JP4944419B2 - Biaxially oriented polyester film for solid polymer electrolyte membrane reinforcement - Google Patents
Biaxially oriented polyester film for solid polymer electrolyte membrane reinforcement Download PDFInfo
- Publication number
- JP4944419B2 JP4944419B2 JP2005291548A JP2005291548A JP4944419B2 JP 4944419 B2 JP4944419 B2 JP 4944419B2 JP 2005291548 A JP2005291548 A JP 2005291548A JP 2005291548 A JP2005291548 A JP 2005291548A JP 4944419 B2 JP4944419 B2 JP 4944419B2
- Authority
- JP
- Japan
- Prior art keywords
- electrolyte membrane
- polyester film
- polymer electrolyte
- oriented polyester
- solid polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000012528 membrane Substances 0.000 title claims description 77
- 229920006267 polyester film Polymers 0.000 title claims description 51
- 239000005518 polymer electrolyte Substances 0.000 title claims description 39
- 239000007787 solid Substances 0.000 title claims description 35
- 230000002787 reinforcement Effects 0.000 title description 2
- -1 polyethylene naphthalene dicarboxylate Polymers 0.000 claims description 54
- 230000003014 reinforcing effect Effects 0.000 claims description 30
- 239000004925 Acrylic resin Substances 0.000 claims description 19
- 229920000178 Acrylic resin Polymers 0.000 claims description 19
- 125000003368 amide group Chemical group 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 9
- 230000014759 maintenance of location Effects 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 2
- 239000010408 film Substances 0.000 description 64
- 239000003792 electrolyte Substances 0.000 description 48
- 239000010410 layer Substances 0.000 description 39
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 18
- 230000007062 hydrolysis Effects 0.000 description 18
- 238000006460 hydrolysis reaction Methods 0.000 description 18
- 239000000446 fuel Substances 0.000 description 15
- 238000000576 coating method Methods 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- 229920000728 polyester Polymers 0.000 description 13
- 229920000642 polymer Polymers 0.000 description 12
- 239000000178 monomer Substances 0.000 description 11
- 239000002245 particle Substances 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 10
- 238000007334 copolymerization reaction Methods 0.000 description 10
- 239000012779 reinforcing material Substances 0.000 description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 9
- 238000009792 diffusion process Methods 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 230000037303 wrinkles Effects 0.000 description 7
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 238000009998 heat setting Methods 0.000 description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
- 230000002093 peripheral effect Effects 0.000 description 6
- 229920000515 polycarbonate Polymers 0.000 description 6
- 239000004417 polycarbonate Substances 0.000 description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- 239000005020 polyethylene terephthalate Substances 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 239000012790 adhesive layer Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 229920006243 acrylic copolymer Polymers 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 4
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 4
- 238000005809 transesterification reaction Methods 0.000 description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 3
- 229920000557 Nafion® Polymers 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- WPUMVKJOWWJPRK-UHFFFAOYSA-N naphthalene-2,7-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=CC2=CC(C(=O)O)=CC=C21 WPUMVKJOWWJPRK-UHFFFAOYSA-N 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 2
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000002737 fuel gas Substances 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000003014 ion exchange membrane Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- DNTMQTKDNSEIFO-UHFFFAOYSA-N n-(hydroxymethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCO DNTMQTKDNSEIFO-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920002215 polytrimethylene terephthalate Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 150000003457 sulfones Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- PGRNEGLBSNLPNP-UHFFFAOYSA-N 1,6-dichloro-3-methylhex-1-ene Chemical compound ClC=CC(C)CCCCl PGRNEGLBSNLPNP-UHFFFAOYSA-N 0.000 description 1
- BDGCRGQZVSMJLJ-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diol;hexane-1,6-diol Chemical compound OCC(C)(C)CO.OCCCCCCO BDGCRGQZVSMJLJ-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 1
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 1
- IJSVVICYGLOZHA-UHFFFAOYSA-N 2-methyl-n-phenylprop-2-enamide Chemical compound CC(=C)C(=O)NC1=CC=CC=C1 IJSVVICYGLOZHA-UHFFFAOYSA-N 0.000 description 1
- XFEGRFIENDJTCK-UHFFFAOYSA-N 2-phenyl-2,3-dihydroindene-1,1-dicarboxylic acid Chemical compound C1C2=CC=CC=C2C(C(=O)O)(C(O)=O)C1C1=CC=CC=C1 XFEGRFIENDJTCK-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- WMRCTEPOPAZMMN-UHFFFAOYSA-N 2-undecylpropanedioic acid Chemical compound CCCCCCCCCCCC(C(O)=O)C(O)=O WMRCTEPOPAZMMN-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
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- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
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- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
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- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- HXBPYFMVGFDZFT-UHFFFAOYSA-N allyl isocyanate Chemical compound C=CCN=C=O HXBPYFMVGFDZFT-UHFFFAOYSA-N 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 229960003237 betaine Drugs 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
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- 239000007822 coupling agent Substances 0.000 description 1
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- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- MHKBNMVNEQRFFF-UHFFFAOYSA-N cyclohexane;methanediol Chemical compound OCO.C1CCCCC1 MHKBNMVNEQRFFF-UHFFFAOYSA-N 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- GYUVMLBYMPKZAZ-UHFFFAOYSA-N dimethyl naphthalene-2,6-dicarboxylate Chemical compound C1=C(C(=O)OC)C=CC2=CC(C(=O)OC)=CC=C21 GYUVMLBYMPKZAZ-UHFFFAOYSA-N 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical group [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- WARQUFORVQESFF-UHFFFAOYSA-N isocyanatoethene Chemical compound C=CN=C=O WARQUFORVQESFF-UHFFFAOYSA-N 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000007759 kiss coating Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 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
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-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
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920006289 polycarbonate film Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- GGUBFICZYGKNTD-UHFFFAOYSA-N triethyl phosphonoacetate Chemical compound CCOC(=O)CP(=O)(OCC)OCC GGUBFICZYGKNTD-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 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
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Description
本発明は、機械的強度、耐熱寸法安定性および耐加水分解性に優れ、固体高分子電解質型燃料電池の固体高分子電解質膜の補強材に適した二軸配向ポリエステルフィルムに関する。更に詳しくは、機械的強度、耐熱寸法安定性および耐加水分解性に優れ、固体高分子電解質膜および拡散層との接着性も兼ね備えた固体高分子電解質膜補強用二軸配向ポリエステルフィルムに関する。 The present invention relates to a biaxially oriented polyester film that is excellent in mechanical strength, heat-resistant dimensional stability, and hydrolysis resistance and is suitable as a reinforcing material for a solid polymer electrolyte membrane of a solid polymer electrolyte fuel cell. More specifically, the present invention relates to a biaxially oriented polyester film for reinforcing a solid polymer electrolyte membrane that is excellent in mechanical strength, heat-resistant dimensional stability and hydrolysis resistance, and also has adhesion to a solid polymer electrolyte membrane and a diffusion layer.
近年、環境問題の観点から燃料電池の開発が積極的に行われている。使用される電解質の種類により、固体高分子電解質型，りん酸型，溶融炭酸塩型，固体酸化物型などの各種の燃料電池が知られている。これらの中でも、固体高分子電解質型燃料電池は反応温度が比較的低い点が注目されている。 In recent years, fuel cells have been actively developed from the viewpoint of environmental problems. Various types of fuel cells such as a solid polymer electrolyte type, a phosphoric acid type, a molten carbonate type, and a solid oxide type are known depending on the type of electrolyte used. Among these, solid polymer electrolyte fuel cells are attracting attention because of their relatively low reaction temperatures.
固体高分子電解質型燃料電池は、分子中にプロトン（水素イオン）交換基を有する高分子樹脂膜を飽和状態にまで含水させた場合に、プロトン導電性電解質として機能することを利用した燃料電池である。固体高分子型燃料電池は、高分子イオン交換膜（陽イオン交換膜）からなる高分子電解質膜と、この電解質の両側にそれぞれ配置されるアノード側電極およびカソード側電極とを有した燃料電池構造体（燃料電池セル）を、セパレータによって挟持することにより構成されている。アノード側電極に供給された燃料ガス、例えば、水素は、触媒電極上で水素イオン化され、適度に加湿された高分子電解質膜を介してカソード側電極側へと移動する。その間に生じた電子が外部回路に取り出され、直流の電気エネルギとして利用される。カソード側電極には、酸化剤ガス、例えば、酸素ガスあるいは空気が供給されているために、このカソード側電極において、前記水素イオン、前記電子および酸素が反応して水が生成される。 A solid polymer electrolyte fuel cell is a fuel cell that utilizes the function as a proton conductive electrolyte when a polymer resin membrane having proton (hydrogen ion) exchange groups in the molecule is hydrated to a saturated state. is there. A solid polymer type fuel cell has a polymer electrolyte membrane made of a polymer ion exchange membrane (cation exchange membrane), and a fuel cell structure having an anode side electrode and a cathode side electrode respectively disposed on both sides of the electrolyte. The body (fuel cell) is sandwiched between separators. The fuel gas, for example, hydrogen supplied to the anode side electrode is hydrogen ionized on the catalyst electrode and moves to the cathode side electrode side through the polymer electrolyte membrane that is appropriately humidified. Electrons generated in the meantime are taken out to an external circuit and used as direct current electric energy. Since the oxidant gas, for example, oxygen gas or air is supplied to the cathode side electrode, water reacts with the hydrogen ions, the electrons and oxygen to generate water.
高分子電解質膜として、パーフルオロスルホン酸樹脂膜（例えば「Ｎａｆｉｏｎ」（デュポン社の登録商標））が使用されており、高分子イオン交換膜の抵抗率を小さくして高い発電効率が得られるようにするために、通常５０℃〜１００℃程度の温度条件で運転される。この高分子電解質膜には、導電率の向上や低コスト化が求められており、極めて薄いフィルム状の素材であることから、取扱いが難しく、それぞれの電極との接合時、複数の単電池を積層してスタックとして組み合わせる組み立て作業時等の際にその周縁部にしわが発生してしまうことがしばしば生じる。また、しわなどが全くない状態であっても、スタックの構成部材の中で最も機械的強度が低いことが問題となっている。 As the polymer electrolyte membrane, a perfluorosulfonic acid resin membrane (for example, “Nafion” (a registered trademark of DuPont)) is used, so that high power generation efficiency can be obtained by reducing the resistivity of the polymer ion exchange membrane. In order to achieve this, it is normally operated under a temperature condition of about 50 ° C to 100 ° C. This polymer electrolyte membrane is required to improve conductivity and reduce costs, and because it is an extremely thin film material, it is difficult to handle, and when joining to each electrode, a plurality of single cells are used. Frequently, wrinkles occur at the peripheral edge during assembly operations such as stacking and combining as a stack. Further, even when there are no wrinkles or the like, there is a problem that the mechanical strength is the lowest among the constituent members of the stack.
そこで、特開平７−６５８４７号公報には、燃料電池セルの周縁部に、電解質膜を機械的に補強するとともに、電解質膜との境界面から燃料ガスや酸化剤ガスが漏れないように気密に接合された補強枠を備えること、また補強枠として、動作温度においても所要の機械的強度，耐食性等を有するものが好ましく、一例としてポリカーボネート、その他ポリエチレンテレフタレート、ガラス繊維強化エポキシ樹脂等の熱硬化性のプラスチック、チタン等の耐食性金属、あるいはカーボンが開示されている。また、特開平１０−１９９５５１号公報には、固体高分子電解質膜の両面に固定された多孔質体の外周端部に、気密性を有した枠部材を用いることが開示されており、補強材の具体的な材料としては、ポリカーボネート、エチレンプロピレン共重合体、ポリエステル、変性ポリフェニレンオキサイド、ポリフェニレンサルファイド、またはアクリロニトリルスチレン等の熱可塑性樹脂が挙げられている。 Therefore, in JP-A-7-65847, an electrolyte membrane is mechanically reinforced at the peripheral portion of the fuel cell, and the fuel gas and the oxidant gas are airtight so as not to leak from the interface with the electrolyte membrane. It is preferable to provide a bonded reinforcing frame, and as the reinforcing frame, those having required mechanical strength, corrosion resistance, etc. even at operating temperature are preferable. For example, thermosetting properties such as polycarbonate, other polyethylene terephthalate, glass fiber reinforced epoxy resin, etc. In other words, plastics, corrosion resistant metals such as titanium, or carbon are disclosed. Japanese Patent Application Laid-Open No. 10-199551 discloses that a frame member having airtightness is used at the outer peripheral end of a porous body fixed on both surfaces of a solid polymer electrolyte membrane. Specific examples of the material include thermoplastic resins such as polycarbonate, ethylene propylene copolymer, polyester, modified polyphenylene oxide, polyphenylene sulfide, and acrylonitrile styrene.
特開平７−６５８４７号公報には、具体的な補強枠部材としてポリカーボネート製のものが例示されているが、ポリカーボネートを用いた場合、５０℃〜１００℃程度の温度条件における耐熱寸法安定性に優れるものの、機械的強度は他の耐熱性樹脂フィルムに較べて低いことから薄肉化に伴い補強効果が低下するため、補強材として更なる補強効果が望まれている。
また、膜電極接合体を作製する際に１４０〜１６０℃前後の温度で熱プレス処理を行う工程があり、ポリカーボネートからなる補強枠部材を用いた場合、加工温度によってはポリカーボネート自身の耐熱寸法安定性が十分ではないことがある。またポリエチレンテレフタレートを補強材として用いた場合も、高温で加工する際、耐熱寸法安定性が十分ではなく、また高湿状態で使用されるため耐加水分解性が十分でないことがあった。そこで、高い機械的強度を有し、耐熱寸法安定性、耐加水分解性に優れた、薄肉フィルムでもより高い補強効果を有する材料が望まれているのが現状である。
Japanese Patent Laid-Open No. 7-65847 discloses a concrete reinforcing frame member made of polycarbonate. However, when polycarbonate is used, it is excellent in heat-resistant dimensional stability under a temperature condition of about 50 ° C. to 100 ° C. However, since the mechanical strength is lower than that of other heat-resistant resin films, the reinforcing effect is reduced as the thickness is reduced. Therefore, a further reinforcing effect is desired as a reinforcing material.
In addition, when a membrane electrode assembly is produced, there is a step of performing a hot press treatment at a temperature of about 140 to 160 ° C. When a reinforcing frame member made of polycarbonate is used, depending on the processing temperature, the heat-resistant dimensional stability of the polycarbonate itself May not be enough. Also, when polyethylene terephthalate is used as a reinforcing material, the heat-resistant dimensional stability is not sufficient when processed at a high temperature, and the hydrolysis resistance may not be sufficient because it is used in a high humidity state. Therefore, there is a demand for a material having high mechanical strength, excellent heat-resistant dimensional stability and hydrolysis resistance, and having a higher reinforcing effect even with a thin film.
本発明の目的は、かかる従来技術の課題を解消し、固体高分子電解質型燃料電池の電解質膜の補強材として高い機械的強度および加工温度・使用温度域において優れた耐熱寸法安定性を有し、また高湿度の使用環境において優れた加水分解性を有する、固体高分子電解質膜の補強材として適した二軸配向ポリエステルフィルムを提供することにある。更に本発明の目的は、機械的強度、耐熱寸法安定性および耐加水分解性に優れ、固体高分子電解質膜および拡散層との接着性も兼ね備えた高分子電解質膜補強用二軸配向ポリエステルフィルムを提供することにある。 The object of the present invention is to eliminate such problems of the prior art and to have high mechanical strength as a reinforcing material for the electrolyte membrane of a solid polymer electrolyte fuel cell and excellent heat-resistant dimensional stability in the processing temperature / use temperature range. Another object of the present invention is to provide a biaxially oriented polyester film having excellent hydrolyzability in a high humidity use environment and suitable as a reinforcing material for a solid polymer electrolyte membrane. Furthermore, an object of the present invention is to provide a biaxially oriented polyester film for reinforcing a polymer electrolyte membrane that has excellent mechanical strength, heat-resistant dimensional stability and hydrolysis resistance, and also has adhesion to a solid polymer electrolyte membrane and a diffusion layer. It is to provide.
本発明者らは、前記課題を解決するために鋭意検討した結果、ポリエチレンナフタレンジカルボキシレートを主たる成分とする層を含む少なくとも１層からなる二軸配向ポリエステルフィルムは、機械的強度に優れるため高分子電解質膜の厚さを非常に薄くしても組み立て作業時にしわが発生せず電解質膜のハンドリング性が向上し、また耐熱寸法安定性に優れることから、５０〜１００℃の使用温度域および１６０℃前後の高温加工温度において、電解質膜に負荷をかけることなく機械的強度を保つことができること、加水分解性に優れ、高湿度の使用環境でも長期に渡り高い機械的強度を維持できることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors have found that a biaxially oriented polyester film comprising at least one layer including a layer containing polyethylene naphthalene dicarboxylate as a main component is excellent in mechanical strength. Even if the thickness of the molecular electrolyte membrane is very thin, wrinkles are not generated during the assembly operation, the handling property of the electrolyte membrane is improved, and the heat resistant dimensional stability is excellent. We found that mechanical strength can be maintained without applying a load to the electrolyte membrane at high temperature processing temperatures around ℃, excellent hydrolyzability, and high mechanical strength can be maintained for a long time even in high humidity usage environments. The present invention has been completed.
すなわち本発明によれば、本発明の目的は、ポリエチレンナフタレンジカルボキシレートを主たる成分とする層を含む少なくとも１層からなり、縦方向および横方向のヤング率がそれぞれ５５００ＭＰａ以上である固体高分子電解質膜補強部材用二軸配向ポリエステルフィルムによって達成される。 That is, according to the present invention, an object of the present invention, Ri Do at least one layer comprising a layer composed mainly of polyethylene naphthalene dicarboxylate, longitudinal and transverse direction Young's modulus solid high Ru der least 5500MPa, respectively This is achieved by a biaxially oriented polyester film for a molecular electrolyte membrane reinforcing member .
また、本発明の固体高分子電解質膜補強部材用二軸配向ポリエステルフィルムは、その好ましい態様として、全繰り返し構造単位のモル数を基準としてエチレン−２，６−ナフタレンジカルボキシレートを８０モル％以上含むこと、下記式（１）で表される破断強度保持率が５０％になるのに要する時間が１００時間以上であること、
破断強度保持率（％）＝（破断強度Ｘ／初期の破断強度Ｘ0）×１００ ・・・(１)
（式中、破断強度Ｘは、１２１℃、２ａｔｍ、１００％ＲＨの条件で所定時間処理後の破断強度、破断強度Ｘ0は処理前の初期の破断強度をそれぞれ表す）
１００℃、３０分熱処理後の縦方向および横方向の熱収縮率がそれぞれ０．５％以下であること、１６０℃、１０分熱処理後の縦方向および横方向の熱収縮率がそれぞれ０．５％以下であること、の少なくともいずれか一つを具備するものも包含する。
Moreover, the biaxially oriented polyester film for a solid polymer electrolyte membrane reinforcing member of the present invention has, as a preferred embodiment, 80 mol% or more of ethylene-2,6-naphthalenedicarboxylate based on the number of moles of all repeating structural units. including it, that the time required for the breaking strength retention represented by the following following formula (1) is 50% is not less than 100 hours,
Breaking strength retention ratio (%) = (breaking strength X / initial breaking strength X 0 ) × 100 (1)
(In the formula, the breaking strength X represents the breaking strength after treatment for a predetermined time under the conditions of 121 ° C., 2 atm, and 100% RH, and the breaking strength X 0 represents the initial breaking strength before the treatment)
The heat shrinkage in the vertical and horizontal directions after heat treatment at 100 ° C. for 30 minutes is 0.5% or less, respectively, and the heat shrinkage in the vertical and horizontal directions after heat treatment at 160 ° C. for 10 minutes is 0.5%, respectively. % Or less is also included.
また本発明の固体高分子電解質膜補強部材用二軸配向ポリエステルフィルムは、ポリエチレンナフタレンジカルボキシレートを主たる成分とする層の少なくとも一方の面にアクリル樹脂を含有する易接着層が積層されていること、アクリル樹脂がアミド基を含有するアクリル樹脂であること、易接着層がポリエチレンナフタレンジカルボキシレートを主たる成分とする層の結晶配向が完了する前に塗布されてなること、の少なくともいずれか一つを具備するものも好ましい態様として包含する。 In the biaxially oriented polyester film for solid polymer electrolyte membrane reinforcing member of the present invention, an easy-adhesion layer containing an acrylic resin is laminated on at least one surface of a layer mainly composed of polyethylene naphthalene dicarboxylate. At least one of the following: the acrylic resin is an acrylic resin containing an amide group, and the easy-adhesion layer is applied before the crystal orientation of the layer mainly composed of polyethylene naphthalene dicarboxylate is completed. What comprises is also included as a preferable aspect.
本発明によれば、ポリエチレンナフタレンジカルボキシレートを主たる成分とする層を含む少なくとも１層からなる二軸配向ポリエステルフィルムは、機械的強度、耐熱寸法安定性および耐加水分解性に優れており、固体高分子電解質型燃料電池の高分子電解質膜の補強材として用いることによって、高分子電解質膜の厚さを非常に薄くしても組み立て作業時にしわが発生せず電解質膜のハンドリング性が向上し、使用温度域および高温加工温度で電解質膜に負荷をかけることなく機械的強度を保つことができること、高湿度の使用環境でも長期に渡り高い機械的強度を維持できることから、固体高分子電解質膜補強用フィルムとして有用であり、該フィルムを固体高分子電解質膜の補強材として含む固体高分子電解質型燃料電池を提供することができ、その工業的価値は極めて高い。 According to the present invention, the biaxially oriented polyester film comprising at least one layer including a layer mainly composed of polyethylene naphthalene dicarboxylate is excellent in mechanical strength, heat-resistant dimensional stability and hydrolysis resistance, and is solid. By using it as a reinforcing material for the polymer electrolyte membrane of the polymer electrolyte fuel cell, even if the thickness of the polymer electrolyte membrane is very thin, wrinkles do not occur during assembly work, and the handling properties of the electrolyte membrane are improved. Because it can maintain mechanical strength without applying a load to the electrolyte membrane in the operating temperature range and high temperature processing temperature, and can maintain high mechanical strength for a long time even in high humidity usage environment, it is for solid polymer electrolyte membrane reinforcement Provided is a solid polymer electrolyte fuel cell that is useful as a film and contains the film as a reinforcing material for a solid polymer electrolyte membrane Door can be, its industrial value is extremely high.
以下、本発明を詳しく説明する。
＜ポリエチレンナフタレンジカルボキシレート＞
本発明のフィルムを構成するポリエチレンナフタレンジカルボキシレートは、主たるジカルボン酸成分としてナフタレンジカルボン酸が用いられ、主たるグリコール成分としてエチレングリコールが用いられる。ナフタレンジカルボン酸としては、たとえば２，６−ナフタレンジカルボン酸、２，７−ナフタレンジカルボン酸、１，５−ナフタレンジカルボン酸を挙げることができ、これらの中で２，６−ナフタレンジカルボン酸が好ましい。ここで「主たる」とは、本発明のフィルムの成分であるポリマーの構成成分において全繰返し単位の８０モル％以上、好ましくは９０モル％以上、さらに好ましくは９５モル％以上を意味する。
The present invention will be described in detail below.
<Polyethylene naphthalene dicarboxylate>
In the polyethylene naphthalene dicarboxylate constituting the film of the present invention, naphthalene dicarboxylic acid is used as the main dicarboxylic acid component, and ethylene glycol is used as the main glycol component. Examples of naphthalenedicarboxylic acid include 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, and 1,5-naphthalenedicarboxylic acid. Among these, 2,6-naphthalenedicarboxylic acid is preferable. Here, “main” means 80 mol% or more, preferably 90 mol% or more, and more preferably 95 mol% or more of all repeating units in the polymer constituting component of the film of the present invention.
本発明のポリエチレンナフタレンジカルボキシレートは、共重合成分が２０モル％以内のポリエチレンナフタレンジカルボキシレート共重合体であってもよい。ポリエチレンナフタレンジカルボキシレートがコポリマーである場合、コポリマーを構成する共重合成分としては、分子内に２つのエステル形成性官能基を有する化合物を用いることができ、かかる化合物としては例えば、蓚酸、アジピン酸、フタル酸、セバシン酸、ドデカンジカルボン酸、イソフタル酸、テレフタル酸、１，４−シクロヘキサンジカルボン酸、４，４’−ジフェニルジカルボン酸、フェニルインダンジカルボン酸、２，７−ナフタレンジカルボン酸、テトラリンジカルボン酸、デカリンジカルボン酸、ジフェニルエーテルジカルボン酸等の如きジカルボン酸、ｐ−オキシ安息香酸、ｐ−オキシエトキシ安息香酸の如きオキシカルボン酸、或いはトリメチレングリコール、テトラメチレングリコール、ヘキサメチレングリコール、シクロヘキサンメチレングリコール、ネオペンチルグリコール、ビスフェノールスルホンのエチレンオキサイド付加物、ビスフェノールＡのエチレンオキサイド付加物、ジエチレングリコール、ポリエチレンオキシドグリコールの如き２価アルコールを好ましく用いることができる。これらの化合物は１種のみ用いてもよく、２種以上を用いることができる。またこれらの中で好ましくは酸成分としては、イソフタル酸、テレフタル酸、４，４’−ジフェニルジカルボン酸、２，７−ナフタレンジカルボン酸、ｐ−オキシ安息香酸であり、グリコール成分としてはトリメチレングリコール、ヘキサメチレングリコールネオペンチルグリコール、ビスフェノールスルホンのエチレンオキサイド付加物である。 The polyethylene naphthalene dicarboxylate of the present invention may be a polyethylene naphthalene dicarboxylate copolymer having a copolymer component within 20 mol%. When the polyethylene naphthalene dicarboxylate is a copolymer, a compound having two ester-forming functional groups in the molecule can be used as the copolymer component constituting the copolymer. Examples of such compounds include oxalic acid and adipic acid. Phthalic acid, sebacic acid, dodecanedicarboxylic acid, isophthalic acid, terephthalic acid, 1,4-cyclohexanedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, phenylindanedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, tetralindicarboxylic acid Dicarboxylic acids such as decalin dicarboxylic acid and diphenyl ether dicarboxylic acid, oxycarboxylic acids such as p-oxybenzoic acid and p-oxyethoxybenzoic acid, or trimethylene glycol, tetramethylene glycol, hexamethyleneglycol Le, cyclohexane methylene glycol, neopentyl glycol, ethylene oxide adduct of bisphenol sulfone, ethylene oxide adduct of bisphenol A, diethylene glycol, can be preferably used dihydric alcohols such as polyethylene oxide glycol. These compounds may be used alone or in combination of two or more. Of these, the acid component is preferably isophthalic acid, terephthalic acid, 4,4′-diphenyldicarboxylic acid, 2,7-naphthalenedicarboxylic acid, p-oxybenzoic acid, and the glycol component is trimethylene glycol. , An ethylene oxide adduct of hexamethylene glycol neopentyl glycol and bisphenol sulfone.
また、ポリエチレンナフタレンジカルボキシレートに混合できるポリエステル或いはポリエステル以外の有機高分子として、例えばポリエチレンテレフタレート、ポリエチレンイソフタレート、ポリトリメチレンテレフタレート、ポリエチレン４，４’−テトラメチレンジフェニルジカルボキシレート、ポリエチレン−２，７−ナフタレンジカルボキシレート、ポリトリメチレン−２，６−ナフタレンジカルボキシレート、ポリネオペンチレン−２，６−ナフタレンジカルボキシレート、ポリ（ビス（４−エチレンオキシフェニル）スルホン）−２，６−ナフタレンジカルボキシレート等のポリエステルを挙げることができ、これらの中でポリエチレンイソフタレート、ポリトリメチレンテレフタレート、ポリトリメチレン−２，６−ナフタレンジカルボキシレート、ポリ（ビス（４−エチレンオキシフェニル）スルホン）−２，６−ナフタレンジカルボキシレートが挙げられる。これらのポリエステルまたはポリエステル以外の有機高分子は、ポリエチレンナフタレンジカルボキシレートを主たる成分とする層を構成するポリマーの全繰り返し構造単位のモル数を基準として２０モル％以下の範囲で用いることが好ましく、１種であっても２種以上を併用してもよい。 Examples of polyesters that can be mixed with polyethylene naphthalene dicarboxylate or organic polymers other than polyester include polyethylene terephthalate, polyethylene isophthalate, polytrimethylene terephthalate, polyethylene 4,4′-tetramethylene diphenyl dicarboxylate, polyethylene-2, 7-naphthalene dicarboxylate, polytrimethylene-2,6-naphthalene dicarboxylate, polyneopentylene-2,6-naphthalene dicarboxylate, poly (bis (4-ethyleneoxyphenyl) sulfone) -2,6 -Polyesters such as naphthalene dicarboxylate can be mentioned, among which polyethylene isophthalate, polytrimethylene terephthalate, polytrimethylene-2,6-naphtha Nji carboxylate, poly (bis (4-ethyleneoxy) sulfone) -2,6-naphthalene dicarboxylate and the like. These polyesters or organic polymers other than polyester are preferably used in a range of 20 mol% or less based on the number of moles of all repeating structural units of the polymer constituting the layer mainly composed of polyethylene naphthalene dicarboxylate, Even if it is 1 type, you may use 2 or more types together.
また、本発明のポリエチレンナフタレンジカルボキシレートは、例えば安息香酸、メトキシポリアルキレングリコールなどの一官能性化合物によって末端の水酸基および／またはカルボキシル基の一部または全部を封鎖したものであってよく、極く少量の例えばグリセリン、ペンタエリスリトール等の如き三官能以上のエステル形成性化合物で実質的に線状のポリマーが得られる範囲内で共重合したものであってもよい。 Further, the polyethylene naphthalene dicarboxylate of the present invention may be one in which a terminal hydroxyl group and / or a carboxyl group is partially or entirely blocked with a monofunctional compound such as benzoic acid or methoxypolyalkylene glycol. It may be copolymerized with a small amount of a trifunctional or higher functional ester-forming compound such as glycerin or pentaerythritol within a range where a substantially linear polymer is obtained.
本発明のポリエチレンナフタレンジカルボキシレートは、従来公知の方法で、例えばジカルボン酸とグリコールの反応で直接低重合度ポリエステルを得る方法や、ジカルボン酸の低級アルキルエステルとグリコールとをエステル交換触媒を用いて反応させた後、重合触媒の存在下で重合反応を行う方法で得ることができる。また、かかる溶融重合によって得られたポリエチレンナフタレンジカルボキシレートをチップ化し、加熱減圧下または窒素などの不活性気流中において固相重合することもできる。固相重合を行うことで、二軸配向フィルムの耐加水分解特性がさらに良好になる。 The polyethylene naphthalene dicarboxylate of the present invention is a conventionally known method, for example, a method of directly obtaining a low-polymerization degree polyester by reaction of dicarboxylic acid and glycol, or a transesterification catalyst of a lower alkyl ester of dicarboxylic acid and glycol. After the reaction, it can be obtained by a method of conducting a polymerization reaction in the presence of a polymerization catalyst. In addition, polyethylene naphthalene dicarboxylate obtained by such melt polymerization can be chipped and subjected to solid phase polymerization under heating under reduced pressure or in an inert gas stream such as nitrogen. By performing solid phase polymerization, the hydrolysis resistance of the biaxially oriented film is further improved.
本発明のポリエチレンナフタレンジカルボキシレートの固有粘度は０.５０ｄｌ／ｇ以上０.９０ｄｌ／ｇ以下であることが好ましい。さらに好ましくは０．５２ｄｌ／ｇ以上０．８５ｄｌ／ｇ以下、特に好ましくは０．５３ｄｌ／ｇ以上０．８０ｄｌ／ｇ以下である。固有粘度が下限に満たない場合、フィルムの製膜時の破断が発生し易くなる他、得られたフィルムが脆くなったり、加水分解特性が低下することがある。また、ポリエチレンナフタレンジカルボキシレートの固有粘度が上限を超えると、ポリマーの固有粘度をかなり高くする必要があり、通常の合成手法では重合に長時間を要し生産性が悪くなる。また二軸配向フィルムに製膜した後のポリエチレンナフタレンジカルボキシレートの固有粘度は０．４５ｄｌ／ｇ以上０．８５ｄｌ／ｇ以下であることが好ましく、さらに好ましくは０．４７ｄｌ／ｇ以上０．８０ｇ／ｄｌ以下、特に好ましくは０．５０ｄｌ／ｇ以上０．７５ｇ／ｄｌ以下の範囲である。なお、固有粘度はｏ−クロロフェノールを溶媒として用いて、３５℃で測定した値（単位：ｄｌ／ｇ）である。 The intrinsic viscosity of the polyethylene naphthalene dicarboxylate of the present invention is preferably 0.50 dl / g or more and 0.90 dl / g or less. More preferably, it is 0.52 dl / g or more and 0.85 dl / g or less, Most preferably, it is 0.53 dl / g or more and 0.80 dl / g or less. When the intrinsic viscosity is less than the lower limit, the film is likely to be broken during film formation, and the obtained film may become brittle or the hydrolysis characteristics may be deteriorated. When the intrinsic viscosity of polyethylene naphthalene dicarboxylate exceeds the upper limit, the intrinsic viscosity of the polymer needs to be considerably increased, and a normal synthesis method requires a long time for polymerization, resulting in poor productivity. The intrinsic viscosity of the polyethylene naphthalene dicarboxylate after forming into a biaxially oriented film is preferably 0.45 dl / g or more and 0.85 dl / g or less, more preferably 0.47 dl / g or more and 0.80 g. / Dl or less, particularly preferably in the range of 0.50 dl / g or more and 0.75 g / dl or less. The intrinsic viscosity is a value (unit: dl / g) measured at 35 ° C. using o-chlorophenol as a solvent.
＜他添加剤＞
本発明の二軸配向ポリステルフィルムは、フィルムの取り扱い性を向上させるため、発明の効果を損なわない範囲で不活性粒子などが添加されていても良い。不活性粒子として、例えば、周期律表第ＩＩＡ、第ＩＩＢ、第ＩＶＡ、第ＩＶＢの元素を含有する無機粒子（例えば、カオリン、アルミナ、酸化チタン、炭酸カルシウム、二酸化ケイ素など）、架橋シリコーン樹脂、架橋ポリスチレン、架橋アクリル樹脂粒子等のごとき耐熱性の高いポリマーよりなる微粒子などを含有させることができる。不活性粒子を含有させる場合、不活性粒子の平均粒径は、０．００１〜５μｍの範囲が好ましく、フィルム全重量に対して０．０１〜１０重量％の範囲で含有されることが好ましい。
また本発明の二軸配向フィルムは、必要に応じて少量の紫外線吸収剤、酸化防止剤、帯電防止剤、光安定剤、熱安定剤を含んでいてもよい。
<Other additives>
In order to improve the handleability of the biaxially oriented polyester film of the present invention, inert particles or the like may be added within a range not impairing the effects of the invention. Examples of the inert particles include inorganic particles containing elements of Periodic Tables IIA, IIB, IVA, and IVB (for example, kaolin, alumina, titanium oxide, calcium carbonate, silicon dioxide, etc.), crosslinked silicone resins, Fine particles made of a polymer having high heat resistance such as crosslinked polystyrene and crosslinked acrylic resin particles can be contained. When the inert particles are contained, the average particle diameter of the inert particles is preferably in the range of 0.001 to 5 μm, and preferably in the range of 0.01 to 10% by weight with respect to the total weight of the film.
Moreover, the biaxially oriented film of the present invention may contain a small amount of an ultraviolet absorber, an antioxidant, an antistatic agent, a light stabilizer, and a heat stabilizer as necessary.
＜ヤング率＞
本発明の二軸配向ポリエステルフィルムは、電解質膜の補強部材として高い機械的特性を有することが好ましく、フィルムの縦方向（以下、連続製膜方向、長手方向またはＭＤ方向と称することがある。）および横方向（以下、幅方向またはＴＤ方向と称することがある。）のヤング率が好ましくはそれぞれ５５００ＭＰａ以上、より好ましくは５７００ＭＰａ以上である。ヤング率が下限に満たない場合、フィルム厚みが薄いと電解質膜に重ね合わせた際の腰が弱く、電解質膜のハンドリング性が悪くなることがある。また、縦方向、横方向のいずれか一方でもヤング率が下限より小さいと、下限に満たない方向における補強効果が充分でないことがある。ヤング率の上限は特に限定されないが、７０００ＭＰａ以上ではフィルム製膜工程でのフィルム切断が多発することがある。フィルムの縦方向および横方向のヤング率は、延伸時の倍率で調整することができる。
<Young's modulus>
The biaxially oriented polyester film of the present invention preferably has high mechanical properties as a reinforcing member for the electrolyte membrane, and is the longitudinal direction of the film (hereinafter sometimes referred to as the continuous film-forming direction, the longitudinal direction, or the MD direction). The Young's modulus in the lateral direction (hereinafter sometimes referred to as the width direction or the TD direction) is preferably 5500 MPa or more, and more preferably 5700 MPa or more. When the Young's modulus is less than the lower limit, if the film thickness is thin, the stiffness when superposed on the electrolyte membrane is weak, and the handleability of the electrolyte membrane may be deteriorated. Further, if the Young's modulus is smaller than the lower limit in either the longitudinal direction or the lateral direction, the reinforcing effect in a direction less than the lower limit may not be sufficient. The upper limit of the Young's modulus is not particularly limited, but when it is 7000 MPa or more, the film may be frequently cut in the film forming process. The Young's modulus in the machine direction and transverse direction of the film can be adjusted by the magnification during stretching.
＜耐加水分解性＞
本発明の二軸配向ポリエステルフィルムは、含水状態にある電解質膜表面に接触しており、５０℃〜１００℃程度の温度域で使用されることから、高湿度環境で長期間、加水分解による強度低下が小さいことが好ましく、下記式（１）で表される破断強度保持率が５０％になるのに要する時間が１００時間以上であることが好ましい。
破断強度保持率（％）＝（破断強度Ｘ／初期の破断強度Ｘ0）×１００ ・・・(１)
（式中、破断強度Ｘは、１２１℃、２ａｔｍ、１００％ＲＨの条件で所定時間処理後の破断強度、破断強度Ｘ0は処理前の初期の破断強度をそれぞれ表す）
破断強度保持率が５０％になるのに要する時間が１００時間に満たない場合、高湿度の使用環境において長期に渡って補強部材として充分な機械的強度を保てなくなることがある。かかる耐加水分解性は、ポリエステルの中でもポリエチレンナフタレンジカルボキシレートを用いることよって達成されるものである。
<Hydrolysis resistance>
Since the biaxially oriented polyester film of the present invention is in contact with the electrolyte membrane surface in a water-containing state and is used in a temperature range of about 50 ° C. to 100 ° C., the strength by hydrolysis for a long time in a high humidity environment. The decrease is preferably small, and the time required for the fracture strength retention represented by the following formula (1) to be 50% is preferably 100 hours or more.
Breaking strength retention ratio (%) = (breaking strength X / initial breaking strength X 0 ) × 100 (1)
(In the formula, the breaking strength X represents the breaking strength after treatment for a predetermined time under the conditions of 121 ° C., 2 atm, and 100% RH, and the breaking strength X 0 represents the initial breaking strength before the treatment)
If the time required for the fracture strength retention rate to reach 50% is less than 100 hours, sufficient mechanical strength as a reinforcing member may not be maintained over a long period of time in a high humidity usage environment. Such hydrolysis resistance is achieved by using polyethylene naphthalene dicarboxylate among polyesters.
＜熱収縮率＞
本発明の二軸配向ポリエステルフィルムは、使用される温度域における耐熱寸法性の観点から、１００℃、３０分間熱処理された後の縦方向および横方向の熱収縮率がそれぞれ０．５％以下であることが好ましく、更に好ましくは０．２％以下、特に好ましくは０．１％以下である。熱収縮率が上限を超えると、電解質膜に負荷がかかるので電解質膜が破れたりしわが発生することがあり、電解質膜の性能に支障が生じることがある。また、縦方向および横方向のいずれか一方が上限を超えると、電解質膜に歪みが生じやすく、本来の電解質膜の性能に支障が生じることがある。かかる熱収縮率の下限は小さければ小さい方が好ましい。１００℃における熱収縮率を上述の範囲にするには、ポリエチレンナフタレンジカルボキシレートを用い、フィルムを所定の延伸倍率で二軸延伸することによって達成される。
<Heat shrinkage>
The biaxially oriented polyester film of the present invention has a heat shrinkage ratio of 0.5% or less in the longitudinal direction and the transverse direction after being heat-treated at 100 ° C. for 30 minutes from the viewpoint of heat-resistant dimensional properties in the temperature range to be used. Preferably, it is 0.2% or less, particularly preferably 0.1% or less. When the heat shrinkage rate exceeds the upper limit, the electrolyte membrane is loaded, so that the electrolyte membrane may be broken or wrinkled, which may hinder the performance of the electrolyte membrane. In addition, when either one of the vertical direction and the horizontal direction exceeds the upper limit, the electrolyte membrane is likely to be distorted, which may hinder the performance of the original electrolyte membrane. The smaller the lower limit of the heat shrinkage rate, the better. In order to make the heat shrinkage rate at 100 ° C. into the above-mentioned range, it is achieved by using polyethylene naphthalene dicarboxylate and biaxially stretching the film at a predetermined stretch ratio.
本発明の二軸配向ポリエステルフィルムは、高温加工温度における耐熱寸法性の観点から、１６０℃、１０分間熱処理された後の縦方向および横方向の熱収縮率がそれぞれ０．５％以下であることが好ましい。熱収縮率が上限を超えると、加工時に電解質膜が破れたりしわが発生することがあり、電解質膜の性能に支障が生じることがある。また、縦方向および横方向のいずれか一方が上限を超えると、電解質膜に歪みが生じやすく、本来の電解質膜の性能に支障が生じることがある。かかる熱収縮率の下限は小さければ小さい方が好ましい。１６０℃における熱収縮率を上述の範囲にするには、ポリエチレンナフタレンジカルボキシレートを用い、フィルムを所定の延伸倍率および熱固定温度で延伸製膜することによって達成される。 The biaxially oriented polyester film of the present invention has a heat shrinkage rate of 0.5% or less in each of the longitudinal direction and the transverse direction after heat treatment at 160 ° C. for 10 minutes from the viewpoint of heat-resistant dimensional properties at a high temperature processing temperature. Is preferred. If the heat shrinkage rate exceeds the upper limit, the electrolyte membrane may be broken or wrinkled during processing, which may hinder the performance of the electrolyte membrane. In addition, when either one of the vertical direction and the horizontal direction exceeds the upper limit, the electrolyte membrane is likely to be distorted, which may hinder the performance of the original electrolyte membrane. The smaller the lower limit of the heat shrinkage rate, the better. In order to make the heat shrinkage rate at 160 ° C. in the above range, it is achieved by using polyethylene naphthalene dicarboxylate and stretching the film at a predetermined stretching ratio and heat setting temperature.
＜フィルム厚み＞
本発明の二軸配向ポリエステルフィルムのフィルム厚みは、１μｍ〜１００μｍであることが好ましい。フィルム厚みの下限はより好ましくは２μｍ以上、さらに好ましくは５μｍ以上である。またフィルム厚みの上限はより好ましくは７５μｍ以下、さらに好ましくは５０μｍ以下である。フィルム厚みが下限に満たない場合、電解質膜の補強材として十分な補強効果が得られないことがある。またフィルム厚みが上限を超える場合、電池のサイズを小さくすることが難しくなる場合がある。
<Film thickness>
The film thickness of the biaxially oriented polyester film of the present invention is preferably 1 μm to 100 μm. The lower limit of the film thickness is more preferably 2 μm or more, and further preferably 5 μm or more. The upper limit of the film thickness is more preferably 75 μm or less, and further preferably 50 μm or less. When the film thickness is less than the lower limit, a sufficient reinforcing effect as a reinforcing material for the electrolyte membrane may not be obtained. When the film thickness exceeds the upper limit, it may be difficult to reduce the battery size.
＜易接着層＞
本発明の二軸配向ポリエステルフィルムは、ポリエチレンナフタレンジカルボキシレートを主たる成分とする層の少なくとも一方の面にアクリル樹脂を含有する易接着層が積層されていることが好ましい。
かかる易接着層は、ポリエチレンナフタレンジカルボキシレートを主たる成分とする層の少なくとも一方の面に積層されることが好ましく、また両面に積層されてもよい。
二軸配向ポリエステルフィルムは、電解質膜の補強部材として枠状の形状で電解質膜の周縁部と貼り合わせて使用される。固体高分子電解質型燃料電池は、電解質の両側に電極層が配置されており、電極層は電解質膜よりも寸法が小さく、本発明の二軸配向ポリエステルフィルムからなる枠状の補強部材は、通常触媒層の外縁を囲むように配置される。これらの電極層の外側には更に、電極層よりも寸法の大きい拡散層が配置されることから、二軸配向ポリエステルフィルムからなる補強部材の一方の面は電解質膜の周縁部と、もう一方の面は拡散層の周縁部とそれぞれ接する。二軸配向ポリエステルフィルムが片面に易接着層を有する場合、易接着層は電解質膜側または拡散層側のいずれの面であっても構わない。また、易接着層と電解質膜または拡散層とは、直接接合されても、接着剤層を介して接合されてもよい。二軸配向ポリエステルフィルムが少なくとも電解質膜または拡散層のいずれかの層と強固に接合されることによって補強部材としての性能がさらに高まる。接着剤層を介する場合、特に種類は限定されないが、電解質膜を構成するポリマー、具体的にはパーフルオロスルホン酸ポリマーを主成分とした接着剤が例示される。
<Easily adhesive layer>
In the biaxially oriented polyester film of the present invention, an easy adhesion layer containing an acrylic resin is preferably laminated on at least one surface of a layer containing polyethylene naphthalene dicarboxylate as a main component.
Such an easy-adhesion layer is preferably laminated on at least one side of a layer mainly composed of polyethylene naphthalene dicarboxylate, and may be laminated on both sides.
The biaxially oriented polyester film is used as a reinforcing member for the electrolyte membrane by being bonded to the peripheral portion of the electrolyte membrane in a frame shape. In the solid polymer electrolyte fuel cell, electrode layers are arranged on both sides of the electrolyte. The electrode layer is smaller in size than the electrolyte membrane, and the frame-shaped reinforcing member made of the biaxially oriented polyester film of the present invention is usually It arrange | positions so that the outer edge of a catalyst layer may be enclosed. Since a diffusion layer having a size larger than that of the electrode layer is further disposed outside these electrode layers, one surface of the reinforcing member made of the biaxially oriented polyester film has a peripheral portion of the electrolyte membrane and the other surface. The surface is in contact with the peripheral edge of the diffusion layer. When the biaxially oriented polyester film has an easy adhesion layer on one side, the easy adhesion layer may be on either the electrolyte membrane side or the diffusion layer side. Further, the easy-adhesion layer and the electrolyte membrane or the diffusion layer may be joined directly or via an adhesive layer. When the biaxially oriented polyester film is firmly bonded to at least one of the electrolyte membrane and the diffusion layer, the performance as a reinforcing member is further enhanced. In the case of using an adhesive layer, the type is not particularly limited, but examples include an adhesive mainly composed of a polymer constituting the electrolyte membrane, specifically, a perfluorosulfonic acid polymer.
易接着層に含有されるアクリル樹脂は、以下に例示するアクリルモノマーからなるアクリル樹脂を挙げることができる。すなわち、アルキルアクリレート、アルキルメタクリレート（アルキル基としては、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｔ−ブチル基、２ーエチルヘキシル基、シクロヘキシル基等）；２ーヒドロキシエチルアクリレート、２ーヒドロキシエチルメタクリレート、２ーヒドロキシプロピルアクリレート、２ーヒドロキシプロピルメタクリレート等のヒドロキシ含有モノマー；グリシジルアクリレート、グリシジルメタクリレート；アクリル酸、メタクリル酸等のモノマーを挙げることができる。これらモノマーは１種あるいは２種以上を共重合成分として用いることができる。特に好ましいアクリルモノマーとして、メチルアクリレート、エチルアクリレート、メチルメタクリレート、エチルメタクリレートなどが挙げられる。
かかるアクリル樹脂には、さらに共重合成分として、イタコン酸、マレイン酸、フマール酸、クロトン酸、スチレンスルホン酸及びその塩（ナトリウム塩、カリウム塩、アンモニウム塩、第三級アミン塩等）等のカルボキシ基またはその塩を含有するモノマー；無水マレイン酸、無水イタコン酸等の酸無水物のモノマー；ビニルイソシアネート、アリルイソシアネート、スチレン、αーメチルスチレン、ビニルメチルエーテル、ビニルエチルエーテル、ビニルトリアルコキシシラン、アルキルマレイン酸モノエステル、アルキルフマール酸モノエステル、アルキルイタコン酸モノエステル、アクリロニトリル、メタクリロニトリル、塩化ビニリデン、エチレン、プロピレン、塩化ビニル、酢酸ビニル、ブタジエン等を用いてもよい。かかる共重合成分の共重合割合は、０．１〜６０モル％の範囲であることが好ましい。この共重合割合の上限は５０モル％であることが更に好ましい。また、この共重合割合の下限は１モル％であることが更に好ましい。
Examples of the acrylic resin contained in the easy-adhesion layer include acrylic resins made of acrylic monomers exemplified below. That is, alkyl acrylate, alkyl methacrylate (alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, 2-ethylhexyl, cyclohexyl, etc.); Examples include hydroxy-containing monomers such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl methacrylate; monomers such as glycidyl acrylate and glycidyl methacrylate; acrylic acid and methacrylic acid. One or more of these monomers can be used as a copolymerization component. Particularly preferred acrylic monomers include methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate and the like.
Such an acrylic resin further contains, as a copolymerization component, carboxy such as itaconic acid, maleic acid, fumaric acid, crotonic acid, styrenesulfonic acid and salts thereof (sodium salt, potassium salt, ammonium salt, tertiary amine salt, etc.). Monomers containing a group or a salt thereof; monomers of acid anhydrides such as maleic anhydride and itaconic anhydride; vinyl isocyanate, allyl isocyanate, styrene, α-methyl styrene, vinyl methyl ether, vinyl ethyl ether, vinyl trialkoxysilane, alkyl malein Acid monoesters, alkyl fumaric acid monoesters, alkylitaconic acid monoesters, acrylonitrile, methacrylonitrile, vinylidene chloride, ethylene, propylene, vinyl chloride, vinyl acetate, butadiene, and the like may be used. The copolymerization ratio of the copolymer component is preferably in the range of 0.1 to 60 mol%. The upper limit of the copolymerization ratio is more preferably 50 mol%. Further, the lower limit of the copolymerization ratio is more preferably 1 mol%.
アクリル樹脂はアミド基を有することがさらに好ましい。アミド基を有するアクリル樹脂として、例えば以下のようなアミド基を有するアクリルモノマーを共重合成分としてアクリル樹脂中に導入することで得ることができる。
アミド基を有するアクリルモノマーとしては、例えば、アクリルアミド、メタクリルアミド、Ｎ−アルキルアクリルアミド、Ｎ−アルキルメタクリルアミド、Ｎ、Ｎ−ジアルキルアクリルアミド、Ｎ、Ｎ−ジアルキルメタクリルアミド（アルキル基としては、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｔ−ブチル基、２−エチルヘキシル基、シクロヘキシル基等）、Ｎーアルコキシアクリルアミド、Ｎ−アルコキシメタクリルアミド、Ｎ、Ｎ−ジアルコキシアクリルアミド、Ｎ、Ｎ−ジアルコキシメタクリルアミド（アルコキシ基としては、メトキシ基、エトキシ基、ブトキシ基、イソブトキシ基等）、Ｎ−メチロールアクリルアミド、Ｎ−メチロールメタクリルアミド、Ｎ−フェニルアクリルアミド、Ｎ−フェニルメタクリルアミド、アクリロイルモルホリン等を挙げることができる。
More preferably, the acrylic resin has an amide group. The acrylic resin having an amide group can be obtained, for example, by introducing an acrylic monomer having an amide group as described below into the acrylic resin as a copolymerization component.
Examples of the acrylic monomer having an amide group include acrylamide, methacrylamide, N-alkylacrylamide, N-alkylmethacrylamide, N, N-dialkylacrylamide, N, N-dialkylmethacrylamide (the alkyl group includes a methyl group, Ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, 2-ethylhexyl group, cyclohexyl group, etc.), N-alkoxyacrylamide, N-alkoxymethacrylamide, N, N-di Alkoxyacrylamide, N, N-dialkoxymethacrylamide (alkoxy groups include methoxy, ethoxy, butoxy, isobutoxy, etc.), N-methylolacrylamide, N-methylolmethacrylamide, N-phenylacrylic Bromide, N- phenyl methacrylamide, can be exemplified acryloyl morpholine.
アミド基を有するアクリル樹脂（以下、アクリル共重合体と称することがある）には、少なくとも１種類の上記のアミド基を有するモノマーが含まれれば良い。アクリル共重合体中にアミド基が存在することで、電解質膜または拡散層、あるいは接着剤層との接着性がさらに良好となる。
特に好ましいアミド基を有するアクリルモノマーとしては、アクリルアミド、メタクリルアミド、Ｎ−アルキルアクリルアミド、Ｎ、Ｎ−ジアルキルアクリルアミド、Ｎ、Ｎ−ジアルキルメタクリレート（アルキル基としては、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｔ−ブチル基、２−エチルヘキシル基、シクロヘキシル基等）、Ｎ−メチロールアクリルアミド、Ｎ−メチロールメタクリルアミド、アクリロイルモルホリンを挙げることができる。
The acrylic resin having an amide group (hereinafter sometimes referred to as an acrylic copolymer) may contain at least one monomer having the above amide group. The presence of an amide group in the acrylic copolymer further improves the adhesion with the electrolyte membrane, the diffusion layer, or the adhesive layer.
Particularly preferred acrylic monomers having an amide group include acrylamide, methacrylamide, N-alkyl acrylamide, N, N-dialkyl acrylamide, N, N-dialkyl methacrylate (alkyl groups include methyl, ethyl, n-propyl groups). Isopropyl group, n-butyl group, isobutyl group, t-butyl group, 2-ethylhexyl group, cyclohexyl group, etc.), N-methylolacrylamide, N-methylolmethacrylamide, and acryloylmorpholine.
アクリル樹脂が、アミド基を有するアクリル共重合体である場合、アミド基を有するアクリル成分の共重合割合は、０．２〜２０モル％の範囲であることが好ましい。この共重合割合の上限は１０モル％であることが更に好ましく、５モル％であることが特に好ましい。また、この共重合割合の下限は１モル％であることが更に好ましく、２モル％であることが特に好ましい。アミド基を有するアクリル成分の共重合割合が上記範囲である場合、電解質膜または拡散層、あるいは接着剤層との接着性をさらに良好なものとすることができる。 When the acrylic resin is an acrylic copolymer having an amide group, the copolymerization ratio of the acrylic component having an amide group is preferably in the range of 0.2 to 20 mol%. The upper limit of the copolymerization ratio is more preferably 10 mol%, particularly preferably 5 mol%. Further, the lower limit of the copolymerization ratio is more preferably 1 mol%, and particularly preferably 2 mol%. When the copolymerization ratio of the acrylic component having an amide group is within the above range, the adhesion with the electrolyte membrane, the diffusion layer, or the adhesive layer can be further improved.
易接着は、上述のアクリル樹脂以外に、その他バインダー成分として、ポリエステル共重合体やウレタン樹脂等やそれらの変性体であるアクリル変性ポリエステル、アクリル変性ウレタン等が混合されても良い。好ましくはポリエステル共重合体との混合が挙げられる。ポリエステル共重合体との混合体である場合、混合割合はアクリル樹脂２０〜８０重量％に対しポリエステル共重合体８０〜２０重量％であることが好ましい。
易接着層には、耐熱性をより良好なものとするためにエポキシ、オキサゾリン、メラミン、イソシアネート、シランカップリング剤、ジルコ−アルミニウムカップリング剤等の架橋剤を添加しても良い。これらのうちエポキシが特に好ましい。
For easy adhesion, in addition to the above-mentioned acrylic resin, a polyester copolymer, urethane resin or the like, or a modified body such as acrylic modified polyester or acrylic modified urethane may be mixed as other binder components. Preferably mixing with a polyester copolymer is mentioned. In the case of a mixture with a polyester copolymer, the mixing ratio is preferably 80 to 20% by weight of the polyester copolymer with respect to 20 to 80% by weight of the acrylic resin.
A cross-linking agent such as epoxy, oxazoline, melamine, isocyanate, silane coupling agent, and zirco-aluminum coupling agent may be added to the easy adhesion layer in order to improve heat resistance. Of these, epoxy is particularly preferred.
易接着層の塗設に用いる塗布液は、水分散性または水性塗布液であることが好ましい。アクリル樹脂や他の添加物に影響を与えない限り、若干の有機溶剤を含んでいてもよい。この塗布液はアニオン型界面活性剤、カチオン型界面活性剤、ノニオン型界面活性剤等の界面活性剤を必要量添加して用いることができる。
かかる界面活性剤としては水性塗布液の表面張力を４０ｍＮ／ｍ以下に低下でき、ポリエステルフィルムへの濡れを促進するものが好ましく、例えばポリオキシエチレンー脂肪酸エステル、ソルビタン脂肪酸エステル、グリセリン脂肪酸エステル、脂肪酸金属石鹸、アルキル硫酸塩、アルキルスルホン酸塩、アルキルスルホコハク酸塩、第４級アンモニウムクロライド塩、アルキルアミン塩酸、ベタイン型界面活性剤等を挙げることができる。
The coating solution used for coating the easy-adhesion layer is preferably a water-dispersible or aqueous coating solution. As long as it does not affect the acrylic resin and other additives, it may contain some organic solvent. This coating solution can be used by adding a necessary amount of a surfactant such as an anionic surfactant, a cationic surfactant, or a nonionic surfactant.
Such surfactants are preferably those that can reduce the surface tension of aqueous coating solutions to 40 mN / m or less and promote wetting on polyester films, such as polyoxyethylene-fatty acid esters, sorbitan fatty acid esters, glycerin fatty acid esters, fatty acids. Examples thereof include metal soaps, alkyl sulfates, alkyl sulfonates, alkyl sulfosuccinates, quaternary ammonium chloride salts, alkylamine hydrochlorides, and betaine surfactants.
易接着層を形成する方法としては、例えば延伸可能なポリエステルフィルムの片面または両面に易接着層を形成する成分を含む水性塗布液を塗布した後、乾燥、延伸し必要に応じて熱処理することにより積層することができる。ここで延伸可能なポリエステルフィルムとは、未延伸ポリエステルフィルム、一軸延伸ポリエステルフィルムまたは二軸延伸ポリエステルフィルムであり、これらの中でもフィルムの押出し方向（縦方向）に一軸延伸した縦延伸ポリエステルフィルムが特に好ましい。 As a method for forming the easy-adhesion layer, for example, by applying an aqueous coating solution containing a component that forms an easy-adhesion layer on one or both sides of a stretchable polyester film, drying, stretching, and heat treatment as necessary Can be stacked. Here, the stretchable polyester film is an unstretched polyester film, a uniaxially stretched polyester film or a biaxially stretched polyester film, and among these, a longitudinally stretched polyester film that is uniaxially stretched in the extrusion direction (longitudinal direction) of the film is particularly preferable. .
ポリエステルフィルムへ塗液を塗布する場合は、通常の塗工工程、すなわち二軸延伸後、熱固定したポリエステルフィルムに該フィルムの製造工程と切り離した工程で行うと、埃、ちり等を巻き込み易い。かかる観点よりクリーンな雰囲気での塗布、すなわちフィルムの製造工程での塗布が好ましい。塗布方法としては、公知の任意の塗布方が適用できる。例えばロールコート法、グラビアコート法、ロールブラッシュ法、スプレーコート法、エアーナイフコート法、含浸法およびカーテンコート法などを単独または組み合わせて用いることが出来る。 When applying a coating liquid to a polyester film, dust, dust, etc. are easily caught when it is performed in a normal coating process, that is, in a process separated from the manufacturing process of the film after heat-fixed polyester film after biaxial stretching. From such a viewpoint, application in a clean atmosphere, that is, application in a film production process is preferable. As a coating method, any known coating method can be applied. For example, a roll coating method, a gravure coating method, a roll brush method, a spray coating method, an air knife coating method, an impregnation method, and a curtain coating method can be used alone or in combination.
＜製膜＞
本発明のポリエステルフィルムは二軸配向されている必要がある。二軸配向されていることにより、機械的強度や寸法変化に関する特性が良好なものとなり、固体高分子電解質膜の補強材として充分な性能を発現することが可能となる。
本発明の二軸配向ポリエステルフィルムは、二軸延伸されるのであれば、公知の製膜方法を用いて製造することができ、例えば十分に乾燥させたポリエチレン―２，６―ナフタレートを融点〜（融点＋７０）℃の温度で溶融押出し、キャスティンクドラム上で急冷して未延伸フィルムとし、次いで該未延伸フィルムを逐次または同時二軸延伸し、熱固定する方法で製造することができる。逐次二軸延伸により製膜する場合、未延伸フィルムを縦方向に１３０〜１７０℃で２．３〜６．５倍、より好ましくは２．５〜５．０倍の範囲で延伸し、次いでステンターにて横方向に１３０〜１５０℃で２．３〜５．５倍、より好ましくは２．５〜５．０倍の範囲で延伸する。熱固定は、２００〜２６０℃、より好ましくは２２０〜２６０℃の温度で緊張下又は制限収縮下で熱固定するのが好ましく、熱固定時間は１〜１０００秒が好ましい。また同時二軸延伸の場合、上記の延伸温度、延伸倍率、熱固定温度等を適用することができる。また、熱固定後に弛緩処理を行ってもよい。
<Film formation>
The polyester film of the present invention needs to be biaxially oriented. By being biaxially oriented, characteristics relating to mechanical strength and dimensional change are improved, and sufficient performance as a reinforcing material for the solid polymer electrolyte membrane can be exhibited.
If the biaxially oriented polyester film of the present invention is biaxially stretched, it can be produced by using a known film forming method. For example, a sufficiently dried polyethylene-2,6-naphthalate has a melting point of-( It can be produced by melt extrusion at a temperature of melting point +70) ° C., quenching on a casting drum to form an unstretched film, and then successively or simultaneously biaxially stretching the unstretched film and heat setting. When forming a film by sequential biaxial stretching, the unstretched film is stretched in the longitudinal direction at 130 to 170 ° C. in a range of 2.3 to 6.5 times, more preferably in a range of 2.5 to 5.0 times, and then a stenter. The film is stretched 2.3 to 5.5 times, more preferably 2.5 to 5.0 times in the transverse direction at 130 to 150 ° C. The heat setting is preferably performed at a temperature of 200 to 260 ° C., more preferably 220 to 260 ° C. under tension or limited shrinkage, and the heat setting time is preferably 1 to 1000 seconds. In the case of simultaneous biaxial stretching, the above stretching temperature, stretching ratio, heat setting temperature and the like can be applied. Moreover, you may perform a relaxation | loosening process after heat setting.
以下、実施例により本発明を詳述するが、本発明はこれらの実施例のみに限定されるものではない。なお、各特性値は以下の方法で測定した。また、実施例中の部および％は、特に断らない限り、それぞれ重量部および重量％を意味する。 EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited only to these Examples. Each characteristic value was measured by the following method. Moreover, unless otherwise indicated, the part and% in an Example mean a weight part and weight%, respectively.
（１）ヤング率
フィルムを１５０ｍｍ長×１０ｍｍ幅に切り出した試験片を用い、オリエンテック社製テンシロンＵＣＴ−１００型を用いて、温度２０℃、湿度５０％に調節された室内において、チャック間１００ｍｍにして引張速度１０ｍｍ／分、チャート速度５００ｍｍ／分で引張り、得られる荷重―伸び曲線の立ち上り部の接線よりヤング率を計算する。なお、縦方向のヤング率とはフィルムの縦方向（ＭＤ方向）を測定方向としたものであり、横方向のヤング率とはフィルムの横方向（幅方向）を測定方向としたものである。各ヤング率はそれぞれ１０回測定し、その平均値を用いた。
(1) Young's modulus 100 mm between chucks in a room adjusted to a temperature of 20 ° C. and humidity of 50% using a Tensilon UCT-100 model manufactured by Orientec, using a test piece obtained by cutting the film into a length of 150 mm × 10 mm. Then, the Young's modulus is calculated from the tangent of the rising portion of the load-elongation curve obtained by pulling at a pulling speed of 10 mm / min and a chart speed of 500 mm / min. The longitudinal Young's modulus is the measurement direction in the longitudinal direction (MD direction) of the film, and the lateral Young's modulus is the measurement direction in the lateral direction (width direction) of the film. Each Young's modulus was measured 10 times and the average value was used.
（２）耐加水分解性
フィルムを１５０ｍｍ長×１０ｍｍ幅に切り出した短冊状の試料片を、１２１℃・２ａｔｍ・濡れ飽和モード・１００％ＲＨに設定した環境試験機内にステンレス製のクリップで吊り下げる。その後、所定時間ごとに試料片を取り出し、破断強度を測定する。測定は５回行い、その平均値を求め、下記式（１）で表される破断強度保持率が初期値の５０％になるまでの時間を求めて、耐加水分解性を評価した。測定装置としてオリエンテック社製テンシロンＵＣＴ−１００型を用いた。
破断強度保持率（％）＝（破断強度Ｘ／初期の破断強度Ｘ0）×１００ ・・・(１)
（式中、破断強度Ｘは、１２１℃、２ａｔｍ、１００％ＲＨの条件で所定時間処理後の破断強度、破断強度Ｘ0は処理前の初期の破断強度をそれぞれ表す）
(2) Hydrolysis resistance A strip-shaped sample piece cut out of a 150 mm length × 10 mm width is suspended with a stainless steel clip in an environmental tester set to 121 ° C., 2 atm, wet saturation mode, and 100% RH. . Then, a sample piece is taken out for every predetermined time, and breaking strength is measured. The measurement was performed 5 times, the average value was obtained, and the time until the breaking strength retention represented by the following formula (1) reached 50% of the initial value was obtained to evaluate the hydrolysis resistance. As a measuring device, Tensilon UCT-100 type manufactured by Orientec Co., Ltd. was used.
Breaking strength retention ratio (%) = (breaking strength X / initial breaking strength X 0 ) × 100 (1)
(In the formula, the breaking strength X represents the breaking strength after treatment for a predetermined time under the conditions of 121 ° C., 2 atm, and 100% RH, and the breaking strength X 0 represents the initial breaking strength before the treatment)
（３）熱収縮率
温度１００℃に設定されたオーブン中に、フィルムの縦方向および横方向がマーキングされ、あらかじめ正確な長さを測定した長さ３０ｃｍ四方のフィルムを無荷重で入れ、３０分間保持処理した後取り出し、室温に戻してからその寸法の変化を読み取る。熱処理前の長さ（Ｌ0）と熱処理による寸法変化量（ΔＬ）より、下記式（２）から縦方向および横方向の熱収縮率をそれぞれ求めた。
熱収縮率（％）＝ΔＬ／Ｌ0×１００ ・・・（２）
１６０℃における熱収縮率も上記方法と同様に、１６０℃の温度で１０分間処理したサンプルから縦方向および横方向の熱収縮率をそれぞれ求めた。
(3) Heat shrinkage rate In a oven set at a temperature of 100 ° C., the film is marked in the longitudinal and transverse directions, and a 30 cm long film with an accurate length measured in advance is placed under no load for 30 minutes. Take out after holding treatment, return to room temperature, and then read the change in dimensions. From the length (L 0 ) before the heat treatment and the dimensional change (ΔL) due to the heat treatment, the thermal contraction rates in the vertical direction and the horizontal direction were obtained from the following formula (2).
Thermal contraction rate (%) = ΔL / L 0 × 100 (2)
Similarly to the above method, the heat shrinkage rate at 160 ° C. was obtained from the sample treated for 10 minutes at a temperature of 160 ° C., respectively.
（４）接着性
電解質膜として５０ｍｍ四方のパーフルオロスルホン酸樹脂（デュポン社製：ナフィオン１１７）を用い、その片面に同サイズのポリエステルフィルムを重ねて１４０℃で熱プレスにより接合した。ポリエステルフィルムが易接着層を有する場合は、易接着層が電解質膜と接するように重ねた。得られた試験片の電解質膜側の面の角を指で１０回こすり、電解質膜の剥離の有無を評価した。
(4) Adhesion A 50 mm square perfluorosulfonic acid resin (manufactured by DuPont: Nafion 117) was used as the electrolyte membrane, and a polyester film of the same size was layered on one side and joined at 140 ° C. by hot pressing. When the polyester film had an easy-adhesion layer, they were stacked so that the easy-adhesion layer was in contact with the electrolyte membrane. The corner of the surface of the obtained test piece on the electrolyte membrane side was rubbed 10 times with a finger to evaluate the presence or absence of peeling of the electrolyte membrane.
（５）電解質膜の形状安定性
電解質膜として１００ｍｍ四方のパーフルオロスルホン酸樹脂（デュポン社製：ナフィオン１１７）を用い、その両面に枠状のポリエステルフィルム（外周１００ｍｍ×１００ｍｍ、内周８０ｍｍ×８０ｍｍ）を重ねて１４０℃で熱プレスにより接合した。処理後のポリエステルフィルム枠の枠内の電解質膜のしわの状態を目視で観察し、形状安定性について以下の基準で評価した。
○： 電解質膜の部分に目視で小さなしわ、波うち状の変形ともに観察されない
△： 電解質膜の部分に目視で波うち状の変形は見られないが、枠近辺に小さなしわが観察される
×： 電解質膜の部分に目視で波うち状の変形が観察される
(5) Shape stability of electrolyte membrane 100 mm square perfluorosulfonic acid resin (manufactured by DuPont: Nafion 117) is used as the electrolyte membrane, and frame-like polyester films (outer circumference 100 mm x 100 mm, inner circumference 80 mm x 80 mm) ) And were joined by hot pressing at 140 ° C. The wrinkled state of the electrolyte membrane in the polyester film frame after the treatment was visually observed, and the shape stability was evaluated according to the following criteria.
○: Small wrinkles and wavy deformation are not observed visually in the electrolyte membrane part △: No wrinkle deformation is visually observed in the electrolyte film part, but small wrinkles are observed near the frame × : Waveform deformation is visually observed in the electrolyte membrane
［実施例１］
２，６−ナフタレンジカルボン酸ジメチル１００重量部、エチレングリコール６０重量部、エステル交換触媒として酢酸マンガン四水塩０．０３重量部、滑剤として平均粒径０．５μｍの炭酸カルシウム粒子を０．２５重量％、平均粒径０．２μｍの球状シリカ粒子を０．０６重量％、および平均粒径０．１μｍの球状シリカ粒子を０．１重量％を含有するように添加して、常法に従ってエステル交換反応をさせた。それぞれの滑剤はフィルム重量に対する配合量を示す。その後、トリエチルホスホノアセテート０．０４２重量部を添加し実質的にエステル交換反応を終了させた。ついで、三酸化アンチモン０．０２４重量部を添加し、引き続き高温、高真空下で常法にて重合反応を行い、固有粘度０．６０ｄｌ／ｇのポリエチレン−２，６−ナフタレンジカルボキシレート（ＰＥＮ Ｔｇ＝１２１℃）を得た。このＰＥＮポリマーを１７５℃で５時間乾燥させた後、押出機に供給し、溶融温度３００℃で溶融し、ダイスリットより押出した後、表面温度５５℃に設定したキャスティングドラム上で冷却固化させて未延伸フィルムを作成した。
この未延伸フィルムを１４０℃にて縦方向（連続製膜方向）に３．０倍延伸し、一軸延伸フィルムを得た。一軸延伸されたフィルムの片面に、固形分濃度３重量％の水性塗布液Ａをキスコート法にて４ｇ／ｍ2塗工した。塗布液Ａは、固形分としてメチルメタクリレート７０モル％／エチルアクリレート２２モル％／Ｎ−メチロールアクリルアミド４モル％／Ｎ，Ｎ−ジメチルアクリルアミド４モル％で構成されているアクリル共重合体９０重量％に、ポリオキシエチレンラウリルエーテル（ｎ＝７）１０重量％を混合したものである。
その後、１３５℃で横方向（幅方向）に３．２倍に逐次二軸延伸し、さらに２４５℃にて熱固定処理し、さらに２４０℃で横方向に２％収縮させながら再熱処理を行い、３８μｍ厚の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１に示す。得られたフィルムは、機械的強度、耐加水分解性、高温での寸法安定性に優れていた。また電解質膜との接着性にも優れていた。
[Example 1]
100 parts by weight of dimethyl 2,6-naphthalenedicarboxylate, 60 parts by weight of ethylene glycol, 0.03 part by weight of manganese acetate tetrahydrate as a transesterification catalyst, and 0.25 weight of calcium carbonate particles having an average particle size of 0.5 μm as a lubricant %, 0.06% by weight of spherical silica particles having an average particle diameter of 0.2 μm, and 0.1% by weight of spherical silica particles having an average particle diameter of 0.1 μm are added, and transesterification is performed according to a conventional method. The reaction was allowed to proceed. Each lubricant shows the compounding quantity with respect to film weight. Thereafter, 0.042 parts by weight of triethylphosphonoacetate was added to substantially complete the transesterification reaction. Subsequently, 0.024 parts by weight of antimony trioxide was added, and then a polymerization reaction was carried out in a conventional manner under high temperature and high vacuum to obtain polyethylene-2,6-naphthalenedicarboxylate (PEN) having an intrinsic viscosity of 0.60 dl / g. Tg = 121 ° C.). This PEN polymer was dried at 175 ° C. for 5 hours, then supplied to an extruder, melted at a melting temperature of 300 ° C., extruded through a die slit, and then cooled and solidified on a casting drum set at a surface temperature of 55 ° C. An unstretched film was created.
This unstretched film was stretched 3.0 times in the longitudinal direction (continuous film-forming direction) at 140 ° C. to obtain a uniaxially stretched film. On one side of the uniaxially stretched film, 4 g / m 2 of aqueous coating solution A having a solid content concentration of 3% by weight was applied by kiss coating. The coating liquid A is 90% by weight of an acrylic copolymer composed of 70% by mole of methyl methacrylate / 22% by mole of ethyl acrylate / 4% by mole of N-methylolacrylamide / 4% by mole of N, N-dimethylacrylamide as a solid content. , 10% by weight of polyoxyethylene lauryl ether (n = 7) is mixed.
Thereafter, the film is sequentially biaxially stretched 3.2 times in the transverse direction (width direction) at 135 ° C., heat-fixed at 245 ° C., and further reheated while shrinking 2% in the transverse direction at 240 ° C., A biaxially oriented polyester film having a thickness of 38 μm was obtained. The properties of the obtained film are shown in Table 1. The obtained film was excellent in mechanical strength, hydrolysis resistance, and dimensional stability at high temperature. Moreover, the adhesiveness with the electrolyte membrane was also excellent.
［実施例２］
一軸延伸されたフィルムの片面に、塗布液を塗布しなかった以外は実施例１と同様にして３８μｍ厚みの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１に示す。得られたフィルムは、機械的強度、耐加水分解性、高温での寸法安定性に優れていた。
[Example 2]
A biaxially oriented polyester film having a thickness of 38 μm was obtained in the same manner as in Example 1 except that the coating solution was not applied to one side of the uniaxially stretched film. The properties of the obtained film are shown in Table 1. The obtained film was excellent in mechanical strength, hydrolysis resistance, and dimensional stability at high temperature.
［実施例３］
未延伸フィルムを１４０℃にて縦方向に２．３倍延伸した後、１２５℃で横方向に３．９倍に逐次二軸延伸し、１６０℃にて熱固定処理し、さらに、この二軸延伸フィルムを１７０℃にて縦方向に２．８倍延伸した後、１９０℃で横方向に１．３倍に逐次二軸延伸した後に２１５℃にて熱固定処理した以外は実施例１と同様にして３８μｍ厚の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１に示す。得られたフィルムは機械的強度、耐加水分解性に優れていたが、高温での寸法変化が若干大きかった。
[Example 3]
The unstretched film was stretched 2.3 times in the longitudinal direction at 140 ° C., and then biaxially stretched 3.9 times in the transverse direction at 125 ° C. and heat-set at 160 ° C. The stretched film was stretched 2.8 times in the machine direction at 170 ° C., then biaxially stretched 1.3 times in the transverse direction at 190 ° C., and then heat set at 215 ° C., as in Example 1. Thus, a biaxially oriented polyester film having a thickness of 38 μm was obtained. The properties of the obtained film are shown in Table 1. The obtained film was excellent in mechanical strength and hydrolysis resistance, but the dimensional change at high temperature was slightly large.
［比較例１］
固有粘度０．６１ｄｌ／ｇのポリエチレンテレフタレート（ＰＥＴ）に平均粒径０．３μｍの球状シリカを０．１重量％添加した。このＰＥＴポリマーを１７０℃で３時間乾燥させた後、押出機に供給し、溶融温度２８０℃で溶融し、ダイスリットより押出し後、表面温度２０℃に設定したキャスティングドラム上で冷却固化させて未延伸フィルムを作成した。この未延伸フィルムを１１０℃にて縦方向に３．０倍延伸し、一軸延伸フィルムを得た。その後、１２０℃で横方向に３．２倍に逐次二軸延伸し、さらに２２０℃にて熱固定処理し、さらに２１０℃で横方向に２％収縮させながら再熱処理を行い、３８μｍ厚の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１に示す。得られたフィルムは耐加水分解性が充分ではなかった。
[Comparative Example 1]
0.1% by weight of spherical silica having an average particle diameter of 0.3 μm was added to polyethylene terephthalate (PET) having an intrinsic viscosity of 0.61 dl / g. This PET polymer was dried at 170 ° C. for 3 hours, then supplied to an extruder, melted at a melting temperature of 280 ° C., extruded through a die slit, and then cooled and solidified on a casting drum set at a surface temperature of 20 ° C. A stretched film was prepared. This unstretched film was stretched 3.0 times in the longitudinal direction at 110 ° C. to obtain a uniaxially stretched film. Subsequently, the film was biaxially stretched 3.2 times in the transverse direction at 120 ° C, heat-fixed at 220 ° C, and re-heat treated while shrinking 2% in the transverse direction at 210 ° C. An axially oriented polyester film was obtained. The properties of the obtained film are shown in Table 1. The obtained film was not sufficiently resistant to hydrolysis.
［比較例２］
ポリカーボネートフィルムとして、帝人化成株式会社製「ピュアエース」を使用した。このフィルムの特性を表１に示す。このフィルムはヤング率で表される機械的強度が十分ではなかった。
[Comparative Example 2]
“Pure Ace” manufactured by Teijin Chemicals Limited was used as the polycarbonate film. The properties of this film are shown in Table 1. This film had insufficient mechanical strength expressed by Young's modulus.
本発明の二軸配向ポリエステルフィルムは、機械的強度、耐熱寸法安定性および耐加水分解性に優れており、固体高分子電解質型燃料電池の高分子電解質膜の補強材として好適に用いられる。 The biaxially oriented polyester film of the present invention is excellent in mechanical strength, heat-resistant dimensional stability and hydrolysis resistance, and is suitably used as a reinforcing material for a polymer electrolyte membrane of a solid polymer electrolyte fuel cell.
Claims (9)
破断強度保持率（％）＝（破断強度Ｘ／初期の破断強度Ｘ0）×１００ ・・・(１)
（式中、破断強度Ｘは、１２１℃、２ａｔｍ、１００％ＲＨの条件で所定時間処理後の破断強度、破断強度Ｘ0は処理前の初期の破断強度をそれぞれ表す） The biaxially oriented polyester film for a solid polymer electrolyte membrane reinforcing member according to claim 1 or 2 , wherein the time required for the breaking strength retention represented by the following formula (1) to be 50% is 100 hours or more.
Breaking strength retention ratio (%) = (breaking strength X / initial breaking strength X 0 ) × 100 (1)
(In the formula, the breaking strength X represents the breaking strength after treatment for a predetermined time under the conditions of 121 ° C., 2 atm, and 100% RH, and the breaking strength X 0 represents the initial breaking strength before the treatment)
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| JP4977540B2 (en) * | 2007-07-03 | 2012-07-18 | 本田技研工業株式会社 | Polymer electrolyte fuel cell |
| JP5145411B2 (en) | 2008-03-26 | 2013-02-20 | 帝人株式会社 | Film for reinforcing electrolyte membrane of polymer electrolyte fuel cell |
| JP5280719B2 (en) * | 2008-03-26 | 2013-09-04 | 帝人デュポンフィルム株式会社 | Biaxially oriented laminated film for reinforcing solid polymer electrolyte membrane and solid polymer electrolyte membrane reinforcing member comprising the same |
| JP5365290B2 (en) * | 2009-03-24 | 2013-12-11 | トヨタ自動車株式会社 | Fuel cell and fuel cell manufacturing method |
| JP2010232047A (en) * | 2009-03-27 | 2010-10-14 | Teijin Dupont Films Japan Ltd | Biaxially oriented polyester film for solid polymer electrolyte membrane protection, and solid polymer electrolyte membrane protection member |
| JP5308210B2 (en) * | 2009-03-30 | 2013-10-09 | 帝人デュポンフィルム株式会社 | Biaxially oriented polyester film for reinforcing solid polymer electrolyte membrane and solid polymer electrolyte membrane reinforcing member comprising the same |
| JP6131115B2 (en) * | 2013-06-13 | 2017-05-17 | パナック株式会社 | RESIN COMPOSITION FOR SOLID POLYMER TYPE FUEL CELL SEAL, SOLID MATERIAL FOR SOLID POLYMER FUEL CELL USING THE RESIN COMPOSITION, AND SOLID POLYMER FUEL CELL USING THE SEAL |
| WO2017026365A1 (en) * | 2015-08-11 | 2017-02-16 | 東洋紡株式会社 | Release film for molding solid polymer fuel cell members |
| JP6945260B2 (en) * | 2016-12-01 | 2021-10-06 | 大和製罐株式会社 | Biaxially oriented polyester film |
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| KR101059718B1 (en) * | 2003-01-21 | 2011-08-29 | 데이진 듀폰 필름 가부시키가이샤 | Laminated film |
| CN100368461C (en) * | 2003-03-05 | 2008-02-13 | 东丽株式会社 | Aromatic polymer, film, electrolyte membrane and separator |
| JP2004276565A (en) * | 2003-03-19 | 2004-10-07 | Toray Ind Inc | Manufacturing process of biaxially oriented polyester film |
| JP2004335517A (en) * | 2003-04-30 | 2004-11-25 | Teijin Dupont Films Japan Ltd | Base film for solar battery |
| JP4456894B2 (en) * | 2004-03-03 | 2010-04-28 | 帝人デュポンフィルム株式会社 | Dye-sensitized solar cell laminated film and dye-sensitized solar cell electrode using the same |
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