JP2023142430A - Method for producing para-type wholly aromatic copolyamide laminated porous film - Google Patents
Method for producing para-type wholly aromatic copolyamide laminated porous film Download PDFInfo
- Publication number
- JP2023142430A JP2023142430A JP2022049343A JP2022049343A JP2023142430A JP 2023142430 A JP2023142430 A JP 2023142430A JP 2022049343 A JP2022049343 A JP 2022049343A JP 2022049343 A JP2022049343 A JP 2022049343A JP 2023142430 A JP2023142430 A JP 2023142430A
- Authority
- JP
- Japan
- Prior art keywords
- para
- wholly aromatic
- aromatic copolyamide
- type wholly
- component
- 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.)
- Pending
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- 125000003118 aryl group Chemical group 0.000 title claims abstract description 116
- 238000004519 manufacturing process Methods 0.000 title claims description 22
- 238000000576 coating method Methods 0.000 claims abstract description 111
- 239000011248 coating agent Substances 0.000 claims abstract description 110
- 239000002904 solvent Substances 0.000 claims abstract description 46
- 239000007788 liquid Substances 0.000 claims abstract description 25
- 229920000098 polyolefin Polymers 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims abstract description 18
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000010954 inorganic particle Substances 0.000 claims abstract description 14
- 150000004985 diamines Chemical class 0.000 claims abstract description 13
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims abstract description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 8
- 239000012528 membrane Substances 0.000 claims description 60
- 229920005989 resin Polymers 0.000 claims description 38
- 239000011347 resin Substances 0.000 claims description 38
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 21
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 claims description 16
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 15
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 claims description 12
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 7
- 239000012046 mixed solvent Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- 229910013063 LiBF 4 Inorganic materials 0.000 claims description 3
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 3
- 239000004745 nonwoven fabric Substances 0.000 claims description 2
- 229910010941 LiFSI Inorganic materials 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract description 55
- 230000035699 permeability Effects 0.000 abstract description 18
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 abstract description 12
- JTERLNYVBOZRHI-RIIGGKATSA-N [(2r)-3-[2-aminoethoxy(hydroxy)phosphoryl]oxy-2-[(5e,8e,11e,14e)-icosa-5,8,11,14-tetraenoyl]oxypropyl] (5e,8e,11e,14e)-icosa-5,8,11,14-tetraenoate Chemical compound CCCCC\C=C\C\C=C\C\C=C\C\C=C\CCCC(=O)OC[C@H](COP(O)(=O)OCCN)OC(=O)CCC\C=C\C\C=C\C\C=C\C\C=C\CCCCC JTERLNYVBOZRHI-RIIGGKATSA-N 0.000 abstract description 12
- 229910001290 LiPF6 Inorganic materials 0.000 abstract description 2
- SXWUDUINABFBMK-UHFFFAOYSA-L dilithium;fluoro-dioxido-oxo-$l^{5}-phosphane Chemical compound [Li+].[Li+].[O-]P([O-])(F)=O SXWUDUINABFBMK-UHFFFAOYSA-L 0.000 abstract 1
- 239000008151 electrolyte solution Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 61
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 58
- 229920000642 polymer Polymers 0.000 description 48
- 238000006116 polymerization reaction Methods 0.000 description 48
- 239000012530 fluid Substances 0.000 description 47
- 230000015271 coagulation Effects 0.000 description 18
- 238000005345 coagulation Methods 0.000 description 18
- 229920003235 aromatic polyamide Polymers 0.000 description 16
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- 239000004760 aramid Substances 0.000 description 13
- 238000006386 neutralization reaction Methods 0.000 description 13
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 12
- 239000000920 calcium hydroxide Substances 0.000 description 12
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 12
- 239000002002 slurry Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 230000007423 decrease Effects 0.000 description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 8
- 239000000835 fiber Substances 0.000 description 8
- 239000010408 film Substances 0.000 description 8
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 7
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 7
- 238000002835 absorbance Methods 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 239000001110 calcium chloride Substances 0.000 description 7
- 229910001628 calcium chloride Inorganic materials 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000004090 dissolution Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 150000004984 aromatic diamines Chemical class 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000001112 coagulating effect Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
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- 230000035515 penetration Effects 0.000 description 2
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- 239000002244 precipitate Substances 0.000 description 2
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- 150000003839 salts Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- YVXLBNXZXSWLIK-UHFFFAOYSA-N 2,5-diaminobenzonitrile Chemical compound NC1=CC=C(N)C(C#N)=C1 YVXLBNXZXSWLIK-UHFFFAOYSA-N 0.000 description 1
- MGLZGLAFFOMWPB-UHFFFAOYSA-N 2-chloro-1,4-phenylenediamine Chemical compound NC1=CC=C(N)C(Cl)=C1 MGLZGLAFFOMWPB-UHFFFAOYSA-N 0.000 description 1
- MSWAXXJAPIGEGZ-UHFFFAOYSA-N 2-chlorobenzene-1,4-dicarbonyl chloride Chemical group ClC(=O)C1=CC=C(C(Cl)=O)C(Cl)=C1 MSWAXXJAPIGEGZ-UHFFFAOYSA-N 0.000 description 1
- RFCNVRJIPJMNBO-UHFFFAOYSA-N 2-cyanobenzene-1,4-dicarbonyl chloride Chemical group C(#N)C1=C(C(=O)Cl)C=CC(=C1)C(=O)Cl RFCNVRJIPJMNBO-UHFFFAOYSA-N 0.000 description 1
- FXFTWEVIIHVHDS-UHFFFAOYSA-N 2-fluorobenzene-1,4-diamine Chemical compound NC1=CC=C(N)C(F)=C1 FXFTWEVIIHVHDS-UHFFFAOYSA-N 0.000 description 1
- QQHCDNARIZUFGB-UHFFFAOYSA-N 2-fluorobenzene-1,4-dicarbonyl chloride Chemical group FC1=CC(C(Cl)=O)=CC=C1C(Cl)=O QQHCDNARIZUFGB-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910001514 alkali metal chloride Inorganic materials 0.000 description 1
- 229910001617 alkaline earth metal chloride Inorganic materials 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- FYXKZNLBZKRYSS-UHFFFAOYSA-N benzene-1,2-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC=C1C(Cl)=O FYXKZNLBZKRYSS-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
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- 239000008119 colloidal silica Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
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- 229910003460 diamond Inorganic materials 0.000 description 1
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- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
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- 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
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- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
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- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
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- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
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- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
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- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
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- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
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- 238000005507 spraying Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- PCHQDTOLHOFHHK-UHFFFAOYSA-L zinc;hydrogen carbonate Chemical compound [Zn+2].OC([O-])=O.OC([O-])=O PCHQDTOLHOFHHK-UHFFFAOYSA-L 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Cell Separators (AREA)
Abstract
Description
本発明は、パラ型全芳香族コポリアミドからなる積層多孔質膜の製造方法に関するものであり、さらに詳しくは、パラ型全芳香族コポリアミドと無機塩、溶媒で構成する積層膜製造用の溶液に、無機粒子とリチウム系制電剤を添加して塗工液とし、該塗工液をポリオレフィン多孔膜に積層する積層多孔質膜の製造方法に関するものである。 The present invention relates to a method for producing a laminated porous membrane made of a para-type wholly aromatic copolyamide, and more specifically, a solution for producing a laminated membrane composed of a para-type wholly aromatic copolyamide, an inorganic salt, and a solvent. The present invention relates to a method for producing a laminated porous membrane, in which inorganic particles and a lithium-based antistatic agent are added to form a coating liquid, and the coating liquid is laminated on a polyolefin porous membrane.
リチウムイオンバッテリーに用いられるセパレータにはポリエチレンやポリプロピレンなどのポリオレフィンの多孔膜が用いられる。電池に何らかの異常が発生した場合には電池内部の温度が上昇することがある。ポリオレフィン多孔膜は温度上昇に伴い多孔が閉塞し電池をシャットダウンさせる（シャットダウン機能）。 A porous membrane of polyolefin such as polyethylene or polypropylene is used as a separator for lithium-ion batteries. If some abnormality occurs in the battery, the temperature inside the battery may rise. As the temperature rises, the pores of the polyolefin porous membrane become clogged, causing the battery to shut down (shutdown function).
更に温度が上昇し、ポリオレフィンの融点を超えると、多孔膜が収縮し、電池が短絡しショートする。その後、電解液や正極の分解反応を伴い、熱暴走反応を引き起こし発火する。この熱暴走反応を防御するためにポリオレフィン多孔膜に耐熱性を持たせることが種々提案されている。 When the temperature rises further and exceeds the melting point of the polyolefin, the porous membrane contracts, causing a short circuit in the battery. Thereafter, a decomposition reaction of the electrolyte and the positive electrode occurs, causing a thermal runaway reaction and ignition. In order to prevent this thermal runaway reaction, various proposals have been made to impart heat resistance to polyolefin porous membranes.
例えば、ポリフッ化ビニリデンや水系アクリル樹脂などをアルミナ等の無機粒子と共にコーティングする技術で耐熱性が高められてきた。しかしより短時間での充電など、電池に求められる耐熱性は年々高まってきている。そこでこれらの樹脂の代わりにアラミド樹脂が使用されている（特許文献１）。 For example, heat resistance has been improved by coating techniques such as polyvinylidene fluoride or water-based acrylic resin together with inorganic particles such as alumina. However, the heat resistance required of batteries, such as faster charging times, is increasing year by year. Therefore, aramid resins are used instead of these resins (Patent Document 1).
しかし、ポリパラフェニレンテレフタルアミドを代表とするアラミド樹脂をコーティングするためには樹脂を溶媒に溶解させる必要があり、低分子量化する必要があった。しかしながら、アラミド樹脂は分子間の相互作用が強いため、結晶が析出しやすく、塗工液の安定性が悪く、生産性が悪い。 However, in order to coat an aramid resin such as polyparaphenylene terephthalamide, it is necessary to dissolve the resin in a solvent, and it is necessary to lower the molecular weight of the resin. However, since aramid resin has strong intermolecular interactions, crystals tend to precipitate, resulting in poor coating liquid stability and poor productivity.
そこで、パラ型アラミドの繊維を微細化あるいはフィラーを形成させ、塗工液に混ぜこむ手法が提案されている（特許文献２、３）。しかしながら、この手法はアラミド繊維を含むため繊維径より薄い薄膜にすることが難しく、実現性に欠ける。 Therefore, a method has been proposed in which para-aramid fibers are made fine or a filler is formed and mixed into the coating liquid (Patent Documents 2 and 3). However, since this method contains aramid fibers, it is difficult to form a thin film that is thinner than the fiber diameter, and it lacks feasibility.
そこで、耐熱性樹脂を使用せずに、ガラス転移温度の低い樹脂を用いて、電極との接着性を高めて収縮を抑制する方法が実施されている（特許文献４）。しかしながら、この方法は、樹脂のガラス転移温度が低いために、さらなる高温に達した時に、急激な劣化が起こるため、好ましくない。 Therefore, a method has been implemented in which a resin with a low glass transition temperature is used without using a heat-resistant resin to improve adhesion to the electrode and suppress shrinkage (Patent Document 4). However, this method is not preferred because the glass transition temperature of the resin is low and rapid deterioration occurs when a higher temperature is reached.
そこでメタアラミド樹脂とパラアラミド樹脂を共重合する案が提案されている（特許文献５）。しかしながら、メタアラミド樹脂とパラアラミド樹脂を共重合した場合は得られる樹脂の伸度が低くなるため、基材となるポリエチレンやポリプロピレン樹脂の伸長に追随することができず、製造工程で耐熱層が剥落することがあった。また、共重合した場合は、その溶液の安定性が十分ではなく、メタアラミド、パラアラミド樹脂の比率によっては重合後に沈降するなど、取り扱い性が限定されるという問題があった。 Therefore, a method of copolymerizing a meta-aramid resin and a para-aramid resin has been proposed (Patent Document 5). However, when meta-aramid resin and para-aramid resin are copolymerized, the elongation of the resulting resin is low, so it cannot follow the elongation of the base material polyethylene or polypropylene resin, and the heat-resistant layer peels off during the manufacturing process. Something happened. Further, when copolymerized, the stability of the solution is not sufficient, and depending on the ratio of meta-aramid and para-aramid resins, there is a problem that the handleability is limited, such as sedimentation after polymerization.
さらに、メタアラミド樹脂とパラアラミド樹脂を共重合した樹脂を用いて積層多孔質膜を製造した場合、電池組立時の注液工程において、積層多孔質膜への電解液の浸透性が悪く、リードタイムが長くなるなどの欠点があった。このため、積層多孔質膜への電解液の浸透性が可及的に改善されたアラミド積層多孔質膜の開発が切望されて来た。 Furthermore, when a laminated porous membrane is manufactured using a resin that is a copolymerization of meta-aramid resin and para-aramid resin, the permeability of the electrolyte into the laminated porous membrane is poor during the injection process during battery assembly, resulting in a long lead time. It had some drawbacks, such as being long. For this reason, there has been a strong desire to develop an aramid laminated porous membrane in which the permeability of an electrolyte into the laminated porous membrane is improved as much as possible.
本発明の目的は、かかる従来技術における問題点を解消し、溶媒への高い溶解性と塗工液の安定性、さらには、得られた積層多孔質膜への電解液の浸透性が可及的に改善されたパラ型全芳香族コポリアミドからなる積層多孔質膜の製造方法を提供することにある。 The purpose of the present invention is to solve the problems in the prior art, and to achieve high solubility in the solvent, stability of the coating solution, and permeability of the electrolyte into the obtained laminated porous membrane. An object of the present invention is to provide a method for producing a laminated porous membrane made of a para-type wholly aromatic copolyamide, which has improved performance.
本発明者は、上記の課題を解決するために鋭意検討をおこなった結果、特定の分子量のパラ型全芳香族コポリアミド樹脂に第三成分として、３，３’オキシジフェニレンジアミン、または３，４’オキシジフェニレンジアミン、または４，４’オキシジフェニレンジアミン、もしくはそれらの混合物を含んだパラ型全芳香族コポリアミドを溶剤に溶解させた樹脂溶液に、リチウム塩を溶解させることで、上記課題を解決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 added 3,3'oxydiphenylene diamine or 3, By dissolving the lithium salt in a resin solution in which a para-type wholly aromatic copolyamide containing 4' oxydiphenylene diamine, 4,4' oxydiphenylene diamine, or a mixture thereof is dissolved in a solvent, the above-mentioned The inventors have discovered that the problem can be solved and have completed the present invention.
すなわち本発明によれば、
１．下記（ａ）に記載のパラ型全芳香族コポリアミドを用い、下記（ｂ）及び（ｃ）の工程を逐次的に実施することを特徴とするパラ型全芳香族コポリアミド積層多孔質膜の製造方法。
（ａ）パラ型全芳香族コポリアミド
酸クロライド成分とジアミン成分から構成されるパラ型全芳香族コポリアミドであって、酸クロライド成分としてテレフタル酸クロライド（以下第一成分という）を含み、ジアミン成分としてパラフェニレンジアミン（以下第二成分という）及び３，３’オキシジフェニレンジアミン、または３，４’オキシジフェニレンジアミン、または４，４’オキシジフェニレンジアミン、もしくはそれらの混合物（以下第三成分という）を含んでなり、該ジアミン成分における第二成分と第三成分とのモル比率が２０／８０～８０／２０であり、且つ、該パラ型全芳香族コポリアミドの重量平均分子量が５０００～１５０，０００である、
（ｂ）パラ型全芳香族コポリアミド塗工液の製造
（ａ）に記載のパラ型全芳香族コポリアミドを、Ｎ－メチル－２－ピロリドン（ＮＭＰ）、ジメチルアセトアミド（ＤＭＡｃ）、ジメチルホルムアミド（ＤＭＦ）、またはＮ－エチル－２－ピロリドン（ＮＥＰ）のいずれか一つの溶媒もしくはそれらの混合溶媒に、０．５～１２質量％の比率で溶解させ、かつ溶解助剤を０．０５～２０質量％含有させたパラ型全芳香族コポリアミド溶液とした後、さらに、六フッ化リン酸リチウム（ＬｉＰＦ６）、ホウフッ化リチウム（ＬｉＢＦ４）、リチウム ビス（フルオロスルホニル）イミド（ＬｉＦＳＩ）、リチウム ビス（トリフルオロメタンスルホニル）イミド（ＬｉＴＦＳＩ）のうちの一つもしくはそれらの混合物を、パラ型全芳香族コポリアミドに対して０．０５～５０重量部混合させ、さらに平均粒径が０．０１～１０μｍの無機粒子を該パラ型全芳香族コポリアミド樹脂に対して１０～９９００重量部を混合させ、樹脂塗工液とする
（ｃ）積層多孔質膜の製造
（ｂ）で得られた樹脂塗工液を、ポリオレフィン多孔膜の上に０．５～１５μｍの厚さでコーティングする、そして、
２．前記ポリオレフィン多孔膜が、ポリエチレン、ポリプロピレンあるいはその混合物からなる不織布、または、多孔質フィルムである上記１に記載の積層多孔質膜の製造方法、
が提供される。
That is, according to the present invention,
1. A para-type fully aromatic copolyamide laminated porous membrane characterized by using the para-type fully aromatic copolyamide described in (a) below and sequentially carrying out the steps (b) and (c) below. Production method.
(a) Para-type wholly aromatic copolyamide A para-type wholly aromatic copolyamide composed of an acid chloride component and a diamine component, which includes terephthalic acid chloride (hereinafter referred to as the first component) as the acid chloride component, and a diamine component. paraphenylenediamine (hereinafter referred to as the second component) and 3,3'oxydiphenylenediamine, or 3,4'oxydiphenylenediamine, or 4,4'oxydiphenylenediamine, or a mixture thereof (hereinafter referred to as the third component). ), the molar ratio of the second component to the third component in the diamine component is from 20/80 to 80/20, and the weight average molecular weight of the para-type wholly aromatic copolyamide is from 5,000 to 5,000. 150,000,
(b) Production of para-type wholly aromatic copolyamide coating liquid DMF) or N-ethyl-2-pyrrolidone (NEP) or a mixed solvent thereof at a ratio of 0.5 to 12% by mass, and a solubilizing agent of 0.05 to 20% by mass. After forming a para-type wholly aromatic copolyamide solution containing % by mass, lithium hexafluorophosphate (LiPF 6 ), lithium borofluoride (LiBF 4 ), lithium bis(fluorosulfonyl)imide (LiFSI), and lithium were further added. 0.05 to 50 parts by weight of one of bis(trifluoromethanesulfonyl)imide (LiTFSI) or a mixture thereof is mixed with the para-type wholly aromatic copolyamide, and the average particle size is 0.01 to 0.01. 10 to 9,900 parts by weight of 10 μm inorganic particles are mixed with the para-type wholly aromatic copolyamide resin to prepare a resin coating solution. (c) Production of laminated porous membrane Resin coating obtained in (b) Coating the solution on the polyolefin porous membrane to a thickness of 0.5 to 15 μm, and
2. The method for producing a laminated porous membrane according to 1 above, wherein the polyolefin porous membrane is a nonwoven fabric or porous film made of polyethylene, polypropylene, or a mixture thereof;
is provided.
本発明によれば、溶媒への高い溶解性と塗工液の安定性、さらには、得られた積層多孔質膜への電解液の浸透性が可及的に改善されたパラ型全芳香族コポリアミドからなる積層多孔質膜が得られるので、リチウムイオンバッテリーに用いられるセパレータなどの用途に好適に用いることができる。 According to the present invention, a para-type wholly aromatic material having high solubility in a solvent, stability of a coating liquid, and further improved permeability of an electrolyte into the obtained laminated porous membrane as much as possible. Since a laminated porous membrane made of copolyamide is obtained, it can be suitably used for applications such as separators used in lithium ion batteries.
以下、本発明について詳細を説明する。 The present invention will be explained in detail below.
＜パラ型全芳香族コポリアミド＞
本発明におけるパラ型全芳香族コポリアミドは、酸クロライド成分とジアミン成分から構成され、化学式（１）に示す如く、１種または２種以上の２価の芳香族基が、アミド結合により直接連結されたポリマーである。そして、本発明におけるパラ型全芳香族コポリアミドは、酸クロライド成分としてテレフタル酸クロライド（以下第一成分という）を含み、ジアミン成分としてパラフェニレンジアミン（以下第二成分という）及び化学式（２）であらわされる、３，３’オキシジフェニレンジアミン、または３，４’オキシジフェニレンジアミン、または４，４’オキシジフェニレンジアミン、もしくはそれらの混合物（以下第三成分という）を含んでなり、該ジアミン成分における第二成分と第三成分とのモル比率が２０／８０～８０／２０である。
<Para-type wholly aromatic copolyamide>
The para-type wholly aromatic copolyamide in the present invention is composed of an acid chloride component and a diamine component, and as shown in chemical formula (1), one or more divalent aromatic groups are directly connected by an amide bond. It is a polymer made by The para-type wholly aromatic copolyamide in the present invention contains terephthalic acid chloride (hereinafter referred to as the first component) as an acid chloride component, para-phenylene diamine (hereinafter referred to as the second component) as a diamine component, and has the chemical formula (2). 3,3' oxydiphenylene diamine, 3,4' oxydiphenylene diamine, 4,4' oxydiphenylene diamine, or a mixture thereof (hereinafter referred to as the third component), the diamine The molar ratio of the second component and the third component in the components is 20/80 to 80/20.
＜パラ型全芳香族コポリアミドの製造方法＞
本発明におけるパラ型全芳香族コポリアミドは、従来公知の方法にしたがって製造することができる。例えば、アミド系極性溶媒中で、芳香族ジカルボン酸ジクロライド（以下「酸クロライド」ともいう）成分と芳香族ジアミン成分とを低温溶液重合、または界面重合などにより反応せしめることにより得ることができる。
<Production method of para-type wholly aromatic copolyamide>
The para-type wholly aromatic copolyamide in the present invention can be produced according to a conventionally known method. For example, it can be obtained by reacting an aromatic dicarboxylic acid dichloride (hereinafter also referred to as "acid chloride") component and an aromatic diamine component in an amide polar solvent by low-temperature solution polymerization, interfacial polymerization, or the like.
［パラ型全芳香族コポリアミドの原料］
（芳香族ジカルボン酸ジクロライド成分）
パラ型全芳香族コポリアミドの製造において使用される芳香族ジカルボン酸クロライド成分としては、上記化学式（１）を満たすものとして、テレフタル酸ジクロライドがあげられる。その他に２－フルオローテレフタル酸クロライド、２―クロローテレフタル酸ジクロライド、２－シアノーテレフタル酸ジクロライドなど官能基のついたものでも構わない。経済合理性の観点から、テレフタル酸ジクロライドが好適である。これを第一成分とする。
[Raw material for para-type wholly aromatic copolyamide]
(Aromatic dicarboxylic acid dichloride component)
As the aromatic dicarboxylic acid chloride component used in the production of the para-type wholly aromatic copolyamide, terephthalic acid dichloride may be mentioned as one satisfying the above chemical formula (1). In addition, compounds with functional groups such as 2-fluoroterephthalic acid chloride, 2-chloroterephthalic acid dichloride, and 2-cyanoterephthalic acid dichloride may also be used. From the viewpoint of economic rationality, terephthalic acid dichloride is preferred. This is the first ingredient.
（芳香族ジアミン成分）
パラ型全芳香族コポリアミドの製造において使用される芳香族ジアミン成分としては、上記化学式（１）を満たすものとして、ｐ－フェニレンジアミンを用いる。また他の芳香環としては２―フルオローパラフェニレンジアミン、２ークロローパラフェニレンジアミン、２ーシアノーパラフェニレンジアミンなどを用いても構わない。経済合理性の観点から、ｐ－フェニレンジアミンが好適である。これを第二成分とする。
(Aromatic diamine component)
As the aromatic diamine component used in the production of the para-type wholly aromatic copolyamide, p-phenylenediamine is used as one that satisfies the above chemical formula (1). Further, as other aromatic rings, 2-fluoro-para-phenylenediamine, 2-chloro-para-phenylenediamine, 2-cyano-para-phenylenediamine, etc. may be used. From the viewpoint of economic rationality, p-phenylenediamine is preferred. This is the second component.
また、上記化学式（２）を満たすものとして、第二成分以外の芳香族ジアミン成分として、３，３’オキシジフェニレンジアミン、または３，４’オキシジフェニレンジアミン、または４，４’オキシジフェニレンジアミン、のうちのいずれか一つもしくは混合物を第三成分とする。 Further, as an aromatic diamine component other than the second component that satisfies the above chemical formula (2), 3,3'oxydiphenylenediamine, 3,4'oxydiphenylenediamine, or 4,4'oxydiphenylene The third component is one or a mixture of diamines.
第三成分は第二成分と混合して用いる。該ジアミン成分における第二成分と第三成分とのモル比率は２０／８０～８０／２０、より好ましくは３０／７０～７０／３０である。第二成分の比率が８０より大きい場合にはポリマーの結晶が析出し、溶液が不安定となる。また、第二成分の比率が２０より小さい場合には得られる積層膜の強度が低下するため好ましくない。 The third component is used in combination with the second component. The molar ratio of the second component to the third component in the diamine component is 20/80 to 80/20, more preferably 30/70 to 70/30. If the ratio of the second component is greater than 80, polymer crystals will precipitate and the solution will become unstable. Moreover, if the ratio of the second component is less than 20, the strength of the resulting laminated film will decrease, which is not preferable.
［重合溶媒］
パラ型全芳香族コポリアミドを重合する際の溶媒としては、例えば、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ－メチル－２－ピロリドン、Ｎ－エチル－２－ピロリドンなどの有機極性アミド系溶媒、テトラヒドロフラン、ジオキサンなどの水溶性エーテル化合物、メタノール、エタノール、エチレングリコールなどの水溶性アルコール系化合物、アセトン、メチルエチルケトンなどの水溶性ケトン系化合物、アセトニトリル、プロピオニトリルなどの水溶性ニトリル化合物などが挙げられる。これらの溶媒は、１種単独であっても、また、２種以上の混合溶媒として使用することも可能である。なお、用いられる溶媒は、脱水されていることが望ましく、水分率が５００ｐｐｍ未満であることが好ましい。
[Polymerization solvent]
Examples of solvents for polymerizing para-type wholly aromatic copolyamides include organic solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and N-ethyl-2-pyrrolidone. Polar amide solvents, water-soluble ether compounds such as tetrahydrofuran and dioxane, water-soluble alcohol compounds such as methanol, ethanol, and ethylene glycol, water-soluble ketone compounds such as acetone and methyl ethyl ketone, and water-soluble nitriles such as acetonitrile and propionitrile. Examples include compounds. These solvents can be used alone or as a mixed solvent of two or more. Note that the solvent used is desirably dehydrated, and preferably has a moisture content of less than 500 ppm.
本発明に用いられるパラ型全芳香族コポリアミドの製造においては、汎用性、有害性、取り扱い性、パラ型全芳香族コポリアミドに対する溶解性等の観点から、Ｎ－メチル－２－ピロリドン（ＮＭＰ）、Ｎ，Ｎ－ジメチルアセトアミド（ＤＭＡｃ）、Ｎ，Ｎ－ジメチルホルムアミド（ＤＭＦ）、Ｎ－エチル－２－ピロリドン（ＮＥＰ）を用いることが好ましい。 In the production of the para-type wholly aromatic copolyamide used in the present invention, N-methyl-2-pyrrolidone (NMP ), N,N-dimethylacetamide (DMAc), N,N-dimethylformamide (DMF), and N-ethyl-2-pyrrolidone (NEP) are preferably used.
［重合体の分子量］
パラ型全芳香族コポリアミドの重量平均分子量（Ｍｗ）は５，０００～１５０，０００であることが必要である。重量平均分子量（Ｍｗ）が５，０００以下の場合には無機粒子と混合した後、ポリオレフィン膜に塗工した後に樹脂が無機粒子を担持することができず粉落ちとなる。一方、重量平均分子量が１５０，０００を超える場合には、塗工液の粘度が高くなりすぎて、生産性が悪化する。
[Molecular weight of polymer]
The para-type wholly aromatic copolyamide needs to have a weight average molecular weight (Mw) of 5,000 to 150,000. When the weight average molecular weight (Mw) is 5,000 or less, the resin cannot support the inorganic particles after being mixed with inorganic particles and coated on a polyolefin film, resulting in powder falling. On the other hand, when the weight average molecular weight exceeds 150,000, the viscosity of the coating liquid becomes too high, resulting in poor productivity.
［重合体の吸光度の比］
パラ型全芳香族コポリアミドの、赤外分光測定により得られる赤外吸収スペクトルの波長１３１８ｃｍ－１の吸光度Ａに対する波長１６５０ｃｍ－１の吸光度Ｂの比（Ｂ／Ａ）は０．９５～２．５であることが好ましい。この比が０．９５より小さい場合は、第三成分の比率が高くなり、強度が低下する。一方、この比が２．５を越える場合は、第三成分の比率が少なくなり、重合後沈降しやすくなるため好ましくない。
[Ratio of absorbance of polymer]
The ratio (B/A) of absorbance B at wavelength 1650 cm -1 to absorbance A at wavelength 1318 cm -1 in the infrared absorption spectrum obtained by infrared spectroscopy of the para-type wholly aromatic copolyamide is 0.95 to 2. It is preferable that it is 5. When this ratio is smaller than 0.95, the ratio of the third component becomes high and the strength decreases. On the other hand, if this ratio exceeds 2.5, the ratio of the third component decreases, which is undesirable because it tends to sediment after polymerization.
［その他重合条件等］
上述の重合溶媒のいずれか一つもしくはそれらの混合溶媒における、パラ型全芳香族コポリアミド重合体の濃度は０．５～１２質量％であることが好ましい。濃度が０．５％未満の場合には粘度が低すぎ、のちに凝固しポリマーを単離する際に工程が安定せず好ましくない。また１２質量％を超えるとポリマーが溶解しきれずに析出するため好ましくない。
[Other polymerization conditions, etc.]
The concentration of the para-type wholly aromatic copolyamide polymer in any one of the above-mentioned polymerization solvents or a mixed solvent thereof is preferably 0.5 to 12% by mass. If the concentration is less than 0.5%, the viscosity is too low and the polymer will coagulate later, making the process unstable when isolating the polymer, which is not preferable. Moreover, if it exceeds 12% by mass, the polymer will not be completely dissolved and will precipitate, which is not preferable.
生成する全芳香族コポリアミド重合体の溶解性を向上させるため、重合前、途中、終了時のいずれかに、一般に公知の無機塩を適当量添加しても差し支えない。このような無機塩としては、例えば、塩化リチウム、塩化ナトリウム、塩化カルシウム等のアルカリ金属の塩化物、および塩化マグネシウム、塩化カルシウム等のアルカリ土類金属の塩化物が挙げられる。このうち塩化リチウム、塩化カルシウムが好ましい。 In order to improve the solubility of the wholly aromatic copolyamide polymer to be produced, an appropriate amount of a generally known inorganic salt may be added before, during or after the polymerization. Examples of such inorganic salts include alkali metal chlorides such as lithium chloride, sodium chloride, and calcium chloride, and alkaline earth metal chlorides such as magnesium chloride and calcium chloride. Among these, lithium chloride and calcium chloride are preferred.
また、パラ型全芳香族コポリアミドの末端は、封止することもできる。末端封止剤を用いて末端を封止する場合には、例えば、フタル酸クロライドおよびその置換体、アニリンおよびその置換体等を末端封止剤として用いることができる。
また、生成する塩化水素のごとき酸を捕捉するために、脂肪族や芳香族のアミン、第４級アンモニウム塩等を併用することもできる。
Furthermore, the terminals of the para-type wholly aromatic copolyamide can also be sealed. When terminals are blocked using an end-capping agent, for example, phthaloyl chloride and its substituted products, aniline and its substituted products, etc. can be used as the terminal-capping agent.
In addition, aliphatic or aromatic amines, quaternary ammonium salts, etc. can also be used in combination to capture acids such as hydrogen chloride.
反応の終了後は、必要に応じて、塩基性の無機化合物、例えば、水酸化ナトリウム、水酸化カリウム、水酸化カルシウム、酸化カルシウム等を添加し、中和反応を実施してもよい。
中和反応後、析出した塩はフィルトレーションのプロセスを経由し除去することが好ましい。
After the reaction is completed, a basic inorganic compound such as sodium hydroxide, potassium hydroxide, calcium hydroxide, calcium oxide, etc. may be added as necessary to carry out a neutralization reaction.
After the neutralization reaction, the precipitated salt is preferably removed through a filtration process.
上記方法により得られたパラ型全芳香族コポリアミド重合体溶液は０～８０℃で溶液状態を維持するため、そのまま、ポリオレフィン多孔膜への塗工液とすることも可能である。また、本発明で得られた、重合体溶液を貧溶媒中に浸漬し、凝固することで、例えば繊維状や他の形状の固形物とすることも可能である。
固形物とする場合には以下の凝固方法により、固形物とし、溶剤に再溶解させる。
Since the para-type wholly aromatic copolyamide polymer solution obtained by the above method maintains a solution state at 0 to 80° C., it can also be used as a coating solution for a porous polyolefin membrane as it is. Further, by immersing the polymer solution obtained in the present invention in a poor solvent and coagulating it, it is also possible to form a solid material in the form of fibers or other shapes, for example.
If it is to be made into a solid, it is made into a solid by the following coagulation method and then redissolved in a solvent.
［凝固方法］
パラ型全芳香族コポリアミド、および溶媒を含む重合体溶液（ドープ）を調整する方法は、貧溶媒への浸漬により凝固させることができる。
重合体溶液（ドープ）の調製に用いられる溶媒としては、例えば、Ｎ－メチル－２－ピロリドン（ＮＭＰ）、ジメチルアセトアミド（ＤＭＡｃ）、ジメチルホルムアミド（ＤＭＦ）、ジメチルスルホキシド（ＤＭＳＯ）、Ｎ－エチル－２－ピロリドン（ＮＥＰ）等を挙げることができる。また、用いられる溶媒は１種単独であっても、２種以上を混合した混合溶媒であってもよい。さらには、パラ型全芳香族コポリアミドの重合に用いた溶媒を、そのまま使用してもよい。
[Coagulation method]
A method for preparing a polymer solution (dope) containing a para-type wholly aromatic copolyamide and a solvent is that it can be coagulated by immersion in a poor solvent.
Examples of the solvent used for preparing the polymer solution (dope) include N-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMAc), dimethylformamide (DMF), dimethylsulfoxide (DMSO), and N-ethyl- Examples include 2-pyrrolidone (NEP). Further, the solvent used may be one type alone or a mixed solvent of two or more types. Furthermore, the solvent used in the polymerization of the para-type wholly aromatic copolyamide may be used as is.
なお、重合体溶液（ドープ）におけるポリマー濃度、すなわちパラ型全芳香族コポリアミドの濃度は、０．５質量％以上１２質量％以下の範囲とすることが好ましい。重合体溶液（ドープ）におけるポリマー濃度が０．５質量％未満の場合には、ポリマーの絡み合いが少ないため、凝固時に必要な粘度が得られず、吐出安定性が低下してしまう。一方で、ポリマー濃度が１２質量％を超える場合には、ドープの粘性が急激に増加するため、吐出安定性が低下し、凝固が困難となりやすい。 Note that the polymer concentration in the polymer solution (dope), that is, the concentration of the para-type wholly aromatic copolyamide, is preferably in the range of 0.5% by mass or more and 12% by mass or less. When the polymer concentration in the polymer solution (dope) is less than 0.5% by mass, there is little entanglement of the polymers, so the necessary viscosity cannot be obtained during coagulation, resulting in a decrease in ejection stability. On the other hand, when the polymer concentration exceeds 12% by mass, the viscosity of the dope increases rapidly, resulting in a decrease in ejection stability and a tendency to make coagulation difficult.
［凝固浴］
本発明における凝固方法は、上記のように重合体を湿式凝固するのであるが、その凝固液の組成としてはパラ型全芳香族コポリアミドの貧溶媒であることが好ましい。凝固液の組成は必ずしも単一である必要はなく、例えばＮＭＰと水との混合溶媒でもよい。溶剤回収の効率性の観点から凝固浴組成（ＮＭＰ／水）としてはＮＭＰ濃度が高い方が好ましく、ＮＭＰ濃度は３０％以上が好ましい。より好ましくは３５％以上である。
[Coagulation bath]
In the coagulation method of the present invention, the polymer is wet-coagulated as described above, and the composition of the coagulation liquid is preferably a poor solvent for the para-type wholly aromatic copolyamide. The coagulation liquid does not necessarily have to have a single composition; for example, it may be a mixed solvent of NMP and water. From the viewpoint of solvent recovery efficiency, the coagulation bath composition (NMP/water) preferably has a high NMP concentration, and the NMP concentration is preferably 30% or more. More preferably, it is 35% or more.
［その他の工程］
凝固液から凝固物を引き上げた後は、凝固浴中で凝固して形成した凝固物を水洗して溶媒を徐々に除去する。そのために水洗浴の温度は６０℃以下が好ましい。
水洗後は１００℃以上の温度で乾燥後、糸条をカットしてもよいし、糸条のままとしてもよい。
[Other processes]
After the coagulated product is pulled up from the coagulation solution, the coagulated product formed by coagulation in the coagulation bath is washed with water to gradually remove the solvent. For this purpose, the temperature of the water washing bath is preferably 60°C or lower.
After washing with water, the yarn may be cut or left as is after drying at a temperature of 100° C. or higher.
［パラ型全芳香族コポリアミド塗工液の製造］
上記重合体溶液或いは凝固物は、そのまま、あるいはカットした状態で溶媒に溶解し、再溶解する。使用する溶媒は特に限定されないが、例えば、Ｎ－メチル－２－ピロリドン（ＮＭＰ）、ジメチルアセトアミド（ＤＭＡｃ）、ジメチルホルムアミド（ＤＭＦ）、ジメチルスルホキシド（ＤＭＳＯ）、Ｎ－エチル－２－ピロリドン（ＮＥＰ）等を挙げることができる。また、用いられる溶媒は１種単独であっても、２種以上を混合した混合溶媒であってもよい。これらの内、Ｎ－メチル－２－ピロリドン（ＮＭＰ）が好ましい。
[Production of para-type wholly aromatic copolyamide coating liquid]
The above polymer solution or coagulated material is dissolved in a solvent as it is or in a cut state, and then redissolved. The solvent used is not particularly limited, but for example, N-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMAc), dimethylformamide (DMF), dimethylsulfoxide (DMSO), N-ethyl-2-pyrrolidone (NEP). etc. can be mentioned. Further, the solvent used may be one type alone or a mixed solvent of two or more types. Among these, N-methyl-2-pyrrolidone (NMP) is preferred.
再溶解には、公知のミキサーを使用することができる、１軸のミキサー、リボンミキサー、プラネタリーミキサーなどを使用することができる。その中でも、プラネタリーミキサーを選定するのが好ましい。溶解にあたっては、溶媒をミキサー内に投入後、糸条あるいはカットされた糸条、粉末状の重合体を溶媒に分散させる。分散させながら、加温を行う。温度は６０℃以上が好ましい。溶解時間を早めることが可能なことから、８０℃以上がなお好ましい。昇温後、さらなる溶解性を高めるために、溶解助剤として塩化リチウム、塩化カルシウム、臭化リチウムなどのハロゲン化金属塩を混ぜ合わせる。 For redissolution, a known mixer can be used, such as a single-shaft mixer, a ribbon mixer, a planetary mixer, etc. Among them, it is preferable to select a planetary mixer. For dissolution, a solvent is introduced into a mixer, and then the threads, cut threads, and powdered polymer are dispersed in the solvent. Heat while dispersing. The temperature is preferably 60°C or higher. A temperature of 80° C. or higher is more preferable since it is possible to speed up the dissolution time. After raising the temperature, a metal halide salt such as lithium chloride, calcium chloride, or lithium bromide is mixed as a dissolution aid in order to further increase solubility.
溶解助剤の濃度は溶媒に対し０．０５～２０．０質量％であることが必要である。該濃度が０．０５質量％未満の場合には溶解助剤として能力が不足しポリマーが溶解しなくなる。一方、該濃度が２０．０質量％を越える場合には得られた溶液の粘度が高くなりすぎる。また、重合体溶液をそのまま塗工液とする場合にも溶液を安定に保つため、ハロゲン化金属塩を加えることが好ましい。 The concentration of the solubilizing agent needs to be 0.05 to 20.0% by mass based on the solvent. If the concentration is less than 0.05% by mass, its ability as a solubilizing agent will be insufficient and the polymer will not dissolve. On the other hand, if the concentration exceeds 20.0% by mass, the viscosity of the resulting solution becomes too high. Further, even when the polymer solution is directly used as a coating solution, it is preferable to add a metal halide salt to the solution in order to keep the solution stable.
パラ型全芳香族コポリアミド樹脂溶液の重合体濃度は０．５質量％以上１２質量％以下である必要がある。重合体の濃度が０．５質量％以下の場合には重合体の量が少なく、粉落ちが発生する恐れがある。一方、重合体濃度が１２質量％を越える場合には塗工液の粘度が高くなりすぎて、生産性が悪化する。 The polymer concentration of the para-type wholly aromatic copolyamide resin solution needs to be 0.5% by mass or more and 12% by mass or less. When the concentration of the polymer is 0.5% by mass or less, the amount of the polymer is small and there is a possibility that powder falling off may occur. On the other hand, if the polymer concentration exceeds 12% by mass, the viscosity of the coating liquid becomes too high, resulting in poor productivity.
重合後の溶液もしくは重合後、ポリマーを単離したのち再度溶剤に溶解させたパラ型全芳香族コポリアミド樹脂溶液に、さらに以下の工程を行い、ポリオレフィン多孔膜に塗工可能な樹脂塗工液を得ることができる。 The following steps are further applied to the solution after polymerization or the para-type wholly aromatic copolyamide resin solution, which is obtained by isolating the polymer and redissolving it in a solvent, to create a resin coating solution that can be coated on a porous polyolefin membrane. can be obtained.
従来、パラ型全芳香族アラミドをコーティングする際には専らポリパラフェニレンテルフタルアミド（ＰＰＴＡ）が用いられてきた（特許文献１）。その際、重合時に溶媒に溶解できる状態とするためには低重合度として使用されてきたが、該溶液の安定性は悪く、アラミド樹脂溶液作成後すぐに塗工する必要があった。そのため、溶液の安定性を阻害する他の成分等を混合することは困難であった。またＰＰＴＡ繊維を使用する場合には、パルプ状やショートカットファイバーなどの形状としたりし、さらに微細化するなどの処置が必要であり、あるいはフィラーを形成するなどの処置が必要であった。さらにこれらをつなぎとめるためにバインダー樹脂が用いられたが、薄膜にすることが困難であった。 Conventionally, polyparaphenylene terphthalamide (PPTA) has been used exclusively when coating para-type wholly aromatic aramid (Patent Document 1). At that time, a low degree of polymerization has been used in order to make it soluble in a solvent during polymerization, but the stability of this solution is poor, and it is necessary to apply it immediately after preparing the aramid resin solution. Therefore, it has been difficult to mix other components that inhibit the stability of the solution. Furthermore, when using PPTA fibers, it is necessary to form them into pulp-like or short-cut fibers, to make them finer, or to form fillers. Furthermore, a binder resin was used to bind these together, but it was difficult to form a thin film.
本発明で用いた溶剤に可溶なパラ型全芳香族コポリアミド樹脂を使用すれば、溶剤に溶解しているため、薄膜化することが可能である。また基材の生産工程でのライン方向への張力にも追随し、積層された耐熱層の脱落も発生しにくい。 If the solvent-soluble para-type wholly aromatic copolyamide resin used in the present invention is used, it is possible to form a thin film because it is dissolved in the solvent. It also follows the tension in the line direction during the base material production process, making it difficult for the stacked heat-resistant layers to fall off.
本発明においては、該パラ型全芳香族コポリアミド溶液に、さらに六フッ化リン酸リチウム（ＬｉＰＦ６）、ホウフッ化リチウム（ＬｉＢＦ４）、リチウム ビス（フルオロスルホニル）イミド（ＬｉＦＳＩ）、リチウム ビス（トリフルオロメタンスルホニル）イミド（ＬｉＴＦＳＩ）のうちの一つもしくはそれらの混合物を混ぜ合わせることで電池組立時の電解液浸透時間が短縮される。 In the present invention, the para-type wholly aromatic copolyamide solution is further added with lithium hexafluorophosphate (LiPF 6 ), lithium borofluoride (LiBF 4 ), lithium bis(fluorosulfonyl)imide (LiFSI), lithium bis( By mixing one of trifluoromethanesulfonyl)imide (LiTFSI) or a mixture thereof, the electrolyte penetration time during battery assembly is shortened.
リチウムイオンは非常に強いルイス酸（電化密度が高い）であるため、解離させるには対イオンとなるアニオンは比較的サイズが大きく電子が非局在化するような構造をもったルイス塩基性の低いものを用いる必要がある。そのようなリチウム塩として六フッ化リン酸リチウム（ＬｉＰＦ６）やホウフッ化リチウム（ＬｉＢＦ４）、リチウム ビス（フルオロスルホニル）イミド（ＬｉＦＳＩ）、リチウム ビス（トリフルオロメタンスルホニル）イミド（ＬｉＴＦＳＩ）が挙げられ、これらのうち一つもしくは混合物をパラ型全芳香族コポリアミド樹脂１００重量部に対して０．０５～５０重量部添加することが必要である。また、必要に応じて、合成ラテックスなどの電極との接着性を上げる剤を添加しても構わない。 Lithium ions are very strong Lewis acids (high charge density), so in order to dissociate them, the counter ion anion must be a Lewis basic one with a relatively large size and a structure in which electrons are delocalized. It is necessary to use a low one. Examples of such lithium salts include lithium hexafluorophosphate (LiPF6), lithium borofluoride (LiBF4), lithium bis(fluorosulfonyl)imide (LiFSI), and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI). It is necessary to add 0.05 to 50 parts by weight of one or a mixture thereof to 100 parts by weight of the para-type wholly aromatic copolyamide resin. Further, if necessary, an agent such as synthetic latex that improves adhesiveness with the electrode may be added.
このパラ型全芳香族コポリアミド樹脂とリチウム塩の混合溶液に無機粒子を混ぜ合わせて、塗工液とする。無機粒子としては湿式あるいは乾式シリカ、コロイダルシリカ、珪酸アルミ、二酸化チタン、炭酸カルシウム、リン酸カルシウム、硫酸バリウム、アルミナ、水酸化アルミニウム、ベーマイト、水酸化マグネシウム、炭酸マグネシウム、炭酸亜鉛、酸化亜鉛、酸化アンチモン、酸化セリウム、二酸化ジルコニウム、酸化錫、酸化ランタン、酸化マグネシウム、炭酸バリウム、炭酸亜鉛、塩基性炭酸塩、硫酸バリウム、硫酸カルシウム、硫酸鉛、硫化亜鉛、マイカ、雲母チタン、タルク、クレー、カオリン、フッ化リチウム及びフッ化カルシウムなどが挙げられる。無機粒子の平均径は０．０１μｍ～１０μｍである。０．０１μｍ以下の場合には取り扱性が困難となり好ましくない。１０μｍ以上の場合には塗工膜を薄くすることができにため、好ましくない。無機粒子の含有量は重合体１００重量部に対して１０～９９００重量部であることが必要である。無機粒子の含有量が１０重量部より少ないと、ポリオレフィン多孔膜が収縮する際の収縮応力に抵抗する粒子間の衝突が起こりにくく好ましくない。一方、無機粒子の含有量が９９００重量部を越える場合には無機粒子に対する重合体の量が少なすぎるため、粒子が担持されずに脱落する、所謂粉落ちが発生するため、好ましくない。 Inorganic particles are mixed with this mixed solution of para-type wholly aromatic copolyamide resin and lithium salt to prepare a coating liquid. Inorganic particles include wet or dry silica, colloidal silica, aluminum silicate, titanium dioxide, calcium carbonate, calcium phosphate, barium sulfate, alumina, aluminum hydroxide, boehmite, magnesium hydroxide, magnesium carbonate, zinc carbonate, zinc oxide, antimony oxide, Cerium oxide, zirconium dioxide, tin oxide, lanthanum oxide, magnesium oxide, barium carbonate, zinc carbonate, basic carbonate, barium sulfate, calcium sulfate, lead sulfate, zinc sulfide, mica, titanium mica, talc, clay, kaolin, fluoride Examples include lithium chloride and calcium fluoride. The average diameter of the inorganic particles is 0.01 μm to 10 μm. If it is less than 0.01 μm, handling becomes difficult, which is not preferable. If it is 10 μm or more, the coating film cannot be made thinner, which is not preferable. The content of inorganic particles needs to be 10 to 9900 parts by weight per 100 parts by weight of the polymer. If the content of the inorganic particles is less than 10 parts by weight, collisions between particles that resist shrinkage stress when the porous polyolefin membrane contracts are unlikely to occur, which is not preferable. On the other hand, if the content of the inorganic particles exceeds 9,900 parts by weight, the amount of polymer relative to the inorganic particles is too small, which is undesirable because the particles are not supported and fall off, which is called powder drop.
［積層多孔質膜の製造］
次に、上記の塗工液を、ポリオレフィン多孔膜の上に０．５～１５μｍの厚さでコーティングし、積層多孔質膜を得る、ポリオレフィン多孔膜への塗工量は２０～８０ｇ／ｍ２程度が好ましい。
該塗工量が２０ｇ／ｍ２未満の場合には、電池が過熱した際にポリオレフィン多孔膜の収縮力に抵抗することができず、積層多孔質膜の収縮率が低下するため好ましくない。該塗工量が８０ｇ／ｍ２を超える場合には、塗工層が厚くなりすぎて、透気度が低下するため、電池の抵抗が高くなり好ましくない。
塗工する方法はドクターナイフ法、ナイフコーター法、グラビアコーター法、スクリーン印刷法、スプレー法、ロールコーター法、コンマコーター法、マイヤーバー法などが挙げられる。
[Manufacture of laminated porous membrane]
Next, the above coating liquid is coated on the polyolefin porous membrane to a thickness of 0.5 to 15 μm to obtain a laminated porous membrane. The coating amount on the polyolefin porous membrane is 20 to 80 g/m 2 degree is preferred.
If the coating amount is less than 20 g/m 2 , it is not preferable because the shrinkage force of the polyolefin porous membrane cannot be resisted when the battery is overheated, and the shrinkage rate of the laminated porous membrane decreases. If the coating amount exceeds 80 g/m 2 , the coating layer becomes too thick and the air permeability decreases, which increases the resistance of the battery, which is not preferable.
Coating methods include a doctor knife method, a knife coater method, a gravure coater method, a screen printing method, a spray method, a roll coater method, a comma coater method, and a Meyer bar method.
本発明においては、表面に芳香族コポリアミド重合体が塗工された積層多孔質膜を乾燥機で乾燥させる。乾燥温度は５０～１００℃が好ましい。より好ましくは６０～８０℃である。１００℃以上の場合にはポリオレフィン多孔膜の多孔が溶融し閉孔する可能性があり、好ましくない。５０℃以下の場合には、生産速度が低下するため好ましくない。乾燥後、残留する溶剤を除去するために、貧溶剤の凝固液に浸漬しても構わない。凝固の方法としては凝固液をスプレーする方法や凝固液に浸漬する方法などが挙げられる。凝固液は前記重合体組成物を凝固することのできる液体であればよいが、本発明では水が好ましい。この純水の導電率が１．０μＳ／ｃｍのものが好ましい。溶剤回収の観点からまた、積層膜の構造を形成する観点から水に重合体組成物に使用している溶剤を０～３０質量％含有しているものが好ましい。凝固時間は１０～３００秒が好ましい。１０秒以下の場合には凝固が不十分となるため、好ましくない。３００秒以上の場合は生産速度が低下し、工業化には適さないため、好ましくない。 In the present invention, a laminated porous membrane whose surface is coated with an aromatic copolyamide polymer is dried in a dryer. The drying temperature is preferably 50 to 100°C. More preferably it is 60 to 80°C. If the temperature is 100° C. or higher, the pores of the polyolefin porous membrane may melt and become closed, which is not preferable. If the temperature is below 50°C, the production rate will decrease, which is not preferable. After drying, in order to remove the remaining solvent, it may be immersed in a poor solvent coagulation solution. Examples of the coagulation method include a method of spraying a coagulating liquid and a method of immersing in a coagulating liquid. The coagulating liquid may be any liquid that can coagulate the polymer composition, but water is preferred in the present invention. It is preferable that the conductivity of this pure water is 1.0 μS/cm. From the viewpoint of solvent recovery and from the viewpoint of forming the structure of a laminated film, it is preferable that the water contains 0 to 30% by mass of the solvent used in the polymer composition. The coagulation time is preferably 10 to 300 seconds. If the time is less than 10 seconds, coagulation will be insufficient, which is not preferable. If it is longer than 300 seconds, the production rate decreases and is not suitable for industrialization, which is not preferable.
このようにして得られた積層多孔質膜は、溶媒への高い溶解性と塗工液の安定性を有しており、さらには、積層多孔質膜への電解液の浸透性が可及的に改善されている。
また、このようにして得られた積層多孔質膜において、積層膜とポリオレフィン多孔膜との透気度の差（Δ透気度）は２５～１２０秒／１００ｃｃであることが好ましい。該透気度の差（Δ透気度）が２５秒／１００ｃｃより小さい場合は、積層膜の構造がルーズになり低収縮が達成できないばかりか、粉落ちが発生し、セパレータとして不適である。一方、該透気度の差（Δ透気度）が１２０秒／１００ｃｃより大きい場合は、低収縮かつ粉落ちの無いセパレータを得ることができるが、正極と負極間のリチウムイオンの移動を阻害し、電池性能を低下させる。
The laminated porous membrane obtained in this way has high solubility in solvents and stability of the coating solution, and furthermore, the permeability of the electrolyte into the laminated porous membrane is as high as possible. has been improved.
Further, in the laminated porous membrane thus obtained, the difference in air permeability (Δ air permeability) between the laminated membrane and the polyolefin porous membrane is preferably 25 to 120 seconds/100cc. If the difference in air permeability (Δ air permeability) is smaller than 25 seconds/100 cc, the structure of the laminated film becomes loose and low shrinkage cannot be achieved, and powder falls off, making it unsuitable as a separator. On the other hand, when the difference in air permeability (Δ air permeability) is larger than 120 seconds/100 cc, a separator with low shrinkage and no powder falling can be obtained, but the movement of lithium ions between the positive electrode and the negative electrode is inhibited. and reduce battery performance.
また、得られた積層多孔質膜の１５０℃での熱収縮率は１０％以下であることが好ましい。該熱収縮率が１０％を越える場合は、寸法変化が大きくなり過ぎ、正極と負極が短絡するため、セパレータとして不適となる場合がある。 Moreover, it is preferable that the heat shrinkage rate of the obtained laminated porous membrane at 150° C. is 10% or less. When the thermal shrinkage rate exceeds 10%, the dimensional change becomes too large and the positive electrode and negative electrode are short-circuited, so that the material may become unsuitable as a separator.
以下、実施例および比較例により、本発明を詳細に説明するが、本発明の範囲は、以下の実施例及び比較例に制限されるものではない。また、実施例中の各物性は以下の方法により測定した。 EXAMPLES Hereinafter, the present invention will be explained in detail with reference to Examples and Comparative Examples, but the scope of the present invention is not limited to the following Examples and Comparative Examples. In addition, each physical property in the examples was measured by the following method.
（１）分子量
重量平均分子量（Ｍｗ）および分子量多分散度（Ｍｗ／Ｍｎ）を、以下の測定条件によりゲル浸透クロマトグラフィー（ＧＰＣ）によって測定した。
装置名 ：高速液体クロマトグラフ ＬＣ－２０Ａシリーズ
カラムオーブン ：ＣＴＯ－２０Ａ
移動相 ：ＮＭＰ
オートサンプラ ：ＳＩＬ－２０ＡＨＴ
ＬＣワークステーション：ＬＣ ｓｏｌｕｔｉｏｎ
流量 ：０．３ｍｌ／分
示差屈折計検出器 ：ＲＩＤ－１０Ａ
オーブン温度 ：６０℃
分子量標準試料 ：ポリスチレン
(1) Molecular weight Weight average molecular weight (Mw) and molecular weight polydispersity (Mw/Mn) were measured by gel permeation chromatography (GPC) under the following measurement conditions.
Equipment name: High performance liquid chromatograph LC-20A series Column oven: CTO-20A
Mobile phase: NMP
Auto sampler: SIL-20AHT
LC workstation: LC solution
Flow rate: 0.3ml/min Differential refractometer detector: RID-10A
Oven temperature: 60℃
Molecular weight standard sample: polystyrene
（２）粘度
ブルックフィールド社のＤＶ２Ｔ型粘度計を用いて粘度を測定した。
(2) Viscosity Viscosity was measured using a Brookfield DV2T viscometer.
（３）積層膜の厚さ
基材となるポリオレフィン多孔膜と積層多孔質膜とをそれぞれ１０ｃｍ×１０ｃｍのサイズに打ち抜き、それぞれの厚さを９点測定し平均値を算出し、以下の計算式より、積層膜の厚さを算出した。
積層膜の厚み＝（積層多孔質膜の厚さの平均値）－（ポリオレフィン多孔膜の厚さの平均値）
(3) Thickness of the laminated membrane The polyolefin porous membrane and the laminated porous membrane serving as the base material were each punched out to a size of 10 cm x 10 cm, and the thickness of each was measured at 9 points and the average value was calculated, using the following calculation formula. From this, the thickness of the laminated film was calculated.
Thickness of laminated membrane = (average thickness of laminated porous membrane) - (average thickness of polyolefin porous membrane)
（４）１５０℃熱収縮率
得られた積層多孔質膜を一定寸法で切り出し、その切片を紙に挟んで１５０℃の温度に設定した乾燥機に６０分入れ、加熱乾燥前後の寸法変化から熱収縮率を測定した。尚、収縮率測定は、基材送り出し方向と平行方向（ＭＤ）と、垂直方向（ＴＤ）の２方向でそれぞれ実施し、その平均値を熱収縮率とした。
(4) Heat shrinkage rate at 150°C Cut out the obtained laminated porous membrane to a certain size, sandwich the cut between pieces of paper and put it in a dryer set at a temperature of 150°C for 60 minutes. The shrinkage rate was measured. The shrinkage rate was measured in two directions, parallel to the base material feeding direction (MD) and perpendicular to the direction (TD), and the average value was taken as the heat shrinkage rate.
（５）浸透性
得られた積層多孔質膜をガラス板上に置き、垂直方向１ｃｍの高さから１０μＬのガンマバレロラクトンを滴下する。滴下１分後の液滴の落下地点から最も遠い浸透場所までの長さを測定する。５点の測定を行い、その平均値を算出する。
(5) Permeability The obtained laminated porous membrane is placed on a glass plate, and 10 μL of gamma valerolactone is dropped from a height of 1 cm in the vertical direction. One minute after dropping, measure the length from the point where the droplet falls to the farthest point of penetration. Measure at 5 points and calculate the average value.
（６）重合体の吸光度の比
積層多孔質膜の表面に形成された積層膜について、下記の方法で赤外分光測定を行った。得られた赤外吸収スペクトルから、波長１３１８ｃｍ－１の吸光度Ａ、及び波長１６５０ｃｍ－１の吸光度Ｂを求め、吸光度比（Ｂ／Ａ）を算出した。
装置：サーモサイエンティフィック製、ニコレ６７００
測定法：ＡＴＲ法（１回反射ＡＴＲ法）
プリズム：ダイアモンド
入射角：４５°
測定波長：４０００－４００ｃｍ－１
積算回数：３２回
(6) Ratio of absorbance of polymers Infrared spectroscopy was performed on the laminated film formed on the surface of the laminated porous membrane by the following method. From the obtained infrared absorption spectrum, absorbance A at a wavelength of 1318 cm-1 and absorbance B at a wavelength of 1650 cm-1 were determined, and the absorbance ratio (B/A) was calculated.
Equipment: Thermo Scientific, Nicolet 6700
Measurement method: ATR method (single reflection ATR method)
Prism: Diamond Incident angle: 45°
Measurement wavelength: 4000-400cm -1
Accumulated number of times: 32 times
＜実施例１＞
［パラ型全芳香族コポリアミドの重合］
Ｎ－メチル－２－ピロリドン（ＮＭＰ）２００ｇ、パラフェニレンジアミン２．２８２２ｇ、３，４’－ジアミノジフェニルエーテル（ＤＡＰＥ）４．２２５９ｇを、常温下で反応容器に入れ、窒素雰囲気中で溶解混合した後、攪拌しながらテレフタル酸クロリド８．９３７８ｇを添加した。引き続き、８５℃で６０分間重合反応せしめることにより、透明で粘稠なポリマー溶液を得た。次いで、２２．５％の水酸化カルシウムのＮＭＰスラリー溶液を１２．１７ｇ添加し、中和反応を行うことにより重合を終了させ、パラ型全芳香族コポリアミド樹脂溶液を得た。得られたパラ型全芳香族コポリアミドの重量平均分子量は８１０００であった。
<Example 1>
[Polymerization of para-type wholly aromatic copolyamide]
200 g of N-methyl-2-pyrrolidone (NMP), 2.2822 g of paraphenylene diamine, and 4.2259 g of 3,4'-diaminodiphenyl ether (DAPE) were placed in a reaction container at room temperature, and dissolved and mixed in a nitrogen atmosphere. , 8.9378 g of terephthalic acid chloride was added with stirring. Subsequently, a polymerization reaction was carried out at 85° C. for 60 minutes to obtain a transparent and viscous polymer solution. Next, 12.17 g of a 22.5% NMP slurry solution of calcium hydroxide was added and a neutralization reaction was performed to terminate the polymerization, thereby obtaining a para-type wholly aromatic copolyamide resin solution. The weight average molecular weight of the obtained para-type wholly aromatic copolyamide was 81,000.
得られたパラ型全芳香族コポリアミド樹脂溶液をそのまま用い、紡糸口金（孔径０．３ｍｍφ、ホール数２００）から、紡糸口金面と凝固浴との距離１０ｍｍのエアーギャップを介して、ＮＭＰ水溶液（ＮＭＰ濃度：４０質量％、温度；２０℃）を凝固液とする凝固浴中に紡出して凝固させ（半乾半湿式）、引き続き、引き上げられた凝固糸を４５℃で水洗し、１７０℃の乾燥ローラー上で２５秒間接触させて乾燥し、繊維状のパラ型全芳香族コポリアミドを得た。
得られたパラ型全芳香族コポリアミド繊維は、総繊度１５４０ｄｔｅｘであった。得られたパラ系共重合芳香族ポリアミド繊維を４０ｍｍにカットし、カットファイバーを得た。
Using the obtained para-type fully aromatic copolyamide resin solution as it is, a NMP aqueous solution ( NMP concentration: 40% by mass, temperature: 20°C) was spun into a coagulation bath using a coagulation liquid and coagulated (semi-dry, semi-wet method), then the pulled coagulated thread was washed with water at 45°C, and then heated at 170°C. The mixture was dried by contacting for 25 seconds on a drying roller to obtain a fibrous para-type wholly aromatic copolyamide.
The obtained para-type wholly aromatic copolyamide fiber had a total fineness of 1540 dtex. The obtained para-copolymerized aromatic polyamide fiber was cut into 40 mm pieces to obtain cut fibers.
［塗工液の作成］
得られたカットファイバーをポリマー濃度が４質量％になるようにＮＭＰを加え、攪拌しながら、８０℃まで加温した。８０℃に到達後、溶解助剤として塩化カルシウムを８質量％となるように加え、６０分間攪拌し、パラ型全芳香族コポリアミド樹脂溶液を得た。
次に、ポリマー量１００重量部に対し、２０重量部のリチウム ビス（トリフルオロメタンスルホニル）イミド（ＬｉＴＦＳＩ）を樹脂溶液に攪拌しながら加えた。均一に攪拌した後、ポリマー１００重量部に対し９００重量部となるよう平均粒径０．３μｍのアルミナを添加し、積層用の塗工液を作成した。
[Creation of coating fluid]
NMP was added to the obtained cut fiber so that the polymer concentration was 4% by mass, and the mixture was heated to 80° C. while stirring. After reaching 80° C., calcium chloride was added as a solubilizing agent to give a concentration of 8% by mass, and the mixture was stirred for 60 minutes to obtain a para-type wholly aromatic copolyamide resin solution.
Next, 20 parts by weight of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) was added to the resin solution with stirring, based on 100 parts by weight of the polymer. After stirring uniformly, alumina having an average particle size of 0.3 μm was added to 900 parts by weight based on 100 parts by weight of the polymer to prepare a coating liquid for lamination.
［塗工液のコーティング］
膜厚が１０μｍで通気度が１７０秒／１００ｃｃのポリオレフィン多孔膜（上海エナジー製）の上にマイヤーバーを使用して片面にコーティングした。コーティング後、水に浸漬し、凝固、乾燥させ、積層多孔質膜を得た。得られた積層多孔質膜の厚さは１４μｍであった。
[Coating fluid coating]
A polyolefin porous membrane (manufactured by Shanghai Energy) having a thickness of 10 μm and an air permeability of 170 seconds/100 cc was coated on one side using a Mayer bar. After coating, it was immersed in water, coagulated, and dried to obtain a laminated porous membrane. The thickness of the obtained laminated porous membrane was 14 μm.
＜実施例２＞
［パラ型全芳香族コポリアミドの重合］
パラフェニレンジアミン３．０４２９ｇ、３，４’－ジアミノジフェニルエーテル（ＤＡＰＥ）５．６３４５ｇ、テレフタル酸クロリド９．７１１７ｇにて重合反応を行い、２２．５％の水酸化カルシウムのＮＭＰスラリー溶液を１４．０８ｇ添加して中和する以外は、実施例１と同様に実施した。得られたパラ型全芳香族コポリアミドの重量平均分子量は５０００であった。
<Example 2>
[Polymerization of para-type wholly aromatic copolyamide]
A polymerization reaction was performed using 3.0429 g of para-phenylene diamine, 5.6345 g of 3,4'-diaminodiphenyl ether (DAPE), and 9.7117 g of terephthalic acid chloride, and 14.08 g of a 22.5% NMP slurry solution of calcium hydroxide was added. The same procedure as in Example 1 was carried out except that the addition and neutralization were carried out. The weight average molecular weight of the obtained para-type wholly aromatic copolyamide was 5,000.
［塗工液の作成］
ポリマー濃度を１０質量％、塩化カルシウム濃度を１０質量％とする以外は実施例１と同様に実施した。
［塗工液のコーティング］
実施例１と同様に実施した。
[Creation of coating fluid]
The same procedure as in Example 1 was carried out except that the polymer concentration was 10% by mass and the calcium chloride concentration was 10% by mass.
[Coating fluid coating]
It was carried out in the same manner as in Example 1.
＜実施例３＞
［パラ型全芳香族コポリアミドの重合］
テレフタル酸クロリド８．４８３４ｇを加えて重合反応を行い、２２．５％の水酸化カルシウムのＮＭＰスラリー溶液を１２．３０ｇ添加して中和する以外は、実施例１と同様に実施した。得られたパラ型全芳香族コポリアミドの重量平均分子量は１５００００であった。
<Example 3>
[Polymerization of para-type wholly aromatic copolyamide]
The same procedure as in Example 1 was carried out, except that 8.4834 g of terephthalic acid chloride was added to conduct a polymerization reaction, and 12.30 g of a 22.5% NMP slurry solution of calcium hydroxide was added for neutralization. The weight average molecular weight of the obtained para-type wholly aromatic copolyamide was 150,000.
［塗工液の作成］
ポリマー濃度を１質量％、塩化カルシウム濃度を２質量％とする以外は実施例１と同様に実施した。
［塗工液のコーティング］
実施例１と同様に実施した。
[Creation of coating fluid]
The same procedure as in Example 1 was carried out except that the polymer concentration was 1% by mass and the calcium chloride concentration was 2% by mass.
[Coating fluid coating]
It was carried out in the same manner as in Example 1.
＜実施例４＞
［パラ型全芳香族コポリアミドの重合］
実施例１と同様に実施した。得られたパラ型全芳香族コポリアミドの重量平均分子量は８１０００であった。
［塗工液の作成］
溶解助剤として塩化リチウム０．０７５質量％を使用した以外は実施例１と同様に実施した。
［塗工液のコーティング］
実施例１と同様に実施した。
<Example 4>
[Polymerization of para-type wholly aromatic copolyamide]
It was carried out in the same manner as in Example 1. The weight average molecular weight of the obtained para-type wholly aromatic copolyamide was 81,000.
[Creation of coating fluid]
The same procedure as in Example 1 was carried out except that 0.075% by mass of lithium chloride was used as the solubilizing agent.
[Coating fluid coating]
It was carried out in the same manner as in Example 1.
＜実施例５＞
［パラ型全芳香族コポリアミドの重合］
パラフェニレンジアミン４．０４４６ｇ、３，４’－ジアミノジフェニルエーテル（ＤＡＰＥ）１．８７２３ｇ、テレフタル酸クロリド９．３０１７ｇにて重合反応を行い、２２．５％の水酸化カルシウムのＮＭＰスラリー溶液を１３．４９ｇ添加して中和する以外は、実施例１と同様に実施した。得られたパラ型全芳香族コポリアミドの重量平均分子量は８２０００であった。
<Example 5>
[Polymerization of para-type wholly aromatic copolyamide]
A polymerization reaction was performed using 4.0446 g of paraphenylene diamine, 1.8723 g of 3,4'-diaminodiphenyl ether (DAPE), and 9.3017 g of terephthalic acid chloride, and 13.49 g of a 22.5% NMP slurry solution of calcium hydroxide was added. The same procedure as in Example 1 was carried out except that the addition and neutralization were carried out. The weight average molecular weight of the obtained para-type wholly aromatic copolyamide was 82,000.
［塗工液の作成］
実施例１と同様に実施した。
［塗工液のコーティング］
実施例１と同様に実施した。
[Creation of coating fluid]
It was carried out in the same manner as in Example 1.
[Coating fluid coating]
It was carried out in the same manner as in Example 1.
＜実施例６＞
［パラ型全芳香族コポリアミドの重合］
パラフェニレンジアミン０．８３２０ｇ、３，４’－ジアミノジフェニルエーテル（ＤＡＰＥ）６．１６２５ｇ、テレフタル酸クロリド７．６５３９ｇにて重合反応を行い、２２．５％の水酸化カルシウムのＮＭＰスラリー溶液を１１．１０ｇ添加して中和する以外は、実施例１と同様に実施した。得られたパラ型全芳香族コポリアミドの重量平均分子量は７９０００であった。
<Example 6>
[Polymerization of para-type wholly aromatic copolyamide]
A polymerization reaction was performed using 0.8320 g of paraphenylene diamine, 6.1625 g of 3,4'-diaminodiphenyl ether (DAPE), and 7.6539 g of terephthalic acid chloride, and 11.10 g of a 22.5% NMP slurry solution of calcium hydroxide was added. The same procedure as in Example 1 was carried out except that the addition and neutralization were carried out. The weight average molecular weight of the obtained para-type wholly aromatic copolyamide was 79,000.
［塗工液の作成］
実施例１と同様に実施した。
［塗工液のコーティング］
実施例１と同様に実施した。
[Creation of coating fluid]
It was carried out in the same manner as in Example 1.
[Coating fluid coating]
It was carried out in the same manner as in Example 1.
＜実施例７＞
［パラ型全芳香族コポリアミドの重合］
３，４’－ジアミノジフェニルエーテル（ＤＡＰＥ）の代わりに４，４’－ジアミノジフェニルエーテル（４，４－ＤＡＰＥ）を使用する以外は実施例６と同様に実施した。得られたパラ型全芳香族コポリアミドの重量平均分子量は８１０００であった。
<Example 7>
[Polymerization of para-type wholly aromatic copolyamide]
The same procedure as Example 6 was carried out except that 4,4'-diaminodiphenyl ether (4,4-DAPE) was used instead of 3,4'-diaminodiphenyl ether (DAPE). The weight average molecular weight of the obtained para-type wholly aromatic copolyamide was 81,000.
［塗工液の作成］
ポリマー濃度を６％にする以外は実施例２と同様に実施した。
［塗工液のコーティング］
実施例１と同様に実施した。
以上、実施例１～７の評価結果を表１に示す。
[Creation of coating fluid]
The same procedure as in Example 2 was carried out except that the polymer concentration was changed to 6%.
[Coating fluid coating]
It was carried out in the same manner as in Example 1.
The evaluation results of Examples 1 to 7 are shown in Table 1.
＜実施例８＞
［パラ型全芳香族コポリアミドの重合］
実施例１と同様に実施した。得られたパラ型全芳香族コポリアミドの重量平均分子量は８１０００であった。
［塗工液の作成］
使用する溶媒をＮ－エチル－２－ピロリドン（ＮＥＰ）に変更する以外は、実施例１と同様に実施した。
［塗工液のコーティング］
実施例１と同様に実施した。
<Example 8>
[Polymerization of para-type wholly aromatic copolyamide]
It was carried out in the same manner as in Example 1. The weight average molecular weight of the obtained para-type wholly aromatic copolyamide was 81,000.
[Creation of coating fluid]
The same procedure as in Example 1 was carried out except that the solvent used was changed to N-ethyl-2-pyrrolidone (NEP).
[Coating fluid coating]
It was carried out in the same manner as in Example 1.
＜実施例９＞
［パラ型全芳香族コポリアミドの重合］
実施例１と同様に実施した。得られたパラ型全芳香族コポリアミドの重量平均分子量は８１０００であった。
［塗工液の作成］
平均粒径３μｍのアルミナを使用する以外は実施例１と同様に実施した。
［塗工液のコーティング］
実施例１と同様に実施した。
<Example 9>
[Polymerization of para-type wholly aromatic copolyamide]
It was carried out in the same manner as in Example 1. The weight average molecular weight of the obtained para-type wholly aromatic copolyamide was 81,000.
[Creation of coating fluid]
The same procedure as in Example 1 was carried out except that alumina having an average particle size of 3 μm was used.
[Coating fluid coating]
It was carried out in the same manner as in Example 1.
＜実施例１０＞
［パラ型全芳香族コポリアミドの重合］
実施例１と同様に実施した。得られたパラ型全芳香族コポリアミドの重量平均分子量は８１０００であった。
［塗工液の作成］
５０重量部のリチウム ビス（トリフルオロメタンスルホニル）イミド（ＬｉＴＦＳＩ）を添加する以外は実施例１と同様に実施した。
［塗工液のコーティング］
実施例１と同様に実施した。
<Example 10>
[Polymerization of para-type wholly aromatic copolyamide]
It was carried out in the same manner as in Example 1. The weight average molecular weight of the obtained para-type wholly aromatic copolyamide was 81,000.
[Creation of coating fluid]
The same procedure as in Example 1 was carried out except that 50 parts by weight of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) was added.
[Coating fluid coating]
It was carried out in the same manner as in Example 1.
＜実施例１１＞
［パラ型全芳香族コポリアミドの重合］
実施例１と同様に実施した。得られたパラ型全芳香族コポリアミドの重量平均分子量は８１０００であった。
［塗工液の作成］
０．０５重量部のリチウム ビス（トリフルオロメタンスルホニル）イミド（ＬｉＴＦＳＩ）を添加する以外は実施例１と同様に実施した。
［塗工液のコーティング］
実施例１と同様に実施した。
<Example 11>
[Polymerization of para-type wholly aromatic copolyamide]
It was carried out in the same manner as in Example 1. The weight average molecular weight of the obtained para-type wholly aromatic copolyamide was 81,000.
[Creation of coating fluid]
The same procedure as in Example 1 was carried out except that 0.05 parts by weight of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) was added.
[Coating fluid coating]
It was carried out in the same manner as in Example 1.
＜実施例１２＞
［パラ型全芳香族コポリアミドの重合］
パラフェニレンジアミン４．０４４６ｇ、３，４’－ジアミノジフェニルエーテル（ＤＡＰＥ）１．８７２３ｇ、テレフタル酸クロリド９．３９６７ｇにて重合反応を行い、２２．５％の水酸化カルシウムのＮＭＰスラリー溶液を１３．６２ｇ添加して中和する以外は、実施例１と同様に実施した。得られたパラ型全芳香族コポリアミドの重量平均分子量は１５００００であった。
<Example 12>
[Polymerization of para-type wholly aromatic copolyamide]
A polymerization reaction was performed using 4.0446 g of paraphenylene diamine, 1.8723 g of 3,4'-diaminodiphenyl ether (DAPE), and 9.3967 g of terephthalic acid chloride, and 13.62 g of a 22.5% NMP slurry solution of calcium hydroxide was prepared. The same procedure as in Example 1 was carried out except that the addition and neutralization were carried out. The weight average molecular weight of the obtained para-type wholly aromatic copolyamide was 150,000.
［塗工液の作成］
ポリマー濃度を５質量％、添加するアルミナを１０重量部とする以外は、実施例１と同様に実施した。
［塗工液のコーティング］
実施例１と同様に実施した。得られた積層多孔質膜の厚さは２５μｍであった。
[Creation of coating fluid]
The same procedure as in Example 1 was carried out except that the polymer concentration was 5% by mass and the alumina added was 10 parts by weight.
[Coating fluid coating]
It was carried out in the same manner as in Example 1. The thickness of the obtained laminated porous membrane was 25 μm.
＜実施例１３＞
［パラ型全芳香族コポリアミドの重合］
パラフェニレンジアミン０．８３２０ｇ、３，４’－ジアミノジフェニルエーテル（ＤＡＰＥ）６．１６２５ｇ、テレフタル酸クロリド７．７３２０ｇにて重合反応を行い、２２．５％の水酸化カルシウムのＮＭＰスラリー溶液を１１．２１ｇ添加して中和する以外は、実施例１と同様に実施した。得られたパラ型全芳香族コポリアミドの重量平均分子量は１５００００であった。
<Example 13>
[Polymerization of para-type wholly aromatic copolyamide]
A polymerization reaction was carried out using 0.8320 g of paraphenylene diamine, 6.1625 g of 3,4'-diaminodiphenyl ether (DAPE), and 7.7320 g of terephthalic acid chloride, and 11.21 g of a 22.5% NMP slurry solution of calcium hydroxide was prepared. The same procedure as in Example 1 was carried out except that the addition and neutralization were carried out. The weight average molecular weight of the obtained para-type wholly aromatic copolyamide was 150,000.
［塗工液の作成］
添加するアルミナを９９００重量部とする以外は、実施例１と同様に実施した。
［塗工液のコーティング］
実施例１と同様に実施した。得られた積層多孔質膜の厚さは２５μｍであった。
[Creation of coating fluid]
The same procedure as in Example 1 was carried out except that 9900 parts by weight of alumina was added.
[Coating fluid coating]
It was carried out in the same manner as in Example 1. The thickness of the obtained laminated porous membrane was 25 μm.
＜実施例１４＞
［パラ型全芳香族コポリアミドの重合］
実施例１と同様に実施した。得られたパラ型全芳香族コポリアミドの重量平均分子量は８１０００であった。
［塗工液の作成］
実施例１と同様に実施した。
［塗工液のコーティング］
片面の厚さを０．５μｍとして、両面にコーティングする以外は実施例１と同様に実施した。
以上、実施例８～１４の評価結果を表２に示す。
<Example 14>
[Polymerization of para-type wholly aromatic copolyamide]
It was carried out in the same manner as in Example 1. The weight average molecular weight of the obtained para-type wholly aromatic copolyamide was 81,000.
[Creation of coating fluid]
It was carried out in the same manner as in Example 1.
[Coating fluid coating]
The same procedure as in Example 1 was carried out except that the thickness of one side was set to 0.5 μm and both sides were coated.
The evaluation results of Examples 8 to 14 are shown in Table 2.
＜比較例１＞
［パラ型全芳香族コポリアミドの重合］
パラフェニレンジアミン２．２８２２ｇ、３，４’－ジアミノジフェニルエーテル（ＤＡＰＥ）４．２２５９ｇ、テレフタル酸クロリド６．４２６９ｇにて重合反応を行い、２２．５％の水酸化カルシウムのＮＭＰスラリー溶液を９．３２ｇ添加して中和する以外は、実施例１と同様に実施した。得られたパラ型全芳香族コポリアミドの重量平均分子量は１２００であった。
<Comparative example 1>
[Polymerization of para-type wholly aromatic copolyamide]
A polymerization reaction was performed using 2.2822 g of paraphenylene diamine, 4.2259 g of 3,4'-diaminodiphenyl ether (DAPE), and 6.4269 g of terephthalic acid chloride, and 9.32 g of a 22.5% NMP slurry solution of calcium hydroxide was added. The same procedure as in Example 1 was carried out except that the addition and neutralization were carried out. The weight average molecular weight of the obtained para-type wholly aromatic copolyamide was 1,200.
［塗工液の作成］
ポリマー濃度を１５質量％とする以外は、実施例１と同様に実施した。
［塗工液のコーティング］
ポリマー濃度が高すぎるため、塗工できなかった。
[Creation of coating fluid]
The same procedure as in Example 1 was carried out except that the polymer concentration was 15% by mass.
[Coating fluid coating]
Coating could not be performed because the polymer concentration was too high.
＜比較例２＞
［パラ型全芳香族コポリアミドの重合］
パラフェニレンジアミン２．２８２２ｇ、３，４’－ジアミノジフェニルエーテル（ＤＡＰＥ）４．２２５９ｇ、テレフタル酸クロリド８．５５２０ｇにて重合反応を行い、２２．５％の水酸化カルシウムのＮＭＰスラリー溶液を１２．４０ｇ添加して中和する以外は、実施例１と同様に実施した。得られたパラ型全芳香族コポリアミドの重量平均分子量は３０００００であった。
<Comparative example 2>
[Polymerization of para-type wholly aromatic copolyamide]
A polymerization reaction was performed using 2.2822 g of paraphenylene diamine, 4.2259 g of 3,4'-diaminodiphenyl ether (DAPE), and 8.5520 g of terephthalic acid chloride, and 12.40 g of a 22.5% NMP slurry solution of calcium hydroxide was added. The same procedure as in Example 1 was carried out except that the addition and neutralization were carried out. The weight average molecular weight of the obtained para-type wholly aromatic copolyamide was 300,000.
［塗工液の作成］
ポリマー濃度を０．５質量％とする以外は実施例１と同様に実施した。
［塗工液のコーティング］
塗工液の粘度が低すぎて塗工できなかった。
[Creation of coating fluid]
The same procedure as in Example 1 was carried out except that the polymer concentration was 0.5% by mass.
[Coating fluid coating]
The viscosity of the coating liquid was too low to coat.
＜比較例３＞
［パラ型全芳香族コポリアミドの重合］
パラフェニレンジアミン４．７１９５ｇ、３，４’－ジアミノジフェニルエーテル（ＤＡＰＥ）０．９７１０ｇ、テレフタル酸クロリド９．６４７９ｇにて重合反応を行い、２２．５％の水酸化カルシウムのＮＭＰスラリー溶液を１３．９９ｇ添加して中和する以外は、実施例１と同様に実施した。得られたパラ型全芳香族コポリアミドの重量平均分子量は８３０００であった。
［塗工液の作成］
重合後、ポリマーが析出し沈降したため、塗工液を作成することができなかった。
<Comparative example 3>
[Polymerization of para-type wholly aromatic copolyamide]
A polymerization reaction was performed using 4.7195 g of para-phenylene diamine, 0.9710 g of 3,4'-diaminodiphenyl ether (DAPE), and 9.6479 g of terephthalic acid chloride, and 13.99 g of a 22.5% NMP slurry solution of calcium hydroxide was prepared. The same procedure as in Example 1 was carried out except that the addition and neutralization were carried out. The weight average molecular weight of the obtained para-type wholly aromatic copolyamide was 83,000.
[Creation of coating fluid]
After polymerization, the polymer precipitated and precipitated, making it impossible to prepare a coating solution.
＜比較例４＞
［パラ型全芳香族コポリアミドの重合］
パラフェニレンジアミン０．４０４１ｇ、３，４’－ジアミノジフェニルエーテル（ＤＡＰＥ）６．７３４０ｇ、テレフタル酸クロリド７．４３４４ｇにて重合反応を行い、２２．５％の水酸化カルシウムのＮＭＰスラリー溶液を１０．７８ｇ添加して中和する以外は、実施例１と同様に実施した。得られたパラ型全芳香族コポリアミドの重量平均分子量は７９０００であった。
<Comparative example 4>
[Polymerization of para-type wholly aromatic copolyamide]
A polymerization reaction was performed using 0.4041 g of paraphenylene diamine, 6.7340 g of 3,4'-diaminodiphenyl ether (DAPE), and 7.4344 g of terephthalic acid chloride, and 10.78 g of a 22.5% NMP slurry solution of calcium hydroxide was added. The same procedure as in Example 1 was carried out except that the addition and neutralization were carried out. The weight average molecular weight of the obtained para-type wholly aromatic copolyamide was 79,000.
［塗工液の作成］
実施例１と同様に実施した。
［塗工液のコーティング］
実施例１と同様に実施した。
結果、収縮率が高く、不適であった。
[Creation of coating fluid]
It was carried out in the same manner as in Example 1.
[Coating fluid coating]
It was carried out in the same manner as in Example 1.
As a result, the shrinkage rate was high and it was unsuitable.
＜比較例５＞
［パラ型全芳香族コポリアミドの重合］
実施例１と同様に実施した。得られたパラ型全芳香族コポリアミドの重量平均分子量は８１０００であった。
［塗工液の作成］
溶解助剤として塩化リチウムを０．０１質量％にする以外は実施例１と同様に実施しようとしたが、ポリマーが溶解しきらず、塗工液を作成できなかった。
<Comparative example 5>
[Polymerization of para-type wholly aromatic copolyamide]
It was carried out in the same manner as in Example 1. The weight average molecular weight of the obtained para-type wholly aromatic copolyamide was 81,000.
[Creation of coating fluid]
An attempt was made to carry out the same procedure as in Example 1 except that lithium chloride was used as a dissolution aid at 0.01% by mass, but the polymer was not completely dissolved and a coating liquid could not be prepared.
＜比較例６＞
［パラ型全芳香族コポリアミドの重合］
実施例１と同様に実施した。得られたパラ型全芳香族コポリアミドの重量平均分子量は８１０００であった。
［塗工液の作成］
溶解助剤として塩化リチウムを２５質量％にする以外は実施例１と同様に実施しようとしたが、室温に静置後、塩化リチウムが析出し、塗工液を作成できなかった。
<Comparative example 6>
[Polymerization of para-type wholly aromatic copolyamide]
It was carried out in the same manner as in Example 1. The weight average molecular weight of the obtained para-type wholly aromatic copolyamide was 81,000.
[Creation of coating fluid]
An attempt was made to carry out the same procedure as in Example 1 except that lithium chloride was used as a dissolution aid at 25% by mass, but after standing at room temperature, lithium chloride precipitated and a coating solution could not be prepared.
＜比較例７＞
［パラ型全芳香族コポリアミドの重合］
実施例１と同様に実施した。得られたパラ型全芳香族コポリアミドの重量平均分子量は８１０００であった。
［塗工液の作成］
平均粒径２０μｍのアルミナを使用する以外は実施例１と同様に実施した。
［塗工液のコーティング］
実施例１と同様に実施したが、表面の凹凸が激しく、セパレータとして不適なものとなった。
<Comparative example 7>
[Polymerization of para-type wholly aromatic copolyamide]
It was carried out in the same manner as in Example 1. The weight average molecular weight of the obtained para-type wholly aromatic copolyamide was 81,000.
[Creation of coating fluid]
The same procedure as in Example 1 was carried out except that alumina having an average particle size of 20 μm was used.
[Coating fluid coating]
Although it was carried out in the same manner as in Example 1, the surface was extremely uneven, making it unsuitable as a separator.
＜比較例８＞
［パラ型全芳香族コポリアミドの重合］
実施例１と同様に実施した。得られたパラ型全芳香族コポリアミドの重量平均分子量は８１０００であった。
［塗工液の作成］
実施例１において、リチウム ビス（トリフルオロメタンスルホニル）イミド（ＬｉＴＦＳＩ）を添加しない以外は、実施例１と同様に実施した。
［塗工液のコーティング］
実施例１と同様に実施した。
結果、溶媒浸透性が悪く、不適であった。
<Comparative example 8>
[Polymerization of para-type wholly aromatic copolyamide]
It was carried out in the same manner as in Example 1. The weight average molecular weight of the obtained para-type wholly aromatic copolyamide was 81,000.
[Creation of coating fluid]
Example 1 was carried out in the same manner as in Example 1 except that lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) was not added.
[Coating fluid coating]
It was carried out in the same manner as in Example 1.
As a result, the solvent permeability was poor and it was unsuitable.
＜比較例９＞
［パラ型全芳香族コポリアミドの重合］
実施例１と同様に実施した。得られたパラ型全芳香族コポリアミドの重量平均分子量は８１０００であった。
［塗工液の作成］
実施例１において、リチウム ビス（トリフルオロメタンスルホニル）イミド（ＬｉＴＦＳＩ）を８０重量部加える以外は、実施例１と同様に実施した。
［塗工液のコーティング］
実施例１と同様に実施しようとしたが、粘度が高くなりすぎ、塗工できなかった。
<Comparative example 9>
[Polymerization of para-type wholly aromatic copolyamide]
It was carried out in the same manner as in Example 1. The weight average molecular weight of the obtained para-type wholly aromatic copolyamide was 81,000.
[Creation of coating fluid]
Example 1 was carried out in the same manner as in Example 1, except that 80 parts by weight of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) was added.
[Coating fluid coating]
An attempt was made to carry out the same procedure as in Example 1, but the viscosity became too high and coating could not be performed.
＜比較例１０＞
［パラ型全芳香族コポリアミドの重合］
実施例１と同様に実施した。得られたパラ型全芳香族コポリアミドの重量平均分子量は８１０００であった。
［塗工液の作成］
実施例１と同様に実施した。
［塗工液のコーティング］
コーティング厚さを０．４μｍとする以外は実施例１４と同様に実施した。
<Comparative example 10>
[Polymerization of para-type wholly aromatic copolyamide]
It was carried out in the same manner as in Example 1. The weight average molecular weight of the obtained para-type wholly aromatic copolyamide was 81,000.
[Creation of coating fluid]
It was carried out in the same manner as in Example 1.
[Coating fluid coating]
The same procedure as Example 14 was carried out except that the coating thickness was 0.4 μm.
＜比較例１１＞
［パラ型全芳香族コポリアミドの重合］
実施例１と同様に実施した。得られたパラ型全芳香族コポリアミドの重量平均分子量は８１０００であった。
［塗工液の作成］
実施例１と同様に実施した。
［塗工液のコーティング］
コーティング厚さを２０μｍとする以外は実施例１と同様に実施した。
結果、塗工層が厚いため、溶媒浸透性が悪く、不適であった。
実施例及び比較例により得られた積層多孔質膜の物性を表１に示す。
以上、比較例１～１１の評価結果を表３に示す。
<Comparative example 11>
[Polymerization of para-type wholly aromatic copolyamide]
It was carried out in the same manner as in Example 1. The weight average molecular weight of the obtained para-type wholly aromatic copolyamide was 81,000.
[Creation of coating fluid]
It was carried out in the same manner as in Example 1.
[Coating fluid coating]
The same procedure as in Example 1 was carried out except that the coating thickness was 20 μm.
As a result, the coating layer was thick and had poor solvent permeability, making it unsuitable.
Table 1 shows the physical properties of the laminated porous membranes obtained in Examples and Comparative Examples.
The evaluation results of Comparative Examples 1 to 11 are shown in Table 3.
溶媒への高い溶解性と塗工液の安定性、さらには、得られた積層多孔質膜への電解液の浸透性が可及的に改善されたパラ型全芳香族コポリアミドからなる積層多孔質膜が得られるので、その工業的価値は極めて大きい。 Laminated porous material made of para-type wholly aromatic copolyamide with high solubility in solvents, stability of coating solution, and improved permeability of electrolyte into the resulting laminated porous membrane. Since a quality membrane can be obtained, its industrial value is extremely large.
Claims (2)
（ａ）パラ型全芳香族コポリアミド
酸クロライド成分とジアミン成分から構成されるパラ型全芳香族コポリアミドであって、酸クロライド成分としてテレフタル酸クロライド（以下第一成分という）を含み、ジアミン成分としてパラフェニレンジアミン（以下第二成分という）及び３，３’オキシジフェニレンジアミン、または３，４’オキシジフェニレンジアミン、または４，４’オキシジフェニレンジアミン、もしくはそれらの混合物（以下第三成分という）を含んでなり、該ジアミン成分における第二成分と第三成分とのモル比率が２０／８０～８０／２０であり、且つ、該パラ型全芳香族コポリアミドの重量平均分子量が５０００～１５０，０００である
（ｂ）パラ型全芳香族コポリアミド塗工液の製造
（ａ）に記載のパラ型全芳香族コポリアミドを、Ｎ－メチル－２－ピロリドン（ＮＭＰ）、ジメチルアセトアミド（ＤＭＡｃ）、ジメチルホルムアミド（ＤＭＦ）、またはＮ－エチル－２－ピロリドン（ＮＥＰ）のいずれか一つの溶媒もしくはそれらの混合溶媒に、０．５～１２質量％の比率で溶解させ、かつ溶解助剤を０．０５～２０質量％含有させたパラ型全芳香族コポリアミド溶液とした後、さらに、六フッ化リン酸リチウム（ＬｉＰＦ６）、ホウフッ化リチウム（ＬｉＢＦ４）、リチウム ビス（フルオロスルホニル）イミド（ＬｉＦＳＩ）、リチウム ビス（トリフルオロメタンスルホニル）イミド（ＬｉＴＦＳＩ）のうちの一つもしくはそれらの混合物を、パラ型全芳香族コポリアミドに対して０．０５～５０重量部混合させ、さらに平均粒径が０．０１～１０μｍの無機粒子を該パラ型全芳香族コポリアミド樹脂に対して１０～９９００重量部を混合させ、樹脂塗工液とする
（ｃ）積層多孔質膜の製造
（ｂ）で得られた樹脂塗工液を、ポリオレフィン多孔膜の上に０．５～１５μｍの厚さでコーティングする A para-type fully aromatic copolyamide laminated porous membrane characterized by using the para-type fully aromatic copolyamide described in (a) below and sequentially carrying out the steps (b) and (c) below. Production method.
(a) Para-type wholly aromatic copolyamide A para-type wholly aromatic copolyamide composed of an acid chloride component and a diamine component, which includes terephthalic acid chloride (hereinafter referred to as the first component) as the acid chloride component, and a diamine component. paraphenylenediamine (hereinafter referred to as the second component) and 3,3'oxydiphenylenediamine, or 3,4'oxydiphenylenediamine, or 4,4'oxydiphenylenediamine, or a mixture thereof (hereinafter referred to as the third component). ), the molar ratio of the second component to the third component in the diamine component is from 20/80 to 80/20, and the weight average molecular weight of the para-type wholly aromatic copolyamide is from 5,000 to 5,000. 150,000 (b) Production of para-type wholly aromatic copolyamide coating liquid ), dimethylformamide (DMF), or N-ethyl-2-pyrrolidone (NEP) or a mixed solvent thereof at a ratio of 0.5 to 12% by mass, and a solubilizing agent is added. After forming a para-type wholly aromatic copolyamide solution containing 0.05 to 20% by mass, lithium hexafluorophosphate (LiPF 6 ), lithium borofluoride (LiBF 4 ), and lithium bis(fluorosulfonyl)imide are further added. (LiFSI), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), or a mixture thereof, is mixed in an amount of 0.05 to 50 parts by weight with respect to the para-type wholly aromatic copolyamide, and the average particle size is 10 to 9900 parts by weight of inorganic particles having a diameter of 0.01 to 10 μm are mixed with the para-type wholly aromatic copolyamide resin to prepare a resin coating liquid (c) Production of a laminated porous membrane (b) The obtained resin coating solution is coated on the polyolefin porous membrane to a thickness of 0.5 to 15 μm.
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