JP5720125B2 - Resin composition for gasket, method for producing the same, and gasket for secondary battery - Google Patents
Resin composition for gasket, method for producing the same, and gasket for secondary battery Download PDFInfo
- Publication number
- JP5720125B2 JP5720125B2 JP2010142584A JP2010142584A JP5720125B2 JP 5720125 B2 JP5720125 B2 JP 5720125B2 JP 2010142584 A JP2010142584 A JP 2010142584A JP 2010142584 A JP2010142584 A JP 2010142584A JP 5720125 B2 JP5720125 B2 JP 5720125B2
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- JP
- Japan
- Prior art keywords
- gasket
- resin composition
- silicone compound
- resin
- molecular weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000011342 resin composition Substances 0.000 title claims description 41
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 229920005989 resin Polymers 0.000 claims description 53
- 239000011347 resin Substances 0.000 claims description 53
- 229920001296 polysiloxane Polymers 0.000 claims description 35
- 150000001875 compounds Chemical class 0.000 claims description 34
- 238000012360 testing method Methods 0.000 claims description 20
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 14
- 229920000412 polyarylene Polymers 0.000 claims description 14
- 238000009826 distribution Methods 0.000 claims description 10
- 239000003792 electrolyte Substances 0.000 claims description 10
- 239000008151 electrolyte solution Substances 0.000 claims description 10
- 238000005227 gel permeation chromatography Methods 0.000 claims description 10
- 238000001746 injection moulding Methods 0.000 claims description 10
- 230000006835 compression Effects 0.000 claims description 8
- 238000007906 compression Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 238000007789 sealing Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 5
- 238000013329 compounding Methods 0.000 claims description 4
- 238000009864 tensile test Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 description 24
- -1 polydimethylsiloxane Polymers 0.000 description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 8
- 239000000835 fiber Substances 0.000 description 8
- 239000004734 Polyphenylene sulfide Substances 0.000 description 7
- 125000000524 functional group Chemical group 0.000 description 7
- 239000008188 pellet Substances 0.000 description 7
- 229920000069 polyphenylene sulfide Polymers 0.000 description 7
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 125000003277 amino group Chemical group 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 229910000077 silane Inorganic materials 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 4
- 229910052979 sodium sulfide Inorganic materials 0.000 description 4
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000010306 acid treatment Methods 0.000 description 3
- 229910052977 alkali metal sulfide Inorganic materials 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011256 inorganic filler Substances 0.000 description 3
- 229910003475 inorganic filler Inorganic materials 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000012779 reinforcing material Substances 0.000 description 3
- 229920002545 silicone oil Polymers 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 229910052582 BN Inorganic materials 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229940117389 dichlorobenzene Drugs 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 150000004677 hydrates Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- HXQGSILMFTUKHI-UHFFFAOYSA-M lithium;sulfanide Chemical compound S[Li] HXQGSILMFTUKHI-UHFFFAOYSA-M 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 229920006122 polyamide resin Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 description 2
- 125000005353 silylalkyl group Chemical group 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 150000003457 sulfones Chemical class 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- JTPNRXUCIXHOKM-UHFFFAOYSA-N 1-chloronaphthalene Chemical compound C1=CC=C2C(Cl)=CC=CC2=C1 JTPNRXUCIXHOKM-UHFFFAOYSA-N 0.000 description 1
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 1
- MZWXWSVCNSPBLH-UHFFFAOYSA-N 3-(3-aminopropyl-methoxy-methylsilyl)oxypropan-1-amine Chemical compound NCCC[Si](C)(OC)OCCCN MZWXWSVCNSPBLH-UHFFFAOYSA-N 0.000 description 1
- ULRCHFVDUCOKTE-UHFFFAOYSA-N 3-[3-aminopropyl(diethoxy)silyl]oxybutan-1-amine Chemical compound NCCC[Si](OCC)(OCC)OC(C)CCN ULRCHFVDUCOKTE-UHFFFAOYSA-N 0.000 description 1
- ZDZYGYFHTPFREM-UHFFFAOYSA-N 3-[3-aminopropyl(dimethoxy)silyl]oxypropan-1-amine Chemical compound NCCC[Si](OC)(OC)OCCCN ZDZYGYFHTPFREM-UHFFFAOYSA-N 0.000 description 1
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 description 1
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- VZXOZSQDJJNBRC-UHFFFAOYSA-N 4-chlorobenzenethiol Chemical compound SC1=CC=C(Cl)C=C1 VZXOZSQDJJNBRC-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 125000004018 acid anhydride group Chemical group 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- IBSGAWQJFSDRBJ-UHFFFAOYSA-M cesium sulfanide Chemical compound [SH-].[Cs+] IBSGAWQJFSDRBJ-UHFFFAOYSA-M 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- QTNDMWXOEPGHBT-UHFFFAOYSA-N dicesium;sulfide Chemical compound [S-2].[Cs+].[Cs+] QTNDMWXOEPGHBT-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000005816 fluoropropyl group Chemical group [H]C([H])(F)C([H])([H])C([H])([H])* 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- YLBPOJLDZXHVRR-UHFFFAOYSA-N n'-[3-[diethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CCO[Si](C)(OCC)CCCNCCN YLBPOJLDZXHVRR-UHFFFAOYSA-N 0.000 description 1
- LIBWSLLLJZULCP-UHFFFAOYSA-N n-(3-triethoxysilylpropyl)aniline Chemical compound CCO[Si](OCC)(OCC)CCCNC1=CC=CC=C1 LIBWSLLLJZULCP-UHFFFAOYSA-N 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 210000000885 nephron Anatomy 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000002347 octyl 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])[H] 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 229920006287 phenoxy resin Polymers 0.000 description 1
- 239000013034 phenoxy resin Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000090 poly(aryl ether) Polymers 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- ZOCLAPYLSUCOGI-UHFFFAOYSA-M potassium hydrosulfide Chemical compound [SH-].[K+] ZOCLAPYLSUCOGI-UHFFFAOYSA-M 0.000 description 1
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910052903 pyrophyllite Inorganic materials 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000012066 reaction slurry Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- LXOXXUIVMOYGST-UHFFFAOYSA-M rubidium(1+);sulfanide Chemical compound [SH-].[Rb+] LXOXXUIVMOYGST-UHFFFAOYSA-M 0.000 description 1
- AHKSSQDILPRNLA-UHFFFAOYSA-N rubidium(1+);sulfide Chemical compound [S-2].[Rb+].[Rb+] AHKSSQDILPRNLA-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Images
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
Description
本発明は、二次電池のガスケットに用いられるガスケット用樹脂組成物、その製造方法及び二次電池用ガスケットに関する。 The present invention relates to a gasket resin composition used for a secondary battery gasket, a method for producing the same, and a secondary battery gasket.
密閉型二次電池は、一般に正極板、負極板及び正極板と負極板との間に配置されたセパレータを含む極板群と、この極板群を浸漬するための電解液とを含む電池素子が一部開口されている電池ケース（外装体）の内部に収容され、電池ケースの開口を封口するための封口体により密閉されている。また、この密閉型二次電池において、例えば正極板と電気的に接続されている正極端子との接点や、負極板と電気的に接続されている負極端子との接点には一対の端子間での短絡防止や電解液の漏出防止のためにガスケットが設けられている。このガスケットには電解液に対する耐電解液性や優れた気密性が要求されている。 A sealed secondary battery generally includes a positive electrode plate, a negative electrode plate, an electrode plate group including a separator disposed between the positive electrode plate and the negative electrode plate, and a battery element including an electrolytic solution for immersing the electrode plate group. Is housed inside a partially opened battery case (exterior body), and is sealed by a sealing body for sealing the opening of the battery case. Further, in this sealed secondary battery, for example, a contact point between the positive electrode terminal electrically connected to the positive electrode plate and a contact point between the negative electrode terminal electrically connected to the negative electrode plate are between a pair of terminals. Gaskets are provided to prevent short circuits and electrolyte leakage. The gasket is required to have resistance to electrolyte and excellent airtightness against the electrolyte.
これらの要求を満たすために、例えば、ガスケット材料として耐湿熱性を向上させたポリアミド樹脂を使用する技術が報告されている（例えば、特許文献１参照。）。しかしながら、耐湿熱性を向上させたポリアミド樹脂の使用により耐湿熱性をわずかに改善することはできるものの、耐電解液性及び気密性の程度はまだ不十分なものであり、近年求められているリチウムイオン二次電池などに代表される密閉型二次電池（蓄電池）に対して要求されるレベルに至るものではなかった。 In order to satisfy these requirements, for example, a technique using a polyamide resin having improved heat and moisture resistance as a gasket material has been reported (for example, see Patent Document 1). However, although the heat and moisture resistance can be slightly improved by using the polyamide resin having improved moisture and heat resistance, the electrolyte solution resistance and the hermeticity are still insufficient. It did not reach the level required for sealed secondary batteries (storage batteries) typified by secondary batteries.
一方、ガスケット材料として、ポリアリーレンスルフィド樹脂又はテトラフルオロエチレン−パーフルオロアルキルビニルエーテル共重合体（ＰＦＡ）樹脂を用いたガスケットが優れた気密性や耐電解液性を有することが報告されている（例えば、特許文献２参照。）。 On the other hand, it has been reported that a gasket using a polyarylene sulfide resin or a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA) resin as a gasket material has excellent airtightness and electrolyte resistance (for example, , See Patent Document 2).
しかしながら、前記特許文献２に記載された材料は、内部媒体の圧力に耐えらず、近年求められているリチウムイオン二次電池等の密閉型二次電池（蓄電池）に対して要求されるレベルに至らず、材料としては不十分であった。
すなわち、近年、高い理論容量の活物質を電極物質として用いることによってリチウムイオン電池の高容量化が進んだ反面、充放電時に３〜４倍といった大きな体積変化を示すようになり、内部媒体の圧力が格段に高くなっている。さらには、ハイブリッド自動車（ＨＶ）や電気自動車（ＥＶ）といった車載用途の比重が高くなった結果、従来よりも高い安全性が要求され、高温・高湿の過酷な条件下でのガスケットの気密性や耐電解液性に対する信頼性が極めて高いレベルで必要となってきている。
このような環境変化のなかで、特に「Ｌｉ／（ＣＦ）n系のコイン型電池」を主として想定し発明された上記樹脂組成物のガスケットでは、気密性及び耐電解質性が不十分なものとなっていた。
そこで、本発明が解決しようとする課題は、リチウムイオン二次電池等の密閉型二次電池（蓄電池）に用いられるガスケット用材料として、より優れた気密性及び耐電解質性を有するガスケット用樹脂組成物、その製造方法及び二次電池用ガスケットを提供することにある。
However, the material described in Patent Document 2 cannot withstand the pressure of the internal medium, and is at a level required for a sealed secondary battery (storage battery) such as a lithium ion secondary battery that has been required in recent years. However, it was insufficient as a material.
That is, in recent years, the use of an active material having a high theoretical capacity as an electrode material has led to an increase in capacity of the lithium ion battery, but on the other hand, a large volume change such as 3 to 4 times during charge / discharge has been shown. Is much higher. Furthermore, as a result of higher specific gravity for in-vehicle applications such as hybrid vehicles (HV) and electric vehicles (EV), higher safety is required than before, and the tightness of gaskets under severe conditions of high temperature and high humidity. And a high level of reliability with respect to electrolyte resistance.
Among such environmental changes, the gasket of the above resin composition invented mainly assuming “Li / (CF) n-based coin-type battery” has insufficient airtightness and electrolyte resistance. It was.
Therefore, the problem to be solved by the present invention is a resin composition for gaskets having better airtightness and electrolyte resistance as a material for gaskets used in sealed secondary batteries (storage batteries) such as lithium ion secondary batteries. An object, a manufacturing method thereof, and a gasket for a secondary battery.
本発明者らは、上記課題を解決すべく鋭意研究した結果、シリコーン化合物と特定範囲のピーク分子量を有したポリアリーレンスルフィド樹脂（以下、「ポリアリーレンスルフィド」は「ＰＡＳ」と略記することがある。）を含有した樹脂組成物が密閉型二次電池用ガスケットとして好ましい応力緩和特性を示し、樹脂組成物を用いた密閉型二次電池用ガスケットが優れた耐電解液性及び気密性を呈することを見いだし、本発明を完成するに至った。 As a result of intensive research aimed at solving the above-mentioned problems, the present inventors have found that polyarylene sulfide resins having a peak molecular weight within a specific range with a silicone compound (hereinafter, “polyarylene sulfide” may be abbreviated as “PAS”). .)) Shows a preferable stress relaxation characteristic as a gasket for a sealed secondary battery, and the sealed secondary battery gasket using the resin composition exhibits excellent electrolytic solution resistance and airtightness. As a result, the present invention has been completed.
すなわち、本発明は、正極、負極、封口体、ガスケット、セパレータ及び電解液から構成される二次電池に用いられるガスケットであって、前記ガスケットがシリコーン化合物（Ａ）及びゲル浸透クロマトグラフィーにより求められる分子量分布のピーク分子量として２８，０００〜１００，０００であるポリアリーレンスルフィド樹脂（Ｂ）を含有するガスケット用樹脂組成物からなることを特徴とする二次電池用ガスケットに関する。
また、本発明は、正極、負極、封口体、ガスケット、セパレータ及び電解液から構成される二次電池に用いられるガスケット用樹脂組成物であって、シリコーン化合物（Ａ）及びゲル浸透クロマトグラフィーにより求められる分子量分布のピーク分子量として２８，０００〜１００，０００であるポリアリーレンスルフィド樹脂（Ｂ）を含有することを特徴とするガスケット用樹脂組成物に関する。
また、本発明は、正極、負極、封口体、ガスケット、セパレータ及び電解液から構成される二次電池に用いられるガスケット用樹脂組成物の製造方法であって、シリコーン化合物（Ａ）及びゲル浸透クロマトグラフィーにより求められる分子量分布のピーク分子量として２８，０００〜１００，０００であるポリアリーレンスルフィド樹脂（Ｂ）を混合することを特徴とするガスケット用樹脂組成物の製造方法に関する。
That is, this invention is a gasket used for the secondary battery comprised from a positive electrode, a negative electrode, a sealing body, a gasket, a separator, and electrolyte solution, Comprising: The said gasket is calculated | required by a silicone compound (A) and gel permeation chromatography. The present invention relates to a gasket for a secondary battery, comprising a gasket resin composition containing a polyarylene sulfide resin (B) having a molecular weight distribution peak molecular weight of 28,000 to 100,000.
Moreover, this invention is a resin composition for gaskets used for the secondary battery comprised from a positive electrode, a negative electrode, a sealing body, a gasket, a separator, and electrolyte solution, Comprising: It calculates | requires by a silicone compound (A) and gel permeation chromatography. The present invention relates to a resin composition for gaskets, which contains a polyarylene sulfide resin (B) having a molecular weight distribution peak molecular weight of 28,000 to 100,000.
The present invention also relates to a method for producing a resin composition for a gasket used in a secondary battery comprising a positive electrode, a negative electrode, a sealing body, a gasket, a separator, and an electrolyte solution, the silicone compound (A) and a gel permeation chromatography. The present invention relates to a method for producing a resin composition for a gasket, comprising mixing a polyarylene sulfide resin (B) having a molecular weight distribution of 28,000 to 100,000 as a peak molecular weight obtained by chromatography.
本発明のガスケット用樹脂組成物は、耐湿熱性及び耐電解液性に優れ、一定歪み下で圧縮されても応力緩和が起こりにくく、ガスケットとして重要な要求特性である気密性を長期間にわたって維持することができる。よって、本発明のガスケット用樹脂組成物は、ノート型パソコン、携帯電話、ビデオカメラ等の電気機器用途、あるいはハイブリッド自動車（ＨＶ）、電気自動車（ＥＶ）等の車載用途に用いられる二次電池、特に高容量リチウムイオン二次電池用のガスケット等に特に有用である。従って、本発明のガスケットは、耐湿熱性及び耐電解液性に優れ、一定歪み下で圧縮されても応力緩和が起こりにくく、長期間にわたって気密性を維持することができる。 The resin composition for gaskets of the present invention is excellent in resistance to moist heat and electrolyte, and is less susceptible to stress relaxation even when compressed under a constant strain, and maintains airtightness, which is an important required characteristic for a gasket, over a long period of time. be able to. Therefore, the resin composition for gaskets of the present invention is a secondary battery used for electric equipment applications such as notebook computers, mobile phones, video cameras, or in-vehicle applications such as hybrid vehicles (HV) and electric vehicles (EV), It is particularly useful for gaskets for high capacity lithium ion secondary batteries. Therefore, the gasket of the present invention is excellent in heat and moisture resistance and electrolytic solution resistance, and even when compressed under a constant strain, stress relaxation hardly occurs and airtightness can be maintained over a long period of time.
本発明で用いるシリコーン化合物（Ａ）は、主鎖にシロキサン結合を有する下記一般式（１）で表されるポリオルガノシロキサンが好ましい。 The silicone compound (A) used in the present invention is preferably a polyorganosiloxane represented by the following general formula (1) having a siloxane bond in the main chain.
Ｒ−〔ＳｉＲ２−Ｏ〕ｎ−Ｒ 一般式（１）
（式中、Ｒは水素原子、有機基を表し、ｎは２以上の整数である。）
R— [SiR 2 —O] n —R Formula (1)
(In the formula, R represents a hydrogen atom or an organic group, and n is an integer of 2 or more.)
これらの中でも、特に上記一般式（１）中のＲが総てメチル基であるポリジメチルシロキサンが好ましく、該ポリジメチルシロキサンのメチル基の一部を、水素原子又はその他の置換基に置き換えたものも好ましい。 Among these, polydimethylsiloxane in which R in the general formula (1) is all methyl groups is preferable, and a part of the methyl groups of the polydimethylsiloxane is replaced with hydrogen atoms or other substituents. Is also preferable.
ここで、その他の置換基としては、炭素原子数２以上のアルキル基、アリール基、ハロゲン化アルキル基、シリルアルキル基、ポリオキシアルキレン基及び反応性官能基が挙げられ、複数のメチル基を置換する場合は、これらの中から、互いに同一あるいは異なるものを選択可能である。 Examples of other substituents include alkyl groups having 2 or more carbon atoms, aryl groups, halogenated alkyl groups, silylalkyl groups, polyoxyalkylene groups, and reactive functional groups. In this case, the same or different ones can be selected from these.
炭素原子数２以上のアルキル基としては、例えばエチル基、プロピル基、ブチル基、オクチル基、ドデシル基等が挙げられる。アリール基としては例えば、フェニル基、トリル基、ナフチル基等が挙げられる。 Examples of the alkyl group having 2 or more carbon atoms include an ethyl group, a propyl group, a butyl group, an octyl group, and a dodecyl group. Examples of the aryl group include a phenyl group, a tolyl group, and a naphthyl group.
ハロゲン化アルキル基としては例えば、フルオロプロピル基、クロロプロピル基等が挙げられる。 Examples of the halogenated alkyl group include a fluoropropyl group and a chloropropyl group.
シリルアルキル基は、下記一般式（２）で表されるものがその代表的な具体例として挙げられる。 Typical examples of the silylalkyl group include those represented by the following general formula (2).
−（ＣＨ２）ｎ−Ｓｉ（ＯＣＨ３）３ 一般式（２）
（式中、ｎは１以上の整数である。）
- (CH 2) n -Si ( OCH 3) 3 Formula (2)
(In the formula, n is an integer of 1 or more.)
ポリオキシアルキレン基は、下記一般式（３）で表されるものがその具体例として挙げられる。 Specific examples of the polyoxyalkylene group include those represented by the following general formula (3).
−〔ＣＨ２〕ｋ−Ｏ−〔Ｃ２Ｈ４Ｏ〕ｌ−〔Ｃ３Ｈ６Ｏ〕ｍ−Ｒ３ 一般式（３）
（式中、ｋ、ｌ、ｍは、０又は正の整数であり、ｌ、ｍは同時に０でない整数をとる。また、Ｒ３は水素原子、アルキル基、アリール基、ハロゲン化アルキル基、シリルアルキル基及び後述する反応性官能基からなる群から選ばれる１種以上の置換基である。）
- [CH 2] k -O- [C 2 H 4 O] l - [C 3 H 6 O] m -R 3 Formula (3)
(In the formula, k, l and m are 0 or a positive integer, and l and m are simultaneously non-zero integers. R 3 is a hydrogen atom, an alkyl group, an aryl group, a halogenated alkyl group, a silyl group. It is one or more substituents selected from the group consisting of an alkyl group and a reactive functional group described later.)
特にシリコーン化合物（Ａ）には、反応性官能基を有することが好ましい。反応性官能基の具体例としては、エポキシ基、アミノ基、メルカプト基、ビニル基、カルボキシル基、水酸基、イソシアネート基、アミド基、アシル基、及びニトリル基、酸無水基等が挙げられる。これらの反応性官能基は主鎖に直接結合していても良く、あるいは主鎖に結合したアルキレン基、ポリオキシアルキレン基等の有機基の末端に結合していても良い。その中で特にカルボキシル基、水酸基、エポキシ基とアミノ基は好ましく、エポキシ基とアミノ基はさらに好ましい。 In particular, the silicone compound (A) preferably has a reactive functional group. Specific examples of the reactive functional group include an epoxy group, amino group, mercapto group, vinyl group, carboxyl group, hydroxyl group, isocyanate group, amide group, acyl group, nitrile group, and acid anhydride group. These reactive functional groups may be directly bonded to the main chain, or may be bonded to the terminal of an organic group such as an alkylene group or a polyoxyalkylene group bonded to the main chain. Among them, a carboxyl group, a hydroxyl group, an epoxy group and an amino group are particularly preferable, and an epoxy group and an amino group are more preferable.
前記シリコーン化合物（Ａ）は、樹脂組成物中で均一に分散されることにより電解液に対する耐久性向上に効果が発揮されるものであり、この観点からシリコーン化合物（Ａ）の粘度（２５℃）は、１０〜１００，０００ｍＰａ・ｓが好ましく、特に１０〜８０，０００ｍＰａ・ｓの範囲にあるオイル状のものが好適である。なお、本発明の樹脂組成物中にシリコーン化合物（Ａ）を均一に分散させるため、シリコーン化合物（Ａ）はシリカなどの無機粉体に担持させたものを用いることが好ましい。 The silicone compound (A) is effective in improving durability against the electrolytic solution by being uniformly dispersed in the resin composition. From this viewpoint, the viscosity (25 ° C.) of the silicone compound (A) Is preferably 10 to 100,000 mPa · s, particularly preferably oily in the range of 10 to 80,000 mPa · s. In addition, in order to disperse | distribute a silicone compound (A) uniformly in the resin composition of this invention, it is preferable to use what carried the silicone compound (A) on inorganic powders, such as a silica.
前記シリコーン化合物（Ａ）中に反応性官能基を含有していると、樹脂組成物へのシリコーン化合物（Ａ）の分散を良好にし、そのため耐衝撃性の向上を計ることができる。さらにシリコーン化合物（Ａ）が成型品表面に滲み出る、いわゆるブリードアウトを抑制する効果がある点からも好ましい。 When a reactive functional group is contained in the silicone compound (A), the silicone compound (A) can be dispersed well in the resin composition, and therefore the impact resistance can be improved. Furthermore, the silicone compound (A) is preferable in that it has an effect of suppressing so-called bleed out, which oozes out on the surface of the molded product.
シリコーン化合物（Ａ）中の反応性官能基の含有率は、耐衝撃性、強靭性の付与により好ましい効果を与えることから、４００ｇ／当量（以下「ｇ／ｅｑ」と略記する。）以上が好ましく、混合の容易さの点で５０，０００ｇ／ｅｑ以下が好ましい。 The content of the reactive functional group in the silicone compound (A) is preferably 400 g / equivalent (hereinafter abbreviated as “g / eq”) or more because it gives a favorable effect by imparting impact resistance and toughness. In view of ease of mixing, 50,000 g / eq or less is preferable.
また、シリコーン化合物（Ａ）の配合量は、ＰＡＳ樹脂（Ｂ）及びシリコーン化合物（Ａ）の合計１００質量部に対して０．１〜１０質量部であることが好ましく、０．３〜５質量部であることがより好ましく、０．５〜３質量部であることが特に好ましい。 Moreover, it is preferable that the compounding quantity of a silicone compound (A) is 0.1-10 mass parts with respect to a total of 100 mass parts of PAS resin (B) and a silicone compound (A), and 0.3-5 mass Part is more preferable, and 0.5 to 3 parts by mass is particularly preferable.
次に、本発明で用いるポリアリーレンスルフィド樹脂（Ｂ）は、ゲル浸透クロマトグラフィーを用いた測定において、２８，０００〜１００，０００の範囲にピーク分子量を有するものであり、より好ましくは３０，０００〜７０，０００の範囲にピーク分子量を有するものである。ピーク分子量が２８，０００未満の場合、靱性不足となるため、一定歪み下での圧縮応力緩和の状況下でクラック等が発生して、気密性が保てない問題がある。一方、ピーク分子量が１００，０００を超える場合は押出機によるペレット化及び射出成形が困難となる問題がある。 Next, the polyarylene sulfide resin (B) used in the present invention has a peak molecular weight in the range of 28,000 to 100,000 in the measurement using gel permeation chromatography, and more preferably 30,000. It has a peak molecular weight in the range of ~ 70,000. When the peak molecular weight is less than 28,000, the toughness is insufficient, so that cracks and the like occur under the condition of relaxation of compressive stress under a constant strain, and there is a problem that the airtightness cannot be maintained. On the other hand, when the peak molecular weight exceeds 100,000, there is a problem that pelletization and injection molding by an extruder are difficult.
前記ポリアリーレンスルフィド樹脂（Ｂ）の樹脂構造は、芳香族環と硫黄原子とが結合した構造を繰り返し単位として有するものであり、具体的には、下記構造式（１）で表される構造部位を繰り返し単位とする樹脂である。 The resin structure of the polyarylene sulfide resin (B) has a structure in which an aromatic ring and a sulfur atom are bonded as a repeating unit, and specifically, a structural site represented by the following structural formula (1) Is a resin having a repeating unit.
ここで、前記構造式（１）で表される構造部位は、特に該式中のＲ１及びＲ２は、前記ＰＡＳ樹脂（Ｂ）の機械的強度の点から水素原子であることが好ましく、その場合、下記構造式（２）で表されるパラ位で結合するもの、及び下記構造式（３）で表されるメタ位で結合するものが挙げられる。 Here, in the structural part represented by the structural formula (1), it is particularly preferable that R 1 and R 2 in the formula are hydrogen atoms from the viewpoint of the mechanical strength of the PAS resin (B), In that case, what couple | bonds in the para position represented by following Structural formula (2) and what couple | bonds in the meta position represented by following Structural formula (3) are mentioned.
これらの中でも、特に繰り返し単位中の芳香族環に対する硫黄原子の結合は前記構造式（２）で表されるパラ位で結合した構造であることが前記ＰＡＳ樹脂（Ｂ）の耐熱性や結晶性の面で好ましい。 Among these, the heat resistance and crystallinity of the PAS resin (B) include that the bond of the sulfur atom to the aromatic ring in the repeating unit is a structure bonded at the para position represented by the structural formula (2). It is preferable in terms of
また、前記ＰＡＳ樹脂（Ｂ）は、前記構造式（１）で表される構造部位のみならず、下記の構造式（４）〜（７）で表される構造部位を、前記構造式（１）で表される構造部位との合計の３０モル％以下で含んでいてもよい。特に本発明では上記構造式（４）〜（７）で表される構造部位は１０モル％以下であることが、ＰＡＳ樹脂（Ｂ）の耐熱性、機械的強度の点から好ましい。前記ＰＡＳ樹脂（Ｂ）中に、上記構造式（４）〜（７）で表される構造部位を含む場合、それらの結合様式としては、ランダム共重合体、ブロック共重合体のいずれであってもよい。 Further, the PAS resin (B) has not only the structural portion represented by the structural formula (1) but also the structural portion represented by the following structural formulas (4) to (7). ) And 30 mol% or less of the total with the structural site represented by. In particular, in the present invention, the structural sites represented by the structural formulas (4) to (7) are preferably 10 mol% or less from the viewpoint of heat resistance and mechanical strength of the PAS resin (B). In the case where the PAS resin (B) includes a structural portion represented by the structural formulas (4) to (7), the bonding mode thereof is either a random copolymer or a block copolymer. Also good.
また、前記ＰＡＳ樹脂（Ｂ）は、その分子構造中に、下記構造式（８）で表される３官能性の構造部位、あるいは、ナフチルスルフィド結合などを有していてもよいが、他の構造部位との合計モル数に対して、１モル％以下であること、特に実質的には含まれないことがＰＡＳ樹脂（Ｂ）中の塩素原子含有量低減の観点から好ましい。 The PAS resin (B) may have a trifunctional structural site represented by the following structural formula (8) or a naphthyl sulfide bond in the molecular structure. From the viewpoint of reducing the chlorine atom content in the PAS resin (B), it is preferably 1 mol% or less, particularly not substantially contained, relative to the total number of moles with the structural site.
前記ＰＡＳ樹脂（Ｂ）は、例えば、下記（１）〜（４）の方法によって製造することができる。
（１）Ｎ−メチルピロリドン、ジメチルアセトアミドなどのアミド系溶剤やスルホラン等のスルホン系溶媒中で硫化ナトリウムとｐ−ジクロロベンゼンを反応させる方法。
（２）ｐ−ジクロロベンゼンを硫黄と炭酸ソーダの存在下で重合させる方法。
（３）ｐ−ジクロロベンゼンを極性溶媒中で硫化ナトリウムあるいは水硫化ナトリウムと水酸化ナトリウム又は硫化水素と水酸化ナトリウムの存在下で重合させる方法。
（４）ｐ−クロロチオフェノールの自己縮合による方法。
The PAS resin (B) can be produced, for example, by the following methods (1) to (4).
(1) A method in which sodium sulfide and p-dichlorobenzene are reacted in an amide solvent such as N-methylpyrrolidone or dimethylacetamide or a sulfone solvent such as sulfolane.
(2) A method of polymerizing p-dichlorobenzene in the presence of sulfur and sodium carbonate.
(3) A method of polymerizing p-dichlorobenzene in a polar solvent in the presence of sodium sulfide or sodium hydrosulfide and sodium hydroxide or hydrogen sulfide and sodium hydroxide.
(4) A method by self-condensation of p-chlorothiophenol.
これらの中でも（１）のＮ−メチルピロリドン、ジメチルアセトアミドなどのアミド系溶剤やスルホラン等のスルホン系溶媒中で硫化ナトリウムとｐ−ジクロロベンゼンを反応させる方法が反応の制御が容易であり、工業的生産性に優れる点から好ましい。 Among these, the method of reacting sodium sulfide and p-dichlorobenzene in an amide solvent such as N-methylpyrrolidone or dimethylacetamide or a sulfolane solvent such as sulfolane in (1) is easy to control the reaction. It is preferable from the viewpoint of excellent productivity.
また、リニアかつ高分子量のＰＡＳ樹脂（Ｂ）を工業的に効率よく製造できる点から前記方法（１）のなかでも、特に、固形のアルカリ金属硫化物、ジクロロベンゼン、アルカリ金属水硫化物、有機酸アルカリ金属塩を必須成分とする反応スラリーを調整し、これを加熱して不均一系で重合を行う方法が特に好ましい。かかる重合方法は具体的には、下記の２つの工程を必須の製造工程とする方法が生産性の点から好ましい。 Among the methods (1), linear and high molecular weight PAS resin (B) can be produced industrially and efficiently. Particularly, solid alkali metal sulfide, dichlorobenzene, alkali metal hydrosulfide, organic Particularly preferred is a method in which a reaction slurry containing an acid alkali metal salt as an essential component is prepared and heated to carry out polymerization in a heterogeneous system. Specifically, such a polymerization method is preferably a method in which the following two steps are essential production steps from the viewpoint of productivity.
［工程１］
含水アルカリ金属硫化物、又は、含水アルカリ金属水硫化物及びアルカリ金属水酸化物と、Ｎ−メチルピロリドンと、非加水分解性有機溶媒とを、脱水させながら反応させて、スラリー（Ｉ）を製造する工程。
［工程２］
次いで、前記スラリー（Ｉ）中、ジクロロベンゼンと、前記アルカリ金属水硫化物と、前記Ｎ−メチルピロリドンの加水分解物のアルカリ金属塩とを、反応させて重合を行う工程。
[Step 1]
Hydrous alkali metal sulfide, or hydrous alkali metal hydrosulfide and alkali metal hydroxide, N-methylpyrrolidone, and non-hydrolyzable organic solvent are reacted while being dehydrated to produce slurry (I). Process.
[Step 2]
Next, in the slurry (I), dichlorobenzene, the alkali metal hydrosulfide, and the alkali metal salt of the hydrolyzate of N-methylpyrrolidone are reacted to perform polymerization.
ここで用いる含水アルカリ金属硫化物は、例えば硫化リチウム、硫化ナトリウム、硫化カリウム、硫化ルビジウム、硫化セシウム等の化合物の液状又は固体状の含水物が挙げられ、その固形分濃度は１０〜８０質量％、特に３５〜６５質量％であることが好ましい。 Examples of the hydrated alkali metal sulfide used here include liquid or solid hydrates of compounds such as lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, and cesium sulfide, and the solid content concentration thereof is 10 to 80% by mass. In particular, it is preferably 35 to 65% by mass.
また、前記含水アルカリ金属水硫化物としては、例えば、水硫化リチウム、水硫化ナトリウム、水硫化カリウム、水硫化ルビジウム及び水硫化セシウム等の化合物の液状又は固体状の含水物が挙げられ、その固形分濃度は１０〜８０質量％であることが好ましい。これらの中でも水硫化リチウムの含水物と水硫化ナトリウムの含水物が好ましく、特に水硫化ナトリウムの含水物が好ましい。 Examples of the hydrous alkali metal hydrosulfide include liquid or solid hydrates of compounds such as lithium hydrosulfide, sodium hydrosulfide, potassium hydrosulfide, rubidium hydrosulfide, and cesium hydrosulfide. The partial concentration is preferably 10 to 80% by mass. Among these, hydrated lithium hydrosulfide and hydrated sodium hydrosulfide are preferable, and hydrated sodium hydrosulfide is particularly preferable.
さらに、前記アルカリ金属水酸化物としては、例えば、水酸化リチウム、水酸化ナトリウム、水酸化カリウム、水酸化ルビジウム、水酸化セシウム、及びこれらの水溶液が挙げられる。なお、該水溶液を用いる場合には、濃度２０質量％以上の水溶液であることが工程１の脱水処理が容易である点から好ましい。これらの中でも特に水酸化リチウムと水酸化ナトリウム及び水酸化カリウムが好ましく、特に水酸化ナトリウムが好ましい。 Furthermore, examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, and aqueous solutions thereof. In addition, when using this aqueous solution, it is preferable that it is aqueous solution with a density | concentration of 20 mass% or more from the point that the spin-drying | dehydration process of the process 1 is easy. Among these, lithium hydroxide, sodium hydroxide, and potassium hydroxide are particularly preferable, and sodium hydroxide is particularly preferable.
また、前記ＰＡＳ樹脂（Ｂ）のピーク分子量及び分子量分布（Ｍｗ／Ｍｎ）は、ゲル浸透クロマトグラフィーを用いて、次の条件で、６種類の単分散ポリスチレンを校正に用いて、測定することができる。 In addition, the peak molecular weight and molecular weight distribution (Mw / Mn) of the PAS resin (B) can be measured using gel permeation chromatography using six types of monodisperse polystyrene for calibration under the following conditions. it can.
［ゲル浸透クロマトグラフィーによる測定条件］
装置：超高温ポリマー分子量分布測定装置（株式会社センシュー科学製「ＳＳＣ−７０００」）
カラム：ＵＴ−８０５Ｌ（昭和電工株式会社製）
カラム温度：２１０℃
溶媒：１−クロロナフタレン
測定方法：ＵＶ検出器（３６０ｎｍ）
で６種類の単分散ポリスチレンを校正に用いて分子量分布とピーク分子量を測定する。
[Measurement conditions by gel permeation chromatography]
Apparatus: Ultra-high temperature polymer molecular weight distribution measuring apparatus (“SSC-7000” manufactured by Senshu Scientific Co., Ltd.)
Column: UT-805L (made by Showa Denko KK)
Column temperature: 210 ° C
Solvent: 1-chloronaphthalene Measurement method: UV detector (360 nm)
The molecular weight distribution and peak molecular weight are measured using 6 types of monodisperse polystyrene for calibration.
この方法により測定された分子量が、２８，０００〜１００，０００の範囲にピークを有するものが好ましく、３０，０００〜７０，０００の範囲にピークを有するものがより好ましい。 The molecular weight measured by this method preferably has a peak in the range of 28,000 to 100,000, and more preferably has a peak in the range of 30,000 to 70,000.
また、前記ＰＡＳ樹脂（Ｂ）の非ニュートン指数は、次の条件で測定することができる。すなわち、前記ＰＡＳ樹脂（Ｂ）をキャピラリーレオメーターにて、温度３００℃の条件下、直径１ｍｍ、長さ４０ｍｍのダイスを用いて１００〜１０００（ ｓｅｃ−１ ）の剪断速度に対する剪断応力を測定し、これらの対数プロットした傾きから計算した値である。
本発明で用いるＰＡＳ樹脂（Ｂ）は、この方法により測定された非ニュートン指数が、１．０〜１．７のものを用いることができるが、特に、１．１０〜１．７０のものを用いることが好ましい。
The non-Newtonian index of the PAS resin (B) can be measured under the following conditions. That is, the PAS resin (B) was measured with a capillary rheometer at a temperature of 300 ° C. using a die having a diameter of 1 mm and a length of 40 mm for a shear rate of 100 to 1000 (sec −1 ). These are values calculated from the slopes of these logarithmic plots.
As the PAS resin (B) used in the present invention, those having a non-Newtonian index measured by this method of 1.0 to 1.7 can be used, and in particular, those of 1.10 to 1.70. It is preferable to use it.
以上詳述したＰＡＳ樹脂（Ｂ）は、さらに、残存金属イオン量を低減して耐湿特性を改善するとともに、重合の際副生する低分子量不純物の残存量を低減できる点から、該ＰＡＳ樹脂（Ｂ）を製造した後に、酸で処理し、次いで、水で洗浄されたものであることが好ましい。 The PAS resin (B) described in detail above further reduces moisture content by reducing the amount of residual metal ions, and further reduces the residual amount of low molecular weight impurities by-produced during polymerization. B) is preferably prepared, treated with acid and then washed with water.
ここで使用し得る酸は、酢酸、塩酸、硫酸、リン酸、珪酸、炭酸、プロピル酸がＰＡＳ樹脂（Ｂ）の分解することなく残存金属イオン量を効率的に低減できる点から好ましく、なかでも酢酸、塩酸が好ましい。 The acid that can be used here is preferable in that acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, silicic acid, carbonic acid, and propyl acid can efficiently reduce the amount of residual metal ions without decomposition of the PAS resin (B). Acetic acid and hydrochloric acid are preferred.
酸処理の方法は、酸又は酸水溶液にＰＡＳ樹脂を浸漬する方法が挙げられる。この際、必要に応じさらに攪拌又は加熱してもよい。 Examples of the acid treatment method include a method of immersing the PAS resin in an acid or an aqueous acid solution. At this time, further stirring or heating may be performed as necessary.
ここで、前記酸処理の具体的方法は、酢酸を用いる場合を例に挙げれば、まずｐＨ４の酢酸水溶液を８０〜９０℃に加熱し、その中にＰＡＳ樹脂（Ｂ）を浸漬し、２０〜４０分間攪拌する方法が挙げられる。 Here, as a specific method of the acid treatment, for example, when acetic acid is used, first, an aqueous acetic acid solution having a pH of 4 is heated to 80 to 90 ° C., and the PAS resin (B) is immersed in the solution. The method of stirring for 40 minutes is mentioned.
このようにして酸処理されたＰＡＳ樹脂（Ｂ）は、残存している酸又は塩等を物理的に除去するため、次いで、水又は温水で数回洗浄する。このときに使用される水としては、蒸留水又は脱イオン水であることが好ましい。 The acid-treated PAS resin (B) is then washed several times with water or warm water in order to physically remove the remaining acid or salt. The water used at this time is preferably distilled water or deionized water.
また、前記酸処理に供せられるＰＡＳ樹脂（Ｂ）は、粉粒体であることが好ましく、具体的には、ペレットのような粒状体でも、重合した後のスラリー状態体にあるものでもよい。 Further, the PAS resin (B) to be subjected to the acid treatment is preferably a granular material, and specifically, it may be a granular material such as a pellet or a slurry state material after polymerization. .
さらに、本発明のガスケット用樹脂組成物は、図１に示すような圧縮応力緩和用試験片（試験片厚さ３ｍｍ、圧縮面側表面積６０ｍｍ２）に成形した後、恒温槽を備えたオートグラフによって１０％歪み下（温度条件：２３℃）で圧縮応力緩和を測定した際の１００時間後における圧縮応力の絶対値は、１０ＭＰａ以上である。通常、圧縮応力は経時的に大きく低下するが、本発明においては、シリコーン化合物（Ａ）及びＰＡＳ樹脂（Ｂ）を含有する樹脂組成物を用いることにより、現行ガスケットとして用いられているＰＦＡよりも圧縮応力が大きいため、二次電池に必要とされる気密性（シール性）を十分に維持することができる。 Furthermore, the resin composition for gaskets of the present invention is formed into a compression stress relaxation test piece (test piece thickness 3 mm, compression surface side surface area 60 mm 2 ) as shown in FIG. Thus, the absolute value of the compressive stress after 100 hours when compressive stress relaxation is measured under 10% strain (temperature condition: 23 ° C.) is 10 MPa or more. Usually, the compressive stress greatly decreases with time, but in the present invention, by using a resin composition containing the silicone compound (A) and the PAS resin (B), the PFA used as a current gasket is used. Since the compressive stress is large, the airtightness (sealability) required for the secondary battery can be sufficiently maintained.
また、本発明のガスケット用樹脂組成物は、オートグラフによる引張試験（ＡＳＴＭ Ｄ６３８）において、引張破断伸びが１０％以上であるものがより好ましい。引張破断伸びが１０％以上であれば、さらに高い靱性を有することになり、靱性不足によるクラック等の発生を防止でき、ガスケットの気密性を維持することができる。 The resin composition for gaskets of the present invention is more preferably one having a tensile elongation at break of 10% or more in an autograph tensile test (ASTM D638). If the tensile elongation at break is 10% or more, it will have higher toughness, cracks due to insufficient toughness and the like can be prevented, and the gas tightness of the gasket can be maintained.
本発明のガスケット用樹脂組成物には、組成物としてシラン化合物を配合してもよい。シラン化合物としては、例えば、アミノアルコキシシラン、エポキシアルコキシシラン、ビニルアルコキシシラン等が挙げられる。これらのシラン化合物は、単独で用いることも２種以上併用することもできる。 You may mix | blend a silane compound with the resin composition for gaskets of this invention as a composition. Examples of the silane compound include aminoalkoxysilane, epoxyalkoxysilane, and vinylalkoxysilane. These silane compounds can be used alone or in combination of two or more.
前記アミノアルコキシシランとしては、１分子中にアミノ基を１つ以上有し、アルコキシ基を２つ以上有するシラン化合物であれば用いることができ、例えば、γ−アミノプロピルトリエトキシシラン、γ−アミノプロピルトリメトキシシラン、γ−アミノプロピルメチルジエトキシシラン、γ−アミノプロピルメチルジメトキシシラン、Ｎ−β（アミノエチル）−γ−アミノプロピルトリエトキシシラン、Ｎ−β（アミノエチル）−γ−アミノプロピルトリメトキシシラン、Ｎ−β（アミノエチル）−γ−アミノプロピルメチルジエトキシシラン、Ｎ−β（アミノエチル）−γ−アミノプロピルメチルジメトキシシラン、Ｎ−フェニル−γ−アミノプロピルトリエトキシシラン、Ｎ−フェニル−γ−アミノプロピルトリメトキシシラン等が挙げられる。 As the aminoalkoxysilane, any silane compound having one or more amino groups and two or more alkoxy groups in one molecule can be used. For example, γ-aminopropyltriethoxysilane, γ-amino Propyltrimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) -γ-aminopropyltriethoxysilane, N-β (aminoethyl) -γ-aminopropyl Trimethoxysilane, N-β (aminoethyl) -γ-aminopropylmethyldiethoxysilane, N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane, N -Phenyl-γ-aminopropyltrimethoxysilane and the like .
また、前記エポキシアルコキシシランとしては、１分子中にエポキシ基を１つ以上有し、アルコキシ基を２つ以上有するシラン化合物であれば用いることができ、例えば、γ−グリシドキシプロピルトリメトキシシラン、β−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン、γ−グリシドキシプロピルトリエトキシシラン等が挙げられる。 The epoxyalkoxysilane may be any silane compound having one or more epoxy groups and two or more alkoxy groups in one molecule. For example, γ-glycidoxypropyltrimethoxysilane , Β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and the like.
さらに、前記ビニルアルコキシシランとしては、１分子中にビニル基を１つ以上有し、アルコキシ基を２つ以上有するシラン化合物であれば用いることができ、例えば、ビニルトリエトキシシラン、ビニルトリメトキシシラン、ビニルトリス（β−メトキシエトキシ）シラン等が挙げられる。 Further, as the vinyl alkoxysilane, any silane compound having one or more vinyl groups and two or more alkoxy groups in one molecule can be used, for example, vinyltriethoxysilane, vinyltrimethoxysilane. Vinyltris (β-methoxyethoxy) silane and the like.
本発明では、さらに上記各成分に加え、本発明の効果を損なわない範囲で繊維状強化材又は無機質フィラーを添加してもよい。 In the present invention, in addition to the above components, a fibrous reinforcing material or an inorganic filler may be added as long as the effects of the present invention are not impaired.
前記繊維状強化材としては、例えば、ガラス繊維、ＰＡＮ系又はピッチ系の炭素繊維、シリカ繊維、シリカ・アルミナ繊維、ジルコニア繊維、窒化ホウ素繊維、窒化ケイ素繊維、ホウ素繊維、ホウ酸アルミニウム繊維、チタン酸カリウム繊維、ステンレス、アルミニウム、チタン、銅、真ちゅう等の金属の繊維状物の無機質繊維状物質、及びアラミド繊維等の有機質繊維状物質等が挙げられる。 Examples of the fibrous reinforcing material include glass fiber, PAN-based or pitch-based carbon fiber, silica fiber, silica-alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, aluminum borate fiber, and titanium. Examples thereof include inorganic fibrous substances such as potassium acid fibers, stainless steel, aluminum, titanium, copper, brass and other metallic fibrous substances, and organic fibrous substances such as aramid fibers.
また、無機質フィラーは、例えば、マイカ、タルク、ワラステナイト、セリサイト、カオリン、クレー、ベントナイト、アスベスト、アルミナシリケート、ゼオライト、パイロフィライト等の珪酸塩や炭酸カルシウム、炭酸マグネシウム、ドロマイト等の炭酸塩、硫酸カルシウム、硫酸バリウム等の硫酸塩、アルミナ、酸化マグネシウム、シリカ、ジルコニア、チタニア、酸化鉄等の金属酸化物、ガラスビーズ、セラミックビーズ、窒化ホウ素、炭化珪素、燐酸カルシウムなどが挙げられる。これらの繊維状強化材及び無機質フィラーは、単独で用いることも２種以上併用することもできる。 Examples of the inorganic filler include silicates such as mica, talc, wollastonite, sericite, kaolin, clay, bentonite, asbestos, alumina silicate, zeolite, pyrophyllite, and carbonates such as calcium carbonate, magnesium carbonate, and dolomite. And sulfates such as calcium sulfate and barium sulfate, metal oxides such as alumina, magnesium oxide, silica, zirconia, titania and iron oxide, glass beads, ceramic beads, boron nitride, silicon carbide, calcium phosphate and the like. These fibrous reinforcing materials and inorganic fillers can be used alone or in combination of two or more.
さらに、本発明のガスケット用樹脂組成物には、本発明の効果を損なわない範囲で、酸化防止剤、安定剤、加工熱安定剤、可塑剤、離型剤、着色剤、滑剤、耐候性安定剤、発泡剤、防錆剤、ワックスを適量配合してもよい。 Furthermore, the resin composition for gaskets of the present invention includes an antioxidant, a stabilizer, a processing heat stabilizer, a plasticizer, a release agent, a colorant, a lubricant, and a stable weather resistance as long as the effects of the present invention are not impaired. An appropriate amount of an agent, a foaming agent, a rust inhibitor, and a wax may be blended.
また、本発明のガスケット用樹脂組成物には、要求される特性に合わせてその他の樹脂成分を適宜配合してもよい。ここで用いることができる樹脂成分としては、エチレン、ブチレン、ペンテン、ブタジエン、イソプレン、クロロプレン、スチレン、α−メチルスチレン、酢酸ビニル、塩化ビニル、アクリル酸エステル、メタクリル酸エステル、（メタ）アクリロニトリルなどの単量体の単独重合体又は共重合体、ポリウレタン、ポリブチレンテレフタレート、ポリエチレンテレフタレート等のポリエステル、ポリアセタール、ポリカーボネ−ト、ポリサルホン、ポリアリルサルホン、ポリエーテルサルホン、ポリフェニレンエーテル、ポリエ−テルケトン、ポリエーテルエーテルケトン、ポリイミド、ポリアミドイミド、ポリエーテルイミド、シリコーン樹脂、エポキシ樹脂、フェノキシ樹脂、液晶ポリマー、ポリアリールエーテルなどの単独重合体、ランダム共重合体又はブロック共重合体、グラフト共重合体等が挙げられる。 Moreover, you may mix | blend other resin components suitably with the resin composition for gaskets of this invention according to the characteristic requested | required. Examples of the resin component that can be used here include ethylene, butylene, pentene, butadiene, isoprene, chloroprene, styrene, α-methylstyrene, vinyl acetate, vinyl chloride, acrylic acid ester, methacrylic acid ester, (meth) acrylonitrile, and the like. Monomers or copolymers of monomers, polyesters such as polyurethane, polybutylene terephthalate, polyethylene terephthalate, polyacetal, polycarbonate, polysulfone, polyallyl sulfone, polyether sulfone, polyphenylene ether, polyetherketone, poly Homopolymers such as ether ether ketone, polyimide, polyamideimide, polyetherimide, silicone resin, epoxy resin, phenoxy resin, liquid crystal polymer, polyaryl ether, Dam or block copolymer, and graft copolymer and the like.
本発明のガスケット用樹脂組成物の製造する方法としては、具体的には、前記シリコーン化合物（Ａ）、ＰＡＳ樹脂（Ｂ）及び必要に応じて配合するその他の配合成分をタンブラー又はヘンシェルミキサーなどで均一に混合し、次いで、その混合物を２軸押出機に投入し、樹脂成分の吐出量（ｋｇ／ｈｒ）とスクリュー回転数（ｒｐｍ）との比率（吐出量／スクリュー回転数）が０．０２〜０．２（ｋｇ／ｈｒ・ｒｐｍ）の範囲となる条件下で溶融混練する方法が挙げられる。 As a method for producing the resin composition for gaskets of the present invention, specifically, the silicone compound (A), the PAS resin (B) and other compounding components to be blended as necessary are tumbler or Henschel mixer. Then, the mixture is introduced into a twin screw extruder, and the ratio of the resin component discharge amount (kg / hr) to the screw rotation speed (rpm) (discharge amount / screw rotation speed) is 0.02. A method of melt-kneading under a condition of ˜0.2 (kg / hr · rpm) can be mentioned.
上記の製造方法について、さらに詳述すれば、前記した各成分を２軸押出機内に投入し、設定温度３３０℃、樹脂温度３５０℃程度の温度条件下に溶融混練する方法が挙げられる。この際、樹脂成分の吐出量は回転数２５０ｒｐｍで５〜５０ｋｇ／ｈｒの範囲となる。なかでも特に分散性の点から２０〜３５ｋｇ／ｈｒであることが好ましい。よって、樹脂成分の吐出量（ｋｇ／ｈｒ）とスクリュー回転数（ｒｐｍ）との比率（吐出量／スクリュー回転数）は、特に０．０８〜０．１４（ｋｇ／ｈｒ・ｒｐｍ）であることが好ましい。 The above production method will be described in more detail. A method in which the above-described components are put into a twin-screw extruder and melt-kneaded under temperature conditions of a preset temperature of 330 ° C. and a resin temperature of about 350 ° C. can be mentioned. At this time, the discharge amount of the resin component is in a range of 5 to 50 kg / hr at a rotation speed of 250 rpm. Especially, it is preferable that it is 20-35 kg / hr from the point of a dispersibility. Therefore, the ratio (discharge amount / screw rotation number) between the resin component discharge amount (kg / hr) and the screw rotation speed (rpm) is particularly 0.08 to 0.14 (kg / hr · rpm). Is preferred.
このようにして溶融混練されたガスケット用樹脂組成物は、通常ペレット状にカッティングされる。また、得られたペレットを成形機に供給して溶融成形することにより、最終的に目的とする形状の成形物が得られる。 The resin composition for gaskets thus melt-kneaded is usually cut into pellets. Further, the obtained pellet is supplied to a molding machine and melt-molded to finally obtain a molded product having a desired shape.
ここで溶融成形する方法は、例えば、射出成形、押出成形、圧縮成形等が挙げられるが、このうち二次電池用ガスケットを成形する方法としては、射出成形が特に好ましい。 Examples of the melt molding method include injection molding, extrusion molding, and compression molding. Among these methods, the injection molding is particularly preferable as a method of molding the secondary battery gasket.
本発明のガスケット用樹脂組成物は、例えば、ノート型パソコン、携帯電話、ビデオカメラ等の電気機器用途、あるいはハイブリッド自動車（ＨＶ）、電気自動車（ＥＶ）等の車載用途に用いられる二次電池、特に高容量リチウムイオン二次電池用のガスケット等に特に有用である。 The resin composition for a gasket of the present invention is, for example, a secondary battery used for electric equipment applications such as notebook computers, mobile phones, video cameras, or in-vehicle applications such as hybrid vehicles (HV) and electric vehicles (EV), It is particularly useful for gaskets for high capacity lithium ion secondary batteries.
以下に、実施例により本発明をさらに詳しく説明する。
実施例１〜５及び比較例１〜４
表１及び表２に記載する配合量にしたがい、シリコーンオイル又はシリコーンオイルを含有したシリコーンパウダー、ＰＡＳ樹脂であるポリフェニレンスルフィド及びその他配合材料をタンブラーで均一に混合した。その後、東芝機械株式会社製ベント付き２軸押出機「ＴＥＭ−３５Ｂ」に前記配合材料を投入し、樹脂成分吐出量２５ｋｇ／ｈｒ、スクリュー回転数２５０ｒｐｍ、樹脂成分の吐出量（ｋｇ／ｈｒ）とスクリュー回転数（ｒｐｍ）との比率（吐出量／スクリュー回転数）＝０．１（ｋｇ／ｈｒ・ｒｐｍ）、設定樹脂温度３３０℃で溶融混練して樹脂組成物のペレットを得た。次いで、このペレットを用いて以下の各種評価試験を行った。試験及び評価の結果は、表１及び２に示す。
Hereinafter, the present invention will be described in more detail with reference to examples.
Examples 1-5 and Comparative Examples 1-4
According to the blending amounts shown in Tables 1 and 2, silicone oil or silicone powder containing silicone oil, polyphenylene sulfide as a PAS resin, and other blending materials were uniformly mixed with a tumbler. Thereafter, the blended material is put into a twin-screw extruder “TEM-35B” manufactured by Toshiba Machine Co., Ltd., and the resin component discharge rate is 25 kg / hr, the screw rotation speed is 250 rpm, and the resin component discharge rate (kg / hr). The ratio of the screw rotation speed (rpm) (discharge amount / screw rotation speed) = 0.1 (kg / hr · rpm) was melt kneaded at a set resin temperature of 330 ° C. to obtain resin composition pellets. Subsequently, the following various evaluation tests were performed using this pellet. The results of the test and evaluation are shown in Tables 1 and 2.
［引張破断伸びの測定］
測定対象樹脂配合物の試験片をＡＳＴＭ４号ダンベル形状で作成し、ＡＳＴＭ Ｄ６３８に従って、株式会社島津製作所製「オートグラフ ＡＧ−５０００Ｃ」にて測定し、引張破断伸びを測定した。
[Measurement of tensile elongation at break]
A test piece of the resin composition to be measured was prepared in ASTM No. 4 dumbbell shape, and measured according to ASTM D638 with “Autograph AG-5000C” manufactured by Shimadzu Corporation to measure the tensile elongation at break.
［圧縮応力緩和試験］
樹脂組成物ペレットを射出成形機を用いて成形し、射出成形機により縦８ｍｍ×横８ｍｍ×厚さ３ｍｍの平板を成形し、図１に示すような圧縮応力緩和用試験片を作製した。この試験片を用い、恒温槽を備えた株式会社島津製作所製「オートグラフ ＡＧ−５０ＫＮＸ」により１０％歪み下（温度条件：２３℃及び６０℃）で圧縮応力緩和を測定し、１００時間後の圧縮応力を求めた。
[Compressive stress relaxation test]
The resin composition pellets were molded using an injection molding machine, and a flat plate of 8 mm length × 8 mm width × 3 mm thickness was molded by the injection molding machine, and a test piece for compressive stress relaxation as shown in FIG. 1 was produced. Using this test piece, compressive stress relaxation was measured under 10% strain (temperature conditions: 23 ° C. and 60 ° C.) by “Autograph AG-50KNX” manufactured by Shimadzu Corporation equipped with a thermostatic bath, and after 100 hours. The compressive stress was determined.
［気密性の評価］
樹脂組成物ペレットを射出成形機を用いて成形し、形状が縦８ｍｍ×横８ｍｍ×高さ１０ｍｍで厚さ０．８ｍｍの箱形成型品を作成した。次いで、この箱形成型品に電解液（１ｍｏｌ／ＬのＬｉＰＦ６／エチレンカーボネート（ＥＣ）：ジメチルカーボネート（ＤＭＣ）（容量１：１混合溶液）溶液、キシダ化学株式会社製）を入れ、圧縮応力緩和試験で用いた縦８ｍｍ×横８ｍｍ×厚さ３ｍｍの平板で一定応力（１０％歪み下）で封をした気密試験用サンプルを作成する。これを６０℃の乾熱下で１００時間放置し、液の漏れ具合について確認した。なお、評価結果は以下のように表示した。
○：１００時間後に液の漏れが生じない。
×：１００時間後に液の漏れが生じる。
[Evaluation of airtightness]
The resin composition pellets were molded using an injection molding machine, and a box-forming product having a shape of 8 mm long × 8 mm wide × 10 mm high and 0.8 mm thick was prepared. Next, an electrolytic solution (1 mol / L LiPF 6 / ethylene carbonate (EC): dimethyl carbonate (DMC) (capacity 1: 1 mixed solution) solution, manufactured by Kishida Chemical Co., Ltd.)) was put into this box forming product, and compression stress was applied. An airtightness test sample sealed with a constant stress (under 10% strain) on a flat plate of 8 mm length × 8 mm width × 3 mm thickness used in the relaxation test is prepared. This was left for 100 hours under dry heat at 60 ° C., and the liquid leakage was confirmed. The evaluation results were displayed as follows.
○: No liquid leakage occurs after 100 hours.
X: Liquid leakage occurs after 100 hours.
なお、表１及び２中の配合樹脂、材料は下記のものである。
（１）ＰＰＳ−１：ポリフェニレンスルフィド（ＤＩＣ株式会社製「ＤＳＰ ＬＤ−１０Ｇ」；ピーク分子量 ３５，０００、非ニュートン指数 １．５６）
（２）ＰＰＳ−２：ポリフェニレンスルフィド（ＤＩＣ株式会社製「ＤＳＰ ＭＬ−３２０」：ピーク分子量 ４１，０００、非ニュートン指数 １．２７）
（３）ＰＰＳ−３：ポリフェニレンスルフィド（ＤＩＣ株式会社製「ＤＳＰ ＬＲ−２Ｇ」；ピーク分子量 ３４，０００、非ニュートン指数 １．１２）
（４）ＰＰＳ−４：ポリフェニレンスルフィド（ＤＩＣ株式会社製「ＤＳＰ ＬＲ−１００Ｇ」；ピーク分子量 ２０，０００、非ニュートン指数 １．０５）
（５）ＰＰＳ−５：ポリフェニレンスルフィド（ＤＩＣ株式会社製「ＤＳＰ ＨＣ−２７０」；ピーク分子量 ３０，０００、非ニュートン指数 １．６２）
（６）ＰＰＳ−６：ポリフェニレンスルフィド（ＤＩＣ株式会社製「ＤＳＰ ＬＲ−３００Ｇ」；ピーク分子量 ２５，０００、非ニュートン指数 １．０８）
（７）Ｓｉ−１：シリコーンパウダー（東レ・ダウコーニング株式会社製「トレフィルＦ−２０２」；無機粉体（シリカ）にシリコーンオイル（粘度（２５℃）：６０，０００ｃｓ（６２，０００ｍＰａ・ｓ））を６０質量％担持したパウダー）
（８）Ｓｉ−２：アミノ基含有シリコーン（信越化学工業株式会社製「ＫＦ−８６８」）
（９）ＰＦＡ：テトラフルオロエチレン−パーフルオロアルキルビニルエーテル共重合体（ダイキン工業株式会社製の「ネオフロンＡＰ−２０１」）
The compounded resins and materials in Tables 1 and 2 are as follows.
(1) PPS-1: Polyphenylene sulfide (“DSP LD-10G” manufactured by DIC Corporation; peak molecular weight 35,000, non-Newtonian index 1.56)
(2) PPS-2: Polyphenylene sulfide (“DSP ML-320” manufactured by DIC Corporation: peak molecular weight 41,000, non-Newtonian index 1.27)
(3) PPS-3: Polyphenylene sulfide (“DSP LR-2G” manufactured by DIC Corporation; peak molecular weight 34,000, non-Newtonian index 1.12)
(4) PPS-4: Polyphenylene sulfide (“DSP LR-100G” manufactured by DIC Corporation; peak molecular weight 20,000, non-Newtonian index 1.05)
(5) PPS-5: Polyphenylene sulfide (“DSP HC-270” manufactured by DIC Corporation; peak molecular weight 30,000, non-Newtonian index 1.62)
(6) PPS-6: Polyphenylene sulfide (“DSP LR-300G” manufactured by DIC Corporation; peak molecular weight 25,000, non-Newtonian index 1.08)
(7) Si-1: Silicone powder (“Torefill F-202” manufactured by Toray Dow Corning Co., Ltd.); Silicone oil (viscosity (25 ° C.): 60,000 cs (62,000 mPa · s)) to inorganic powder (silica) ) 60% by weight of powder)
(8) Si-2: amino group-containing silicone (“KF-868” manufactured by Shin-Etsu Chemical Co., Ltd.)
(9) PFA: Tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (“Nephron AP-201” manufactured by Daikin Industries, Ltd.)
表１に示した評価結果より、本発明のガスケット用樹脂組成物は、ガスケットとして用いた場合、優れた気密性を有し、二次電池に必要とされる気密性を維持することができることが分かった。 From the evaluation results shown in Table 1, the resin composition for a gasket of the present invention has excellent airtightness when used as a gasket, and can maintain the airtightness required for a secondary battery. I understood.
一方、表２に示した評価結果より、比較例１及び２は、シリコーン化合物（Ａ）を配合しなかった例であるが、引張破断伸びが低く、気密性が不十分であることが分かった。また、比較例３及び４は、ゲル浸透クロマトグラフィーにより求められる分子量分布のピーク分子量が２８，０００未満であるＰＡＳ樹脂を用いた例であるが、引張破断伸びが低く、気密性が不十分であることが分かった。さらに、比較例５は、従来、ガスケットとして用いられてきているＰＦＡ樹脂の例であるが、引張破断伸びは高いが、１０％歪み下（温度条件：２３℃、６０℃）での１００時間後圧縮応力の絶対値は、６ＭＰａ及び５ＭＰａとなり、本発明のガスケット用樹脂組成物の２０〜４０ＭＰａと比較して大幅に低く、結果として気密性が不十分であることが分かった。 On the other hand, from the evaluation results shown in Table 2, Comparative Examples 1 and 2 were examples in which the silicone compound (A) was not blended, but it was found that the tensile elongation at break was low and the airtightness was insufficient. . Comparative Examples 3 and 4 are examples using a PAS resin having a peak molecular weight of less than 28,000 in the molecular weight distribution obtained by gel permeation chromatography, but the tensile elongation at break is low and the airtightness is insufficient. I found out. Further, Comparative Example 5 is an example of a PFA resin that has been conventionally used as a gasket, but the tensile elongation at break is high, but after 100 hours under 10% strain (temperature conditions: 23 ° C., 60 ° C.). The absolute values of the compressive stress were 6 MPa and 5 MPa, which was significantly lower than 20 to 40 MPa of the gasket resin composition of the present invention, and as a result, it was found that the airtightness was insufficient.
Claims (10)
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| CN106129280A (en) * | 2016-08-10 | 2016-11-16 | 东莞永蓝电子科技有限公司 | Electrokinetic cell top cover compound inslation block |
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| JPS53122727A (en) * | 1977-04-01 | 1978-10-26 | Hitachi Ltd | Alkaline battery |
| JP3620197B2 (en) * | 1996-02-28 | 2005-02-16 | 東レ株式会社 | Polyphenylene sulfide resin composition |
| JPH10302737A (en) * | 1997-04-22 | 1998-11-13 | Fuji Film Selltec Kk | Battery gasket and battery using the same |
| JP2000048803A (en) * | 1998-07-27 | 2000-02-18 | Japan Storage Battery Co Ltd | Organic electrolyte battery |
| JP2000156210A (en) * | 1998-11-18 | 2000-06-06 | Toray Ind Inc | Gasket for battery and its manufacture |
| JP4277368B2 (en) * | 1999-06-16 | 2009-06-10 | Ｄｉｃ株式会社 | Polyarylene sulfide resin composition |
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| JP2003077430A (en) * | 2001-09-05 | 2003-03-14 | Mitsubishi Cable Ind Ltd | Sealed battery |
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| JP5182838B2 (en) * | 2006-07-25 | 2013-04-17 | 株式会社デンソー | Sealing plate for lithium battery container, manufacturing method thereof and lithium battery |
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