JP5151033B2 - Porous film composed of aromatic polyamide, battery separator, and method for producing the same - Google Patents
Porous film composed of aromatic polyamide, battery separator, and method for producing the same Download PDFInfo
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- JP5151033B2 JP5151033B2 JP2006022082A JP2006022082A JP5151033B2 JP 5151033 B2 JP5151033 B2 JP 5151033B2 JP 2006022082 A JP2006022082 A JP 2006022082A JP 2006022082 A JP2006022082 A JP 2006022082A JP 5151033 B2 JP5151033 B2 JP 5151033B2
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- film
- porous film
- weight
- aromatic polyamide
- porous
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- 239000004760 aramid Substances 0.000 title claims description 29
- 229920003235 aromatic polyamide Polymers 0.000 title claims description 29
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 125000003118 aryl group Chemical group 0.000 claims description 29
- 239000002245 particle Substances 0.000 claims description 28
- 230000035699 permeability Effects 0.000 claims description 18
- 230000003068 static effect Effects 0.000 claims description 16
- 238000003851 corona treatment Methods 0.000 claims description 14
- 239000012298 atmosphere Substances 0.000 claims description 8
- 239000010954 inorganic particle Substances 0.000 claims description 6
- 239000011146 organic particle Substances 0.000 claims description 6
- 239000010408 film Substances 0.000 description 133
- 229920000642 polymer Polymers 0.000 description 43
- 239000000243 solution Substances 0.000 description 24
- 238000000034 method Methods 0.000 description 18
- 239000004642 Polyimide Substances 0.000 description 17
- 229920001721 polyimide Polymers 0.000 description 17
- 238000012545 processing Methods 0.000 description 17
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 16
- 238000010438 heat treatment Methods 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 238000004804 winding Methods 0.000 description 12
- 238000005259 measurement Methods 0.000 description 11
- 239000011550 stock solution Substances 0.000 description 11
- 239000002904 solvent Substances 0.000 description 10
- 239000003792 electrolyte Substances 0.000 description 9
- 229920001223 polyethylene glycol Polymers 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 230000037303 wrinkles Effects 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000008119 colloidal silica Substances 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 230000010220 ion permeability Effects 0.000 description 6
- 239000005486 organic electrolyte Substances 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 238000001374 small-angle light scattering Methods 0.000 description 6
- 239000010409 thin film Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 150000004985 diamines Chemical class 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 239000002798 polar solvent Substances 0.000 description 5
- -1 polyethylene Polymers 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 238000010521 absorption reaction Methods 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
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 229920005575 poly(amic acid) Polymers 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 229910013372 LiC 4 Inorganic materials 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 229910052801 chlorine Chemical group 0.000 description 3
- 239000000460 chlorine Chemical group 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 3
- QILCUDCYZVIAQH-UHFFFAOYSA-N 1-$l^{1}-oxidanyl-2,2,5,5-tetramethylpyrrole-3-carboxylic acid Chemical compound CC1(C)C=C(C(O)=O)C(C)(C)N1[O] QILCUDCYZVIAQH-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000000149 argon plasma sintering Methods 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 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
- 238000007599 discharging Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 125000005462 imide group Chemical group 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
- 239000007788 liquid Substances 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 239000013557 residual solvent Substances 0.000 description 2
- 229920002379 silicone rubber Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 235000014692 zinc oxide Nutrition 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-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 compound ClC(=O)C1=CC=C(C(Cl)=O)C(Cl)=C1 MSWAXXJAPIGEGZ-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 229910000004 White lead Inorganic materials 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
- 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
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 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
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 238000004380 ashing Methods 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
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 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
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
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- 238000004132 cross linking Methods 0.000 description 1
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- 238000002425 crystallisation Methods 0.000 description 1
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- 238000004807 desolvation Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
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- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
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- 150000004820 halides Chemical class 0.000 description 1
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- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
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- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
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- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
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- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
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- 238000000691 measurement method Methods 0.000 description 1
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- 230000010355 oscillation Effects 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
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- 239000000843 powder Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
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- 150000003839 salts Chemical class 0.000 description 1
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- 238000001308 synthesis method Methods 0.000 description 1
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- 150000000000 tetracarboxylic acids Chemical class 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
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- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 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
- 239000013585 weight reducing agent Substances 0.000 description 1
- 238000003466 welding Methods 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
- 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
- 229910001928 zirconium oxide Inorganic materials 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
- Y02E60/10—Energy storage using batteries
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Cell Separators (AREA)
Description
本発明は、フィルター、分離膜、プリント基板、電池用セパレータ等に好適に使用できる芳香族ポリアミドまたは芳香族ポリイミドを含む多孔質フィルムに関するものである。 The present invention relates to a porous film containing an aromatic polyamide or an aromatic polyimide that can be suitably used for a filter, a separation membrane, a printed board, a battery separator, and the like.
高容量、高電圧、高エネルギー密度の達成が可能な電池として、種々の有機電解液二次電池が知られている。この有機電解液二次電池、例えば、リチウムイオン電池においては、対向配置される正極および負極間に、電解液とともに、両極間にイオンの流通が可能な多孔性高分子フィルムがセパレータとして設けられている。 Various organic electrolyte secondary batteries are known as batteries that can achieve high capacity, high voltage, and high energy density. In this organic electrolyte secondary battery, for example, a lithium ion battery, a separator is provided with a porous polymer film as a separator between the positive electrode and the negative electrode arranged opposite to each other, together with the electrolyte, and capable of flowing ions between the two electrodes. Yes.
このセパレータには、特にリチウムイオン電池の場合、安全性の面から高耐熱化を、軽量化及び小スペース化の点からは薄膜化が求められている。しかし、現在、一般に使用されているポリエチレンフィルムあるいはポリプロピレンフィルムは、耐熱性に劣るだけでなく、必要とされる強度を保って薄膜化することに限界がある。すなわち、このようなフィルムを単に薄膜化すると、局部的に強度が不十分な箇所や、高温時にセパレータとしての形態保持性が不十分になる箇所が生じることがあり、電池中で引火等の不都合が生じるおそれがあるとともに、所望のイオン透過性を備えたセパレータが形成されなくなるおそれがある。これに対して、芳香族ポリアミドや芳香族ポリイミドの多孔質フィルムは、剛性が高く薄膜化が可能で、かつ、実質的に融点を持たず耐熱性の高いことから、このような用途に好適である。 In particular, in the case of a lithium ion battery, the separator is required to have a high heat resistance from the viewpoint of safety, and a thin film from the viewpoint of weight reduction and space saving. However, currently used polyethylene film or polypropylene film is not only inferior in heat resistance, but also has a limit in thinning while maintaining the required strength. That is, if such a film is simply thinned, there may be a location where the strength is locally insufficient, or a location where the shape retention as a separator is insufficient at high temperatures, which may cause inconvenience such as ignition in the battery. May occur, and a separator having desired ion permeability may not be formed. In contrast, porous films of aromatic polyamides and aromatic polyimides are suitable for such applications because they have high rigidity and can be thinned, and have substantially no melting point and high heat resistance. is there.
芳香族ポリアミドを含む多孔質フィルムに関しては、例えば、製造方法の開示が特許文献１〜５に、多孔性フィルムに関する開示が特許文献６及び７に、電池用セパレータへの応用例が特許文献８〜１０に挙げられている。これらの発明は、特許文献６及び７は膨張係数を制御して、温度や湿度に対する変化を小さくすることを、特許文献８及び９は孔径や空孔率を制御して必要なイオン透過性を得ることを、特許文献１０は表面に無機薄膜を形成することによって耐正極酸化性の向上を目的としたものである。 Regarding the porous film containing aromatic polyamide, for example, the disclosure of the production method is disclosed in Patent Documents 1 to 5, the disclosure of the porous film is disclosed in Patent Documents 6 and 7, and the application examples to the battery separator are disclosed in Patent Documents 8 to 8. No. 10. In these inventions, Patent Documents 6 and 7 control the expansion coefficient to reduce changes with respect to temperature and humidity, and Patent Documents 8 and 9 control the pore diameter and porosity to provide the necessary ion permeability. Patent Document 10 aims to improve the positive electrode oxidation resistance by forming an inorganic thin film on the surface.
また、芳香族ポリイミドを含む多孔質フィルムに関しては、例えば、多孔性フィルム及び製造方法の開示が特許文献１１〜１３に、電池用セパレータへの応用例が特許文献１４に挙げられている。 Regarding porous films containing aromatic polyimide, for example, disclosure of porous films and production methods is disclosed in Patent Documents 11 to 13, and application examples to battery separators are listed in Patent Document 14.
しかし、生産性を向上させるためにフィルム製造（製膜）ならびに二次加工工程の速度を上げたり、１巻当たりの巻き長を長くしたりすると、次のような問題が発生する。まず、多孔性フィルムの摩擦係数が大きいと、フィルム同士あるいはフィルムとロール等との摩擦により、表層のポリマーの脱落やフィルム破れが起こり、生産性が低下することがある。特に、高速製膜時にはこの問題が顕著となる。また、逆に、摩擦係数が小さいと滑りやすくなりすぎて、巻きずれやしわが発生することがある。特に、１巻当たりの巻き長が長くなるとこの問題が顕著になる。
本発明は上記課題に鑑み、フィルム製造（製膜）工程や二次加工工程の速度を上げることにより生産性を向上させることが可能であり、かつ長尺巻き取り時に必要な滑り性や耐しわ性を有する芳香族ポリアミドから構成される多孔質フィルムを提供することを目的とする。 In view of the above problems, the present invention can improve the productivity by increasing the speed of the film production (film formation) process and the secondary processing process, and also has slipperiness and wrinkle resistance required for long winding. and to provide a porous film composed of an aromatic polyamide-de having sex.
上記目的を達成するための本発明は、芳香族ポリアミドから構成される多孔質フィルムであって、フィルム同士の静摩擦係数μｓが０．３〜１．８の範囲である多孔質フィルムであることを特徴とする。 The present invention for achieving the above object, a porous film composed of an aromatic polyamide-de, that static friction coefficient between the films μs is a porous film in the range of 0.3 to 1.8 It is characterized by.
本発明によれば、以下に記すような芳香族ポリアミドの優れた特性を保持した微多孔構造を持つフィルムを得ることができ、かつ、生産性良く長尺品を製造できることから、フィルター、分離膜、プリント基板、電池用セパレータ等として好適に用いることのできる芳香族ポリアミドから構成される多孔質フィルムを提供することができる。 According to the present invention, it is possible to obtain a film having a microporous structure which holds excellent properties of aromatic polyamide de as described below, and, because it can produce with good productivity a long article, filters, separation film, printed circuit board, it is possible to provide a porous film composed of an aromatic polyamide de which can be suitably used as a battery separator or the like.
（１）製造・加工工程の高速化と長尺化により、製品の低価格化が可能である。 (1) It is possible to reduce the price of products by speeding up and lengthening manufacturing and processing processes.
（２）ガーレ透気度（空孔率）を広い範囲で制御でき、ガーレ透気度が小さい（空孔率が大きい）ものは、電池のセパレータとした時に、電解液保持性及びイオン伝導性に優れ、ガーレ透気度が大きい（空孔率が小さい）ものは、フィルターや分離膜として使用した時に、分離能力に優れる。 (2) The Gurley permeability (porosity) can be controlled in a wide range, and those having a low Gurley permeability (large porosity) when used as a battery separator, retain the electrolyte and maintain ionic conductivity. Those having a high Gurley air permeability (low porosity) have excellent separation ability when used as a filter or a separation membrane.
（３）低熱収縮率で熱寸法安定性に優れており、高温使用に耐えることができる。 (3) It has a low thermal shrinkage rate and excellent thermal dimensional stability, and can withstand high temperature use.
本発明における芳香族ポリアミドとしては、例えば、次の式（１）及び／又は式（２）で表される繰り返し単位を有するものが好ましい。
式（１）：
As an aromatic polyamide in this invention, what has a repeating unit represented, for example by following formula (1) and / or Formula (2) is preferable.
Formula (1):
式（２）： Formula (2):
ここで、Ａｒ１、Ａｒ２、Ａｒ３の基としては、例えば、 Here, as the group of Ar 1 , Ar 2 , Ar 3 , for example,
等が挙げられ、Ｘ、Ｙの基は、−Ｏ−、−ＣＨ２−、−ＣＯ−、−ＣＯ２−、−Ｓ−、−ＳＯ２−、−Ｃ（ＣＨ３）２−等から選ばれるが、これらに限定されるものではない。 Etc. can be mentioned, X, group Y is, -O -, - CH 2 - , - CO -, - CO 2 -, - S -, - SO 2 -, - C (CH 3) 2 - selected from such However, it is not limited to these.
更に、これら芳香環上の水素原子の一部が、フッ素や臭素、塩素等のハロゲン基（特に塩素）、ニトロ基、メチルやエチル、プロピル等のアルキル基（特にメチル基）、メトキシやエトキシ、プロポキシ等のアルコキシ基等の置換基で置換されているものが、吸湿率を低下させ、湿度変化による寸法変化が小さくなるため好ましい。また、重合体を構成するアミド結合中の水素が他の置換基によって置換されていてもよい。 Furthermore, some of the hydrogen atoms on these aromatic rings are halogen groups such as fluorine, bromine and chlorine (especially chlorine), nitro groups, alkyl groups such as methyl, ethyl and propyl (especially methyl groups), methoxy and ethoxy, Those substituted with a substituent such as an alkoxy group such as propoxy are preferred because they lower the moisture absorption rate and reduce the dimensional change due to changes in humidity. In addition, hydrogen in the amide bond constituting the polymer may be substituted with another substituent.
本発明に用いられる芳香族ポリアミドは、上記の芳香環がパラ配向性を有しているものが、全芳香環の８０モル％以上、より好ましくは９０モル％以上を占めていることが好ましい。ここでいうパラ配向性とは、芳香環上主鎖を構成する２価の結合手が互いに同軸または平行にある状態をいう。このパラ配向性が８０モル％未満の場合、フィルムの剛性および耐熱性が不十分となる場合がある。更に、芳香族ポリアミドが式（３）で表される繰り返し単位を６０モル％以上含有する場合、延伸性及びフィルム物性が特に優れることから好ましい。
式（３）：
In the aromatic polyamide used in the present invention, the above aromatic ring having para-orientation preferably accounts for 80 mol% or more, more preferably 90 mol% or more of the total aromatic ring. Para-orientation here means a state in which the divalent bonds constituting the main chain on the aromatic ring are coaxial or parallel to each other. When this para orientation is less than 80 mol%, the rigidity and heat resistance of the film may be insufficient. Further, when the aromatic polyamide contains 60 mol% or more of the repeating unit represented by the formula (3), it is preferable because the stretchability and the film physical properties are particularly excellent.
Formula (3):
本発明における芳香族ポリイミドとしては、重合体の繰り返し単位の中に芳香環とイミド環を１つ以上含むものが好ましく、式（４）及び／又は式（５）で示される繰り返し単位を５０モル％以上含むものが好ましく、より好ましくは７０モル％以上である。
式（４）
As the aromatic polyimide in the present invention, those containing at least one aromatic ring and imide ring in the repeating unit of the polymer are preferable, and the repeating unit represented by the formula (4) and / or the formula (5) is 50 mol. % Or more is preferable, and more preferably 70 mol% or more.
Formula (4)
式（５） Formula (5)
ここでＡｒ４、Ａｒ６は少なくとも１個の芳香環を含み、イミド環を形成する２つのカルボニル基は芳香環上の隣接する炭素原子に結合している。このＡｒ４は、芳香族テトラカルボン酸あるいはこの無水物に由来する。代表例としては次の構造を有するものが挙げられる。 Here, Ar 4 and Ar 6 include at least one aromatic ring, and two carbonyl groups forming an imide ring are bonded to adjacent carbon atoms on the aromatic ring. This Ar 4 is derived from an aromatic tetracarboxylic acid or an anhydride thereof. Representative examples include those having the following structure.
ここでＺは、−Ｏ−、−ＣＨ２−、−ＣＯ−、−ＣＯ２−、−Ｓ−、−ＳＯ２−、−Ｃ（ＣＨ３）２−等から選ばれるが、これに限定されるものではない。また、Ａｒ６ は無水カルボン酸あるいはこのハライドに由来する。Ａｒ５、Ａｒ７は例えば Wherein Z is, -O -, - CH 2 - , - CO -, - CO 2 -, - S -, - SO 2 -, - C (CH 3) 2 - is chosen from such, it is limited to It is not something. Ar 6 is derived from carboxylic anhydride or this halide. Ar 5 and Ar 7 are for example
等が挙げられ、Ｘ、Ｙは、−Ｏ−、−ＣＨ２−、−ＣＯ−、−ＣＯ２−、−Ｓ−、−ＳＯ２−、−Ｃ（ＣＨ３）２−等から選ばれるが、これに限定されるものではない。更にこれらの芳香環上の水素原子の一部が、ハロゲン基（特に塩素）、ニトロ基、メチルやエチル、プロピル等のアルキル基（特にメチル基）、メトキシやエトキシ、プロポキシ等のアルコキシ基等の置換基で置換されているものも含み、また、重合体中にアミド結合を含む場合は、アミド結合中の水素が他の置換基によって置換されているものも含む。 Etc. can be mentioned, X, Y are, -O -, - CH 2 - , - CO -, - CO 2 -, - S -, - SO 2 -, - C (CH 3) 2 - is chosen from such However, the present invention is not limited to this. Furthermore, some of the hydrogen atoms on these aromatic rings are halogen groups (especially chlorine), nitro groups, alkyl groups such as methyl, ethyl and propyl (especially methyl groups), alkoxy groups such as methoxy, ethoxy and propoxy. Also included are those substituted with a substituent, and when the polymer contains an amide bond, includes those in which the hydrogen in the amide bond is substituted with another substituent.
本発明における芳香族ポリイミドは、一般式（４）および／または一般式（５）で表される繰り返し単位を５０モル％以上含むものが好ましく、５０モル％未満は他の繰り返し単位が共重合、またはブレンドされていても差し支えない。 The aromatic polyimide in the present invention preferably contains 50 mol% or more of the repeating unit represented by the general formula (4) and / or the general formula (5), and less than 50 mol% is copolymerized with other repeating units. Or it may be blended.
本発明の多孔質フィルムは、フィルム同士の（フィルム両面を重ね合わせたときの）静摩擦係数μｓが、０．３〜１．８の範囲である。静摩擦係数μｓが０．３未満では、フィルムが滑り過ぎて、長尺に巻き取る際に巻きずれやしわが発生することがある。一方、μｓが１．８を超えると、フィルム製造（製膜）ならびに二次加工工程で、フィルム同士あるいはフィルムとロール等との摩擦により、表層のポリマーの脱落やフィルム破れが起こり、生産性が低下することがある。生産性がより向上することから、μｓは０．３〜１．５であることがより好ましく、０．５〜１．５であることが更に好ましい。 In the porous film of the present invention, the static friction coefficient μs between films (when both film surfaces are superposed) is in the range of 0.3 to 1.8. If the static friction coefficient μs is less than 0.3, the film may slip excessively, and winding deviation or wrinkle may occur when winding the film long. On the other hand, if μs exceeds 1.8, the polymer of the surface layer may fall off or the film may be broken due to friction between the films or between the film and the roll in the film production (film formation) and the secondary processing step. May decrease. Since productivity improves more, it is more preferable that microseconds is 0.3-1.5, and it is still more preferable that it is 0.5-1.5.
静摩擦係数μｓは、ＪＩＳ−Ｋ７１２５（１９９９年）に準じて、フィルム同士を重ねて摩擦させて測定する。初期の立ち上がり抵抗値から求めることができる。ここで、フィルム同士を重ねるとは、長尺フィルムから切り出した２枚のフィルムを、一方のフィルム上に、他方のフィルムを反対側の面が接するように重ねる（表面と裏面とが接するように重ねる）ことをいう。 The static friction coefficient μs is measured by overlapping and rubbing films according to JIS-K7125 (1999). It can be obtained from the initial rise resistance value. Here, stacking the films means that two films cut out from a long film are stacked on one film so that the other film is in contact with the other film (so that the front surface and the back surface are in contact with each other). It means to overlap).
本発明の多孔質フィルムは、フィルムに含まれる芳香族ポリアミドポリマーまたは芳香族ポリイミドポリマーの数平均分子量Ｍｎが、５×１０３≦Ｍｎ≦１×１０５であることが好ましい。Ｍｎが１×１０５より大きいとポリマー溶液の粘度が高くなりすぎて製膜が困難になり、ポリマー濃度を下げざるを得ず、生産性が低下したり、本発明が規定する多孔構造を得ることが困難なことがある。一方、Ｍｎが５×１０３より小さいとフィルムの伸度が低下し、フィルム破れが発生することがある。特に、粒子を添加する場合は、フィルム中に異物が混在するため、より破れやすくなることから、１×１０４≦Ｍｎ≦１×１０５とすることがより好ましい。更に、生産性がより良く、必要な多孔構造をすみやかに得ることが可能なことから、１×１０４≦Ｍｎ≦５×１０４を満たすことがより好ましい。 In the porous film of the present invention, the aromatic polyamide polymer or aromatic polyimide polymer contained in the film preferably has a number average molecular weight Mn of 5 × 10 3 ≦ Mn ≦ 1 × 10 5 . If Mn is greater than 1 × 10 5, the viscosity of the polymer solution becomes too high, making film formation difficult, the polymer concentration has to be lowered, productivity is lowered, and a porous structure defined by the present invention is obtained. Can be difficult. On the other hand, if Mn is smaller than 5 × 10 3 , the elongation of the film is lowered, and film tearing may occur. In particular, when particles are added, foreign matters are mixed in the film, and the film is more easily broken. Therefore, 1 × 10 4 ≦ Mn ≦ 1 × 10 5 is more preferable. Furthermore, it is more preferable to satisfy 1 × 10 4 ≦ Mn ≦ 5 × 10 4 because productivity is better and a necessary porous structure can be obtained quickly.
また、該芳香族ポリアミドまたは芳香族ポリイミドは、重量平均分子量Ｍｗと数平均分子量Ｍｎの比Ｍｗ／Ｍｎが、１．３≦Ｍｗ／Ｍｎ≦４．５を満たすことが好ましい。この値が４．５を超えると低分子量成分の影響が無視できなくなり、芳香族ポリアミド本来の力学的性質や耐熱性が損なわれることがある。また、この値が１．３より小さいと結晶化し易くなるので、熱処理時に破れることがある。力学的性質や耐熱性がより良くなることから、１．３≦Ｍｗ／Ｍｎ≦３．５を満たすことがより好ましく、１．３≦Ｍｗ／Ｍｎ≦２．５を満たすことが更に好ましい。 In the aromatic polyamide or aromatic polyimide, the ratio Mw / Mn of the weight average molecular weight Mw and the number average molecular weight Mn preferably satisfies 1.3 ≦ Mw / Mn ≦ 4.5. If this value exceeds 4.5, the influence of low molecular weight components cannot be ignored, and the inherent mechanical properties and heat resistance of the aromatic polyamide may be impaired. Further, if this value is smaller than 1.3, crystallization is likely to occur and may be broken during heat treatment. It is more preferable to satisfy 1.3 ≦ Mw / Mn ≦ 3.5, and it is even more preferable to satisfy 1.3 ≦ Mw / Mn ≦ 2.5 because mechanical properties and heat resistance are improved.
数平均分子量Ｍｎ及び重量平均分子量Ｍｗの測定は以下のように行うことができる。ゲル浸透クロマトグラフ（ＧＰＣ）に、低角度レ−ザー光散乱光度計及び示差屈折率計を組み入れ、ＧＰＣでサイズ分別された溶液の光散乱強度及び屈折率差を溶出時間を追って測定することにより、溶質の分子量とその含有率を順次、計算する。 The number average molecular weight Mn and the weight average molecular weight Mw can be measured as follows. By incorporating a low-angle laser light scattering photometer and a differential refractometer into the gel permeation chromatograph (GPC), and measuring the light scattering intensity and refractive index difference of the solution separated by size by GPC along the elution time. Calculate the molecular weight of the solute and its content sequentially.
本発明の多孔質フィルムは、ガーレ透気度が５〜８００秒を満たしていることが好ましい。ガーレ透気度が上記範囲内にあれば、電池用セパレータとして使用する場合、フィルムの強度を維持しつつ、必要なイオン透過性が得られる。ガーレ透気度が５秒未満の場合、フィルムの伸度が著しく低下することがあり、ガーレ透気度が８００秒より大きいと、イオン透過性が十分でなく、繰り返し使用すると電池性能が低下することや電解液がフィルム中に浸透せず、セパレータとして機能しないことがある。フィルムの伸度とイオン透過性がよりバランス良く両立できることから、ガーレ透気度は１０〜６００秒であることがより好ましく、３０〜４００秒であることが更に好ましい。 The porous film of the present invention preferably has a Gurley permeability of 5 to 800 seconds. If the Gurley air permeability is within the above range, the required ion permeability can be obtained while maintaining the strength of the film when used as a battery separator. When the Gurley air permeability is less than 5 seconds, the elongation of the film may be remarkably reduced. When the Gurley air permeability is greater than 800 seconds, the ion permeability is not sufficient, and the battery performance decreases when repeatedly used. In some cases, the electrolyte does not penetrate into the film and does not function as a separator. The Gurley air permeability is more preferably 10 to 600 seconds, and even more preferably 30 to 400 seconds, since the film elongation and ion permeability can be achieved in a more balanced manner.
なお、ガーレ透気度の測定は、ＪＩＳ−Ｐ８１１７（１９９８年）に規定された方法に従って空気１００ｃｃが通過する時間を測定する。 In addition, the measurement of Gurley air permeability measures the time for 100cc of air to pass according to the method prescribed | regulated to JIS-P8117 (1998).
測定は、多孔質フィルムの一方向に５ｃｍ間隔で５カ所測定を行い、平均値を求めた。 The measurement was performed at 5 points at intervals of 5 cm in one direction of the porous film, and the average value was obtained.
本発明の多孔質フィルムは、少なくとも一方向の２００℃における熱収縮率が０〜２％であることが好ましい。２％を超える場合、電池を高温で使用する場合や長時間使用して蓄熱した場合、セパレータの収縮によって短絡が起こることがある。下限は０％である。耐熱性がより高くなり、安全性も向上することから、２００℃における熱収縮率が０〜１．５％であることがより好ましくは、０〜１．０％であることが更に好ましい。 The porous film of the present invention preferably has a thermal shrinkage rate at 200 ° C. in at least one direction of 0 to 2%. If it exceeds 2%, a short circuit may occur due to the shrinkage of the separator when the battery is used at a high temperature or stored for a long time. The lower limit is 0%. Since heat resistance becomes higher and safety is improved, the thermal shrinkage at 200 ° C. is more preferably 0 to 1.5%, still more preferably 0 to 1.0%.
熱収縮率の測定は以下のように行うことができる。多孔質フィルムを、幅１ｃｍ、長さ２２ｃｍの短冊状に、長辺が測定方向になるように切り取る。長辺の両端から１ｃｍの部分に印をつけ、２００℃の熱風オーブン中で３０分間、実質的に張力を掛けない状態で熱処理を行った後、印の間隔を測定し、下記の式で計算する。 The measurement of the heat shrinkage rate can be performed as follows. The porous film is cut into a strip shape having a width of 1 cm and a length of 22 cm so that the long side is in the measurement direction. Mark 1cm from both ends of the long side, heat-treat in a hot air oven at 200 ° C for 30 minutes without applying any tension, measure the distance between the marks, and calculate with the following formula To do.
熱収縮率（％）＝（（熱処理前の間隔−熱処理し冷却後の間隔）／熱処理前の間隔）×１００
本発明の多孔質フィルムは、少なくとも一方向の破断強度が５０〜３００ＭＰａであることが好ましい。強度が５０ＭＰａ未満の場合、加工時の高張力、張力変動に対抗することができず、フィルム破れが発生し、生産性が低下することがある。生産性がより良くなることから、強度は１００〜３００ＭＰａであることがより好ましく、１５０〜３００ＭＰａであることが更に好ましい。
Thermal shrinkage rate (%) = ((interval before heat treatment−interval after heat treatment and cooling) / interval before heat treatment) × 100
The porous film of the present invention preferably has a breaking strength in at least one direction of 50 to 300 MPa. When the strength is less than 50 MPa, high tension during processing and tension fluctuation cannot be counteracted, film tearing may occur, and productivity may be reduced. Since productivity becomes better, the strength is more preferably 100 to 300 MPa, and further preferably 150 to 300 MPa.
本発明の多孔質フィルムは少なくとも一方向のヤング率が３〜１０ＧＰａであることが好ましい。ヤング率が高いことにより、薄膜化しても、加工時のハンドリング性を良好に保つことができる。より薄膜化しやすくなることから、ヤング率は４．５〜１０ＧＰａであることがより好ましく、６〜１０ＧＰａであることが更に好ましい。 The porous film of the present invention preferably has a Young's modulus in at least one direction of 3 to 10 GPa. Due to the high Young's modulus, it is possible to maintain good handling properties during processing even if the film thickness is reduced. The Young's modulus is more preferably 4.5 to 10 GPa and even more preferably 6 to 10 GPa because it becomes easier to reduce the thickness.
本発明の多孔質フィルムは少なくとも一方向の破断伸度が３〜５０％であることが好ましい。伸度が高いことにより、スリット時のフィルム破れを低減することができ、高速で加工することも可能となり、生産性が良好となる。スリットがより向上することから、伸度は１０〜５０％であることがより好ましく、１５〜５０％であることが更に好ましい。 The porous film of the present invention preferably has a breaking elongation in at least one direction of 3 to 50%. Since the elongation is high, film breakage at the time of slitting can be reduced, high-speed processing is possible, and productivity is improved. Since the slit is further improved, the elongation is more preferably 10 to 50%, and further preferably 15 to 50%.
本発明の多孔質フィルムは、厚みが２〜２０μｍであることが好ましい。厚みが２０μｍを超える場合、電池１個当たりの容量が十分でないことがあり、厚みが２μｍ未満の場合、強度が不足することがある。電池１個当たりの容量を増やすことができることから、３〜１５μｍであることがより好ましく、４〜１０μｍであることが更に好ましい。 The porous film of the present invention preferably has a thickness of 2 to 20 μm. When the thickness exceeds 20 μm, the capacity per battery may not be sufficient, and when the thickness is less than 2 μm, the strength may be insufficient. Since the capacity per battery can be increased, it is more preferably 3 to 15 μm, and further preferably 4 to 10 μm.
次に、本発明の多孔質フィルムの製造方法について、以下説明するが、これに限定されるものではない。
まず、芳香族ポリアミドであるが、例えば、酸クロライドとジアミンから得る場合には、Ｎ−メチルピロリドン、ジメチルアセトアミド、ジメチルホルムアミド等の非プロトン性有機極性溶媒中で溶液重合により合成する方法や、水系媒体を使用する界面重合等で合成する方法をとることができる。ただし、ポリマーの分子量を制御しやすいことから、非プロトン性有機極性溶媒中での溶液重合が好ましい。
Next, although the manufacturing method of the porous film of this invention is demonstrated below, it is not limited to this.
First, it is an aromatic polyamide. For example, when it is obtained from acid chloride and diamine, a method of synthesis by solution polymerization in an aprotic organic polar solvent such as N-methylpyrrolidone, dimethylacetamide, dimethylformamide, A synthesis method such as interfacial polymerization using a medium can be employed. However, solution polymerization in an aprotic organic polar solvent is preferable because the molecular weight of the polymer can be easily controlled.
溶液重合の場合、ポリマーの分子量を本発明の範囲内にするために、重合に使用する溶媒の水分率を５００ｐｐｍ以下とすることが好ましく、２００ｐｐｍ以下とすることがより好ましい。使用するジアミン及び酸クロライドは、純度の高いものを用いることは言うまでもないが、モル比を、一方が他方の９７〜９９．５％、より好ましくは９８〜９９％になるように調整することが好ましい。
また、芳香族ポリアミドの重合反応は発熱を伴うが、重合中の溶液の温度を４０℃以下にすることが好ましい。４０℃を超えると、副反応が起きて、Ｍｗ／Ｍｎ＞４．５となることがある。ポリマーの分子量を本発明の範囲内に制御しやすくなることから、重合中の溶液の温度は３０℃以下にすることがより好ましい。
更に、重合反応に伴って塩化水素が副生するが、これを中和する場合には水酸化カルシウム、炭酸カルシウム、炭酸リチウムなどの無機の中和剤、またエチレンオキサイド、プロピレンオキサイド、アンモニア、トリエチルアミン、トリエタノールアミン、ジエタノールアミン等の有機の中和剤を使用するとよい。
In the case of solution polymerization, in order to make the molecular weight of the polymer within the range of the present invention, the water content of the solvent used for the polymerization is preferably 500 ppm or less, and more preferably 200 ppm or less. Needless to say, the diamine and acid chloride used are of high purity, but the molar ratio can be adjusted so that one is 97 to 99.5%, more preferably 98 to 99% of the other. preferable.
The polymerization reaction of the aromatic polyamide is accompanied by heat generation, but the temperature of the solution during polymerization is preferably 40 ° C. or lower. When it exceeds 40 degreeC, a side reaction may occur and it may become Mw / Mn> 4.5. Since the molecular weight of the polymer can be easily controlled within the range of the present invention, the temperature of the solution during the polymerization is more preferably 30 ° C. or less.
In addition, hydrogen chloride is produced as a by-product of the polymerization reaction. When neutralizing this, inorganic neutralizers such as calcium hydroxide, calcium carbonate, lithium carbonate, ethylene oxide, propylene oxide, ammonia, triethylamine are used. Organic neutralizers such as triethanolamine and diethanolamine may be used.
一方、芳香族ポリイミドあるいはポリアミド酸の溶液は次のようにして得られる。即ち、ポリアミド酸はＮ−メチルピロリドン、ジメチルアセトアミド、ジメチルホルムアミド等の非プロトン性有機極性溶媒中で、テトラカルボン酸無水物と芳香族ジアミンを反応させて調製することができる。この時、芳香族ポリアミドと同様に、重合中の溶液の温度を４０℃以下にすることが好ましい。また、芳香族ポリイミドは前記のポリアミド酸を含有する溶液を加熱したり、ピリジンなどのイミド化剤を添加してポリイミドの粉末を得、これを再度溶媒に溶解して調製できる。 On the other hand, an aromatic polyimide or polyamic acid solution is obtained as follows. That is, the polyamic acid can be prepared by reacting a tetracarboxylic acid anhydride and an aromatic diamine in an aprotic organic polar solvent such as N-methylpyrrolidone, dimethylacetamide, or dimethylformamide. At this time, like the aromatic polyamide, the temperature of the solution during polymerization is preferably 40 ° C. or lower. The aromatic polyimide can be prepared by heating a solution containing the above polyamic acid or adding an imidizing agent such as pyridine to obtain a polyimide powder, which is dissolved again in a solvent.
本発明の多孔性フィルムを得るためにはポリマーの固有粘度ηｉｎｈ（ポリマー０．５ｇを９８重量％硫酸中で１００ｍｌの溶液として３０℃で測定した値）は、０．５（ｄｌ／ｇ）以上であることが多孔性フィルムとした時に伸度が高くなり、ハンドリング性が良くなるので好ましい。 In order to obtain the porous film of the present invention, the intrinsic viscosity η inh of the polymer (value measured at 30 ° C. as a 100 ml solution of 0.5 g of polymer in 98 wt% sulfuric acid) is 0.5 (dl / g) The above is preferable because the elongation becomes high when the porous film is formed and the handling property is improved.
製膜原液としては、中和後のポリマー溶液に、ポリマーの溶解性を調整する目的で、貧溶媒である水溶性アルコール類を混合して用いてもよい。また、ポリマーを単離後、非プロトン性有機極性溶媒に再溶解し、水溶性アルコール類を混合して用いてもよい。水溶性アルコール類としては、ポリエチレングリコール、ポリプロピレングリコール、ポリビニルアルコール等が挙げられる。また、速やかにポリマーを析出させるために、混合される水溶性アルコール類の添加量は、２〜４０重量％であることが好ましく、より好ましくは５〜３０重量％、更に好ましくは１０〜２５重量％である。 As the film-forming stock solution, a water-soluble alcohol that is a poor solvent may be mixed and used in the polymer solution after neutralization for the purpose of adjusting the solubility of the polymer. Further, after the polymer is isolated, it may be redissolved in an aprotic organic polar solvent and mixed with water-soluble alcohols. Examples of water-soluble alcohols include polyethylene glycol, polypropylene glycol, and polyvinyl alcohol. Moreover, in order to precipitate a polymer rapidly, it is preferable that the addition amount of the water-soluble alcohol mixed is 2 to 40% by weight, more preferably 5 to 30% by weight, and further preferably 10 to 25% by weight. %.
製膜原液中のポリマー濃度は２〜３０重量％が好ましい。ポリマー濃度が２重量％未満の場合、フィルムの伸度が本発明の範囲を満たさないことがあり、３０重量％を超える場合、溶液の粘度が高すぎて、薄膜化が難しい。より薄く、安定した多孔性フィルムを効率良く得られることから、より好ましくは５〜２５重量％、さらに好ましくは８〜２０重量％である。 The polymer concentration in the film-forming stock solution is preferably 2 to 30% by weight. When the polymer concentration is less than 2% by weight, the elongation of the film may not satisfy the range of the present invention, and when it exceeds 30% by weight, the viscosity of the solution is too high and it is difficult to make a thin film. Since a thinner and stable porous film can be obtained efficiently, it is more preferably 5 to 25% by weight, still more preferably 8 to 20% by weight.
本発明の多孔質フィルムは、フィルム中に添加物を含有しなくても静摩擦係数を本発明の規定する範囲に制御できるが、無機粒子または有機粒子を添加することで表面に突起を形成すると、静摩擦係数をより制御しやすくなることから好ましい。無機粒子、有機粒子としては以下のような物質が挙げられる。 The porous film of the present invention can control the coefficient of static friction within the range defined by the present invention without containing any additive in the film, but when forming protrusions on the surface by adding inorganic particles or organic particles, This is preferable because the static friction coefficient can be more easily controlled. Examples of the inorganic particles and organic particles include the following substances.
無機粒子は、例えば、湿式および乾式シリカ、コロイダルシリカ、珪酸アルミ、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、炭酸マグネシウム、炭酸亜鉛、酸化チタン、酸化亜鉛（亜鉛華）、酸化アンチモン、酸化セリウム、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、塩基性炭酸鉛（鉛白）、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等が挙げられる。 Inorganic particles include, for example, wet and dry silica, colloidal silica, aluminum silicate, titanium oxide, calcium carbonate, calcium phosphate, barium sulfate, alumina, magnesium carbonate, zinc carbonate, titanium oxide, zinc oxide (zinc white), antimony oxide, oxidation Cerium, zirconium oxide, tin oxide, lanthanum oxide, magnesium oxide, barium carbonate, zinc carbonate, basic lead carbonate (lead white), barium sulfate, calcium sulfate, lead sulfate, zinc sulfide, mica, titanium mica, talc, clay, Examples include kaolin, lithium fluoride, and calcium fluoride.
有機粒子は、例えば、高分子化合物を架橋剤を用いて架橋した粒子が挙げられる。このような架橋粒子として、ポリメトキシシラン系化合物の架橋粒子、ポリスチレン系化合物の架橋粒子、アクリル系化合物の架橋粒子、ポリウレタン系化合物の架橋粒子、ポリエステル系化合物の架橋粒子、フッソ系化合物の架橋粒子、もしくはこれらの混合物が挙げられる。 Examples of the organic particles include particles obtained by crosslinking a polymer compound using a crosslinking agent. Examples of such crosslinked particles include crosslinked particles of polymethoxysilane compounds, crosslinked particles of polystyrene compounds, crosslinked particles of acrylic compounds, crosslinked particles of polyurethane compounds, crosslinked particles of polyester compounds, and crosslinked particles of fluorine compounds. Or a mixture thereof.
上記粒子の中でも、特に、電池用セパレータとして使用した場合、電解液に対する耐久性が高いことからシリカ粒子が好ましい。 Among the above particles, particularly when used as a battery separator, silica particles are preferred because of their high durability against electrolytes.
該無機粒子および有機粒子は球状で、その平均粒径は１５ｎｍ〜２μｍの範囲であることが好ましい。平均粒径が１５ｎｍ未満では突起が十分形成されず、静摩擦係数が本発明の規定する範囲より大きくなることがあり、２μｍを超えると粒子の脱落や静摩擦係数が小さくなりすぎて滑りやすくなり、巻きずれやしわが発生することがある。 The inorganic particles and organic particles are preferably spherical, and the average particle size is preferably in the range of 15 nm to 2 μm. When the average particle size is less than 15 nm, sufficient protrusions are not formed, and the static friction coefficient may be larger than the range specified by the present invention. When the average particle diameter exceeds 2 μm, the particles fall off or the static friction coefficient becomes too small and slipping easily occurs. Deviations and wrinkles may occur.
該無機粒子および有機粒子は、粒子の総含有量が０．２〜１５重量％となるように添加することが好ましい。含有量が０．２重量％未満では突起が十分形成されず、静摩擦係数が本発明の規定する範囲より大きくなることがあり、１５重量％を超えると粒子の脱落やフィルムの伸度が低下することがある。 The inorganic particles and organic particles are preferably added so that the total content of the particles is 0.2 to 15% by weight. When the content is less than 0.2% by weight, the protrusions are not sufficiently formed, and the static friction coefficient may be larger than the range defined by the present invention. When the content exceeds 15% by weight, the dropout of the particles and the elongation of the film are lowered. Sometimes.
粒子の含有量は、製膜時の仕込量から計算できるが、フィルムから測定する場合は、フィルムを灰化後、塩酸を加えて加熱溶解した容液について、ＩＣＰ発光分光分析法（例えばセイコー電子工業製ＩＣＰ発光分光分析装置ＳＰＳ１２００ＶＲを用いて測定できる）により求めることができる。 The content of the particles can be calculated from the amount charged at the time of film formation. However, when measuring from a film, ICP emission spectroscopy (for example, Seiko Electronics Co., Ltd.) is used for a solution obtained by ashing the film and then adding hydrochloric acid to heat. It can be determined by using an ICP emission spectroscopic analyzer SPS1200VR manufactured by Kogyo).
上記のようにして調製された製膜原液は、いわゆる溶液製膜法により、多孔質フィルムとすることができる。 The film-forming stock solution prepared as described above can be made into a porous film by a so-called solution film-forming method.
まず、製膜原液は、口金やダイコーターを用いて、エンドレスベルト、ドラム、フィルム等の支持体上に吐出させて、芳香族ポリアミドまたは芳香族ポリイミドの薄膜を形成する。この時、吐出量と支持体の走行速度で薄膜の厚みを制御できる。 First, the raw film forming solution is discharged onto a support such as an endless belt, a drum, or a film using a die or a die coater to form a thin film of aromatic polyamide or aromatic polyimide. At this time, the thickness of the thin film can be controlled by the discharge amount and the running speed of the support.
次に、多孔質化を行うが、多孔質化の方法としては、湿式浴への導入、高湿度雰囲気下での吸湿、冷却等により、ポリマーの溶解性を低下させて、相分離または析出させることが好ましい。特に、溶解性の制御が難しい芳香族ポリアミド及び芳香族ポリイミドでは、均一な多孔質構造を短時間で形成できることから、高湿度雰囲気下で吸湿させる方法が特に好ましい。 Next, the porosity is made. As a method of making the pores, the solubility of the polymer is lowered by introduction into a wet bath, moisture absorption in a high humidity atmosphere, cooling, or the like, and phase separation or precipitation is performed. It is preferable. Particularly for aromatic polyamides and aromatic polyimides whose solubility is difficult to control, a uniform porous structure can be formed in a short time, and therefore, a method of absorbing moisture in a high humidity atmosphere is particularly preferable.
湿式浴を用いて多孔質化する方法では、芳香族ポリアミドまたは芳香族ポリイミドの良溶媒である有機極性溶媒を２０重量％以上添加した浴、または塩化カルシウム、塩化リチウム、臭化リチウム等の無機塩を１０重量％以上添加した浴を用いることが好ましい。水のみの浴では、急激に脱溶媒が進み、表面に緻密な層ができて多孔質構造が形成されないことがある。浴の通過時間は、３〜６０分にすることが好ましい。時間が長くなるほど孔径が大きくなるが、６０分程度で一定の値となる。３分未満の場合、ガーレ透気度が本発明の範囲外になることがあり、６０分を超えると製膜速度が遅く、生産性が悪化する。 In the method of making porous using a wet bath, a bath to which an organic polar solvent, which is a good solvent for aromatic polyamide or aromatic polyimide, is added in an amount of 20% by weight or more, or an inorganic salt such as calcium chloride, lithium chloride, or lithium bromide. It is preferable to use a bath to which 10% by weight or more is added. In a water-only bath, desolvation proceeds rapidly, and a dense layer may be formed on the surface and a porous structure may not be formed. The passage time of the bath is preferably 3 to 60 minutes. The longer the time, the larger the pore size, but it becomes a constant value in about 60 minutes. If it is less than 3 minutes, the Gurley air permeability may be outside the range of the present invention, and if it exceeds 60 minutes, the film-forming speed is slow and the productivity is deteriorated.
高湿度雰囲気下で吸湿させて多孔質化する方法では、雰囲気の温度を５〜５０℃、相対湿度を５０〜９５％ＲＨとすることが好ましい。温度が５℃未満では、絶対湿度が低いため吸湿が十分でなく、ポリマーの溶解性が低下しないことから、多孔質構造が形成されないことがあり、５０℃を超えると表面に緻密な層ができて多孔質構造が形成されないことがある。また、相対湿度が５０％未満では、吸湿が十分でなくポリマーの溶解性が低下しないことから、多孔質構造が形成されないことがあり、９５％ＲＨを超えると表面に緻密な層ができて多孔質構造が形成されないことがある。 In the method of absorbing moisture in a high-humidity atmosphere, the atmosphere temperature is preferably 5 to 50 ° C. and the relative humidity is preferably 50 to 95% RH. If the temperature is less than 5 ° C, the absolute humidity is low, so the moisture absorption is not sufficient, and the solubility of the polymer does not decrease. Therefore, a porous structure may not be formed, and if it exceeds 50 ° C, a dense layer is formed on the surface. As a result, a porous structure may not be formed. Also, if the relative humidity is less than 50%, the moisture absorption is not sufficient and the solubility of the polymer does not decrease, so that a porous structure may not be formed. If the relative humidity exceeds 95% RH, a dense layer is formed on the surface and a porous layer is formed. The quality structure may not be formed.
ガーレ透気度を本発明の範囲内で、より大きくする（空孔率を小さくする）には、高温・高湿度条件で速やかに析出させることが好ましく、この様な条件として、温度：２０〜５０℃、相対湿度：７５〜９５％ＲＨとすることが好ましい。また、ガーレ透気度を本発明の範囲内で、より小さくする場合（空孔率を大きくする場合）は、低温・低湿度条件でゆっくり析出させることが好ましく、このような条件として、温度：５〜１５℃、相対湿度：５０〜７５％ＲＨとすることが好ましい。 In order to further increase the Gurley air permeability within the scope of the present invention (decrease the porosity), it is preferable to quickly deposit under high-temperature and high-humidity conditions. 50 ° C. and relative humidity: 75 to 95% RH are preferable. Further, when the Gurley air permeability is made smaller within the scope of the present invention (when increasing the porosity), it is preferable to deposit slowly under low temperature and low humidity conditions. It is preferable to set it as 5-15 degreeC and relative humidity: 50-75% RH.
また、調温・調湿された空気は風速０．５〜３ｍ／分で薄膜化した製膜原液の表面に吹き付けることが好ましい。風速が０．５ｍ／分未満の場合、多孔質構造の形成が遅いために、孔径等にムラができることがあり、風速が３ｍ／分を超えると塗布層の表面のみが固まり、多孔質構造を形成しないことがある。調温・調湿された空気に接する時間は、３〜２０分にすることが好ましい。接する時間が長くなるほど孔径が大きくなるが、２０分程度で一定の値となる。３分未満の場合、ガーレ透気度が本発明の範囲外になることがあり、２０分を超えると製膜速度が遅く、生産性が悪化する場合がある。 Moreover, it is preferable to spray the temperature-controlled and humidity-controlled air on the surface of the film-forming stock solution thinned at a wind speed of 0.5 to 3 m / min. When the wind speed is less than 0.5 m / min, the formation of the porous structure is slow, so the pore diameter may be uneven. When the wind speed exceeds 3 m / min, only the surface of the coating layer is hardened, May not form. The time of contact with the temperature-controlled and humidity-controlled air is preferably 3 to 20 minutes. The longer the contact time, the larger the hole diameter, but it becomes a constant value in about 20 minutes. If it is less than 3 minutes, the Gurley air permeability may be out of the range of the present invention, and if it exceeds 20 minutes, the film-forming speed may be slow and productivity may be deteriorated.
冷却して芳香族ポリアミドを多孔質化する方法では、−３０〜０℃の雰囲気下で冷却することが好ましい。−３０℃未満の場合、ポリマーの析出が急激に起こり、ガーレ透気度が本発明の範囲を満たさないことがあり、０℃を超える場合は、ポリマーの溶解性の低下が十分でなく析出が起こらないため、多孔質構造が形成されないことがある。冷却時間は、１〜２０分であることが好ましい。１分未満ではガーレ透気度が十分でなく、イオン透過性が悪化することがあり、２０分を超えると製膜速度が遅く、生産性が悪化することがある。 In the method of cooling to make the aromatic polyamide porous, it is preferable to cool in an atmosphere of −30 to 0 ° C. When the temperature is lower than −30 ° C., the precipitation of the polymer occurs abruptly, and the Gurley permeability may not satisfy the range of the present invention. When the temperature exceeds 0 ° C., the solubility of the polymer is not sufficiently lowered and the precipitation is not performed. Since it does not occur, a porous structure may not be formed. The cooling time is preferably 1 to 20 minutes. If it is less than 1 minute, the Gurley air permeability is not sufficient and the ion permeability may be deteriorated, and if it exceeds 20 minutes, the film-forming speed is slow and the productivity may be deteriorated.
多孔質化された芳香族ポリアミドまたは芳香族ポリイミドの薄膜は、上記いずれの方法を用いた場合も、支持体ごとあるいは支持体から剥離して水浴に導入され、残存溶媒および中和塩等の不要な添加物の除去が行われる。水浴は、残存溶媒等を効率的に除去できることから、３０〜６０℃であることが好ましい。導入時間は、３〜２０分にすることが好ましい。３分未満の場合、除去が不十分でないことがあり、２０分を超えると製膜速度が遅く、生産性が悪化することがある。 Porous aromatic polyamide or aromatic polyimide thin film is peeled off from the support or from the support and introduced into a water bath, and any remaining solvent, neutralization salt, etc. are not required, regardless of which method is used. Additive removal is performed. The water bath preferably has a temperature of 30 to 60 ° C. because it can efficiently remove residual solvent and the like. The introduction time is preferably 3 to 20 minutes. If it is less than 3 minutes, the removal may not be sufficient, and if it exceeds 20 minutes, the film-forming speed may be slow and productivity may be deteriorated.
次に、水浴から引き出された多孔質フィルムは、テンター等で熱処理及び延伸が行われる。 Next, the porous film drawn out from the water bath is subjected to heat treatment and stretching with a tenter or the like.
熱処理の初期温度は、８０〜１００℃とし、水を十分に蒸発させた後、より高温で加熱することが好ましい。初期から１００℃を超えた温度で加熱すると、急激に水分が蒸発することによってポリマー構造が破壊され、フィルム破れが発生したり、伸度が低下することがある。更にこの工程で、幅方向に２〜７％収縮させると、水分の蒸発に伴って多孔構造が若干縮んで表面にうねりが形成され、静摩擦係数を本発明の範囲内に制御することができる。粒子等の添加物のみで静摩擦係数を本発明の範囲内に制御しようとすると、添加量を極端に多くする必要があり、伸度が低下することがある。幅方向の収縮が２％未満では、静摩擦係数μｓが１．８を超えることがあり、７％を超えると、μｓが０．３未満になることがある。 It is preferable that the initial temperature of the heat treatment is 80 to 100 ° C., and the water is sufficiently evaporated and then heated at a higher temperature. When heated at a temperature exceeding 100 ° C. from the beginning, the polymer structure is destroyed due to rapid evaporation of the water, and film breakage may occur or the elongation may decrease. Further, in this process, when shrinking in the width direction by 2 to 7%, the porous structure is slightly shrunk with the evaporation of moisture, and undulation is formed on the surface, and the static friction coefficient can be controlled within the range of the present invention. If an attempt is made to control the coefficient of static friction within the scope of the present invention using only additives such as particles, the amount added needs to be extremely increased, and the elongation may be lowered. If the shrinkage in the width direction is less than 2%, the static friction coefficient μs may exceed 1.8, and if it exceeds 7%, μs may be less than 0.3.
次に、高温での熱処理は、用いたポリマーの熱分解温度以下の範囲で、できるだけ高い温度で行うことが、熱収縮等の高温時の寸法安定性が向上するため好ましい。芳香族ポリアミドは、一般に３５０℃以上の温度で熱分解が起こるため、２００〜３５０℃とすることが好ましく、芳香族ポリイミドでは、一般に５００℃以上の温度で熱分解が起こるため、３００〜５００℃とすることが好ましい。熱処理温度が２００℃未満では、熱収縮が大きくなり、本発明の範囲外となることがある。 Next, it is preferable that the heat treatment at a high temperature is performed at a temperature as high as possible within the range of the thermal decomposition temperature of the polymer used or higher because dimensional stability at a high temperature such as heat shrinkage is improved. Since aromatic polyamide generally undergoes thermal decomposition at a temperature of 350 ° C. or higher, it is preferably 200 to 350 ° C., and aromatic polyimide generally undergoes thermal decomposition at a temperature of 500 ° C. or higher, and therefore 300 to 500 ° C. It is preferable that When the heat treatment temperature is less than 200 ° C., the thermal shrinkage becomes large and may fall outside the scope of the present invention.
また、熱処理時に、延伸を行うことでフィルムの強度やヤング率を向上させることが可能である。ただし、初期乾燥時に形成した表面に微細な凹凸が扁平化しないように、延伸倍率を１．０〜１．２倍とすることが好ましい。 Moreover, it is possible to improve the intensity | strength and Young's modulus of a film by extending | stretching at the time of heat processing. However, the draw ratio is preferably 1.0 to 1.2 times so that fine irregularities are not flattened on the surface formed during initial drying.
本発明の芳香族ポリアミド又は芳香族ポリイミドの多孔質フィルムは、粒子を含有する場合、そのような粒子を含む多孔性フィルムに、空気雰囲気下でコロナ処理を施すことによって粒子の一部を露出させて得ることが好ましく、これにより、フィルム巻き取り時の静電気の発生を抑制することができ、巻きずれやしわの発生をより低減でき、スリット性も良好となる。 When the porous film of the aromatic polyamide or aromatic polyimide of the present invention contains particles, a part of the particles is exposed by subjecting the porous film containing such particles to corona treatment in an air atmosphere. Thus, the generation of static electricity during film winding can be suppressed, the occurrence of winding deviation and wrinkles can be further reduced, and the slit property can be improved.
コロナ処理の好ましい条件は、例えば、電源の周波数としては、８ＫＨｚから６０ＫＨｚの範囲が好ましい。また、印加電圧は、１００〜１，０００Ｖが好ましく、１５０〜５００Ｖがより好ましい。印加電圧が１００Ｖ未満ではフィルム表面が充分に酸化処理されず粒子が露出しないことがあり、１，０００Ｖを超えるとフィルムへのダメージが大きく、伸度が低下することがある。 As a preferable condition for the corona treatment, for example, the frequency of the power source is preferably in the range of 8 KHz to 60 KHz. The applied voltage is preferably 100 to 1,000 V, more preferably 150 to 500 V. If the applied voltage is less than 100 V, the film surface may not be sufficiently oxidized and the particles may not be exposed. If the applied voltage exceeds 1,000 V, the film may be greatly damaged and the elongation may be lowered.
放電電極の材質としては、アルミニウムまたはステンレスが好ましく、放電電極の形状はナイフエッジ状、バー状、またはワイヤー状であることが好ましい。また、放電電極の本数はフィルム表面を均一処理する為に、２本以上であることが好ましい。処理ロールは、コロナ放電を行う場合の対極となるものであるが、少なくとも表面の材質は誘電体である必要がある。誘電体材質としては、シリコンゴム、ハイパロンゴム、ＥＰＴゴム等を用いることが好ましく、少なくともロール表面を１ｍｍ厚以上の厚さで被覆することが好ましい。また、放電電極とフィルム処理面のギャップは０．２ｍｍ〜５ｍｍ程度の範囲内であることが好ましい。 The material of the discharge electrode is preferably aluminum or stainless steel, and the shape of the discharge electrode is preferably a knife edge shape, a bar shape, or a wire shape. Further, the number of discharge electrodes is preferably 2 or more in order to uniformly treat the film surface. The treatment roll serves as a counter electrode when corona discharge is performed, but at least the surface material needs to be a dielectric. As the dielectric material, silicon rubber, hyperon rubber, EPT rubber or the like is preferably used, and at least the roll surface is preferably coated with a thickness of 1 mm or more. The gap between the discharge electrode and the film processing surface is preferably in the range of about 0.2 mm to 5 mm.
本発明の多孔性フィルムは、フィルター、分離膜、プリント基板、電池用セパレータ等に好適に使用できるが、特に、リチウムイオン電池等の有機電解液二次電池のセパレータとして好適に使用できる。電池用セパレータとして使用される場合は、対向配置される正極と負極間に、電解液とともに設けられる。電解液としては、少なくとも１００℃において引火しない電解液、より好ましくは実質的に引火点をもたない電解液とともに使用されることがより好ましい。 The porous film of the present invention can be suitably used for a filter, a separation membrane, a printed board, a battery separator, and the like, but can be particularly suitably used as a separator for an organic electrolyte secondary battery such as a lithium ion battery. When used as a battery separator, it is provided with an electrolytic solution between a positive electrode and a negative electrode arranged opposite to each other. More preferably, the electrolyte is used together with an electrolyte that does not ignite at least at 100 ° C., more preferably an electrolyte that does not substantially have a flash point.
［物性の測定方法ならびに効果の評価方法］
実施例における物性の測定方法、効果の評価方法は次の方法に従って行った。
[Methods for measuring physical properties and methods for evaluating effects]
The physical property measurement method and the effect evaluation method in the examples were performed according to the following methods.
（１）静摩擦係数μｓ
東洋精機（株）製スリップテスターを用いて、ＪＩＳ−Ｋ７１２５（１９９９年）に準じて、フィルムの両面を重ねて摩擦させた時の初期の立ち上がり抵抗値を測定し、静摩擦係数μｓとした。サンプルは、幅８０ｍｍ、長さ２００ｍｍの長方形とし、長方形の長さ方向が製膜方向になるようにロールから３セット（６枚）切り出した。３回測定を行い、平均値を求めた。
(1) Static friction coefficient μs
Using a slip tester manufactured by Toyo Seiki Co., Ltd., according to JIS-K7125 (1999), the initial rising resistance value was measured when both surfaces of the film were rubbed and rubbed, and the coefficient of static friction was μs. The sample was a rectangle having a width of 80 mm and a length of 200 mm, and three sets (six pieces) were cut from the roll so that the length direction of the rectangle was the film forming direction. Three measurements were taken and the average value was determined.
（２）数平均分子量Ｍｎ、重量平均分子量Ｍｗ
ゲル浸透クロマトグラフ（ＧＰＣ）に、低角度レ−ザ−光散乱光度計（ＬＡＬＬＳ）および示差屈折率計（ＲＩ）を組み入れ、ＧＰＣ装置でサイズ分別された溶液の光散乱強度および屈折率差を溶出時間を追って測定することにより、溶質の分子量とその含有率を順次計算し、最終的には、高分子物質の絶対分子量分布および絶対平均分子量値を求めた。測定条件を以下に示す。
(2) Number average molecular weight Mn, weight average molecular weight Mw
The gel permeation chromatograph (GPC) incorporates a low-angle laser-light scattering photometer (LALLS) and a differential refractometer (RI) to determine the light scattering intensity and refractive index difference of the size-separated solution by the GPC device. By measuring the elution time later, the molecular weight of the solute and the content thereof were sequentially calculated, and finally the absolute molecular weight distribution and the absolute average molecular weight value of the polymer substance were obtained. The measurement conditions are shown below.
Ａ．ＧＰＣ
装置 ：２４４型ゲル浸透クロマトグラフ（ＷＡＴＥＲＳ社製）
カラム ：ＴＲＣ−ＧＭ（２本）（東レリサ−チセンター社製），
Ｓｈｏｄｅｘ ＫＤ−８０２（１本）（昭和電工社製）
溶媒 ：ＮＭＰ（０．０１Ｎ塩化リチウム添加）
流速 ：０．６ｍｌ／ｍｉｎ
温度 ：２３℃
試料濃度 ：０．１０１％（（ポリマー重量／溶液重量）×１００）
溶解性 ：完全溶解
ろ過 ：Ｓｈｏｄｅｘ ＤＴ ＥＤ−１３ＣＲ（０．４５μ）（昭和電工社製）
注入量 ：０．２ｍｌ
濃度検出器：示差屈折率検出器、Ｒ−４０１（ＷＡＴＥＲＳ社製）
Ｂ．ＬＡＬＬＳ
装置 ：ＣＭＸ−１００型低角度レ−ザ−光散乱光度計
（Ｃｈｒｏｍａｔｉｘ社製）
波長 ：６３３nm（Ｈｅ−Ｎｅ）
第２ビリアル係数（Ａ２）：０ｍｌ・ｍｏｌｅ／g
屈折率濃度変化（dn/dc）：０．２１５ｍｌ／ｇ（実測値）
ゲイン ：Ｐ０＝２００ｍＶ
温度 ：２３℃
フィルタ− ：０.４５μ−Ｆｌｕｏｒｏ Ｐｏｒｅ ＦＰ−０４５
（住友電工社製）
Ｃ．データ処理：ＧＰＣ−ＬＡＬＬＳデ−タ処理システム（東レリサ−チセンター社製）
（３）ガーレ透気度
（３）ガーレ透気度
ＪＩＳ−Ｐ８１１７（１９９８年）に規定された方法に従って、多孔質フィルムの一方向に５ｃｍ間隔で５カ所測定を行い、平均値を求めた。
A. GPC
Apparatus: 244 type gel permeation chromatograph (manufactured by WATERS)
Column: TRC-GM (2) (manufactured by Toray Research Center),
Shodex KD-802 (1) (Showa Denko)
Solvent: NMP (0.01N lithium chloride added)
Flow rate: 0.6 ml / min
Temperature: 23 ° C
Sample concentration: 0.101% ((polymer weight / solution weight) × 100)
Solubility: Complete dissolution Filtration: Shodex DT ED-13CR (0.45μ) (manufactured by Showa Denko KK)
Injection volume: 0.2ml
Concentration detector: differential refractive index detector, R-401 (manufactured by WATERS)
B. LALLS
Apparatus: CMX-100 type low angle laser light scattering photometer
(Chromatix)
Wavelength: 633 nm (He-Ne)
Second virial coefficient (A 2 ): 0 ml · mole / g
Refractive index concentration change (dn / dc): 0.215 ml / g (actual value)
Gain: P0 = 200mV
Temperature: 23 ° C
Filter: 0.45 μ-Fluoro Pore FP-045
(Manufactured by Sumitomo Electric)
C. Data processing: GPC-LALLS data processing system (manufactured by Toray Research Center)
(3) Gurley Air Permeability (3) Gurley Air Permeability According to the method defined in JIS-P8117 (1998), measurement was made at five locations at intervals of 5 cm in one direction of the porous film, and the average value was obtained.
測定装置として、Ｂ型ガーレーデンソメーター（安田精機製作所製）を使用した。測定手順は、各測定個所において、試料の多孔性フィルムを直径２８．６ｍｍ、面積６４５ｍｍ２の円孔に締め付け、内筒により（内筒重量５６７ｇ）、筒内の空気を試験円孔部から筒外へ通過させ、空気１００ｃｃが通過する時間を測定した。 A B-type Gurley Densometer (manufactured by Yasuda Seiki Seisakusho) was used as a measuring device. The measurement procedure is as follows. At each measurement location, the porous film of the sample is fastened to a circular hole having a diameter of 28.6 mm and an area of 645 mm 2 , and the air in the cylinder is transferred from the test circular hole to The time for 100 cc of air to pass was measured.
（４）熱収縮率
多孔性フィルムを、幅１ｃｍ、長さ２２ｃｍの短冊状に、長辺が測定方向になるように切り取った。長辺の両端から１ｃｍの部分に印をつけ、２００℃の熱風オーブン中で３０分間、実質的に張力を掛けない状態で熱処理を行った後、印の間隔を測定し、下記の式で計算した。フィルムの長手方向および幅方向にそれぞれ５回測定し、平均値を求めた。
(4) Thermal contraction rate The porous film was cut into a strip shape having a width of 1 cm and a length of 22 cm so that the long side was in the measurement direction. Mark 1cm from both ends of the long side, heat-treat in a hot air oven at 200 ° C for 30 minutes without applying any tension, measure the distance between the marks, and calculate with the following formula did. The film was measured 5 times in the longitudinal direction and the width direction of the film, and the average value was obtained.
熱収縮率（％）＝（（熱処理前の間隔−熱処理し冷却後の間隔）／熱処理前の間隔）×１００
（５）ヤング率および伸度
ロボットテンシロンＲＴＡ（オリエンテック社製）を用いて２３℃、相対湿度６５％において測定した。試験片は幅１０ｍｍ、長さ１００ｍｍの短冊状に、長辺が測定方向になるように切り取った。引っ張り速度は３００ｍｍ／分である。フィルムの長手方向および幅方向にそれぞれ５回測定し、平均値を求めた。
Thermal shrinkage rate (%) = ((interval before heat treatment−interval after heat treatment and cooling) / interval before heat treatment) × 100
(5) Young's modulus and elongation It measured at 23 degreeC and relative humidity 65% using Robot Tensilon RTA (made by Orientec). The test piece was cut into a strip shape having a width of 10 mm and a length of 100 mm so that the long side was in the measurement direction. The pulling speed is 300 mm / min. The film was measured 5 times in the longitudinal direction and the width direction of the film, and the average value was obtained.
（６）長尺巻き取り性
熱処理の完了した多孔質フィルムを１ｍ幅で５，０００ｍ巻き取ったロールの外観を見て、以下のように評価した。
(6) Long roll-up property The appearance of a roll obtained by winding a heat-treated porous film having a width of 1 m and a width of 5,000 m was evaluated as follows.
◎：製品ロールの巻きずれが１ｍｍ未満、かつ、表面にしわが見られない。
○：製品ロールの端部に１ｍｍ以上３ｍｍ未満の巻きずれが見られる、又は表面に幅１ｍｍ未満のしわが見られる。
△：製品ロールの端部に３ｍｍ以上５ｍｍ未満の巻きずれが見られる、又は表面に幅１ｍｍ以上３ｍｍ未満のしわが見られる。
×：製品ロールの端部に５ｍｍ以上を超える巻きずれが見られる、又は表面に幅３ｍｍ以上のしわが見られる。
A: The roll of the product roll is less than 1 mm, and the surface is not wrinkled.
○: Winding deviation of 1 mm or more and less than 3 mm is observed at the end of the product roll, or wrinkles having a width of less than 1 mm are observed on the surface.
(Triangle | delta): The winding shift | offset | difference of 3 mm or more and less than 5 mm is seen in the edge part of a product roll, or the wrinkle of width 1 mm or more and less than 3 mm is seen on the surface.
X: Winding displacement exceeding 5 mm or more is observed at the end of the product roll, or wrinkles having a width of 3 mm or more are observed on the surface.
（７）高速スリット性
幅１ｍ、長さ５，０００ｍのロールから、速度４０ｍ／分で２５ｃｍ幅のフィルムを３本スリットした（両端１２．５ｃｍは破棄した）。スリット途中でフィルム破れが発生した回数を数え、以下のように評価した。
(7) High-speed slit property Three 25 cm wide films were slit at a speed of 40 m / min from a roll having a width of 1 m and a length of 5,000 m (both ends 12.5 cm were discarded). The number of times the film was broken in the slit was counted and evaluated as follows.
○：フィルム破れの発生した回数が３本合計で０〜１回であった。 A: The number of occurrences of film breakage was 0 to 1 in total.
△：フィルム破れの発生した回数が３本合計で２〜４回であった。 (Triangle | delta): The frequency | count that the film tear occurred was 2 to 4 times in total.
×：フィルム破れが３本合計で５回目以上発生した。５回目に達した段階でテストを中止した。 X: Film breakage occurred 5 times or more in total for 3 films. The test was stopped when the fifth time was reached.
（８）電池特性
Ａ．電解液の調製
ＬｉＣ４Ｆ９ＳＯ３をリン酸トリメチルに溶解させたのち、プロピレンカーボネートを加えて混合し、プロピレンカーボネートとリン酸トリメチルとの体積比が１：２の混合溶媒にＬｉＣ４Ｆ９ＳＯ３を０．６モル／リットル溶解させた有機電解液を調製した。このようにして得られた有機電解液の引火点を調べるため、この電解液を所定の温度まで加熱して液面近傍に火を近づけ、引火するかどうかを調べた。１００℃、１５０℃、２００℃におけるテストにおいて引火せず、この電解液の引火点は２００℃以上であることが分かった。
(8) Battery characteristics A. Preparation of Electrolytic Solution After dissolving LiC 4 F 9 SO 3 in trimethyl phosphate, propylene carbonate was added and mixed, and LiC 4 F 9 was added to a mixed solvent having a volume ratio of propylene carbonate to trimethyl phosphate of 1: 2. An organic electrolyte solution in which SO 3 was dissolved at 0.6 mol / liter was prepared. In order to investigate the flash point of the organic electrolyte solution thus obtained, the electrolyte solution was heated to a predetermined temperature, and a fire was brought close to the liquid surface to investigate whether it would ignite. In the tests at 100 ° C., 150 ° C., and 200 ° C., there was no ignition, and it was found that the flash point of this electrolyte was 200 ° C. or higher.
Ｂ．電池の作成
リチウムコバルト酸化物（ＬｉＣｏＯ２）に黒鉛とポリフッ化ビニリデンとを加え、溶剤で分散させたスラリーを、厚さ１０μｍの正極集電体用アルミニウム箔の両面に均一に塗布して乾燥し、圧縮成形して帯状の正極を作製した。正極の厚みは４０μｍ、幅２００ｍｍ、長さ４，０００ｍｍであった。
B. Preparation of Battery A slurry in which graphite and polyvinylidene fluoride were added to lithium cobalt oxide (LiCoO 2 ) and dispersed with a solvent was uniformly applied to both surfaces of a 10 μm-thick aluminum foil for a positive electrode current collector and dried. The belt-shaped positive electrode was produced by compression molding. The positive electrode had a thickness of 40 μm, a width of 200 mm, and a length of 4,000 mm.
また、コークスと、粘着剤としてのポリフッ化ビニリデンとを混合して負極合剤とし、これを溶剤で分散させてスラリーにした。この負極合剤スラリーを、負極集電体として、厚さが１０μｍの帯状銅箔の両面に均一に塗布して乾燥し、圧縮成形して帯状の負極前駆体を作製した。負極前駆体の処理液として、ＬｉＣ４Ｆ９ＳＯ３をリン酸トリメチルに溶解させたのち、エチレンカーボネートを加えて混合することにより、処理液を調製した。負極前駆体の両側に処理液を含浸させたセパレータを介してリード体を圧着したＬｉフォイルで鋏み込み、ホルダーに入れ、負極前駆体を正極、Ｌｉ極を負極として、放電および充電を行った。その後、ホルダーを分解し、分解し、負極前駆体をジメチルカーボネートで洗浄し、乾燥して、負極を作製した。負極の厚みは５０μｍ、幅２００ｍｍ、長さ４，０００ｍｍであった。 Also, coke and polyvinylidene fluoride as an adhesive were mixed to form a negative electrode mixture, which was dispersed with a solvent to form a slurry. This negative electrode mixture slurry was applied uniformly on both sides of a 10 μm-thick strip-shaped copper foil as a negative electrode current collector, dried, and compression molded to prepare a strip-shaped negative electrode precursor. As a processing solution for the negative electrode precursor, LiC 4 F 9 SO 3 was dissolved in trimethyl phosphate, and then ethylene carbonate was added and mixed to prepare a processing solution. The lead body was squeezed with Li foil through a separator impregnated with a treatment liquid on both sides of the negative electrode precursor, placed in a holder, and discharged and charged using the negative electrode precursor as the positive electrode and the Li electrode as the negative electrode. Thereafter, the holder was disassembled and disassembled, and the negative electrode precursor was washed with dimethyl carbonate and dried to produce a negative electrode. The thickness of the negative electrode was 50 μm, the width was 200 mm, and the length was 4,000 mm.
次に、上記の帯状正極を、各実施例・比較例のセパレータ用フィルムを介して、上記シート状負極と重ね、渦巻状に巻回して渦巻状電極体としたのち、有底円筒状の電池ケース内に充填し、正極および負極のリード体の溶接を行った後、上記電解液を電池ケース内に注入した。電池ケースの開口部を封口し、電池の予備充電を行い、筒形の有機電解液二次電池を作製した。各実施例・比較例につき、電池を５個ずつ作成した。 Next, the above belt-like positive electrode is overlapped with the sheet-like negative electrode through the separator film of each Example / Comparative Example and wound into a spiral to form a spiral electrode body, and then a bottomed cylindrical battery After filling the case and welding the positive and negative electrode lead bodies, the electrolyte was poured into the battery case. The opening of the battery case was sealed and the battery was precharged to produce a cylindrical organic electrolyte secondary battery. Five batteries were prepared for each example and comparative example.
Ｃ．電池特性
作成した各二次電池について、５０℃の雰囲気下、充電を１，６００ｍＡで４．２Ｖまで３．５時間、放電を１，６００ｍＡで２．７Ｖまで１．０時間とする充放電操作を繰り返した。１サイクル目と１，０００サイクル目の放電容量を、１サイクル目の放電容量を基準とし、１，０００サイクル目の放電容量を以下の基準で評価した。△、○が実用範囲である。
C. Battery characteristics Charging / discharging operation for each created secondary battery under an atmosphere of 50 ° C. with charging at 1,600 mA to 4.2 V for 3.5 hours and discharging at 1,600 mA to 2.7 V for 1.0 hour Was repeated. The discharge capacity at the first cycle and the 1,000th cycle was evaluated based on the discharge capacity at the first cycle, and the discharge capacity at the 1,000th cycle was evaluated according to the following criteria. Δ and ○ are practical ranges.
○：９５％以上
△：９０％以上９５％未満
×：９０％未満
以下に実施例に基づいて本発明をより具体的に説明するが、本発明はこれらに限定されるものでないことは言うまでもない。
○: 95% or more Δ: 90% or more and less than 95% ×: less than 90% The present invention will be more specifically described below based on examples, but it goes without saying that the present invention is not limited thereto. .
（実施例１）
脱水したＮ−メチル−２−ピロリドン（以下、ＮＭＰと記す）に、ジアミン全量に対して８０モル％に相当する２−クロルパラフェニレンジアミンと、ジアミン全量に対して２０モル％に相当する４、４’−ジアミノジフェニルエーテルとを溶解させ、これにジアミン全量に対して９８．５モル％に相当する２−クロルテレフタル酸クロリド（以下、ＣＴＰＣと記す）を添加し、２時間撹拌により重合し、芳香族ポリアミドの溶液を得た。重合開始時の溶液温度は４℃で、ＣＴＰＣを１０等分し、１０分間隔で添加することにより、重合中の温度上昇を２８℃までに抑えた。この溶液を水とともにミキサーに投入し、攪拌しながらポリマーを沈殿させて、取り出した。
Example 1
To dehydrated N-methyl-2-pyrrolidone (hereinafter referred to as NMP), 2-chloroparaphenylenediamine corresponding to 80 mol% with respect to the total amount of diamine, and 4, corresponding to 20 mol% with respect to the total amount of diamine, 4'-Diaminodiphenyl ether was dissolved, and 2-chloroterephthalic acid chloride (hereinafter referred to as CTPC) corresponding to 98.5 mol% with respect to the total amount of the diamine was added thereto, and polymerized by stirring for 2 hours. A solution of a group polyamide was obtained. The solution temperature at the start of the polymerization was 4 ° C., CTPC was divided into 10 equal parts and added at 10 minute intervals to suppress the temperature rise during the polymerization to 28 ° C. This solution was put into a mixer together with water, and the polymer was precipitated while stirring, and then taken out.
このポリマーを、一次粒径８０ｎｍのコロイダルシリカを分散させたＮ−メチル−２−ピロリドンに溶解させた後、平均分子量が２００のポリエチレングリコール（以下、ＰＥＧと記す）を加え、均一に完全相溶した製膜原液を得た。それぞれの添加量は、ポリマー１０重量％、ＮＭＰ６９．９７重量％、ＰＥＧ２０重量％、コロイダルシリカ０．０３重量％となるように調製した。 This polymer was dissolved in N-methyl-2-pyrrolidone in which colloidal silica having a primary particle size of 80 nm was dispersed, and then polyethylene glycol having an average molecular weight of 200 (hereinafter referred to as PEG) was added to achieve complete and complete compatibility. A film-forming stock solution was obtained. Each addition amount was adjusted to be 10% by weight of polymer, 69.97% by weight of NMP, 20% by weight of PEG, and 0.03% by weight of colloidal silica.
この製膜原液を、ダイコーターで１００μｍのポリエチレンテレフタレートフィルム上に厚み約７５μｍの膜状に塗布し、温度１５℃、相対湿度７０％ＲＨの調湿空気中で１０分間処理した。調湿空気は風速１．５ｍ／分で膜表面に吹き付けた。次に、失透した多孔質層を剥離後、３０℃の水浴に３分間導入し、溶媒の抽出を行った。続いて、テンター中で最初は８０℃で１分、幅方向に４．５％収縮させながら熱処理を行った。最後に、幅方向はそのままで、２５０℃で２分間の熱処理を行い、多孔質フィルムを得た。 This film-forming stock solution was coated on a 100 μm polyethylene terephthalate film in a film shape with a thickness of about 75 μm with a die coater and treated for 10 minutes in humidity-conditioned air at a temperature of 15 ° C. and a relative humidity of 70% RH. Humidified air was blown onto the film surface at a wind speed of 1.5 m / min. Next, the devitrified porous layer was peeled off, and then introduced into a 30 ° C. water bath for 3 minutes to extract the solvent. Subsequently, heat treatment was initially performed in the tenter while shrinking 4.5% in the width direction at 80 ° C. for 1 minute. Finally, heat treatment was performed at 250 ° C. for 2 minutes while maintaining the width direction, and a porous film was obtained.
この後、以下の条件でコロナ処理を行った。高周波電源装置は春日電機社製装置を使用し、発振周波数は４５ＫＨｚプラスマイナス３ＫＨｚ、処理電極はアルミニウム製のバー型電極、処理電極とフィルム間のギャップは０．５ｍｍ、処理ロールは表面材質がシリコンゴム製のものを使用し、処理ロール表面温度は４０℃であった。 Thereafter, the corona treatment was performed under the following conditions. The high-frequency power supply uses a device manufactured by Kasuga Denki Co., Ltd., the oscillation frequency is 45 kHz plus or minus 3 kHz, the processing electrode is an aluminum bar electrode, the gap between the processing electrode and the film is 0.5 mm, and the processing roll is made of silicon. The thing made from rubber was used and the processing roll surface temperature was 40 degreeC.
コロナ処理後の多孔質フィルムを用いて、上記の方法で評価した結果、特性は全て良好であった。 As a result of evaluating by the above method using the porous film after the corona treatment, all the characteristics were good.
主な製造条件を表１に、評価結果を表２に示した。表１において、延伸倍率が１倍未満のものは、収縮させたことを表し、延伸倍率０．９５５倍は４．５％収縮させることを表す。 Main production conditions are shown in Table 1, and evaluation results are shown in Table 2. In Table 1, those having a draw ratio of less than 1 represent shrinkage, and the draw ratio of 0.955 represents shrinkage of 4.5%.
（実施例２）
コロナ処理を行わない以外は実施例１と同様な方法で多孔質フィルムを得た。電池の特性は全て実用範囲内であった。
(Example 2)
A porous film was obtained in the same manner as in Example 1 except that the corona treatment was not performed. All the characteristics of the battery were within the practical range.
（実施例３）
製膜原液を、ポリマー１０重量％、ＮＭＰ６９．９９重量％、ＰＥＧ２０重量％、コロイダルシリカ０．０１重量％となるように調製し、コロナ処理を行わない以外は実施例１と同様な方法で多孔質フィルムを得た。電池の特性は全て実用範囲内であった。
(Example 3)
A film-forming stock solution was prepared to be 10% by weight of polymer, 69.99% by weight of NMP, 20% by weight of PEG, and 0.01% by weight of colloidal silica, and porous in the same manner as in Example 1 except that no corona treatment was performed. A quality film was obtained. All the characteristics of the battery were within the practical range.
（実施例４）
製膜原液を、ポリマー１０重量％、ＮＭＰ５６重量％、ＰＥＧ２０重量％、コロイダルシリカ１４重量％となるように調製し、コロナ処理を行わない以外は実施例１と同様な方法で多孔質フィルムを得た。電池の特性は全て実用範囲内であった。
Example 4
A film-forming stock solution was prepared to be 10% by weight of polymer, 56% by weight of NMP, 20% by weight of PEG, and 14% by weight of colloidal silica, and a porous film was obtained in the same manner as in Example 1 except that no corona treatment was performed. It was. All the characteristics of the battery were within the practical range.
（実施例５〜８）
製膜原液を、ポリマー１０重量％、ＮＭＰ７０重量％、ＰＥＧ２０重量％となるように調製し、多孔質化条件を表１のとおりに変更し、コロナ処理を行わなかった以外は実施例１と同様な方法で多孔質フィルムを得た。電池の特性は全て実用範囲内であった。
(Examples 5 to 8)
A film-forming stock solution was prepared so as to be 10% by weight of polymer, 70% by weight of NMP, and 20% by weight of PEG, and the porous conditions were changed as shown in Table 1, except that no corona treatment was performed. A porous film was obtained by various methods. All the characteristics of the battery were within the practical range.
（実施例９〜１３、参考例１４）
ポリマー重合条件を表１のとおりに変更し、コロナ処理を行わなかった以外は実施例１と同様な方法で多孔質フィルムを得た。
(Examples 9 to 13 , Reference Example 14 )
The polymer polymerization conditions were changed as shown in Table 1, and a porous film was obtained in the same manner as in Example 1 except that the corona treatment was not performed .
（実施例１５）
２段階目の熱処理温度を１８０℃に変更し、コロナ処理を行わなかった以外は実施例１と同様な方法で多孔質フィルムを得た。電池の特性は全て実用範囲内であった。
(Example 15)
A porous film was obtained in the same manner as in Example 1 except that the heat treatment temperature at the second stage was changed to 180 ° C. and the corona treatment was not performed. All the characteristics of the battery were within the practical range.
（実施例１６、１７）
１段階目の熱処理時の延伸倍率を表１のとおりに変更し、コロナ処理を行わなかった以外は実施例１と同様な方法で多孔質フィルムを得た。電池の特性は全て実用範囲内であった。
(Examples 16 and 17)
A porous film was obtained in the same manner as in Example 1 except that the draw ratio during the first heat treatment was changed as shown in Table 1 and the corona treatment was not performed. All the characteristics of the battery were within the practical range.
（実施例１８）
添加する粒子をポリエステル系架橋粒子に、添加量を２重量％に変更した以外は実施例１と同様な方法で多孔質フィルムを得た。電池の特性は全て実用範囲内であった。
(Example 18)
A porous film was obtained in the same manner as in Example 1 except that the particles to be added were changed to polyester-based crosslinked particles and the addition amount was changed to 2% by weight. All the characteristics of the battery were within the practical range.
（実施例１９）
脱水したＮ−メチル−２−ピロリドンに１００モル％に相当するパラフェニレンジアミンを溶解させ、これに９８．５モル％に相当する３，３’，４，４’−ビフェニルテトラカルボン酸二無水物を添加し、２時間撹拌により重合後、ポリマー濃度が１３重量％の芳香族ポリアミド酸溶液を得た。この溶液を水とともにミキサーに投入し、攪拌しながらポリマーを沈殿させて取り出した。
(Example 19)
Paraphenylenediamine corresponding to 100 mol% is dissolved in dehydrated N-methyl-2-pyrrolidone, and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride corresponding to 98.5 mol% is dissolved in this. And polymerized by stirring for 2 hours to obtain an aromatic polyamic acid solution having a polymer concentration of 13% by weight. This solution was poured into a mixer together with water, and the polymer was precipitated while stirring.
以後、２段階目の熱処理温度を４００℃に変更した以外は実施例１と同様な方法で多孔質フィルムを得た。電池の特性は全て実用範囲内であった。 Thereafter, a porous film was obtained in the same manner as in Example 1 except that the second stage heat treatment temperature was changed to 400 ° C. All the characteristics of the battery were within the practical range.
（比較例１〜３）
製膜原液を、ポリマー１０重量％、ＮＭＰ７０重量％、ＰＥＧ２０重量％となるように調製し、１段階目の熱処理時の延伸倍率を表１のとおりに変更し、コロナ処理を行わなかった以外は実施例１と同様な方法で多孔質フィルムを得た。電池の特性は実用範囲を満たさなかった。
(Comparative Examples 1-3)
The film forming stock solution was prepared so as to be 10% by weight of polymer, 70% by weight of NMP, and 20% by weight of PEG, and the draw ratio during the first stage heat treatment was changed as shown in Table 1, except that no corona treatment was performed. A porous film was obtained in the same manner as in Example 1. The characteristics of the battery did not meet the practical range.
（比較例４）
製膜原液を、ポリマー１０重量％、ＮＭＰ６８．４重量％、ＰＥＧ２０重量％、コロイダルシリカ１．６重量％となるように調製し、コロナ処理を行わない以外は実施例１と同様な方法で多孔質フィルムを得た。伸度が低いため、電池特性の評価は行えなかった。
(Comparative Example 4)
A film-forming stock solution was prepared to be 10% by weight of polymer, 68.4% by weight of NMP, 20% by weight of PEG, and 1.6% by weight of colloidal silica, and porous in the same manner as in Example 1 except that no corona treatment was performed. A quality film was obtained. Since the elongation was low, the battery characteristics could not be evaluated.
（比較例５）
実施例１と同様にして得た沈澱ポリマーを用いて、ポリマーを１０重量％、Ｎ−メチル−２−ピロリドンを９０重量％として製膜溶液を作成した。この溶液をエンドレスベルト上に厚みが約１３０μｍになるように流延し、１８０℃の熱風で２分間加熱して溶媒を蒸発させ、自己保持性を得たフィルムをベルトから連続的に剥離した。次に、５０℃の水槽内へフィルムを導入して残存溶媒と中和で生じた無機塩の水抽出を行った。この後、テンターでまず８０℃で３０秒予備乾燥を行った後、２８０℃で１．５分間熱処理しながら横方向に１．１倍の延伸を行い、厚さ１２μｍの芳香族ポリアミドフィルムを得た。
(Comparative Example 5)
Using the precipitated polymer obtained in the same manner as in Example 1, a film-forming solution was prepared with 10% by weight of polymer and 90% by weight of N-methyl-2-pyrrolidone. The solution was cast on an endless belt to a thickness of about 130 μm, heated with hot air at 180 ° C. for 2 minutes to evaporate the solvent, and the film having self-holding property was continuously peeled from the belt. Next, the film was introduced into a 50 ° C. water tank, and the residual solvent and the inorganic salt produced by neutralization were extracted with water. Then, after preliminary drying at 80 ° C. for 30 seconds with a tenter, the film was stretched 1.1 times in the transverse direction while being heat-treated at 280 ° C. for 1.5 minutes to obtain an aromatic polyamide film having a thickness of 12 μm. It was.
このフィルムを、５０〜６０μｍの粒径で鋭い角部を有する多数の合成ダイアモンド粒子が表面に電着された鉄製ロールとシリコーンゴム製ロール間を圧力下で通過させ、芳香族ポリアミド多孔性フィルムを得た。 This film is passed under pressure between an iron roll and a silicone rubber roll, on which a large number of synthetic diamond particles having a particle size of 50 to 60 μm and sharp corners are electrodeposited, and an aromatic polyamide porous film is obtained. Obtained.
ＳＥＭの観察から、ストレートホールが形成されていることが分かった。特性は全て悪かった。 From the SEM observation, it was found that straight holes were formed. All the characteristics were bad.
本発明は、フィルター、分離膜、プリント基板等、電池用セパレータとして好適に使用することができる芳香族ポリアミド及び／又は芳香族ポリイミドを主成分とする多孔質フィルムである。 The present invention is a porous film mainly composed of an aromatic polyamide and / or an aromatic polyimide that can be suitably used as a battery separator such as a filter, a separation membrane, and a printed board.
Claims (7)
１．３≦Ｍｗ／Ｍｎ≦４．５ ・・・（３）
（１）
1.3 ≦ Mw / Mn ≦ 4.5 (3)
(1)
５×１０3≦Ｍｎ≦１×１０5
を満足している、請求項１または２に記載の多孔質フィルム。 The number average molecular weight Mn of the aromatic polyamide is
5 × 10 3 ≦ Mn ≦ 1 × 10 5
The porous film according to claim 1 or 2 , wherein
A battery separator comprising the porous film according to any one of claims 1 to 5 or the porous film obtained by the production method according to claim 6 .
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