 RH% using an advanced accelerated life test apparatus EHS-221 (manufactured by Espec). The elongation of the film before and after the treatment was measured using Tensilon under conditions of an original length (distance between chucks) of 100 mm and a pulling speed of 200 mm / min. In addition, about the elongation, it was set as the average value measured by N = 5, respectively. For the obtained film elongation, the value obtained by dividing the elongation after the treatment by the elongation before the treatment was defined as the elongation retention in the direction of the maximum value of the ultrasonic conduction velocity in the wet heat resistance evaluation.
なお、伸度保持率５０％以上が合格範囲、６０％以上が良好、７０％以上が特に良好である。 The elongation retention rate of 50% or more is an acceptable range, 60% or more is good, and 70% or more is particularly good.
（８−２）超音波伝導速度の最小値の方向における耐湿熱性評価
（７）項にて測定した超音波伝導速度の最小値の方向が長さ方向となるように、幅１０ｍｍ、長さ２５０ｍｍの短冊状に切り出した伸度測定用のフィルム試料を準備した。(8-2) Evaluation of moisture and heat resistance in the direction of the minimum value of ultrasonic conduction velocity 10 mm in width and 250 mm in length so that the direction of the minimum value of ultrasonic conduction velocity measured in (7) is the length direction. A film sample for measuring elongation was cut out into a strip shape.
準備された試料を用いて、（８−１）と同様の方法で、伸度保持率を求め、これを耐湿熱評価における超音波伝導速度の最小値の方向の伸度保持率とした。 Using the prepared sample, the elongation retention rate was determined by the same method as in (8-1), and this was defined as the elongation retention rate in the direction of the minimum value of the ultrasonic conduction velocity in the wet heat resistance evaluation.
なお、以下の実施例や比較例においては、ポリエステルフィルムの中間ロールを一旦得た後に、その中間ロールをフィルムの幅方向にスリットして、数本のロール（最終製品）を得る方法が採用されている。そして、以下の実施例や比較例においては、中間ロールの中央部に対応するロール（最終製品）と、中間ロールの最端部に対応するロール（最終製品）のそれぞれについて、超音波伝導速度の最大値の方向の伸度保持率と超音波伝導速度の最小値の方向の伸度保持率が測定されている。また、フィルムロール（最終製品）からフィルム試料の採取に際しては、ロールの幅方向の中央部から採取されている。 In the following Examples and Comparative Examples, a method of obtaining several rolls (final product) by once obtaining an intermediate roll of a polyester film and then slitting the intermediate roll in the width direction of the film is adopted. ing. In the following examples and comparative examples, the ultrasonic conduction velocity of each of the roll (final product) corresponding to the center portion of the intermediate roll and the roll (final product) corresponding to the outermost end portion of the intermediate roll is determined. The elongation retention in the direction of the maximum value and the elongation retention in the direction of the minimum value of the ultrasonic conduction velocity are measured. Further, when a film sample is collected from a film roll (final product), the film sample is collected from the central portion in the width direction of the roll.
（９）フィルムの熱収縮率
幅方向３００ｍｍ、長手方向３００ｍｍのフィルム試料を採取した。試料の中央部に、長手方向、幅方向それぞれについて、原長（Ｌ０）として２００ｍｍの間隔となるように一対の印をつけた。試料をオーブン中で１５０℃にて３０分処理をした後に室温まで冷却し、一対の印間の距離を測定し、処理後の長さ（Ｌ１）とした。そして、フィルム長手方向および幅方向における熱収縮率を、１００×（Ｌ０−Ｌ１）／Ｌ０に従い、それぞれ算出した。(9) Thermal contraction rate of film A film sample having a width direction of 300 mm and a longitudinal direction of 300 mm was collected. A pair of marks was placed at the center of the sample so that the original length (L0) was 200 mm apart in each of the longitudinal direction and the width direction. The sample was treated in an oven at 150 ° C. for 30 minutes and then cooled to room temperature, and the distance between the pair of marks was measured to obtain the length after treatment (L1). And the thermal contraction rate in a film longitudinal direction and the width direction was computed according to 100x (L0-L1) / L0, respectively.
なお、以下の実施例や比較例においては、ポリエステルフィルムの中間ロールを一旦得た後に、その中間ロールをフィルムの幅方向にスリットして、数本のロール（最終製品）を得る方法が採用されている。そして、以下の実施例や比較例においては、中間ロールの中央部に対応するロール（最終製品）と、中間ロールの最端部に対応するロール（最終製品）のそれぞれについて、長手方向における熱収縮率と幅方向における熱収縮率が測定されている。また、フィルムロール（最終製品）からフィルム試料の採取に際しては、ロールの幅方向の中央部から採取されている。また、以下の実施例や比較例においては、中間ロールの中央部に対応するロール（最終製品）を用いて求められた長手方向における熱収縮率と、中間ロールの最端部に対応するロール（最終製品）を用いて求められた長手方向における熱収縮率の平均値も併せて算出されている。同様に、中間ロールの中央部に対応するロール（最終製品）を用いて求められた幅方向における熱収縮率と、中間ロールの最端部に対応するロール（最終製品）を用いて求められた幅方向における熱収縮率の平均値も併せて算出されている。 In the following Examples and Comparative Examples, a method of obtaining several rolls (final product) by once obtaining an intermediate roll of a polyester film and then slitting the intermediate roll in the width direction of the film is adopted. ing. In the following examples and comparative examples, thermal contraction in the longitudinal direction is performed for each of the roll (final product) corresponding to the center portion of the intermediate roll and the roll (final product) corresponding to the outermost end portion of the intermediate roll. The rate of heat shrinkage in the width direction is measured. Further, when a film sample is collected from a film roll (final product), the film sample is collected from the central portion in the width direction of the roll. Further, in the following examples and comparative examples, the thermal contraction rate in the longitudinal direction obtained using the roll (final product) corresponding to the center portion of the intermediate roll, and the roll corresponding to the endmost portion of the intermediate roll ( The average value of the heat shrinkage in the longitudinal direction obtained using the final product is also calculated. Similarly, it was calculated | required using the roll (final product) corresponding to the thermal contraction rate in the width direction calculated | required using the roll (final product) corresponding to the center part of an intermediate | middle roll, and the endmost part of an intermediate roll. The average value of the heat shrinkage rate in the width direction is also calculated.
（１０）透過光学濃度
ポリエステルフィルムを光学濃度計（Ｍａｃｂｅｔｈ社製ＴＲ５２４）を用いＪＩＳ Ｋ７６０５（１９７６）に準じて入射光束と透過光束からフィルムの透過光学濃度を算出した。なお、測定時のフィルターには、Ｖｉｓｕａｌフィルターを用いた。(10) Transmission Optical Density The transmission optical density of the polyester film was calculated from the incident light flux and the transmitted light flux according to JIS K7605 (1976) using an optical densitometer (TR524 manufactured by Macbeth). A Visual filter was used as a filter at the time of measurement.
（１１）製膜性
実施例・比較例の条件にて製膜を実施した際の破れ回数を１日当たりに換算した計算値を用いて下記の基準にて判定した。Ｂ以上が実用可能な範囲である。(11) Film-forming property It judged on the following reference | standard using the calculated value which converted the frequency | count of tear at the time of implementing film-forming on the conditions of an Example and a comparative example per day. B or more is a practical range.
Ｓ：１日当たりの破れが１回以下
Ａ：１日当たりの破れが１回を越えて２回以下
Ｂ：１日当たりの破れが２回を越えて３回以下
Ｃ：１日当たりの破れが３回を越える。S: No more than 1 break per day A: No more than 2 breaks per day B: No more than 2 breaks per day C: No more than 3 breaks per day Over.
（１２）加工性（打抜性）
得られたフィルムを３枚重ねてトムソン型打ち抜きカッターにて型抜きをし、切断面を目視観察し、以下基準に従って判定した。Ｂ以上が実用可能な範囲である。(12) Workability (punchability)
Three of the obtained films were overlapped and punched with a Thomson punching cutter, and the cut surface was visually observed and judged according to the following criteria. B or more is a practical range.
Ｓ：バリやヒゲが全く見られない
Ａ：バリ、ヒゲが切断面の長さ０．３ｍあたり１ヶ以下
Ｂ：バリ、ヒゲが切断面の長さ０．３ｍあたり１ヶを越えて３ヶ以下
Ｃ：バリ、ヒゲが切断面の長さ０．３ｍあたり３ヶを越える。S: No burrs or whiskers are observed. A: Burrs and whiskers are 1 or less per 0.3 m length of the cut surface. B: Burrs and whiskers are more than 1 per 0.3 m length of the cut surface. C: Burrs and whiskers exceed 3 per 0.3 m length of the cut surface.
（１３）微小吸熱ピーク温度（Ｔｍｅｔａ）
フィルムを示差走査熱量計（ＴＡ Ｉｎｓｔｒｕｍｅｎｔｓ社製ＤＳＣ Ｑ１００）により、２０℃／分の昇温速度にて３０℃〜２８０℃の範囲で測定を実施した。この測定により得られた示差走査熱量測定チャートにおけるポリエステル結晶融解ピーク前の微小吸熱ピーク温度をＴｍｅｔａ（℃）とした。なおＴｍｅｔａはポリエステルフィルムに対する熱処理温度の履歴として出現する。(13) Minute endothermic peak temperature (Tmeta)
The film was measured with a differential scanning calorimeter (DSC Q100 manufactured by TA Instruments) at a temperature rising rate of 20 ° C./min in the range of 30 ° C. to 280 ° C. The minute endothermic peak temperature before the polyester crystal melting peak in the differential scanning calorimetry chart obtained by this measurement was defined as Tmeta (° C.). Tmeta appears as a history of the heat treatment temperature for the polyester film.
各実施例・比較例で用いる樹脂等（原料）の調整法を参考例として示す。 The adjustment method of resin etc. (raw material) used in each example and comparative example is shown as a reference example.
[参考例１] ポリエステル樹脂１の調製
第一工程として、テレフタル酸ジメチル１００質量部とエチレングリコール３８．１５質量部、ジエチレングリコール０．２５質量部を窒素雰囲気下、温度２６０℃にて混合した。その後温度を２２５℃へ降下させ、酢酸マンガン４水和物０．０６８質量部、三酸化アンチモン０．０２９質量部を添加後攪拌しながら、更にエチレングリコール１５．９質量部とジエチレングリコール０．１０質量部の混合物を２時間かけて徐々に添加しながらメタノールを留出させ、エステル交換反応を終了した。第二工程として、エステル交換反応終了後、反応系内のポリエステルの温度を２２５℃とし、リン酸０．０１５質量部（１．５モル／ｔ相当）とリン酸二水素ナトリウム２水和物０．０２７質量部（１．５モル／ｔ相当）をエチレングリコール６．８質量部に溶解したエチレングリコール溶液（リン化合物の濃度０．４質量％）を添加した。引き続き第三工程として、重合反応を最終到達温度２８５℃、圧力１３Ｐａの減圧下で行い、固有粘度０．５４、カルボキシル基末端基数１７当量／ｔのポリエステルを得た。さらに、第四工程として、得られたポリエチレンテレフタレートを１６０℃で６時間乾燥、結晶化させたのち、圧力６５Ｐａの減圧条件下にて２３０℃、１０時間の固相重合を行い、固有粘度（ＩＶ）０．８２、カルボキシル基末端基量９．７当量／ｔ、ジエチレングリコール含有量１．２０質量％、融点２６０℃、ガラス転移温度Ｔｇ８１℃のポリエステルを得た。Reference Example 1 Preparation of Polyester Resin 1 As the first step, 100 parts by mass of dimethyl terephthalate, 38.15 parts by mass of ethylene glycol, and 0.25 parts by mass of diethylene glycol were mixed at a temperature of 260 ° C. in a nitrogen atmosphere. Thereafter, the temperature was lowered to 225 ° C., 0.068 parts by mass of manganese acetate tetrahydrate and 0.029 parts by mass of antimony trioxide were added, and then 15.9 parts by mass of ethylene glycol and 0.10 parts by mass of diethylene glycol while stirring. Part of the mixture was gradually added over 2 hours while distilling methanol to complete the transesterification reaction. As the second step, after completion of the transesterification reaction, the temperature of the polyester in the reaction system is set to 225 ° C., 0.015 part by mass of phosphoric acid (corresponding to 1.5 mol / t) and sodium dihydrogen phosphate dihydrate 0 An ethylene glycol solution (phosphorus compound concentration 0.4 mass%) in which 0.027 mass parts (equivalent to 1.5 mol / t) was dissolved in 6.8 mass parts of ethylene glycol was added. Subsequently, as the third step, the polymerization reaction was carried out under a reduced pressure with a final temperature of 285 ° C. and a pressure of 13 Pa to obtain a polyester having an intrinsic viscosity of 0.54 and a carboxyl group terminal group number of 17 equivalents / t. Further, as a fourth step, the obtained polyethylene terephthalate was dried and crystallized at 160 ° C. for 6 hours, and then subjected to solid phase polymerization at 230 ° C. for 10 hours under a reduced pressure of 65 Pa to obtain an intrinsic viscosity (IV ) 0.82, a carboxyl group terminal group amount of 9.7 equivalent / t, a diethylene glycol content of 1.20% by mass, a melting point of 260 ° C., and a glass transition temperature of Tg 81 ° C. were obtained.
[参考例２] ポリエステル樹脂２〜２６の調製
表１−１、表１−２に示した条件を用いた以外は参考例１と同様の方法を用いてポリエステル樹脂を得た。なお、ポリエステル樹脂５については、テレフタル酸ジメチル１００質量部の変わりにテレフタル酸８５．６質量部を、ポリエステル樹脂１１，１２については、リン酸二水素ナトリウム２水和物の替わりにリン酸二水素カリウムを用いた。また、ポリエステル樹脂８，９，２３については、第四工程を表１−１、表１−２に示した固有粘度になるように、固相重合時間を調整した。またポリエステル樹脂２４については、第三工程でのポリエステルを固有粘度０．５０、カルボキシル基末端基数２７当量／ｔとし、引き続き第四工程にて固有粘度０．７３となるまで固相重合を実施した。
得られたポリエステルの特性を評価した結果を表１−１、表１−２に示す。[Reference Example 2] Preparation of polyester resins 2 to 26 A polyester resin was obtained in the same manner as in Reference Example 1 except that the conditions shown in Table 1-1 and Table 1-2 were used. For polyester resin 5, 85.6 parts by mass of terephthalic acid instead of 100 parts by mass of dimethyl terephthalate, and for polyester resins 11 and 12, dihydrogen phosphate instead of sodium dihydrogen phosphate dihydrate. Potassium was used. For polyester resins 8, 9, and 23, the solid phase polymerization time was adjusted so that the fourth step had intrinsic viscosities shown in Table 1-1 and Table 1-2. For the polyester resin 24, the polyester in the third step was subjected to solid phase polymerization with an intrinsic viscosity of 0.50 and a carboxyl group terminal group number of 27 equivalents / t, and then in the fourth step until the intrinsic viscosity was 0.73. .
The results of evaluating the properties of the obtained polyester are shown in Table 1-1 and Table 1-2.
[参考例３] 二酸化珪素含有ポリエステル樹脂Ａの調製
参考例１で得られた９５質量部のポリエステル樹脂１に、平均粒径４．３μｍの二酸化珪素粒子５質量部を２軸押出機にて２９０℃にて混練し、二酸化珪素含有ポリエステル樹脂Ａを得た。[Reference Example 3] Preparation of Silicon Dioxide-Containing Polyester Resin A To 95 parts by mass of the polyester resin 1 obtained in Reference Example 1, 5 parts by mass of silicon dioxide particles having an average particle size of 4.3 μm was 290 by a twin screw extruder. The mixture was kneaded at 0 ° C. to obtain a silicon dioxide-containing polyester resin A.
[参考例４] ルチル型二酸化チタン含有ポリエステル樹脂Ｂの調製
参考例１で得られた５０質量部のポリエステル樹脂１に、平均粒径０．３μｍの塩素法ルチル型二酸化チタン粒子５０質量部を２軸押出機にて２９０℃にて混練し、ルチル型二酸化チタン含有ポリエステル樹脂Ｂを得た。[Reference Example 4] Preparation of Rutile Titanium Dioxide-Containing Polyester Resin B To 50 parts by mass of the polyester resin 1 obtained in Reference Example 1, 2 parts by mass of 50 parts by mass of chlorine method rutile type titanium dioxide particles having an average particle size of 0.3 μm. The mixture was kneaded at 290 ° C. with a screw extruder to obtain a rutile-type titanium dioxide-containing polyester resin B.
[実施例１]
参考例に従って調整した９９．５質量部のポリエステル樹脂１と、０．５質量部の二酸化珪素含有ポリエステル樹脂Ａとの混合物を圧力１ｋＰａの減圧条件下、温度１７０℃で４時間乾燥した後、押出機に供給し２８５℃で溶融押出を行った。[Example 1]
A mixture of 99.5 parts by mass of polyester resin 1 prepared according to Reference Example and 0.5 parts by mass of silicon dioxide-containing polyester resin A was dried at a temperature of 170 ° C. for 4 hours under a reduced pressure of 1 kPa, and then extruded. The melt was extruded at 285 ° C.
ステンレス鋼繊維を焼結圧縮した平均目開き６０μｍのフィルターで濾過した後、Ｔ字型口金よりシート状に押し出し、静電印加キャスト法を用いて表面温度２０℃の鏡面キャスティングドラムに巻き付けて冷却固化せしめた。この未延伸フィルムを予熱ロールにて８５℃に予熱後、上下方向からラジエーションヒーターを用いて１００℃まで加熱しつつロール間の周速差を利用して長手方向に延伸速度３，５００％／秒にて３．５倍延伸し、引き続き冷却ロールにて２５℃まで冷却し、一軸配向（一軸延伸）フィルムとした。 After filtering with stainless steel fiber sintered and compressed through a filter with an average opening of 60 μm, it is extruded into a sheet form from a T-shaped die, wound around a mirror casting drum having a surface temperature of 20 ° C. using an electrostatic application casting method, and cooled and solidified. I was damned. This unstretched film is preheated to 85 ° C. with a preheating roll, and then heated up to 100 ° C. using a radiation heater from above and below, while using a peripheral speed difference between the rolls, a stretching speed of 3,500% / second in the longitudinal direction. And then cooled to 25 ° C. with a cooling roll to obtain a uniaxially oriented (uniaxially stretched) film.
次いで、一軸配向（一軸延伸）フィルムをクリップで把持してオーブン中にて１００℃の熱風にて予熱し、引き続き連続的に延伸工程において１２０℃熱風で加熱しながら幅方向に３．８倍延伸した。なお、幅方向の延伸については、延伸工程の中間点における延伸倍率を３．０倍とし、中間点にて幅方向延伸の７１％が完了するように設定した。得られた二軸配向（二軸延伸）フィルムを中間工程を経て熱処理工程に導き、第１の熱処理として２００℃の熱風にて３．５秒、第２の熱処理として２１０℃の熱風にて３．５秒、第３の熱処理として２１５℃の熱風にて７秒間熱処理を行った。なお、中間工程は周囲を断熱壁で囲われており、熱風等による加熱は実施せず、工程内の排気のみを行い、雰囲気温度を１６０℃に調整した。また、中間工程のフィルム通過時間は３．５秒であった。熱処理工程を経たフィルムを２１５℃から１００℃まで冷却しながら５％の弛緩処理を施し、続けて８０℃まで冷却した。次いで、フィルムをオーブンより引き出し、幅方向両端部を除去した後に巻き取り、厚さ１２５μｍ、幅５．４ｍ、１５０℃３０分での熱収縮率が長手方向１．６％、幅方向０．７％のポリエステルフィルム中間ロールを得た。得られたポリエステルフィルムの特性を表３−１、表４−１に示す。 Next, a uniaxially oriented (uniaxially stretched) film is gripped with a clip, preheated with hot air of 100 ° C. in an oven, and continuously stretched 3.8 times in the width direction while continuously heated with 120 ° C. hot air in a stretching process. did. In addition, about extending | stretching of the width direction, it set so that the draw ratio in the intermediate point of an extending process shall be 3.0 time, and 71% of width direction extending | stretching may be completed at an intermediate point. The obtained biaxially oriented (biaxially stretched) film is led to a heat treatment step through an intermediate step, and the first heat treatment is performed with hot air at 200 ° C. for 3.5 seconds, and the second heat treatment is performed with hot air at 210 ° C. for 3 seconds. Heat treatment was performed for 7 seconds with hot air at 215 ° C. as a third heat treatment for 5 seconds. In the intermediate process, the periphery was surrounded by a heat insulating wall, and heating with hot air or the like was not performed. Only the exhaust in the process was performed, and the ambient temperature was adjusted to 160 ° C. Further, the film passing time in the intermediate process was 3.5 seconds. The film subjected to the heat treatment step was subjected to a relaxation treatment of 5% while being cooled from 215 ° C. to 100 ° C., and subsequently cooled to 80 ° C. Next, the film was drawn out from the oven, and after removing both ends in the width direction, the film was wound up. The thickness was 125 μm, the width was 5.4 m, and the heat shrinkage rate at 150 ° C. for 30 minutes was 1.6% in the longitudinal direction, 0.7 % Polyester film intermediate roll. The characteristics of the obtained polyester film are shown in Table 3-1 and Table 4-1.
さらに得られたポリエステルフィルムをスリッターにて上記中間ロールを幅１０００ｍｍ×５本となるように切断しながら内径１５２．５ｍｍ、外径１６７ｍｍのコアに巻き取りポリエステルフィルムロールを得た。また、中間ロールのロール（フィルム）幅方向の中央部に対応するポリエステルフィルムロールと、中間ロールのロール（フィルム）幅方向の最端部に対応するポリエステルフィルムロールを用いて測定されたフィルムの特性を表に示す（表において、「中間ロール中央部」とは、中間ロールの中央部に対応するポリエステルフィルムロールを用いて測定されたこと示す。また、「中間ロール端部」とは、中間ロールの最端部に対応するポリエステルフィルムロールを用いて測定されたこと示す）。 Furthermore, the obtained polyester film was wound around a core having an inner diameter of 152.5 mm and an outer diameter of 167 mm while obtaining a polyester film roll while cutting the intermediate roll so as to have a width of 1000 mm × 5 with a slitter. Moreover, the characteristic of the film measured using the polyester film roll corresponding to the center part of the roll (film) width direction of an intermediate roll, and the polyester film roll corresponding to the extreme end part of the roll (film) width direction of an intermediate roll (In the table, “intermediate roll central portion” indicates that measurement was made using a polyester film roll corresponding to the central portion of the intermediate roll. Also, “intermediate roll end portion” refers to the intermediate roll. It shows that it was measured using the polyester film roll corresponding to the most end part of).
得られたフィルムは中間ロールの中央部、端部ともに、方向によらず高い耐湿熱性能を有しており、非常に優れた耐久性を有するフィルムであった。また、分子配向制御のための延伸条件での製膜にも関わらず、フィルム破れが全くなく、裁断端面でのバリも発生しない、生産性・加工性に優れた二軸配向ポリエステルフィルムであった。 The obtained film had a high heat and humidity resistance regardless of the direction at both the center and the end of the intermediate roll, and was a film having excellent durability. In addition, it was a biaxially oriented polyester film with excellent productivity and workability, with no film breakage and no burrs on the cut end face, despite film formation under stretching conditions for molecular orientation control. .
[実施例２〜２７、２９]
表２−１、表２−２の原料と製膜条件を適用した以外は実施例１と同様にして二軸配向ポリエステルフィルムを得た。得られたフィルムの特性を表３−１、表３−２、表４−１，表４−２に示す。[Examples 2-27, 29]
Biaxially oriented polyester films were obtained in the same manner as in Example 1 except that the raw materials and film forming conditions in Table 2-1 and Table 2-2 were applied. The characteristics of the obtained film are shown in Table 3-1, Table 3-2, Table 4-1, and Table 4-2.
[実施例２８]
参考例に従って調整した９５質量部のポリエステル樹脂１と５質量部のルチル型二酸化チタン含有ポリエステル樹脂Ｂとの混合物を圧力１ｋＰａの減圧条件下、温度１７０℃で４時間乾燥した後、押出機Ａに供給し２８５℃で溶融押出を行った。また、参考例に従って調整した６０質量部のポリエステル樹脂１と、４０質量部のルチル型二酸化チタン含有ポリエステル樹脂Ｂとの混合物を圧力１ｋＰａの減圧条件下、温度１７０℃で４時間乾燥した後押出機Ｂに供給し２８５℃で溶融押出を行った。押出機Ａから押出された溶融樹脂と押出機Ｂから押出された溶融樹脂は、それぞれステンレス鋼繊維を焼結圧縮した平均目開き６０μｍのフィルターで濾過した後にフィードブロックにて厚さ方向に２層に積層し、引き続きＴ字型口金よりシート状に押し出し、静電印加キャスト法を用いて表面温度２０℃の鏡面キャスティングドラムに巻き付けて冷却固化せしめた。得られた未延伸シートを実施例１と同様の方法を用いる事で、押出機Ａ側の樹脂：押出機Ｂ側の樹脂が厚さ方向に６：１に積層された積層二軸配向ポリエステルフィルムを得た。得られたフィルムの特性を表３−２、表４−２に示す。[Example 28]
A mixture of 95 parts by weight of polyester resin 1 prepared according to the reference example and 5 parts by weight of rutile-type titanium dioxide-containing polyester resin B was dried at a temperature of 170 ° C. for 4 hours under a reduced pressure of 1 kPa, Then, melt extrusion was performed at 285 ° C. Also, a mixture of 60 parts by mass of polyester resin 1 prepared according to the reference example and 40 parts by mass of rutile-type titanium dioxide-containing polyester resin B was dried at a temperature of 170 ° C. for 4 hours under a reduced pressure of 1 kPa, and then an extruder. B was supplied to B and melt extrusion was performed at 285 ° C. The molten resin extruded from the extruder A and the molten resin extruded from the extruder B are each filtered through a filter having an average opening of 60 μm obtained by sintering and compressing stainless steel fibers, and then two layers in the thickness direction using a feed block. And then extruded into a sheet form from a T-shaped die, wound around a mirror casting drum having a surface temperature of 20 ° C. using an electrostatic application casting method, and solidified by cooling. By using the same method as in Example 1 for the obtained unstretched sheet, a laminated biaxially oriented polyester film in which the resin on the extruder A side: the resin on the extruder B side was laminated 6: 1 in the thickness direction Got. The characteristics of the obtained film are shown in Table 3-2 and Table 4-2.
[実施例３０]
中間ロール（中間製品）をスリッターにて幅１２５０ｍｍ×４本となるように切断しながら内径１５２．５ｍｍ、外径１６７ｍｍのコアに巻き取った以外は実施例１と同様にして二軸配向ポリエステルフィルムを得た。得られたフィルムロール４本のうち、中間ロールの最端部に対応するポリエステルフィルムロールと、中間ロールの中央部に対応するポリエステルフィルムロール（フィルム幅方向において、中間ロールの最端部に対応するポリエステルフィルムロールの隣に位置するポリエステルフィルムロール）を用いて測定されたフィルムの特性を表３−２および表４−２に示す。[Example 30]
Biaxially oriented polyester film in the same manner as in Example 1 except that an intermediate roll (intermediate product) was cut into a 1250 mm × 4 width with a slitter and wound around a core having an inner diameter of 152.5 mm and an outer diameter of 167 mm. Got. Of the four film rolls obtained, the polyester film roll corresponding to the endmost part of the intermediate roll and the polyester film roll corresponding to the center part of the intermediate roll (corresponding to the endmost part of the intermediate roll in the film width direction) Table 3-2 and Table 4-2 show the characteristics of the film measured using a polyester film roll located next to the polyester film roll.
[実施例３１、３２]
表２−２の原料と製膜条件を適用し、中間ロール（中間製品）の幅を３．４ｍ、中間ロールをスリッターにて幅１０００ｍｍ×３本となるように切断しながら内径１５２．５ｍｍ、外径１６７ｍｍのコアに巻き取った以外は実施例１と同様にして二軸配向ポリエステルフィルムを得た。得られたフィルムロール３本のうち、中間ロールの中央部に対応するポリエステルフィルムロールと、中間ロールの最端部に対応するポリエステルフィルムロールを用いて測定されたフィルムの特性を表３―２および表４−２に示す。[Examples 31 and 32]
Applying the raw materials and film forming conditions shown in Table 2-2, the inner roll (intermediate product) has a width of 3.4 m, and the intermediate roll is cut by a slitter so that the width becomes 1000 mm × 3. A biaxially oriented polyester film was obtained in the same manner as in Example 1 except that it was wound around a core having an outer diameter of 167 mm. Of the three film rolls obtained, the film properties measured using the polyester film roll corresponding to the middle part of the intermediate roll and the polyester film roll corresponding to the endmost part of the intermediate roll are shown in Table 3-2 and Shown in Table 4-2.
[実施例３３]
第２の熱処理工程を２２５℃、第３の熱処理工程を２３５℃、熱処理を経たフィルムを２１５℃にて幅方向に５％の弛緩処理を実施した後に、２００℃にて長手方向に１．５％の弛緩処理を行い、続けて８０℃まで冷却した事以外は実施例１と同様にして二軸配向ポリエステルフィルムを得た。得られたフィルムの特性を表３−２、表４−２に示す。[Example 33]
The second heat treatment step was 225 ° C., the third heat treatment step was 235 ° C., and the heat-treated film was subjected to a relaxation treatment of 5% in the width direction at 215 ° C., and then at 200 ° C. in the longitudinal direction at 1.5%. % Biaxially-oriented polyester film was obtained in the same manner as in Example 1 except that it was subjected to a relaxation treatment of% and subsequently cooled to 80 ° C. The characteristics of the obtained film are shown in Table 3-2 and Table 4-2.
[実施例３４，３５]
表２−２の原料と製膜条件を適用した事以外は実施例３３と同様にして二軸配向ポリエステルフィルムを得た。得られたフィルムの特性を表３−２、表４−２に示す。[Examples 34 and 35]
A biaxially oriented polyester film was obtained in the same manner as in Example 33 except that the raw materials and film forming conditions in Table 2-2 were applied. The characteristics of the obtained film are shown in Table 3-2 and Table 4-2.
[実施例３６]
表２−３の原料と製膜条件を適用し、中間ロール（中間製品）をスリッターにて幅１２５０ｍｍ×４本となるように切断しながら内径１５２．５ｍｍ、外径１６７ｍｍのコアに巻き取った以外は実施例３３と同様にして二軸配向ポリエステルフィルムを得た。得られたフィルムロール４本のうち、中間ロールの最端部に対応するポリエステルフィルムロールと、中間ロールの中央部に対応するポリエステルフィルムロール（フィルム幅方向において、中間ロールの最端部に対応するポリエステルフィルムロールの隣に位置するポリエステルフィルムロール）を用いて測定されたフィルムの特性を表３−３および表４−３に示す。[Example 36]
The raw materials and film forming conditions shown in Table 2-3 were applied, and the intermediate roll (intermediate product) was wound around a core having an inner diameter of 152.5 mm and an outer diameter of 167 mm while being cut to a width of 1250 mm × 4 with a slitter. Otherwise in the same manner as in Example 33, a biaxially oriented polyester film was obtained. Of the four film rolls obtained, the polyester film roll corresponding to the endmost part of the intermediate roll and the polyester film roll corresponding to the center part of the intermediate roll (corresponding to the endmost part of the intermediate roll in the film width direction) Tables 3-3 and 4-3 show the characteristics of the film measured using a polyester film roll located next to the polyester film roll.
[実施例３７，３８]
表２−３の原料と製膜条件を適用し、中間ロール（中間製品）の幅を３．４ｍ、中間ロールをスリッターにて幅１０００ｍｍ×３本となるように切断しながら内径１５２．５ｍｍ、外径１６７ｍｍのコアに巻き取った以外は、実施例３３と同様にして二軸配向ポリエステルフィルムを得た。得られたフィルムロール３本のうち、中間ロールの中央部に対応するポリエステルフィルムロールと、最端部に対応するポリエステルフィルムロールを用いて測定されたフィルムの特性を表３−３および表４−３に示す。[Examples 37 and 38]
Applying the raw materials and film forming conditions shown in Table 2-3, the intermediate roll (intermediate product) has a width of 3.4 m, and the intermediate roll is cut by a slitter so that the width becomes 1000 mm × 3. A biaxially oriented polyester film was obtained in the same manner as in Example 33 except that the film was wound around a core having an outer diameter of 167 mm. Of the three film rolls obtained, the film properties measured using the polyester film roll corresponding to the middle part of the intermediate roll and the polyester film roll corresponding to the outermost part are shown in Tables 3-3 and 4- 3 shows.
[実施例３９]
表２−３の原料と製膜条件を適用した事以外は実施例２８と同様にして積層二軸配向ポリエステルフィルムを得た。得られたフィルムの特性を表３−３および表４−３に示す。[Example 39]
A laminated biaxially oriented polyester film was obtained in the same manner as in Example 28 except that the raw materials and film forming conditions shown in Table 2-3 were applied. The properties of the obtained film are shown in Table 3-3 and Table 4-3.
[比較例１〜１１]
表２−３の原料と製膜条件を適用した以外は実施例１と同様にして二軸配向ポリエステルフィルムを得た。得られたフィルムの特性を表３−３、表４−３に示す。[Comparative Examples 1 to 11]
A biaxially oriented polyester film was obtained in the same manner as in Example 1 except that the raw materials and film forming conditions shown in Table 2-3 were applied. The characteristics of the obtained film are shown in Tables 3-3 and 4-3.
[比較例１２，１３]
表２−３の原料と製膜条件を適用した以外は実施例３６と同様にして二軸配向ポリエステルフィルムを得た。得られたフィルムロール４本のうち、中間ロールの最端部に対応するポリエステルフィルムロールと、中間ロールの中央部に対応するポリエステルフィルムロール（フィルム幅方向において、中間ロールの最端部に対応するポリエステルフィルムロールの隣に位置するポリエステルフィルムロール）を用いて測定されたフィルムの特性を表３−３、表４−３に示す。[Comparative Examples 12 and 13]
A biaxially oriented polyester film was obtained in the same manner as in Example 36 except that the raw materials and film forming conditions shown in Table 2-3 were applied. Of the four film rolls obtained, the polyester film roll corresponding to the endmost part of the intermediate roll and the polyester film roll corresponding to the center part of the intermediate roll (corresponding to the endmost part of the intermediate roll in the film width direction) Tables 3-3 and 4-3 show the characteristics of the film measured using a polyester film roll located next to the polyester film roll.
[結果のまとめ]
リン酸アルカリ金属塩を０．１〜５．０モル／ｔ含有したポリエステル樹脂を原料として使用し、かつ末端カルボキシル基量２０当量／ｔ以下、固有粘度（ＩＶ）０．６５〜０．８０、ジエチレングリコール量が０．９〜３．０質量％の範囲であるポリエステル樹脂から構成されるポリエステルフィルムにおいて、耐湿熱性と生産性・加工性の全てが良好な結果となった。ジエチレングリコール（ＤＥＧ）含有量が上記範囲以下である比較例１では、安定した製膜を行うことが出来ず、耐湿熱性評価や超音波伝導速度測定を行うためのサンプルを得ることが出来なかった。長手方向および幅方向の延伸倍率・速度を低減させた比較例１０では、破れは低減されたサンプルを得ることが出来たが、超音波伝導速度が低下し耐加水分解性が悪い結果であった。また、ジエチレングリコール（ＤＥＧ）含有量が上記範囲以上である比較例２やリン酸アルカリ金属塩の含有量が範囲外である比較例３〜５、固有粘度が範囲外である比較例６，７、末端カルボキシル基量が範囲外である比較例８は、湿熱環境下での耐久性または生産性のどちらかが悪い結果となった。また、異物については、ポリエステル樹脂重合時のリン酸アルカリ金属塩添加時のポリエステルの温度およびエチレングリコール中のリン酸アルカリ金属塩の濃度のいずれも高い比較例９では、フィルム中にリン元素を含有する異物量が多く、また、ポリエステル樹脂重合時の出発原料としてテレフタル酸を用いた実施例５や、リン酸アルカリ金属塩の添加時のポリエステルの温度が高い実施例１６およびエチレングリコール中のリン酸アルカリ金属塩の濃度が高い実施例１７ではリンを含む異物量が合格範囲ではあるが増加する傾向が見られた。[Summary of results]
A polyester resin containing 0.1 to 5.0 mol / t of an alkali metal phosphate is used as a raw material, and the terminal carboxyl group amount is 20 equivalent / t or less, intrinsic viscosity (IV) 0.65 to 0.80, In the polyester film comprised from the polyester resin whose amount of diethylene glycol is in the range of 0.9 to 3.0% by mass, all of the heat-and-moisture resistance and productivity / workability were satisfactory. In Comparative Example 1 in which the diethylene glycol (DEG) content is not more than the above range, stable film formation could not be performed, and a sample for performing wet heat resistance evaluation and ultrasonic conduction velocity measurement could not be obtained. In Comparative Example 10 in which the stretching ratio and speed in the longitudinal direction and the width direction were reduced, a sample with reduced tearing could be obtained, but the ultrasonic conduction speed was lowered and the hydrolysis resistance was poor. . Further, Comparative Example 2 in which the diethylene glycol (DEG) content is not less than the above range, Comparative Examples 3 to 5 in which the content of the alkali metal phosphate is out of the range, Comparative Examples 6 and 7 in which the intrinsic viscosity is out of the range, In Comparative Example 8 in which the terminal carboxyl group amount was out of the range, either durability or productivity in a wet heat environment was poor. As for foreign matter, in Comparative Example 9 in which both the temperature of the polyester during addition of the alkali metal phosphate during polymerization of the polyester resin and the concentration of the alkali metal phosphate in ethylene glycol are high, the film contains a phosphorus element. Example 5 using terephthalic acid as a starting material during polymerization of polyester resin, Example 16 having a high polyester temperature when adding alkali metal phosphate, and phosphoric acid in ethylene glycol In Example 17 in which the concentration of the alkali metal salt was high, there was a tendency that the amount of foreign matter containing phosphorus was in the acceptable range but increased.
フィルム特性としては、全方位における超音波伝導速度の平均値が２．２０ｋｍ／秒以上である場合は、耐湿熱性が良好な結果となり、２．２０ｋｍ／秒に満たない比較例２、５、９、１１、１２、１３では耐湿熱時の耐久性が悪化した。さらに最大値と最小値の比率が１．００〜１．３０の範囲内である場合は、特に配向軸が１０°以上ずれている、すなわち角度θが１０°〜８０°の範囲となる端部位置においても耐湿熱特性の方向によるバラツキが軽減され、超音波伝導速度が最小となる方向においても耐湿熱性が保持されており、さらに好ましい結果となった。これらは、前記［１０］で示される長手方向延伸工程、幅方向延伸工程および中間工程を有することで、製品部分として幅５ｍの広幅フィルムを製造した場合の端部位置でも上記の特性を満たすことが可能となった。 As film properties, when the average value of the ultrasonic conduction velocity in all directions is 2.20 km / second or more, the results of good heat and humidity resistance are obtained, and Comparative Examples 2, 5, 9 which are less than 2.20 km / second. 11, 12, 13, the durability at the time of moisture and heat resistance deteriorated. Further, when the ratio between the maximum value and the minimum value is in the range of 1.00 to 1.30, particularly the end portion where the orientation axis is shifted by 10 ° or more, that is, the angle θ is in the range of 10 ° to 80 °. Even in the position, the variation due to the direction of the moisture and heat resistance is reduced, and the moisture and heat resistance is maintained even in the direction where the ultrasonic conduction velocity is minimized. These include the longitudinal direction stretching step, the width direction stretching step and the intermediate step shown in the above [10], and thus satisfy the above characteristics even at the end position when a wide film having a width of 5 m is manufactured as a product part. Became possible.
熱寸法安定性の観点では、実施例３３〜３９に示されるように、Ｔｍｅｔａが２２０℃以上となるような高い温度での熱処理と長手方向の緩和処理を組み合わせることで、特に長手方向の熱収縮率が低減された良好な特性となっている。なお従来技術ではこのように高温にてフィルム中の分子配向を緩和させると耐湿熱性が大幅に悪化するが、本発明の技術を用いる事で耐湿熱性も十分高い状態が維持可能で、従来技術では非常に困難であった耐久性と熱寸法安定性の両立が可能となった。 From the viewpoint of thermal dimensional stability, as shown in Examples 33 to 39, a combination of heat treatment at a high temperature at which Tmeta is 220 ° C. or higher and longitudinal relaxation treatment, in particular, thermal shrinkage in the longitudinal direction. It has good characteristics with a reduced rate. In the prior art, when the molecular orientation in the film is relaxed at such a high temperature as described above, the heat and humidity resistance is greatly deteriorated. However, by using the technology of the present invention, the state of sufficiently high moisture and heat resistance can be maintained. It was possible to achieve both durability and thermal dimensional stability, which were very difficult.
また、実施例２７、２８、３９については、ルチル型二酸化チタンを含有することで、フィルムの隠蔽性や紫外線耐久性が向上しており、特に太陽電池封止フィルム用途など屋外で使用される用途の場合に好ましい。また実施例２８については、厚さ方向にルチル型二酸化チタンの含有量多い層と少ない層が積層された構成となっており、触媒活性の高い二酸化チタン含有時においても、特に実施例３９の様に熱寸法安定性を向上させるために厳しい成膜条件を適用した場合でも高い耐湿熱性が保持されており、非常に好ましい結果であった。 Moreover, about Example 27,28,39, the concealability of a film and ultraviolet-ray durability are improving by containing rutile type titanium dioxide, The use used outdoors, such as a solar cell sealing film use especially. It is preferable in the case of. Further, Example 28 has a structure in which a layer containing a large amount of rutile titanium dioxide and a layer containing a small amount of rutile titanium dioxide are laminated in the thickness direction. In addition, even when severe film forming conditions were applied to improve thermal dimensional stability, high heat and humidity resistance was maintained, which was a very favorable result.
なお、表において、「ＭＡＸ」は「フィルムの超音波伝導速度の最大値」を、「ＭＩＮ」は「フィルムの超音波伝導速度の最小値」を、「ＭＡＸ方向」は「フィルムの超音波伝導速度が最大値を示す方向」を、「ＭＩＮ方向」は「フィルムの超音波伝導速度が最小値を示す方向」をそれぞれ示す。 In the table, “MAX” is “maximum value of ultrasonic conduction velocity of film”, “MIN” is “minimum value of ultrasonic conduction velocity of film”, and “MAX direction” is “ultrasonic conduction velocity of film”. The direction in which the speed shows the maximum value is shown, and the “MIN direction” shows the “direction in which the ultrasonic conduction speed of the film shows the minimum value”.
また、表において「中間ロール中央部」と「中間ロール端部」に分けて記載されていない特性は、「中間ロール中央部」にて測定された値と「中間ロール端部」にて測定された値が同じであった。 In addition, the characteristics that are not described separately in the table as “intermediate roll center” and “intermediate roll end” are measured at “intermediate roll center” and “intermediate roll end”. The values were the same.
本発明にかかる耐久性ポリエステルフィルムは、高温高湿下での耐久性及び生産性に優れた内部欠陥が少ないフィルムであるため、太陽電池封止シート、銅貼り積層板、粘着テープ、フレキシブルプリント基板、メンブレンスイッチ、面状発熱体、もしくはフラットケーブルなどの電気絶縁材料、コンデンサ用材料、自動車用材料、建築材料を初めとした耐久性が重視されるような用途に好適に使用することができる Since the durable polyester film according to the present invention is a film having excellent durability and productivity under high temperature and high humidity, and having few internal defects, it is a solar cell encapsulating sheet, a copper-clad laminate, an adhesive tape, and a flexible printed circuit board. It can be suitably used for applications where durability is important, including electrical insulation materials such as membrane switches, sheet heating elements, or flat cables, capacitor materials, automotive materials, and building materials.
Claims (13)
（１）長手方向に延伸速度２,０００％／秒〜１０,０００％／秒にて３．０〜４．５倍延伸する工程
（２）幅方向に３．５〜４．５倍延伸し、かつ幅方向延伸工程開始前のフィルム幅をＷ０、幅方向延伸工程の中間点でのフィルム幅をＷ１、幅方向延伸工程終了後でのフィルム幅をＷ２とした場合、以下の式（Ａ）を満たす工程
６０ ≦ １００×（Ｗ１−Ｗ０）／（Ｗ２−Ｗ０）≦ ８０ ・・・ 式（Ａ）
（３）幅方向延伸工程と熱処理工程の間に中間工程を有し、該中間工程の温度が幅方向延伸工程の最終区間の温度：Ｔｓ（℃）と熱処理工程最初の区間にあたる第１の熱処理工程温度：Ｔｈ（℃）との間の温度であり、かつ中間工程をフィルムが通過する時間をＳｍ（秒）とした時に以下式（Ｂ）を満たす工程
（Ｔｈ−Ｔｓ）／Ｓｍ ≦ ５０ ・・・ 式（Ｂ）A step of melting a polyester resin containing 0.1 mol / t or more and 5.0 mol / t or less of an alkali metal phosphate and molding it into a sheet, and the longitudinal direction described in (1) to (3) below. It has a stretching process in the width direction and a heat treatment process, the intrinsic viscosity (IV) of the polyester resin constituting the film is 0.65 to 0.80, the amount of terminal carboxyl groups is 20 equivalents / t or less, and the diethylene glycol content is 0.00. The manufacturing method of the biaxially-oriented polyester film which is 9 mass% or more and 3.0 mass% or less, and whose average ultrasonic conduction velocity of a film is 2.20 km / sec or more.
(1) Step of stretching 3.0 to 4.5 times in the longitudinal direction at a stretching speed of 2,000% / second to 10,000% / second (2) Stretching to 3.5 to 4.5 times in the width direction When the film width before starting the width direction stretching step is W0, the film width at the midpoint of the width direction stretching step is W1, and the film width after the end of the width direction stretching step is W2, the following formula (A) The process which satisfy | fills 60 <= 100 * (W1-W0) / (W2-W0) <= 80 ... Formula (A)
(3) There is an intermediate step between the width direction stretching step and the heat treatment step, and the temperature of the intermediate step is the temperature of the last section of the width direction stretching step: Ts (° C.) and the first heat treatment corresponding to the first section of the heat treatment step Process temperature: a temperature between Th (° C.) and satisfying the following formula (B) when the time for the film to pass through the intermediate process is Sm (seconds) (Th−Ts) / Sm ≦ 50 ..Formula (B)
（４）前記ポリエステル樹脂を合成する重合工程において、リン酸アルカリ金属塩を添加する事
（５）リン酸アルカリ金属塩をジオール成分に溶解または混合し、リン酸アルカリ金属塩の濃度が１質量％以下の溶液またはスラリー状態として添加する事
（６）前記リン酸アルカリ金属塩を添加する時の反応物の温度が２５０℃以下である事。The manufacturing method of the biaxially-oriented polyester film of Claim 10 manufactured by the process in which the polyester resin containing the said alkali metal phosphate is satisfy | filled following (4)-(6).
(4) In the polymerization step of synthesizing the polyester resin, adding an alkali metal phosphate (5) dissolving or mixing the alkali metal phosphate in the diol component, the concentration of the alkali metal phosphate being 1% by mass (6) The temperature of the reaction product when adding the alkali metal phosphate is 250 ° C. or lower.
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| JP5836775B2 (en) * | 2010-12-15 | 2015-12-24 | 富士フイルム株式会社 | Polyester film manufacturing method, polyester film for solar cell, and solar cell power generation module |
| JP5765639B2 (en) * | 2011-03-04 | 2015-08-19 | 東レ株式会社 | POLYESTER COMPOSITION AND FILM, SHEET-LIKE STRUCTURE, ELECTRIC INSULATING SHEET, SOLAR CELL BACK SHEET, AND PRODUCTION METHODS |
| JP5998541B2 (en) * | 2012-03-13 | 2016-09-28 | 東レ株式会社 | Method for producing polyester composition |
-
2013
- 2013-07-16 JP JP2013553171A patent/JP5979157B2/en not_active Expired - Fee Related
- 2013-07-16 KR KR1020147030283A patent/KR102131627B1/en active IP Right Grant
- 2013-07-16 CN CN201380028403.0A patent/CN104350090B/en not_active Expired - Fee Related
- 2013-07-16 WO PCT/JP2013/069295 patent/WO2014021095A1/en active Application Filing
- 2013-07-23 TW TW102126192A patent/TWI616311B/en not_active IP Right Cessation
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014088541A (en) * | 2012-10-02 | 2014-05-15 | Toray Ind Inc | Durable polyester film and method for producing the same, and film for sealing solar cell using the same |
| JP2014156579A (en) * | 2013-01-18 | 2014-08-28 | Toray Ind Inc | Biaxially oriented polyester film and method for manufacturing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI616311B (en) | 2018-03-01 |
| KR102131627B1 (en) | 2020-07-08 |
| TW201406526A (en) | 2014-02-16 |
| KR20150035686A (en) | 2015-04-07 |
| CN104350090A (en) | 2015-02-11 |
| WO2014021095A1 (en) | 2014-02-06 |
| CN104350090B (en) | 2017-03-01 |
| JPWO2014021095A1 (en) | 2016-07-21 |
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