JP6194938B2 - Laminated porous stretched film, battery separator and battery using the same - Google Patents
Laminated porous stretched film, battery separator and battery using the same Download PDFInfo
- Publication number
- JP6194938B2 JP6194938B2 JP2015207325A JP2015207325A JP6194938B2 JP 6194938 B2 JP6194938 B2 JP 6194938B2 JP 2015207325 A JP2015207325 A JP 2015207325A JP 2015207325 A JP2015207325 A JP 2015207325A JP 6194938 B2 JP6194938 B2 JP 6194938B2
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- Prior art keywords
- layer
- acid
- resin
- magnesium
- oxide
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- -1 polypropylene Polymers 0.000 claims description 181
- 229920005989 resin Polymers 0.000 claims description 156
- 239000011347 resin Substances 0.000 claims description 156
- 239000013078 crystal Substances 0.000 claims description 97
- 239000004743 Polypropylene Substances 0.000 claims description 96
- 229920001155 polypropylene Polymers 0.000 claims description 59
- 238000002844 melting Methods 0.000 claims description 41
- 230000008018 melting Effects 0.000 claims description 41
- 239000003484 crystal nucleating agent Substances 0.000 claims description 35
- 230000000694 effects Effects 0.000 claims description 32
- 230000015556 catabolic process Effects 0.000 claims description 25
- 229920005992 thermoplastic resin Polymers 0.000 claims description 24
- 230000035699 permeability Effects 0.000 claims description 21
- 239000011342 resin composition Substances 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 10
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 6
- 229920000306 polymethylpentene Polymers 0.000 claims description 6
- 239000011116 polymethylpentene Substances 0.000 claims description 6
- 229920001225 polyester resin Polymers 0.000 claims description 5
- 239000004645 polyester resin Substances 0.000 claims description 5
- 229920005990 polystyrene resin Polymers 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 3
- 229920005629 polypropylene homopolymer Polymers 0.000 claims description 3
- 230000035515 penetration Effects 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 140
- QWDJLDTYWNBUKE-UHFFFAOYSA-L magnesium bicarbonate Chemical compound [Mg+2].OC([O-])=O.OC([O-])=O QWDJLDTYWNBUKE-UHFFFAOYSA-L 0.000 description 70
- 125000004432 carbon atom Chemical group C* 0.000 description 35
- 238000000034 method Methods 0.000 description 31
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- 238000004519 manufacturing process Methods 0.000 description 26
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- 229910052698 phosphorus Inorganic materials 0.000 description 17
- 239000011574 phosphorus Substances 0.000 description 17
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 15
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 15
- 229910001416 lithium ion Inorganic materials 0.000 description 15
- 239000011777 magnesium Substances 0.000 description 15
- 229910052749 magnesium Inorganic materials 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- 125000000753 cycloalkyl group Chemical group 0.000 description 14
- 150000002681 magnesium compounds Chemical class 0.000 description 14
- 125000000217 alkyl group Chemical group 0.000 description 13
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 11
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- 125000001931 aliphatic group Chemical group 0.000 description 6
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- 125000000304 alkynyl group Chemical group 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
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- JBDSSBMEKXHSJF-UHFFFAOYSA-N cyclopentanecarboxylic acid Chemical compound OC(=O)C1CCCC1 JBDSSBMEKXHSJF-UHFFFAOYSA-N 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 238000003475 lamination Methods 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
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- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 4
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- 238000003303 reheating Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
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- 239000002904 solvent Substances 0.000 description 4
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 238000004804 winding Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 230000002862 amidating effect Effects 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- 159000000007 calcium salts Chemical class 0.000 description 3
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 3
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- 229910001381 magnesium hypophosphite Inorganic materials 0.000 description 3
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- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
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- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 2
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- 159000000002 lithium salts Chemical class 0.000 description 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 1
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- GPSDUZXPYCFOSQ-UHFFFAOYSA-N m-toluic acid Chemical compound CC1=CC=CC(C(O)=O)=C1 GPSDUZXPYCFOSQ-UHFFFAOYSA-N 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- PJJZFXPJNUVBMR-UHFFFAOYSA-L magnesium benzoate Chemical compound [Mg+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 PJJZFXPJNUVBMR-UHFFFAOYSA-L 0.000 description 1
- ARIXXGBZIGZIKW-UHFFFAOYSA-L magnesium dioxidophosphanium Chemical class [Mg++].[O-][PH2]=O.[O-][PH2]=O ARIXXGBZIGZIKW-UHFFFAOYSA-L 0.000 description 1
- CQQJGTPWCKCEOQ-UHFFFAOYSA-L magnesium dipropionate Chemical compound [Mg+2].CCC([O-])=O.CCC([O-])=O CQQJGTPWCKCEOQ-UHFFFAOYSA-L 0.000 description 1
- ATYSJAJVVFHRKR-UHFFFAOYSA-L magnesium octacosanoate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O ATYSJAJVVFHRKR-UHFFFAOYSA-L 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- 229940091250 magnesium supplement Drugs 0.000 description 1
- GMIMAWFYOOIAQD-GNNYBVKZSA-L magnesium;(z,12r)-12-hydroxyoctadec-9-enoate Chemical compound [Mg+2].CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O.CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O GMIMAWFYOOIAQD-GNNYBVKZSA-L 0.000 description 1
- VIALJPAGUCTUBQ-UHFFFAOYSA-L magnesium;12-hydroxyoctadecanoate Chemical compound [Mg+2].CCCCCCC(O)CCCCCCCCCCC([O-])=O.CCCCCCC(O)CCCCCCCCCCC([O-])=O VIALJPAGUCTUBQ-UHFFFAOYSA-L 0.000 description 1
- XGIJWNPXLLJTTB-UHFFFAOYSA-L magnesium;butanoate Chemical compound [Mg+2].CCCC([O-])=O.CCCC([O-])=O XGIJWNPXLLJTTB-UHFFFAOYSA-L 0.000 description 1
- WWRYOAYBSQIWNU-UHFFFAOYSA-L magnesium;decanoate Chemical compound [Mg+2].CCCCCCCCCC([O-])=O.CCCCCCCCCC([O-])=O WWRYOAYBSQIWNU-UHFFFAOYSA-L 0.000 description 1
- LTZZKILZCADVRM-UHFFFAOYSA-L magnesium;decyl phosphate Chemical compound [Mg+2].CCCCCCCCCCOP([O-])([O-])=O LTZZKILZCADVRM-UHFFFAOYSA-L 0.000 description 1
- OBQVOBQZMOXRAL-UHFFFAOYSA-L magnesium;docosanoate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCCCCCC([O-])=O OBQVOBQZMOXRAL-UHFFFAOYSA-L 0.000 description 1
- BJZBHTNKDCBDNQ-UHFFFAOYSA-L magnesium;dodecanoate Chemical compound [Mg+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O BJZBHTNKDCBDNQ-UHFFFAOYSA-L 0.000 description 1
- YPEFBMUHVPWWMN-UHFFFAOYSA-L magnesium;dodecyl phosphate Chemical compound [Mg+2].CCCCCCCCCCCCOP([O-])([O-])=O YPEFBMUHVPWWMN-UHFFFAOYSA-L 0.000 description 1
- FKZRUGSMXUERAD-UHFFFAOYSA-L magnesium;hexanoate Chemical compound [Mg+2].CCCCCC([O-])=O.CCCCCC([O-])=O FKZRUGSMXUERAD-UHFFFAOYSA-L 0.000 description 1
- WMJYMUUIWPPMGJ-UHFFFAOYSA-L magnesium;icosanoate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCCCC([O-])=O WMJYMUUIWPPMGJ-UHFFFAOYSA-L 0.000 description 1
- VMDYXCZMLYOOOR-UHFFFAOYSA-L magnesium;octadecyl phosphate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCCOP([O-])([O-])=O VMDYXCZMLYOOOR-UHFFFAOYSA-L 0.000 description 1
- HPBJPFJVNDHMEG-UHFFFAOYSA-L magnesium;octanoate Chemical compound [Mg+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O HPBJPFJVNDHMEG-UHFFFAOYSA-L 0.000 description 1
- APLYTANMTDCWTA-UHFFFAOYSA-L magnesium;phthalate Chemical compound [Mg+2].[O-]C(=O)C1=CC=CC=C1C([O-])=O APLYTANMTDCWTA-UHFFFAOYSA-L 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 229940127554 medical product Drugs 0.000 description 1
- 239000002931 mesocarbon microbead Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000005394 methallyl group Chemical group 0.000 description 1
- AXLHVTKGDPVANO-UHFFFAOYSA-N methyl 2-amino-3-[(2-methylpropan-2-yl)oxycarbonylamino]propanoate Chemical compound COC(=O)C(N)CNC(=O)OC(C)(C)C AXLHVTKGDPVANO-UHFFFAOYSA-N 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- ZFCYQBRMDFUTCG-UHFFFAOYSA-N n,n-dicyclohexyl-4-[3-[4-(dicyclohexylcarbamoyl)phenyl]-2,4,8,10-tetraoxaspiro[5.5]undecan-9-yl]benzamide Chemical compound C=1C=C(C2OCC3(CO2)COC(OC3)C=2C=CC(=CC=2)C(=O)N(C2CCCCC2)C2CCCCC2)C=CC=1C(=O)N(C1CCCCC1)C1CCCCC1 ZFCYQBRMDFUTCG-UHFFFAOYSA-N 0.000 description 1
- OGCMGQVAZUIRNZ-UHFFFAOYSA-N n-(1-adamantyl)-4-[3-[4-(1-adamantylcarbamoyl)phenyl]-2,4,8,10-tetraoxaspiro[5.5]undecan-9-yl]benzamide Chemical compound C1C(C2)CC(C3)CC2CC13NC(=O)C(C=C1)=CC=C1C(OC1)OCC1(CO1)COC1C(C=C1)=CC=C1C(=O)NC1(C2)CC(C3)CC2CC3C1 OGCMGQVAZUIRNZ-UHFFFAOYSA-N 0.000 description 1
- BGBHHERYEGLHMF-UHFFFAOYSA-N n-(2,4-ditert-butylcyclohexyl)-4-[3-[4-[(2,4-ditert-butylcyclohexyl)carbamoyl]phenyl]-2,4,8,10-tetraoxaspiro[5.5]undecan-9-yl]benzamide Chemical compound CC(C)(C)C1CC(C(C)(C)C)CCC1NC(=O)C1=CC=C(C2OCC3(CO2)COC(OC3)C=2C=CC(=CC=2)C(=O)NC2C(CC(CC2)C(C)(C)C)C(C)(C)C)C=C1 BGBHHERYEGLHMF-UHFFFAOYSA-N 0.000 description 1
- GSUVDDINWMUONZ-UHFFFAOYSA-N n-(4-tert-butylcyclohexyl)-4-[3-[4-[(4-tert-butylcyclohexyl)carbamoyl]phenyl]-2,4,8,10-tetraoxaspiro[5.5]undecan-9-yl]benzamide Chemical compound C1CC(C(C)(C)C)CCC1NC(=O)C1=CC=C(C2OCC3(CO2)COC(OC3)C=2C=CC(=CC=2)C(=O)NC2CCC(CC2)C(C)(C)C)C=C1 GSUVDDINWMUONZ-UHFFFAOYSA-N 0.000 description 1
- YAADMTDSEMJUCB-UHFFFAOYSA-N n-(4-tert-butylphenyl)-4-[3-[4-[(4-tert-butylphenyl)carbamoyl]phenyl]-2,4,8,10-tetraoxaspiro[5.5]undecan-9-yl]benzamide Chemical compound C1=CC(C(C)(C)C)=CC=C1NC(=O)C1=CC=C(C2OCC3(CO2)COC(OC3)C=2C=CC(=CC=2)C(=O)NC=2C=CC(=CC=2)C(C)(C)C)C=C1 YAADMTDSEMJUCB-UHFFFAOYSA-N 0.000 description 1
- TVIDDXQYHWJXFK-UHFFFAOYSA-N n-Dodecanedioic acid Natural products OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- JOKYEDJSHIKSBI-UHFFFAOYSA-N n-cyclohexyl-4-[3-[4-(cyclohexylcarbamoyl)phenyl]-2,4,8,10-tetraoxaspiro[5.5]undecan-9-yl]benzamide Chemical compound C=1C=C(C2OCC3(CO2)COC(OC3)C=2C=CC(=CC=2)C(=O)NC2CCCCC2)C=CC=1C(=O)NC1CCCCC1 JOKYEDJSHIKSBI-UHFFFAOYSA-N 0.000 description 1
- XDVZMXVMSOUEJF-UHFFFAOYSA-N n-octadecyl-4-[3-[4-(octadecylcarbamoyl)phenyl]-2,4,8,10-tetraoxaspiro[5.5]undecan-9-yl]benzamide Chemical compound C1=CC(C(=O)NCCCCCCCCCCCCCCCCCC)=CC=C1C1OCC2(COC(OC2)C=2C=CC(=CC=2)C(=O)NCCCCCCCCCCCCCCCCCC)CO1 XDVZMXVMSOUEJF-UHFFFAOYSA-N 0.000 description 1
- ABMFBCRYHDZLRD-UHFFFAOYSA-N naphthalene-1,4-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1 ABMFBCRYHDZLRD-UHFFFAOYSA-N 0.000 description 1
- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1N KQSABULTKYLFEV-UHFFFAOYSA-N 0.000 description 1
- HRRDCWDFRIJIQZ-UHFFFAOYSA-N naphthalene-1,8-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=C2C(C(=O)O)=CC=CC2=C1 HRRDCWDFRIJIQZ-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- WPUMVKJOWWJPRK-UHFFFAOYSA-N naphthalene-2,7-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=CC2=CC(C(=O)O)=CC=C21 WPUMVKJOWWJPRK-UHFFFAOYSA-N 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 description 1
- QXHVOXBWUFHWDW-UHFFFAOYSA-N octacosyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCOP(O)(O)=O QXHVOXBWUFHWDW-UHFFFAOYSA-N 0.000 description 1
- 150000005677 organic carbonates Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- LRTFPLFDLJYEKT-UHFFFAOYSA-N para-isopropylaniline Chemical compound CC(C)C1=CC=C(N)C=C1 LRTFPLFDLJYEKT-UHFFFAOYSA-N 0.000 description 1
- IGEIPFLJVCPEKU-UHFFFAOYSA-N pentan-2-amine Chemical compound CCCC(C)N IGEIPFLJVCPEKU-UHFFFAOYSA-N 0.000 description 1
- WTSXICLFTPPDTL-UHFFFAOYSA-N pentane-1,3-diamine Chemical compound CCC(N)CCN WTSXICLFTPPDTL-UHFFFAOYSA-N 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- DAFOCGYVTAOKAJ-UHFFFAOYSA-N phenibut Chemical compound OC(=O)CC(CN)C1=CC=CC=C1 DAFOCGYVTAOKAJ-UHFFFAOYSA-N 0.000 description 1
- 229950009215 phenylbutanoic acid Drugs 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920002589 poly(vinylethylene) polymer Polymers 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920000379 polypropylene carbonate Polymers 0.000 description 1
- 229920002215 polytrimethylene terephthalate Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 125000001844 prenyl group Chemical group [H]C([*])([H])C([H])=C(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 239000002296 pyrolytic carbon Substances 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- UQDJGEHQDNVPGU-UHFFFAOYSA-N serine phosphoethanolamine Chemical compound [NH3+]CCOP([O-])(=O)OCC([NH3+])C([O-])=O UQDJGEHQDNVPGU-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229940077386 sodium benzenesulfonate Drugs 0.000 description 1
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 description 1
- HIEHAIZHJZLEPQ-UHFFFAOYSA-M sodium;naphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 HIEHAIZHJZLEPQ-UHFFFAOYSA-M 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000005017 substituted alkenyl group Chemical group 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 125000004426 substituted alkynyl group Chemical group 0.000 description 1
- 125000005346 substituted cycloalkyl group Chemical group 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- OKUCEQDKBKYEJY-UHFFFAOYSA-N tert-butyl 3-(methylamino)pyrrolidine-1-carboxylate Chemical compound CNC1CCN(C(=O)OC(C)(C)C)C1 OKUCEQDKBKYEJY-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 150000005691 triesters Chemical class 0.000 description 1
- CENHPXAQKISCGD-UHFFFAOYSA-N trioxathietane 4,4-dioxide Chemical compound O=S1(=O)OOO1 CENHPXAQKISCGD-UHFFFAOYSA-N 0.000 description 1
- 229940070710 valerate Drugs 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
- 238000004736 wide-angle X-ray diffraction Methods 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
- AXORVIZLPOGIRG-UHFFFAOYSA-N β-methylphenethylamine Chemical compound NCC(C)C1=CC=CC=C1 AXORVIZLPOGIRG-UHFFFAOYSA-N 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)
- Laminated Bodies (AREA)
- Molding Of Porous Articles (AREA)
- Cell Separators (AREA)
Description
本発明は、包装用品、衛生用品、畜産用品、農業用品、建築用品、医療用品、分離膜、光拡散板、電池用セパレータとして利用でき、特に非水電解液電池用セパレータとして好適に利用できる積層多孔性延伸フィルム、それを利用した電池用セパレータ及び電池に関するものである。 INDUSTRIAL APPLICABILITY The present invention can be used as a packaging product, sanitary product, livestock product, agricultural product, building product, medical product, separation membrane, light diffusion plate, battery separator, and particularly a laminate that can be suitably used as a nonaqueous electrolyte battery separator. The present invention relates to a porous stretched film , a battery separator using the same, and a battery .
二次電池はOA、FA、家庭用電器または通信機器等のポータブル機器用電源として幅広く使用されている。特に機器に装備した場合に容積効率がよく機器の小型化および軽量化につながることからリチウムイオン二次電池を使用したポータブル機器が増加している。
一方、大型の二次電池はロードレベリング、UPS、電気自動車をはじめ、エネルギー/環境問題に関連する多くの分野において研究開発が進められ、大容量、高出力、高電圧および長期保存性に優れている点より非水電解液二次電池の一種であるリチウムイオン二次電池の用途が広がっている。
Secondary batteries are widely used as power sources for portable devices such as OA, FA, household electric appliances and communication devices. In particular, portable devices using lithium ion secondary batteries are increasing because they have a high volumetric efficiency when mounted on devices, leading to a reduction in size and weight of the devices.
On the other hand, large-sized secondary batteries are being researched and developed in many fields related to energy / environmental issues, including road leveling, UPS, and electric vehicles, and are excellent in large capacity, high output, high voltage, and long-term storage. Therefore, the use of lithium ion secondary batteries, which are a kind of non-aqueous electrolyte secondary battery, is expanding.
リチウムイオン二次電池の使用電圧は通常4.1Vから4.2Vを上限として設計されている。このような高電圧では水溶液は電気分解を起こすので電解液として使うことができない。そのため、高電圧でも耐えられる電解液として有機溶媒を使用したいわゆる非水電解液が用いられている。
非水電解液用の溶媒としては、より多くのリチウムイオンを存在させることができる高誘電率有機溶媒が用いられ、該高誘電率有機溶媒としてポリプロピレンカーボネートやエチレンカーボネート等の有機炭酸エステルが主に使用されている。溶媒中でリチウムイオン源となる支持電解質として、6フッ化リン酸リチウム等の反応性の高い電解質を溶媒中に溶かして使用している。
The working voltage of a lithium ion secondary battery is usually designed with an upper limit of 4.1V to 4.2V. At such a high voltage, the aqueous solution causes electrolysis and cannot be used as an electrolyte. Therefore, so-called non-aqueous electrolytes using organic solvents are used as electrolytes that can withstand high voltages.
As the solvent for the non-aqueous electrolyte, a high dielectric constant organic solvent capable of making more lithium ions exist is used, and organic carbonates such as polypropylene carbonate and ethylene carbonate are mainly used as the high dielectric constant organic solvent. It is used. As a supporting electrolyte that becomes a lithium ion source in the solvent, a highly reactive electrolyte such as lithium hexafluorophosphate is dissolved in the solvent and used.
リチウムイオン二次電池には内部短絡の防止の点からセパレータが正極と負極の間に介在されている。当該セパレータにはその役割から当然絶縁性が要求される。また、リチウムイオンの通路となる透気性と電解液の拡散・保持機能を付与するために微細孔構造である必要がある。これらの要求を満たすためセパレータとしては多孔性フィルムが使用されている。 In the lithium ion secondary battery, a separator is interposed between the positive electrode and the negative electrode from the viewpoint of preventing an internal short circuit. Of course, the separator is required to have insulating properties due to its role. Moreover, it is necessary to have a microporous structure in order to provide air permeability as a lithium ion passage and a function of diffusing and holding the electrolyte. In order to satisfy these requirements, a porous film is used as a separator.
最近の電池の高容量化に伴い、電池の安全性に対する重要度が増してきている。
電池用セパレータの安全に寄与する特性として、ブレイクダウン特性(以後、BD特性)がある。このBD特性は、電池が異常を起こし熱暴走して160℃程度以上高温の状態となった場合でも、フィルムが破膜せず、正極と負極を隔て続けるという機能である。BD特性を有すれば高温になっても絶縁を保ち、電極間の広範囲な短絡を防止することができるため、電池の異常発熱による発火等の事故を防止できる。そのため、電池用セパレータとして使用する場合はこのBD特性も具備していることが好ましく、破膜が生じる最低温度を指すブレイクダウン温度はより高い温度であることが好ましい。
With the recent increase in battery capacity, the importance of battery safety has increased.
A characteristic that contributes to the safety of battery separators is breakdown characteristics (hereinafter referred to as BD characteristics). This BD characteristic is a function that the film does not break and keeps the positive electrode and the negative electrode separated even when the battery becomes abnormal and the thermal runaway causes a high temperature of about 160 ° C. or more. If it has BD characteristics, insulation can be maintained even at high temperatures, and a wide range of short-circuits between electrodes can be prevented, thereby preventing accidents such as ignition due to abnormal heat generation of the battery. Therefore, when it is used as a battery separator, it preferably has this BD characteristic, and the breakdown temperature indicating the lowest temperature at which film breakage occurs is preferably a higher temperature.
このような要望に対して、特許2883726号公報(特許文献1)ではポリエチレンとポリプロピレンの積層フィルムを1軸方向に温度を変えて2段階で延伸することにより多孔質化せしめることを特徴とする電池用セパレータの製造方法が提案されている。
当該製造方法により製造されたセパレータは従来のポリエチレン単層のセパレータに比べて結晶融解ピーク温度がより高いポリプロピレン層が積層されているため耐熱性を有しBD特性の観点からは有利である。しかしながら、最近の電池の高エネルギー密度化に伴い、ポリプロピレンでは耐熱性が十分とは言い難くなってきており、より高い温度でもBD特性を発揮できることが求められている。
さらに、当該製造方法により製造されたセパレータは延伸方向と直角な方向の引裂きに非常に弱く、延伸方向に裂け目が生じやすいという強度面からの問題点もある。
また、当該製造方法は厳密な製造条件の制御を必要とし、かつ生産性が良いとは言い難い。
In response to such a demand, Japanese Patent No. 2883726 (Patent Document 1) is characterized in that a laminated film of polyethylene and polypropylene is made porous by changing the temperature in one axial direction and stretching in two stages. A separator manufacturing method has been proposed.
The separator manufactured by the manufacturing method has heat resistance because a polypropylene layer having a higher crystal melting peak temperature than that of a conventional polyethylene single layer separator is laminated, and is advantageous from the viewpoint of BD characteristics. However, with the recent increase in energy density of batteries, it is difficult to say that heat resistance is sufficient for polypropylene, and it is required that BD characteristics can be exhibited even at higher temperatures.
Furthermore, the separator manufactured by the manufacturing method is very weak against tearing in a direction perpendicular to the stretching direction, and there is a problem in terms of strength that a tear is easily generated in the stretching direction.
In addition, the manufacturing method requires strict control of manufacturing conditions, and it is difficult to say that productivity is good.
一方、多孔性フィルムの透過性を高めるために、結晶形態の一つであるβ晶を多く含むポリプロピレンシートを延伸して多孔性フィルムを得る方法として、特許2509030号公報(特許文献2)、国際公開2002/066233号(特許文献3)等が提案されている。
しかしながら、いずれの多孔性フィルムも電池用セパレータとして使用するには耐熱性が十分とは言えず、電池の安全性を確保するという点で問題があり、ブレイクダウン温度がより高温となるように改良することが要望されている。
On the other hand, as a method for obtaining a porous film by stretching a polypropylene sheet containing a large amount of β crystals, which is one of crystal forms, in order to increase the permeability of the porous film, Japanese Patent No. 2509030 (Patent Document 2), International Publication 2002/066233 (Patent Document 3) has been proposed.
However, the heat resistance is not sufficient to use any porous film as a battery separator, and there is a problem in securing the safety of the battery, and the breakdown temperature is improved to be higher. It is requested to do.
本発明は、優れた透気特性と機械的強度を有し、かつ従来のポリプロピレン多孔性フィルムよりも優れたブレイクダウン特性を発揮できる積層多孔性延伸フィルム、それを利用した電池用セパレータ及び電池を提案することを課題とする。 The present invention relates to a laminated porous stretched film having excellent air permeability and mechanical strength and capable of exhibiting a breakdown characteristic superior to that of a conventional polypropylene porous film , a battery separator and a battery using the same. The challenge is to propose.
前記課題を解決するため、本発明は、少なくとも第1層と第2層の多孔質層を有する積層多孔性延伸フィルムであって、
前記第1層は、ポリプロピレン系樹脂に、結晶融解ピーク温度が170℃以上である熱可塑性樹脂を混合した樹脂組成物からなる層であり、
前記第2層は、β晶核剤を配合したポリプロピレン系樹脂に、前記結晶融解ピーク温度が170℃以上である熱可塑性樹脂は混合していない樹脂組成物からなり、β活性及び/又はβ晶生成力を有する層であり、
透気抵抗が1〜10000秒/100mlであり、ピン刺し強度が1.5N以上であり、ブレイクダウン温度が200℃以上である、積層多孔性フィルムを提供する。
また、前記積層多孔性延伸フィルムからなり、透気抵抗が5〜3000秒/mlである、電池用セパレータ、及び、前記電池用セパレータが組み込まれている、電池を提供する。
To solve the above problems, the present invention is a laminated porous expanded fill beam having a porous layer of at least first and second layers,
The first layer, the polypropylene-based resin, Ri layer der ing a resin composition crystal melting peak temperature is mixed with the thermoplastic resin is 170 ° C. or higher,
The second layer is composed of a resin composition in which a thermoplastic resin having a crystal melting peak temperature of 170 ° C. or higher is not mixed with a polypropylene resin blended with a β crystal nucleating agent, and has β activity and / or β crystal. A layer having a generating power ,
An air resistance is 1-10000 seconds / 100 ml, the pin stab strength of not less than 1.5 N, the breakdown temperature of 200 ° C. or higher, that provides a laminated porous film.
Moreover, the battery separator which consists of the said laminated porous stretched film and whose air permeation resistance is 5-3000 second / ml, and the battery separator are incorporated are provided.
削除 Delete
本発明の積層多孔性延伸フィルムは、第1層をポリプロピレン系樹脂と結晶融解ピーク温度が170℃以上である熱可塑性樹脂との混合樹脂を含む樹脂組成物から形成しているため、耐熱性に優れた層となり、従来のポリプロピレン多孔性フィルムよりも優れたブレイクダウン特性を発揮させることができる。また、第2層はポリプロピレン系樹脂に前記熱可塑性樹脂を配合せず、ポリプロピレン系樹脂を多くしていることにより機械的強度に優れた層とすることができる。このように、本発明の積層多孔性延伸フィルムは優れた機械的強度とブレイクダウン特性とを兼ね備えたものとすることができ、本発明の積層多孔性延伸フィルムを電池用セパレータに用いた場合、電池の安全性確保に大きく貢献する。
さらに、本発明の積層多孔性延伸フィルムは、β活性および/又はβ晶生成力を有するので、微細孔を有し、十分な連通性を確保することができ、透気特性にも優れている。
また、電池製造における電極とセパレータを捲回する際、あるいは充放電において電極が膨張・収縮を繰り返す際に、電極凹凸やバリによってセパレータが破膜し、両電極間の短絡を生じせしめるということが起こりにくくすることができる。
Product layer porous stretched film of the present invention, since the first layer is formed from a resin composition crystal melting peak temperature and the polypropylene resin comprises a mixed resin of the thermoplastic resin is 170 ° C. or higher, heat resistance It is possible to exhibit a breakdown characteristic superior to that of a conventional polypropylene porous film. In addition, the second layer can be made a layer having excellent mechanical strength by increasing the amount of polypropylene resin without blending the thermoplastic resin with polypropylene resin. Thus, the laminated porous stretched film of the present invention can have excellent mechanical strength and breakdown characteristics, and when the laminated porous stretched film of the present invention is used for a battery separator, Contributes greatly to ensuring battery safety.
Furthermore, since the laminated porous stretched film of the present invention has β activity and / or β crystal generation ability, it has fine pores, can ensure sufficient communication, and has excellent air permeability. .
Also, when winding the electrode and separator in battery manufacturing, or when the electrode repeatedly expands and contracts during charge and discharge, the separator breaks due to electrode irregularities and burrs, causing a short circuit between the two electrodes. It can be hard to happen.
以下、本発明の積層多孔性延伸フィルムの実施形態、ならびに電池用セパレータとしての電池への適応形態について詳細に説明する。
本発明の積層多孔性延伸フィルムは、いずれの実施形態においても、少なくとも第1層の多孔質層と第2層の多孔質層の2層の多孔質層を備えた構成としている。
Hereinafter, embodiments of the product layer porous stretched film of the present invention, as well as the adaptations to the battery as a battery separator will be described in detail.
Product layer porous stretched film of the present invention, in any embodiment, is configured to include a porous layer of at least two layers of a first layer porous layer and a porous layer of the second layer of.
[第1実施形態]
第1実施形態の積層多孔性フィルムは、β晶核剤を配合したポリプロピレン系樹脂(以下「PP樹脂」と称す)と結晶融解ピーク温度が170℃以上である熱可塑性樹脂(以下「HM樹脂」と称す)との混合樹脂を含む組成物から形成した第1層と
β晶核剤を配合したポリプロピレン系樹脂を含み、前記結晶融解ピーク温度が170℃以上である熱可塑性樹脂(HM樹脂)を含まず、結晶融解ピーク温度が100℃以上170℃未満である第2層とを備えている。
前記第1層は特にブレイクダウン特性を奏する層とし、第2層は機械的強度を付与する層としている。
[First Embodiment]
The laminated porous film of the first embodiment includes a polypropylene resin (hereinafter referred to as “PP resin”) containing a β crystal nucleating agent and a thermoplastic resin (hereinafter referred to as “HM resin”) having a crystal melting peak temperature of 170 ° C. or higher. A thermoplastic resin (HM resin) having a crystal melting peak temperature of 170 ° C. or higher, and a polypropylene resin containing a first layer formed from a composition containing a mixed resin and a β crystal nucleating agent And a second layer having a crystal melting peak temperature of 100 ° C. or higher and lower than 170 ° C.
In particular, the first layer is a layer that exhibits breakdown characteristics, and the second layer is a layer that imparts mechanical strength.
本発明の積層多孔性フィルムは、前記β活性と前記β晶生成力のうち、少なくとも1つを有することを重要な特徴としている。
β活性とβ晶生成力はいずれも、延伸前の膜状物においてポリプロピレン系樹脂がβ晶を生成していたことを示す一指標と捉えることができる。延伸前の膜状物中のポリプロピレン系樹脂がβ晶を生成していれば、その後延伸を施すことで微細孔が形成されるため、透気特性を有する積層多孔性フィルムを得ることができる。
The laminated porous film of the present invention is characterized by having at least one of the β activity and the β crystal generation force.
Both β activity and β crystal forming power can be regarded as one index indicating that the polypropylene resin has generated β crystals in the film-like material before stretching. If the polypropylene-based resin in the film-like material before stretching produces β crystals, fine pores are formed by subsequent stretching, and thus a laminated porous film having air permeability characteristics can be obtained.
前記のβ活性の有無は、示差走査型熱量計を用いて、積層多孔性フィルムの示差熱分析を行い、ポリプロピレン系樹脂のβ晶に由来する結晶融解ピーク温度が検出されるか否かで判断している。
具体的には、示差走査型熱量計で積層多孔性フィルムを25℃から240℃まで加熱速度10℃/分で昇温後1分間保持し、次に240℃から25℃まで冷却速度10℃/分で降温後1分間保持し、更に25℃から240℃まで加熱速度10℃/分で再昇温させた際に、ポリプロピレン系樹脂のβ晶に由来する結晶融解ピーク温度(Tmβ)が検出された場合、β活性を有すると判断している。
Presence or absence of the β activity is determined by performing differential thermal analysis of the laminated porous film using a differential scanning calorimeter and determining whether or not a crystal melting peak temperature derived from β crystals of the polypropylene resin is detected. doing.
Specifically, the laminated porous film is heated at a heating rate of 10 ° C./min from 25 ° C. to 240 ° C. for 1 minute with a differential scanning calorimeter, and then cooled from 240 ° C. to 25 ° C. at a cooling rate of 10 ° C. / When the temperature is lowered for 1 minute and held for 1 minute, and when the temperature is raised again from 25 ° C. to 240 ° C. at a heating rate of 10 ° C./min, the crystal melting peak temperature (Tmβ) derived from the β crystal of the polypropylene resin is detected. In that case, it is determined to have β activity.
また、前記積層多孔性フィルムのβ活性度は、検出されるポリプロピレン系樹脂のα晶由来の結晶融解熱量(ΔHmα)とβ晶由来の結晶融解熱量(ΔHmβ)を用いて下記式で計算している。
β活性度(%)=〔ΔHmβ/(ΔHmβ+ΔHmα)〕×100
例えば、ポリプロピレン系樹脂がホモポリプロピレンの場合は、主に145℃以上160℃未満の範囲で検出されるβ晶由来の結晶融解熱量(ΔHmβ)と、主に160℃以上175℃以下に検出されるα晶由来の結晶融解熱量(ΔHmα)から計算することができる。また、例えばエチレンが1〜4モル%共重合されているランダムポリプロピレンの場合は、主に120℃以上140℃未満の範囲で検出されるβ晶由来の結晶融解熱量(ΔHmβ)と、主に140℃以上165℃以下の範囲に検出されるα晶由来の結晶融解熱量(ΔHmα)から計算することができる。
In addition, the β activity of the laminated porous film is calculated by the following formula using the heat of crystal melting derived from the α crystal of the polypropylene resin (ΔHmα) and the heat of crystal melting derived from the β crystal (ΔHmβ). Yes.
β activity (%) = [ΔHmβ / (ΔHmβ + ΔHmα)] × 100
For example, when the polypropylene resin is homopolypropylene, the amount of heat of crystal melting derived from the β crystal (ΔHmβ) detected mainly in the range of 145 ° C. or higher and lower than 160 ° C., and mainly detected at 160 ° C. or higher and 175 ° C. or lower. It can be calculated from the heat of crystal melting (ΔHmα) derived from the α crystal. Further, for example, in the case of random polypropylene copolymerized with 1 to 4 mol% of ethylene, the crystal melting heat amount (ΔHmβ) derived from the β crystal detected mainly in the range of 120 ° C. or more and less than 140 ° C., and mainly 140 It can be calculated from the crystal melting calorie (ΔHmα) derived from the α crystal detected in the range of from 0 ° C. to 165 ° C.
前記積層多孔性フィルムのβ活性度は大きい方が好ましく、β活性度は20%以上であることが好ましい。40%以上であることがさらに好ましく、60%以上であることが特に好ましい。積層多孔性フィルムが20%以上のβ活性度を有すれば、延伸前の膜状物中においてもポリプロピレン系樹脂のβ晶が多く生成することができることを示し、延伸により微細かつ均一な孔が多く形成され、結果として機械的強度が高く、透気性能に優れたリチウムイオン電池用セパレータとすることができる。
β活性度の上限値は特に限定されないが、β活性度が高いほど前記効果がより有効に得られるので100%に近いほど好ましい。
The laminated porous film preferably has a high β activity, and the β activity is preferably 20% or more. More preferably, it is 40% or more, and particularly preferably 60% or more. If the laminated porous film has a β activity of 20% or more, it indicates that a large amount of β crystals of polypropylene resin can be produced in the film-like material before stretching, and fine and uniform pores are formed by stretching. As a result, a separator for a lithium ion battery having high mechanical strength and excellent air permeability can be obtained.
The upper limit of β activity is not particularly limited, but the higher the β activity, the more effective the effect is obtained.
前記β晶生成力の有無は、特定の熱処理を施した積層多孔性フィルムの広角X線測定により得られる回折プロファイルで判断している。
詳細には、ポリプロピレン系樹脂(PP樹脂)の融点を超える温度である170℃〜190℃の熱処理を施し、徐冷してβ晶を生成・成長させた積層多孔性フィルムについて広角X線測定を行い、ポリプロピレン系樹脂のβ晶の(300)面に由来する回折ピークが2θ=16.0°〜16.5°の範囲に検出された場合、β晶生成力が有ると判断している。
ポリプロピレン系樹脂のβ晶構造と広角X線回折に関する詳細は、Macromol.Chem.187,643−652(1986)、Prog.Polym.Sci.Vol.16,361−404(1991)、Macromol.Symp.89,499−511(1995)、Macromol.Chem.75,134(1964)、及びこれらの文献中に挙げられた参考文献を参照することができる。β晶生成力の詳細な評価方法については、後述の実施例にて示す。
The presence or absence of the β crystal generation force is determined by a diffraction profile obtained by wide-angle X-ray measurement of a laminated porous film subjected to a specific heat treatment.
Specifically, wide-angle X-ray measurement is performed on a laminated porous film that has been subjected to heat treatment at 170 ° C. to 190 ° C., which is a temperature exceeding the melting point of polypropylene resin (PP resin), and slowly cooled to produce and grow β crystals. When a diffraction peak derived from the (300) plane of the β crystal of the polypropylene resin is detected in the range of 2θ = 16.0 ° to 16.5 °, it is determined that there is β crystal forming power.
Details on the β crystal structure and wide angle X-ray diffraction of polypropylene resins can be found in Macromol. Chem. 187, 643-652 (1986), Prog. Polym. Sci. Vol. 16, 361-404 (1991), Macromol. Symp. 89, 499-511 (1995), Macromol. Chem. 75, 134 (1964), and references cited therein. A detailed evaluation method of the β crystal forming power will be described in the examples described later.
前述した多孔質層のβ活性および/又はβ晶生成力を得る方法としては、ポリプロピレン系樹脂のα晶の生成を促進させる物質を添加しない方法や、特許3739481号公報に記載されているように過酸化ラジカルを発生させる処理を施したポリプロピレンを添加する方法、及び組成物にβ晶核剤を添加する方法などが挙げられる。
本発明では、前記第1層の組成物及び/又は第2層の組成物にβ晶核剤を添加してβ活性および/又はβ晶生成力を得ている。β晶核剤を添加することで、より均質に効率的にポリプロピレン系樹脂のβ晶の生成を促進させることができ、β活性および/又はβ晶生成力を有する積層多孔性フィルムを得ることができる。
As a method for obtaining the β activity and / or β crystal generation power of the porous layer described above, as described in a method in which a substance that promotes the formation of α crystal of a polypropylene resin is not added, or as described in Japanese Patent No. 3739481 The method of adding the polypropylene which performed the process which generates a peroxide radical, the method of adding a (beta) crystal nucleating agent to a composition, etc. are mentioned.
In the present invention, a β crystal nucleating agent is added to the composition of the first layer and / or the composition of the second layer to obtain β activity and / or β crystal generation power. By adding a β crystal nucleating agent, it is possible to promote the generation of β crystals of polypropylene resin more uniformly and efficiently, and to obtain a laminated porous film having β activity and / or β crystal generation ability. it can.
本発明において、β晶核剤は、ポリプロピレン系樹脂に配合している。前記ポリプロピレン系樹脂に添加するβ晶核剤の割合は、β晶核剤の種類またはポリプロピレン系樹脂の組成などにより適宜調整することが必要であるが、ポリプロピレン系樹脂100質量部に対しβ晶核剤0.0001〜5.0質量部が好ましい。0.001〜3.0質量部がより好ましく、0.01〜1.0質量部が更に好ましい。0.0001質量部以上であれば、製造時において十分にポリプロピレン系樹脂のβ晶を生成・成長させることができ、セパレータとした際にも十分なβ活性および/又はβ晶生成力が確保でき、所望の透気性能が得られる。また、5.0質量部以下の添加であれば、経済的にも有利になるほか、積層多孔性フィルム表面へのβ晶核剤のブリ−ドなどがなく好ましい。
本発明において、第1層と第2層のそれぞれでβ晶核剤の添加量は同じであっても、異なっていても良い。β晶核剤の添加量を変更することで各層の多孔構造を適宜調整することができる。
In the present invention, the β crystal nucleating agent is blended in a polypropylene resin. The ratio of the β-crystal nucleating agent added to the polypropylene resin needs to be appropriately adjusted depending on the type of the β-crystal nucleating agent or the composition of the polypropylene-based resin. 0.0001 to 5.0 parts by mass of the agent is preferred. 0.001-3.0 mass parts is more preferable, and 0.01-1.0 mass part is still more preferable. If it is 0.0001 part by mass or more, β-crystals of polypropylene resin can be sufficiently produced and grown during production, and sufficient β-activity and / or β-crystal-forming power can be secured even when used as a separator. Desired air permeation performance can be obtained. The addition of 5.0 parts by mass or less is preferable because it is economically advantageous and there is no β crystal nucleating agent on the surface of the laminated porous film.
In the present invention, the addition amount of the β crystal nucleating agent may be the same or different between the first layer and the second layer. The porous structure of each layer can be appropriately adjusted by changing the addition amount of the β crystal nucleating agent.
前記第1層においては、PP樹脂とHM樹脂との総和質量は第1層の全質量に対し70質量%以上であることが好ましい。好ましくは80質量%以上、さらに好ましくは90質量%以上を占める。
PP樹脂とHM樹脂との混合質量比は、PP樹脂/HM樹脂=10〜90/90〜10であることが好ましく、20〜80/80〜20がより好ましく、30〜70/70〜30が更に好ましい。HM樹脂の含有量がPP樹脂とHM樹脂との総和質量100質量%中10質量%以上であれば、適度な温度でBD特性を発現することが可能である。一方、HM樹脂の含有量がPP樹脂とHM樹脂との総和質量100質量%中90質量%以下であれば、第1層の多孔化が容易となり好ましい。
なかでもPP樹脂の含有量が多い方が好ましく、特にPP樹脂/HM樹脂=60〜90/40〜10であることがより好ましく、60〜70/40〜30であることがさらに好ましい。
In the first layer, the total mass of the PP resin and the HM resin is preferably 70% by mass or more based on the total mass of the first layer. Preferably it accounts for 80% by mass or more, more preferably 90% by mass or more.
The mixing mass ratio of PP resin and HM resin is preferably PP resin / HM resin = 10 to 90/90 to 10, more preferably 20 to 80/80 to 20, and 30 to 70/70 to 30. Further preferred. When the content of the HM resin is 10% by mass or more in the total mass of 100% by mass of the PP resin and the HM resin, it is possible to develop the BD characteristics at an appropriate temperature. On the other hand, when the content of the HM resin is 90% by mass or less in the total mass of 100% by mass of the PP resin and the HM resin, the first layer is easily made porous, which is preferable.
Of these, a higher PP resin content is preferred, with PP resin / HM resin = 60-90 / 40-10 being more preferred, and 60-70 / 40-30 being even more preferred.
積層多孔性フィルムを3層以上とし、前記第1層を複数層以上存在させる場合は、1つの第1層におけるPP樹脂とHM樹脂との混合質量比を前記規定の範囲内としている。
それ以外の層におけるPP樹脂とHM樹脂との混合質量比は、PP樹脂/HM樹脂=10〜99/90〜1であることが好ましく、30〜99/70〜1がより好ましく、60〜99/40〜1が更に好ましく、60〜90/40〜10が特に好ましい。
BD特性を発現する層は少なくとも1層存在すればよいから、それ以外の第1層についてはBD特性を必ずしも必要とされない。ゆえに、それ以外の第1層についてはHM樹脂の含有量がPP樹脂とHM樹脂との総和質量100質量%中1質量%以上であればよい。もちろん第1層の全てがBD特性を発現してもなんら問題はなく、むしろその方が好ましい。一方、HM樹脂の含有量がPP樹脂とHM樹脂との総和質量100質量%中90質量%以下であれば、第1層の多孔化が容易となり好ましい。
When the laminated porous film has three or more layers and the plurality of first layers are present, the mixing mass ratio of the PP resin and the HM resin in one first layer is within the specified range.
The mixing mass ratio of PP resin and HM resin in the other layers is preferably PP resin / HM resin = 10 to 99/90 to 1, more preferably 30 to 99/70 to 1, and 60 to 99. / 40-1 is more preferable, and 60-90 / 40-10 is particularly preferable.
Since it is sufficient that at least one layer that exhibits the BD characteristic exists, the BD characteristic is not necessarily required for the other first layers. Therefore, about 1st mass other than that, content of HM resin should just be 1 mass% or more in 100 mass% of total mass of PP resin and HM resin. Of course, there is no problem even if all of the first layer develops the BD characteristic, but it is preferable. On the other hand, when the content of the HM resin is 90% by mass or less in the total mass of 100% by mass of the PP resin and the HM resin, the first layer is easily made porous, which is preferable.
前記第2層においては、PP樹脂の含有量が第2層の全質量に対し70質量%以上占めることが好ましい。さらに好ましくは80質量%以上、最も好ましくは90質量%以上を占める構成としている。なお、機械的強度を向上させるために、PP樹脂に他の熱可塑性樹脂を組み合わせても良い。 In the second layer, the content of the PP resin is preferably 70% by mass or more based on the total mass of the second layer. More preferably, it is configured to occupy 80% by mass or more, and most preferably 90% by mass or more. In addition, in order to improve mechanical strength, you may combine another thermoplastic resin with PP resin.
以下に、本発明の積層多孔性フィルムを構成する各成分について説明する。
[ポリプロピレン系樹脂(PP樹脂)の説明]
ポリプロピレン系樹脂としては、ホモプロピレン(プロピレン単独重合体)、またはプロピレンとエチレン、1−ブテン、1−ペンテン、1−へキセン、1−へプテン、1−オクテン、1−ノネンもしくは1−デセンなどα−オレフィンとのランダム共重合体またはブロック共重合体などが挙げられる。この中でも、積層多孔性フィルムの機械的強度の観点からはホモポリプロピレンがより好適に使用される。
Below, each component which comprises the laminated porous film of this invention is demonstrated.
[Description of polypropylene resin (PP resin)]
Examples of polypropylene resins include homopropylene (propylene homopolymer), or propylene and ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, etc. Examples thereof include random copolymers with α-olefins and block copolymers. Among these, homopolypropylene is more preferably used from the viewpoint of the mechanical strength of the laminated porous film.
また、ポリプロピレン系樹脂としては、立体規則性を示すアイソタクチックペンタッド分率(mmmm分率)が80〜99%であることが好ましい。より好ましくは83〜98%、更に好ましくは85〜97%であるものを使用する。アイソタクチックペンタッド分率が低すぎるとフィルムの機械的強度が低下するおそれがある。一方、アイソタクチックペンタッド分率の上限については現時点において工業的に得られる上限値で規定しているが、将来的に工業レベルで更に規則性の高い樹脂が開発された場合についてはこの限りではない。
アイソタクチックペンタッド分率(mmmm分率)とは、任意の連続する5つのプロピレン単位で構成される炭素−炭素結合による主鎖に対して側鎖である5つのメチル基がいずれも同方向に位置する立体構造あるいはその割合を意味する。メチル基領域のシグナルの帰属は、A.Zambelli et al(Macromolecules8,687,(1975))に準拠している。
Moreover, as a polypropylene resin, it is preferable that the isotactic pentad fraction (mmmm fraction) which shows stereoregularity is 80 to 99%. More preferably 83-98%, still more preferably 85-97%. If the isotactic pentad fraction is too low, the mechanical strength of the film may be reduced. On the other hand, the upper limit of the isotactic pentad fraction is defined by the upper limit that can be obtained industrially at the present time, but this is not the case when a more regular resin is developed in the industrial level in the future. is not.
The isotactic pentad fraction (mmmm fraction) is the same direction for all five methyl groups that are side chains with respect to the main chain of carbon-carbon bonds composed of arbitrary five consecutive propylene units. Means the three-dimensional structure located at or its proportion. Assignment of the signal of the methyl group region is based on A. Zambelli et al (Macromolecules 8, 687, (1975)).
また、ポリプロピレン系樹脂(A)は、分子量分布を示すパラメータであるMw/Mnが2.0〜10.0であることが好ましい。より好ましくは2.0〜8.0、更に好ましくは2.0〜6.0であるものが使用される。Mw/Mnが小さいほど分子量分布が狭いことを意味するが、Mw/Mnが2.0未満であると押出成形性が低下する等の問題が生じるほか、工業的に生産することも困難である。一方、Mw/Mnが10.0を超えた場合は低分子量成分が多くなり、積層多孔性フィルムの機械的強度が低下しやすい。Mw/MnはGPC(ゲルパーミエーションクロマトグラフィー)法によって得られる。 Moreover, it is preferable that Mw / Mn which is a parameter which shows molecular weight distribution of a polypropylene resin (A) is 2.0-10.0. More preferably, 2.0 to 8.0, and still more preferably 2.0 to 6.0 is used. This means that the smaller the Mw / Mn is, the narrower the molecular weight distribution is. However, when the Mw / Mn is less than 2.0, problems such as a decrease in extrusion moldability occur, and it is difficult to produce industrially. . On the other hand, when Mw / Mn exceeds 10.0, low molecular weight components increase, and the mechanical strength of the laminated porous film tends to decrease. Mw / Mn is obtained by GPC (gel permeation chromatography) method.
また、ポリプロピレン系樹脂のメルトフローレート(MFR)は特に制限されるものではないが、通常、MFRは0.5〜15g/10分であることが好ましく、1.0〜10g/10分であることがより好ましい。MFRが0.5g/10分未満では成形加工時の樹脂の溶融粘度が高く生産性が低下する。一方、15g/10分を超えると得られる積層多孔性フィルムの機械的強度が不足するため実用上問題が生じやすい。MFRはJIS K7210に従い、温度230℃、荷重2.16kgの条件で測定している。 Further, the melt flow rate (MFR) of the polypropylene-based resin is not particularly limited, but usually the MFR is preferably 0.5 to 15 g / 10 minutes, and 1.0 to 10 g / 10 minutes. It is more preferable. When the MFR is less than 0.5 g / 10 min, the resin has a high melt viscosity at the time of molding and the productivity is lowered. On the other hand, when it exceeds 15 g / 10 minutes, the mechanical strength of the obtained laminated porous film is insufficient, and thus problems are likely to occur in practice. MFR is measured according to JIS K7210 under conditions of a temperature of 230 ° C. and a load of 2.16 kg.
[β晶核剤の説明]
本発明で用いるβ晶核剤としては以下に示すものが挙げられるが、ポリプロピレン系樹脂のβ晶の生成・成長を増加させるものであれば特に限定される訳ではなく、また2種類以上を混合して用いても良い。
β晶核剤としては、例えば、アミド化合物;テトラオキサスピロ化合物;キナクリドン類;ナノスケールのサイズを有する酸化鉄;1,2−ヒドロキシステアリン酸カリウム、安息香酸マグネシウムもしくはコハク酸マグネシウム、フタル酸マグネシウムなどに代表されるカルボン酸のアルカリもしくはアルカリ土類金属塩;ベンゼンスルホン酸ナトリウムもしくはナフタレンスルホン酸ナトリウムなどに代表される芳香族スルホン酸化合物;二もしくは三塩基カルボン酸のジもしくはトリエステル類;フタロシアニンブルーなどに代表されるフタロシアニン系顔料;有機二塩基酸である成分Aと周期律表第IIA族金属の酸化物、水酸化物もしくは塩である成分Bとからなる二成分系化合物;環状リン化合物とマグネシウム化合物からなる組成物などが挙げられるが、その中でも特に好ましいものを以下に示す。
[Description of β crystal nucleating agent]
Examples of the β crystal nucleating agent used in the present invention include those shown below, but are not particularly limited as long as they increase the formation and growth of β crystals of polypropylene resin, and two or more types are mixed. May be used.
Examples of the β crystal nucleating agent include amide compounds; tetraoxaspiro compounds; quinacridones; iron oxides having a nanoscale size; potassium 1,2-hydroxystearate, magnesium benzoate or magnesium succinate, magnesium phthalate, etc. Alkali or alkaline earth metal salts of carboxylic acids represented by: aromatic sulfonic acid compounds represented by sodium benzenesulfonate or sodium naphthalenesulfonate; di- or triesters of dibasic or tribasic carboxylic acids; phthalocyanine blue Phthalocyanine pigments typified by: a two-component compound comprising component A which is an organic dibasic acid and a component B which is an oxide, hydroxide or salt of a Group IIA metal of the periodic table; a cyclic phosphorus compound; Made of magnesium compound And the like formed product, but shows a particularly preferred among them below.
好ましいβ晶核剤としては、一般式(I);
RIb―NHCO―RIa―CONH―RIc (I)
一般式(II);
RIIb―CONH―RIIa―CONH―RIIc (II)
または、一般式(III);
RIIIb―CONH―RIIIa―NHCO―RIIIc (III)
(各式中、RIa、RIIaおよびRIIIaは同一または異なって炭素数1〜28の置換されていてもよい二価の炭化水素基を表し、
RIb、RIc、RIIb、RIIc、RIIIbおよびRIIIcは同一または異なって炭素数1〜18の置換されていてもよい炭化水素基を表す。)
で示されるアミド化合物が挙げられる。
Preferred β crystal nucleating agents include those represented by general formula (I);
R Ib —NHCO—R Ia —CONH—R Ic (I)
General formula (II);
R IIb -CONH-R IIa -CONH-R IIc (II)
Or general formula (III);
R IIIb -CONH-R IIIa -NHCO-R IIIc (III)
(In each formula, R Ia , R IIa and R IIIa are the same or different and each represents a divalent hydrocarbon group having 1 to 28 carbon atoms which may be substituted;
R Ib , R Ic , R IIb , R IIc , R IIIb and R IIIc are the same or different and each represents an optionally substituted hydrocarbon group having 1 to 18 carbon atoms. )
An amide compound represented by
なかでも、前記一般式(I)、(II)、(III)で示されるアミド化合物として、下記一般式(1)、(2)または(3)で表されるアミド化合物が特に好ましいβ晶核剤の一態様として挙げられる。
前記一般式(I)に含まれる一般式(1)で表されるアミド化合物は、
R2―NHCO―R1―CONH―R3 (1)
(式中、R1は炭素数1〜28の飽和または不飽和の脂肪族、脂環族または芳香族のジカルボン酸残基を表し、
R2およびR3は同一または異なって良く、炭素数3〜18のシクロアルキル基、シクロアルケニル基、
下記式(a);
下記式(b);
下記式(c);
または、下記式(d);
で示される基を表す。化学式1〜4において、R4およびR5は同一または異なって水素原子、炭素数1〜12の直鎖状または分岐鎖状のアルキル基、R6およびR7は同一または異なって炭素数1〜12の直鎖状または分岐状のアルキレン基を表す。)
で示される化合物である。
Among these, as the amide compound represented by the general formula (I), (II), or (III), an amide compound represented by the following general formula (1), (2), or (3) is particularly preferable. It is mentioned as one aspect | mode of an agent.
The amide compound represented by the general formula (1) included in the general formula (I) is:
R 2 —NHCO—R 1 —CONH—R 3 (1)
(In the formula, R 1 represents a saturated or unsaturated aliphatic, alicyclic or aromatic dicarboxylic acid residue having 1 to 28 carbon atoms;
R 2 and R 3 may be the same or different, and a cycloalkyl group having 3 to 18 carbon atoms, a cycloalkenyl group,
The following formula (a);
Following formula (b);
Following formula (c);
Or the following formula (d);
Represents a group represented by In Chemical Formulas 1-4, R 4 and R 5 are the same or different and are a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, and R 6 and R 7 are the same or different and have 1 to 1 carbon atoms. 12 linear or branched alkylene groups are represented. )
It is a compound shown by these.
前記一般式(II)に含まれる一般式(2)で表されるアミド化合物は、
R8―CONH―R9―CONH―R10 (2)
(式中、R8は炭素数1〜28の飽和または不飽和の脂肪族、脂環族または芳香族のアミノ酸残基を表し、
R9およびR10は同一または異なって良く、炭素数3〜12のシクロアルキル基、シクロアルケニル基、
下記式(e);
下記式(f);
下記式(g);
または、下記式(h);
で示される基を表す。化学式5〜8において、R11は水素原子、炭素数1〜12の直鎖状もしくは分岐鎖状のアルキル基、アルケニル基、シクロアルキル基またはフェニル基を表し、R12は炭素数1〜12の直鎖状もしくは分岐状のアルキル基、シクロアルキル基またはフェニル基を表す。R13およびR14は同一または異なって、炭素数1〜4の直鎖状または分岐鎖状のアルキレン基を表す。)
で示される化合物である。
なお、R8で示される「アミノ酸残基」におけるアミノ酸としては、天然のアミノ酸に限らず非天然のアミノ酸であってもよく、D−体またはL−体のいずれでもよく、α−、β−、γ−、ε−型のいずれのものでもよい。
The amide compound represented by the general formula (2) contained in the general formula (II) is:
R 8 -CONH-R 9 -CONH-R 10 (2)
(Wherein R 8 represents a saturated or unsaturated aliphatic, alicyclic or aromatic amino acid residue having 1 to 28 carbon atoms,
R 9 and R 10 may be the same or different, and a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group,
Following formula (e);
The following formula (f);
Following formula (g);
Or the following formula (h);
Represents a group represented by In Chemical Formulas 5 to 8, R 11 represents a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, an alkenyl group, a cycloalkyl group, or a phenyl group, and R 12 has 1 to 12 carbon atoms. A linear or branched alkyl group, a cycloalkyl group or a phenyl group is represented. R 13 and R 14 are the same or different and each represents a linear or branched alkylene group having 1 to 4 carbon atoms. )
It is a compound shown by these.
The amino acid in the “amino acid residue” represented by R 8 is not limited to a natural amino acid but may be a non-natural amino acid, either a D-form or an L-form, and α-, β- , Γ-, and ε-types may be used.
前記一般式(III)に含まれる一般式(3)で表されるアミド化合物は、
R15―CONH―R16―NHCO―R17 (3)
(式中、R15は炭素数1〜24の脂肪族ジアミン残基、脂環族ジアミン残基または芳香族ジアミノ酸残基を表し、
R16およびR17は同一または異なって良く、それぞれ炭素数3〜12のシクロアルケニル基、シクロアルキル基、
下記式(i);
下記式(j);
下記式(k);
または、下記式(l);
で示される基を表す。化学式9〜12において、R18は水素原子、炭素数1〜4の直鎖状もしくは分岐鎖状のアルキル基、アルケニル基を示し、R19は炭素数1〜12の直鎖状もしくは分岐状のアルキル基、シクロアルキル基またはフェニル基を表し、R20およびR21は同一または異なって、炭素数1〜3の直鎖状若しくは分岐鎖状のアルキレン基を表す。)
で示される化合物である。
The amide compound represented by the general formula (3) contained in the general formula (III) is
R 15 —CONH—R 16 —NHCO—R 17 (3)
(In the formula, R 15 represents an aliphatic diamine residue having 1 to 24 carbon atoms, an alicyclic diamine residue or an aromatic diamino acid residue;
R 16 and R 17 may be the same or different and each is a C 3-12 cycloalkenyl group, cycloalkyl group,
Following formula (i);
Following formula (j);
Following formula (k);
Or the following formula (l);
Represents a group represented by In Chemical Formulas 9 to 12, R 18 represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or an alkenyl group, and R 19 is a linear or branched group having 1 to 12 carbon atoms. Represents an alkyl group, a cycloalkyl group or a phenyl group, and R 20 and R 21 are the same or different and each represents a linear or branched alkylene group having 1 to 3 carbon atoms. )
It is a compound shown by these.
前記一般式(1)で表されるアミド系化合物は、ジカルボン酸とモノアミンとをアミド化することにより調製することができる。
前記ジカルボン酸としては、例えば、マロン酸、ジフェニルマロン酸、コハク酸、フェニルコハク酸、ジフェニルコハク酸、グルタル酸、3,3−ジメチルグルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、1,12−ドデカン二酸、1,14−テトラデカン二酸、1,18−オクタデカン二酸、1,2−シクロヘキサンジカルボン酸、1,4−シクロヘキサンジカルボン酸、1,4−シクロヘキサンジ酢酸、p−フェニレンジ酢酸、p−フェニレンジエタン酸、フタル酸、4−tert−ブチルフタル酸、イソフタル酸、5−tert−ブチルイソフタル酸、テレフタル酸、1,8−ナフタル酸、1,4−ナフタレンジカルボン酸、2,6−ナフタレンジカルボン酸、2,7−ナフタレンジカルボン酸、ジフェン酸、3,3’−ビフェニルジカルボン酸、4,4’−ビフェニルジカルボン酸、4,4’−ビナフチルジカルボン酸、ビス(3−カルボキシフェニル)メタン、ビス(4−カルボキシフェニル)メタン、2,2−ビス(3−カルボキシフェニル)プロパン、2,2−ビス(4−カルボキシフェニル)プロパン、3,3’−スルホニルジ安息香酸、4,4’−スルホニルジ安息香酸、3,3’−オキシジ安息香酸、4,4’−オキシジ安息香酸、3,3’−カルボニルジ安息香酸、4,4’−カルボニルジ安息香酸、3,3’−チオジ安息香酸、4,4’−チオジ安息香酸、4,4’−(p−フェニレンジオキシ)ジ安息香酸、4,4’−イソフタロイルジ安息香酸、4,4’−テレフタロイルジ安息香酸、ジチオサリチル酸等が挙げられる。
The amide compound represented by the general formula (1) can be prepared by amidating a dicarboxylic acid and a monoamine.
Examples of the dicarboxylic acid include malonic acid, diphenylmalonic acid, succinic acid, phenylsuccinic acid, diphenylsuccinic acid, glutaric acid, 3,3-dimethylglutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid Acid, 1,12-dodecanedioic acid, 1,14-tetradecanedioic acid, 1,18-octadecanedioic acid, 1,2-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,4-cyclohexanediacetic acid, p-phenylenediacetic acid, p-phenylenediethanoic acid, phthalic acid, 4-tert-butylphthalic acid, isophthalic acid, 5-tert-butylisophthalic acid, terephthalic acid, 1,8-naphthalic acid, 1,4-naphthalenedicarboxylic Acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, diph Acid, 3,3′-biphenyldicarboxylic acid, 4,4′-biphenyldicarboxylic acid, 4,4′-binaphthyldicarboxylic acid, bis (3-carboxyphenyl) methane, bis (4-carboxyphenyl) methane, 2, 2-bis (3-carboxyphenyl) propane, 2,2-bis (4-carboxyphenyl) propane, 3,3′-sulfonyldibenzoic acid, 4,4′-sulfonyldibenzoic acid, 3,3′-oxydi Benzoic acid, 4,4′-oxydibenzoic acid, 3,3′-carbonyldibenzoic acid, 4,4′-carbonyldibenzoic acid, 3,3′-thiodibenzoic acid, 4,4′-thiodibenzoic acid, 4,4 '-(p-phenylenedioxy) dibenzoic acid, 4,4'-isophthaloyl dibenzoic acid, 4,4'-terephthaloyl dibenzoic acid, dithiosalicylic acid and the like.
前記モノアミンとしては、例えば、シクロプロピルアミン、シクロブチルアミン、シクロペンチルアミン、シクロヘキシルアミン、2−メチルシクロヘキシルアミン、3−メチルシクロヘキシルアミン、4−メチルシクロヘキシルアミン、2−エチルシクロヘキシルアミン、4−エチルシクロヘキシルアミン、2−プロピルシクロヘキシルアミン、2−イソプロピルシクロヘキシルアミン、4−プロピルシクロヘキシルアミン、4−イソプロピルシクロヘキシルアミン、2−tert−ブチルシクロヘキシルアミン、4−n−ブチルシクロヘキシルアミン、4−イソブチルシクロヘキシルアミン、4−sec−ブチルシクロヘキシルアミン、4−tert−ブチルシクロヘキシルアミン、4−n−ペンチルシクロヘキシルアミン、4−イソペンチルシクロヘキシルアミン、4−sec−ペンチルシクロヘキシルアミン、4−tert−ペンチルシクロヘキシルアミン、4−ヘキシルシクロヘキシルアミン、4−ヘプチルシクロヘキシルアミン、4−オクチルシクロヘキシルアミン、4−ノニルシクロヘキシルアミン、4−デシルシクロヘキシルアミン、4−ウンデシルシクロヘキシルアミン、4−ドデシルシクロヘキシルアミン、4−シクロヘキシルシクロヘキシルアミン、4−フェニルシクロヘキシルアミン、シクロヘプチルアミン、シクロドデシルアミン、シクロヘキシルメチルアミン、α−シクロヘキシルエチルアミン、β−シクロヘキシルエチルアミン、α−シクロヘキシルプロピルアミン、β−シクロヘキシルプロピルアミン、γ−シクロヘキシルプロピルアミン、アニリン、o−トルイジン、m−トルイジン、p−トルイジン、o−エチルアニリン、p−エチルアニリン、o−プロピルアニリン、m−プロピルアニリン、p−プロピルアニリン、o−クミジン、m−クミジン、p−クミジン、o−tert−ブチルアニリン、p−n−ブチルアニリン、p−イソブチルアニリン、p−sec−ブチルアニリン、p−tert−ブチルアニリン、p−n−アミルアニリン、p−イソアミルアニリン、p−sec−アミルアニリン、p−tert−アミルアニリン、p−ヘキシルアニリン、p−ヘプチルアニリン、p−オクチルアニリン、p−ノニルアニリン、p−デシルアニリン、p−ウンデシルアニリン、p−ドデシルアニリン、p−シクロヘキシルアニリン、o−アミノジフェニル、m−アミノジフェニル、p−アミノジフェニル、p−アミノスチレン、ベンジルアミン、α−フェニルエチルアミン、β−フェニルエチルアミン、α−フェニルプロピルアミン、β−フェニルプロピルアミン、γ−フェニルプロピルアミン等が挙げられる。 Examples of the monoamine include cyclopropylamine, cyclobutylamine, cyclopentylamine, cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine, 4-methylcyclohexylamine, 2-ethylcyclohexylamine, 4-ethylcyclohexylamine, 2-propylcyclohexylamine, 2-isopropylcyclohexylamine, 4-propylcyclohexylamine, 4-isopropylcyclohexylamine, 2-tert-butylcyclohexylamine, 4-n-butylcyclohexylamine, 4-isobutylcyclohexylamine, 4-sec- Butylcyclohexylamine, 4-tert-butylcyclohexylamine, 4-n-pentylcyclohexylamine, 4-isopepe Tilcyclohexylamine, 4-sec-pentylcyclohexylamine, 4-tert-pentylcyclohexylamine, 4-hexylcyclohexylamine, 4-heptylcyclohexylamine, 4-octylcyclohexylamine, 4-nonylcyclohexylamine, 4-decylcyclohexylamine, 4-undecylcyclohexylamine, 4-dodecylcyclohexylamine, 4-cyclohexylcyclohexylamine, 4-phenylcyclohexylamine, cycloheptylamine, cyclododecylamine, cyclohexylmethylamine, α-cyclohexylethylamine, β-cyclohexylethylamine, α-cyclohexyl Propylamine, β-cyclohexylpropylamine, γ-cyclohexylpropylamine, aniline o-toluidine, m-toluidine, p-toluidine, o-ethylaniline, p-ethylaniline, o-propylaniline, m-propylaniline, p-propylaniline, o-cumidine, m-cumidine, p-cumidine, o -Tert-butylaniline, pn-butylaniline, p-isobutylaniline, p-sec-butylaniline, p-tert-butylaniline, pn-amylaniline, p-isoamylaniline, p-sec-amylaniline P-tert-amylaniline, p-hexylaniline, p-heptylaniline, p-octylaniline, p-nonylaniline, p-decylaniline, p-undecylaniline, p-dodecylaniline, p-cyclohexylaniline, o -Aminodiphenyl, m-aminodiphenyl, p Diaminodiphenyl, p- aminostyrene, benzylamine, alpha-phenylethylamine, beta-phenylethylamine, alpha-phenylpropylamine, beta-phenylpropylamine, .gamma.-phenylpropyl amine.
前記一般式(2)で示されるアミド系化合物は、アミノ酸とモノカルボン酸およびモノアミンとをアミド化することにより調製することができる。
前記アミノ酸としては、例えば、アミノ酢酸、α−アミノプロピオン酸、β−アミノプロピオン酸、α−アミノアクリル酸、α−アミノブタン酸、β−アミノブタン酸、γ−アミノブタン酸、α−アミノ−α−メチルブタン酸、γ−アミノ−α−メチレンブタン酸、α−アミノイソブタン酸、β−アミノイソブタン酸、α−アミノ−n−ペンタン酸、δ−アミノ−n−ペンタン酸、β−アミノクロトン酸、α−アミノ−β−メチルペンタン酸、α−アミノイソペンタン酸、2−アミノ−4−ペンテノイック酸、α−アミノ−n−カプロン酸、6−アミノカプロン酸、α−アミノイソカプロン酸、7−アミノヘプタン酸、α−アミノ−n−カプリル酸、8−アミノカプリル酸、9−アミノノナン酸、11−アミノウンデカン酸、12−アミノドデカン酸、1−アミノシクロヘキサンカルボン酸、2−アミノシクロヘキサンカルボン酸、3−アミノシクロヘキサンカルボン酸、4−アミノシクロヘキサンカルボン酸、p−アミノメチルシクロヘキサンカルボン酸、2−アミノ−2−ノルボルナンカルボン酸、α−アミノフェニル酢酸、α−アミノ−β−フェニルプロピオン酸、2−アミノ−2−フェニルプロピオン酸、3−アミノ−3−フェニルプロピオン酸、α−アミノ桂皮酸、2−アミノ−4−フェニルブタン酸、4−アミノ−3−フェニルブタン酸、アントラニル酸、m−アミノ安息香酸、p−アミノ安息香酸、2−アミノ−4−メチル安息香酸、2−アミノ−6−メチル安息香酸、3−アミノ−4−メチル安息香酸、2−アミノ−3−メチル安息香酸、2−アミノ−5−メチル安息香酸、4−アミノ−2−メチル安息香酸、4−アミノ−3−メチル安息香酸、2−アミノ−3−メトキシ安息香酸、3−アミノ−4−メトキシ安息香酸、4−アミノ−2−メトキシ安息香酸、4−アミノ−3−メトキシ安息香酸、2−アミノ−4,5−ジメトキシ安息香酸、o−アミノフェニル酢酸、m−アミノフェニル酢酸、p−アミノフェニル酢酸、4−(4−アミノフェニル)ブタン酸、4−アミノメチル安息香酸、4−アミノメチルフェニル酢酸、o−アミノ桂皮酸、m−アミノ桂皮酸、p−アミノ桂皮酸、p−アミノ馬尿酸、2−アミノ−1−ナフトエ酸、3−アミノ−1−ナフトエ酸、4−アミノ−1−ナフトエ酸、5−アミノ−1−ナフトエ酸、6−アミノ−1−ナフトエ酸、7−アミノ−1−ナフトエ酸、8−アミノ−1−ナフトエ酸、1−アミノ−2−ナフトエ酸、3−アミノ−2−ナフトエ酸、4−アミノ−2−ナフトエ酸、5−アミノ−2−ナフトエ酸、6−アミノ−2−ナフトエ酸、7−アミノ−2−ナフトエ酸、8−アミノ−2−ナフトエ酸等が挙げられる。
The amide compound represented by the general formula (2) can be prepared by amidating an amino acid with a monocarboxylic acid and a monoamine.
Examples of the amino acid include aminoacetic acid, α-aminopropionic acid, β-aminopropionic acid, α-aminoacrylic acid, α-aminobutanoic acid, β-aminobutanoic acid, γ-aminobutanoic acid, and α-amino-α-methylbutane. Acid, γ-amino-α-methylenebutanoic acid, α-aminoisobutanoic acid, β-aminoisobutanoic acid, α-amino-n-pentanoic acid, δ-amino-n-pentanoic acid, β-aminocrotonic acid, α- Amino-β-methylpentanoic acid, α-aminoisopentanoic acid, 2-amino-4-pentenoic acid, α-amino-n-caproic acid, 6-aminocaproic acid, α-aminoisocaproic acid, 7-aminoheptanoic acid, α-amino-n-caprylic acid, 8-aminocaprylic acid, 9-aminononanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, 1- Minocyclohexanecarboxylic acid, 2-aminocyclohexanecarboxylic acid, 3-aminocyclohexanecarboxylic acid, 4-aminocyclohexanecarboxylic acid, p-aminomethylcyclohexanecarboxylic acid, 2-amino-2-norbornanecarboxylic acid, α-aminophenylacetic acid, α-amino-β-phenylpropionic acid, 2-amino-2-phenylpropionic acid, 3-amino-3-phenylpropionic acid, α-aminocinnamic acid, 2-amino-4-phenylbutanoic acid, 4-amino- 3-phenylbutanoic acid, anthranilic acid, m-aminobenzoic acid, p-aminobenzoic acid, 2-amino-4-methylbenzoic acid, 2-amino-6-methylbenzoic acid, 3-amino-4-methylbenzoic acid 2-amino-3-methylbenzoic acid, 2-amino-5-methylbenzoic acid, 4-amino No-2-methylbenzoic acid, 4-amino-3-methylbenzoic acid, 2-amino-3-methoxybenzoic acid, 3-amino-4-methoxybenzoic acid, 4-amino-2-methoxybenzoic acid, 4- Amino-3-methoxybenzoic acid, 2-amino-4,5-dimethoxybenzoic acid, o-aminophenylacetic acid, m-aminophenylacetic acid, p-aminophenylacetic acid, 4- (4-aminophenyl) butanoic acid, 4 -Aminomethylbenzoic acid, 4-aminomethylphenylacetic acid, o-aminocinnamic acid, m-aminocinnamic acid, p-aminocinnamic acid, p-aminohippuric acid, 2-amino-1-naphthoic acid, 3-amino- 1-naphthoic acid, 4-amino-1-naphthoic acid, 5-amino-1-naphthoic acid, 6-amino-1-naphthoic acid, 7-amino-1-naphthoic acid, 8-amino-1-naphthoic acid, 1 Amino-2-naphthoic acid, 3-amino-2-naphthoic acid, 4-amino-2-naphthoic acid, 5-amino-2-naphthoic acid, 6-amino-2-naphthoic acid, 7-amino-2-naphthoic acid Acid, 8-amino-2-naphthoic acid and the like.
前記モノカルボン酸としては、例えば、シクロプロパンカルボン酸、シクロブタンカルボン酸、シクロペンタンカルボン酸、1−メチルシクロペンタンカルボン酸、2−メチルシクロペンタンカルボン酸、3−メチルシクロペンタンカルボン酸、1−フェニルシクロペンタンカルボン酸、シクロペンテンカルボン酸、シクロヘキサンカルボン酸、1−メチルシクロヘキサンカルボン酸、2−メチルシクロヘキサンカルボン酸、3−メチルシクロヘキサンカルボン酸、4−メチルシクロヘキサンカルボン酸、4−プロピルシクロヘキサンカルボン酸、4−ブチルシクロヘキサンカルボン酸、4−ペンチルシクロヘキサンカルボン酸、4−ヘキシルシクロヘキサンカルボン酸、4−フェニルシクロヘキサンカルボン酸、1−フェニルシクロヘキサンカルボン酸、シクロヘキセンカルボン酸、4−ブチルシクロヘキセンカルボン酸、シクロヘプタンカルボン酸、1−シクロヘプテンカルボン酸、1−メチルシクロヘプタンカルボン酸、4−メチルシクロヘプタンカルボン酸、シクロヘキシル酢酸、安息香酸、o−メチル−安息香酸、m−メチル−安息香酸、p−メチル−安息香酸、p−エチル−安息香酸、p−プロピル−安息香酸、p−ブチル安息香酸、p−tert−ブチル安息香酸、p−ペンチル安息香酸、p−ヘキシル安息香酸、o−フェニル安息香酸、p−フェニル安息香酸、p−シクロヘキシル安息香酸、フェニル酢酸、フェニルプロピオン酸、フェニルブタン酸等が挙げられる。 Examples of the monocarboxylic acid include cyclopropanecarboxylic acid, cyclobutanecarboxylic acid, cyclopentanecarboxylic acid, 1-methylcyclopentanecarboxylic acid, 2-methylcyclopentanecarboxylic acid, 3-methylcyclopentanecarboxylic acid, and 1-phenyl. Cyclopentanecarboxylic acid, cyclopentenecarboxylic acid, cyclohexanecarboxylic acid, 1-methylcyclohexanecarboxylic acid, 2-methylcyclohexanecarboxylic acid, 3-methylcyclohexanecarboxylic acid, 4-methylcyclohexanecarboxylic acid, 4-propylcyclohexanecarboxylic acid, 4- Butylcyclohexanecarboxylic acid, 4-pentylcyclohexanecarboxylic acid, 4-hexylcyclohexanecarboxylic acid, 4-phenylcyclohexanecarboxylic acid, 1-phenylcyclohexa Carboxylic acid, cyclohexenecarboxylic acid, 4-butylcyclohexenecarboxylic acid, cycloheptanecarboxylic acid, 1-cycloheptenecarboxylic acid, 1-methylcycloheptanecarboxylic acid, 4-methylcycloheptanecarboxylic acid, cyclohexylacetic acid, benzoic acid, o -Methyl-benzoic acid, m-methyl-benzoic acid, p-methyl-benzoic acid, p-ethyl-benzoic acid, p-propyl-benzoic acid, p-butylbenzoic acid, p-tert-butylbenzoic acid, p- Examples include pentylbenzoic acid, p-hexylbenzoic acid, o-phenylbenzoic acid, p-phenylbenzoic acid, p-cyclohexylbenzoic acid, phenylacetic acid, phenylpropionic acid, and phenylbutanoic acid.
前記モノアミンとしては、一般式(1)で表されるアミド系化合物の原料であるモノアミンと同様のものが挙げられる。 As said monoamine, the thing similar to the monoamine which is a raw material of the amide type compound represented by General formula (1) is mentioned.
前記一般式(3)で示されるアミド系化合物は、ジアミンとモノカルボン酸とをアミド化することにより調製することができる。
前記ジアミンとしては、例えば、1,2−ジアミノプロパン、1,3−ジアミノプロパン、1,4−ジアミノブタン、1,3−ジアミノペンタン、1,5−ジアミノペンタン、1,6−ジアミノヘキサン、1,2−ジアミノシクロヘキサン、1,4−ジアミノシクロヘキサン、4,4’−ジアミノジシクロヘキシルメタン、4,4’−ジアミノ−3,3’−ジメチルジシクロヘキシルメタン、1,3−ビス(アミノメチル)シクロヘキサン、1,4−ビス(アミノメチル)シクロヘキサン、イソホロンジアミン、メンセンジアミン、o−フェニレンジアミン、m−フェニレンジアミン、p−フェニレンジアミン、1,5−ジアミノナフタレン、4,4’−ジアミノジフェニルメタン、4,4’−ジアミノジフェニルエーテル、4,4’−ジアミノジフェニルスルフォン等が挙げられる。
前記モノカルボン酸としては、一般式(2)で表されるアミド系化合物の原料であるモノカルボン酸と同様のものが挙げられる。
The amide compound represented by the general formula (3) can be prepared by amidating a diamine and a monocarboxylic acid.
Examples of the diamine include 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,3-diaminopentane, 1,5-diaminopentane, 1,6-diaminohexane, , 2-diaminocyclohexane, 1,4-diaminocyclohexane, 4,4′-diaminodicyclohexylmethane, 4,4′-diamino-3,3′-dimethyldicyclohexylmethane, 1,3-bis (aminomethyl) cyclohexane, 1 , 4-bis (aminomethyl) cyclohexane, isophoronediamine, mensendiamine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 1,5-diaminonaphthalene, 4,4'-diaminodiphenylmethane, 4,4 '-Diaminodiphenyl ether, 4,4'-diaminodiph Nirusurufon, and the like.
As said monocarboxylic acid, the thing similar to the monocarboxylic acid which is a raw material of the amide type compound represented by General formula (2) is mentioned.
特に好ましいβ晶核剤の他の態様としては、下記一般式(4);
(式中のR41およびR42は同一でも異なっても良く、水素原子または炭素数1〜18の置換されていてもよい炭化水素基、好ましくは水素原子、アルキル基、シクロアルキル基またはアリール基を表すか、或いはR41、R42および窒素原子が共同して含窒素複素環基を表し、好ましくはR41およびR42はそれぞれの端で相互に結合して共同して炭素数2〜6のアルキレン基を表す。)
で示されるテトラオキサスピロ化合物が挙げられる。
As another aspect of the particularly preferred β crystal nucleating agent, the following general formula (4):
(In the formula, R 41 and R 42 may be the same or different, and may be a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 18 carbon atoms, preferably a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group. R 41 , R 42 and a nitrogen atom jointly represent a nitrogen-containing heterocyclic group, and preferably R 41 and R 42 are bonded to each other at each end to jointly have 2 to 6 carbon atoms. Represents an alkylene group of
The tetraoxaspiro compound shown by these is mentioned.
テトラオキサスピロ化合物を具体的に例示すると、3,9−ビス[4−(N−シクロヘキシルカルバモイル)フェニル]−2,4,8,10−テトラオキサスピロ[5.5]ウンデカン、3,9−ビス{4−[N−(4−t−ブチルシクロヘキシル)カルバモイル]フェニル}−2,4,8,10−テトラオキサスピロ[5.5]ウンデカン、3,9−ビス{4−[N−(2,4−ジ−t−ブチルシクロヘキシル)カルバモイル]フェニル}−2,4,8,10−テトラオキサスピロ[5.5]ウンデカン、3,9−ビス{4−[N−(1−アダマンチル)カルバモイル]フェニル}−2,4,8,10−テトラオキサスピロ[5.5]ウンデカン、3,9−ビス[4−(N−フェニルカルバモイル)フェニル]−2,4,8,10−テトラオキサスピロ[5.5]ウンデカン、3,9−ビス{4−[N−(4−t−ブチルフェニル)カルバモイル]フェニル}−2,4,8,10−テトラオキサスピロ[5.5]ウンデカン、3,9−ビス{4−[N−(2,4−ジ−t−ブチルフェニル)カルバモイル)フェニル]−2,4,8,10−テトラオキサスピロ[5.5]ウンデカン、3,9−ビス{4−[N−(1−ナフチル)カルバモイル]フェニル}−2,4,8,10−テトラオキサスピロ[5.5]ウンデカン、3,9−ビス[4−(N−n−ブチルカルバモイル)フェニル]−2,4,8,10−テトラオキサスピロ[5.5]ウンデカン、3,9−ビス[4−(N−n−ヘキシルカルバモイル)フェニル]−2,4,8,10−テトラオキサスピロ[5.5]ウンデカン、3,9−ビス[4−(N−n−ドデシルカルバモイル)フェニル]−2,4,8,10−テトラオキサスピロ[5.5]ウンデカン、3,9−ビス[4−(N−n−オクタデシルカルバモイル)フェニル]−2,4,8,10−テトラオキサスピロ[5.5]ウンデカン、3,9−ビス(4−カルバモイルフェニル)−2,4,8,10−テトラオキサスピロ[5.5]ウンデカン、3,9−ビス[4−(N,N−ジシクロヘキシルカルバモイル)フェニル]−2,4,8,10−テトラオキサスピロ[5.5]ウンデカン、3,9−ビス[4−(N,N−ジフェニルカルバモイル)フェニル]−2,4,8,10−テトラオキサスピロ[5.5]ウンデカン、3,9−ビス[4−(N−n−ブチル−N−シクロヘキシルカルバモイル)フェニル]−2,4,8,10−テトラオキサスピロ[5.5]ウンデカン、3,9−ビス[4−(N−n−ブチル−N−フェニルカルバモイル)フェニル]−2,4,8,10−テトラオキサスピロ[5.5]ウンデカン、3,9−ビス[4−(1−ピロリジニルカルボニル)フェニル]−2,4,8,10−テトラオキサスピロ[5.5]ウンデカン、3,9−ビス[4−(1−ピペリジニルカルボニル)フェニル]−2,4,8,10−テトラオキサスピロ[5.5]ウンデカン等が好適に使用することができる。 Specific examples of the tetraoxaspiro compound include 3,9-bis [4- (N-cyclohexylcarbamoyl) phenyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9- Bis {4- [N- (4-t-butylcyclohexyl) carbamoyl] phenyl} -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis {4- [N- ( 2,4-di-t-butylcyclohexyl) carbamoyl] phenyl} -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis {4- [N- (1-adamantyl) Carbamoyl] phenyl} -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis [4- (N-phenylcarbamoyl) phenyl] -2,4,8,10-tetra Oxaspiro [5.5] undecane, 3,9-bis {4- [N- (4-t-butylphenyl) carbamoyl] phenyl} -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis {4- [N- (2,4-di-t-butylphenyl) carbamoyl) phenyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9- Bis {4- [N- (1-naphthyl) carbamoyl] phenyl} -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis [4- (Nn-butylcarbamoyl) ) Phenyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis [4- (Nn-hexylcarbamoyl) phenyl] -2,4,8,10-tetra Oxaspiro [5.5] Unde 3,9-bis [4- (Nn-dodecylcarbamoyl) phenyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis [4- (N- n-octadecylcarbamoyl) phenyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis (4-carbamoylphenyl) -2,4,8,10-tetraoxaspiro [ 5.5] undecane, 3,9-bis [4- (N, N-dicyclohexylcarbamoyl) phenyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis [4 -(N, N-diphenylcarbamoyl) phenyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis [4- (Nn-butyl-N-cyclohexylcarbamoyl) Phenyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis [4- (Nn-butyl-N-phenylcarbamoyl) phenyl] -2,4,8, 10-tetraoxaspiro [5.5] undecane, 3,9-bis [4- (1-pyrrolidinylcarbonyl) phenyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 3 , 9-bis [4- (1-piperidinylcarbonyl) phenyl] -2,4,8,10-tetraoxaspiro [5.5] undecane and the like can be suitably used.
特に好ましいβ晶核剤の他の態様としては、例えばキナクリドン、ジメチルキナクリドンおよびジメトキシキナクリドンなどのキナクリドン型化合物、;例えばキナクリドンキノン、5,12−ジヒドロ(2,3b)アクリジン−7−1,4−ジオンとキノ(2,3b)アクリジン−6,7,13−1,4−(5H,12H)−テトロンの混合結晶、およびジメトキシキナクリドンキノンなどのキナクリドンキノン型化合物、:例えばジヒドロキナクリドン、ジメトキシヒドロキナクリドンおよびジベンゾジヒドロキナクリドンなどのジヒドロキナクリドン型化合物が挙げられる。 Other particularly preferred β crystal nucleating agents include quinacridone type compounds such as quinacridone, dimethylquinacridone and dimethoxyquinacridone; for example, quinacridonequinone, 5,12-dihydro (2,3b) acridine-7-1,4- Mixed crystals of dione and quino (2,3b) acridine-6,7,13-1,4- (5H, 12H) -tetron, and quinacridonequinone type compounds such as dimethoxyquinacridonequinone: for example, dihydroquinacridone, dimethoxyhydroquinacridone And dihydroquinacridone type compounds such as dibenzodihydroquinacridone.
特に好ましいβ晶核剤の他の態様としては、例えばピメリン酸のカルシウム塩およびスベリン酸のカルシウム塩などの周期律表のIIa族からの金属のジカルボン酸塩、ならびにジカルボン酸と周期律表のIIa族からの金属塩の混合物が挙げられる。
なかでも、周期律表のIIa族からの金属と式(5);
(式中、nは1〜12の自然数であり、
R51は水素原子、カルボキシル基、炭素数1〜12の置換されていてもよい炭化水素基、好ましくは水素原子、カルボキシル基、炭素数1〜12の直鎖状もしくは分岐鎖状のアルキル基、炭素数5〜8のシクロアルキル基または炭素数6〜12のアリール基を表し、
Xは炭素数1〜12の置換されていてもよい二価の炭化水素基、好ましくは置換されていてもよい炭素数6〜12の二価の芳香族炭化水素基、より好ましくは炭素数1〜12のアルキル基、炭素数5〜8のシクロアルキル基または炭素数6〜12のアリール基で置換されていてもよい炭素数6〜12の二価の芳香族炭化水素基を表す。)
で示されるイミド酸との塩が特に好ましい。
当該塩としては、例えば、フタロイルグリシン、ヘキサヒドロフタロイルグリシン、N−ナフタロイルアラニンまたはN−4−メチルフタロイルグリシンのカルシウム塩が例示できる。
Other particularly preferred β crystal nucleating agents include, for example, dicarboxylic acid salts of metals from group IIa of the periodic table, such as calcium salts of pimelic acid and calcium salt of suberic acid, and dicarboxylic acids and IIa of the periodic table. Mention may be made of mixtures of metal salts from the group.
Among them, metal from group IIa of the periodic table and formula (5);
(In the formula, n is a natural number of 1 to 12,
R 51 represents a hydrogen atom, a carboxyl group, an optionally substituted hydrocarbon group having 1 to 12 carbon atoms, preferably a hydrogen atom, a carboxyl group, a linear or branched alkyl group having 1 to 12 carbon atoms, A cycloalkyl group having 5 to 8 carbon atoms or an aryl group having 6 to 12 carbon atoms,
X is an optionally substituted divalent hydrocarbon group having 1 to 12 carbon atoms, preferably an optionally substituted divalent aromatic hydrocarbon group having 6 to 12 carbon atoms, more preferably 1 carbon atom. Represents a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms which may be substituted with an alkyl group having -12 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms or an aryl group having 6 to 12 carbon atoms. )
A salt with imide acid represented by is particularly preferred.
Examples of such salts include calcium salts of phthaloyl glycine, hexahydrophthaloyl glycine, N-naphthaloylalanine or N-4-methylphthaloyl glycine.
特に好ましいβ晶核剤の他の態様としては、一般式(6)で示される環状リン化合物と、脂肪酸マグネシウム、脂肪族リン酸マグネシウム、酸化マグネシウム、水酸化マグネシウム、炭酸マグネシウム、一般式(7)で示される環状リン化合物のマグネシウム塩および一般式(8)で示されるマグネシウムフォスフィネート系化合物からなる群から選ばれる少なくとも1種のマグネシウム化合物とからなる組成物、または、一般式(9)で示される環状リン化合物と、前記一般式(8)で示されるマグネシウムフォスフィネート系化合物、硫酸マグネシウムおよびタルクからなる群から選ばれる少なくとも1種のマグネシウム化合物とからなる組成物が挙げられる。 As other aspects of the β crystal nucleating agent that is particularly preferred, the cyclic phosphorus compound represented by the general formula (6), fatty acid magnesium, aliphatic magnesium phosphate, magnesium oxide, magnesium hydroxide, magnesium carbonate, general formula (7) A composition comprising at least one magnesium compound selected from the group consisting of a magnesium salt of a cyclic phosphorus compound represented by formula (8) and a magnesium phosphinate compound represented by formula (8), or a formula (9) And a composition comprising the cyclic phosphorus compound shown and at least one magnesium compound selected from the group consisting of a magnesium phosphinate compound represented by the general formula (8), magnesium sulfate and talc.
一般式(6)で示される環状リン化合物は、
(式中、Ar1およびAr2は同一または異なって、置換されていてもよい炭素数6〜12の二価の芳香族炭化水素基、好ましくは置換されていてもよい炭素数1〜18の炭化水素基で置換されていてもよいアリーレン基、より好ましくはアリーレン基、アルキルアリーレン基、シクロアルキルアリーレン基、アリールアリーレン基またはアラルキルアリーレン基を表す。)
で示される化合物である。
The cyclic phosphorus compound represented by the general formula (6) is
(In the formula, Ar 1 and Ar 2 are the same or different and may be substituted divalent aromatic hydrocarbon groups having 6 to 12 carbon atoms, preferably optionally substituted 1 to 18 carbon atoms. An arylene group which may be substituted with a hydrocarbon group, more preferably an arylene group, an alkylarylene group, a cycloalkylarylene group, an arylarylene group or an aralkylarylene group.
It is a compound shown by these.
一般式(7)で示される環状リン化合物のマグネシウム塩は、
(式中、Ar3およびAr4は同一または異なって、置換されていてもよい炭素数6〜12の二価の芳香族炭化水素基、好ましくは置換されていてもよい炭素数1〜18の炭化水素基で置換されていてもよいアリーレン基、より好ましくはアリーレン基、アルキルアリーレン基、シクロアルキルアリーレン基、アリールアリーレン基またはアラルキルアリーレン基を表す。)
The magnesium salt of the cyclic phosphorus compound represented by the general formula (7) is
(In the formula, Ar 3 and Ar 4 are the same or different and may be substituted divalent aromatic hydrocarbon groups having 6 to 12 carbon atoms, preferably optionally substituted 1 to 18 carbon atoms. An arylene group which may be substituted with a hydrocarbon group, more preferably an arylene group, an alkylarylene group, a cycloalkylarylene group, an arylarylene group or an aralkylarylene group.
一般式(8)で示されるマグネシウムフォスフィネート系化合物は、
(式中、Ar5およびAr6は同一または異なって、置換されていてもよい炭素数6〜12の二価の芳香族炭化水素基、好ましくは置換されていてもよい炭素数1〜18の炭化水素基で置換されていてもよいアリーレン基、より好ましくはアリーレン基、アルキルアリーレン基、シクロアルキルアリーレン基、アリールアリーレン基またはアラルキルアリーレン基を表す。)
で示される化合物である。
The magnesium phosphinate compound represented by the general formula (8) is:
(In the formula, Ar 5 and Ar 6 are the same or different and may be substituted divalent aromatic hydrocarbon groups having 6 to 12 carbon atoms, preferably optionally substituted 1 to 18 carbon atoms. An arylene group which may be substituted with a hydrocarbon group, more preferably an arylene group, an alkylarylene group, a cycloalkylarylene group, an arylarylene group or an aralkylarylene group.
It is a compound shown by these.
一般式(9)で示される環状リン化合物は、
(式中、Ar7およびAr8は同一または異なって、置換されていてもよい炭素数6〜12の二価の芳香族炭化水素基、好ましくは置換されていてもよい炭素数1〜18の炭化水素基で置換されていてもよいアリーレン基、より好ましくはアリーレン基、アルキルアリーレン基、シクロアルキルアリーレン基、アリールアリーレン基またはアラルキルアリーレン基を表す。)
で示される化合物である。
The cyclic phosphorus compound represented by the general formula (9) is
(In the formula, Ar 7 and Ar 8 are the same or different and may be substituted divalent aromatic hydrocarbon groups having 6 to 12 carbon atoms, preferably optionally substituted 1 to 18 carbon atoms. An arylene group which may be substituted with a hydrocarbon group, more preferably an arylene group, an alkylarylene group, a cycloalkylarylene group, an arylarylene group or an aralkylarylene group.
It is a compound shown by these.
前記一般式(6)で示される環状リン化合物としては、10−ヒドロキシ−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、1−メチル−10−ヒドロキシ−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、2−メチル−10−ヒドロキシ−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、6−メチル−10−ヒドロキシ−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、7−メチル−10−ヒドロキシ−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、8−メチル−10−ヒドロキシ−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、6,8−ジメチル−10−ヒドロキシ−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、2,6,8−トリメチル−10−ヒドロキシ−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、2−エチル−10−ヒドロキシ−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、6−エチル−10−ヒドロキシ−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、8−エチル−10−ヒドロキシ−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、6,8−ジエチル−10−ヒドロキシ−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、2,6,8−トリエチル−10−ヒドロキシ−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、2−i−プロピル−10−ヒドロキシ−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、6−i−プロピル−10−ヒドロキシ−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、8−i−プロピル−10−ヒドロキシ−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、6,8−ジ−i−プロピル−10−ヒドロキシ−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、2,6,8−トリ−i−プロピル−10−ヒドロキシ−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、2−s−ブチル−10−ヒドロキシ−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、6−s−ブチル−10−ヒドロキシ−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、8−s−ブチル−10−ヒドロキシ−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、1,8−ジ−s−ブチル−10−ヒドロキシ−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、2,6,8−トリ−s−ブチル−10−ヒドロキシ−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、2−t−ブチル−10−ヒドロキシ−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、6−t−ブチル−10−ヒドロキシ−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、8−t−ブチル−10−ヒドロキシ−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、1,6−ジ−t−ブチル−10−ヒドロキシ−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、2,6−ジ−t−ブチル−10−ヒドロキシ−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、2,7−ジ−t−ブチル−10−ヒドロキシ−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、2,8−ジ−t−ブチル−10−ヒドロキシ−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、6,8−ジ−t−ブチル−10−ヒドロキシ−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、2,6,8−トリ−t−ブチル−10−ヒドロキシ−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、2−t−アミル−10−ヒドロキシ−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、6−t−アミル−10−ヒドロキシ−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、8−t−アミル−10−ヒドロキシ−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、6,8−ジ−t−アミル−10−ヒドロキシ−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、2,6,8−トリ−t−アミル−10−ヒドロキシ−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、2−t−オクチル−10−ヒドロキシ−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、6−t−オクチル−10−ヒドロキシ−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、8−t−オクチル−10−ヒドロキシ−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、6,8−ジ−t−オクチル−10−ヒドロキシ−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、2,6,8−トリ−t−オクチル−10−ヒドロキシ−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、2−シクロヘキシル−10−ヒドロキシ−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、6−シクロヘキシル−10−ヒドロキシ−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、8−シクロヘキシル−10−ヒドロキシ−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、6,8−ジ−シクロヘキシル−10−ヒドロキシ−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、2,6,8−トリ−シクロヘキシル−10−ヒドロキシ−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、6−フェニル−10−ヒドロキシ−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、2−ベンジル−10−ヒドロキシ−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、6−ベンジル−10−ヒドロキシ−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、8−ベンジル−10−ヒドロキシ−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、6,8−ジ−ベンジル−10−ヒドロキシ−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、2,6,8−トリ−ベンジル−10−ヒドロキシ−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、2−(α−メチルベンジル)−10−ヒドロキシ−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、6−(α−メチルベンジル)−10−ヒドロキシ−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、8−(α−メチルベンジル)−10−ヒドロキシ−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、6,8−ジ(α−メチルベンジル)−10−ヒドロキシ−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、2,6,8−トリ(α−メチルベンジル)−10−ヒドロキシ−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、2,6−ジ(α,α−ジメチルベンジル)−10−ヒドロキシ−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、6−t−ブチル−8−メチル−10−ヒドロキシ−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、6−ベンジル−8−メチル−10−ヒドロキシ−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、6−シクロヘキシル−8−t−ブチル−10−ヒドロキシ−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、6−ベンジル−8−t−ブチル−10−ヒドロキシ−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、6−(α−メチルベンジル)−8−t−ブチル−10−ヒドロキシ−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、6−t−ブチル−8−シクロヘキシル−10−ヒドロキシ−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、6−ベンジル−8−シクロヘキシル−10−ヒドロキシ−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、6−t−ブチル−8−ベンジル−10−ヒドロキシ−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、6−シクロヘキシル−8−ベンジル−10−ヒドロキシ−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、2,6−ジ−t−ブチル−8−ベンジル−10−ヒドロキシ−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイドおよび2,6−ジシクロヘキシル−8−ベンジル−10−ヒドロキシ−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイドなどを例示できる。
これら環状リン化合物の単独使用はもちろんのこと2種以上の環状リン化合物を併用することもできる。
Examples of the cyclic phosphorus compound represented by the general formula (6) include 10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 1-methyl-10-hydroxy-9. , 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2-methyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphenanthrene-10-oxide 6-methyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 7-methyl-10-hydroxy-9,10-dihydro-9-oxa-10 -Phosphaphenanthrene-10-oxide, 8-methyl-10-hydroxy-9,10-dihydro-9-oxa-10- Phosphaphenanthrene-10-oxide, 6,8-dimethyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphophenanthrene-10-oxide, 2,6,8-trimethyl- 10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2-ethyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphenance Len-10-oxide, 6-ethyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 8-ethyl-10-hydroxy-9,10-dihydro- 9-oxa-10-phosphaphenanthrene-10-oxide, 6,8-diethyl-10-hydroxy-9,10 Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,6,8-triethyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphenanthrene-10- Oxide, 2-i-propyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6-i-propyl-10-hydroxy-9,10-dihydro- 9-oxa-10-phosphaphenanthrene-10-oxide, 8-i-propyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphenanthrene-10-oxide, 6, 8-di-i-propyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-o 2,6,8-tri-i-propyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2-s-butyl-10-hydroxy- 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6-s-butyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphenanthrene- 10-oxide, 8-s-butyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 1,8-di-s-butyl-10-hydroxy- 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,6,8-tri-s-butyl-10-hydroxy-9, 0-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2-t-butyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphenanthrene-10- Oxide, 6-t-butyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 8-t-butyl-10-hydroxy-9,10-dihydro- 9-oxa-10-phosphaphenanthrene-10-oxide, 1,6-di-tert-butyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphenanthrene-10- Oxide, 2,6-di-t-butyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxy 2,7-di-t-butyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,8-di-t-butyl-10- Hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6,8-di-t-butyl-10-hydroxy-9,10-dihydro-9-oxa-10- Phosphaphenanthrene-10-oxide, 2,6,8-tri-t-butyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphenanthrene-10-oxide, 2- t-amyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6-t-amyl-10-hydroxy-9,10 -Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 8-t-amyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphenanthrene-10-oxide 6,8-di-t-amyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,6,8-tri-t-amyl-10 -Hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2-t-octyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphafe Nanthrene-10-oxide, 6-t-octyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10 Oxide, 8-t-octyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6,8-di-t-octyl-10-hydroxy-9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,6,8-tri-t-octyl-10-hydroxy-9,10-dihydro-9-oxa-10-phospho Phenanthrene-10-oxide, 2-cyclohexyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6-cyclohexyl-10-hydroxy-9,10- Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 8-cyclohexyl-10-hydroxy 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6,8-dicyclohexyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphafenance Len-10-oxide, 2,6,8-tri-cyclohexyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6-phenyl-10-hydroxy- 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2-benzyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphenanthrene-10- Oxide, 6-benzyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene -10-oxide, 8-benzyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6,8-di-benzyl-10-hydroxy-9,10 -Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,6,8-tri-benzyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphenanthrene -10-oxide, 2- (α-methylbenzyl) -10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6- (α-methylbenzyl) -10 -Hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 8- (α-methylbenzyl)- 0-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6,8-di (α-methylbenzyl) -10-hydroxy-9,10-dihydro-9- Oxa-10-phosphaphenanthrene-10-oxide, 2,6,8-tri (α-methylbenzyl) -10-hydroxy-9,10-dihydro-9-oxa-10-phosphenanthrene- 10-oxide, 2,6-di (α, α-dimethylbenzyl) -10-hydroxy-9,10-dihydro-9-oxa-10-phosphenanthrene-10-oxide, 6-t-butyl- 8-Methyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6-benzyl-8-methyl-1 0-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6-cyclohexyl-8-t-butyl-10-hydroxy-9,10-dihydro-9-oxa 10-phosphaphenanthrene-10-oxide, 6-benzyl-8-t-butyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphenanthrene-10-oxide, 6- (Α-methylbenzyl) -8-t-butyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6-t-butyl-8-cyclohexyl-10 -Hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6-benzyl-8-cycl Hexyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6-t-butyl-8-benzyl-10-hydroxy-9,10-dihydro-9- Oxa-10-phosphaphenanthrene-10-oxide, 6-cyclohexyl-8-benzyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphophenanthrene-10-oxide, 2, 6-di-t-butyl-8-benzyl-10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 2,6-dicyclohexyl-8-benzyl-10- Examples include hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide. Yes.
These cyclic phosphorus compounds can be used alone, or two or more cyclic phosphorus compounds can be used in combination.
本発明で用いられるβ晶核剤として前述の一般式(6)で示される環状リン化合物と併用するマグネシウム化合物としては、酢酸マグネシウム、プロピオン酸マグネシウム、n−酪酸マグネシウム、i−酪酸マグネシウム、n−吉草酸マグネシウム、i−吉草酸マグネシウム、n−ヘキサン酸マグネシウム、n−オクタン酸マグネシウム、2−エチルヘキサン酸マグネシウム、デカン酸マグネシウム、ラウリン酸マグネシウム、ミリスチン酸マグネシウム、ミリストレイン酸マグネシウム、パルミチン酸マグネシウム、パルミトレイン酸マグネシウム、ステアリン酸マグネシウム、オレイン酸マグネシウム、リノール酸マグネシウム、リノレン酸マグネシウム、アラキン酸マグネシウム、ベヘン酸マグネシウム、エルカ酸マグネシウム、リグノセリン酸マグネシウム、セロチン酸マグネシウム、モンタン酸マグネシウム、メリシン酸マグネシウム、12−ヒドロキシオクタデカン酸マグネシウム、リシノール酸マグネシウム、セレブロン酸マグネシウム、(モノ,ジミックスド)ヘキシルリン酸マグネシウム、(モノ,ジミックスド)オクチルリン酸マグネシウム、(モノ,ジミックスド)2−エチルヘキシルリン酸マグネシウム、(モノ,ジミックスド)デシルリン酸マグネシウム、(モノ,ジミックスド)ラウリルリン酸マグネシウム、(モノ,ジミックスド)ミリスチルリン酸マグネシウム、(モノ,ジミックスド)パルミチルリン酸マグネシウム、(モノ,ジミックスド)ステアリルリン酸マグネシウム、(モノ,ジミックスド)オレイルリン酸マグネシウム、(モノ,ジミックスド)リノールリン酸マグネシウム、(モノ,ジミックスド)リノリルリン酸マグネシウム、(モノ,ジミックスド)ドコシルリン酸マグネシウム、(モノ,ジミックスド)エルシルリン酸マグネシウム、(モノ,ジミックスド)テトラコシルリン酸マグネシウム、(モノ,ジミックスド)ヘキサコシルリン酸マグネシウム、(モノ,ジミックスド)オクタコシルリン酸マグネシウム、酸化マグネシウム、水酸化マグネシウム、炭酸マグネシウムが挙げられる。 Examples of the magnesium compound used in combination with the cyclic phosphorus compound represented by the general formula (6) as the β crystal nucleating agent used in the present invention include magnesium acetate, magnesium propionate, magnesium n-butyrate, magnesium i-butyrate, n- Magnesium valerate, magnesium i-valerate, magnesium n-hexanoate, magnesium n-octanoate, magnesium 2-ethylhexanoate, magnesium decanoate, magnesium laurate, magnesium myristate, magnesium myristate, magnesium palmitate, Magnesium palmitolate, magnesium stearate, magnesium oleate, magnesium linoleate, magnesium linolenate, magnesium arachidate, magnesium behenate, magnesium erucate, rig Magnesium serinate, magnesium serinate, magnesium montanate, magnesium melicinate, magnesium 12-hydroxyoctadecanoate, magnesium ricinoleate, magnesium cerebronate, magnesium (mono, dimixed) hexyl phosphate, (mono, dimixed) magnesium octyl phosphate, (Mono, dimixed) 2-ethylhexyl magnesium phosphate, (mono, dimixed) magnesium decyl phosphate, (mono, dimixed) magnesium lauryl phosphate, (mono, dimixed) magnesium myristyl phosphate, (mono, dimixed) magnesium palmitate (Mono, dimixed) magnesium stearyl phosphate, (mono, dimixed) magnesium oleyl phosphate, (mono, dimi Xdo) magnesium linoleate phosphate, (mono, dimixed) magnesium linoleyl phosphate, (mono, dimixed) magnesium docosyl phosphate, (mono, dimixed) magnesium erucyl phosphate, (mono, dimixed) magnesium tetracosyl phosphate, (mono, dimixed) Examples include magnesium hexacosyl phosphate, magnesium (mono, dimixed) octacosyl phosphate, magnesium oxide, magnesium hydroxide, and magnesium carbonate.
本発明で用いられるβ晶核剤として前述の一般式(6)で示される環状リン化合物と併用するマグネシウム化合物としては、さらに、一般式(6)で示される環状リン化合物として例示した前記化合物のマグネシウム塩、マグネシウム−ビス(1’−ヒドロキシ−2,2’−ビフェニレンフォスフィネート)、マグネシウム−ビス(5−メチル−1’−ヒドロキシ−2,2’−ビフェニレンフォスフィネート)、マグネシウム−ビス(6−メチル−1’−ヒドロキシ−2,2’−ビフェニレンフォスフィネート)、マグネシウム−ビス(1’−ヒドロキシ−4’−メチル−2,2’−ビフェニレンフォスフィネート)、マグネシウム−ビス(1’−ヒドロキシ−5’−メチル−2,2’−ビフェニレンフォスフィネート)、マグネシウム−ビス(1’−ヒドロキシ−6’−メチル−2,2’−ビフェニレンフォスフィネート)、マグネシウム−ビス(1’−ヒドロキシ−4’,6’−ジメチル−2,2’−ビフェニレンフォスフィネート)、マグネシウム−ビス(5,4’,6’−トリメチル−1’−ヒドロキシ−2,2’−ビフェニレンフォスフィネート)、マグネシウム−ビス(5−エチル−1’−ヒドロキシ−2,2’−ビフェニレンフォスフィネート)、マグネシウム−ビス(1’−ヒドロキシ−4’−エチル−2,2’−ビフェニレンフォスフィネート)、マグネシウム−ビス(1’−ヒドロキシ−6’−エチル−2,2’−ビフェニレンフォスフィネート)、マグネシウム−ビス(1’−ヒドロキシ−4’,6’−ジエチル−2,2’−ビフェニレンフォスフィネート)、マグネシウム−ビス(5,4’,6’−トリエチル−1’−ヒドロキシ−2,2’−ビフェニレンフォスフィネート)、マグネシウム−ビス(5−i−プロピル−1’−ヒドロキシ−2,2’−ビフェニレンフォスフィネート)、マグネシウム−ビス(1’−ヒドロキシ−4’−i−プロピル−2,2’−ビフェニレンフォスフィネート)、マグネシウム−ビス(1’−ヒドロキシ−6’−i−プロピル−2,2’−ビフェニレンフォスフィネート)、マグネシウム−ビス(1’−ヒドロキシ−4’,6’−ジ−i−プロピル−2,2’−ビフェニレンフォスフィネート)、マグネシウム−ビス(5,4’,6’−トリ−i−プロピル−1’−ヒドロキシ−2,2’−ビフェニレンフォスフィネート)、マグネシウム−ビス(5−s−ブチル−1’−ヒドロキシ−2,2’−ビフェニレンフォスフィネート)、マグネシウム−ビス(1’−ヒドロキシ−4’−s−ブチル−2,2’−ビフェニレンフォスフィネート)、マグネシウム−ビス(1’−ヒドロキシ−6’−s−ブチル−2,2’−ビフェニレンフォスフィネート)、マグネシウム−ビス(6,6’−ジ−s−ブチル−1’−ヒドロキシ−2,2’−ビフェニレンフォスフィネート)、マグネシウム−ビス(5,4’,6’−トリ−s−ブチル−1’−ヒドロキシ−2,2’−ビフェニレンフォスフィネート)、マグネシウム−ビス(5−t−ブチル−1’−ヒドロキシ−2,2’−ビフェニレンフォスフィネート)、マグネシウム−ビス(1’−ヒドロキシ−4’−t−ブチル−2,2’−ビフェニレンフォスフィネート)、マグネシウム−ビス(1’−ヒドロキシ−6’−t−ブチル−2,2’−ビフェニレンフォスフィネート)、マグネシウム−ビス(5,6’−ジ−t−ブチル−1’−ヒドロキシ−2,2’−ビフェニレンフォスフィネート)、マグネシウム−ビス(5,4’−ジ−t−ブチル−1’−ヒドロキシ−2,2’−ビフェニレンフォスフィネート)、マグネシウム−ビス(5,5’−ジ−t−ブチル−1’−ヒドロキシ−2,2’−ビフェニレンフォスフィネート)、マグネシウム−ビス(6,4’−ジ−t−ブチル−1’−ヒドロキシ−2,2’−ビフェニレンフォスフィネート)、マグネシウム−ビス(1’−ヒドロキシ−4’,6’−ジ−t−ブチル−2,2’−ビフェニレンフォスフィネート)、マグネシウム−ビス(5,4’,6’−トリ−t−ブチル−1’−ヒドロキシ−2,2’−ビフェニレンフォスフィネート)、マグネシウム−ビス(5−t−アミル−1’−ヒドロキシ−2,2’−ビフェニレンフォスフィネート)、マグネシウム−ビス(1’−ヒドロキシ−4’−t−アミル−2,2’−ビフェニレンフォスフィネート)、マグネシウム−ビス(1’−ヒドロキシ−6’−t−アミル−2,2’−ビフェニレンフォスフィネート)、マグネシウム−ビス(1’−ヒドロキシ−4’,6’−ジ−t−アミル−2,2’−ビフェニレンフォスフィネート)、マグネシウム−ビス(5,4’,6’−トリ−t−アミル−1’−ヒドロキシ−2,2’−ビフェニレンフォスフィネート)、マグネシウム−ビス(5−t−オクチル−1’−ヒドロキシ−2,2’−ビフェニレンフォスフィネート)、マグネシウム−ビス(1’−ヒドロキシ−4’−t−オクチル−2,2’−ビフェニレンフォスフィネート)、マグネシウム−ビス(1’−ヒドロキシ−6’−t−オクチル−2,2’−ビフェニレンフォスフィネート)、マグネシウム−ビス(1’−ヒドロキシ−4’,6’−ジ−t−オクチル−2,2’−ビフェニレンフォスフィネート)、マグネシウム−ビス(5,4’,6’−トリ−t−オクチル−1’−ヒドロキシ−2,2’−ビフェニレンフォスフィネート)、マグネシウム−ビス(5−シクロヘキシル−1’−ヒドロキシ−2,2’−ビフェニレンフォスフィネート)、マグネシウム−ビス(1’−ヒドロキシ−4’−シクロヘキシル−2,2’−ビフェニレンフォスフィネート)、マグネシウム−ビス(1’−ヒドロキシ−6’−シクロヘキシル−2,2’−ビフェニレンフォスフィネート)、マグネシウム−ビス(1’−ヒドロキシ−4’,6’−ジ−シクロヘキシル−2,2’−ビフェニレンフォスフィネート)、マグネシウム−ビス(5,4’,6’−トリ−シクロヘキシル−1’−ヒドロキシ−2,2’−ビフェニレンフォスフィネート)、マグネシウム−ビス(1’−ヒドロキシ−4’−フェニル−2,2’−ビフェニレンフォスフィネート)、マグネシウム−ビス(5−ベンジル−1’−ヒドロキシ−2,2’−ビフェニレンフォスフィネート)、マグネシウム−ビス(1’−ヒドロキシ−4’−ベンジル−2,2’−ビフェニレンフォスフィネート)、マグネシウム−ビス(1’−ヒドロキシ−6’−ベンジル−2,2’−ビフェニレンフォスフィネート)、マグネシウム−ビス(1’−ヒドロキシ−4’,6’−ジ−ベンジル−2,2’−ビフェニレンフォスフィネート)、マグネシウム−ビス(5,4’,6’−トリ−ベンジル−1’−ヒドロキシ−2,2’−ビフェニレンフォスフィネート)、マグネシウム−ビス[5−(α−メチルベンジル)−1’−ヒドロキシ−2,2’−ビフェニレンフォスフィネート]、マグネシウム−ビス[1’−ヒドロキシ−4’−(α−メチルベンジル)−2,2’−ビフェニレンフォスフィネート]、マグネシウム−ビス[1’−ヒドロキシ−6’−(α−メチルベンジル)−2,2’−ビフェニレンフォスフィネート]、マグネシウム−ビス[1’−ヒドロキシ−4’,6’−ジ(α−メチルベンジル)−2,2’−ビフェニレンフォスフィネート]、マグネシウム−ビス[5,4’,6’−トリ(α−メチルベンジル)−1’−ヒドロキシ−2,2’−ビフェニレンフォスフィネート]、マグネシウム−ビス[5,4’−ジ(α,α−ジメチルベンジル)−1’−ヒドロキシ−2,2’−ビフェニレンフォスフィネート]、マグネシウム−ビス(1’−ヒドロキシ−4’−t−ブチル−6’−メチル−2,2’−ビフェニレンフォスフィネート)、マグネシウム−ビス(1’−ヒドロキシ−4’−ベンジル−6’−メチル−2,2’−ビフェニレンフォスフィネート)、マグネシウム−ビス(1’−ヒドロキシ−4’−シクロヘキシル−6’−t−ブチル−2,2’−ビフェニレンフォスフィネート)、マグネシウム−ビス(1’−ヒドロキシ−4’−ベンジル−6’−t−ブチル−2,2’−ビフェニレンフォスフィネート)、マグネシウム−ビス[1’−ヒドロキシ−4’−(α−メチルベンジル)−6’−t−ブチル−2,2’−ビフェニレンフォスフィネート]、マグネシウム−ビス(1’−ヒドロキシ−4’−t−ブチル−6’−シクロヘキシル−2,2’−ビフェニレンフォスフィネート)、マグネシウム−ビス(1’−ヒドロキシ−4’−ベンジル−6’−シクロヘキシル−2,2’−ビフェニレンフォスフィネート)、マグネシウム−ビス(1’−ヒドロキシ−4’−t−ブチル−6’−ベンジル−2,2’−ビフェニレンフォスフィネート)、マグネシウム−ビス(1’−ヒドロキシ−4’−シクロヘキシル−6’−ベンジル−2,2’−ビフェニレンフォスフィネート)、マグネシウム−ビス(5,4’−ジ−t−ブチル−6’−ベンジル−1’−ヒドロキシ−2,2’−ビフェニレンフォスフィネート)およびマグネシウム−ビス(5,4’−ジシクロヘキシル−6’−ベンジル−1’−ヒドロキシ−2,2’−ビフェニレンフォスフィネート)などを例示できる。
これらマグネシウム化合物の単独使用はもちろんのこと2種以上のマグネシウム化合物を併用することもできる。
As the magnesium compound used in combination with the cyclic phosphorus compound represented by the above general formula (6) as the β crystal nucleating agent used in the present invention, the compound exemplified above as the cyclic phosphorus compound represented by the general formula (6) Magnesium salt, magnesium-bis (1′-hydroxy-2,2′-biphenylene phosphinate), magnesium-bis (5-methyl-1′-hydroxy-2,2′-biphenylene phosphinate), magnesium-bis (6-methyl-1′-hydroxy-2,2′-biphenylene phosphinate), magnesium-bis (1′-hydroxy-4′-methyl-2,2′-biphenylene phosphinate), magnesium-bis ( 1′-hydroxy-5′-methyl-2,2′-biphenylene phosphinate), magnesium-bis (1′-hydroxy) -6'-methyl-2,2'-biphenylene phosphinate), magnesium bis (1'-hydroxy-4 ', 6'-dimethyl-2,2'-biphenylene phosphinate), magnesium bis (5 , 4 ′, 6′-trimethyl-1′-hydroxy-2,2′-biphenylene phosphinate), magnesium-bis (5-ethyl-1′-hydroxy-2,2′-biphenylene phosphinate), magnesium -Bis (1'-hydroxy-4'-ethyl-2,2'-biphenylene phosphinate), magnesium-bis (1'-hydroxy-6'-ethyl-2,2'-biphenylene phosphinate), magnesium -Bis (1'-hydroxy-4 ', 6'-diethyl-2,2'-biphenylene phosphinate), magnesium-bis (5,4', 6'-triethyl) 1'-hydroxy-2,2'-biphenylene phosphinate), magnesium-bis (5-i-propyl-1'-hydroxy-2,2'-biphenylene phosphinate), magnesium-bis (1'-hydroxy -4′-i-propyl-2,2′-biphenylene phosphinate), magnesium bis (1′-hydroxy-6′-i-propyl-2,2′-biphenylene phosphinate), magnesium bis ( 1′-hydroxy-4 ′, 6′-di-i-propyl-2,2′-biphenylene phosphinate), magnesium-bis (5,4 ′, 6′-tri-i-propyl-1′-hydroxy -2,2'-biphenylene phosphinate), magnesium-bis (5-s-butyl-1'-hydroxy-2,2'-biphenylene phosphinate), magnesium Bis (1′-hydroxy-4′-s-butyl-2,2′-biphenylene phosphinate), magnesium-bis (1′-hydroxy-6′-s-butyl-2,2′-biphenylene phosphinate) ), Magnesium-bis (6,6′-di-s-butyl-1′-hydroxy-2,2′-biphenylene phosphinate), magnesium-bis (5,4 ′, 6′-tri-s-butyl) -1′-hydroxy-2,2′-biphenylene phosphinate), magnesium bis (5-tert-butyl-1′-hydroxy-2,2′-biphenylene phosphinate), magnesium bis (1′- Hydroxy-4′-t-butyl-2,2′-biphenylene phosphinate), magnesium-bis (1′-hydroxy-6′-t-butyl-2,2′-biphenylene phosphinate) Magnesium-bis (5,6′-di-t-butyl-1′-hydroxy-2,2′-biphenylene phosphinate), magnesium-bis (5,4′-di-t-butyl-1′-hydroxy -2,2'-biphenylene phosphinate), magnesium-bis (5,5'-di-t-butyl-1'-hydroxy-2,2'-biphenylene phosphinate), magnesium-bis (6,4 '-Di-t-butyl-1'-hydroxy-2,2'-biphenylene phosphinate), magnesium-bis (1'-hydroxy-4', 6'-di-t-butyl-2,2'- Biphenylene phosphinate), magnesium bis (5,4 ′, 6′-tri-t-butyl-1′-hydroxy-2,2′-biphenylene phosphinate), magnesium bis (5-t-amyl-) 1'-hydro Xy-2,2′-biphenylene phosphinate), magnesium bis (1′-hydroxy-4′-t-amyl-2,2′-biphenylene phosphinate), magnesium bis (1′-hydroxy-6) '-T-amyl-2,2'-biphenylene phosphinate), magnesium-bis (1'-hydroxy-4', 6'-di-t-amyl-2,2'-biphenylene phosphinate), magnesium -Bis (5,4 ', 6'-tri-t-amyl-1'-hydroxy-2,2'-biphenylene phosphinate), magnesium-bis (5-t-octyl-1'-hydroxy-2, 2'-biphenylene phosphinate), magnesium bis (1'-hydroxy-4'-t-octyl-2,2'-biphenylene phosphinate), magnesium bis (1'-hydride) Xy-6'-t-octyl-2,2'-biphenylene phosphinate), magnesium-bis (1'-hydroxy-4 ', 6'-di-t-octyl-2,2'-biphenylene phosphinate) ), Magnesium-bis (5,4 ′, 6′-tri-t-octyl-1′-hydroxy-2,2′-biphenylene phosphinate), magnesium-bis (5-cyclohexyl-1′-hydroxy-2) , 2′-biphenylene phosphinate), magnesium-bis (1′-hydroxy-4′-cyclohexyl-2,2′-biphenylene phosphinate), magnesium-bis (1′-hydroxy-6′-cyclohexyl-2). , 2'-biphenylene phosphinate), magnesium-bis (1'-hydroxy-4 ', 6'-di-cyclohexyl-2,2'-biphenylene phospho) Finate), magnesium-bis (5,4 ′, 6′-tri-cyclohexyl-1′-hydroxy-2,2′-biphenylene phosphinate), magnesium-bis (1′-hydroxy-4′-phenyl-2) , 2′-biphenylene phosphinate), magnesium-bis (5-benzyl-1′-hydroxy-2,2′-biphenylene phosphinate), magnesium-bis (1′-hydroxy-4′-benzyl-2, 2'-biphenylene phosphinate), magnesium bis (1'-hydroxy-6'-benzyl-2,2'-biphenylene phosphinate), magnesium bis (1'-hydroxy-4 ', 6'-di) -Benzyl-2,2'-biphenylene phosphinate), magnesium-bis (5,4 ', 6'-tri-benzyl-1'-hydroxy-2, '-Biphenylene phosphinate), magnesium-bis [5- (α-methylbenzyl) -1'-hydroxy-2,2'-biphenylene phosphinate], magnesium-bis [1'-hydroxy-4'-( α-methylbenzyl) -2,2′-biphenylene phosphinate], magnesium-bis [1′-hydroxy-6 ′-(α-methylbenzyl) -2,2′-biphenylene phosphinate], magnesium-bis [1′-hydroxy-4 ′, 6′-di (α-methylbenzyl) -2,2′-biphenylene phosphinate], magnesium-bis [5,4 ′, 6′-tri (α-methylbenzyl) -1′-hydroxy-2,2′-biphenylene phosphinate], magnesium-bis [5,4′-di (α, α-dimethylbenzyl) -1′-hydroxy-2,2′- Phenylene phosphinate], magnesium-bis (1′-hydroxy-4′-t-butyl-6′-methyl-2,2′-biphenylene phosphinate), magnesium-bis (1′-hydroxy-4′-) Benzyl-6′-methyl-2,2′-biphenylene phosphinate), magnesium-bis (1′-hydroxy-4′-cyclohexyl-6′-t-butyl-2,2′-biphenylene phosphinate), Magnesium-bis (1′-hydroxy-4′-benzyl-6′-t-butyl-2,2′-biphenylene phosphinate), magnesium-bis [1′-hydroxy-4 ′-(α-methylbenzyl) −6′-t-butyl-2,2′-biphenylene phosphinate], magnesium-bis (1′-hydroxy-4′-t-butyl-6′-cyclohexyl-2, '-Biphenylene phosphinate), magnesium-bis (1'-hydroxy-4'-benzyl-6'-cyclohexyl-2,2'-biphenylene phosphinate), magnesium-bis (1'-hydroxy-4'-) t-butyl-6′-benzyl-2,2′-biphenylene phosphinate), magnesium-bis (1′-hydroxy-4′-cyclohexyl-6′-benzyl-2,2′-biphenylene phosphinate), Magnesium-bis (5,4′-di-t-butyl-6′-benzyl-1′-hydroxy-2,2′-biphenylene phosphinate) and magnesium-bis (5,4′-dicyclohexyl-6′-) Benzyl-1′-hydroxy-2,2′-biphenylene phosphinate) and the like.
These magnesium compounds can be used alone or in combination of two or more magnesium compounds.
前述の一般式(6)で示される環状リン化合物と前記マグネシウム化合物との混合物の質量比率は特に限定されないが、通常環状リン化合物1質量部に対してマグネシウム化合物を0.01〜100質量部、好ましくは0.1〜10質量部の比率である。 The mass ratio of the mixture of the cyclic phosphorus compound represented by the general formula (6) and the magnesium compound is not particularly limited, but is usually 0.01 to 100 parts by mass of the magnesium compound with respect to 1 part by mass of the cyclic phosphorus compound. The ratio is preferably 0.1 to 10 parts by mass.
本発明で用いられるβ晶核剤として前述の一般式(9)で示される環状リン化合物としては、9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、1−メチル−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、2−メチル−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、6−メチル−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、7−メチル−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、8−メチル−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、6,8−ジメチル−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、2,6,8−トリメチル−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、2−エチル−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、6−エチル−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、8−エチル−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、6,8−ジエチル−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、2,6,8−トリエチル−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、2−i−プロピル−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、6−i−プロピル−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、8−i−プロピル−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、6,8−ジ−i−プロピル−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、2,6,8−トリ−i−プロピル−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、2−s−ブチル−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、6−s−ブチル−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、8−s−ブチル−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、1,8−ジ−s−ブチル−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、2,6,8−トリ−s−ブチル−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、2−t−ブチル−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、6−t−ブチル−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、8−t−ブチル−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、1,6−ジ−t−ブチル−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、2,6−ジ−t−ブチル−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、2,7−ジ−t−ブチル−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、2,8−ジ−t−ブチル−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、6,8−ジ−t−ブチル−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、2,6,8−トリ−t−ブチル−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、2−t−アミル−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、6−t−アミル−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、8−t−アミル−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、6,8−ジ−t−アミル−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、2,6,8−トリ−t−アミル−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、2−t−オクチル−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、6−t−オクチル−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、8−t−オクチル−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、6,8−ジ−t−オクチル−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、2,6,8−トリ−t−オクチル−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、2−シクロヘキシル−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、6−シクロヘキシル−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、8−シクロヘキシル−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、6,8−ジ−シクロヘキシル−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、2,6,8−トリ−シクロヘキシル−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、6−フェニル−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、2−ベンジル−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、6−ベンジル−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、8−ベンジル−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、6,8−ジ−ベンジル−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、2,6,8−トリ−ベンジル−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、2−(α−メチルベンジル)−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、6−(α−メチルベンジル)−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、8−(α−メチルベンジル)−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、6,8−ジ(α−メチルベンジル)−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、2,6,8−トリ(α−メチルベンジル)−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、2,6−ジ(α,α−ジメチルベンジル)−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、6−t−ブチル−8−メチル−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、6−ベンジル−8−メチル−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、6−シクロヘキシル−8−t−ブチル−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、6−ベンジル−8−t−ブチル−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、6−(α−メチルベンジル)−8−t−ブチル−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、6−t−ブチル−8−シクロヘキシル−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、6−ベンジル−8−シクロヘキシル−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、6−t−ブチル−8−ベンジル−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、6−シクロヘキシル−8−ベンジル−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイド、2,6−ジ−t−ブチル−8−ベンジル−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイドおよび2,6−ジシクロヘキシル−8−ベンジル−9,10−ジヒドロ−9−オキサ−10−フォスファフェナンスレン−10−オキサイドなどを例示できる。
これら環状リン化合物の単独使用はもちろんのこと2種以上の環状リン化合物を併用することもできる。
Examples of the cyclic phosphorus compound represented by the general formula (9) as the β crystal nucleating agent used in the present invention include 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 1- Methyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2-methyl-9,10-dihydro-9-oxa-10-phosphenanthrene-10-oxide, 6-methyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 7-methyl-9,10-dihydro-9-oxa-10-phosphenanthrene-10- Oxide, 8-methyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6,8-dimethyl-9,10-di Dro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,6,8-trimethyl-9,10-dihydro-9-oxa-10-phosphenanthrene-10-oxide, 2- Ethyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6-ethyl-9,10-dihydro-9-oxa-10-phosphenanthrene-10-oxide, 8-ethyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6,8-diethyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene- 10-oxide, 2,6,8-triethyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2- i-propyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6-i-propyl-9,10-dihydro-9-oxa-10-phosphenanthrene- 10-oxide, 8-i-propyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6,8-di-i-propyl-9,10-dihydro-9- Oxa-10-phosphenanthrene-10-oxide, 2,6,8-tri-i-propyl-9,10-dihydro-9-oxa-10-phosphenanthrene-10-oxide, 2- s-butyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6-s-butyl-9,10-dihydro-9-oxa-1 -Phosphaphenanthrene-10-oxide, 8-s-butyl-9,10-dihydro-9-oxa-10-phosphenanthrene-10-oxide, 1,8-di-s-butyl-9 , 10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,6,8-tri-s-butyl-9,10-dihydro-9-oxa-10-phosphenanthrene -10-oxide, 2-t-butyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6-t-butyl-9,10-dihydro-9-oxa-10 -Phosphaphenanthrene-10-oxide, 8-t-butyl-9,10-dihydro-9-oxa-10-phosphenanthrene-10-oxide, 1,6- -T-butyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,6-di-t-butyl-9,10-dihydro-9-oxa-10-phos Phaphenanthrene-10-oxide, 2,7-di-t-butyl-9,10-dihydro-9-oxa-10-phosphophenanthrene-10-oxide, 2,8-di-t-butyl -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6,8-di-t-butyl-9,10-dihydro-9-oxa-10-phosphenanthrene -10-oxide, 2,6,8-tri-t-butyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2-t-amyl-9,10-dihydro -9-oxa-10-phosphaphenanthrene-10-oxide, 6-t-amyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 8-t-amyl -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6,8-di-t-amyl-9,10-dihydro-9-oxa-10-phosphenanthrene -10-oxide, 2,6,8-tri-t-amyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2-t-octyl-9,10-dihydro -9-oxa-10-phosphaphenanthrene-10-oxide, 6-t-octyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10- X-oxide, 8-t-octyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6,8-di-t-octyl-9,10-dihydro-9-oxa 10-phosphenanthrene-10-oxide, 2,6,8-tri-t-octyl-9,10-dihydro-9-oxa-10-phosphenanthrene-10-oxide, 2-cyclohexyl- 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6-cyclohexyl-9,10-dihydro-9-oxa-10-phosphenanthrene-10-oxide, 8- Cyclohexyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6,8-dicyclohexyl 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,6,8-tri-cyclohexyl-9,10-dihydro-9-oxa-10-phosphenanthrene- 10-oxide, 6-phenyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2-benzyl-9,10-dihydro-9-oxa-10-phosphenance Len-10-oxide, 6-benzyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 8-benzyl-9,10-dihydro-9-oxa-10-phospho Phenanthrene-10-oxide, 6,8-di-benzyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene -10-oxide, 2,6,8-tri-benzyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2- (α-methylbenzyl) -9,10- Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6- (α-methylbenzyl) -9,10-dihydro-9-oxa-10-phosphenanthrene-10-oxide, 8 -(Α-Methylbenzyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6,8-di (α-methylbenzyl) -9,10-dihydro-9- Oxa-10-phosphaphenanthrene-10-oxide, 2,6,8-tri (α-methylbenzyl) -9,10-dihydro-9-oxa-10-phosphafena Nsulene-10-oxide, 2,6-di (α, α-dimethylbenzyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6-t-butyl-8- Methyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6-benzyl-8-methyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene- 10-oxide, 6-cyclohexyl-8-t-butyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6-benzyl-8-t-butyl-9,10- Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6- (α-methylbenzyl) -8-t-butyl-9,10-dihydro-9-o Sa-10-phosphaphenanthrene-10-oxide, 6-t-butyl-8-cyclohexyl-9,10-dihydro-9-oxa-10-phosphenanthrene-10-oxide, 6-benzyl- 8-cyclohexyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6-t-butyl-8-benzyl-9,10-dihydro-9-oxa-10-phospho Phenanthrene-10-oxide, 6-cyclohexyl-8-benzyl-9,10-dihydro-9-oxa-10-phosphophenanthrene-10-oxide, 2,6-di-t-butyl-8- Benzyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 2,6-dicyclohexyl And which may or may not be 8-benzyl-9,10-dihydro-9-oxa-10-phosphatonin phenanthrene-10-oxide.
These cyclic phosphorus compounds can be used alone, or two or more cyclic phosphorus compounds can be used in combination.
本発明で用いられるβ晶核剤として前述の一般式(9)で示される環状リン化合物と併用するマグネシウム化合物としては、前述の各種マグネシウムフォスフィネート系化合物、硫酸マグネシウム、塩基性硫酸マグネシウム(マグネシウムオキシサルフェート)、タルクなどを例示できる。これらマグネシウム化合物の単独使用はもちろんのこと2種以上のマグネシウム化合物を併用することもできる。
一般式(9)で示される環状リン化合物とマグネシウム化合物との混合物の質量比率は特に限定されないが、通常環状リン化合物1質量部に対してマグネシウム化合物を0.01〜100質量部、好ましくは0.1〜10質量部の比率である。
Examples of the magnesium compound used in combination with the cyclic phosphorus compound represented by the general formula (9) as the β crystal nucleating agent used in the present invention include the above-mentioned various magnesium phosphinate compounds, magnesium sulfate, and basic magnesium sulfate (magnesium). Examples thereof include oxysulfate) and talc. These magnesium compounds can be used alone or in combination of two or more magnesium compounds.
Although the mass ratio of the mixture of the cyclic phosphorus compound and the magnesium compound represented by the general formula (9) is not particularly limited, the magnesium compound is usually 0.01 to 100 parts by mass, preferably 0 with respect to 1 part by mass of the cyclic phosphorus compound. .1 to 10 parts by mass.
本明細書において「置換されていてもよい二価の炭化水素基」の「二価の炭化水素基」としては、飽和の直鎖状の二価の炭化水素基、不飽和の直鎖状の二価の炭化水素基、飽和の環状の二価の炭化水素基または不飽和の環状の二価の炭化水素基が挙げられる。
飽和の直鎖状の二価の炭化水素基としては、直鎖状のアルキル基(例えばメチル、エチル、n−プロピル、n−ブチル、n−ペンチル、n−ヘキシル、n−ヘプチル、n−オクチル、n−ノニル等のC1-10アルキル基等)からその末端の水素原子を1個取り除いた基が挙げられ、具体的には例えばメチレン、エチレン、プロピレン、ブチレン、ペンチレンなどの直鎖状のC1-6アルキレンなどが挙げられる。
不飽和の直鎖状の二価の炭化水素基としては、直鎖状のアルケニル基(例えばビニル、アリル、1−プロペニル、1−ブテニル、2−ブテニル、3−ブテニル、1−ペンテニル、2−ペンテニル、3−ペンテニル、4−ペンテニル、1−ヘキセニル、2−ヘキセニル、3−ヘキセニル、4−ヘキセニル、5−ヘキセニル等のC2-6アルケニル基等)等または直鎖状のアルキニル基(例えばエチニル、1−プロピニル、2−プロピニル、1−ブチニル、2−ブチニル、3−ブチニル、1−ペンチニル、2−ペンチニル、3−ペンチニル、4−ペンチニル、1−ヘキシニル、2−ヘキシニル、3−ヘキシニル、4−ヘキシニル、5−ヘキシニル等のC2-6アルキニル基等)等からその末端の水素原子を1個取り除いた基が挙げられ、具体的には例えば直鎖状のC2-6アルケニレンまたはC2-6アルキニレンなどが挙げられる。
In the present specification, the “divalent hydrocarbon group” of the “optionally substituted divalent hydrocarbon group” includes a saturated linear divalent hydrocarbon group and an unsaturated linear group. Examples thereof include a divalent hydrocarbon group, a saturated cyclic divalent hydrocarbon group, and an unsaturated cyclic divalent hydrocarbon group.
Saturated linear divalent hydrocarbon groups include linear alkyl groups (eg, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl). C 1-10 alkyl group such as n-nonyl, etc.), and a group obtained by removing one terminal hydrogen atom, specifically, linear groups such as methylene, ethylene, propylene, butylene, pentylene, etc. And C 1-6 alkylene.
Examples of the unsaturated linear divalent hydrocarbon group include linear alkenyl groups (for example, vinyl, allyl, 1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2- Pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl and other C 2-6 alkenyl groups, etc.) or a linear alkynyl group (eg ethynyl) 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4 - hexynyl, it includes C 2-6 1 or a group obtained by removing a hydrogen atom of the terminal alkynyl groups, etc.) and the like of 5-hexynyl and the like, in particular even Such as linear C 2-6 alkenylene or C 2-6 alkynylene and the like.
飽和の環状の二価の炭化水素基としては、シクロアルキル基(例えば、シクロプロピル、シクロブチル、シクロペンチル、シクロヘキシル、シクロヘプチル、シクロオクチル、シクロノニル等のC3-9シクロアルキル等)等の任意の位置(好ましくは、結合手を有する炭素原子と異なる炭素原子、さらに好ましくは、最も離れた位置の炭素原子)の水素原子を1個取り除いた基(例えば、C5-7シクロアルキレンなど)が挙げられる。
不飽和の環状の二価の炭化水素基としては、シクロアルケニル基(例えば、2−シクロペンテン−1−イル、3−シクロペンテン−1−イル、2−シクロヘキセン−1−イル、3−シクロヘキセン−1−イル、1−シクロブテン−1−イル、1−シクロペンテン−1−イル等のC3-6シクロアルケニル基等)、シクロアルカンジエニル基(例えば、2,4−シクロペンタンジエン−1−イル、2,4−シクロヘキサンジエン−1−イル、2,5−シクロヘキサンジエン−1−イル等のC4-6シクロアルカンジエニル基等)、アリール基(例えば、フェニル、ナフチル等のC6-12アリール基等)等の任意の位置(好ましくは、結合手を有する炭素原子と異なる炭素原子、さらに好ましくは最も離れた位置の炭素原子)の水素原子を1個取り除いた基(例えばC6-12アリレーンなど)が挙げられる。
The saturated cyclic divalent hydrocarbon group may be any position such as a cycloalkyl group (eg, C 3-9 cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, etc.) A group obtained by removing one hydrogen atom (preferably a carbon atom different from a carbon atom having a bond, more preferably a carbon atom at the most distant position) (for example, C 5-7 cycloalkylene). .
Examples of the unsaturated cyclic divalent hydrocarbon group include cycloalkenyl groups (for example, 2-cyclopenten-1-yl, 3-cyclopenten-1-yl, 2-cyclohexen-1-yl, 3-cyclohexene-1- Yl, C 3-6 cycloalkenyl groups such as 1-cyclobuten-1-yl, 1-cyclopenten-1-yl, etc.), cycloalkanedienyl groups (for example, 2,4-cyclopentanedien-1-yl, 2 , 4-cyclohexanedien-1-yl, C 4-6 cycloalkanedienyl groups such as 2,5-cyclohexanedien-1-yl), aryl groups (eg, C 6-12 aryl groups such as phenyl, naphthyl, etc.) A group in which one hydrogen atom at any position (preferably a carbon atom different from a carbon atom having a bond, more preferably a carbon atom at the most distant position) is removed (example: For example, C 6-12 arylene).
前記「置換されていてもよい二価の炭化水素基」の置換基としては、例えば水酸基、ハロゲン原子(例えばフッ素、塩素、臭素、ヨウ素等)、ニトロ基、シアノ基、置換されていてもよいアミノ基、置換されていてもよい低級アルキル基、1ないし5個のハロゲン原子(例えばフッ素、塩素、臭素、ヨウ素等)で置換されていてもよい低級アルコキシ基、エステル化されていてもよいカルボキシル基、置換されていてもよいカルバモイル基等が挙げられる。これらの任意の置換基は化学的に許容される位置に1ないし3個(好ましくは1ないし2個)置換されていてよい。 Examples of the substituent of the “optionally substituted divalent hydrocarbon group” include a hydroxyl group, a halogen atom (eg, fluorine, chlorine, bromine, iodine, etc.), a nitro group, a cyano group, and an optionally substituted group. Amino group, optionally substituted lower alkyl group, 1 to 5 halogen atoms (eg, fluorine, chlorine, bromine, iodine etc.) optionally substituted lower alkoxy group, esterified carboxyl Group, an optionally substituted carbamoyl group, and the like. These optional substituents may be substituted at 1 to 3 (preferably 1 to 2) at chemically acceptable positions.
本明細書において「置換されていてもよい炭化水素基」の炭化水素基としては、例えば脂肪族鎖式炭化水素基、脂環式炭化水素基、アリール基およびアラルキル基等が挙げられる。
炭化水素基の例としての「脂肪族鎖式炭化水素基」としては、例えばアルキル基、アルケニル基、アルキニル基等の直鎖状または分枝鎖状の脂肪族炭化水素基が挙げられる。
アルキル基としては、例えばメチル、エチル、n−プロピル、イソプロピル、n−ブチル、イソブチル、sec−ブチル、tert−ブチル、n−ペンチル、イソペンチル、ネオペンチル、1−メチルプロピル、n−ヘキシル、イソヘキシル、1,1−ジメチルブチル、2,2−ジメチルブチル、3,3−ジメチルブチル、3,3−ジメチルプロピル、2−エチルブチル、n−ヘプチル、1−メチルヘプチル、1−エチルヘキシル、n−オクチル、1−メチルヘプチル、ノニル等のC1-10アルキル基(好ましくはC1-6アルキル等)等が挙げられる。
アルケニル基としては、例えばビニル、アリル、イソプロペニル、2−メチルアリル、1−プロペニル、2−メチル−1−プロペニル、1−ブテニル、2−ブテニル、3−ブテニル、2−エチル−1−ブテニル、2−メチル−2−ブテニル、3−メチル−2−ブテニル、1−ペンテニル、2−ペンテニル、3−ペンテニル、4−ペンテニル、4−メチル−3−ペンテニル、1−ヘキセニル、2−ヘキセニル、3−ヘキセニル、4−ヘキセニル、5−ヘキセニル等のC2-6アルケニル基等が挙げられる。
アルキニル基としては、例えばエチニル、1−プロピニル、2−プロピニル、1−ブチニル、2−ブチニル、3−ブチニル、1−ペンチニル、2−ペンチニル、3−ペンチニル、4−ペンチニル、1−ヘキシニル、2−ヘキシニル、3−ヘキシニル、4−ヘキシニル、5−ヘキシニル等のC2-6アルキニル基が挙げられる。
In the present specification, examples of the hydrocarbon group of the “optionally substituted hydrocarbon group” include an aliphatic chain hydrocarbon group, an alicyclic hydrocarbon group, an aryl group, and an aralkyl group.
Examples of the “aliphatic chain hydrocarbon group” as an example of the hydrocarbon group include linear or branched aliphatic hydrocarbon groups such as an alkyl group, an alkenyl group, and an alkynyl group.
Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, 1-methylpropyl, n-hexyl, isohexyl, 1 , 1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 3,3-dimethylpropyl, 2-ethylbutyl, n-heptyl, 1-methylheptyl, 1-ethylhexyl, n-octyl, 1- Examples thereof include C 1-10 alkyl groups (preferably C 1-6 alkyl etc.) such as methyl heptyl and nonyl.
Examples of the alkenyl group include vinyl, allyl, isopropenyl, 2-methylallyl, 1-propenyl, 2-methyl-1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-ethyl-1-butenyl, 2 -Methyl-2-butenyl, 3-methyl-2-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 4-methyl-3-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl C 2-6 alkenyl groups such as 4-hexenyl and 5-hexenyl.
Examples of the alkynyl group include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-hexynyl, 2- C 2-6 alkynyl groups such as hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl and the like can be mentioned.
炭化水素基の例としての「脂環式炭化水素基」としては、例えばシクロアルキル基、シクロアルケニル基、シクロアルカンジエニル基等の飽和または不飽和の脂環式炭化水素基が挙げられる。
「シクロアルキル基」としては、例えばシクロプロピル、シクロブチル、シクロペンチル、シクロヘキシル、シクロヘプチル、シクロオクチル、シクロノニル等のC3-9シクロアルキル等が挙げられる。
「シクロアルケニル基」としては、例えば2−シクロペンテン−1−イル、3−シクロペンテン−1−イル、2−シクロヘキセン−1−イル、3−シクロヘキセン−1−イル、1−シクロブテン−1−イル、1−シクロペンテン−1−イル等のC3-6シクロアルケニル基等が挙げられる。
「シクロアルカンジエニル基」としては、例えば2,4−シクロペンタンジエン−1−イル、2,4−シクロヘキサンジエン−1−イル、2,5−シクロヘキサンジエン−1−イル等のC4-6シクロアルカンジエニル基等が挙げられる。
Examples of the “alicyclic hydrocarbon group” as an example of the hydrocarbon group include saturated or unsaturated alicyclic hydrocarbon groups such as a cycloalkyl group, a cycloalkenyl group, and a cycloalkanedienyl group.
Examples of the “cycloalkyl group” include C 3-9 cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and the like.
Examples of the “cycloalkenyl group” include 2-cyclopenten-1-yl, 3-cyclopenten-1-yl, 2-cyclohexen-1-yl, 3-cyclohexen-1-yl, 1-cyclobuten-1-yl, 1 -C 3-6 cycloalkenyl groups such as -cyclopenten-1-yl and the like.
Examples of the “cycloalkanedienyl group” include C 4-6 such as 2,4-cyclopentanedien-1-yl, 2,4-cyclohexanedien-1-yl, 2,5-cyclohexanedien-1-yl and the like. And cycloalkanedienyl group.
炭化水素基の例としての「アリール基」としては、単環式または縮合多環式芳香族炭化水素基が挙げられ、具体的には例えばフェニル、ナフチル、アントリル、フェナントリル、アセナフチレニル等のC6-14アリール基等が挙げられる。
炭化水素基の例としての「アラルキル基」としては、例えば、ベンジル、フェネチル、ジフェニルメチル、1−ナフチルメチル、2−ナフチルメチル、2,2−ジフェニルエチル、3−フェニルプロピル、4−フェニルブチル、5−フェニルペンチル、2−ビフェニリルメチル、3−ビフェニリルメチル、4−ビフェニリルメチル等のC7−19アラルキル基等が挙げられる。
Examples of the “aryl group” as an example of the hydrocarbon group include a monocyclic or condensed polycyclic aromatic hydrocarbon group, specifically, C 6- such as phenyl, naphthyl, anthryl, phenanthryl, acenaphthylenyl and the like. And 14 aryl group.
Examples of the “aralkyl group” as an example of the hydrocarbon group include benzyl, phenethyl, diphenylmethyl, 1-naphthylmethyl, 2-naphthylmethyl, 2,2-diphenylethyl, 3-phenylpropyl, 4-phenylbutyl, Examples thereof include C 7-19 aralkyl groups such as 5-phenylpentyl, 2-biphenylylmethyl, 3-biphenylylmethyl, 4-biphenylylmethyl, and the like.
「置換されていてもよい炭化水素基」の置換基としては、例えば置換されていてもよいアルキル基、置換されていてもよいアルケニル基、置換されていてもよいアルキニル基、置換されていてもよいアリール基、置換されていてもよいシクロアルキル基もしくはシクロアルケニル基、置換されていてもよい複素環基、置換されていてもよいアミノ基、置換されていてもよいイミドイル基、置換されていてもよいアミジノ基、置換されていてもよい水酸基、置換されていてもよいチオール基、エステル化されていてもよいカルボキシル基、置換されていてもよいカルバモイル基、置換されていてもよいチオカルバモイル基、ハロゲン原子(例えばフッ素、塩素、臭素、ヨウ素等、好ましくは塩素、臭素等)、シアノ基、ニトロ基、スルホン酸由来のアシル基、カルボン酸由来のアシル基等が挙げられる。これらの任意の置換基は化学的に許容される位置に1ないし3個(好ましくは1ないし2個)置換されていてよい。 Examples of the substituent of the “optionally substituted hydrocarbon group” include an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, and optionally substituted. A good aryl group, an optionally substituted cycloalkyl or cycloalkenyl group, an optionally substituted heterocyclic group, an optionally substituted amino group, an optionally substituted imidoyl group, a substituted An amidino group, an optionally substituted hydroxyl group, an optionally substituted thiol group, an optionally esterified carboxyl group, an optionally substituted carbamoyl group, an optionally substituted thiocarbamoyl group Halogen atoms (eg fluorine, chlorine, bromine, iodine, etc., preferably chlorine, bromine, etc.), cyano groups, nitro groups, sulfonic acid Acyl group, and the like acyl group derived from a carboxylic acid. These optional substituents may be substituted at 1 to 3 (preferably 1 to 2) at chemically acceptable positions.
これら特に好ましいβ晶核剤の具体例としては新日本理化社製β晶核剤『エヌジェスターNU−100』、β晶核剤の添加されたポリプロピレン系樹脂の具体例としては、Aristech社製ポリプロピレン『Bepol B−022SP』、Borealis社製ポリプロピレン『Beta(β)−PP BE60−7032』、mayzo社製ポリプロピレン『BNX BETAPP−LN』などが挙げられる。 Specific examples of these particularly preferable β crystal nucleating agents include β crystal nucleating agent “NJESTER NU-100” manufactured by Shin Nippon Rika Co., Ltd., and specific examples of polypropylene resins to which β crystal nucleating agents are added include polypropylene manufactured by Aristech. “Bepol B-022SP”, polypropylene manufactured by Borealis “Beta (β) -PP BE60-7032”, polypropylene manufactured by mayzo “BNX BETAPP-LN”, and the like.
[結晶融解ピーク温度が170℃以上である熱可塑性樹脂(HM樹脂)の説明]
前記結晶融解ピーク温度が170℃以上である熱可塑性樹脂(HM樹脂)は結晶融解ピーク温度が170℃以上であることが重要であり、該熱可塑性樹脂を第1層に含むことにより、本発明の積層多孔性フィルムに優れた耐熱性を付与し、優れたブレイクダウン特性を発現することができるようになる。前記熱可塑性樹脂(HM樹脂)の結晶融解ピ−ク温度の上限については特に制限しないが350℃以下であれば、成形加工時に樹脂が劣化することが抑制され、得られる積層多孔性フィルムの機械的強度が保持できるため好ましい。上限はより好ましくは300℃以下である。
ここでHM樹脂は、JIS K7121に準拠して、示差走査型熱量計を用いて、25℃〜400℃まで加熱速度10℃/分で昇温させた際に、検出される結晶融解温度のピーク値が170℃以上である樹脂を示す。
[Description of Thermoplastic Resin (HM Resin) with Crystal Melting Peak Temperature of 170 ° C. or More]
It is important that the thermoplastic resin (HM resin) having a crystal melting peak temperature of 170 ° C. or higher has a crystal melting peak temperature of 170 ° C. or higher, and the thermoplastic resin is contained in the first layer. The laminated porous film can be provided with excellent heat resistance and can exhibit excellent breakdown characteristics. The upper limit of the crystal melting peak temperature of the thermoplastic resin (HM resin) is not particularly limited, but if it is 350 ° C. or lower, the deterioration of the resin during molding is suppressed, and the resulting laminated porous film machine It is preferable because the mechanical strength can be maintained. The upper limit is more preferably 300 ° C. or lower.
Here H M resin, in compliance with JIS K7121, using a differential scanning calorimeter, when the temperature was raised at a heating rate 10 ° C. / min to 25 ° C. to 400 ° C., the crystalline melting temperature detected A resin having a peak value of 170 ° C. or higher is shown.
HM樹脂としては、前記ポリプロピレン系樹脂(PP樹脂)とは異なる樹脂で、かつ、前記結晶融解ピーク温度の条件を満たすものであれば特に限定されるものではない。また、必要に応じて二種類以上の樹脂の混合物を用いても良い。
具体的には、例えば、ポリメチルペンテン等のポリオレフィン系樹脂;ポリアセタール、ポリエーテルエーテルケトン、もしくはポリフェニレンサルファイド等のポリエーテル系樹脂;6ナイロン、6−6ナイロンもしくは6−12ナイロン等のポリアミド系樹脂;ポリスチレン系樹脂;ポリ塩化ビニル樹脂;フッ素系樹脂;ポリエステル系樹脂;アラミド樹脂等の耐熱性熱可塑性樹脂が挙げられる。
これらは単独で用いても良いし、2種以上混合してもよい。
中でも、ポリエステル系樹脂、ポリスチレン系樹脂、フッ素系樹脂、ポリメチルペンテンからなる群から選択される1種以上の樹脂を好適に使用することができる。
混合するポリプロピレン系樹脂との相溶性の観点から、ポリメチルペンテンが特に好ましい。
H The M resin, with the polypropylene resin (PP resin) is different from the resin, and is not particularly limited as long as it satisfies the requirement of the crystal melting peak temperature. Moreover, you may use the mixture of 2 or more types of resin as needed.
Specifically, for example, polyolefin resins such as polymethyl pentene; polyacetals, Po Riete ether ketone, polyether resins such as also properly polyphenylene sulfide; 6 nylon, 6-6 nylon or 6-12 polyamides such as nylon system resin; polystyrene resins; Po polyvinyl chloride resin; fluorine resin; polyester resins; heat-resistant thermoplastic resin aramid resins.
These may be used alone or in combination of two or more.
Among these, one or more resins selected from the group consisting of polyester resins, polystyrene resins, fluorine resins, and polymethylpentene can be suitably used.
From the viewpoint of compatibility with the polypropylene resin to be mixed, polymethylpentene is particularly preferable.
前記ポリエステル系樹脂としては、ジカルボン酸とジアルコール成分の共重合体が挙げられる。より具体的には、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリトリメチレンテレフタレートまたはポリエチレンナフタレートなどが挙げられるが、本発明の積層多孔性フィルムの耐熱性の向上の観点からは結晶性が高く結晶化速度の大きいポリブチレンテレフタレートがより好適に使用される。
前記ポリエステル系樹脂は公知の方法で製造することもできるし、市販品を使用してもよい。例えば、ポリブチレンテレフタレートとしては商品名「ジュラネックス」(ポリプラスチックス株式会社製)、商品名「ノバデュラン」(三菱エンジニアリングプラスチックス株式会社製)が市販品として入手できる。
Examples of the polyester resin include a copolymer of a dicarboxylic acid and a dialcohol component. More specifically, examples include polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, or polyethylene naphthalate. From the viewpoint of improving the heat resistance of the laminated porous film of the present invention, the crystallization rate is high. A polybutylene terephthalate having a large size is more preferably used.
The polyester resin can be produced by a known method, or a commercially available product may be used. For example, as the polybutylene terephthalate, a trade name “Duranex” (manufactured by Polyplastics Co., Ltd.) and a trade name “Novaduran” (manufactured by Mitsubishi Engineering Plastics Co., Ltd.) are available as commercial products.
前記ポリスチレン系樹脂としてはスチレンの単独重合体が挙げられる。より具体的には、アタクチックポリスチレン、シンジオタクチックポリスチレン等が挙げられる。
これらの中でも、本発明のリチウムイオン電池用セパレータの耐熱性の向上の観点から、結晶性の高いシンジオタクチックポリスチレンがより好適に使用される。
前記ポリスチレン系樹脂は公知の方法で製造することもできるし、市販品を使用してもよい。例えば、シンジオタクチックポリスチレンとしては商品名「ザレック」(出光興産株式会社製)が市販品として入手できる。
Examples of the polystyrene-based resin include homopolymers of styrene. More specifically, examples include atactic polystyrene and syndiotactic polystyrene.
Among these, syndiotactic polystyrene with high crystallinity is more preferably used from the viewpoint of improving the heat resistance of the lithium ion battery separator of the present invention.
The polystyrene resin can be produced by a known method, or a commercially available product may be used. For example, as syndiotactic polystyrene, the trade name “Zarek” (manufactured by Idemitsu Kosan Co., Ltd.) is available as a commercial product.
前記フッ素系樹脂としてはポリテトラフロオロエチレン、エチレン−テトラフルオロエチレン共重合体、テトラフルオロエチレン−ヘキサフルオロプロピレン共重合体、テトラフルオロエチレン−パーフルオロアルコキシビニルエーテル共重合体、ポリフッ化ビニリデンなどが挙げられる。この中でも、成形加工性の観点からポリフッ化ビニリデンが好適に使用される。
前記フッ素系樹脂は公知の方法で製造することもできるし、市販品を使用してもよい。例えば、エチレン−テトラフルオロエチレン共重合体としては商品名「フルオン」(旭硝子株式会社製)、ポリテトラフロオロエチレンとしては「ポリフロン」(ダイキン株式会社製)が市販品として入手できる。
Examples of the fluororesin include polytetrafluoroethylene, ethylene-tetrafluoroethylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoroalkoxy vinyl ether copolymer, and polyvinylidene fluoride. It is done. Among these, polyvinylidene fluoride is preferably used from the viewpoint of moldability.
The fluororesin can be produced by a known method, or a commercially available product may be used. For example, the trade name “Fluon” (manufactured by Asahi Glass Co., Ltd.) is available as an ethylene-tetrafluoroethylene copolymer, and “Polyfluorone” (manufactured by Daikin Co., Ltd.) is commercially available as polytetrafluoroethylene.
前記HM樹脂の溶融時の粘度は特に制限されるものではないが、成形加工時においてPP樹脂との分散状態を向上させ、より均一性・均質性の高い積層多孔性フィルムとするためには、PP樹脂に類似した粘度のものを選ぶことが好ましい。溶融粘度は一般に、樹脂の分子量により調整可能である。 The viscosity at the time of melting of the HM resin is not particularly limited, but in order to improve the dispersion state with the PP resin at the time of molding and to make a laminated porous film with higher uniformity and homogeneity, It is preferable to select one having a viscosity similar to that of PP resin. The melt viscosity can generally be adjusted by the molecular weight of the resin.
[他の成分の説明]
第1層および第2層のいずれにおいても前述した成分のほか、本発明の効果を著しく阻害しない範囲内で、一般に樹脂組成物に配合される添加剤を適宜添加できる。前記添加剤としては、成形加工性、生産性および積層多孔性フィルムの諸物性を改良・調整する目的で添加される、耳などのトリミングロス等から発生するリサイクル樹脂やシリカ、タルク、カオリン、炭酸カルシウム等の無機粒子、酸化チタン、カーボンブラック等の顔料、難燃剤、耐候性安定剤、耐熱安定剤、帯電防止剤、溶融粘度改良剤、架橋剤、滑剤、核剤、可塑剤、老化防止剤、酸化防止剤、光安定剤、紫外線吸収剤、中和剤、防曇剤、アンチブロッキング剤、スリップ剤または着色剤などの添加剤が挙げられる。具体的には、「プラスチックス配合剤」のP154〜P158に記載されている酸化防止剤、P178〜P182に記載されている紫外線吸収剤、P271〜P275に記載されている帯電防止剤としての界面活性剤、P283〜294に記載されている滑剤などが挙げられる。
[Description of other ingredients]
In any of the first layer and the second layer, in addition to the components described above, additives generally blended in the resin composition can be added as appropriate within a range that does not significantly impair the effects of the present invention. Examples of the additive include recycling resin, silica, talc, kaolin, carbonic acid, etc., which are added for the purpose of improving / adjusting the processability, productivity, and various physical properties of the laminated porous film. Inorganic particles such as calcium, pigments such as titanium oxide and carbon black, flame retardants, weathering stabilizers, heat stabilizers, antistatic agents, melt viscosity improvers, crosslinking agents, lubricants, nucleating agents, plasticizers, anti-aging agents And additives such as antioxidants, light stabilizers, ultraviolet absorbers, neutralizers, antifogging agents, antiblocking agents, slip agents, and coloring agents. Specifically, the interfaces as antioxidants described in P154 to P158 of PLASTICS compounding agents, UV absorbers described in P178 to P182, and antistatic agents described in P271 to P275 Activators, lubricants described in P283-294, and the like.
また、必要に応じて第1層および第2層には、積層多孔性フィルムの耐熱特性、具体的にはBD特性を損なわない範囲で熱可塑性エラストマー等のゴム成分と呼ばれているものを添加しても良い。熱可塑性エラストマーとしては、スチレン・ブタジエン系、ポリオレフィン系、ウレタン系、ポリエステル系、ポリアミド系、1,2−ポリブタジエン、ポリ塩化ビニル系、アイオノマーなどが挙げられる。 If necessary, the first layer and the second layer may be added with what is called a rubber component such as a thermoplastic elastomer within a range that does not impair the heat resistance characteristics of the laminated porous film, specifically, the BD characteristics. You may do it. Examples of the thermoplastic elastomer include styrene / butadiene, polyolefin, urethane, polyester, polyamide, 1,2-polybutadiene, polyvinyl chloride, and ionomer.
[積層多孔性フィルムの構成の説明]
第1実施形態の積層多孔性フィルムの構成は、基本的な構成となる第1層と第2層が少なくとも存在すれば特に限定されるものではない。本発明の積層多孔性フィルムの機能を妨げない範囲で、他の層を積層してもよいし、公知の処理を適宜施すなどしてもよい。
最も単純な構造は、第1層/第2層と積層した2層構造である。
次に単純な構造は、第1層/第2層/第1層、第2層/第1層/第2層として積層した3層構造である。前者の構成の場合、2つある第1層においてHM樹脂の含有量は同じであってもよいし、異なっていても良い。
また、他の機能を持つ層と組み合わせて3種3層の様な形態も可能である。この場合、第1層と第2層と他の機能を持つ層との積層順序は特に問わない。
更に層数としては4層、5層、6層、7層と必要に応じて増やしても良い。第1層が2つ以上ある場合、それぞれの第1層でHM樹脂の含有量が同じであってもよいし、異なっていても良い。
特に好適な実施形態のひとつとして第2層/第1層/第2層の3層構成が例示できる。この3層構成を採用することにより、優れた透気特性と機械的強度を有し、かつBD特性を具備した積層多孔性フィルムを、より一層生産性、経済性よく得ることができる。
[Description of composition of laminated porous film]
The configuration of the laminated porous film of the first embodiment is not particularly limited as long as at least the first layer and the second layer, which are basic configurations, are present. As long as the function of the laminated porous film of the present invention is not hindered, other layers may be laminated, or a known treatment may be appropriately performed.
The simplest structure is a two-layer structure laminated with a first layer / second layer.
Next, a simple structure is a three-layer structure in which a first layer / second layer / first layer and a second layer / first layer / second layer are stacked. In the case of the former configuration, the content of the HM resin in the two first layers may be the same or different.
In addition, it is possible to adopt a form of three types and three layers in combination with layers having other functions. In this case, the stacking order of the first layer, the second layer, and the layer having other functions is not particularly limited.
Further, the number of layers may be increased as necessary to 4 layers, 5 layers, 6 layers, and 7 layers. When there are two or more first layers, the content of the HM resin in each first layer may be the same or different.
One particularly preferred embodiment is a three-layer configuration of second layer / first layer / second layer. By adopting this three-layer structure, a laminated porous film having excellent air permeability characteristics and mechanical strength and having BD characteristics can be obtained with higher productivity and economy.
第1層と第2層との積層比については、第2層(2層以上ある場合はその厚みの合計)/第1層(2層以上ある場合はその厚みの合計)の値が0.1〜10であり、好ましくは0.3〜5であり、より好ましくは0.5〜3である。0.1より小さい場合は第2層が実質的にないものと同じで機械的強度が十分に発揮できないおそれがある。また10より大きい場合は、BD特性が不足するという観点から電池の安全性を確保し難い。また、第1層および第2層以外の他の層が存在する場合は、当該他の層の厚みの合計が全体の厚み1に対し0.1〜0.5、好ましくは0.1〜0.3となるようにしている。 Regarding the stacking ratio between the first layer and the second layer, the value of the second layer (the total thickness when there are two or more layers) / the first layer (the total thickness when there are two or more layers) is 0. It is 1-10, Preferably it is 0.3-5, More preferably, it is 0.5-3. If it is less than 0.1, the mechanical strength may not be sufficiently exhibited because the second layer is substantially absent. On the other hand, when the ratio is larger than 10, it is difficult to ensure the safety of the battery from the viewpoint that the BD characteristics are insufficient. Moreover, when other layers other than a 1st layer and a 2nd layer exist, the sum total of the thickness of the said other layer is 0.1-0.5 with respect to the whole thickness 1, Preferably it is 0.1-0 .3.
[積層多孔性フィルムの形状及び物性の説明]
第1実施形態の積層多孔性フィルムの形態としては平面状、チューブ状の何れであってもよいが、幅方向に製品として数丁取りが可能であることから生産性がよく、さらに内面にコートなどの処理が可能できること等の観点から、平面状がより好ましい。
本発明の積層多孔性フィルムの厚みは1〜500μmであり、好ましくは5〜300μm、更に好ましくは7〜100μmである。特に電池用セパレータとして使用する場合は1〜50μmが好ましく、10〜30μmがより好ましい。電池用セパレータとして使用する場合、厚みが1μm以上、好ましくは10μm以上であれば、実質的に必要な電気絶縁性を得ることができ、例えば大きな電圧がかかった場合にも短絡しにくく安全性に優れる。また、厚みが50μm以下、好ましくは30μm以下であれば、積層多孔性フィルムの電気抵抗が小さくできるので電池の性能を十分に確保することができる。
[Description of shape and physical properties of laminated porous film]
The form of the laminated porous film of the first embodiment may be either a flat shape or a tube shape. However, it is possible to take several products as products in the width direction, and the productivity is good, and the inner surface is coated. The planar shape is more preferable from the viewpoint of being capable of processing such as.
The thickness of the laminated porous film of the present invention is 1 to 500 μm, preferably 5 to 300 μm, and more preferably 7 to 100 μm. When using as a battery separator especially, 1-50 micrometers is preferable and 10-30 micrometers is more preferable. When used as a battery separator, if the thickness is 1 μm or more, preferably 10 μm or more, substantially necessary electrical insulation can be obtained. For example, even when a large voltage is applied, it is difficult to short-circuit and is safe. Excellent. Further, if the thickness is 50 μm or less, preferably 30 μm or less, the electric resistance of the laminated porous film can be reduced, so that the battery performance can be sufficiently secured.
本発明の積層多孔性フィルムの物性は、層構成や積層比、各層の組成、製造方法によって自由に調整できる。
本発明の積層多孔性フィルムは200℃以上でBD特性を発現することが好ましい。すなわち、本発明の積層多孔性フィルムのブレイクダウン温度は200℃以上であることが好ましく、220℃以上であることがより好ましく、240℃以上であることがさらに好ましい。ブレイクダウン温度が200℃以上であれば、例えば本発明の積層多孔性フィルムを電池用セパレータとして電池に組み込んだ際に、電池が蓄熱または発熱し電池用セパレータが高温下に晒された際にも当該電池用セパレータは破膜せず、電池として安全性に優れる。一方、ブレイクダウン温度の上限は特に制限されるものではないが、原材料の加工温度等の関係から400℃程度である。
ここで、「ブレイクダウン温度」とは、実施例に記載の方法で加熱したときに本発明の積層多孔性フィルムが破膜する温度のうち最も低い温度をいう。
ブレイクダウン温度の調整は、HM樹脂の質量比率を増加させる、第1層の層比を大きくするなどして行うことができる。
The physical properties of the laminated porous film of the present invention can be freely adjusted by the layer constitution, the lamination ratio, the composition of each layer, and the production method.
The laminated porous film of the present invention preferably exhibits BD characteristics at 200 ° C. or higher. That is, the breakdown temperature of the laminated porous film of the present invention is preferably 200 ° C. or higher, more preferably 220 ° C. or higher, and further preferably 240 ° C. or higher. If the breakdown temperature is 200 ° C. or higher, for example, when the laminated porous film of the present invention is incorporated into a battery as a battery separator, the battery also stores or generates heat and the battery separator is exposed to a high temperature. The battery separator does not break, and is excellent in safety as a battery. On the other hand, the upper limit of the breakdown temperature is not particularly limited, but is about 400 ° C. due to the processing temperature of raw materials.
Here, the “breakdown temperature” refers to the lowest temperature among the temperatures at which the laminated porous film of the present invention breaks when heated by the method described in the examples.
The breakdown temperature can be adjusted by increasing the mass ratio of the HM resin, increasing the layer ratio of the first layer, or the like.
本発明の積層多孔性フィルムの透気抵抗は1〜10000秒/100mlであり、好ましくは5〜3000秒/100mlであり、更に好ましくは10〜2000秒/100mlである。透気抵抗が10000秒/100mlより大きければ、測定上、透気抵抗の数値は出るものの、連通性のかなり乏しい構造であることを意味しているので、実質的には連通性が無い場合が多い。
透気抵抗はフィルム厚み方向の空気の通り抜け難さを表し、具体的には100mlの空気が該フィルムを通過するのに必要な秒数で表現されている。そのため、数値が小さい方が通り抜け易く、数値が大きい方が通り抜け難いことを意味する。すなわち、その数値が小さい方がフィルムの厚み方向の連通性が良いことを意味し、その数値が大きい方がフィルムの厚み方向の連通性が悪いことを意味する。連通性とはフィルム厚み方向の孔のつながり度合いである。本発明の積層多孔性フィルムの透気抵抗が低ければ様々な用途に使用することができる。例えばリチウムイオン二次電池のセパレータとして使用した場合、透気抵抗が低いということはリチウムイオンの移動が容易であることを意味し、電池性能に優れるため好ましい。
The air-permeable resistance of the laminated porous film of the present invention is 1 to 10,000 seconds / 100 ml, preferably 5 to 3000 seconds / 100 ml, and more preferably 10 to 2000 seconds / 100 ml. If the air resistance is greater than 10,000 seconds / 100 ml, the numerical value of the air resistance will be obtained in the measurement, but it means that the structure is quite poor in communication, so there may be substantially no communication. Many.
The air permeation resistance represents the difficulty of air passage in the film thickness direction, and is specifically expressed in the number of seconds required for 100 ml of air to pass through the film. Therefore, it means that the smaller the numerical value is, the easier it is to pass through, and the higher numerical value is, the more difficult it is to pass. That is, a smaller value means better communication in the thickness direction of the film, and a larger value means poor communication in the thickness direction of the film. Communication is the degree of connection of holes in the film thickness direction. If the air permeability resistance of the laminated porous film of the present invention is low, it can be used for various applications. For example, when used as a separator of a lithium ion secondary battery, a low air permeability resistance means that lithium ions can be easily transferred, which is preferable because the battery performance is excellent.
本発明の積層多孔性フィルムにおいては空孔率が5〜80%であることが好ましく、更に好ましくは20〜70%である。空孔率は多孔構造を規定する為の重要なファクターである。空孔率が5%以上であれば、連通性を確保し透気特性に優れた積層多孔性フィルムとすることができる。一方、空孔率が80%以下であれば、微細孔が増えすぎてフィルムの機械的強度が低下する問題もなくなり、ハンドリングの観点からも好ましい。
例えば、空孔率を増加する手段としては、第1層におけるHM樹脂の質量比率を増加させる手段があるほか、延伸温度を本発明で規定する範囲内でより低い温度とする手段が有効である。
なお、空孔率は実施例に記載の方法で測定している。
In the laminated porous film of the present invention, the porosity is preferably 5 to 80%, more preferably 20 to 70%. The porosity is an important factor for defining the porous structure. When the porosity is 5% or more, it is possible to obtain a laminated porous film that ensures communication and has excellent air permeability. On the other hand, if the porosity is 80% or less, there is no problem that the fine pores increase and the mechanical strength of the film decreases, which is preferable from the viewpoint of handling.
For example, as a means for increasing the porosity, there is a means for increasing the mass ratio of the HM resin in the first layer, and a means for setting the stretching temperature to a lower temperature within the range defined by the present invention is effective. .
The porosity is measured by the method described in the examples.
本発明の積層多孔性フィルムにおいては、厚みにかかわらず、ピン刺し強度が好ましくは1.5N以上、より好ましくは2.0N以上、さらに好ましくは3.0N以上である。
ピン刺し強度は、積層多孔性フィルムの面へ針を突き刺した際の破断強度の値であり、フィルムの機械的強度の指標となる値である。具体的には、実施例に記載の方法で測定している。
ピン刺し強度は、特に本発明の積層多孔性フィルムを電池用セパレータとして使用する場合、電池作製時の短絡、生産性に大きく寄与する。ピン刺し強度が1.5Nより低いと電池作製時に金属エッジ、突起物に接触した際にフィルムが破れやすく、結果として正極と負極が直接接触することによる短絡の発生確率が高くなる。
一方、ピン刺し強度の上限値は特に規定するものではないが、ハンドリングなどの観点から通常10N以下のものが使用される。
In the laminated porous film of the present invention, the pin penetration strength is preferably 1.5 N or more, more preferably 2.0 N or more, and further preferably 3.0 N or more, regardless of the thickness.
The pin puncture strength is a value of breaking strength when a needle is pierced into the surface of the laminated porous film, and is a value serving as an index of mechanical strength of the film. Specifically, it is measured by the method described in the examples.
Pin puncture strength greatly contributes to short-circuiting and productivity during battery production, particularly when the laminated porous film of the present invention is used as a battery separator. If the pin piercing strength is lower than 1.5N, the film is easily broken when contacting the metal edge or protrusion during battery production, and as a result, the probability of occurrence of a short circuit due to direct contact between the positive electrode and the negative electrode increases.
On the other hand, the upper limit value of the pin puncture strength is not particularly defined, but a value of 10 N or less is usually used from the viewpoint of handling.
また、本発明の積層多孔性フィルムにおいては、フィルム物性の観点からその異方性が小さいことが好ましい。異方性の指標として、MD方向(引き取り(流れ)方向)とTD方向(MDの直角方向)の引張強度の比やMD方向とTD方向の引き裂き強度の比で表すことが出来る。
例えば、引張強度を例に挙げると、その比率の割合としては「MD強度/TD強度比」の下限値は、0.05以上、好ましくは0.1以上、より好ましくは0.3以上である。「MD強度/TD強度比」が0.05以上であれば、物性的なバランスが取れており、ハンドリングの他、最終的には多孔構造もより異方性が小さいフィルムとなる。また、「MD強度/TD強度比」の上限値は20以下、好ましくは10以下、より好ましくは7以下である。「MD強度/TD強度比」が20以下であれば、物性的なバランスが取れており、ハンドリングの他、最終的には多孔構造もより異方性が小さいフィルムとなる。
Moreover, in the laminated porous film of this invention, it is preferable that the anisotropy is small from a viewpoint of film physical property. As an anisotropy index, it can be expressed by a ratio of tensile strength in the MD direction (take-off (flow) direction) and TD direction (perpendicular to MD) or a ratio of tear strength in the MD direction and TD direction.
For example, taking tensile strength as an example, the lower limit value of the “MD strength / TD strength ratio” is 0.05 or more, preferably 0.1 or more, more preferably 0.3 or more as a ratio of the ratio. . If the “MD strength / TD strength ratio” is 0.05 or more, the physical properties are balanced, and in addition to handling, the porous structure finally has a smaller anisotropy film. Further, the upper limit value of the “MD strength / TD strength ratio” is 20 or less, preferably 10 or less, more preferably 7 or less. If the “MD strength / TD strength ratio” is 20 or less, the physical properties are balanced, and in addition to handling, the porous structure finally has a smaller anisotropy film.
[積層多孔性フィルムの製造方法の説明]
次に本発明の積層多孔性フィルムの製造方法について説明する。
本発明の積層多孔性フィルムの製造方法は、多孔化と積層の順序によって次の2つに大別される。
(a)各層を多孔化したのち、多孔化された各層をラミネートしたり接着剤等で接着したりして積層する方法。(請求項3に相当する前記第二の発明の製造方法)
(b)各層を積層して積層無孔膜状物を作製し、ついで当該無孔膜状物を多孔化する方法。(請求項1に相当する前記第一の発明の製造方法)
本発明においては、その工程の簡略さ、生産性の観点から(b)の方法を用いることが好ましく、なかでも2層の層間接着性を確保するため共押出で直接積層無孔膜状物を作製した後多孔化する方法が特に好ましい。
[Description of Method for Producing Laminated Porous Film]
Next, the manufacturing method of the laminated porous film of this invention is demonstrated.
The manufacturing method of the laminated porous film of this invention is divided roughly into the following two by the order of porous formation and lamination.
(A) A method of laminating each porous layer after laminating each porous layer or bonding with an adhesive or the like. (Production method of the second invention corresponding to claim 3)
(B) A method of laminating each layer to produce a laminated nonporous film-like material and then making the nonporous film-like material porous. (Production method of the first invention corresponding to claim 1)
In the present invention, it is preferable to use the method (b) from the viewpoint of simplification of the process and productivity, and in particular, in order to ensure the interlayer adhesion between the two layers, a directly laminated nonporous film-like material is formed by coextrusion. A method of forming a porous layer after production is particularly preferred.
前記第一の発明の製造方法では、具体的には、PP樹脂およびHM樹脂を含む第1層用の熱可塑性樹脂組成物と、PP樹脂を含みHM樹脂を含まない第2層用の熱可塑性樹脂組成物を用いて、共押出により第1層と第2層の少なくとも2層からなる積層無孔膜状物を作製し、当該積層無孔膜状物を延伸することにより厚み方向に連通性を有する微細孔を多数形成している。
また、前記製造方法においても、共押出における層間接着性を確保するためには、各層のPP樹脂の比率が50質量%以上であることが好ましい。
In the manufacturing method of the first invention, specifically, the thermoplastic resin composition for the first layer containing PP resin and HM resin, and the thermoplastic for the second layer containing PP resin and no HM resin. Using the resin composition, a laminated non-porous film-like material composed of at least two layers of a first layer and a second layer is produced by coextrusion, and the laminated non-porous film-like material is stretched to communicate in the thickness direction. A large number of micropores having the above are formed.
Moreover, also in the said manufacturing method, in order to ensure the interlayer adhesiveness in coextrusion, it is preferable that the ratio of PP resin of each layer is 50 mass% or more.
積層無孔膜状物の作製方法は特に限定されず公知の方法を用いてよいが、例えば押出機を用いて熱可塑性樹脂組成物を溶融し、Tダイから共押出し、キャストロールで冷却固化するという方法が挙げられる。また、チューブラー法により製造した膜状物を切り開いて平面状とする方法も適用できる。
積層無孔膜状物の延伸方法については、ロール延伸法、圧延法、テンター延伸法、同時二軸延伸法などの手法があり、これらを単独あるいは2つ以上組み合わせて一軸延伸あるいは二軸延伸を行う。中でも、多孔構造制御の観点から二軸延伸が好ましい。
The production method of the laminated non-porous film is not particularly limited, and a known method may be used. For example, the thermoplastic resin composition is melted using an extruder, coextruded from a T die, and cooled and solidified with a cast roll. The method is mentioned. Moreover, the method of cutting open the film-like thing manufactured by the tubular method and making it planar is also applicable.
Regarding the stretching method of the laminated non-porous film-like material, there are methods such as a roll stretching method, a rolling method, a tenter stretching method, and a simultaneous biaxial stretching method, and these methods are used alone or in combination of two or more to perform uniaxial stretching or biaxial stretching. Do. Among these, biaxial stretching is preferable from the viewpoint of controlling the porous structure.
以下に、第1実施形態の積層多孔性フィルムの製造方法の詳細を説明する。なお、後述する第2実施形態の積層多孔性フィルムの製造方法に関しても第2層の成分が異なる以外は全く同様である。
まず、第1層を構成することになるPP樹脂およびHM樹脂を含む熱可塑性樹脂組成物を作製する。
例えば、ポリプロピレン系樹脂、β晶核剤、HM樹脂および所望によりその他添加物等の原材料を、好ましくはヘンシェルミキサー、スーパーミキサー、タンブラー型ミキサー等を用いて、または袋の中に全成分を入れてハンドブレンドにて混合した後、一軸あるいは二軸押出機、ニーダー等、好ましくは二軸押出機で溶融混練後、ペレット化し、第1層用樹脂組成物のペレットとする。
Below, the detail of the manufacturing method of the lamination | stacking porous film of 1st Embodiment is demonstrated. The manufacturing method of the laminated porous film of the second embodiment to be described later is exactly the same except that the components of the second layer are different.
First, a thermoplastic resin composition containing PP resin and HM resin that will constitute the first layer is prepared.
For example, raw materials such as polypropylene resin, β crystal nucleating agent, HM resin and other additives as required, preferably using a Henschel mixer, a super mixer, a tumbler type mixer, etc., or putting all ingredients in a bag After mixing by hand blending, it is melt-kneaded with a single-screw or twin-screw extruder, a kneader or the like, preferably a twin-screw extruder, and then pelletized to obtain pellets of the resin composition for the first layer.
次に、第2層を構成することになるPP樹脂を含みHM樹脂を含まない熱可塑性樹脂組成物を作製する。
例えば、ポリプロピレン系樹脂、β晶核剤および所望によりその他添加物等の原材料を、好ましくはヘンシェルミキサー、スーパーミキサー、タンブラー型ミキサー等を用いて、または袋の中に全成分を入れてハンドブレンドにて混合した後、一軸あるいは二軸押出機、ニーダー等、好ましくは二軸押出機で溶融混練後、ペレット化し、第2層用樹脂組成物のペレットとする。
Next, a thermoplastic resin composition that includes the PP resin that will form the second layer and does not include the HM resin is prepared.
For example, raw materials such as polypropylene resin, β crystal nucleating agent and other additives as required, preferably by using a Henschel mixer, a super mixer, a tumbler type mixer, etc. Are mixed and then melt-kneaded with a single-screw or twin-screw extruder, a kneader or the like, preferably a twin-screw extruder, and then pelletized to obtain pellets of the resin composition for the second layer.
前記第1層用樹脂組成物のペレットと前記第2層用樹脂組成物のペレットを別個の押出機に投入し、Tダイ共押出用口金から押出して膜状物を成形する。Tダイの種類としては特に限定されない。例えば本発明の積層多孔性フィルムが2種3層構造をとる場合、Tダイは2種3層用マルチマニホールドタイプでも構わないし、2種3層用フィードブロックタイプでも構わない。
使用するTダイのギャップは、最終的に必要なフィルムの厚み、延伸条件、ドラフト率、各種条件等から決定されるが、一般的には0.1〜3.0mm程度、好ましくは0.5〜1.0mmである。0.1mm未満では生産速度という観点から好ましくなく、また3.0mmより大きければ、ドラフト率が大きくなるので生産安定性の観点から好ましくない。
The pellets of the resin composition for the first layer and the pellets of the resin composition for the second layer are put into separate extruders and extruded from a die for T-die coextrusion to form a film. The type of T die is not particularly limited. For example, when the laminated porous film of the present invention has a two-kind three-layer structure, the T die may be a two-kind three-layer multi-manifold type or a two-kind three-layer feed block type.
The gap of the T die to be used is determined from the final required film thickness, stretching conditions, draft rate, various conditions, etc., but is generally about 0.1 to 3.0 mm, preferably 0.5. -1.0 mm. If it is less than 0.1 mm, it is not preferable from the viewpoint of production speed, and if it is more than 3.0 mm, it is not preferable from the viewpoint of production stability because the draft rate increases.
押出成形において、押出加工温度は樹脂組成物の流動特性や成形性等によって適宜調整されるが、概ね180〜350℃が好ましく、200〜330℃がより好ましく、220〜310℃が更に好ましい。180℃以上の場合、溶融樹脂の粘度が十分に低く成形性に優れ生産性が向上することから好ましい。一方、350℃以下にすることにより、樹脂組成物の劣化、ひいては得られる積層多孔性フィルムの機械的強度の低下を抑制できる。
キャストロールによる冷却固化温度は本発明において非常に重要であり、PP樹脂のβ晶を生成・成長させ、膜状物中のPP樹脂のβ晶の比率を調整することができる。キャストロールの冷却固化温度は好ましくは80〜150℃、より好ましくは90〜140℃、更に好ましくは100〜130℃である。冷却固化温度を80℃以上とすることで冷却固化させた膜状物中のβ晶の比率を十分に増加させることができ好ましい。また、150℃以下とすることで押出された溶融樹脂がキャストロールへ粘着し巻き付いてしまうなどのトラブルが起こりにくく、効率よく膜状物化することが可能であるので好ましい。
In extrusion molding, the extrusion temperature is appropriately adjusted depending on the flow characteristics and moldability of the resin composition, but is generally preferably 180 to 350 ° C, more preferably 200 to 330 ° C, and still more preferably 220 to 310 ° C. A temperature of 180 ° C. or higher is preferable because the viscosity of the molten resin is sufficiently low and the moldability is excellent and the productivity is improved. On the other hand, by setting the temperature to 350 ° C. or lower, it is possible to suppress the deterioration of the resin composition, and hence the mechanical strength of the resulting laminated porous film.
The cooling and solidification temperature by the cast roll is very important in the present invention, and β crystal of PP resin can be generated and grown, and the ratio of β crystal of PP resin in the film can be adjusted. The cooling and solidification temperature of the cast roll is preferably 80 to 150 ° C, more preferably 90 to 140 ° C, and still more preferably 100 to 130 ° C. By setting the cooling and solidifying temperature to 80 ° C. or higher, the ratio of β crystals in the cooled and solidified film can be sufficiently increased, which is preferable. Further, it is preferable to set the temperature to 150 ° C. or lower because troubles such as the extruded molten resin sticking to and wrapping around the cast roll hardly occur and the film can be efficiently formed into a film.
前記温度範囲にキャストロールを設定することで、延伸前の膜状物のPP樹脂のβ晶比率は30〜100%に調整することが好ましい。40〜100%がより好ましく、50〜100%が更に好ましく、60〜100%が最も好ましい。延伸前の膜状物中のβ晶比率を30%以上とすることで、その後の延伸操作により多孔化が行われやすく、透気特性の良い積層多孔性フィルムを得ることができる。
延伸前の膜状物中のβ晶比率は、示差走査型熱量計を用いて、該膜状物を25℃から240℃まで加熱速度10℃/分で昇温させた際に、検出されるポリプロピレン系樹脂のα晶由来の結晶融解熱量(ΔHmα)とβ晶由来の結晶融解熱量(ΔHmβ)を用いて下記式で計算される。
β晶比率(%)=〔ΔHmβ/(ΔHmβ+ΔHmα)〕×100
It is preferable to adjust the β crystal ratio of the PP resin of the film-like material before stretching to 30 to 100% by setting a cast roll in the temperature range. 40-100% is more preferable, 50-100% is still more preferable, and 60-100% is the most preferable. By setting the β crystal ratio in the film-like material before stretching to 30% or more, a porous film can be easily made porous by a subsequent stretching operation, and a laminated porous film having good air permeability can be obtained.
The β crystal ratio in the film before stretching is detected when the film is heated from 25 ° C. to 240 ° C. at a heating rate of 10 ° C./min using a differential scanning calorimeter. It is calculated by the following formula using the heat of crystal melting derived from the α crystal of the polypropylene resin (ΔHmα) and the heat of crystal melting derived from the β crystal (ΔHmβ).
β crystal ratio (%) = [ΔHmβ / (ΔHmβ + ΔHmα)] × 100
ついで、得られた積層無孔膜状物を二軸延伸する。二軸延伸は同時二軸延伸であってもよいし、逐次二軸延伸であってもよい。なかでも、各延伸工程で延伸条件を選択でき、多孔構造を制御し易い逐次二軸延伸がより好ましい。なお、膜状物の引き取り(流れ)方向への延伸を「縦延伸」(MD)と、その直角方向への延伸を「横延伸」(TD)という。 Next, the obtained laminated nonporous membrane is biaxially stretched. Biaxial stretching may be simultaneous biaxial stretching or sequential biaxial stretching. Among these, sequential biaxial stretching is more preferable because the stretching conditions can be selected in each stretching step and the porous structure can be easily controlled. In addition, extending | stretching to the take-up (flow) direction of a film-form thing is called "longitudinal stretching" (MD), and extending | stretching to the orthogonal | vertical direction is called "lateral stretching" (TD).
逐次二軸延伸を用いる場合、延伸温度は用いる樹脂組成物の組成、HM樹脂の結晶融解ピーク温度、PP樹脂の結晶化度等によって適時選択する必要があるが、下記条件の範囲内で選択することが好ましい。
縦延伸での延伸温度は概ね20℃〜130℃、好ましくは40℃〜120℃、更に好ましくは60℃〜110℃の範囲で制御される。また、縦延伸倍率は好ましくは2〜10倍、より好ましくは3〜8倍、更に好ましくは3〜7倍である。前記範囲内で縦延伸を行うことで、延伸時の破断を抑制しつつ、適度な空孔起点を発現させることができる。
縦延伸における延伸温度が20℃以上であれば、延伸時の破断が抑制され、均一な延伸が行われるため好ましい。一方、縦延伸における延伸温度が130℃以下であれば、PP樹脂中の空孔形成と、PP樹脂とHM樹脂の界面剥離による空孔形成の2種の空孔形成が起こるため、効率よく空孔形成を行うことができる。また、このようにして形成された空孔は後の横延伸によって閉塞され難く、例えば横延伸温度を高くした場合にも透気特性を発現することができ、生産上非常に有用である。縦延伸における延伸温度を110℃以下にすれば、当該効果がより顕著に表れる。
When sequential biaxial stretching is used, the stretching temperature needs to be appropriately selected depending on the composition of the resin composition used, the crystal melting peak temperature of the HM resin, the crystallinity of the PP resin, etc., but is selected within the range of the following conditions. It is preferable.
The stretching temperature in the longitudinal stretching is generally controlled in the range of 20 ° C to 130 ° C, preferably 40 ° C to 120 ° C, more preferably 60 ° C to 110 ° C. The longitudinal draw ratio is preferably 2 to 10 times, more preferably 3 to 8 times, and still more preferably 3 to 7 times. By performing longitudinal stretching within the above range, it is possible to develop an appropriate pore starting point while suppressing breakage during stretching.
A stretching temperature in the longitudinal stretching of 20 ° C. or higher is preferable because breakage during stretching is suppressed and uniform stretching is performed. On the other hand, if the stretching temperature in the longitudinal stretching is 130 ° C. or lower, two types of hole formation, namely, hole formation in the PP resin and hole formation by interfacial separation between the PP resin and the HM resin occur. Hole formation can be performed. Further, the pores formed in this way are not easily blocked by the subsequent transverse stretching, and can exhibit air permeability characteristics even when the transverse stretching temperature is raised, for example, which is very useful in production. If the stretching temperature in the longitudinal stretching is set to 110 ° C. or less, the effect becomes more prominent.
一方、横延伸での延伸温度は概ね100℃〜160℃、好ましくは110℃〜150℃、更に好ましくは120℃〜140℃である。また、横延伸倍率は好ましくは2〜10倍、より好ましくは3〜8倍、更に好ましくは4〜7倍である。前記範囲内で横延伸することで、縦延伸により形成された空孔起点を適度に拡大させ、微細な多孔構造を発現させることができるため、結果として優れた透気特性を有する積層多孔性フィルムを得ることができる。
特に、前記のように比較的低い温度で縦延伸をすれば空孔が閉塞されにくくなっているため、横延伸での延伸温度は120℃以上とするほうが延伸性に優れ、生産性が向上する点から好ましい。
On the other hand, the stretching temperature in transverse stretching is generally 100 ° C to 160 ° C, preferably 110 ° C to 150 ° C, more preferably 120 ° C to 140 ° C. The transverse draw ratio is preferably 2 to 10 times, more preferably 3 to 8 times, and further preferably 4 to 7 times. By transversely stretching within the above range, the pore starting point formed by longitudinal stretching can be appropriately expanded and a fine porous structure can be expressed, and as a result, a laminated porous film having excellent air permeability characteristics. Can be obtained.
In particular, if the longitudinal stretching is performed at a relatively low temperature as described above, the pores are less likely to be clogged. Therefore, the stretching temperature in the lateral stretching is superior to the stretchability and the productivity is improved when the stretching temperature is 120 ° C. It is preferable from the point.
本発明においては、延伸工程での多孔化を制御し、理想的な多孔構造を形成させることで優れた透気特性を発揮させるために、横(TD)延伸における延伸温度(TTD)と縦(MD)延伸における延伸温度(TMD)との差、TTD−TMDが30℃〜60℃であることが好ましく、40℃〜55℃であることがより好ましい。 In the present invention, the stretching temperature (T TD ) and the longitudinal length in transverse (TD) stretching are used to control the porosity in the stretching step and to exhibit excellent air permeability properties by forming an ideal porous structure. (MD) the difference between the stretching temperature (T MD) in the stretching is preferably T TD -T MD is 30 ° C. to 60 ° C., and more preferably 40 ° C. to 55 ° C..
前記延伸工程の延伸速度としては、500〜12000%/分が好ましく、1500〜10000%/分がより好ましく、2500〜8000%/分であることが更に好ましい。この範囲の延伸速度であれば効率よく本発明の積層多孔性フィルムを製造することができる。 The stretching speed in the stretching step is preferably 500 to 12000% / min, more preferably 1500 to 10,000% / min, and further preferably 2500 to 8000% / min. When the stretching speed is in this range, the laminated porous film of the present invention can be produced efficiently.
このようにして得られた積層多孔性フィルムは、寸法安定性の改良等を目的として100℃〜170℃、好ましくは120℃〜150℃程度の温度で熱処理を行うことが好ましい。熱処理工程中には、必要に応じて1〜15%の弛緩処理を施しても良い。この熱処理後均一に冷却して巻き取ることにより、本発明の積層多孔性フィルムが得られる。 The laminated porous film thus obtained is preferably heat-treated at a temperature of about 100 ° C. to 170 ° C., preferably about 120 ° C. to 150 ° C. for the purpose of improving dimensional stability. During the heat treatment step, a relaxation treatment of 1 to 15% may be performed as necessary. The laminated porous film of the present invention can be obtained by uniformly cooling and winding after this heat treatment.
本発明の製造方法で製造した積層多孔性フィルムは、透気性が要求される種々の用途に応用することができる。電池用セパレータ;使い捨て紙オムツ、生理用品等の体液吸収用パットもしくはベッドシーツ等の衛生材料;手術衣もしくは温湿布用基材等の医療用材料;ジャンパー、スポーツウエアもしくは雨着等の衣料用材料;壁紙、屋根防水材、断熱材、吸音材等の建築用材料;乾燥剤;防湿剤;脱酸素剤;使い捨てカイロ;鮮度保持包装もしくは食品包装等の包装材料等の資材として極めて好適に使用できる。 The laminated porous film produced by the production method of the present invention can be applied to various uses that require air permeability. Battery separators; Sanitary materials such as disposable paper diapers and sanitary items such as pads and bed sheets for absorbing body fluids; Medical materials such as surgical clothing or base materials for hot compresses; Materials for clothing such as jumpers, sportswear, and rainwear ; Building materials such as wallpaper, roof waterproofing material, heat insulating material, sound absorbing material; desiccant; moisture-proofing agent; oxygen scavenger; disposable body warmer; can be used very suitably as a material for packaging materials such as freshness preservation packaging or food packaging .
[参考第2実施形態の説明]
参考第2実施形態は、第2層もPP樹脂とHM樹脂との混合樹脂とし、該HM樹脂の配合割合を第1層よりも小さくしている点で、第1実施形態と相違する。即ち、参考第2実施形態ではPP樹脂とHM樹脂との混合樹脂を含む層を複数層設け、これらの層のHM樹脂の配合割合を相違させている。
[Description of Reference Second Embodiment]
The reference second embodiment is different from the first embodiment in that the second layer is also a mixed resin of PP resin and HM resin, and the blending ratio of the HM resin is smaller than that of the first layer. That is, in the reference second embodiment, a plurality of layers containing a mixed resin of PP resin and HM resin are provided, and the blending ratio of HM resin in these layers is made different.
具体的には、HM樹脂の含有量が最も多い層(第1層)におけるHM樹脂の含有率(質量%)と、HM樹脂の含有量が最も少ない層(第2層)におけるHM樹脂の含有率(質量%)との差は、1〜50質量%が好ましく、5〜40質量%がより好ましく、10〜30質量%がさらに好ましい。
前記第1層と第2層以外の層におけるPP樹脂とHM樹脂との混合質量比は、PP樹脂/HM樹脂=10〜99/90〜1であることが好ましく、30〜99/70〜1がより好ましく、60〜99/40〜1が更に好ましく、60〜90/40〜10が特に好ましい。
BD特性を発現する層は第1層の少なくとも1層存在すればよいから、それ以外の層についてはBD特性を必ずしも必要とされない。ゆえに、HM樹脂の含有量がPP樹脂とHM樹脂との総和質量100質量%中1質量%以上であればよい。一方、HM樹脂の含有量がPP樹脂とHM樹脂との総和質量100質量%中90質量%を超えると多孔化が難しくなる。
他の成分および構成は第1実施形態と同様のため説明を省略する。
Specifically, the content (mass%) of the HM resin in the layer having the highest content of HM resin (first layer) and the content of the HM resin in the layer having the lowest content of HM resin (second layer). The difference from the rate (% by mass) is preferably 1 to 50% by mass, more preferably 5 to 40% by mass, and still more preferably 10 to 30% by mass.
The mixed mass ratio of the PP resin and the HM resin in the layers other than the first layer and the second layer is preferably PP resin / HM resin = 10 to 99/90 to 1, and 30 to 99/70 to 1 Is more preferable, 60 to 99/40 to 1 is still more preferable, and 60 to 90/40 to 10 is particularly preferable.
Since it is sufficient that at least one layer of the first layer is present in the BD characteristic, the BD characteristic is not necessarily required for the other layers. Therefore, the content of the HM resin may be 1% by mass or more in 100% by mass of the total mass of the PP resin and the HM resin. On the other hand, if the content of the HM resin exceeds 90% by mass in 100% by mass of the total mass of the PP resin and the HM resin, it becomes difficult to make the material porous.
Since other components and configurations are the same as those in the first embodiment, description thereof is omitted.
前記第1実施形態の積層多孔性フィルムは各種電子機器等の電源として利用されるリチウムイオン二次電池等の非水電解液電池用セパレータとして好適に用いられる。
前記電池用セパレータとして使用する場合は、透気抵抗を5〜3000秒/100mlにすることが好ましく、より好ましくは20〜2000秒/100mlであり、更に好ましくは50〜1000秒/100mlであり、最も好ましくは50〜500秒/100mlである。
透気抵抗が3000秒/100mlより大きければ、測定上、透気抵抗の数値は出るものの、連通性のかなり乏しい構造であることを意味しているので、実質的には電池用セパレータとして利用できる程度の連通性は無い場合が多い。すなわち、透気抵抗が3000秒/100ml以下であればイオン伝導性を確保し十分な電池特性を得ることができるため好ましい。一方、透気抵抗が5秒/100ml以上であれば孔径が適度に小さく、積層多孔性フィルムの機械的強度が維持できるため好ましい。
透気抵抗はセパレータの厚み方向の空気の通り抜け難さを表し、具体的には100mlの空気が該セパレータを通過するのに必要な秒数で表現されている。そのため、数値が小さい方が通り抜け易く、数値が大きい方が通り抜け難いことを意味する。すなわち、その数値が小さい方がセパレータの厚み方向の連通性が良いことを意味し、その数値が大きい方がセパレータの厚み方向の連通性が悪いことを意味する。連通性とはセパレータの厚み方向の孔のつながり度合いである。本発明のリチウムイオン電池用セパレータの透気抵抗が低いということはリチウムイオンの移動が容易であることを意味し、電池性能に優れるため好ましい。
The laminated porous film of the first embodiment is suitably used as a separator for a non-aqueous electrolyte battery such as a lithium ion secondary battery used as a power source for various electronic devices.
When used as the battery separator, the air permeability resistance is preferably 5 to 3000 seconds / 100 ml, more preferably 20 to 2000 seconds / 100 ml, still more preferably 50 to 1000 seconds / 100 ml, Most preferably, it is 50 to 500 seconds / 100 ml.
If the air resistance is greater than 3000 seconds / 100 ml, the numerical value of the air resistance is obtained in the measurement, but it means that the structure is quite poor in communication, so it can be practically used as a battery separator. There is often no degree of connectivity. That is, it is preferable that the air permeation resistance is 3000 seconds / 100 ml or less because ion conductivity can be secured and sufficient battery characteristics can be obtained. On the other hand, if the air permeation resistance is 5 seconds / 100 ml or more, it is preferable because the pore diameter is appropriately small and the mechanical strength of the laminated porous film can be maintained.
The air permeation resistance represents the difficulty of air passing through in the thickness direction of the separator, and is specifically expressed by the number of seconds required for 100 ml of air to pass through the separator. Therefore, it means that the smaller the numerical value is, the easier it is to pass through, and the higher numerical value is, the more difficult it is to pass. That is, a smaller value means that the separator in the thickness direction is better, and a larger value means that the separator is less in the thickness direction. Communicability is the degree of connection of holes in the thickness direction of the separator. The low air permeability resistance of the lithium ion battery separator of the present invention means that lithium ions can be easily transferred, which is preferable because of excellent battery performance.
また本発明の積層多孔性フィルムを電池用セパレータとして使用する場合、空孔率は30〜70%であることが好ましく、更には40〜65%であることが特に好ましい。空孔率が30%以上であるとイオン透過性を確保して十分な電池性能を得ることができる。一方で、電池の安全性の観点からは空孔率が70%以下であることが好ましい。 When the laminated porous film of the present invention is used as a battery separator, the porosity is preferably 30 to 70%, more preferably 40 to 65%. If the porosity is 30% or more, ion permeability can be ensured and sufficient battery performance can be obtained. On the other hand, from the viewpoint of battery safety, the porosity is preferably 70% or less.
[電池用セパレータの説明]
次に、前記積層多孔性フィルムを電池用セパレータとして収容している非水電解液電池について、図1を参照して説明する。
正極板21、負極板22の両極は電池用セパレータ10を介して互いに重なるようにして渦巻き状に捲回し、巻き止めテープで外側を止めて捲回体としている。この渦巻き状に巻回する際、電池用セパレータ10は厚みが5〜40μmであることがなかでも好ましく、5〜30μmであることが特に好ましい。厚みを5μm以上とすることにより電池用セパレータが破れにくくなり、40μm以下にすることにより所定の電池缶に捲回して収納する際電池面積を大きくとることができ、ひいては電池容量を大きくすることができる。
[Explanation of battery separator]
Next, a non-aqueous electrolyte battery containing the laminated porous film as a battery separator will be described with reference to FIG.
Both electrodes of the positive electrode plate 21 and the negative electrode plate 22 are wound in a spiral shape so as to overlap each other via the battery separator 10, and the outside is stopped with a winding tape to form a wound body. When winding in this spiral shape, the battery separator 10 preferably has a thickness of 5 to 40 μm, particularly preferably 5 to 30 μm. When the thickness is 5 μm or more, the battery separator is not easily broken, and when the thickness is 40 μm or less, the battery area can be increased when wound into a predetermined battery can and thus the battery capacity can be increased. it can.
前記正極板21、電池用セパレータ10および負極板22を一体的に巻き付けた捲回体を有底円筒状の電池ケース内に収容し、正極および負極のリード体24、25と溶接する。ついで、前記電解質を電池缶内に注入し、電池用セパレータ10などに十分に電解質が浸透した後、電池缶の開口周縁にガスケット26を介して正極蓋27を封口し、予備充電、エージングを行い、筒型の非水電解液電池を作製している。 A wound body in which the positive electrode plate 21, the battery separator 10 and the negative electrode plate 22 are integrally wound is housed in a bottomed cylindrical battery case and welded to the positive and negative electrode lead bodies 24 and 25. Next, the electrolyte is injected into the battery can, and after the electrolyte has sufficiently penetrated into the battery separator 10 or the like, the positive electrode lid 27 is sealed around the opening periphery of the battery can via the gasket 26, and precharging and aging are performed. A cylindrical non-aqueous electrolyte battery is manufactured.
電解液としては、リチウム塩を電解液とし、これを有機溶媒に溶解した電解液が用いられる。有機溶媒としては特に限定されるものではないが、例えばプロピレンカーボネート、エチレンカーボネート、ブチレンカーボネート、γ−ブチロラクトン、γ−バレロラクトン、ジメチルカーボネート、プロピオン酸メチルもしくは酢酸ブチルなどのエステル類、アセトニトリル等のニトリル類、1,2−ジメトキシエタン、1,2−ジメトキシメタン、ジメトキシプロパン、1,3−ジオキソラン、テトラヒドロフラン、2−メチルテトラヒドロフランもしくは4−メチル−1,3−ジオキソランなどのエーテル類、またはスルホランなどが挙げられ、これらを単独でまたは二種類以上を混合して用いることができる。
なかでも、エチレンカーボネート1質量部に対してメチルエチルカーボネートを2質量部混合した溶媒中に六フッ化リン酸リチウム(LiPF6)を1.4mol/Lの割合で溶解した電解質が好ましい。
As the electrolytic solution, an electrolytic solution in which a lithium salt is used as an electrolytic solution and is dissolved in an organic solvent is used. The organic solvent is not particularly limited, but for example, propylene carbonate, ethylene carbonate, butylene carbonate, γ-butyrolactone, γ-valerolactone, esters such as dimethyl carbonate, methyl propionate or butyl acetate, and nitriles such as acetonitrile. 1,2-dimethoxyethane, 1,2-dimethoxymethane, dimethoxypropane, 1,3-dioxolane, ethers such as tetrahydrofuran, 2-methyltetrahydrofuran or 4-methyl-1,3-dioxolane, or sulfolane These may be used alone or in combination of two or more.
Among them, an electrolyte obtained by dissolving lithium hexafluorophosphate (LiPF 6) at a rate of 1.4 mol / L in a solvent obtained by mixing 2 parts by mass of methyl ethyl carbonate relative to ethylene carbonate 1 part by weight is preferred.
負極としてはアルカリ金属またはアルカリ金属を含む化合物をステンレス鋼製網などの集電材料と一体化させたものが用いられる。前記アルカリ金属としては、例えばリチウム、ナトリウムまたはカリウムなどが挙げられる。前記アルカリ金属を含む化合物としては、例えばアルカリ金属とアルミニウム、鉛、インジウム、カリウム、カドミウム、スズもしくはマグネシウムなどとの合金、さらにはアルカリ金属と炭素材料との化合物、低電位のアルカリ金属と金属酸化物もしくは硫化物との化合物などが挙げられる。
負極に炭素材料を用いる場合、炭素材料としてはリチウムイオンをドープ、脱ドープできるものであればよく、例えば黒鉛、熱分解炭素類、コークス類、ガラス状炭素類、有機高分子化合物の焼成体、メソカーボンマイクロビーズ、炭素繊維、活性炭などを用いることができる。
As the negative electrode, an alkali metal or a compound containing an alkali metal integrated with a current collecting material such as a stainless steel net is used. Examples of the alkali metal include lithium, sodium, and potassium. Examples of the compound containing an alkali metal include an alloy of an alkali metal and aluminum, lead, indium, potassium, cadmium, tin or magnesium, a compound of an alkali metal and a carbon material, a low potential alkali metal and a metal oxide, and the like. Or a compound with a sulfide or the like.
When a carbon material is used for the negative electrode, the carbon material may be any material that can be doped and dedoped with lithium ions, such as graphite, pyrolytic carbons, cokes, glassy carbons, a fired body of an organic polymer compound, Mesocarbon microbeads, carbon fibers, activated carbon and the like can be used.
本実施形態では、負極として、フッ化ビニリデンをN−メチルピロリドンに溶解させた溶液に平均粒径10μmの炭素材料を混合してスラリーとし、この負極合剤スラリーを70メッシュの網を通過させて大きな粒子を取り除いた後、厚み18μmの帯状の銅箔からなる負極集電体の両面に均一に塗布して乾燥させ、その後、ロールプレス機により圧縮成形した後、切断し、帯状の負極板としたものを用いている。 In this embodiment, as a negative electrode, a carbon material having an average particle size of 10 μm is mixed with a solution in which vinylidene fluoride is dissolved in N-methylpyrrolidone to form a slurry, and this negative electrode mixture slurry is passed through a 70-mesh net. After removing the large particles, uniformly apply to both sides of the negative electrode current collector made of a strip-shaped copper foil having a thickness of 18 μm and dry, then compress and mold with a roll press machine, cut, and strip the negative electrode plate. We use what we did.
正極としては、リチウムコバルト酸化物、リチウムニッケル酸化物、リチウムマンガン酸化物、二酸化マンガン、五酸化バナジウムもしくはクロム酸化物などの金属酸化物、二硫化モリブデンなどの金属硫化物などが活物質として用いられ、これらの正極活物質に導電助剤やポリテトラフルオロエチレンなどの結着剤などを適宜添加した合剤を、ステンレス鋼製網などの集電材料を芯材として成形体に仕上げたものが用いられる。 As the positive electrode, lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, manganese dioxide, metal oxide such as vanadium pentoxide or chromium oxide, metal sulfide such as molybdenum disulfide, etc. are used as active materials. , These positive electrode active materials are combined with conductive additives and binders such as polytetrafluoroethylene as appropriate, and finished with a current collector material such as a stainless steel mesh as a core material. It is done.
本実施形態では、正極としては、下記のようにして作製される帯状の正極板を用いている。すなわち、リチウムコバルト酸化物(LiCoO2)に導電助剤としてリン状黒鉛を(リチウムコバルト酸化物:リン状黒鉛)の質量比90:5で加えて混合し、この混合物と、ポリフッ化ビニリデンをN−メチルピロリドンに溶解させた溶液とを混合してスラリーにする。この正極合剤スラリーを70メッシュの網を通過させて大きな粒子を取り除いた後、厚み20μmのアルミニウム箔からなる正極集電体の両面に均一に塗布して乾燥し、その後、ロールプレス機により圧縮成形した後、切断し、帯状の正極板としている。 In the present embodiment, a strip-like positive electrode plate produced as follows is used as the positive electrode. That is, lithium graphite oxide (LiCoO 2 ) is added with phosphorous graphite as a conductive additive at a mass ratio of 90: 5 (lithium cobalt oxide: phosphorous graphite) and mixed, and this mixture and polyvinylidene fluoride are mixed with N -Mix with a solution dissolved in methylpyrrolidone to make a slurry. This positive electrode mixture slurry is passed through a 70-mesh net to remove large particles, and then uniformly applied to both sides of a positive electrode current collector made of an aluminum foil having a thickness of 20 μm, dried, and then compressed by a roll press. After forming, it is cut into a strip-like positive electrode plate.
[実施例の説明]
次に実施例および比較例を示し、本発明の積層多孔性フィルムについて更に詳細に説明するが、本発明はこれらに限定されるものではない。
なお、積層多孔性フィルムの引き取り(流れ)方向を「縦」方向、その直角方向を「横」方向と記載する。
[Description of Examples]
The following Comparative Example and Contact embodiment, will be described in more detail the laminated porous film of the present invention, but the present invention is not limited thereto.
The take-up (flow) direction of the laminated porous film is referred to as a “longitudinal” direction, and the direction perpendicular thereto is referred to as a “lateral” direction.
(実施例、比較例)
表1に示すように、第1層の各原材料をテクノベル株式会社製の同方向2軸押出機(口径30mmφ、L/D=30)に、第2層の各原材料を東芝機械株式会社製の同方向2軸押出機(口径40mmφ、L/D=32)に投入し、290℃で溶融混合後、表1に記載の層構成に応じて単層、2種2層または2種3層のフィードブロックを通じてTダイより押出し、表1に記載の温度のキャストロールで引き取り、冷却固化させて、幅300mm、厚み180μmの未延伸膜状物を得た。この際、溶融樹脂膜状物とキャストロールの(冷却)接触時間は12秒であった。
次いで、得られた未延伸膜状物に対し、フィルムロール縦延伸機を用い、ロール間で表1に記載の延伸温度および延伸倍率で縦方向に延伸を行った後、次いで京都機械社製フィルムテンター設備にて、表1に記載の延伸温度および延伸倍率で横方向に延伸した。更に表1に記載の条件で熱弛緩を行い、積層多孔性フィルムを得た。
(Example, the ratio Comparative Examples)
As shown in Table 1, each raw material of the first layer was transferred to the same direction twin screw extruder (caliber: 30 mmφ, L / D = 30) manufactured by Technobel, and each raw material of the second layer was manufactured by Toshiba Machine Co., Ltd. Into the same direction twin screw extruder (caliber 40 mmφ, L / D = 32), melt and mix at 290 ° C., then, depending on the layer structure described in Table 1, single layer, two types or two layers It was extruded from a T-die through a feed block, taken up with a cast roll having the temperature shown in Table 1, and cooled and solidified to obtain an unstretched film having a width of 300 mm and a thickness of 180 μm. At this time, the (cooling) contact time between the molten resin film and the cast roll was 12 seconds.
Next, the obtained unstretched film-like material was stretched in the longitudinal direction at a stretching temperature and a stretching ratio shown in Table 1 between rolls using a film roll longitudinal stretching machine, and then a film manufactured by Kyoto Machine Co., Ltd. In a tenter facility, the film was stretched in the transverse direction at the stretching temperature and stretch ratio shown in Table 1. Furthermore, thermal relaxation was performed under the conditions described in Table 1 to obtain a laminated porous film.
実施例、比較例で使用した原材料は以下の通りである。
なお、各ポリプロピレン系樹脂(PP−1、βPP−1、βPP−2)については、パーキンエルマー社製の示差走査型熱量計(DSC−7)を用いて、25℃から240℃まで加熱速度10℃/分で昇温後1分間保持し、次に240℃から25℃まで冷却速度10℃/分で降温後1分間保持し、更に25℃から240℃まで加熱速度10℃/分で再昇温させた場合に、再昇温時に145℃以上160℃未満の範囲にβ晶由来の結晶融解ピーク(Tmβ)が検出されるか否かを併記した。
Example, raw materials were used in the ratio Comparative Examples are as follows.
In addition, about each polypropylene-type resin (PP-1, (beta) PP-1, (beta) PP-2), the heating rate 10 from 25 degreeC to 240 degreeC using the differential scanning calorimeter (DSC-7) by Perkin-Elmer Co., Ltd. Hold at 1 ° C./min and hold for 1 minute, then cool down from 240 ° C. to 25 ° C. at a cooling rate of 10 ° C./min and hold for 1 min. Whether or not a crystal melting peak (Tmβ) derived from the β crystal is detected in the range of 145 ° C. or more and less than 160 ° C. when the temperature is increased again is described.
(a)ポリプロピレン系樹脂
・PP−1:プライムポリプロ社製「プライムPP F300SV(商品名)」(MFR3.0g/10分)
再昇温時には166℃にポリプロピレンのα晶に由来する結晶融解ピーク温度(Tmα)のみが検出され、β晶に由来する結晶融解ピーク温度(Tmβ)は検出されなかった。すなわち、PP−1のみではβ活性を有していなかった。
・βPP−1
前記ポリプロピレン系樹脂(PP−1)100質量部にβ晶核剤であるN,N’−ジシクロヘキシル−2,6−ナフタレンジカルボン酸アミドを0.1質量部添加した後、ハンドブレンドし、東芝機械株式会社製の2軸押出機(口径40mmφ、L/D=32)に投入し、設定温度280℃で溶融混合後、水槽にてストランドを冷却固化し、ペレタイザーにてストランドをカットし、ポリプロピレン系樹脂(PP−1)とβ晶核剤の混合ペレットを作製した。
再昇温時には、ポリプロピレンのβ晶に由来する結晶融解ピーク温度(Tmβ)が154℃に、α晶に由来する結晶融解ピーク温度(Tmα)が168℃に検出された。
すなわち、βPP−1はβ活性を有しており、下記式から算出したβ活性度は80%であった。
β活性度(%)=〔ΔHmβ/(ΔHmβ+ΔHmα)〕×100
ΔHmβ:145℃以上160℃未満の範囲で検出されるβ晶由来の結晶融解熱量
ΔHmα:160℃以上175℃以下に検出されるα晶由来の結晶融解熱量
・βPP−2:β晶核剤の配合されたポリプロピレン樹脂であるAristech社製「Bepol B−022SP(商品名)」(MFR0.3g/10分)のペレットを用いた。
再昇温時には、ポリプロピレンのβ晶に由来する結晶融解ピーク温度(Tmβ)が151℃に、α晶に由来する結晶融解ピーク温度(Tmα)が169℃に検出された。
すなわち、βPP−2はβ活性を有しており、前記式から算出したβ活性度は78%であった。
(A) Polypropylene resin / PP-1: “Prime PP F300SV (trade name)” manufactured by Prime Polypro Co., Ltd. (MFR 3.0 g / 10 min)
At the time of reheating, only the crystal melting peak temperature (Tmα) derived from polypropylene α crystal was detected at 166 ° C., and the crystal melting peak temperature (Tmβ) derived from β crystal was not detected. That is, PP-1 alone did not have β activity.
・ ΒPP-1
After adding 0.1 part by mass of N, N′-dicyclohexyl-2,6-naphthalenedicarboxylic acid amide, which is a β crystal nucleating agent, to 100 parts by mass of the polypropylene resin (PP-1), hand blending is performed. Put into a twin screw extruder manufactured by Co., Ltd. (caliber 40 mmφ, L / D = 32), melt and mix at a set temperature of 280 ° C., cool and solidify the strand in a water bath, cut the strand with a pelletizer, and polypropylene A mixed pellet of resin (PP-1) and β crystal nucleating agent was prepared.
At the time of reheating, a crystal melting peak temperature (Tmβ) derived from polypropylene β crystal was detected at 154 ° C., and a crystal melting peak temperature (Tmα) derived from α crystal was detected at 168 ° C.
That is, βPP-1 has β activity, and the β activity calculated from the following formula was 80%.
β activity (%) = [ΔHmβ / (ΔHmβ + ΔHmα)] × 100
ΔHmβ: Crystal heat of fusion derived from β crystal detected in the range of 145 ° C. or higher and lower than 160 ° C. ΔHmα: Crystal heat of fusion derived from α crystal detected from 160 ° C. or higher and 175 ° C. or lower; βPP-2: β crystal nucleating agent Pellets of “Bepol B-022SP (trade name)” (MFR 0.3 g / 10 min) manufactured by Aristech, which is a blended polypropylene resin, were used.
At the time of reheating, the crystal melting peak temperature (Tmβ) derived from the β crystal of polypropylene was detected at 151 ° C., and the crystal melting peak temperature (Tmα) derived from the α crystal was detected at 169 ° C.
That is, βPP-2 has β activity, and the β activity calculated from the above formula was 78%.
(b)結晶融解ピーク温度が170℃以上である熱可塑性樹脂(HM樹脂)
・SPS:出光興産社製 シンジオタクチックポリスチレン「ZAREC 90Z(商品名)」(Tm272℃、密度1.04g/cm3)
・PBT:ポリプラスチックス社製 ポリブチレンテレフタレート「ジュラコン 600FP(商品名)」(Tm224℃、密度1.43g/cm3)
・PMP:三井化学社製 ポリメチルペンテン「TPX 18R(商品名)」
(Tm237℃、密度0.833g/cm3)
(c)HM樹脂以外の熱可塑性樹脂
・HDPE:プライムポリマ−社製 高密度ポリエチレン「ハイゼックスHZ2200J(商品名)」(Tm134℃、密度0.964g/cm3)
(B) Thermoplastic resin (HM resin) having a crystal melting peak temperature of 170 ° C. or higher.
SPS: Idemitsu Kosan Co., Ltd. Syndiotactic polystyrene “ZAREC 90Z (trade name)” (Tm 272 ° C., density 1.04 g / cm 3 )
PBT: Polybutylene terephthalate “Duracon 600FP (trade name)” manufactured by Polyplastics Co., Ltd. (Tm 224 ° C., density 1.43 g / cm 3 )
・ PMP: Polymethylpentene “TPX 18R (trade name)” manufactured by Mitsui Chemicals
(Tm237 ° C., density 0.833 g / cm 3 )
(C) Thermoplastic resin other than HM resin / HDPE: High-density polyethylene “Hi-Zex HZ2200J (trade name)” manufactured by Prime Polymer Co., Ltd. (Tm 134 ° C., density 0.964 g / cm 3 )
得られた多孔性フィルムについて次のようにして各種特性の測定および評価を行い、その結果を表2にまとめた。 The obtained porous film was measured and evaluated for various properties as follows, and the results are summarized in Table 2.
(1)層比
積層多孔性フィルムの断面を切り出し、走査型電子顕微鏡(日立製作所社製、S−4500)にて観察し、その層構成及び厚みから層比を測定した。
(1) Layer ratio A cross section of the laminated porous film was cut out and observed with a scanning electron microscope (S-4500, manufactured by Hitachi, Ltd.), and the layer ratio was measured from the layer configuration and thickness.
(2)ブレイクダウン温度
得られたフィルムを縦60mm×横60mm角に切り出し、図2(A)に示すように、中央部に40mmΦの円状の穴を空けたアルミ板(材質:JIS規格A5052、サイズ:縦60mm、横60mm、厚み1mm)2枚の間にはさみ、図2(B)に示すように周囲をクリップ(KOKUYO社製、ダブルクリップ『クリ−J35(商品名)』)で拘束した。
アルミ板2枚に拘束した状態のフィルムを150℃以上の5℃刻みの各温度(150℃,155℃,160℃,165℃・・・)に設定したオ−ブン(タバイエスペック社製、タバイギヤオ−ブン『GPH200』、ダンパー閉状態)に入れ、オーブン内部温度が各温度に上がってから、3分間保持した後、取り出して冷却し、フィルムの破膜状態を観察した。破膜が認められた温度をブレイクダウン温度とした。
なお、フィルム片が60mm×60mm角に切り出せない場合は、中央部に40mmΦの円状の穴にフィルムが設置されるように調整し、試料を作成しても構わない。
(2) Breakdown temperature The obtained film was cut into 60 mm × 60 mm square, and as shown in FIG. 2 (A), an aluminum plate (material: JIS standard A5052) with a 40 mmφ circular hole in the center. , Size: 60mm long, 60mm wide, 1mm thick) sandwiched between two sheets and restrained by a clip (manufactured by KOKUYO, double clip “Kuri-J35 (trade name)”) as shown in FIG. 2 (B) did.
An oven (Tabai Espec Co., Ltd., Tabai Giao, Inc.) set to a temperature of 150 ° C or higher in increments of 5 ° C (150 ° C, 155 ° C, 160 ° C, 165 ° C ...). -Bun "GPH200", damper closed state) After the oven internal temperature rose to each temperature, the oven was held for 3 minutes, then taken out and cooled, and the film breaking state was observed. The temperature at which film breakage was observed was taken as the breakdown temperature.
When the film piece cannot be cut into a 60 mm × 60 mm square, the sample may be prepared by adjusting so that the film is placed in a circular hole of 40 mmΦ in the center.
(3)ピン刺し強度
日本農林規格告示1019号に準じ、ピン径1.0mm、先端部0.5R、ピン刺し速度300mm/分の条件で測定した。
ピン刺し強度が3.0N以上の場合を「◎」と、ピン刺し強度が1.5N以上3.0N未満の場合を「○」と、ピン刺し強度が1.5N未満の場合を「×」と評価した。
(3) Pin puncture strength According to Japanese Agricultural Standards Notification No. 1019, the pin puncture strength was measured under the conditions of a pin diameter of 1.0 mm, a tip portion of 0.5R, and a pin puncture speed of 300 mm / min.
“◎” when the pin puncture strength is 3.0N or more, “◯” when the pin puncture strength is 1.5N or more and less than 3.0N, and “X” when the pin puncture strength is less than 1.5N. It was evaluated.
(4)透気抵抗(ガーレ値)
JIS P8117に準拠して透気抵抗(秒/100ml)を測定した。
透気抵抗が500秒/100ml以下の場合を「◎」と、透気抵抗が500秒/100mlを超えて2000秒/100ml以下の場合を「○」と、透気抵抗が2000秒/100mlを超える場合を「×」と評価した。
(4) Air resistance (Gurley value)
The air resistance (second / 100 ml) was measured according to JIS P8117.
When the air permeability resistance is 500 seconds / 100 ml or less, “◎”, when the air resistance exceeds 500 seconds / 100 ml and 2000 seconds / 100 ml or less, “◯” indicates that the air resistance is 2000 seconds / 100 ml. The case where it exceeded was evaluated as "x".
(6)厚み
1/1000mmのダイアルゲージにて、面内の厚みを不特定に30箇所測定しその平均を厚みとした。
(6) Thickness A thickness of 1/1000 mm was used to measure 30 in-plane thicknesses unspecified, and the average was taken as the thickness.
(7)空孔率
空孔率は多孔性フィルム中の空間部分の割合を示す数値である。空孔率は、多孔性フィルムの実質量W1を測定し、樹脂組成物の密度と厚みから空孔率0%の場合の質量W0を計算し、それらの値から下記式に基づき算出した。
空孔率Pv(%)={(W0−W1)/W0}×100
(7) Porosity The porosity is a numerical value indicating the proportion of the space portion in the porous film. The porosity was determined by measuring the substantial amount W1 of the porous film, calculating the mass W0 when the porosity was 0% from the density and thickness of the resin composition, and calculating from these values based on the following formula.
Porosity Pv (%) = {(W0−W1) / W0} × 100
(8)β活性
フィルムをパーキンエルマー社製の示差走査型熱量計(DSC−7)を用いて、25℃から240℃まで加熱速度10℃/分で昇温後1分間保持し、次に240℃から25℃まで冷却速度10℃/分で降温後1分間保持し、更に25℃から240℃まで加熱速度10℃/分で再昇温した。再昇温時にポリプロピレンのβ晶に由来する結晶融解ピーク温度(Tmβ)である145℃〜160℃にピークが検出されるか否かにより、以下のようにβ活性の有無を評価した。
○:Tmβが145℃〜160℃の範囲内に検出された場合(β活性有り)
×:Tmβが145℃〜160℃の範囲内に検出されなかった場合(β活性なし)
なお、β活性の測定は、試料量10mgで、雰囲気ガスを窒素として行った。
(8) β activity The film was heated from 25 ° C. to 240 ° C. at a heating rate of 10 ° C./min for 1 minute using a differential scanning calorimeter (DSC-7) manufactured by PerkinElmer, and then held for 240 minutes. The temperature was lowered from 10 ° C. to 25 ° C. at a cooling rate of 10 ° C./min, held for 1 minute, and further heated from 25 ° C. to 240 ° C. at a heating rate of 10 ° C./min. The presence or absence of β activity was evaluated as follows depending on whether a peak was detected at 145 ° C. to 160 ° C., which is the crystal melting peak temperature (Tmβ) derived from the β crystal of polypropylene at the time of reheating.
○: When Tmβ is detected within the range of 145 ° C to 160 ° C (with β activity)
X: When Tmβ is not detected within the range of 145 ° C to 160 ° C (no β activity)
Note that the β activity was measured with a sample amount of 10 mg and the atmosphere gas as nitrogen.
(9)β晶生成力
前記ブレイクダウン温度の測定の場合と同様に、フィルムを縦60mm×横60mm角に切り出し、図2(A)(B)に示すように固定した。
アルミ板2枚に拘束した状態のフィルムを設定温度180℃、表示温度180℃である送風定温恒温器(ヤマト科学株式会社製、型式DKN602)に入れ3分間保持した後、設定温度を100℃に変更し、10分以上の時間をかけて100℃まで徐冷を行った。表示温度が100℃になった時点でフィルムを取り出し、アルミ板2枚に拘束した状態のまま25℃の雰囲気下で5分間冷却して得られたフィルムについて、以下の測定条件で、中央部の40mmΦの円状の部分について広角X線測定を行った。
・広角X線測定装置:マックサイエンス社製 型番XMP18A
・X線源:CuKα線、出力:40kV、200mA
・走査方法:2θ/θスキャン、2θ範囲:5°〜25°、走査間隔:0.05°、走査速度:5°/min
得られた回折プロファイルについて、ポリプロピレンのβ晶の(300)面に由来するピークより、β晶生成力の有無を以下のように評価した。
○:ピークが2θ=16.0°〜16.5°の範囲に検出された場合(β晶生成力有り)
×:ピークが2θ=16.0°〜16.5°の範囲に検出されなかった場合(β晶生成力なし)
なお、フィルム片が60mm×60mm角に切り出せない場合は、中央部に40mmΦの円状の穴にフィルムが設置されるように調整し、試料を作成しても構わない。
(9) β Crystal Forming Power As in the case of the measurement of the breakdown temperature, the film was cut into a 60 mm × 60 mm square and fixed as shown in FIGS.
The film in a state of being restrained by two aluminum plates is placed in a ventilation constant temperature thermostat (model DKN602, manufactured by Yamato Kagaku Co., Ltd.) having a set temperature of 180 ° C. and a display temperature of 180 ° C., and held for 3 minutes. The temperature was changed and gradually cooled to 100 ° C. over 10 minutes. When the display temperature reaches 100 ° C., the film is taken out and cooled in an atmosphere of 25 ° C. for 5 minutes while being restrained by two aluminum plates. Wide-angle X-ray measurement was performed on a 40 mmφ circular portion.
-Wide-angle X-ray measuring device: manufactured by Mac Science Co., Ltd. Model No. XMP18A
X-ray source: CuKα ray, output: 40 kV, 200 mA
Scanning method: 2θ / θ scan, 2θ range: 5 ° to 25 °, scanning interval: 0.05 °, scanning speed: 5 ° / min
About the obtained diffraction profile, the presence or absence of the β crystal generation force was evaluated from the peak derived from the (300) plane of the β crystal of polypropylene as follows.
◯: When a peak is detected in the range of 2θ = 16.0 ° to 16.5 ° (with β crystal forming ability)
X: When a peak was not detected in the range of 2θ = 16.0 ° to 16.5 ° (no β crystal formation ability)
When the film piece cannot be cut into a 60 mm × 60 mm square, the sample may be prepared by adjusting so that the film is placed in a circular hole of 40 mmΦ in the center.
第1層の組成物に結晶融解ピーク温度が170℃以上である熱可塑性樹脂を混合しなかった比較例1は、ブレイクダウン温度が190℃であり、十分なブレイクダウン特性を発現しなかった。また、ポリプロピレン系樹脂の単層多孔性フィルムからなる比較例2は、ブレイクダウン温度が195℃であり、十分なブレイクダウン特性を発現しなかった。
ポリプロピレン系樹脂と結晶融解ピーク温度が170℃以上である熱可塑性樹脂との混合樹脂を混合した組成物で形成された第1層のみからなる比較例3は、ピン刺し強度が1.10Nと低く、機械的強度が低かった。
これに対し、本発明で規定する範囲内で構成された実施例の積層多孔性フィルムは、ブレイクダウン温度が235℃以上と優れたブレイクダウン特性を具備し、かつ、機械的強度を有し、優れた透気特性も備えており、優れていた。
Comparative Example 1 in which the thermoplastic resin having a crystal melting peak temperature of 170 ° C. or higher was not mixed with the composition of the first layer had a breakdown temperature of 190 ° C. and did not exhibit sufficient breakdown characteristics. Moreover, the comparative example 2 which consists of a single layer porous film of a polypropylene-type resin had a breakdown temperature of 195 degreeC, and did not express sufficient breakdown characteristics.
Comparative Example 3 consisting only of the first layer formed of a composition in which a mixed resin of a polypropylene resin and a thermoplastic resin having a crystal melting peak temperature of 170 ° C. or higher is mixed has a low pin puncture strength of 1.10 N. The mechanical strength was low.
On the other hand, the laminated porous film of the example constituted within the range defined in the present invention has an excellent breakdown characteristic with a breakdown temperature of 235 ° C. or more, and has mechanical strength, It also had excellent air permeability and was excellent.
本発明の製造方法で製造した積層多孔性フィルムは、優れた透気特性と機械的強度と耐熱性を有しているため、電池用セパレータに好適に利用することができる。 Since the laminated porous film produced by the production method of the present invention has excellent air permeability, mechanical strength and heat resistance, it can be suitably used for a battery separator.
10 電池用セパレータ
20 非水電解質電池
21 正極板
22 負極板
DESCRIPTION OF SYMBOLS 10 Battery separator 20 Nonaqueous electrolyte battery 21 Positive electrode plate 22 Negative electrode plate
Claims (10)
前記第1層は、アミド化合物からなるβ晶核剤を配合したポリプロピレン系樹脂に、結晶融解ピーク温度が170℃以上である熱可塑性樹脂を混合した樹脂組成物からなる層であり、
前記第2層は、アミド化合物からなるβ晶核剤を配合したポリプロピレン系樹脂に、前記結晶融解ピーク温度が170℃以上である熱可塑性樹脂は混合していない樹脂組成物からなり、β活性及び/又はβ晶生成力を有する層であり、
透気抵抗が1〜10000秒/100mlであり、ピン刺し強度が1.5N以上であり、ブレイクダウン温度が200℃以上である、積層多孔性延伸フィルム。 A laminated porous stretched film having at least a first layer and a second porous layer,
The first layer is a layer made of a resin composition obtained by mixing a thermoplastic resin having a crystal melting peak temperature of 170 ° C. or higher with a polypropylene resin containing a β crystal nucleating agent made of an amide compound .
The second layer comprises a resin composition in which a thermoplastic resin having a crystal melting peak temperature of 170 ° C. or higher is not mixed with a polypropylene resin in which a β crystal nucleating agent composed of an amide compound is blended, and β activity and / Or a layer having β-crystal formation power,
A laminated porous stretched film having an air permeability resistance of 1 to 10,000 seconds / 100 ml, a pin puncture strength of 1.5 N or more, and a breakdown temperature of 200 ° C. or more.
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