JP7151938B2 - Aqueous Resin Composition for Lithium Ion Secondary Battery Separator Heat-Resistant Layer Binder - Google Patents
Aqueous Resin Composition for Lithium Ion Secondary Battery Separator Heat-Resistant Layer Binder Download PDFInfo
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- JP7151938B2 JP7151938B2 JP2022521343A JP2022521343A JP7151938B2 JP 7151938 B2 JP7151938 B2 JP 7151938B2 JP 2022521343 A JP2022521343 A JP 2022521343A JP 2022521343 A JP2022521343 A JP 2022521343A JP 7151938 B2 JP7151938 B2 JP 7151938B2
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- 239000011342 resin composition Substances 0.000 title claims description 32
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims description 28
- 229910001416 lithium ion Inorganic materials 0.000 title claims description 28
- 239000000178 monomer Substances 0.000 claims description 59
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 239000011230 binding agent Substances 0.000 claims description 23
- 229920000642 polymer Polymers 0.000 claims description 23
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 17
- 239000002994 raw material Substances 0.000 claims description 16
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 12
- 239000012736 aqueous medium Substances 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 42
- -1 2-ethylhexyl Chemical group 0.000 description 31
- 150000003254 radicals Chemical class 0.000 description 17
- 239000003995 emulsifying agent Substances 0.000 description 16
- 239000000203 mixture Substances 0.000 description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 5
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000012874 anionic emulsifier Substances 0.000 description 4
- 150000007514 bases Chemical class 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 239000011256 inorganic filler Substances 0.000 description 4
- 229910003475 inorganic filler Inorganic materials 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
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- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 150000005215 alkyl ethers Chemical class 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
- 230000000052 comparative effect Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000010556 emulsion polymerization method Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 239000000049 pigment Substances 0.000 description 3
- 229920001515 polyalkylene glycol Polymers 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 2
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- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000003429 antifungal agent Substances 0.000 description 2
- 229940121375 antifungal agent Drugs 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
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- 229920005672 polyolefin resin Polymers 0.000 description 2
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- 238000002360 preparation method Methods 0.000 description 2
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- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000002981 blocking agent 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
- NWEKXBVHVALDOL-UHFFFAOYSA-N butylazanium;hydroxide Chemical compound [OH-].CCCC[NH3+] NWEKXBVHVALDOL-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-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
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent 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
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 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
- ZLNAFSPCNATQPQ-UHFFFAOYSA-N ethenyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C=C ZLNAFSPCNATQPQ-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229910052621 halloysite Inorganic materials 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000010954 inorganic particle 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
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- XMYQHJDBLRZMLW-UHFFFAOYSA-N methanolamine Chemical group NCO XMYQHJDBLRZMLW-UHFFFAOYSA-N 0.000 description 1
- CAAULPUQFIIOTL-UHFFFAOYSA-N methyl dihydrogen phosphate Chemical compound COP(O)(O)=O CAAULPUQFIIOTL-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- UTSYWKJYFPPRAP-UHFFFAOYSA-N n-(butoxymethyl)prop-2-enamide Chemical compound CCCCOCNC(=O)C=C UTSYWKJYFPPRAP-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229950010765 pivalate Drugs 0.000 description 1
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229910052903 pyrophyllite Inorganic materials 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 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
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000004079 stearyl 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])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])[H] 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- WYKYCHHWIJXDAO-UHFFFAOYSA-N tert-butyl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)C WYKYCHHWIJXDAO-UHFFFAOYSA-N 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-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
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/42—Acrylic resins
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
-
- 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
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明は、リチウムイオン二次電池セパレータ耐熱層バインダー用水性樹脂組成物に関する。 TECHNICAL FIELD The present invention relates to an aqueous resin composition for lithium ion secondary battery separator heat-resistant layer binder.
リチウムイオン二次電池の製造に使用するセパレータとしては、一般に、ポリオレフィン樹脂等を用いて得られる多孔体を使用することが多い。リチウムイオン二次電池は、通常、電解液中のイオンが前記セパレータを構成する孔を介して移動することによって、電池としての機能を発揮する。 As a separator used for manufacturing a lithium ion secondary battery, a porous body obtained by using a polyolefin resin or the like is generally used in many cases. Lithium ion secondary batteries normally function as batteries when ions in the electrolyte move through the pores that form the separator.
一方、前記リチウムイオン二次電池の出力が増大するなかで、前記リチウムイオン二次電池には、異常発熱に起因した発火等を引き起こす可能性があるという問題が懸念されている。 On the other hand, as the output of the lithium ion secondary battery increases, there is a concern that the lithium ion secondary battery may cause ignition due to abnormal heat generation.
前記発火等を防止する方法としては、例えば前記リチウムイオン二次電池が発熱した際に、前記セパレータの微多孔がその熱の影響によって無孔化しうるセパレータを使用する方法が知られている。これにより、電解液内におけるイオンの伝導を停止し、さらなる発熱や発火を防止することが期待されている。 As a method for preventing the ignition, for example, when the lithium ion secondary battery generates heat, a method is known in which the microporosity of the separator can be rendered non-porous by the influence of heat. This is expected to stop the conduction of ions in the electrolytic solution and prevent further heat generation and ignition.
しかし、前記セパレータは、その熱の影響によって著しい収縮を引き起こし、その結果、電解液内におけるイオンの伝導を停止することができず、リチウムイオン二次電池の短絡を引き起こす可能性を有していた。 However, the separator shrinks significantly under the influence of heat, and as a result, the ion conduction in the electrolytic solution cannot be stopped, which may cause a short circuit in the lithium ion secondary battery. .
熱収縮を引き起こしにくいセパレータとしては、ポリオレフィン樹脂等を用いて得られる多孔体の表面に、多孔状の耐熱層を設けたものが知られており、例えば、ポリオレフィン樹脂を主成分とする多孔膜の少なくとも片面に、無機粒子と樹脂製バインダーとを含む多孔層を備えた多層多孔膜であって、前記樹脂製バインダーが、（メタ）アクリル酸エステル単量体から選ばれる１種以上の単量体と、不飽和カルボン酸単量体と、架橋性単量体とを原料単位として含む共重合体であることを特徴とする多層多孔膜が知られている（例えば、特許文献１参照。）。 As a separator that does not easily cause heat shrinkage, there is known a separator in which a porous heat-resistant layer is provided on the surface of a porous body obtained using polyolefin resin or the like. A multilayer porous film having a porous layer containing inorganic particles and a resin binder on at least one side, wherein the resin binder is one or more monomers selected from (meth)acrylic acid ester monomers. , an unsaturated carboxylic acid monomer, and a crosslinkable monomer as raw material units.
しかしながら、この材料は耐熱層として一定の効果を発現するものの、１８０℃等の高温環境下においては、耐熱性が不十分であるため、異常発熱の際に電池の短絡を引き起こす可能性があった。 However, although this material exhibits a certain effect as a heat-resistant layer, it has insufficient heat resistance in a high-temperature environment such as 180°C, so there is a possibility of short-circuiting the battery when abnormal heat is generated. .
本発明が解決しようとする課題は、耐熱収縮性に優れたリチウムイオン二次電池セパレータ耐熱層バインダー用水性樹脂組成物を提供することである。 The problem to be solved by the present invention is to provide an aqueous resin composition for a lithium ion secondary battery separator heat-resistant layer binder which is excellent in heat shrinkage resistance.
本発明者等は、上記課題を解決すべく鋭意研究を重ねた結果、特定のラジカル重合体、及び水性媒体を含有する水性樹脂組成物を用いることで、上記課題を解決できることを見出し、本発明を完成した。 The inventors of the present invention have conducted intensive studies to solve the above problems, and found that the above problems can be solved by using an aqueous resin composition containing a specific radical polymer and an aqueous medium. completed.
すなわち、本発明は、炭素原子数４～１８のアルキル基を有するアクリル単量体（ａ１）、ジアセトン(メタ）アクリルアミド及びＮ－メチロール(メタ)アクリルアミドから選ばれる少なくとも１以上の単量体（ａ２）、カルボキシル基を有する不飽和単量体（ａ３）、及びアクリロニトリル（ａ４）、を必須原料とするラジカル重合体（Ａ）と、水性媒体（Ｂ）とを含有するリチウムイオン二次電池セパレータ耐熱層バインダー用水性樹脂組成物であって、前記ラジカル重合体（Ａ）の単量体原料中の前記アクリロニトリル（ａ４）が５～３０質量％であることを特徴とするリチウムイオン二次電池セパレータ耐熱層バインダー用水性樹脂組成物に関するものである。 That is, the present invention provides at least one monomer (a2 ), an unsaturated monomer having a carboxyl group (a3), and acrylonitrile (a4) as essential raw materials, a radical polymer (A), and an aqueous medium (B) Lithium ion secondary battery separator heat resistant Lithium ion secondary battery separator heat resistant, which is an aqueous resin composition for a layer binder, wherein the acrylonitrile (a4) in the monomer raw material of the radical polymer (A) is 5 to 30% by mass. The present invention relates to an aqueous resin composition for a layer binder.
本発明のリチウムイオン二次電池セパレータ耐熱層バインダー用水性樹脂組成物は、耐熱収縮性に優れるセパレータが得られることから、リチウムイオン二次電池セパレータ耐熱層のバインダーに好適に用いることができる。 The aqueous resin composition for a lithium ion secondary battery separator heat-resistant layer binder of the present invention can be suitably used as a binder for a lithium ion secondary battery separator heat-resistant layer because a separator having excellent heat shrinkage resistance can be obtained.
本発明のリチウムイオン二次電池セパレータ耐熱層バインダー用水性樹脂組成物は、炭素原子数４～１８のアルキル基を有するアクリル単量体（ａ１）、ジアセトン(メタ）アクリルアミド及びＮ－メチロール(メタ)アクリルアミドから選ばれる少なくとも１以上の単量体（ａ２）、カルボキシル基を有する不飽和単量体（ａ３）、及びアクリロニトリル（ａ４）、を必須原料とするラジカル重合体（Ａ）と、水性媒体（Ｂ）とを含有するリチウムイオン二次電池セパレータ耐熱層バインダー用水性樹脂組成物であって、前記ラジカル重合体（Ａ）の単量体原料中の前記アクリロニトリル（ａ４）が５～３０質量％であるものである。 The aqueous resin composition for a lithium ion secondary battery separator heat-resistant layer binder of the present invention comprises an acrylic monomer (a1) having an alkyl group having 4 to 18 carbon atoms, diacetone (meth)acrylamide and N-methylol (meth). A radical polymer (A) comprising as essential raw materials at least one or more monomers (a2) selected from acrylamide, an unsaturated monomer (a3) having a carboxyl group, and acrylonitrile (a4), and an aqueous medium ( B), wherein the acrylonitrile (a4) in the monomer raw material of the radical polymer (A) is 5 to 30% by mass. There is something.
まず、前記ラジカル重合体（Ａ）について説明する。前記アクリル単量体（ａ１）は、炭素原子数４～１８のアルキル基を有するアクリル単量体であるが、例えば、ｎ－ブチル（メタ）アクリレート、ｉ－ブチル（メタ）アクリレート、ｔ－ブチル（メタ）アクリレート、ｎ－ヘキシル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ｎ－オクチル(メタ)アクリレート、ラウリル（メタ）アクリレート、ステアリル（メタ）アクリレート等が挙げられる。これらのアクリル単量体（ａ１）は、単独で用いることも２種以上併用することもできる。これらの中でも、ブチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレートを用いるのが好ましい。 First, the radical polymer (A) will be described. The acrylic monomer (a1) is an acrylic monomer having an alkyl group having 4 to 18 carbon atoms, such as n-butyl (meth)acrylate, i-butyl (meth)acrylate, t-butyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate and the like. . These acrylic monomers (a1) can be used alone or in combination of two or more. Among these, butyl (meth)acrylate and 2-ethylhexyl (meth)acrylate are preferably used.
なお、本発明において、「（メタ）アクリレート」とは、アクリレートとメタクリレートの一方又は両方をいい、「（メタ）アクリルアミド」とは、アクリルアミドとメタクリルアミドの一方又は両方をいい、「(メタ)アクリル酸」とは、アクリル酸とメタクリル酸の一方又は両方をいい、「（メタ）アクリロイル」とは、アクリロイルとメタクリロイルの一方又は両方をいう。 In the present invention, "(meth)acrylate" refers to one or both of acrylate and methacrylate, "(meth)acrylamide" refers to one or both of acrylamide and methacrylamide, and "(meth)acrylamide" "Acid" refers to one or both of acrylic acid and methacrylic acid, and "(meth)acryloyl" refers to one or both of acryloyl and methacryloyl.
前記単量体（ａ２）は、ジアセトン（メタ）アクリルアミド及びＮ－メチロール（メタ）アクリルアミドから選ばれる少なくとも１以上のアクリル単量体である。 The monomer (a2) is at least one acrylic monomer selected from diacetone (meth)acrylamide and N-methylol (meth)acrylamide.
前記不飽和単量体（ａ３）は、カルボキシル基を有する不飽和単量体であるが、例えば、（メタ）アクリル酸、クロトン酸等の不飽和モノカルボン酸、無水マレイン酸、マレイン酸、無水イタコン酸、イタコン酸、フマル酸等の不飽和ジカルボン酸などが挙げられるが、耐熱収縮性がより向上することから、（メタ）アクリル酸が好ましい。なお、これらの単量体（ａ３）は、単独で用いることも２種以上併用することもできる。 The unsaturated monomer (a3) is an unsaturated monomer having a carboxyl group, and examples thereof include unsaturated monocarboxylic acids such as (meth)acrylic acid and crotonic acid, maleic anhydride, maleic Unsaturated dicarboxylic acids such as itaconic acid, itaconic acid, and fumaric acid are included, but (meth)acrylic acid is preferred because it further improves heat shrinkage resistance. These monomers (a3) can be used alone or in combination of two or more.
前記ラジカル重合体（Ａ）は、前記アクリル単量体（ａ１）、前記単量体（ａ２）、前記不飽和単量体（ａ３）、及びアクリロニトリル（ａ４）を必須原料とするが、これら以外のその他の単量体（ａ５）を単量体原料として使用してもよい。 The radical polymer (A) contains the acrylic monomer (a1), the monomer (a2), the unsaturated monomer (a3), and acrylonitrile (a4) as essential raw materials, but other than these You may use the other monomer (a5) as a monomer raw material.
前記単量体（ａ５）としては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート等のアルキル（メタ）アクリレート；２－ヒドロキシエチル（メタ）アクリレート、３－ヒドロキシプロピル（メタ）アクリレート、４－ヒドロキシ－ｎ－ブチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシ－ｎ－ブチル（メタ）アクリレート、３－ヒドロキシ－ｎ－ブチル（メタ）アクリレート、１，４－シクロヘキサンジメタノールモノ（メタ）アクリレート、Ｎ－（２－ヒドロキシエチル）（メタ）アクリルアミド、グリセリンモノ（メタ）アクリレート、ポリエチレングリコールモノ（メタ）アクリレート、ポリプロピレングリコールモノ（メタ）アクリレート、２－ヒドロキシ－３－フェノキシプロピル（メタ）アクリレート、２－（メタ）アクリロイルオキシエチル－２－ヒドロキシエチルフタレート、末端に水酸基を有するラクトン変性（メタ）アクリレート等の水酸基を有する単量体；Ｎ，Ｎ－ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ－ジエチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ－ジメチルアミノプロピル（メタ）アクリレート、Ｎ，Ｎ－ジエチルアミノプロピル（メタ）アクリレート等のアミノ基を有する（メタ）アクリレート、（メタ）アクリルアミド等のＮ－ヒドロキシメチルアミド基を有する単量体、Ｎ－ブトキシメチルアクリルアミド等のＮ－アルコキシメチルアミド基を有する単量体などの窒素原子を有する単量体；グリシジル（メタ）アクリレート等のグリシジル基を有する（メタ）アクリレート；ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルメチルジメトキシシラン、３－（メタ）アクリロイルオキシプロピルトリメトキシシラン、３－（メタ）アクリロイルオキシプロピルトリエトキシシラン、３－（メタ）アクリロイルオキシプロピルメチルジメトキシシラン等のアルコキシシリル基を有する単量体；ポリエチレングリコール（メタ）アクリレート、メトキシポリエチレングリコール（メタ）アクリレート、ポリプロピレングリコール（メタ）アクリレート、メトキシポリプロピレングリコール（メタ）アクリレート、ポリブチレングリコール（メタ）アクリレート、メトキシポリブチレングリコール（メタ）アクリレート等のポリアルキレングリコール（メタ）アクリレート；スチレン、α－メチルスチレン、パラメチルスチレン、クロロメチルスチレン、酢酸ビニル等のビニル単量体；テトラヒドロフルフリル（メタ）アクリレート、ベンジル（メタ）アクリレート；エチレングリコールジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート等のジ（メタ）アクリレートなどが挙げられる。なお、これらの単量体（ａ５）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 monomer (a5) include alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate and propyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate and 3-hydroxypropyl (meth) acrylate, 4-hydroxy-n-butyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-n-butyl (meth) acrylate, 3-hydroxy-n-butyl (meth) acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, N-(2-hydroxyethyl)(meth)acrylamide, glycerin mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, 2 -Hydroxy-3-phenoxypropyl (meth)acrylate, 2-(meth)acryloyloxyethyl-2-hydroxyethyl phthalate, monomers having hydroxyl groups such as lactone-modified (meth)acrylates having terminal hydroxyl groups; N, N -Dimethylaminoethyl (meth) acrylate, N,N-diethylaminoethyl (meth) acrylate, N,N-dimethylaminopropyl (meth) acrylate, N,N-diethylaminopropyl (meth) having an amino group (meth) ) Monomers having a nitrogen atom such as monomers having an N-hydroxymethylamide group such as acrylates and (meth)acrylamide, and monomers having an N-alkoxymethylamide group such as N-butoxymethylacrylamide; glycidyl (Meth)acrylates having a glycidyl group such as (meth)acrylate; vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, 3-(meth)acryloyloxypropyltrimethoxysilane, 3-(meth)acryloyloxypropyl Monomers having an alkoxysilyl group such as triethoxysilane, 3-(meth)acryloyloxypropylmethyldimethoxysilane; polyethylene glycol (meth)acrylate, methoxypolyethyleneglycol (meth)acrylate, polypropyleneglycol (meth)acrylate, methoxypolypropylene Polyalkylene glycol (meth)acrylate such as glycol (meth)acrylate, polybutylene glycol (meth)acrylate, methoxypolybutylene glycol (meth)acrylate, etc. ) acrylate; vinyl monomers such as styrene, α-methylstyrene, paramethylstyrene, chloromethylstyrene, and vinyl acetate; tetrahydrofurfuryl (meth)acrylate, benzyl (meth)acrylate; ethylene glycol di(meth)acrylate, propylene and di(meth)acrylates such as glycol di(meth)acrylate. These monomers (a5) can be used alone or in combination of two or more.
前記ラジカル重合体（Ａ）の単量体原料中の前記単量体（ａ１）は、基材密着性がより向上することから、５０～８０質量％が好ましく、５５～７５質量％がより好ましい。 The amount of the monomer (a1) in the monomer raw material of the radical polymer (A) is preferably 50 to 80% by mass, more preferably 55 to 75% by mass, because the substrate adhesion is further improved. .
前記ラジカル重合体（Ａ）の単量体原料中の前記単量体（ａ２）は、耐熱収縮性がより向上することから、１～２０質量％が好ましく、３～２０質量％がより好ましく、５～１５質量％がさらに好ましい。 The monomer (a2) in the monomer raw material of the radical polymer (A) is preferably 1 to 20% by mass, more preferably 3 to 20% by mass, because the heat shrinkage resistance is further improved. 5 to 15% by mass is more preferable.
前記ラジカル重合体（Ａ）の単量体原料中の前記単量体（ａ３）は、耐熱収縮性がより向上することから、０．５～５質量％が好ましく、０．５～３質量％がより好ましい。 The monomer (a3) in the monomer raw material of the radical polymer (A) is preferably 0.5 to 5% by mass, more preferably 0.5 to 3% by mass, because the heat shrinkage resistance is further improved. is more preferred.
前記ラジカル重合体（Ａ）の単量体原料中のアクリロニトリル（ａ４）は、５～３５質量％であるが、耐熱収縮性がより向上することから、１０～３５質量％が好ましく、２０～３５質量％がより好ましい。 The acrylonitrile (a4) in the monomer raw material of the radical polymer (A) is 5 to 35% by mass, but is preferably 10 to 35% by mass, more preferably 20 to 35%, because the heat shrinkage resistance is further improved. % by mass is more preferred.
前記ラジカル重合体（Ａ）の製造方法としては、各種の方法が挙げられるが、簡便に前記ラジカル重合体（Ａ）を得られることから、水中重合法若しくは乳化重合法が好ましい。 As a method for producing the radical polymer (A), there are various methods, but an underwater polymerization method or an emulsion polymerization method is preferable because the radical polymer (A) can be obtained easily.
乳化重合法により、前記ラジカル重合体（Ａ）を得る方法としては、例えば、前記ラジカル重合体（Ａ）の原料となる前記単量体（ａ１）等を、水性媒体中で、乳化剤及び重合開始剤存在下、５０～１００℃の温度でラジカル重合する方法が挙げられる。 As a method of obtaining the radical polymer (A) by an emulsion polymerization method, for example, the monomer (a1), which is a raw material of the radical polymer (A), is added in an aqueous medium with an emulsifier and a polymerization initiator. A method of radical polymerization at a temperature of 50 to 100° C. in the presence of an agent may be mentioned.
前記乳化剤としては、例えば、高級アルコールの硫酸エステル及びその塩、アルキルベンゼンスルホン酸塩、ポリオキシエチレンアルキルフェニルスルホン酸塩、ポリオキシエチレンアルキルジフェニルエーテルスルホン酸塩、ポリオキシエチレンア
ルキルエーテルの硫酸ハーフエステル塩、アルキルジフェニルエーテルジスルホン酸塩、コハク酸ジアルキルエステルスルホン酸塩等の陰イオン性乳化剤；ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル、ポリオキシエチレンジフェニルエーテル、ポリオキシエチレン－ポリオキシプロピレンブロック共重合体、アセチレンジオール系等の非イオン性乳化剤；アルキルアンモニウム塩等の陽イオン性乳化剤；アルキル（アミド）ベタイン、アルキルジメチルアミンオキシド等の両イオン性乳化剤などが挙げられる。なお、これらの乳化剤は、単独で用いることも２種以上併用することもできる。なお、前記単量体（ａ１）を乳化剤として使用することもできる。Examples of the emulsifier include sulfuric acid esters of higher alcohols and salts thereof, alkylbenzene sulfonates, polyoxyethylene alkylphenyl sulfonates, polyoxyethylene alkyldiphenyl ether sulfonates, sulfuric acid half ester salts of polyoxyethylene alkyl ethers, Anionic emulsifiers such as alkyldiphenyl ether disulfonates and dialkyl succinate sulfonates; polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene diphenyl ethers, polyoxyethylene-polyoxypropylene block copolymers, nonionic emulsifiers such as acetylene diol; cationic emulsifiers such as alkylammonium salts; and amphoteric emulsifiers such as alkyl(amide)betaines and alkyldimethylamine oxides. These emulsifiers can be used alone or in combination of two or more. The monomer (a1) can also be used as an emulsifier.
前記重合開始剤としては、例えば、２，２’－アゾビス（イソブチロニトリル）、２，２’－アゾビス（２－メチルブチロニトリル）、アゾビスシアノ吉草酸等のアゾ化合物；ｔｅｒｔ－ブチルパーオキシピバレート、ｔｅｒｔ－ブチルパーオキシベンゾエート、ｔｅｒｔ－ブチルパーオキシ－２－エチルヘキサノエート、ジ－ｔｅｒｔ－ブチルパーオキサイド、クメンハイドロパーオキサイド、ベンゾイルパーオキサイド、ｔｅｒｔ－ブチルハイドロパーオキサイド等の有機過酸化物；過酸化水素、過硫酸アンモニウム、過硫酸カリウム、過硫酸ナトリウム等の無機過酸化物などが挙げられる。なお、これらの重合体開始剤は、単独で用いることも２種以上併用することもできる。また、これらの重合開始剤は、重合体の原料となる単量体の合計に対して、０．１～１０質量％の範囲内で使用することが好ましい。 Examples of the polymerization initiator include 2,2′-azobis(isobutyronitrile), 2,2′-azobis(2-methylbutyronitrile), azo compounds such as azobiscyanovaleric acid; tert-butyl peroxy organic peroxides such as pivalate, tert-butyl peroxybenzoate, tert-butyl peroxy-2-ethylhexanoate, di-tert-butyl peroxide, cumene hydroperoxide, benzoyl peroxide, tert-butyl hydroperoxide; Oxides; inorganic peroxides such as hydrogen peroxide, ammonium persulfate, potassium persulfate and sodium persulfate; These polymer initiators can be used alone or in combination of two or more. These polymerization initiators are preferably used within a range of 0.1 to 10% by weight with respect to the total amount of monomers that are raw materials for the polymer.
前記ラジカル重合体（Ａ）の分散安定性がより向上することから、塩基性化合物及び／又は酸性化合物により、ｐＨを調整することが好ましく、前記塩基性化合物としては、例えば、メチルアミン、ジメチルアミン、トリメチルアミン、エチルアミン、ジエチルアミン、トリエチルアミン、２－アミノエタノール、２－ジメチルアミノエタノール等の有機アミン；アンモニア（水）、水酸化ナトリウム、水酸化カリウム等の無機塩基性化合物；テトラメチルアンモニウムハイドロオキサイド、テトラ－ｎ－ブチルアンモニウムハイドロオキサイド、トリメチルベンジルアンモニウムハイドロオキサイドの四級アンモニウムハイドロオキサイドなどが挙げられる。なお、これらの塩基性化合物は、単独で用いることも２種以上併用することもできる。 Since the dispersion stability of the radical polymer (A) is further improved, it is preferable to adjust the pH with a basic compound and/or an acidic compound. Examples of the basic compound include methylamine and dimethylamine. , trimethylamine, ethylamine, diethylamine, triethylamine, 2-aminoethanol, 2-dimethylaminoethanol and other organic amines; ammonia (water), sodium hydroxide, inorganic basic compounds such as potassium hydroxide; tetramethylammonium hydroxide, tetra quaternary ammonium hydroxides such as n-butylammonium hydroxide and trimethylbenzylammonium hydroxide; These basic compounds can be used alone or in combination of two or more.
前記酸性化合物としては、例えば、蟻酸、酢酸、プロピオン酸または乳酸等のカルボン酸化合物；燐酸モノメチルエステル、燐酸ジメチルエステル等の燐酸のモノエステルまたはジエステル；メタンスルホン酸、ベンゼンスルホン酸、ドデシルベンゼンスルホン酸等の有機スルホン酸化合物；塩酸、硫酸、硝酸、燐酸等の無機酸などである。これらの中でも、カルボン酸化合物が好ましい。なお、これらの酸性化合物は、単独で用いることも２種以上併用することもできる。 Examples of the acidic compound include carboxylic acid compounds such as formic acid, acetic acid, propionic acid and lactic acid; phosphoric acid monoesters and diesters such as phosphoric acid monomethyl ester and phosphoric acid dimethyl ester; methanesulfonic acid, benzenesulfonic acid and dodecylbenzenesulfonic acid. organic sulfonic acid compounds such as; inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid; Among these, carboxylic acid compounds are preferred. These acidic compounds can be used alone or in combination of two or more.
前記水性媒体（Ｂ）としては、水、水と混和する有機溶剤、及び、これらの混合物が挙げられる。水と混和する有機溶剤としては、例えば、メタノール、エタノール、ｎ－プロパノール及びイソプロパノール等のアルコール；アセトン、メチルエチルケトン等のケトン；エチレングリコール、ジエチレングリコール、プロピレングリコール等のポリアルキレングリコール；ポリアルキレングリコールのアルキルエーテル；Ｎ－メチル－２－ピロリドン等のラクタム等が挙げられる。本発明では、水のみを用いても良く、また水及び水と混和する有機溶剤との混合物を用いても良く、水と混和する有機溶剤のみを用いても良い。安全性や環境に対する負荷の点から、水のみ、または、水及び水と混和する有機溶剤との混合物が好ましく、水のみを使用することが特に好ましい。 Examples of the aqueous medium (B) include water, organic solvents miscible with water, and mixtures thereof. Examples of water-miscible organic solvents include alcohols such as methanol, ethanol, n-propanol and isopropanol; ketones such as acetone and methyl ethyl ketone; polyalkylene glycols such as ethylene glycol, diethylene glycol and propylene glycol; and alkyl ethers of polyalkylene glycols. and lactams such as N-methyl-2-pyrrolidone. In the present invention, only water may be used, a mixture of water and an organic solvent miscible with water may be used, or only an organic solvent miscible with water may be used. From the viewpoint of safety and environmental load, water alone or a mixture of water and an organic solvent miscible with water is preferred, and water alone is particularly preferred.
前記水性媒体（Ｂ）は、前記重合体（Ａ）を水中重合法および乳化重合法により製造する際に使用される水性媒体をそのまま使用することが、簡便であり好ましい。 For the aqueous medium (B), it is convenient and preferable to use the aqueous medium as it is that is used when the polymer (A) is produced by an aqueous polymerization method or an emulsion polymerization method.
本発明の水性樹脂組成物は、前記ラジカル重合体（Ａ）及び前記水性媒体（Ｂ）を含有するものであるが、乳化重合法等により得られた、前記ラジカル重合体（Ａ）が前記水性媒体（Ｂ）に分散したものであることが好ましい。 The aqueous resin composition of the present invention contains the radical polymer (A) and the aqueous medium (B). It is preferably dispersed in the medium (B).
また、必要に応じて脱溶剤工程を経ることにより、本発明の樹脂組成物中の有機溶剤量を低減することができる。 Moreover, the organic solvent amount in the resin composition of this invention can be reduced by passing through a solvent removal process as needed.
前記方法で得られた本発明の水性樹脂組成物は、塗工作業性がより向上することから、水性樹脂組成物の全量に対して前記ラジカル重合体（Ａ）を５～６０質量％の範囲で含有するものが好ましく、１０～５０質量％の範囲で含有するものがより好ましい。 The water-based resin composition of the present invention obtained by the above method has a further improved coating workability. is preferably contained, more preferably in the range of 10 to 50% by mass.
また、本発明の水性樹脂組成物は、塗工作業性がより向上することから、水性樹脂組成物の全量に対して前記水性媒体（Ｂ）を９５～４０質量％の範囲で含有するものが好ましく、９０～５０質量％の範囲で含有するものがより好ましい。 Further, since the aqueous resin composition of the present invention further improves the coating workability, those containing the aqueous medium (B) in the range of 95 to 40% by mass with respect to the total amount of the aqueous resin composition More preferably, it is contained in the range of 90 to 50% by mass.
本発明の水性樹脂組成物は、必要に応じて、硬化剤、硬化触媒、潤滑剤、充填剤、チキソ付与剤、粘着付与剤、ワックス、熱安定剤、耐光安定剤、蛍光増白剤、発泡剤等の添加剤、ｐＨ調整剤、レベリング剤、ゲル化防止剤、分散安定剤、酸化防止剤、ラジカル捕捉剤、耐熱性付与剤、無機充填剤、有機充填剤、可塑剤、補強剤、触媒、抗菌剤、防カビ剤、防錆剤、熱可塑性樹脂、熱硬化性樹脂、顔料、染料、導電性付与剤、帯電防止剤、透湿性向上剤、撥水剤、撥油剤、中空発泡体、結晶水含有化合物、難燃剤、吸水剤、吸湿剤、消臭剤、整泡剤、消泡剤、防黴剤、防腐剤、防藻剤、顔料分散剤、ブロッキング防止剤、加水分解防止剤、顔料を併用することができる。 The aqueous resin composition of the present invention may optionally contain a curing agent, a curing catalyst, a lubricant, a filler, a thixotropic agent, a tackifier, a wax, a heat stabilizer, a light stabilizer, a fluorescent brightener, and a foaming agent. additives such as agents, pH adjusters, leveling agents, anti-gelling agents, dispersion stabilizers, antioxidants, radical scavengers, heat resistance imparting agents, inorganic fillers, organic fillers, plasticizers, reinforcing agents, catalysts , antibacterial agents, antifungal agents, rust inhibitors, thermoplastic resins, thermosetting resins, pigments, dyes, conductivity imparting agents, antistatic agents, moisture permeability improvers, water repellent agents, oil repellent agents, hollow foams, Crystalline water-containing compound, flame retardant, water absorbing agent, moisture absorbent, deodorant, foam stabilizer, antifoaming agent, antifungal agent, antiseptic agent, anti-algae agent, pigment dispersant, anti-blocking agent, anti-hydrolysis agent, A pigment can be used in combination.
なお、前記単量体（ａ２）として、ジアセトン(メタ）アクリルアミドを使用する際は、ジヒドラジド化合物を併用することが好ましい。 When using diacetone (meth)acrylamide as the monomer (a2), it is preferable to use a dihydrazide compound together.
本発明の水性樹脂組成物は、熱収縮率の小さいセパレータが得られることから、リチウムイオン二次電池耐熱層のバインダーとして好適に用いることができる。 The aqueous resin composition of the present invention can be suitably used as a binder for a heat-resistant layer of a lithium-ion secondary battery, since a separator having a small heat shrinkage can be obtained.
本発明の水性樹脂組成物に無機充填剤を添加することで、優れた耐熱性を有する耐熱層が得られる。 By adding an inorganic filler to the aqueous resin composition of the present invention, a heat-resistant layer having excellent heat resistance can be obtained.
前記無機充填剤としては、例えば、シリカ、アルミナ、チタニア、ジルコニア、マグネシア、酸化亜鉛、酸化鉄等の酸化物、窒化ケイ素、窒化チタン、窒化ホウ素等の窒化物、シリコンカーバイド、炭酸カルシウム、硫酸マグネシウム、硫酸アルミニウム、水酸化アルミニウム、水酸化酸化アルミニウム、チタン酸カリウム、タルク、カオリナイト、ディカイト、ナクライト、ハロイサイト、パイロフィライト、モンモリロナイト、セリサイト、マイカ、アメサイト、ベントナイト、アスベスト、ゼオライト、ケイ酸カルシウム、ケイ酸マグネシウム、ケイ藻土、ケイ砂、焼成カオリンなどを使用することができる。これらの中でも、焼成カオリンまたはアルミナを使用することが、より一層、耐熱性に優れた耐熱層を形成するうえで好ましい。 Examples of the inorganic filler include oxides such as silica, alumina, titania, zirconia, magnesia, zinc oxide and iron oxide, nitrides such as silicon nitride, titanium nitride and boron nitride, silicon carbide, calcium carbonate, and magnesium sulfate. , aluminum sulfate, aluminum hydroxide, aluminum hydroxide oxide, potassium titanate, talc, kaolinite, dakite, nacrite, halloysite, pyrophyllite, montmorillonite, sericite, mica, amesite, bentonite, asbestos, zeolite, silicic acid Calcium, magnesium silicate, diatomaceous earth, silica sand, calcined kaolin, and the like can be used. Among these, it is preferable to use calcined kaolin or alumina in order to form a heat-resistant layer with even more excellent heat resistance.
前記無機充填剤と本発明の水性樹脂組成物との固形分質量比が１／１，０００～１／５となる範囲で使用することが、イオンを伝導可能な程度の連通孔を備えたセパレータを形成し、かつ耐熱性に優れたセパレータを形成するうえで好ましい。 A separator having communicating pores capable of conducting ions can be used in a range where the solid content mass ratio between the inorganic filler and the water-based resin composition of the present invention is 1/1,000 to 1/5. and forming a separator excellent in heat resistance.
以下に本発明を具体的な実施例を挙げてより詳細に説明する。 The present invention will be described in more detail below with specific examples.
（実施例１：リチウムイオン二次電池セパレータ耐熱層バインダー用水性樹脂組成物（１）の合成及び評価）
攪拌機、温度計および冷却器、窒素ブローを取り付けた１．０Ｌの反応容器中に、イオン交換水１１２．０質量部、を仕込み６０℃まで加熱したのち、これにアクリル酸１．０質量部、Ｎ－メチロールアクリルアミド５．０質量部、ｎ－ブチルアクリレート６０．０質量部、アクリロニトリル３４．０質量部の混合物を、乳化剤（第一工業製薬製「ハイテノールＮ－０８」、アニオン乳化剤）１．５質量部をイオン交換水３５．５質量部に溶解した乳化剤水溶液にて乳化し、モノマープレミックスとした。このモノマープレミックスと過硫酸アンモニウム０．４質量部とをイオン交換水３５質量部で溶解した水溶液を３時間滴下し、反応を行った。反応終了後同温度にて２時間ホールド後、冷却を行った。
冷却後イオン交換水および１２．５質量％アンモニア水溶液を用い不揮発分３９．８質量％、ｐＨ３．８に調整を行った。このときの粘度は１８５ｍＰａ・ｓであった。なお、粘度は、ＢＭ型粘度計（２５℃、φＮｏ．２、６０ｒｐｍ）で測定した値である。(Example 1: Synthesis and evaluation of aqueous resin composition (1) for lithium ion secondary battery separator heat-resistant layer binder)
Into a 1.0 L reaction vessel equipped with a stirrer, a thermometer, a cooler, and a nitrogen blower, 112.0 parts by mass of ion-exchanged water was charged and heated to 60° C., followed by adding 1.0 parts by mass of acrylic acid, A mixture of 5.0 parts by mass of N-methylolacrylamide, 60.0 parts by mass of n-butyl acrylate, and 34.0 parts by mass of acrylonitrile was added to an emulsifier (Daiichi Kogyo Seiyaku "Hitenol N-08", an anionic emulsifier). 5 parts by mass of the mixture was emulsified with an emulsifier aqueous solution prepared by dissolving 5 parts by mass of the mixture in 35.5 parts by mass of deionized water to obtain a monomer premix. An aqueous solution prepared by dissolving this monomer premix and 0.4 parts by mass of ammonium persulfate in 35 parts by mass of ion-exchanged water was added dropwise for 3 hours to carry out a reaction. After completion of the reaction, the mixture was held at the same temperature for 2 hours and then cooled.
After cooling, ion-exchanged water and 12.5% by mass ammonia aqueous solution were used to adjust the non-volatile content to 39.8% by mass and pH to 3.8. The viscosity at this time was 185 mPa·s. The viscosity is a value measured with a BM type viscometer (25° C., φ No. 2, 60 rpm).
［耐熱層スラリーの調製］
ホモディスパーで５，０００回転にて撹拌しながら１質量％カルボキシメチルセルロース（ダイセル化学株式会社性「ＤＮ－８００Ｈ」）１００質量部にアルミナ（住友化学株式会社製「ＡＫＰ－５０」）１００質量部を徐々に加え、分散を行った。これらが均一混合された後、上記で合成した水性樹脂組成物（１）２０．０質量部、イオン交換水３０５．０質量部を添加し、均一に混合し、耐熱層スラリー（１）を調製した。[Preparation of heat-resistant layer slurry]
100 parts by mass of alumina ("AKP-50" by Sumitomo Chemical Co., Ltd.) was added to 100 parts by mass of 1% by mass carboxymethyl cellulose ("DN-800H" by Daicel Chemical Co., Ltd.) while stirring at 5,000 rpm with a homodisper. Gradually added and dispersed. After these are uniformly mixed, 20.0 parts by mass of the aqueous resin composition (1) synthesized above and 305.0 parts by mass of ion-exchanged water are added and uniformly mixed to prepare heat-resistant layer slurry (1). did.
［耐熱層を有するセパレータの作製］
厚み１２μｍのポリエチレンセパレータ基材両面に上記で得た耐熱層スラリー（１）をバーコーターにて乾燥後の膜厚が４μｍとなるように塗工し、セパレータ（１）を得た。乾燥温度は６０℃、乾燥時間は５分間とした。[Preparation of separator having heat-resistant layer]
The heat-resistant layer slurry (1) obtained above was coated on both sides of a polyethylene separator base material having a thickness of 12 μm with a bar coater so that the film thickness after drying was 4 μm to obtain a separator (1). The drying temperature was 60° C. and the drying time was 5 minutes.
［耐熱収縮性の評価］
上記で作成した耐熱層を有するセパレータを５ｃｍ角に切り、厚紙に挟んだ状態で１８０℃温風乾燥機に１時間静置し、耐熱性試験を行った。試験後のセパレータの縦、横各々の長さを測定し、縦方向の収縮率（ＭＤ収縮率（％））及び横方向の収縮率（ＴＤ収縮率（％））を算出し、耐熱収縮性を評価した。
収縮率（％）＝試験後のセパレータの長さ／試験前のセパレータの長さ×１００（％）[Evaluation of heat shrinkage resistance]
The separator having the heat-resistant layer prepared above was cut into 5 cm squares, sandwiched between cardboard sheets, and allowed to stand in a hot air dryer at 180° C. for 1 hour to conduct a heat resistance test. The vertical and horizontal lengths of the separator after the test are measured, and the shrinkage rate in the vertical direction (MD shrinkage rate (%)) and the shrinkage rate in the horizontal direction (TD shrinkage rate (%)) are calculated. evaluated.
Shrinkage rate (%) = length of separator after test/length of separator before test x 100 (%)
（実施例２：リチウムイオン二次電池セパレータ耐熱層バインダー用水性樹脂組成物（２）の合成及び評価）
攪拌機、温度計および冷却器、窒素ブローを取り付けた１．０Ｌの反応容器中に、イオン交換水１１２．０質量部、を仕込み６０℃まで加熱したのち、これにアクリル酸３．０質量部、Ｎ－メチロールアクリルアミド１０．０質量部、ｎ－ブチルアクリレート６０．０質量部、アクリロニトリル２７．０質量部の混合物を、乳化剤（第一工業製薬製「ハイテノールＮ－０８」、アニオン乳化剤）１．５質量部をイオン交換水３５．５質量部に溶解した乳化剤水溶液にて乳化し、モノマープレミックスとした。このモノマープレミックスと過硫酸アンモニウム０．４質量部とをイオン交換水３５質量部で溶解した水溶液を３時間滴下し、反応を行った。反応終了後同温度にて２時間ホールド後、冷却を行った。
冷却後イオン交換水および１２．５質量％アンモニア水溶液を用い不揮発分３９．９質量％、ｐＨ３．９に調整を行った。このときの粘度は３１５ｍＰａ・ｓであった。(Example 2: Synthesis and evaluation of aqueous resin composition (2) for lithium ion secondary battery separator heat-resistant layer binder)
Into a 1.0 L reaction vessel equipped with a stirrer, a thermometer, a cooler, and a nitrogen blower, 112.0 parts by mass of ion-exchanged water was charged and heated to 60° C., followed by adding 3.0 parts by mass of acrylic acid, A mixture of 10.0 parts by mass of N-methylolacrylamide, 60.0 parts by mass of n-butyl acrylate, and 27.0 parts by mass of acrylonitrile was added to an emulsifier (Daiichi Kogyo Seiyaku "Hitenol N-08", an anionic emulsifier). 5 parts by mass of the mixture was emulsified with an emulsifier aqueous solution prepared by dissolving 5 parts by mass of the mixture in 35.5 parts by mass of deionized water to obtain a monomer premix. An aqueous solution prepared by dissolving this monomer premix and 0.4 parts by mass of ammonium persulfate in 35 parts by mass of ion-exchanged water was added dropwise for 3 hours to carry out a reaction. After completion of the reaction, the mixture was held at the same temperature for 2 hours and then cooled.
After cooling, ion-exchanged water and 12.5% by mass ammonia aqueous solution were used to adjust the non-volatile content to 39.9% by mass and pH to 3.9. The viscosity at this time was 315 mPa·s.
実施例１で用いたリチウムイオン二次電池セパレータ耐熱層バインダー用水性樹脂組成物（１）をリチウムイオン二次電池セパレータ耐熱層バインダー用水性樹脂組成物（２）に変更した以外は、実施例１と同様に操作することにより、耐熱層スラリー（２）及びセパレータ（２）を作製し、耐熱収縮性を評価した。 Example 1 except that the aqueous resin composition for lithium ion secondary battery separator heat-resistant layer binder (1) used in Example 1 was changed to lithium ion secondary battery separator heat-resistant layer binder aqueous resin composition (2) A heat-resistant layer slurry (2) and a separator (2) were prepared by operating in the same manner as in , and the heat shrinkage resistance was evaluated.
（実施例３：リチウムイオン二次電池セパレータ耐熱層バインダー用水性樹脂組成物（３）の合成及び評価）
攪拌機、温度計および冷却器、窒素ブローを取り付けた１．０Ｌの反応容器中に、イオン交換水１１２．０質量部、を仕込み６０℃まで加熱したのち、これにアクリル酸３．０質量部、ジアセトンアクリルアミド１０．０質量部、ｎ－ブチルアクリレート６０．０質量部、アクリロニトリル２７．０質量部の混合物を、乳化剤（第一工業製薬製「ハイテノールＮ－０８」、アニオン乳化剤）１．５質量部をイオン交換水３５．５質量部に溶解した乳化剤水溶液にて乳化し、モノマープレミックスとした。このモノマープレミックスと過硫酸アンモニウム０．４質量部とをイオン交換水３５質量部で溶解した水溶液を３時間滴下し、反応を行った。反応終了後同温度にて２時間ホールド後、冷却を行った。
冷却後アジピン酸ジヒドラジド５．０質量部添加溶解後、イオン交換水および１２．５質量％アンモニア水溶液を用い不揮発分４０．１質量％、ｐＨ４．１に調整を行った。このときの粘度は１２８ｍＰａ・ｓであった。(Example 3: Synthesis and evaluation of aqueous resin composition (3) for lithium ion secondary battery separator heat-resistant layer binder)
Into a 1.0 L reaction vessel equipped with a stirrer, a thermometer, a cooler, and a nitrogen blower, 112.0 parts by mass of ion-exchanged water was charged and heated to 60° C., followed by adding 3.0 parts by mass of acrylic acid, A mixture of 10.0 parts by mass of diacetone acrylamide, 60.0 parts by mass of n-butyl acrylate, and 27.0 parts by mass of acrylonitrile was mixed with an emulsifier (Daiichi Kogyo Seiyaku "Hitenol N-08", an anionic emulsifier) 1.5. A part by mass of the mixture was dissolved in 35.5 parts by mass of ion-exchanged water and emulsified with an emulsifier aqueous solution to obtain a monomer premix. An aqueous solution prepared by dissolving this monomer premix and 0.4 parts by mass of ammonium persulfate in 35 parts by mass of ion-exchanged water was added dropwise for 3 hours to carry out a reaction. After completion of the reaction, the mixture was held at the same temperature for 2 hours and then cooled.
After cooling, 5.0 parts by mass of adipic acid dihydrazide was added and dissolved, and the non-volatile content was adjusted to 40.1% by mass and pH to 4.1 using deionized water and 12.5% by mass aqueous ammonia solution. The viscosity at this time was 128 mPa·s.
実施例１で用いたリチウムイオン二次電池セパレータ耐熱層バインダー用水性樹脂組成物（１）をリチウムイオン二次電池セパレータ耐熱層バインダー用水性樹脂組成物（３）に変更した以外は、実施例１と同様に操作することにより、耐熱層スラリー（３）及びセパレータ（３）を作製し、耐熱収縮性を評価した。 Example 1 except that the aqueous resin composition for lithium ion secondary battery separator heat-resistant layer binder (1) used in Example 1 was changed to lithium ion secondary battery separator heat-resistant layer binder aqueous resin composition (3) A heat-resistant layer slurry (3) and a separator (3) were prepared by operating in the same manner as in , and the heat shrinkage resistance was evaluated.
（比較例１：リチウムイオン二次電池セパレータ耐熱層バインダー用水性樹脂組成物（Ｒ１）の合成及び評価）
攪拌機、温度計および冷却器、窒素ブローを取り付けた１．０Ｌの反応容器中に、イオン交換水１１２．０質量部、を仕込み６０℃まで加熱したのち、これにメタクリル酸２．０質量部、アクリルアミド１．６質量部、ｎ－ブチルアクリレート９２．８質量部、アクリロニトリル２．０質量部の混合物を、乳化剤（第一工業製薬製「ハイテノールＮ－０８」、アニオン乳化剤）１．５質量部をイオン交換水３５．５質量部に溶解した乳化剤水溶液にて乳化し、モノマープレミックスとした。このモノマープレミックスと過硫酸アンモニウム０．４質量部とをイオン交換水３５質量部で溶解した水溶液を３時間滴下し、反応を行った。反応終了後同温度にて２時間ホールド後、冷却を行った。
冷却後イオン交換水および５質量％水酸化ナトリウム水溶液を用い不揮発分３９．９質量％、ｐＨ６．０に調整を行った。このときの粘度は３５ｍＰａ・ｓであった。(Comparative Example 1: Synthesis and evaluation of aqueous resin composition (R1) for lithium ion secondary battery separator heat-resistant layer binder)
Into a 1.0 L reactor equipped with a stirrer, a thermometer, a cooler, and a nitrogen blower, 112.0 parts by mass of ion-exchanged water was charged and heated to 60° C., then 2.0 parts by mass of methacrylic acid, A mixture of 1.6 parts by mass of acrylamide, 92.8 parts by mass of n-butyl acrylate, and 2.0 parts by mass of acrylonitrile was added to 1.5 parts by mass of an emulsifier (Daiichi Kogyo Seiyaku "Hitenol N-08", an anionic emulsifier). was dissolved in 35.5 parts by mass of ion-exchanged water and emulsified with an aqueous emulsifier solution to obtain a monomer premix. An aqueous solution prepared by dissolving this monomer premix and 0.4 parts by mass of ammonium persulfate in 35 parts by mass of ion-exchanged water was added dropwise for 3 hours to carry out a reaction. After completion of the reaction, the mixture was held at the same temperature for 2 hours and then cooled.
After cooling, ion-exchanged water and a 5% by mass sodium hydroxide aqueous solution were used to adjust the non-volatile content to 39.9% by mass and pH to 6.0. The viscosity at this time was 35 mPa·s.
実施例１で用いたリチウムイオン二次電池セパレータ耐熱層バインダー用水性樹脂組成物（１）をリチウムイオン二次電池セパレータ耐熱層バインダー用水性樹脂組成物（Ｒ１）に変更した以外は、実施例１と同様に操作することにより、耐熱層スラリー（Ｒ１）及びセパレータ（Ｒ１）を作製し、耐熱収縮性を評価した。 Example 1 except that the aqueous resin composition (1) for the lithium ion secondary battery separator heat-resistant layer binder used in Example 1 was changed to the lithium ion secondary battery separator heat-resistant layer binder aqueous resin composition (R1). A heat-resistant layer slurry (R1) and a separator (R1) were prepared by operating in the same manner as in , and heat shrinkage resistance was evaluated.
上記の実施例１～３及び比較例１の評価結果を表１に示す。 Table 1 shows the evaluation results of Examples 1 to 3 and Comparative Example 1 described above.
本発明の水性樹脂組成物である実施例１～３のものから得られる耐熱層は、耐熱収縮性に優れることが確認された。 It was confirmed that the heat-resistant layers obtained from the water-based resin compositions of Examples 1 to 3 are excellent in heat shrinkage resistance.
一方、比較例１は、単量体原料中の前記アクリロニトリル（ａ４）が、本発明の下限である５質量％未満の例であるが、得られる耐熱層の耐熱収縮性が劣ることが確認された。 On the other hand, Comparative Example 1 is an example in which the acrylonitrile (a4) in the monomer raw material is less than 5% by mass, which is the lower limit of the present invention, but it was confirmed that the heat shrinkage resistance of the obtained heat-resistant layer was inferior. rice field.
Claims (2)
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| PCT/JP2021/019097 WO2021251092A1 (en) | 2020-06-11 | 2021-05-20 | Aqueous resin composition for binder for lithium ion secondary battery separator heat-resistant layers |
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| JP5323590B2 (en) | 2009-06-19 | 2013-10-23 | 旭化成イーマテリアルズ株式会社 | Multilayer porous membrane, resin binder and coating solution |
| JP6430472B2 (en) * | 2016-01-15 | 2018-11-28 | 関西ペイント株式会社 | Conductive paste for lithium ion battery positive electrode and composite paste for lithium ion battery positive electrode |
| JP6941431B2 (en) * | 2016-11-30 | 2021-09-29 | 旭化成株式会社 | A binder composition for a power storage device, a slurry for a porous layer of a power storage device, a porous layer of a power storage device, a separator with a porous layer of the power storage device and a lithium ion secondary battery, and a method for improving the separability. |
| CN107384261A (en) * | 2017-07-21 | 2017-11-24 | 中国乐凯集团有限公司 | A kind of lithium ion battery separator refractory layer aqueous binder, preparation method and applications |
| CN108929401A (en) * | 2018-06-25 | 2018-12-04 | 重庆云天化瀚恩新材料开发有限公司 | A kind of lithium battery silicium cathode adhesive and preparation method thereof |
| KR102277492B1 (en) * | 2018-11-20 | 2021-07-14 | 주식회사 엘지화학 | Electrode binder composition for rechargeable battery and electrode mixture including the same |
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| WO2013146515A1 (en) | 2012-03-28 | 2013-10-03 | 日本ゼオン株式会社 | Porous membrane for secondary batteries, method for producing same, electrode for secondary batteries, separator for secondary batteries, and secondary battery |
| WO2014148577A1 (en) | 2013-03-21 | 2014-09-25 | 日本ゼオン株式会社 | Slurry for lithium ion secondary battery porous film, production method therefor, separator for lithium ion secondary battery, and lithium ion secondary battery |
| JP2015041603A (en) | 2013-08-23 | 2015-03-02 | 日本ゼオン株式会社 | Adhesive agent for lithium ion secondary batteries, separator with adhesion layer, electrode with adhesion layer, and lithium ion secondary battery |
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| JP2020087591A (en) | 2018-11-20 | 2020-06-04 | 三井化学株式会社 | Raw material of coating material for secondary battery separator, method for manufacturing raw material of coating material for secondary battery separator, coating material for secondary battery separator, secondary battery separator, method for manufacturing secondary battery separator, and secondary battery |
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