JP6864523B2 - Core-shell type particles and their uses and manufacturing methods - Google Patents
Core-shell type particles and their uses and manufacturing methods Download PDFInfo
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- JP6864523B2 JP6864523B2 JP2017072852A JP2017072852A JP6864523B2 JP 6864523 B2 JP6864523 B2 JP 6864523B2 JP 2017072852 A JP2017072852 A JP 2017072852A JP 2017072852 A JP2017072852 A JP 2017072852A JP 6864523 B2 JP6864523 B2 JP 6864523B2
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- 239000002245 particle Substances 0.000 title claims description 160
- 239000011258 core-shell material Substances 0.000 title claims description 74
- 238000004519 manufacturing process Methods 0.000 title claims description 19
- 229920000642 polymer Polymers 0.000 claims description 96
- -1 halogenated alkyl vinyl compound Chemical class 0.000 claims description 77
- 150000001875 compounds Chemical class 0.000 claims description 66
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 63
- 239000008199 coating composition Substances 0.000 claims description 51
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 38
- 239000000178 monomer Substances 0.000 claims description 38
- 125000004429 atom Chemical group 0.000 claims description 33
- 239000006185 dispersion Substances 0.000 claims description 27
- 125000004432 carbon atom Chemical group C* 0.000 claims description 26
- 125000005842 heteroatom Chemical group 0.000 claims description 24
- 238000002844 melting Methods 0.000 claims description 24
- 230000008018 melting Effects 0.000 claims description 24
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- 239000007788 liquid Substances 0.000 claims description 21
- 125000000217 alkyl group Chemical group 0.000 claims description 20
- 239000002612 dispersion medium Substances 0.000 claims description 20
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 17
- 239000000470 constituent Substances 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 13
- 239000000945 filler Substances 0.000 claims description 11
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 11
- 238000007731 hot pressing Methods 0.000 claims description 10
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
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- 238000007720 emulsion polymerization reaction Methods 0.000 description 16
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- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 15
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000002835 absorbance Methods 0.000 description 6
- 239000003125 aqueous solvent Substances 0.000 description 6
- 239000001768 carboxy methyl cellulose Substances 0.000 description 6
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- 239000002033 PVDF binder Substances 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
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- 238000001035 drying Methods 0.000 description 5
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- 239000010419 fine particle Substances 0.000 description 5
- 125000001153 fluoro group Chemical group F* 0.000 description 5
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 5
- 239000003002 pH adjusting agent Substances 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- SNGREZUHAYWORS-UHFFFAOYSA-M 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctanoate Chemical compound [O-]C(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-M 0.000 description 4
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 4
- ZZAGLMPBQOKGGT-UHFFFAOYSA-N [4-[4-(4-prop-2-enoyloxybutoxy)benzoyl]oxyphenyl] 4-(4-prop-2-enoyloxybutoxy)benzoate Chemical compound C1=CC(OCCCCOC(=O)C=C)=CC=C1C(=O)OC(C=C1)=CC=C1OC(=O)C1=CC=C(OCCCCOC(=O)C=C)C=C1 ZZAGLMPBQOKGGT-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 230000000855 fungicidal effect Effects 0.000 description 4
- 239000000417 fungicide Substances 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- 238000007719 peel strength test Methods 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 229920001447 polyvinyl benzene Polymers 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 239000007774 positive electrode material Substances 0.000 description 4
- 238000004062 sedimentation Methods 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 239000000080 wetting agent Substances 0.000 description 4
- WLIVGKZSWFDOQX-UHFFFAOYSA-N 2-(3-prop-2-enoyloxypropyl)butanedioic acid Chemical compound C(C=C)(=O)OCCCC(C(=O)O)CC(=O)O WLIVGKZSWFDOQX-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- 239000012790 adhesive layer Substances 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000005587 bubbling Effects 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- 239000002609 medium Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 229920002239 polyacrylonitrile Polymers 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
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- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- IEQWWMKDFZUMMU-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethyl)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)CCOC(=O)C=C IEQWWMKDFZUMMU-UHFFFAOYSA-N 0.000 description 2
- JJYPMNFTHPTTDI-UHFFFAOYSA-N 3-methylaniline Chemical compound CC1=CC=CC(N)=C1 JJYPMNFTHPTTDI-UHFFFAOYSA-N 0.000 description 2
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- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
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- 238000004458 analytical method Methods 0.000 description 2
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- YOALFLHFSFEMLP-UHFFFAOYSA-N azane;2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctanoic acid Chemical compound [NH4+].[O-]C(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YOALFLHFSFEMLP-UHFFFAOYSA-N 0.000 description 2
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- 238000007872 degassing Methods 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
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- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
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- PQLMXFQTAMDXIZ-UHFFFAOYSA-N isoamyl butyrate Chemical compound CCCC(=O)OCCC(C)C PQLMXFQTAMDXIZ-UHFFFAOYSA-N 0.000 description 2
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- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 2
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000012966 redox initiator Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
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- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
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- 239000010936 titanium Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- AOAGVPIEEAAAOL-RXSVEWSESA-N (2r)-2-[(1s)-1,2-dihydroxyethyl]-3,4-dihydroxy-2h-furan-5-one;hydrogen peroxide Chemical compound OO.OC[C@H](O)[C@H]1OC(=O)C(O)=C1O AOAGVPIEEAAAOL-RXSVEWSESA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- H01M50/411—Organic material
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/18—Monomers containing fluorine
- C08F214/22—Vinylidene fluoride
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F216/14—Monomers containing only one unsaturated aliphatic radical
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/08—Anhydrides
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- C—CHEMISTRY; METALLURGY
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F259/00—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00
- C08F259/08—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00 on to polymers containing fluorine
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Description
本発明は、コアシェル型粒子、分散液、コーティング組成物、セパレータ、二次電池およびコアシェル型粒子の製造方法に関する。 The present invention relates to core-shell particles, dispersions, coating compositions, separators, secondary batteries and methods for producing core-shell particles.
近年、電子技術の発展はめざましく、小型携帯機器の高機能化が進んでいる。そのため、これらに使用される電源には小型化および軽量化、すなわち高エネルギー密度化が求められている。高いエネルギー密度を有する電池として、リチウムイオン二次電池等に代表される非水電解質二次電池が、広く使用されている。 In recent years, the development of electronic technology has been remarkable, and the functionality of small mobile devices has been improved. Therefore, the power supplies used for these are required to be smaller and lighter, that is, to have higher energy density. As a battery having a high energy density, a non-aqueous electrolyte secondary battery represented by a lithium ion secondary battery or the like is widely used.
また、非水電解質二次電池は、地球環境問題および省エネルギーの観点から、二次電池とエンジンとを組み合わせたハイブリッド自動車、および二次電池を電源にした電気自動車などにも利用されており、その用途が拡大している。 In addition, non-aqueous electrolyte secondary batteries are also used in hybrid vehicles that combine secondary batteries and engines, and electric vehicles that use secondary batteries as a power source, from the viewpoint of global environmental issues and energy saving. Applications are expanding.
非水電解質二次電池の電極（正極および負極）の間にはセパレータが設けられている。電極とセパレータとの間に隙間が形成されると、サイクル寿命を悪化させることがある。そのため、電極およびセパレータ等の接着部の接着性を向上させることが求められている。 A separator is provided between the electrodes (positive electrode and negative electrode) of the non-aqueous electrolyte secondary battery. If a gap is formed between the electrode and the separator, the cycle life may be deteriorated. Therefore, it is required to improve the adhesiveness of the adhesive portion such as the electrode and the separator.
そこで、電極との接着性を向上させたセパレータが開発されている（例えば、特許文献１）。特許文献１には、多孔質基材の少なくとも一方の面にポリフッ化ビニリデン（ＰＶＤＦ）系樹脂を含む所定量の微粒子の集合体層である接着層を設けることによって、イオン透過性およびハンドリング性に優れ、電極との接着性を向上させた、非水系二次電池用セパレータが開示されている。 Therefore, a separator having improved adhesiveness to an electrode has been developed (for example, Patent Document 1). Patent Document 1 provides ion permeability and handleability by providing an adhesive layer which is an aggregate layer of a predetermined amount of fine particles containing a polyvinylidene fluoride (PVDF) resin on at least one surface of a porous substrate. A separator for a non-aqueous secondary battery, which is excellent and has improved adhesiveness to an electrode, is disclosed.
しかしながら、特許文献１に記載の非水系二次電池用セパレータでは、電池の製造工程において熱プレスをする際に、ＰＶＤＦ系樹脂を含む微粒子が溶融してつぶれてしまい、セパレータを構成する多孔質基材の表面の孔が塞がれてしまう。その結果、セパレータにおけるイオン透過性が悪化するという問題がある。 However, in the separator for a non-aqueous secondary battery described in Patent Document 1, when hot pressing is performed in the battery manufacturing process, fine particles containing a PVDF resin are melted and crushed, and the porous group constituting the separator is formed. The holes on the surface of the material are blocked. As a result, there is a problem that the ion permeability of the separator deteriorates.
本発明は、上記課題を鑑みてなされたものであり、その目的は、電極に対する高い接着性を有しつつ、熱プレスの工程を経てもセパレータの表面の孔を塞ぐことが低減された接着層を与えるフッ化ビニリデン粒子を提供することにある。 The present invention has been made in view of the above problems, and an object of the present invention is an adhesive layer which has high adhesiveness to electrodes and is reduced in blocking holes on the surface of a separator even through a heat pressing process. The purpose of the present invention is to provide vinylidene fluoride particles.
本発明に係るコアシェル型粒子は、上記課題を解決するために、コア部と、当該コア部の周囲を取り囲んでいるシェル部と、を含み、当該コア部は、フッ化ビニリデンに由来する構成単位を主構成単位とする第１の重合体を含み、当該シェル部は、フッ化ビニリデンに由来する構成単位を主構成単位とする第２の重合体を含み、当該第２の重合体は、下記式（１）で表される化合物に由来する構成単位、下記式（２）で表される化合物に由来する構成単位および下記式（３）で表される化合物に由来する構成単位の少なくとも何れかをさらに含む。
また、本発明に係るコアシェル型粒子では、上記式（１）で表される化合物は、下記式（４）で表される化合物であることが好ましい。
また、本発明に係るコアシェル型粒子では、上記コア部に含まれる上記第１の重合体および／または上記シェル部に含まれる上記第２の重合体には、ハロゲン化アルキルビニル化合物に由来する構成単位がさらに含まれていることが好ましい。 Further, in the core-shell type particles according to the present invention, the first polymer contained in the core portion and / or the second polymer contained in the shell portion has a configuration derived from a halogenated alkyl vinyl compound. It is preferable that additional units are included.
また、本発明に係るコアシェル型粒子では、上記コアシェル型粒子の融点が１４５℃以上であることが好ましい。 Further, in the core-shell type particles according to the present invention, the melting point of the core-shell type particles is preferably 145 ° C. or higher.
また、本発明に係るコアシェル型粒子では、上記第１の重合体の構成単位は、フッ化ビニリデンに由来する構成単位のみであってもよい。 Further, in the core-shell type particles according to the present invention, the structural unit of the first polymer may be only the structural unit derived from vinylidene fluoride.
また、本発明に係るコアシェル型粒子および分散媒を含む分散液も本発明に含まれる。 The present invention also includes a dispersion liquid containing the core-shell type particles and the dispersion medium according to the present invention.
また、二次電池における負極層と正極層との間に設けられるセパレータの少なくとも一方の面に設けられる多孔質のフッ素樹脂層の形成のためのコーティング組成物であって、本発明に係るコアシェル型粒子を含むコーティング組成物も本発明に含まれる。 Further, it is a coating composition for forming a porous fluororesin layer provided on at least one surface of a separator provided between a negative electrode layer and a positive electrode layer in a secondary battery, and is a core-shell type according to the present invention. Coating compositions containing particles are also included in the present invention.
また、本発明に係るコーティング組成物は、増粘剤をさらに含んでいてもよい。 In addition, the coating composition according to the present invention may further contain a thickener.
また、本発明に係るコーティング組成物は、フィラーをさらに含んでいてもよい。 Further, the coating composition according to the present invention may further contain a filler.
また、本発明に係るコーティング組成物が少なくとも一方の面に塗布されているセパレータも本発明に含まれる。 The present invention also includes a separator in which the coating composition according to the present invention is applied to at least one surface.
また、本発明に係るコーティング組成物から形成されたフッ素樹脂層が設けられている二次電池であって、上記フッ素樹脂層は、上記負極層と上記正極層と上記セパレータとを熱プレスすることによって形成されてなる上記第２の重合体を含む層を有しており、上記第２の重合体を含む層には、上記第１の重合体を含む粒子が含まれている二次電池も本発明に含まれる。 Further, in a secondary battery provided with a fluororesin layer formed from the coating composition according to the present invention, the fluororesin layer is obtained by hot-pressing the negative electrode layer, the positive electrode layer, and the separator. It has a layer containing the second polymer formed by the above, and the layer containing the second polymer also contains a secondary battery containing particles containing the first polymer. Included in the present invention.
また、二次電池における負極層と正極層との間に設けられるセパレータに接するように、当該負極層および当該正極層の少なくとも何れかの少なくとも一方の面に設けられるフッ素樹脂層の形成のためのコーティング組成物であって、本発明に係るコアシェル型粒子を含むコーティング組成物も本発明に含まれる。 Further, for forming a fluororesin layer provided on at least one surface of the negative electrode layer and the positive electrode layer so as to be in contact with a separator provided between the negative electrode layer and the positive electrode layer in the secondary battery. A coating composition containing core-shell type particles according to the present invention is also included in the present invention.
本発明に係るコアシェル型粒子の製造方法は、上記課題を解決するために、コア部と、当該コア部の周囲を取り囲んでいるシェル部と、を含むコアシェル型粒子の製造方法であって、フッ化ビニリデンに由来する構成単位を主構成単位とする第１の重合体を含むコア部を形成するコア部形成工程と、フッ化ビニリデンに由来する構成単位を主構成単位とする第２の重合体を含むシェル部を形成するシェル部形成工程と、を含み、当該シェル部形成工程では、当該コア部形成工程により形成されたコア部を含む分散液において、上記式（１）で表される化合物、上記式（２）で表される化合物および上記式（３）で表される化合物の少なくとも何れかと、フッ化ビニリデンとを含む、当該第２の重合体を構成するための単量体を重合反応させることにより当該コア部の周囲に当該シェル部を形成する。 The method for producing core-shell type particles according to the present invention is a method for producing core-shell type particles including a core portion and a shell portion surrounding the core portion in order to solve the above problems. A core portion forming step of forming a core portion containing a first polymer having a constituent unit derived from vinylidene conjugation as a main constituent unit, and a second polymer having a constituent unit derived from vinylidene fluoride as a main constituent unit. In the shell portion forming step, the compound represented by the above formula (1) is contained in the dispersion liquid containing the core portion formed by the core portion forming step. , A monomer for forming the second polymer, which comprises at least one of the compound represented by the above formula (2) and the compound represented by the above formula (3), and vinylidene fluoride is polymerized. By reacting, the shell portion is formed around the core portion.
本発明によれば、電極に対する高い接着性を有しつつ、熱プレスの工程を経てもセパレータの表面の孔を塞ぐことが低減された接着層を与えるフッ化ビニリデン粒子が提供される。 INDUSTRIAL APPLICABILITY According to the present invention, vinylidene fluoride particles are provided that provide an adhesive layer that has high adhesiveness to an electrode and is less likely to block holes on the surface of a separator even after undergoing a heat pressing step.
以下、本発明に係るコアシェル型粒子、分散液、コーティング組成物、セパレータおよび二次電池ならびにコアシェル型粒子の製造方法の一実施形態について詳細に説明する。 Hereinafter, an embodiment of a core-shell type particle, a dispersion liquid, a coating composition, a separator, a secondary battery, and a method for producing the core-shell type particle according to the present invention will be described in detail.
〔コアシェル型粒子〕
本実施形態において「コアシェル型粒子」とは、コア部と、コア部の周囲を取り囲んでいるシェル部とを含んでいる粒子を指す。
[Core-shell type particles]
In the present embodiment, the “core-shell type particle” refers to a particle including a core portion and a shell portion surrounding the core portion.
（コア部）
コア部は、フッ化ビニリデンに由来する構成単位を主構成単位とする第１の重合体を含んでおり、コア部は、第１の重合体を含むフッ化ビニリデン粒子である。本明細書において「主構成単位」とは、重合体を構成する構成単位のうち、最も多くの割合（モル％）を占める構成単位を指す。また、本明細書において「フッ化ビニリデン粒子」とは、フッ化ビニリデンに由来する構成単位を主構成単位とする重合体の粒子を指し、当該重合体には、フッ化ビニリデンの単独重合体、およびフッ化ビニリデンと他の単量体との共重合体が包含される。
(Core part)
The core portion contains a first polymer having a constituent unit derived from vinylidene fluoride as a main constituent unit, and the core portion is vinylidene fluoride particles containing the first polymer. As used herein, the term "main structural unit" refers to a structural unit that occupies the largest proportion (mol%) of the structural units that make up the polymer. Further, in the present specification, the “vinylidene fluoride particles” refers to the particles of a polymer having a structural unit derived from vinylidene fluoride as a main constituent unit, and the polymer is a homopolymer of vinylidene fluoride. And copolymers of vinylidene fluoride and other monomers are included.
第１の重合体における、フッ化ビニリデンに由来する構成単位の割合は、９５モル％以上であることが好ましく、９８モル％以上であることがより好ましい。また、第１の重合体は、一例において、フッ化ビニリデンに由来する構成単位のみで構成されていることが特に好ましい。フッ化ビニリデンに由来する構成単位を９８モル％以上とすることで、電解液存在下における第１の重合体の溶融温度が、後述する熱プレス工程の通常行われる温度よりも高くなる。その結果、本実施形態に係るコアシェル型粒子では、熱プレス工程においてコア部がつぶされる（溶融する）ことが低減される。ここで「電解液存在下における第１の重合体の溶融温度」は、電解液の組成等にもよるが、例えば第１の重合体の融点より６０〜７０℃程度低い温度となり得る。 The proportion of the structural unit derived from vinylidene fluoride in the first polymer is preferably 95 mol% or more, more preferably 98 mol% or more. Further, in one example, it is particularly preferable that the first polymer is composed of only the structural units derived from vinylidene fluoride. By setting the constituent unit derived from vinylidene fluoride to 98 mol% or more, the melting temperature of the first polymer in the presence of the electrolytic solution becomes higher than the temperature usually performed in the heat pressing step described later. As a result, in the core-shell type particles according to the present embodiment, the core portion is less likely to be crushed (melted) in the heat pressing process. Here, the "melting temperature of the first polymer in the presence of the electrolytic solution" may be, for example, a temperature about 60 to 70 ° C. lower than the melting point of the first polymer, although it depends on the composition of the electrolytic solution and the like.
第１の重合体は、第１の重合体を構成する他の構成単位として、フッ化ビニリデン以外の化合物に由来する構成単位をさらに含んでいてもよい。フッ化ビニリデン以外の化合物としては、例えば、ハロゲン化アルキルビニル化合物、炭化水素系単量体、ジメタクリル酸（ポリ）アルキレングリコールエステル、ジアクリル酸（ポリ）アルキレングリコールエステルおよびポリビニルベンゼン等が挙げられる。ハロゲン化アルキルビニル化合物としては、例えば、フッ化アルキルビニル化合物が挙げられ、具体的には、ヘキサフルオロプロピレン、クロロトリフルオロエチレン、トリフルオロエチレン、テトラフルオロエチレン、ヘキサフルオロエチレンおよびフルオロアルキルビニルエーテル等が挙げられ、なかでもヘキサフルオロプロピレンが好ましい。炭化水素系単量体としては、例えば、エチレン、プロピレンおよびスチレン等が挙げられる。 The first polymer may further contain a structural unit derived from a compound other than vinylidene fluoride as another structural unit constituting the first polymer. Examples of the compound other than vinylidene fluoride include a halogenated alkyl vinyl compound, a hydrocarbon-based monomer, a dimethacrylic acid (poly) alkylene glycol ester, a diacrylic acid (poly) alkylene glycol ester, and polyvinylbenzene. Examples of the halogenated alkyl vinyl compound include a fluoroalkyl vinyl compound, and specific examples thereof include hexafluoropropylene, chlorotrifluoroethylene, trifluoroethylene, tetrafluoroethylene, hexafluoroethylene and fluoroalkyl vinyl ether. Hexafluoropropylene is preferable. Examples of the hydrocarbon-based monomer include ethylene, propylene and styrene.
第１の重合体を構成する他の構成単位としてフッ化ビニリデン以外の化合物に由来する構成単位を含む場合、フッ化ビニリデン以外の化合物に由来する構成単位の割合は、耐酸化性および結晶性が損なわれる虞を低減する観点から、例えば、５モル％以下であることが好ましく、２モル％以下であることがより好ましい。ハロゲン化アルキルビニル化合物に由来する構成単位の含有量が２モル％以下である場合には、電池の製造工程における熱プレス時にコアシェル粒子が溶融してつぶれてしまう可能性をより一層低減することができる。 When a structural unit derived from a compound other than vinylidene fluoride is included as another structural unit constituting the first polymer, the proportion of the structural unit derived from the compound other than vinylidene fluoride has an oxidation resistance and crystallinity. From the viewpoint of reducing the risk of damage, for example, it is preferably 5 mol% or less, and more preferably 2 mol% or less. When the content of the structural unit derived from the halogenated alkyl vinyl compound is 2 mol% or less, the possibility that the core-shell particles are melted and crushed during hot pressing in the battery manufacturing process can be further reduced. it can.
また、コア部は、第１の重合体以外の化合物をさらに含んでいてもよい。第１の重合体以外の化合物としては、例えば、ハロゲン化アルキルビニル化合物、炭化水素系単量体、ジメタクリル酸（ポリ）アルキレングリコールエステル、ジアクリル酸（ポリ）アルキレングリコールエステルおよびポリビニルベンゼンおよび架橋剤等が挙げられる。ハロゲン化アルキルビニル化合物としては、例えば、フッ化アルキルビニル化合物が挙げられ、具体的には、ヘキサフルオロプロピレン、クロロトリフルオロエチレン、トリフルオロエチレン、テトラフルオロエチレン、ヘキサフルオロエチレンおよびフルオロアルキルビニルエーテル等が挙げられる。炭化水素系単量体としては、例えば、エチレン、プロピレンおよびスチレン等が挙げられる。 Further, the core portion may further contain a compound other than the first polymer. Compounds other than the first polymer include, for example, halogenated alkyl vinyl compounds, hydrocarbon-based monomers, dimethacrylic acid (poly) alkylene glycol esters, diacrylic acid (poly) alkylene glycol esters, polyvinylbenzene, and cross-linking agents. And so on. Examples of the halogenated alkyl vinyl compound include a fluoroalkyl vinyl compound, and specific examples thereof include hexafluoropropylene, chlorotrifluoroethylene, trifluoroethylene, tetrafluoroethylene, hexafluoroethylene and fluoroalkyl vinyl ether. Can be mentioned. Examples of the hydrocarbon-based monomer include ethylene, propylene and styrene.
また、第１の重合体の融点は、イオン透過性の観点から、１５０℃以上であることが好ましく、１５５℃以上であることがより好ましく、１６０℃以上であることがさらに好ましい。本実施形態に係る第１の重合体の融点の測定方法は、後述する実施例において説明する。 The melting point of the first polymer is preferably 150 ° C. or higher, more preferably 155 ° C. or higher, and even more preferably 160 ° C. or higher, from the viewpoint of ion permeability. The method for measuring the melting point of the first polymer according to the present embodiment will be described in Examples described later.
また、第１の重合体の平均粒子径は、特に限定されないが、例えば、１０ｎｍ以上１μｍ以下である。本実施形態に係る第１の重合体の平均粒子径の測定方法は、後述する実施例において説明する。 The average particle size of the first polymer is not particularly limited, but is, for example, 10 nm or more and 1 μm or less. The method for measuring the average particle size of the first polymer according to the present embodiment will be described in Examples described later.
（シェル部）
シェル部は、フッ化ビニリデンに由来する構成単位を主構成単位とする第２の重合体を含んでいる。第２の重合体としては、第１の重合体とは異なる重合体が用いられる。第２の重合体は、下記式（１）で表される化合物に由来する構成単位、下記式（２）で表される化合物に由来する構成単位および下記式（３）で表される化合物に由来する構成単位の少なくとも何れかをさらに含んでいる。
The shell portion contains a second polymer having a structural unit derived from vinylidene fluoride as a main structural unit. As the second polymer, a polymer different from the first polymer is used. The second polymer is a structural unit derived from the compound represented by the following formula (1), a structural unit derived from the compound represented by the following formula (2), and a compound represented by the following formula (3). It further comprises at least one of the building blocks of origin.
本実施形態に係るコアシェル型粒子は、第２の重合体が式（１）で表される化合物に由来する構成単位、式（２）で表される化合物に由来する構成単位および式（３）で表される化合物に由来する構成単位の少なくとも何れかをさらに含むことにより、電極と後述するフッ素樹脂層との間の接着性をより高め得る。また、第２の重合体が式（１）で表される化合物に由来する構成単位および式（２）で表される化合物に由来する構成単位の少なくとも何れかを含む場合には、セパレータ基材とフッ素樹脂層との間の接着性もより高め得る。 In the core-shell type particles according to the present embodiment, the second polymer is a structural unit derived from the compound represented by the formula (1), a structural unit derived from the compound represented by the formula (2), and the formula (3). By further containing at least one of the structural units derived from the compound represented by, the adhesiveness between the electrode and the fluororesin layer described later can be further enhanced. When the second polymer contains at least one of a structural unit derived from the compound represented by the formula (1) and a structural unit derived from the compound represented by the formula (2), the separator base material. The adhesiveness between the and the fluororesin layer can also be further enhanced.
［式（１）で表される化合物］
Ｒ１、Ｒ２、およびＲ３は、それぞれ独立に水素原子、フッ素原子、塩素原子または炭素数１〜５のアルキル基である。炭素数１〜５のアルキル基としては、メチル基、エチル基、プロピル基およびイソプロピル基が挙げられる。このなかでも、Ｒ１は水素原子またはメチル基であることが好ましく、水素原子であることがより好ましい。Ｒ２は水素原子またはメチル基であることが好ましく、水素原子であることがより好ましい。Ｒ３は水素原子、フッ素原子、またはメチル基であることが好ましく、水素原子であることがより好ましい。
[Compound represented by formula (1)]
R 1 , R 2 , and R 3 are independently hydrogen atoms, fluorine atoms, chlorine atoms, or alkyl groups having 1 to 5 carbon atoms, respectively. Examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, a propyl group and an isopropyl group. Among these, R 1 is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom. R 2 is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom. R 3 is preferably a hydrogen atom, a fluorine atom, or a methyl group, and more preferably a hydrogen atom.
Ｘ１を構成する主鎖は、原子数１〜１９であり、原子数１〜１４であることが好ましく、原子数１〜９であることがより好ましい。主鎖を構成する原子としては、例えば、炭素原子および後述するヘテロ原子等が挙げられる。なお、主鎖の原子数に水素原子の原子数は含まない。また、主鎖の原子数とは、Ｘ１の右側に記載されたカルボキシル基と、Ｘ１の左側に記載された基（Ｒ１Ｒ２Ｃ＝ＣＲ３‐ＣＯ‐）とを、最も少ない原子数で結ぶ鎖の骨格部分の原子数を意味している。 The main chain constituting X 1 has 1 to 19 atoms, preferably 1 to 14 atoms, and more preferably 1 to 9 atoms. Examples of the atom constituting the main chain include a carbon atom and a hetero atom described later. The number of atoms in the main chain does not include the number of hydrogen atoms. Further, the number of atoms of the main chain, and a carboxyl group described in the right side of the X 1, and radicals according to the left of X 1 (R 1 R 2 C = CR 3 -CO-), the smallest atom It means the number of atoms in the skeleton of the chain connected by numbers.
Ｘ１の原子団の分子量は４７２以下であり、１７２以下であることがより好ましい。また、原子団である場合の分子量の下限としては特に限定はないが、通常は１５である。 The molecular weight of the atomic group of X 1 is 472 or less, more preferably 172 or less. The lower limit of the molecular weight in the case of an atomic group is not particularly limited, but is usually 15.
またＸ１は、酸素原子および窒素原子から選ばれる少なくとも一つのヘテロ原子を含む。また上述の原子団は、ヘテロ原子を少なくとも一つ含んでいればよく、複数含んでいてもよい。フッ化ビニリデンとの共重合性の観点から、ヘテロ原子は、酸素原子であることが好ましい。なお、ヘテロ原子は原子団の主鎖と側鎖との両方に含まれていてもよいし、どちらか一方のみに含まれていてもよい。また原子団の側鎖に１つ以上のカルボキシル基を含んでいてもよい。 Further, X 1 contains at least one hetero atom selected from an oxygen atom and a nitrogen atom. Further, the above-mentioned atomic group may contain at least one heteroatom, and may contain a plurality of heteroatoms. From the viewpoint of copolymerizability with vinylidene fluoride, the hetero atom is preferably an oxygen atom. The hetero atom may be contained in both the main chain and the side chain of the atomic group, or may be contained in only one of them. Further, the side chain of the atomic group may contain one or more carboxyl groups.
また、式（１）で表される化合物は、下記式（４）で表される化合物であることが好ましい。
式（４）で表される化合物におけるＸ３を構成する主鎖は、原子数１〜１８であり、原子数１〜１３であることが好ましく、原子数１〜８であることがより好ましい。主鎖を構成する原子としては、例えば、炭素原子および後述するヘテロ原子等が挙げられる。なお、主鎖の原子数に水素原子の原子数は含まない。また、主鎖の原子数とは、Ｘ３の右側に記載されたカルボキシル基と、Ｘ３の左側に記載された基（Ｒ１Ｒ２Ｃ＝ＣＲ３‐ＣＯ‐Ｏ‐）とを、最も少ない原子数で結ぶ鎖の骨格部分の原子数を意味している。 Main chain constituting the X 3 in the compound represented by formula (4) is an atom number 1 to 18, preferably an atomic number 1 to 13, and more preferably an atomic number of 1 to 8. Examples of the atom constituting the main chain include a carbon atom and a hetero atom described later. The number of atoms in the main chain does not include the number of hydrogen atoms. Further, the number of atoms of the main chain, and a carboxyl group described in the right side of X 3, the radicals (R 1 R 2 C = CR 3 -CO-O-) and according to the left of X 3, most It means the number of atoms in the skeleton of the chain connected by a small number of atoms.
式（４）で表される化合物におけるＸ３の原子団の分子量は４５６以下であり、１５６以下であることが好ましい。また、原子団である場合の分子量の下限としては特に限定はないが、通常は１４である。 The molecular weight of the atomic group X 3 in the compound represented by formula (4) is at least 456 or less and preferably 156 or less. The lower limit of the molecular weight in the case of an atomic group is not particularly limited, but is usually 14.
またＸ３は、酸素原子および窒素原子から選ばれる少なくとも一つのヘテロ原子を含んでいてもよいし、複数のヘテロ原子を含んでいてもよい。なお、ヘテロ原子は原子団の主鎖と側鎖との両方に含まれていてもよいし、どちらか一方のみに含まれていてもよい。 Further X 3 may be include at least one hetero atom selected from oxygen atom and nitrogen atom, may contain a plurality of heteroatoms. The hetero atom may be contained in both the main chain and the side chain of the atomic group, or may be contained in only one of them.
式（１）で表される化合物としては、例えば、アクリロイロキシプロピルコハク酸、アクリロイロキシエチルコハク酸、メタクリロイロキシエチルコハク酸、メタクリロイロキシプロピルコハク酸、２−カルボキシエチルアクリレート、２−カルボキシエチルメタクリレート、アクリロイロキシエチルフタル酸、メタクリロイロキシエチルフタル酸、Ｎ−カルボキシエチル（メタ）アクリルアミド、およびカルボキシエチルチオ（メタ）アクリレート等が挙げられる。式（１）で表される化合物としては、電極とフッ素樹脂層との間の接着性およびセパレータ基材とフッ素樹脂層との間の接着性の観点から、アクリロイロキシプロピルコハク酸および／またはアクリロイロキシエチルコハク酸であることが好ましい。 Examples of the compound represented by the formula (1) include acryloyloxypropyl succinic acid, acryloyloxyethyl succinic acid, methacryloyloxyethyl succinic acid, methacryloyloxypropyl succinic acid, 2-carboxyethyl acrylate, 2-. Examples thereof include carboxyethyl methacrylate, acryloyloxyethyl phthalic acid, methacryloyloxyethyl phthalic acid, N-carboxyethyl (meth) acrylamide, and carboxyethyl thio (meth) acrylate. The compound represented by the formula (1) includes acryloyloxypropyl succinic acid and / or from the viewpoint of the adhesiveness between the electrode and the fluororesin layer and the adhesiveness between the separator base material and the fluororesin layer. It is preferably acryloyloxyethyl succinic acid.
［式（２）で表される化合物］
Ｒ４、Ｒ５およびＲ６は、それぞれ独立に水素原子、フッ素原子、塩素原子または炭素数１〜５のアルキル基である。炭素数１〜５のアルキル基としては、メチル基、エチル基、プロピル基およびイソプロピル基が挙げられる。このなかでも、Ｒ４は水素原子またはメチル基であることが好ましく、水素原子であることがより好ましい。Ｒ５は水素原子またはメチル基であることが好ましく、水素原子であることがより好ましい。Ｒ６は水素原子、フッ素原子、またはメチル基であることが好ましく、水素原子であることがより好ましい。
[Compound represented by formula (2)]
R 4 , R 5 and R 6 are independently hydrogen atoms, fluorine atoms, chlorine atoms or alkyl groups having 1 to 5 carbon atoms, respectively. Examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, a propyl group and an isopropyl group. Among this, it is preferable that R 4 is a hydrogen atom or a methyl group, and more preferably a hydrogen atom. R 5 is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom. R 6 is preferably a hydrogen atom, a fluorine atom, or a methyl group, and more preferably a hydrogen atom.
Ｘ２を構成する主鎖は、原子数１〜１９であり、原子数１〜１４であることが好ましく、原子数１〜９であることがより好ましい。主鎖を構成する原子としては、例えば、炭素原子および後述するヘテロ原子等が挙げられる。なお、主鎖の原子数に水素原子の原子数は含まない。また、主鎖の原子数とは、Ｘ２の右側に記載されたカルボキシル基と、Ｘ２の左側に記載された基（Ｒ４Ｒ５Ｃ＝ＣＲ６‐Ｏ‐）とを、最も少ない原子数で結ぶ鎖の骨格部分の原子数を意味している。 The main chain constituting X 2 has 1 to 19 atoms, preferably 1 to 14 atoms, and more preferably 1 to 9 atoms. Examples of the atom constituting the main chain include a carbon atom and a hetero atom described later. The number of atoms in the main chain does not include the number of hydrogen atoms. Further, the number of atoms of the main chain, and a carboxyl group which is on the right side of X 2, and radicals according to the left of X 2 (-O- R 4 R 5 C = CR 6), the smallest atom It means the number of atoms in the skeleton of the chain connected by a number.
Ｘ２の原子団の分子量は４８４以下であり、１８４以下であることが好ましい。また、原子団である場合の分子量の下限としては特に限定はないが、通常は１４である。 The molecular weight of the atomic group of X 2 is 484 or less, preferably 184 or less. The lower limit of the molecular weight in the case of an atomic group is not particularly limited, but is usually 14.
またＸ２は、酸素原子および窒素原子から選ばれる少なくとも一つのヘテロ原子を含む。また上述の原子団は、ヘテロ原子を少なくとも一つ含んでいればよく、複数含んでいてもよい。フッ化ビニリデンとの共重合性の観点から、ヘテロ原子は、酸素原子であることが好ましい。なお、ヘテロ原子は原子団の主鎖と側鎖との両方に含まれていてもよく、どちらか一方のみに含まれていてもよい。また原子団の側鎖に１つ以上のカルボキシル基を含んでいてもよい。 X 2 also contains at least one heteroatom selected from oxygen and nitrogen atoms. Further, the above-mentioned atomic group may contain at least one heteroatom, and may contain a plurality of heteroatoms. From the viewpoint of copolymerizability with vinylidene fluoride, the hetero atom is preferably an oxygen atom. The hetero atom may be contained in both the main chain and the side chain of the atomic group, or may be contained in only one of them. Further, the side chain of the atomic group may contain one or more carboxyl groups.
式（２）で表される化合物としては、例えば、ビニルカルボキシアルキルエーテル類が挙げられ、具体的には、ビニルカルボキシメチルエーテルおよびビニルカルボキシエチルエーテル等が挙げられる。 Examples of the compound represented by the formula (2) include vinyl carboxyalkyl ethers, and specific examples thereof include vinyl carboxymethyl ether and vinyl carboxyethyl ether.
［式（３）で表される化合物］
Ｒ７、Ｒ８およびＲ９は、それぞれ独立に水素原子、フッ素原子、塩素原子または炭素数１〜５のアルキル基である。炭素数１〜５のアルキル基としては、メチル基、エチル基、プロピル基およびイソプロピル基等が挙げられる。このなかでも、Ｒ７、Ｒ８およびＲ９は、それぞれ水素原子であることが好ましい。
[Compound represented by formula (3)]
R 7 , R 8 and R 9 are independently hydrogen atoms, fluorine atoms, chlorine atoms or alkyl groups having 1 to 5 carbon atoms, respectively. Examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, a propyl group and an isopropyl group. Of these, R 7 , R 8 and R 9 are preferably hydrogen atoms, respectively.
Ｒ１０は、水素原子、または少なくとも一つのヒドロキシル基を含む炭素数１〜５の炭化水素部分である。ヒドロキシル基を含む炭素数１〜５の炭化水素部分としては、例えば、ヒドロキシエチル基およびヒドロキシプロピル基等が挙げられる。 R 10 is a hydrocarbon moiety having 1 to 5 carbon atoms containing a hydrogen atom or at least one hydroxyl group. Examples of the hydrocarbon moiety having 1 to 5 carbon atoms containing a hydroxyl group include a hydroxyethyl group and a hydroxypropyl group.
式（３）で表される化合物としては、例えば、アクリル酸、メタクリル酸、ヒドロキシエチルアクリレート、および２−ヒドロキシプロピルアクリレート等が挙げられる。式（３）で表される化合物は、電極とフッ素樹脂層との間の接着性およびセパレータとフッ素樹脂層との間の接着性の観点から、アクリル酸であること好ましい。 Examples of the compound represented by the formula (3) include acrylic acid, methacrylic acid, hydroxyethyl acrylate, 2-hydroxypropyl acrylate and the like. The compound represented by the formula (3) is preferably acrylic acid from the viewpoint of the adhesiveness between the electrode and the fluororesin layer and the adhesiveness between the separator and the fluororesin layer.
［他の構成単位］
第２の重合体は、第２の重合体を構成する他の構成単位として、フッ化ビニリデンおよび上記式（１）〜（３）で表される化合物以外の化合物に由来する構成単位をさらに含んでいてもよい。そのような化合物としては、例えば、ハロゲン化アルキルビニル化合物、炭化水素化単量体、ジメタクリル酸（ポリ）アルキレングリコールエステル、ジアクリル酸（ポリ）アルキレングリコールエステル、およびポリビニルベンゼン等が挙げられる。
[Other building blocks]
The second polymer further contains vinylidene fluoride and a structural unit derived from a compound other than the compounds represented by the above formulas (1) to (3) as other structural units constituting the second polymer. You may be. Examples of such a compound include a halogenated alkyl vinyl compound, a hydrocarbon monomer, a dimethacrylic acid (poly) alkylene glycol ester, a diacrylic acid (poly) alkylene glycol ester, and polyvinylbenzene.
ハロゲン化アルキルビニル化合物としては、例えば、フッ化アルキルビニル化合物が挙げられ、具体的には、ヘキサフルオロプロピレン、クロロトリフルオロエチレン、トリフルオロエチレン、テトラフルオロエチレン、ヘキサフルオロエチレン、およびフルオロアルキルビニルエーテル等が挙げられ、なかでもヘキサフルオロプロピレンが好ましい。炭化水素系単量体としては、例えばエチレン、プロピレンおよびスチレン等が挙げられる。ハロゲン化アルキルビニル化合物を含むことにより、電解液を含んだ状態での電極との熱プレスにおいて接着性が向上し得る。 Examples of the halogenated alkyl vinyl compound include a fluoroalkyl vinyl compound, and specific examples thereof include hexafluoropropylene, chlorotrifluoroethylene, trifluoroethylene, tetrafluoroethylene, hexafluoroethylene, and fluoroalkyl vinyl ether. Among them, hexafluoropropylene is preferable. Examples of the hydrocarbon-based monomer include ethylene, propylene and styrene. By containing the halogenated alkyl vinyl compound, the adhesiveness can be improved in hot pressing with the electrode in a state containing the electrolytic solution.
［構成単位の割合］
第２の重合体における、フッ化ビニリデンに由来する構成単位の割合は、イオン透過性の観点から、５０モル％以上であることが好ましく、７０モル％以上であることがより好ましく、９０モル％以上であることがさらに好ましい。また、密着性の観点から、９９モル％以下であることが好ましく、９８モル％以下であることがより好ましく、９５モル％以下であることがさらに好ましい。
[Percentage of constituent units]
From the viewpoint of ion permeability, the proportion of the constituent unit derived from vinylidene fluoride in the second polymer is preferably 50 mol% or more, more preferably 70 mol% or more, and 90 mol% or more. The above is more preferable. Further, from the viewpoint of adhesion, it is preferably 99 mol% or less, more preferably 98 mol% or less, and further preferably 95 mol% or less.
また、第２の重合体における、上記式（１）で表される化合物に由来する構成単位、上記式（２）で表される化合物に由来する構成単位および上記式（３）で表される化合物に由来する構成単位の合計の割合は、特に限定されないが、密着性の観点から、０．０１モル％以上であることが好ましく、０．０２モル％以上であることがより好ましく、０．０３モル％以上であることがさらに好ましい。また、生産性の観点から、５モル％以下であることが好ましく、４モル％以下であることがより好ましく、３モル％以下であることがさらに好ましい。 Further, in the second polymer, a structural unit derived from the compound represented by the above formula (1), a structural unit derived from the compound represented by the above formula (2), and a structural unit represented by the above formula (3). The total ratio of the constituent units derived from the compound is not particularly limited, but from the viewpoint of adhesion, it is preferably 0.01 mol% or more, more preferably 0.02 mol% or more, and 0. It is more preferably 03 mol% or more. Further, from the viewpoint of productivity, it is preferably 5 mol% or less, more preferably 4 mol% or less, and further preferably 3 mol% or less.
第２の重合体を構成する他の構成単位としてハロゲン化アルキルビニル化合物に由来する構成単位を含む場合、ハロゲン化アルキルビニル化合物に由来する構成単位の割合は、特に限定されないが、密着性の観点から、０．５モル％以上であることが好ましく、１モル％以上であることがより好ましく、２モル％以上であることがさらに好ましい。また、イオン透過性の観点から、５０モル％以下であることが好ましく、３０モル％以下であることがより好ましく、２０モル％以下であることがさらに好ましい。 When a structural unit derived from a halogenated alkyl vinyl compound is included as another structural unit constituting the second polymer, the proportion of the structural unit derived from the halogenated alkyl vinyl compound is not particularly limited, but from the viewpoint of adhesion. Therefore, it is preferably 0.5 mol% or more, more preferably 1 mol% or more, and further preferably 2 mol% or more. Further, from the viewpoint of ion permeability, it is preferably 50 mol% or less, more preferably 30 mol% or less, and further preferably 20 mol% or less.
また、シェル部は、第２の重合体以外の化合物をさらに含んでいてもよい。第２の重合体以外の化合物としては、例えば、ハロゲン化アルキルビニル化合物、炭化水素系単量体、ジメタクリル酸（ポリ）アルキレングリコールエステル、ジアクリル酸（ポリ）アルキレングリコールエステルおよびポリビニルベンゼンおよび架橋剤等が挙げられる。ハロゲン化アルキルビニル化合物としては、例えば、フッ化アルキルビニル化合物が挙げられ、具体的には、ヘキサフルオロプロピレン、クロロトリフルオロエチレン、トリフルオロエチレン、テトラフルオロエチレン、ヘキサフルオロエチレンおよびフルオロアルキルビニルエーテル等が挙げられる。炭化水素系単量体としては、例えば、エチレン、プロピレンおよびスチレン等が挙げられる。 Further, the shell portion may further contain a compound other than the second polymer. Compounds other than the second polymer include, for example, halogenated alkyl vinyl compounds, hydrocarbon-based monomers, dimethacrylic acid (poly) alkylene glycol esters, diacrylic acid (poly) alkylene glycol esters, polyvinylbenzene, and cross-linking agents. And so on. Examples of the halogenated alkyl vinyl compound include a fluoroalkyl vinyl compound, and specific examples thereof include hexafluoropropylene, chlorotrifluoroethylene, trifluoroethylene, tetrafluoroethylene, hexafluoroethylene and fluoroalkyl vinyl ether. Can be mentioned. Examples of the hydrocarbon-based monomer include ethylene, propylene and styrene.
本実施形態に係るコアシェル型粒子の構成単位の帰属方法は、１９Ｆ−ＮＭＲで得られるピーク面積比および吸光度比（ＩＲ比）ＡＲを検出することによって求められる。ピーク面積比および吸光度比（ＩＲ比）ＡＲの検出方法は、後述する実施例において説明する。 Assignment method of the structural units of the core-shell particles according to the present embodiment, peak area ratio obtained by 19 F-NMR and absorbance ratio (IR ratio) obtained by detecting the A R. Detection method of the peak area ratio and absorbance ratio (IR ratio) A R will be described in Examples below.
また、第１の重合体および第２の重合体の少なくとも何れかに、ハロゲン化アルキルビニル化合物に由来する構成単位が含まれていることが好ましい。コアシェル型粒子におけるハロゲン化アルキルビニル化合物に由来する構成単位の割合は、特に限定されないが、１モル％以上であることが好ましく、１．５モル％以上であることがより好ましい。また、５モル％以下であることが好ましく、３．５モル％以下であることがより好ましい。 Further, it is preferable that at least one of the first polymer and the second polymer contains a structural unit derived from the halogenated alkyl vinyl compound. The proportion of the structural unit derived from the halogenated alkyl vinyl compound in the core-shell type particles is not particularly limited, but is preferably 1 mol% or more, and more preferably 1.5 mol% or more. Further, it is preferably 5 mol% or less, and more preferably 3.5 mol% or less.
（コアシェル型粒子の融点）
第１の重合体の融点は第２の重合体の融点よりも高いことが好ましい。そのため、コアシェル型粒子は、第１の重合体よりも融点が低い。コアシェル型粒子の融点は、１４５℃以上であることが好ましく、また、１６４℃未満であることが好ましい。本実施形態に係るコアシェル型粒子の融点の測定方法は、後述する実施例において説明する。
(Melting point of core-shell type particles)
The melting point of the first polymer is preferably higher than the melting point of the second polymer. Therefore, the core-shell type particles have a lower melting point than the first polymer. The melting point of the core-shell type particles is preferably 145 ° C. or higher, and preferably less than 164 ° C. The method for measuring the melting point of the core-shell type particles according to this embodiment will be described in Examples described later.
（粒子径）
本実施形態に係るコアシェル型粒子の平均粒子径は、特に限定されないが、例えば、１０ｎｍ以上１μｍ以下である。本実施形態に係るコアシェル型粒子の平均粒子径の測定方法は、後述する実施例において説明する。
(Particle size)
The average particle size of the core-shell type particles according to the present embodiment is not particularly limited, but is, for example, 10 nm or more and 1 μm or less. The method for measuring the average particle size of the core-shell type particles according to this embodiment will be described in Examples described later.
（用途）
本実施形態に係るコアシェル型粒子は、二次電池（特には、非水電解質二次電池）におけるセパレータ基材または電極に塗布されるコーティング組成物の構成材料として好適に用いられる。
(Use)
The core-shell type particles according to the present embodiment are suitably used as a constituent material of a coating composition applied to a separator base material or an electrode in a secondary battery (particularly, a non-aqueous electrolyte secondary battery).
本実施形態に係るコアシェル型粒子をコーティング組成物に含有させることで、後述のように、電極に対する高い接着性を有しつつ、電池の製造工程において熱プレスする際に、コア部に含まれるフッ化ビニリデン粒子がつぶれることを低減することができる。したがって、熱プレスの工程を経てもセパレータの表面の孔を塞ぐことが低減される。 By incorporating the core-shell type particles according to the present embodiment into the coating composition, as will be described later, while having high adhesiveness to the electrodes, the foot contained in the core portion when hot-pressed in the battery manufacturing process. It is possible to reduce the crushing of vinylidene particles. Therefore, it is possible to reduce the blockage of the holes on the surface of the separator even after the heat pressing process.
〔コアシェル型粒子の製造方法〕
本実施形態に係るコアシェル型粒子の製造方法は、第１の重合体を含むコア部を形成するコア部形成工程と、第２の重合体を含むシェル部を形成するシェル部形成工程とを含んでいる。
[Manufacturing method of core-shell type particles]
The method for producing core-shell type particles according to the present embodiment includes a core portion forming step of forming a core portion containing a first polymer and a shell portion forming step of forming a shell portion containing a second polymer. I'm out.
コア部形成工程では、第１の重合体を構成するための単量体であるフッ化ビニリデンを重合する。第１の重合体を構成する構成単位として、フッ化ビニリデン以外の他の化合物に由来する構成単位をさらに含む場合は、フッ化ビニリデンと当該他の化合物とを重合する。 In the core portion forming step, vinylidene fluoride, which is a monomer for forming the first polymer, is polymerized. When the structural unit constituting the first polymer further contains a structural unit derived from a compound other than vinylidene fluoride, vinylidene fluoride and the other compound are polymerized.
コア部形成工程における、フッ化ビニリデンの仕込み量は、コア部形成工程の全単量体の総量を１００質量部とすると、９０質量部以上であることが好ましく、９２質量部以上であることがより好ましく、９５質量部以上であることがさらに好ましい。また、フッ化ビニリデンのみを用いてもよい。 The amount of vinylidene fluoride charged in the core portion forming step is preferably 90 parts by mass or more, preferably 92 parts by mass or more, assuming that the total amount of all the monomers in the core portion forming step is 100 parts by mass. More preferably, it is 95 parts by mass or more. Moreover, you may use only vinylidene fluoride.
他の化合物としてハロゲン化アルキルビニル化合物を添加する場合、ハロゲン化アルキルビニル化合物の仕込み量は、コア部形成工程の全単量体の総量を１００質量部とすると、イオン透過性の観点から、１０質量部以下であることが好ましく、８質量部以下であることがより好ましく、５質量部以下であることがさらに好ましい。 When the halogenated alkyl vinyl compound is added as another compound, the amount of the halogenated alkyl vinyl compound charged is 10 from the viewpoint of ion permeability, assuming that the total amount of all the monomers in the core portion forming step is 100 parts by mass. It is preferably less than or equal to parts by mass, more preferably less than 8 parts by mass, and even more preferably less than or equal to 5 parts by mass.
上記重合によって得られたコア部は、続いて行うシェル部形成工程において、コア部形成工程で得られた粒子を含んだ分散液のまま使用してもよいし、塩析、凍結粉砕、スプレードライ、およびフリーズドライ等から選ばれる少なくとも１種類の方法で粉体化して使用してもよい。また、そのまま使用する場合、コア部形成工程における重合に用いた分散媒に分散させたままであってもよいし、別途用意した水などの分散媒に物理的または化学的に再分散させてもよい。また、粉体化したコア部は、水などの分散媒に物理的または化学的に再分散させて使用してもよい。未処理のコア部を含む分散液または上記操作等によって処理済みのコア部を含む分散液は、界面活性剤、ｐＨ調整剤、沈降防止剤、分散安定剤、腐食防止剤、防カビ剤、湿潤剤等をさらに含ませてもよいし、透析膜またはイオン交換樹脂などによって不純物を除去してもよい。 The core portion obtained by the above polymerization may be used as it is in the dispersion liquid containing the particles obtained in the core portion forming step in the subsequent shell portion forming step, or may be salted out, freeze-crushed, or spray-dried. , And freeze-drying, etc., may be powdered and used by at least one method selected. When used as it is, it may remain dispersed in the dispersion medium used for the polymerization in the core portion forming step, or it may be physically or chemically redispersed in a dispersion medium such as water prepared separately. .. Further, the powdered core portion may be used by physically or chemically redispersing it in a dispersion medium such as water. The dispersion liquid containing the untreated core portion or the dispersion liquid containing the core portion treated by the above operation or the like is a surfactant, a pH adjuster, a sedimentation inhibitor, a dispersion stabilizer, a corrosion inhibitor, a fungicide, and a wetting agent. An agent or the like may be further contained, or impurities may be removed by a dialysis membrane, an ion exchange resin, or the like.
シェル部形成工程では、コア部形成工程により形成されたコア部を含む分散液において、上記式（１）表される化合物、上記式（２）表される化合物および上記式（３）で表される化合物の少なくとも何れかと、フッ化ビニリデンとを含む、第２の重合体を構成するための単量体とを重合反応させる。これら単量体を添加するタイミングは特に限定されず、重合反応の開始前に全ての単量体を添加してもよいし、重合反応の開始後に一部の単量体を添加してもよいし、それらを組み合わせてもよい。この重合において、第１の重合体粒子にこれら単量体を浸透させずに重合する。そうすることによって、第１の重合体と第２の重合体とが相互に絡み合ったＩＰＮ構造のようなポリマーアロイ粒子ではなく、第１の重合体粒子の周囲を第２の重合体が取り囲むように形成されるコアシェル粒子を重合することができる。この重合により、フッ化ビニリデン粒子のコア部の周囲にシェル部が形成される。 In the shell portion forming step, in the dispersion liquid containing the core portion formed by the core portion forming step, the compound represented by the above formula (1), the compound represented by the above formula (2) and the above formula (3) are represented. A polymerization reaction is carried out between at least one of the compounds and a monomer for forming a second polymer, which contains vinylidene fluoride. The timing of adding these monomers is not particularly limited, and all the monomers may be added before the start of the polymerization reaction, or some monomers may be added after the start of the polymerization reaction. And they may be combined. In this polymerization, the first polymer particles are polymerized without infiltrating these monomers. By doing so, the second polymer surrounds the first polymer particles instead of the polymer alloy particles such as the IPN structure in which the first polymer and the second polymer are intertwined with each other. The core-shell particles formed in can be polymerized. By this polymerization, a shell portion is formed around the core portion of the vinylidene fluoride particles.
シェル部形成工程における、フッ化ビニリデンの仕込み量は、シェル部形成工程の全単量体の総量を１００質量部とすると、５０質量部以上であることが好ましく、６０質量部以上であることがより好ましく、７０質量部以上であることがさらに好ましい。 The amount of vinylidene fluoride charged in the shell portion forming step is preferably 50 parts by mass or more, preferably 60 parts by mass or more, assuming that the total amount of all the monomers in the shell portion forming step is 100 parts by mass. More preferably, it is 70 parts by mass or more.
また、上記式（１）表される化合物、上記式（２）表される化合物および上記式（３）で表される化合物の仕込み量の合計は、シェル部形成工程の全単量体の総量を１００質量部とすると、密着性の観点から、０．０３質量部以上であることが好ましく、０．１質量部以上であることがより好ましく、０．３質量部以上であることがさらに好ましい。また製造性の観点から、２質量部以下であることが好ましく、１質量部以下であることがより好ましく、０．５質量部以下であることがさらに好ましい。 Further, the total amount of the compound represented by the above formula (1), the compound represented by the above formula (2) and the compound represented by the above formula (3) is the total amount of all the monomers in the shell portion forming step. Is 100 parts by mass, preferably 0.03 parts by mass or more, more preferably 0.1 parts by mass or more, and further preferably 0.3 parts by mass or more from the viewpoint of adhesion. .. Further, from the viewpoint of manufacturability, it is preferably 2 parts by mass or less, more preferably 1 part by mass or less, and further preferably 0.5 part by mass or less.
他の化合物としてハロゲン化アルキルビニル化合物を添加する場合、ハロゲン化アルキルビニル化合物の仕込み量は、シェル部形成工程の全単量体の総量を１００質量部とすると、密着性の観点から、５質量部以上であることが好ましく、１０質量部以上であることがより好ましく、２０質量部以上であることがさらに好ましい。また、イオン透過性の観点から、５０質量部以下であることが好ましく、４０質量部以下であることがより好ましく、３０質量部以下であることがさらに好ましい。 When the halogenated alkyl vinyl compound is added as another compound, the amount of the halogenated alkyl vinyl compound charged is 5% by mass from the viewpoint of adhesion, assuming that the total amount of all the monomers in the shell portion forming step is 100 parts by mass. It is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and further preferably 20 parts by mass or more. Further, from the viewpoint of ion permeability, it is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and further preferably 30 parts by mass or less.
コア部形成工程とシェル部形成工程とは、同一の反応器で行ってもよいし、別々の反応器で行ってもよい。コア部形成工程とシェル部形成工程とを同一の反応器で連続的に行う場合、例えば、コア部形成工程の終了後に反応器内の残存ガスモノマーをパージし、次いでシェル部形成工程において用いられる単量体等を反応器に添加すればよい。 The core portion forming step and the shell portion forming step may be performed by the same reactor or may be performed by different reactors. When the core portion forming step and the shell portion forming step are continuously performed in the same reactor, for example, the residual gas monomer in the reactor is purged after the completion of the core portion forming step, and then used in the shell portion forming step. Monomers and the like may be added to the reactor.
コア部形成工程およびシェル部形成工程において、第１の重合体および第２の重合体を重合する方法としては、特に限定はなく、従来公知の重合方法を用いることができる。重合方法としては、例えば懸濁重合、乳化重合、ソープフリー乳化重合、ミニエマルション重合、シード乳化重合および溶液重合等が挙げられるが、そのなかでも乳化重合、ソープフリー乳化重合、ミニエマルション重合、シード乳化重合が特に好ましい。 The method for polymerizing the first polymer and the second polymer in the core portion forming step and the shell portion forming step is not particularly limited, and a conventionally known polymerization method can be used. Examples of the polymerization method include suspension polymerization, emulsion polymerization, soap-free emulsion polymerization, mini-emulsion polymerization, seed emulsion polymerization and solution polymerization, among which emulsion polymerization, soap-free emulsion polymerization, mini-emulsion polymerization and seeds. Emulsion polymerization is particularly preferred.
乳化重合とは、ラジカル重合の一種であり、水等の媒体と、媒体に難溶な単量体と乳化剤（以下、界面活性剤とも記す）とを混合し、そこに媒体に溶解可能な重合開始剤を加えて行う重合方法である。乳化重合において、フッ化ビニリデンおよびその他の単量体の他に、分散媒、界面活性剤および重合開始剤が用いられる。 Emulsion polymerization is a type of radical polymerization in which a medium such as water is mixed with a monomer poorly soluble in the medium and an emulsifier (hereinafter, also referred to as a surfactant), and the polymerization is soluble in the medium. This is a polymerization method in which an initiator is added. In emulsion polymerization, in addition to vinylidene fluoride and other monomers, dispersion media, surfactants and polymerization initiators are used.
懸濁重合とは、懸濁剤などを含む水中で油溶性の重合開始剤を非水溶性のモノマーに溶かし、これを機械的撹拌により懸濁および分散させて行われる重合方法である。懸濁重合では、モノマー液滴中で重合が進行することで、フッ化ビニリデン粒子が得られる。 Suspension polymerization is a polymerization method in which an oil-soluble polymerization initiator is dissolved in a water-insoluble monomer in water containing a suspending agent or the like, and the polymerization initiator is suspended and dispersed by mechanical stirring. In suspension polymerization, vinylidene fluoride particles are obtained by proceeding with the polymerization in the monomer droplets.
ソープフリー乳化重合とは、上記乳化重合を行う際に用いるような通常の乳化剤を用いることなく行われる乳化重合である。ソープフリー乳化重合によって得られたフッ化ビニリデン粒子は、乳化剤が重合体粒子内に残存しないため好ましい。 The soap-free emulsion polymerization is an emulsion polymerization carried out without using an ordinary emulsifier as used in carrying out the above emulsion polymerization. Vinylidene fluoride particles obtained by soap-free emulsion polymerization are preferable because the emulsifier does not remain in the polymer particles.
ミニエマルション重合とは、超音波発振器などを用いて強いせん断力をかけることでモノマー液滴をサブミクロンサイズまで微細化して行われる重合方法である。ミニエマルション重合では、微細化されたモノマー液滴を安定化させるために、ハイドロホープという難水溶性物質を添加する。理想的なミニエマルション重合では、モノマー液滴が重合することで、それぞれフッ化ビニリデン重合体の微粒子となる。 Miniemulsion polymerization is a polymerization method in which monomer droplets are refined to a submicron size by applying a strong shearing force using an ultrasonic oscillator or the like. In miniemulsion polymerization, a poorly water-soluble substance called hydrohope is added in order to stabilize the finely divided monomer droplets. In the ideal miniemulsion polymerization, the monomer droplets are polymerized to form fine particles of vinylidene fluoride polymer.
シード乳化重合とは、上記のような重合方法で得られた微粒子を他の単量体からなる重合体で被覆する重合である。微粒子の分散液に、さらにフッ化ビニリデンおよびその他の単量体と、分散媒、界面活性剤、重合開始剤等が用いられる。 The seed emulsion polymerization is a polymerization in which fine particles obtained by the above-mentioned polymerization method are coated with a polymer composed of other monomers. Further, vinylidene fluoride and other monomers, a dispersion medium, a surfactant, a polymerization initiator and the like are used as the dispersion liquid of the fine particles.
［分散媒］
用いることができる分散媒としては特に限定はなく、従来公知のものを用いることができるが、分散媒として水を用いることが好ましい。
[Dispersion medium]
The dispersion medium that can be used is not particularly limited, and conventionally known ones can be used, but it is preferable to use water as the dispersion medium.
［界面活性剤］
用いる界面活性剤は、非イオン性界面活性剤、カチオン性界面活性剤、アニオン性界面活性剤および両性界面活性剤の何れであってもよく、複数種類を組み合わせて使用してもよい。界面活性剤としては、ポリフッ化ビニリデンの重合に従来から使用されている過フッ素化界面活性剤、部分フッ素化界面活性剤および非フッ素化界面活性剤等が好適である。それらのうち、パーフルオロアルキルスルホン酸およびその塩、パーフルオロアルキルカルボン酸およびその塩、フルオロカーボン鎖またはフルオロポリエーテル鎖を有するフッ素系界面活性剤を使用することが好ましく、パーフルオロアルキルカルボン酸およびその塩を用いることがより好ましい。本実施形態では、乳化剤として、上記のうちから選択される１種単独または２種以上を使用することができる。
[Surfactant]
The surfactant to be used may be any of a nonionic surfactant, a cationic surfactant, an anionic surfactant and an amphoteric surfactant, and a plurality of types may be used in combination. As the surfactant, a perfluorinated surfactant, a partially fluorinated surfactant, a non-fluorinated surfactant and the like conventionally used for the polymerization of polyvinylidene fluoride are suitable. Among them, it is preferable to use a perfluoroalkyl sulfonic acid and a salt thereof, a perfluoroalkyl carboxylic acid and a salt thereof, a fluorine-based surfactant having a fluorocarbon chain or a fluoropolyether chain, and the perfluoroalkyl carboxylic acid and its salt. It is more preferable to use salt. In the present embodiment, as the emulsifier, one or more selected from the above can be used.
乳化剤の添加量は、重合に用いられる全単量体の総量を１００質量部とすると、０．００５〜２２質量部であることが好ましく、０．２〜２０質量部であることがより好ましい。 The amount of the emulsifier added is preferably 0.005 to 22 parts by mass, more preferably 0.2 to 20 parts by mass, assuming that the total amount of all the monomers used in the polymerization is 100 parts by mass.
［重合開始剤］
用いることができる重合開始剤としては、特に限定はなく、従来公知のものを用いることができる。重合開始剤としては、水溶性過酸化物、水溶性アゾ系化合物またはレドックス開始剤系が用いられる。水溶性過酸化物としては、例えば、過硫酸アンモニウムおよび過硫酸カリウム等が挙げられる。水溶性アゾ系化合物としては、例えば、ＡＩＢＮおよびＡＭＢＮ等が挙げられる。レドックス開始剤系としては、例えば、アスコルビン酸−過酸化水素が挙げられる。重合開始剤は好ましくは水溶性過酸化物である。これらの重合開始剤は、１種単独または２種以上を組み合わせて用いることができる。
[Polymerization initiator]
The polymerization initiator that can be used is not particularly limited, and conventionally known ones can be used. As the polymerization initiator, a water-soluble peroxide, a water-soluble azo compound or a redox initiator system is used. Examples of the water-soluble peroxide include ammonium persulfate and potassium persulfate. Examples of the water-soluble azo compound include AIBN and AMBN. Examples of the redox initiator system include ascorbic acid-hydrogen peroxide. The polymerization initiator is preferably a water-soluble peroxide. These polymerization initiators can be used alone or in combination of two or more.
重合開始剤の添加量は、重合に用いられる全単量体の総量を１００質量部とすると、０．０１〜５質量部であることが好ましく、０．０２〜４質量部であることがより好ましい。 The amount of the polymerization initiator added is preferably 0.01 to 5 parts by mass, more preferably 0.02 to 4 parts by mass, assuming that the total amount of all the monomers used in the polymerization is 100 parts by mass. preferable.
［他の成分］
乳化重合において、得られるコアシェル型粒子の重合度を調節するために、連鎖移動剤を用いてもよい。連鎖移動剤としては、例えば、酢酸エチル、酢酸メチル、炭酸ジエチル、アセトン、エタノール、ｎ−プロパノール、アセトアルデヒド、プロピルアルデヒド、プロピオン酸エチル、および四塩化炭素等を挙げることができる。
[Other ingredients]
In emulsion polymerization, a chain transfer agent may be used to control the degree of polymerization of the resulting core-shell type particles. Examples of the chain transfer agent include ethyl acetate, methyl acetate, diethyl carbonate, acetone, ethanol, n-propanol, acetaldehyde, propylaldehyde, ethyl propionate, carbon tetrachloride and the like.
また、必要に応じてｐＨ調整剤を用いてもよい。ｐＨ調整剤としては、リン酸二水素ナトリウム、リン酸水素二ナトリウムおよびリン酸二水素カリウム等の緩衝能を有する電解質物質、ならびに水酸化ナトリウム、水酸化カリウム、水酸化バリウム、水酸化カルシウム、アンモニア等の塩基性物質が挙げられる。 Moreover, you may use a pH adjuster if necessary. Examples of the pH adjuster include electrolyte substances having a buffering ability such as sodium dihydrogen phosphate, disodium hydrogen phosphate and potassium dihydrogen phosphate, and sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide and ammonia. And other basic substances.
また、必要に応じて、沈降防止剤、分散安定剤、腐食防止剤、防カビ剤および湿潤剤等を用いてもよい。 Further, if necessary, a sedimentation inhibitor, a dispersion stabilizer, a corrosion inhibitor, a fungicide, a wetting agent and the like may be used.
他の成分の添加量は、重合に用いられる全単量体の総量を１００質量部とすると、０．０１〜１０質量部であることが好ましく、０．０２〜７質量部であることがより好ましい。 The amount of other components added is preferably 0.01 to 10 parts by mass, more preferably 0.02 to 7 parts by mass, assuming that the total amount of all the monomers used in the polymerization is 100 parts by mass. preferable.
（重合条件）
重合温度は、重合開始剤の種類等によって、適宜選択すればよいが、例えば、０〜１２０℃の範囲とすればよく、２０〜１１０℃の範囲であることが好ましく、４０〜１００℃の範囲であることがより好ましい。
(Polymerization conditions)
The polymerization temperature may be appropriately selected depending on the type of polymerization initiator and the like. For example, the polymerization temperature may be in the range of 0 to 120 ° C., preferably in the range of 20 to 110 ° C., and in the range of 40 to 100 ° C. Is more preferable.
また、重合圧力は、例えば、０〜１０ＭＰａの範囲とすればよく、０．５〜８ＭＰａの範囲であることが好ましく、１〜６ＭＰａの範囲であることがより好ましい。 The polymerization pressure may be, for example, in the range of 0 to 10 MPa, preferably in the range of 0.5 to 8 MPa, and more preferably in the range of 1 to 6 MPa.
重合時間は、特に制限されないが、生産性等を考慮すると、１〜２４時間の範囲であることが好ましい。 The polymerization time is not particularly limited, but is preferably in the range of 1 to 24 hours in consideration of productivity and the like.
〔分散液〕
本実施形態に係る分散液は、本実施形態に係るコアシェル型粒子および分散媒を含んでいる。
[Dispersion]
The dispersion liquid according to the present embodiment contains the core-shell type particles and the dispersion medium according to the present embodiment.
本実施形態に係る分散液における分散媒は、例えば、水であることが好ましいが、水と混和する任意の非水溶媒と水との混合液であって、フッ化ビニリデン樹脂を溶解せず、分散、懸濁、または乳化し得る液体であれば特に限定されるものではない。上記非水溶媒としては、例えば、Ｎ−メチルピロリドン、ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド等のアミド化合物；トルエン、キシレン、ｎ−ドデカン、テトラリン等の炭化水素；メタノール、エタノール、イソプロピルアルコール、２−エチル−１−ヘキサノール、１−ノナノール、ラウリルアルコール等のアルコール；アセトン、メチルエチルケトン、シクロヘキサノン、ホロン、アセトフェノン、イソホロン等のケトン；酢酸ベンジル、酪酸イソペンチル、乳酸メチル、乳酸エチル、乳酸ブチル等のエステル；ｏ−トルイジン、ｍ−トルイジン、ｐ−トルイジン等のアミン化合物；γ−ブチロラクトン、δ−ブチロラクトン等のラクトン；ジメチルスルホキシド、スルホラン等のスルホキシド化合物およびスルホン化合物；ならびにテトラヒドロフランおよび酢酸エチル等が挙げられる。これらの非水溶媒は、水と任意の割合で混合して用いることができる。水は単独で用いてもよいし、水とこれら非水溶媒のうちの一種類または二種類以上とを混合した混合分散媒であってもよい。 The dispersion medium in the dispersion liquid according to the present embodiment is preferably water, for example, but is a mixed liquid of any non-aqueous solvent miscible with water and water, which does not dissolve the vinylidene fluoride resin. The liquid is not particularly limited as long as it can be dispersed, suspended, or emulsified. Examples of the non-aqueous solvent include amide compounds such as N-methylpyrrolidone, dimethylformamide, and N, N-dimethylacetamide; hydrocarbons such as toluene, xylene, n-dodecane, and tetralin; methanol, ethanol, isopropyl alcohol, and 2 -Alcohols such as ethyl-1-hexanol, 1-nonanol, lauryl alcohol; ketones such as acetone, methyl ethyl ketone, cyclohexanone, holon, acetphenone, isophorone; esters such as benzyl acetate, isopentyl butyrate, methyl lactate, ethyl lactate, butyl lactate; Examples include amine compounds such as o-toluidine, m-toluidine and p-toluidine; lactones such as γ-butyrolactone and δ-butyrolactone; sulfoxide compounds and sulfone compounds such as dimethylsulfoxide and sulfolane; and tetrahydrofuran and ethyl acetate. These non-aqueous solvents can be used by mixing with water in an arbitrary ratio. Water may be used alone, or may be a mixed dispersion medium in which water and one or more of these non-aqueous solvents are mixed.
また、必要に応じて、ｐＨ調整剤、沈降防止剤、分散安定剤、腐食防止剤、防カビ剤および／または湿潤剤等を用いてもよい。 Further, if necessary, a pH adjuster, a sedimentation inhibitor, a dispersion stabilizer, a corrosion inhibitor, a fungicide and / or a wetting agent and the like may be used.
本実施形態に係る分散液におけるコアシェル型粒子の含有量は、分散液の全量を１００質量部とすると、６０質量部以下であることが好ましい。 The content of the core-shell type particles in the dispersion liquid according to the present embodiment is preferably 60 parts by mass or less, assuming that the total amount of the dispersion liquid is 100 parts by mass.
〔コーティング組成物〕
本実施形態に係るコーティング組成物は、負極層および正極層（電極）とその間に設けられるセパレータとを備える二次電池において、電極とセパレータとの接着性を向上させる多孔質のフッ素樹脂層を形成するために用いられる組成物である。
[Coating composition]
The coating composition according to the present embodiment forms a porous fluororesin layer that improves the adhesiveness between the electrode and the separator in a secondary battery including a negative electrode layer and a positive electrode layer (electrode) and a separator provided between them. It is a composition used for the purpose.
本実施形態に係るコーティング組成物は、本実施形態に係るコアシェル型粒子を含む。本実施形態に係るコーティング組成物は、コアシェル型粒子のみを含むものであってもよいし、コアシェル型粒子を分散する分散媒をさらに含んでいてもよい。分散媒の具体的な説明は、上記〔分散液〕の欄を参照することができる。一例において、本実施形態に係るコーティング組成物は、上述の分散液であり得る。 The coating composition according to this embodiment contains core-shell type particles according to this embodiment. The coating composition according to the present embodiment may contain only core-shell type particles, or may further contain a dispersion medium for dispersing core-shell type particles. For a specific description of the dispersion medium, the above [dispersion liquid] column can be referred to. In one example, the coating composition according to this embodiment can be the above-mentioned dispersion liquid.
本実施形態に係るコーティング組成物を調製するにあたり、コアシェル型粒子は、塩析、凍結粉砕、スプレードライ、およびフリーズドライ等から選ばれる少なくとも１種類の方法で粉体化してそのままコーティング組成物としてもよいし、このように粉体化したコアシェル型粒子を水などの分散媒に物理的または化学的に再分散させてコーティング組成物としてもよい。あるいは、重合に用いた分散媒にコアシェル型粒子が分散された分散液をそのままコーティング組成物としてもよいし、別途用意した水などの分散媒にコアシェル型粒子を物理的または化学的に再分散させてコーティング組成物としてもよい。 In preparing the coating composition according to the present embodiment, the core-shell type particles may be powdered by at least one method selected from salting out, freeze-grinding, spray-drying, freeze-drying and the like to form the coating composition as it is. Alternatively, the core-shell type particles powdered in this way may be physically or chemically redispersed in a dispersion medium such as water to obtain a coating composition. Alternatively, the dispersion liquid in which the core-shell type particles are dispersed in the dispersion medium used for the polymerization may be used as it is as a coating composition, or the core-shell type particles are physically or chemically redispersed in a separately prepared dispersion medium such as water. It may be used as a coating composition.
分散媒を用いる場合、コーティング組成物が含有する分散媒の含有量は、コアシェル型粒子の含有量を１００質量部とすると、６５〜３５００質量部であることが好ましく、３００〜２０００質量部であることがより好ましい。 When a dispersion medium is used, the content of the dispersion medium contained in the coating composition is preferably 65 to 3500 parts by mass, preferably 300 to 2000 parts by mass, assuming that the content of the core-shell type particles is 100 parts by mass. Is more preferable.
また、本実施形態に係るコーティング組成物は、必要に応じて、フィラーを含ませてもよい。フィラーを含むことで、セパレータの耐熱性を向上させることができる。フィラーとしては、例えば、二酸化ケイ素（ＳｉＯ２）、アルミナ（Ａｌ２〇３）、二酸化チタン（ＴｉＯ２）、酸化カルシウム（ＣａＯ）、酸化ストロンチウム（ＳｒＯ）、酸化バリウム（ＢａＯ）、酸化マグネシウム（ＭｇＯ）、酸化亜鉛（ＺｎＯ）、チタン酸バリウム（ＢａＴｉＯ３）等の酸化物；水酸化マグネシウム（Ｍｇ（ＯＨ）２）、水酸化カルシウム（Ｃａ（ＯＨ）２）、水酸化亜鉛（Ｚｎ（ＯＨ）２）、水酸化アルミニウム（Ａｌ（ＯＨ）３）、水酸化酸化アルミニウム（ＡｌＯ（ＯＨ））等の水酸化物；炭酸カルシウム（ＣａＣＯ３）等の炭酸塩；硫酸バリウム等の硫酸塩；窒化物；粘土鉱物；およびベーマイト等が挙げられる。フィラーとしては、電池の安全性および塗液安定性の観点から、アルミナ、二酸化ケイ素、酸化マグネシウム、水酸化マグネシウム、炭酸マグネシウム、酸化亜鉛およびベーマイトが好ましい。フィラーは、単独で用いてもよいし、二種以上を用いてもよい。 In addition, the coating composition according to the present embodiment may contain a filler, if necessary. By including the filler, the heat resistance of the separator can be improved. As the filler, for example, silicon dioxide (SiO 2), alumina (Al 2 〇 3), titanium (TiO 2) dioxide, calcium oxide (CaO), strontium oxide (SrO), barium oxide (BaO), magnesium oxide (MgO ), Oxides such as zinc oxide (ZnO) and barium titanate (BaTIO 3 ); magnesium hydroxide (Mg (OH) 2 ), calcium hydroxide (Ca (OH) 2 ), zinc hydroxide (Zn (OH)) 2 ), hydroxides such as aluminum hydroxide (Al (OH) 3 ) and aluminum hydroxide (AlO (OH)); carbonates such as calcium carbonate (CaCO 3 ); sulfates such as barium sulfate; nitrides ; Clay minerals; and boehmite and the like. As the filler, alumina, silicon dioxide, magnesium oxide, magnesium hydroxide, magnesium carbonate, zinc oxide and boehmite are preferable from the viewpoint of battery safety and coating stability. The filler may be used alone or in combination of two or more.
また、本実施形態に係るコーティング組成物は、増粘剤をさらに含んでもよい。増粘剤を含むことで、コーティング組成物の粘度の調整ならびにコアシェル型粒子およびフィラーの分散性を向上させることができる。増粘剤としては、例えば、カルボキシメチルセルロース、メチルセルロース、ヒドロキシプロピルセルロース、ヒドロキシプロピルメチルセルロース、ヒドロキシエチルセルロース等のセルロース化合物；上記セルロース化合物のアンモニウム塩またはアルカリ金属塩；ポリ（メタ）アクリル酸、変性ポリ（メタ）アクリル酸等のポリカルボン酸；上記ポリカルボン酸のアルカリ金属塩；ポリビニルアルコール、変性ポリビニルアルコール、エチレン−ビニルアルコール共重合体等のポリビニルアルコール系（共）重合体；（メタ）アクリル酸、マレイン酸およびフマル酸等の不飽和カルボン酸と、ポリビニルピロリドン、ポリビニルブチラールまたはビニルエステルとの共重合体の鹸化物等の水溶性ポリマー等が挙げられる。なかでも、セルロース化合物およびその塩が好ましい。 In addition, the coating composition according to the present embodiment may further contain a thickener. By including the thickener, it is possible to adjust the viscosity of the coating composition and improve the dispersibility of the core-shell type particles and the filler. Examples of the thickener include cellulose compounds such as carboxymethyl cellulose, methyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, and hydroxyethyl cellulose; ammonium salts or alkali metal salts of the above cellulose compounds; poly (meth) acrylic acid, modified poly (meth). ) Polycarboxylic acids such as acrylic acid; alkali metal salts of the above polycarboxylic acids; polyvinyl alcohol-based (co) polymers such as polyvinyl alcohol, modified polyvinyl alcohol, and ethylene-vinyl alcohol copolymers; (meth) acrylic acid, malein Examples thereof include water-soluble polymers such as a saponified product of an unsaturated carboxylic acid such as acid and fumaric acid and a copolymer of polyvinylpyrrolidone, polyvinylbutyral or vinyl ester. Of these, cellulose compounds and salts thereof are preferable.
フィラーを含ませる場合、フィラーの添加量は、コアシェル型粒子の含有量を１００質量部とすると、１０〜９００質量部であることが好ましい。 When the filler is contained, the amount of the filler added is preferably 10 to 900 parts by mass, assuming that the content of the core-shell type particles is 100 parts by mass.
増粘剤を含む場合、コーティング組成物に対する増粘剤の添加量は、コアシェル型粒子、フィラーおよび増粘剤の総量のうち１０質量部以下であることが好ましく、５質量部以下であることがより好ましい。 When the thickener is contained, the amount of the thickener added to the coating composition is preferably 10 parts by mass or less, and preferably 5 parts by mass or less of the total amount of the core-shell type particles, the filler and the thickener. More preferred.
また、本実施形態に係るコーティング組成物は、必要に応じて、界面活性剤、ｐＨ調整剤、沈降防止剤、腐食防止剤、分散安定剤、防カビ剤、湿潤剤および／または消泡剤等をさらに含んでもよい。 Further, the coating composition according to the present embodiment may contain, if necessary, a surfactant, a pH adjuster, a sedimentation inhibitor, a corrosion inhibitor, a dispersion stabilizer, a fungicide, a wetting agent and / or an antifoaming agent, etc. May be further included.
〔フッ素樹脂層〕
本実施形態におけるフッ素樹脂層は、本実施形態に係るコーティング組成物を、セパレータまたは電極に塗布し、乾燥させることによって形成される。具体的には、まずセパレータまたは電極のいずれかの少なくとも一方の面にコーティング組成物を塗布し、塗布したコーティング組成物を乾燥させる。乾燥させたセパレータと電極とを重ね合わせ、電解液やその他必要な部材とを外装材に入れ、外装材ごと熱プレスしてセパレータと電極とを接着させる。この段階で、コアシェル粒子のシェル部が熱によって溶融してフッ素樹脂層が形成される。
[Fluororesin layer]
The fluororesin layer in the present embodiment is formed by applying the coating composition according to the present embodiment to a separator or an electrode and drying it. Specifically, first, the coating composition is applied to at least one surface of either the separator or the electrode, and the applied coating composition is dried. The dried separator and the electrode are overlapped with each other, the electrolytic solution and other necessary members are put into the exterior material, and the exterior material is heat-pressed to bond the separator and the electrode. At this stage, the shell portion of the core-shell particles is melted by heat to form a fluororesin layer.
フッ素樹脂層の膜厚は、特に限定されるものではないが、０．１μｍ以上１０μｍ以下であることが好ましく、０．２μｍ以上９．５μｍ以下であることがより好ましく、０．３μｍ以上９μｍ以下であることがさらに好ましい。本実施形態に係るコーティング組成物は、フッ素樹脂層の膜厚が上記の範囲内に収まるように塗布される。 The film thickness of the fluororesin layer is not particularly limited, but is preferably 0.1 μm or more and 10 μm or less, more preferably 0.2 μm or more and 9.5 μm or less, and 0.3 μm or more and 9 μm or less. Is more preferable. The coating composition according to the present embodiment is applied so that the film thickness of the fluororesin layer falls within the above range.
コーティング組成物を塗布する方法としては、例えばドクターブレード法、リバースロール法、コンマバー法、グラビヤ法、エアーナイフ法、ダイコート法およびディップコート法等の方法を適用することができる。塗膜の乾燥処理は、好ましくは４０〜１５０℃、より好ましくは４５〜１３０℃の温度範囲において、好ましくは１〜５００分間、より好ましくは２〜３００分間の処理時間で行われる。 As a method for applying the coating composition, for example, a doctor blade method, a reverse roll method, a comma bar method, a gravure method, an air knife method, a die coating method, a dip coating method and the like can be applied. The coating film is dried, preferably in a temperature range of 40 to 150 ° C., more preferably 45 to 130 ° C., with a treatment time of preferably 1 to 500 minutes, more preferably 2 to 300 minutes.
また、本実施形態におけるフッ素樹脂層は、負極層とセパレータとの間に設けられてもよいし、セパレータと正極層との間に設けられてもよいし、その両方に設けられてもよい。 Further, the fluororesin layer in the present embodiment may be provided between the negative electrode layer and the separator, may be provided between the separator and the positive electrode layer, or may be provided in both of them.
本実施形態におけるフッ素樹脂層は、セパレータと電極との間に設けられることによって、セパレータと電極との間に十分な接着性を与えることができる。本実施形態におけるフッ素樹脂層を設けられたセパレータと電極との剥離強度は、例えば、０．２〜２．７ｇｆ／ｍｍである。剥離強度の測定方法は、後述する実施例において説明する。 By providing the fluororesin layer in the present embodiment between the separator and the electrode, sufficient adhesiveness can be provided between the separator and the electrode. The peel strength between the separator provided with the fluororesin layer and the electrode in the present embodiment is, for example, 0.2 to 2.7 gf / mm. The method for measuring the peel strength will be described in Examples described later.
本実施形態におけるフッ素樹脂層は、後述する非水電解質電池の製造工程の一部である熱プレスの工程が行われた後において、溶融した第２の重合体を含む層を含んでいる。すなわち、フッ素樹脂層は、一例において、負極層と正極層とセパレータとを熱プレスすることによって形成されてなる第２の重合体を含む層を有している。この第２の重合体を含む層には、第１の重合体を含む粒子が含まれている。このような構造を有することによって、熱プレスの工程を経てもセパレータの表面の孔を塞ぐことが低減されている。従って、本実施形態におけるフッ素樹脂層は、多孔質である。本実施形態におけるフッ素樹脂層によってセパレータの表面の孔が塞がれていないことは、ＳＥＭ観察によって確認することができる。ＳＥＭ観察用フッ素樹脂層コーティングセパレータの作製方法は、後述する実施例において説明する。 The fluororesin layer in the present embodiment includes a layer containing a second polymer that has been melted after the heat pressing step, which is a part of the manufacturing step of the non-aqueous electrolyte battery described later, has been performed. That is, in one example, the fluororesin layer has a layer containing a second polymer formed by hot-pressing the negative electrode layer, the positive electrode layer, and the separator. The layer containing the second polymer contains particles containing the first polymer. By having such a structure, it is reduced that the holes on the surface of the separator are closed even after the heat pressing process. Therefore, the fluororesin layer in this embodiment is porous. It can be confirmed by SEM observation that the pores on the surface of the separator are not blocked by the fluororesin layer in the present embodiment. A method for producing a fluororesin layer-coated separator for SEM observation will be described in Examples described later.
〔セパレータ〕
本実施形態に係るセパレータは、電気的に安定であり、電気伝導性を有していない。また本実施形態に係るセパレータは、内部に空孔または空隙を有する多孔質基材が用いられイオン透過性に優れている。多孔質基材としては、例えば、ポリオレフィン系高分子（例えば、ポリエチレン、ポリプロピレン等）、ポリエステル系高分子（例えば、ポリエチレンテレフタレート等）、ポリイミド系高分子（例えば、芳香族ポリアミド系高分子、ポリエーテルイミド等）、ポリエーテルスルホン、ポリスルホン、ポリエーテルケトン、ポリスチレン、ポリエチレンオキサイド、ポリカーボネート、ポリ塩化ビニル、ポリアクリロニトリル、ポリメチルメタクリレート、セラミックス等、およびこれらの少なくとも２種の混合物からなる単層または多層の多孔膜；不織布；ガラス；並びに紙等を挙げることができる。なお、前述のポリマーとしては、変性されたものが挙げられる。
[Separator]
The separator according to this embodiment is electrically stable and does not have electrical conductivity. Further, the separator according to the present embodiment uses a porous base material having pores or voids inside, and has excellent ion permeability. Examples of the porous substrate include polyolefin-based polymers (for example, polyethylene, polypropylene, etc.), polyester-based polymers (for example, polyethylene terephthalate, etc.), polyimide-based polymers (for example, aromatic polyamide-based polymers, polyether). (Imid etc.), polyethersulfone, polysulfone, polyetherketone, polystyrene, polyethylene oxide, polycarbonate, polyvinyl chloride, polyacrylonitrile, polymethylmethacrylate, ceramics, etc., and a single layer or multilayer consisting of a mixture of at least two of these. Perforated film; non-polymer; glass; as well as paper and the like. Examples of the above-mentioned polymer include modified polymers.
多孔質基材としては、ポリオレフィン系高分子（例えば、ポリエチレン、ポリプロピレン等）を含むものが好ましい。多孔質基材は、シャットダウン機能の観点から、ポリエチレンを含むことがより好ましく、シャットダウン機能と耐熱性との両立の観点から、ポチエチレンとポリプロピレンとを含むことがより好ましく、９５質量％以上のポリエチレンと５質量％以下のポリプロピレンとを含むことがさらに好ましい。 As the porous base material, those containing a polyolefin-based polymer (for example, polyethylene, polypropylene, etc.) are preferable. The porous base material more preferably contains polyethylene from the viewpoint of the shutdown function, and more preferably contains polyethylene and polypropylene from the viewpoint of achieving both the shutdown function and heat resistance, and 95% by mass or more of polyethylene. And 5% by mass or less of polypropylene are more preferably contained.
また、多孔質基材の厚さは、力学特性および内部抵抗の観点から、３μｍ以上２５μｍ以下であることが好ましく、５μｍ以上２５μｍであることがより好ましい。 The thickness of the porous substrate is preferably 3 μm or more and 25 μm or less, and more preferably 5 μm or more and 25 μm, from the viewpoint of mechanical properties and internal resistance.
多孔質基材の表面には、コーティング組成物との濡れ性を向上させる目的で、コロナ処理、プラズマ処理、火炎処理、または紫外線照射処理等が施されていてもよい。 The surface of the porous substrate may be subjected to corona treatment, plasma treatment, flame treatment, ultraviolet irradiation treatment, or the like for the purpose of improving the wettability with the coating composition.
本実施形態に係るセパレータは、一例において、本実施形態に係るコーティング組成物が、負極層および正極層に対向する面のうち少なくとも一方の面に塗布されている。 In the separator according to the present embodiment, in one example, the coating composition according to the present embodiment is applied to at least one of the surface facing the negative electrode layer and the positive electrode layer.
〔電極〕
本実施形態における負極層および正極層は、特に限定されず、例えば、二次電池における公知の負極層および正極層を用いることができる。
〔electrode〕
The negative electrode layer and the positive electrode layer in the present embodiment are not particularly limited, and for example, known negative electrode layers and positive electrode layers in the secondary battery can be used.
一例において、負極層および正極層は、電極合剤の層が集電体上に設けられた構成である。電極合剤層は、集電体の少なくとも一方の面に形成されていればよい。 In one example, the negative electrode layer and the positive electrode layer have a structure in which a layer of an electrode mixture is provided on a current collector. The electrode mixture layer may be formed on at least one surface of the current collector.
電極合剤は、例えば、電極活物質とバインダー組成物とを含有し得る。 The electrode mixture may contain, for example, an electrode active material and a binder composition.
電極活物質は、特に限定されるものではなく、例えば、従来公知の負極用の電極活物質（負極活物質）または正極用の電極活物質（正極活物質）を用いることができる。 The electrode active material is not particularly limited, and for example, a conventionally known electrode active material for a negative electrode (negative electrode active material) or an electrode active material for a positive electrode (positive electrode active material) can be used.
負極活物質としては、例えば、人工黒鉛、天然黒鉛、難黒鉛化炭素、易黒鉛化炭素、活性炭、またはフェノール樹脂およびピッチ等を焼成炭化したもの等の炭素材料；Ｃｕ、Ｌｉ、Ｍｇ、Ｂ、Ａｌ、Ｇａ、Ｉｎ、Ｓｉ、Ｇｅ、Ｓｎ、Ｐｂ、Ｓｂ、Ｂｉ、Ｃｄ、Ａｇ、Ｚｎ、Ｈｆ、ＺｒおよびＹ等の金属材料および合金材料；ならびにＧｅＯ、ＧｅＯ２、ＳｎＯ、ＳｎＯ２、ＰｂＯおよびＰｂＯ２等の金属酸化物等が挙げられる。 Examples of the negative electrode active material include artificial graphite, natural graphite, non-graphitized carbon, easily graphitized carbon, activated carbon, or carbon materials such as phenolic resins and calcined carbon materials such as pitch; Cu, Li, Mg, B, Metallic and alloying materials such as Al, Ga, In, Si, Ge, Sn, Pb, Sb, Bi, Cd, Ag, Zn, Hf, Zr and Y; and GeO, GeO 2 , SnO, SnO 2 , PbO and Examples thereof include metal oxides such as PbO 2.
正極活物質としては、少なくともリチウムを含むリチウム系正極活物質が好ましい。リチウム系正極活物質としては例えば、ＬｉＣｏＯ２、ＬｉＮｉｘＣｏ１−ｘＯ２（０≦ｘ≦１）、ＬｉＮｉＣｏＭｎＯ２等の一般式ＬｉＭＹ２（Ｍは、Ｃｏ、Ｎｉ、Ｆｅ、Ｍｎ、Ｃｒ、Ｖ等の遷移金属の少なくとも一種：ＹはＯ、Ｓ等のカルコゲン元素）で表わされる複合金属カルコゲン化合物、ＬｉＭｎ２Ｏ４などのスピネル構造をとる複合金属酸化物、およびＬｉＦｅＰＯ４などのオリビン型リチウム化合物等が挙げられる。 As the positive electrode active material, a lithium-based positive electrode active material containing at least lithium is preferable. Examples of the lithium-based positive electrode active material include LiCoO 2 , LiNi x Co 1-x O 2 (0 ≦ x ≦ 1), LiNiCoMnO 2, and other general formulas LiMY 2 (M is Co, Ni, Fe, Mn, Cr, At least one kind of transition metal such as V: Y is a chalcogen compound represented by (chalcogen elements such as O and S), a composite metal oxide having a spinel structure such as LiMn 2 O 4 , and an olivine-type lithium such as LiFePO 4. Examples include compounds.
バインダー組成物としては、フッ化ビニリデン重合体、ポリテトラフルオロエチレン（ＰＴＦＥ）、スチレンブタジエンゴム（ＳＢＲ）、ポリアクリル酸、ポリイミド、カルボキシメチルセルロース等のセルロース化合物、セルロース化合物のアンモニウム塩およびアルカリ金属塩、ならびにポリアクリロニトリル（ＰＡＮ）等を含むものが挙げられる。 Examples of the binder composition include cellulose compounds such as vinylidene fluoride polymer, polytetrafluoroethylene (PTFE), styrene butadiene rubber (SBR), polyacrylic acid, polyimide, and carboxymethyl cellulose, ammonium salts and alkali metal salts of cellulose compounds, and the like. In addition, those containing polyacrylonitrile (PAN) and the like can be mentioned.
電極合剤は、例えば、カーボンブラック、アセチレンブラック、ケッチェンブラック、黒鉛粉末、カーボンファイバー、カーボンナノチューブ等の導電助剤；ポリビニルピロリドンなどの顔料分散剤；およびポリアクリル酸、ポリメタクリル酸などの接着補助剤等をさらに含んでいてもよい。 The electrode mixture is, for example, a conductive auxiliary agent such as carbon black, acetylene black, ketjen black, graphite powder, carbon fiber, carbon nanotube; a pigment dispersant such as polyvinylpyrrolidone; and adhesion of polyacrylic acid, polymethacrylic acid and the like. Auxiliary agents and the like may be further contained.
集電体は負極層および正極層の基材であり、電気を取り出すための端子である。集電体の材質としては、特に限定されるものではなく、アルミニウム、銅、鉄、ステンレス鋼、鋼、ニッケルおよびチタン等の金属箔または金属鋼などを用いることができる。集電体の厚さは、特に限定されるものではないが、５〜１００μｍであることが好ましく、５〜７０μｍであることがより好ましい。 The current collector is a base material of the negative electrode layer and the positive electrode layer, and is a terminal for extracting electricity. The material of the current collector is not particularly limited, and metal foils such as aluminum, copper, iron, stainless steel, steel, nickel and titanium, or metal steel can be used. The thickness of the current collector is not particularly limited, but is preferably 5 to 100 μm, and more preferably 5 to 70 μm.
電極合剤層の厚さは、特に限定されるものではないが、通常は６〜１０００μｍであり、７〜５００μｍであることが好ましい。 The thickness of the electrode mixture layer is not particularly limited, but is usually 6 to 1000 μm, preferably 7 to 500 μm.
本実施形態における電極では、フッ素樹脂層が、負極層および正極層の少なくとも何れかにおいて、セパレータと接するように設けられてもよく、一例において、正極層に設けられることが好ましい。また、本実施形態における電極では、一例において、本実施形態に係るコーティング組成物が、負極層および正極層の少なくとも何れかの少なくとも一方の面に塗布されている。 In the electrode of the present embodiment, the fluororesin layer may be provided in contact with the separator in at least one of the negative electrode layer and the positive electrode layer, and in one example, it is preferably provided in the positive electrode layer. Further, in the electrode of the present embodiment, in one example, the coating composition according to the present embodiment is applied to at least one surface of at least one of the negative electrode layer and the positive electrode layer.
〔電解質〕
本実施形態における二次電池に用いられる電解質は、特に限定されず、例えば、二次電池における公知の電解質を用いることができる。電解質としては、例えば、例えば、ＬｉＰＦ４、ＬｉＢＦ４、ＬｉＣｌＯ４、ＬｉＡｓＦ６、ＬｉＳｂＦ６、ＬｉＣＦ３ＳＯ３、Ｌｉ（ＣＦ３ＳＯ２）２Ｎ、ＬｉＣ４Ｆ９ＳＯ３、Ｌｉ（ＣＦ３ＳＯ２）３Ｃ、およびＬｉＢＰｈ４等が挙げられる。本実施形態における二次電池では、電解質を非水系溶媒に溶解させた電解液を用いることもできる。非水系溶媒としては、例えば、エチレンカーボネート、プロピレンカーボネート、ブチレンカーボネート、フロロエチレンカーボネート、ジフロロエチレンカーボネート等の環状カーボネート、ジメチルカーボネート、ジエチルカーボネート、エチルメチルカーボネート、及びそのフッ素置換体等の鎖状カーボネート、γ−ブチロラクトン、γ−バレロラクトン等の環状エステルあるいはこれらの混合溶媒等が挙げられる。
〔Electrolytes〕
The electrolyte used in the secondary battery in the present embodiment is not particularly limited, and for example, a known electrolyte in the secondary battery can be used. As the electrolyte, for example, for example, LiPF 4, LiBF 4, LiClO 4, LiAsF 6, LiSbF 6, LiCF 3 SO 3, Li (CF 3 SO 2) 2 N, LiC 4 F 9 SO 3, Li (CF 3 SO 2) 3 C, and LiBPh 4, and the like. In the secondary battery of the present embodiment, an electrolytic solution in which an electrolyte is dissolved in a non-aqueous solvent can also be used. Examples of the non-aqueous solvent include cyclic carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, fluoroethylene carbonate, and difluoroethylene carbonate, dimethyl carbonate, diethyl carbonate, ethylmethyl carbonate, and chain carbonates such as fluorine-substituted compounds thereof. , Γ-Butyrolactone, cyclic ester such as γ-valerolactone, or a mixed solvent thereof and the like.
〔二次電池〕
本実施形態に係る二次電池は、本実施形態に係るコーティング組成物から形成されたフッ素樹脂層が設けられている。一例において、セパレータは上記で説明したセパレータである。また、一例において、電極は上記で説明した電極である。
[Secondary battery]
The secondary battery according to the present embodiment is provided with a fluororesin layer formed from the coating composition according to the present embodiment. In one example, the separator is the separator described above. Further, in one example, the electrode is the electrode described above.
本実施形態に係る二次電池は、例えば電解質の種類によって分類することができる。具体的には、例えば、非水電解質二次電池、および固体電解質二次電池等が挙げられ、なかでも非水電解質二次電池が好ましい。 The secondary battery according to the present embodiment can be classified according to, for example, the type of electrolyte. Specific examples thereof include a non-aqueous electrolyte secondary battery and a solid electrolyte secondary battery, and among them, a non-aqueous electrolyte secondary battery is preferable.
本実施形態に係る非水電解質二次電池としては、例えば、ゲル電解質を含むポリマー電池等も含まれる。非水電解質二次電池における他の部材については特に限定されるものでなく、例えば、従来用いられている部材を用いることができる。 The non-aqueous electrolyte secondary battery according to the present embodiment also includes, for example, a polymer battery containing a gel electrolyte and the like. The other members of the non-aqueous electrolyte secondary battery are not particularly limited, and for example, conventionally used members can be used.
非水電解質二次電池の製造方法としては、例えば、負極層と正極層とをセパレータを介して重ね合わせ、電池容器に入れ、電池容器に電解液を注入して封口する方法が挙げられる。この製造方法において、電解液の注入後の熱プレスによって、コーティング組成物に含まれていたコアシェル型粒子の一部（理想的にはシェル部のみ）が溶融し、形成されたフッ素樹脂層によって電極とセパレータとが接着する。 Examples of the method for manufacturing a non-aqueous electrolyte secondary battery include a method in which a negative electrode layer and a positive electrode layer are overlapped with each other via a separator, placed in a battery container, and an electrolytic solution is injected into the battery container to seal the battery. In this manufacturing method, a part of the core-shell type particles (ideally only the shell part) contained in the coating composition is melted by a hot press after injecting the electrolytic solution, and the electrode is formed by the fluororesin layer formed. And the separator adhere.
熱プレスの温度は、第１の重合体の溶融温度とコアシェル型粒子の溶融温度とに応じて決定されており、例えば、３０〜１５０℃とすることができる。また、熱プレスの圧力は、特に限定されないが、例えば、１〜３０ＭＰａとすることができる。 The temperature of the hot press is determined according to the melting temperature of the first polymer and the melting temperature of the core-shell type particles, and can be, for example, 30 to 150 ° C. The pressure of the hot press is not particularly limited, but can be, for example, 1 to 30 MPa.
本実施形態に係るコアシェル型粒子によれば、電解液存在下における第１の重合体の溶融温度が熱プレスの温度より高いため、熱プレスによってコア部のフッ化ビニリデン粒子がつぶされることを低減することができる。 According to the core-shell type particles according to the present embodiment, since the melting temperature of the first polymer in the presence of the electrolytic solution is higher than the temperature of the hot press, it is possible to reduce the crushing of vinylidene fluoride particles in the core portion by the hot press. can do.
以下に実施例を示し、本発明の実施の形態についてさらに詳しく説明する。もちろん、本発明は以下の実施例に限定されるものではなく、細部については様々な態様が可能であることはいうまでもない。さらに、本発明は上述した実施形態に限定されるものではなく、請求項に示した範囲で種々の変更が可能であり、それぞれ開示された技術的手段を適宜組み合わせて得られる実施形態についても本発明の技術的範囲に含まれる。また、本明細書中に記載された文献の全てが参考として援用される。 Examples are shown below, and embodiments of the present invention will be described in more detail. Of course, the present invention is not limited to the following examples, and it goes without saying that various aspects can be used for details. Furthermore, the present invention is not limited to the above-described embodiment, and various modifications can be made within the scope of the claims, and the present invention also relates to an embodiment obtained by appropriately combining the disclosed technical means. It is included in the technical scope of the invention. In addition, all the documents described in the present specification are incorporated by reference.
後述のように、本発明に係るコアシェル型粒子およびフッ化ビニリデン粒子（以下、まとめてフッ素ポリマー粒子とも記す）を作製し、当該フッ素ポリマー粒子の物性を測定した。また、当該フッ素ポリマー粒子を用いて、セパレータを製造し、それを用いて剥離強度試験およびＳＥＭ観察を行った。なお、具体的な実施例の説明の前に、本明細書における「固形分濃度」および「粒子径」の算出方法について以下に記載する。 As will be described later, core-shell type particles and vinylidene fluoride particles (hereinafter collectively referred to as fluoropolymer particles) according to the present invention were prepared, and the physical properties of the fluoropolymer particles were measured. In addition, a separator was produced using the fluoropolymer particles, and a peel strength test and SEM observation were performed using the separator. Prior to the description of specific examples, the calculation method of "solid content concentration" and "particle size" in the present specification will be described below.
〔固形分濃度〕
重合により調製したフッ素ポリマー粒子を含む分散液（以下、ラテックスとも記す）約５ｇをアルミ製のカップに入れ、８０℃で３時間乾燥し、乾燥前後の重量を測定することによって濃度を算出した。
[Solid content concentration]
About 5 g of a dispersion liquid (hereinafter, also referred to as latex) containing fluoropolymer particles prepared by polymerization was placed in an aluminum cup, dried at 80 ° C. for 3 hours, and the concentration was calculated by measuring the weight before and after drying.
〔粒子径〕
フッ素ポリマー粒子の粒子径は、動的光散乱法の正則化解析によって算出した。具体的には、ＢＥＣＫＭＡＮ ＣＯＵＬＴＥＲ社製「ＤｅｌｓａＭａｘＣＯＲＥ」を使用し、ＪＩＳ Ｚ ８８２８に準拠して測定し、正則化解析によって得られる大小２つのピークのうち、大きいピークを粒子径とした。
〔Particle size〕
The particle size of the fluoropolymer particles was calculated by a regularized analysis of the dynamic light scattering method. Specifically, "DelsaMaxCORE" manufactured by BECKMAN COULTER was used, and the measurement was performed in accordance with JIS Z 8828, and the larger peak was defined as the particle size among the two large and small peaks obtained by the regularization analysis.
各実施例および各比較例における、フッ素ポリマー粒子の調製方法について以下に記載する。 The method for preparing the fluoropolymer particles in each Example and each Comparative Example is described below.
〔実施例１〕
コア部の重合：オートクレーブにイオン交換水２８０質量部を入れ、３０分間の窒素バブリングによって脱気を行った。次に、リン酸水素二ナトリウム０．２質量部、パーフルオロオクタン酸アンモニウム塩（ＰＦＯＡ）１．０質量部を仕込み、４．５ＭＰａまで加圧して窒素置換を３回行った。酢酸エチル０．０５質量部、フッ化ビニリデン（ＶＤＦ）３５質量部を上記オートクレーブ中に添加した。撹拌下で８０℃に昇温後、５ｗｔ％過硫酸アンモニウム水溶液を過硫酸アンモニウム換算で０．０６質量部に相当する量を入れて重合を開始した。この時の缶内圧力は４．３ＭＰａであった。反応開始後、２．５ＭＰａまで圧力が降下したところで、ＶＤＦ６５質量部を缶内圧力が２．５ＭＰａで維持するように連続添加した。添加終了後、１．５ＭＰａまで圧力が降下したところで重合を完了とし、コア部の粒子を含むラテックスを得た。得られたラテックスの固形分濃度は２４．０ｗｔ％であり、粒子径は１４０ｎｍであった。
シェル部の重合：オートクレーブにイオン交換水７００質量部を入れ、３０分間の窒素バブリングによって脱気を行った。次に、水分散したコア部の粒子１００質量部、ＰＦＯＡ０．５質量部を仕込み、４．５ＭＰａまで加圧して窒素置換を３回行った。酢酸エチル０．０５質量部、ＶＤＦ７０質量部、ヘキサフルオロプロピレン（ＨＦＰ）３０質量部、アクリロイロキシプロピルコハク酸（ＡＰＳ）０．０６質量部を上記オートクレーブ中に添加した。撹拌下で８０℃に昇温後、５ｗｔ％過硫酸アンモニウム水溶液を過硫酸アンモニウム換算で０．１質量部に相当する量を入れて重合を開始した。この時の缶内圧力は３．３ＭＰａであった。反応開始後、１．５ＭＰａまで圧力が降下したところでシェル部の重合を完了とし、コアシェル型の粒子を含むラテックスを得た。得られたラテックスの固形分濃度は１３．５ｗｔ％であり、粒子径は１７０ｎｍであった。
[Example 1]
Polymerization of core: 280 parts by mass of ion-exchanged water was placed in an autoclave and degassed by nitrogen bubbling for 30 minutes. Next, 0.2 parts by mass of disodium hydrogen phosphate and 1.0 part by mass of ammonium perfluorooctanoate (PFOA) were charged, and the pressure was increased to 4.5 MPa to perform nitrogen substitution three times. 0.05 parts by mass of ethyl acetate and 35 parts by mass of vinylidene fluoride (VDF) were added to the autoclave. After raising the temperature to 80 ° C. under stirring, a 5 wt% ammonium persulfate aqueous solution was added in an amount corresponding to 0.06 parts by mass in terms of ammonium persulfate to initiate polymerization. The pressure inside the can at this time was 4.3 MPa. After the reaction was started, when the pressure dropped to 2.5 MPa, 65 parts by mass of VDF was continuously added so that the pressure inside the can was maintained at 2.5 MPa. After the addition was completed, the polymerization was completed when the pressure dropped to 1.5 MPa to obtain a latex containing particles in the core portion. The solid content concentration of the obtained latex was 24.0 wt%, and the particle size was 140 nm.
Polymerization of the shell part: 700 parts by mass of ion-exchanged water was placed in an autoclave, and degassing was performed by nitrogen bubbling for 30 minutes. Next, 100 parts by mass of water-dispersed core particles and 0.5 part by mass of PFOA were charged, pressurized to 4.5 MPa, and subjected to nitrogen substitution three times. 0.05 parts by mass of ethyl acetate, 70 parts by mass of VDF, 30 parts by mass of hexafluoropropylene (HFP), and 0.06 parts by mass of acryloyloxypropylsuccinic acid (APS) were added to the autoclave. After raising the temperature to 80 ° C. under stirring, a 5 wt% ammonium persulfate aqueous solution was added in an amount corresponding to 0.1 parts by mass in terms of ammonium persulfate to initiate polymerization. The pressure inside the can at this time was 3.3 MPa. After the reaction was started, the polymerization of the shell portion was completed when the pressure dropped to 1.5 MPa, and a latex containing core-shell type particles was obtained. The solid content concentration of the obtained latex was 13.5 wt%, and the particle size was 170 nm.
〔実施例２〕
コア部の重合：実施例１と同様にコア部のフッ化ビニリデン粒子を得た。
シェル部の重合：ＶＤＦを７０質量部から７８質量部、ＨＦＰを３０質量部から２２質量部、ＡＰＳを０．０６質量部から０．１質量部に変更した以外は実施例１と同様に重合して、コアシェル型の粒子を含むラテックスを得た。得られたラテックスの固形分濃度は１３．３ｗｔ％であり、粒子径は１７０ｎｍであった。
[Example 2]
Polymerization of the core portion: Vinyl fluoride particles in the core portion were obtained in the same manner as in Example 1.
Polymerization of shell part: Polymerization as in Example 1 except that VDF was changed from 70 parts by mass to 78 parts by mass, HFP was changed from 30 parts by mass to 22 parts by mass, and APS was changed from 0.06 parts by mass to 0.1 parts by mass. Then, a latex containing core-shell type particles was obtained. The solid content concentration of the obtained latex was 13.3 wt%, and the particle size was 170 nm.
〔実施例３〕
コア部の重合：実施例１と同様にコア部のフッ化ビニリデン粒子を得た。
シェル部の重合：過硫酸アンモニウムを０．１質量部から０．４質量部、ＡＰＳを０．１質量部から０．５質量部に変更した以外は実施例２と同様に重合して、コアシェル型の粒子を含むラテックスを得た。得られたラテックスの固形分濃度は１３．３ｗｔ％であり、粒子径は１７０ｎｍであった。
[Example 3]
Polymerization of the core portion: Vinyl fluoride particles in the core portion were obtained in the same manner as in Example 1.
Polymerization of shell part: Polymerization was carried out in the same manner as in Example 2 except that ammonium persulfate was changed from 0.1 part by mass to 0.4 part by mass and APS was changed from 0.1 part by mass to 0.5 part by mass. A latex containing the particles of was obtained. The solid content concentration of the obtained latex was 13.3 wt%, and the particle size was 170 nm.
〔実施例４〕
コア部の重合：実施例１と同様にコア部のフッ化ビニリデン粒子を得た。
シェル部の重合：ＡＰＳをアクリル酸（ＡＡ）に変更した以外は実施例２と同様に重合して、コアシェル型の粒子を含むラテックスを得た。得られたラテックスの固形分濃度は１３．６ｗｔ％であり、粒子径は１８０ｎｍであった。
[Example 4]
Polymerization of the core portion: Vinyl fluoride particles in the core portion were obtained in the same manner as in Example 1.
Polymerization of shell portion: Polymerization was carried out in the same manner as in Example 2 except that APS was changed to acrylic acid (AA) to obtain a latex containing core-shell type particles. The solid content concentration of the obtained latex was 13.6 wt%, and the particle size was 180 nm.
〔実施例５〕
コア部の重合：オートクレーブに添加するＶＤＦを３５質量部から３０質量部に変更し、さらにＨＦＰ５．０質量部を添加した以外は実施例１と同様に重合してコア部の粒子を含むラテックスを得た。得られたラテックスの固形分濃度は２１．５ｗｔ％であり、粒子径は１４０ｎｍであった。
シェル部の重合：実施例２と同様に重合して、コアシェル型の粒子を含むラテックスを得た。得られたラテックスの固形分濃度は１３．１ｗｔ％であり、粒子径は１７０ｎｍであった。
[Example 5]
Polymerization of the core part: The latex containing the particles of the core part was polymerized in the same manner as in Example 1 except that the VDF added to the autoclave was changed from 35 parts by mass to 30 parts by mass and 5.0 parts by mass of HFP was further added. Obtained. The solid content concentration of the obtained latex was 21.5 wt%, and the particle size was 140 nm.
Polymerization of shell portion: Polymerization was carried out in the same manner as in Example 2 to obtain a latex containing core-shell type particles. The solid content concentration of the obtained latex was 13.1 wt%, and the particle size was 170 nm.
〔実施例６〕
コア部の重合：実施例５と同様にコア部のフッ化ビニリデン粒子を得た。
シェル部の重合：実施例４と同様に重合して、コアシェル型粒子を含むラテックスを得た。得られたラテックスの固形分濃度は１３．２ｗｔ％であり、粒子径は１７０ｎｍであった。
[Example 6]
Polymerization of the core portion: Vinylidene fluoride particles in the core portion were obtained in the same manner as in Example 5.
Polymerization of shell portion: Polymerization was carried out in the same manner as in Example 4 to obtain a latex containing core-shell type particles. The solid content concentration of the obtained latex was 13.2 wt%, and the particle size was 170 nm.
〔実施例７〕
コア部の重合：オートクレーブに添加するＶＤＦを３０質量部から２５質量部、ＨＦＰを５．０質量部から１０質量部に変更した以外は実施例５と同様に重合してコア部のフッ化ビニリデン粒子を含むラテックスを得た。得られたラテックスの固形分濃度は２１．４ｗｔ％であり、粒子径は１４０ｎｍであった。
シェル部の重合：実施例２と同様に重合して、コアシェル型粒子を含むラテックスを得た。得られたラテックスの固形分濃度は１３．２ｗｔ％であり、粒子径は１８０ｎｍであった。
[Example 7]
Polymerization of core part: VDF added to the autoclave was changed from 30 parts by mass to 25 parts by mass, and HFP was changed from 5.0 parts by mass to 10 parts by mass. Latex containing particles was obtained. The solid content concentration of the obtained latex was 21.4 wt%, and the particle size was 140 nm.
Polymerization of shell portion: Polymerization was carried out in the same manner as in Example 2 to obtain a latex containing core-shell type particles. The solid content concentration of the obtained latex was 13.2 wt%, and the particle size was 180 nm.
〔比較例１〕
コア部の重合：実施例１と同様にコア部のフッ化ビニリデン粒子を得た。
シェル部の重合：ＡＰＳを添加せずに、反応開始後、１．５ＭＰａまで圧力が降下したところでシェル部の重合を完了とした以外は実施例１と同様に重合して、コアシェル型粒子を含むラテックスを得た。得られたラテックスの固形分濃度は１３．５ｗｔ％であり、粒子径は１７０ｎｍであった。
[Comparative Example 1]
Polymerization of the core portion: Vinyl fluoride particles in the core portion were obtained in the same manner as in Example 1.
Polymerization of the shell part: Polymerization was carried out in the same manner as in Example 1 except that the polymerization of the shell part was completed when the pressure dropped to 1.5 MPa after the reaction was started without adding APS, and contained core-shell type particles. Obtained latex. The solid content concentration of the obtained latex was 13.5 wt%, and the particle size was 170 nm.
〔比較例２〕
コア部の重合：実施例１と同様にコア部のフッ化ビニリデン粒子を得た。
シェル部の重合：ＡＰＳを添加せずに、反応開始後、１．５ＭＰａまで圧力が降下したところでシェル部の重合を完了とした以外は実施例２と同様に重合して、コアシェル型粒子を含むラテックスを得た。得られたラテックスの固形分濃度は１３．４ｗｔ％であり、粒子径は１７０ｎｍであった。
[Comparative Example 2]
Polymerization of the core portion: Vinyl fluoride particles in the core portion were obtained in the same manner as in Example 1.
Polymerization of the shell part: Polymerization was carried out in the same manner as in Example 2 except that the polymerization of the shell part was completed when the pressure dropped to 1.5 MPa after the reaction was started without adding APS, and contained core-shell type particles. Obtained latex. The solid content concentration of the obtained latex was 13.4 wt%, and the particle size was 170 nm.
〔比較例３〕
オートクレーブにイオン交換水２８０質量部を入れ、３０分間の窒素バブリングによって脱気を行った。次に、パーフルオロオクタン酸アンモニウム塩（ＰＦＯＡ）０．５質量部を仕込み、４．５ＭＰａまで加圧して窒素置換を３回行った。酢酸エチル０．０５質量部、フッ化ビニリデン（ＶＤＦ）３０質量部、ＨＦＰ５．０質量部を上記オートクレーブ中に添加した。撹拌下で８０℃に昇温後、５ｗｔ％過硫酸アンモニウム水溶液を過硫酸アンモニウム換算で０．１質量部に相当する量を入れて重合を開始した。この時の缶内圧力は３．１ＭＰａであった。反応開始後、缶内圧力が２．５ＭＰａまで圧力が降下したところで、ＶＤＦ６５質量部を缶内圧力が２．５ＭＰａで維持するように連続添加した。連続添加ＶＤＦのうち５０質量％以上消費された時点でＡＰＳ０．０６質量部を添加した。反応開始後、１．５ＭＰａまで圧力が降下したところで重合を完了とし、フッ化ビニリデン粒子を含むラテックスを得た。得られたラテックスの固形分濃度は１９．６ｗｔ％であり、粒子径は２００ｎｍであった。
[Comparative Example 3]
280 parts by mass of ion-exchanged water was placed in an autoclave, and degassing was performed by nitrogen bubbling for 30 minutes. Next, 0.5 parts by mass of ammonium perfluorooctanoate (PFOA) was charged, pressurized to 4.5 MPa, and subjected to nitrogen substitution three times. 0.05 parts by mass of ethyl acetate, 30 parts by mass of vinylidene fluoride (VDF), and 5.0 parts by mass of HFP were added to the autoclave. After raising the temperature to 80 ° C. under stirring, a 5 wt% ammonium persulfate aqueous solution was added in an amount corresponding to 0.1 parts by mass in terms of ammonium persulfate to initiate polymerization. The pressure inside the can at this time was 3.1 MPa. After the reaction was started, when the pressure inside the can dropped to 2.5 MPa, 65 parts by mass of VDF was continuously added so that the pressure inside the can was maintained at 2.5 MPa. 0.06 part by mass of APS was added when 50% by mass or more of the continuously added VDF was consumed. After the reaction was started, the polymerization was completed when the pressure dropped to 1.5 MPa to obtain a latex containing vinylidene fluoride particles. The solid content concentration of the obtained latex was 19.6 wt%, and the particle size was 200 nm.
〔比較例４〕
ＰＦＯＡを０．５質量部から１．０質量部に、ＡＰＳをＡＡに変更した以外は比較例３と同様に重合して、フッ化ビニリデン粒子を含むラテックスを得た。得られたラテックスの固形分濃度は２１．０ｗｔ％であり、粒子径は１３０ｎｍであった。
[Comparative Example 4]
Polymerization was carried out in the same manner as in Comparative Example 3 except that PFOA was changed from 0.5 parts by mass to 1.0 part by mass and APS was changed to AA to obtain a latex containing vinylidene fluoride particles. The solid content concentration of the obtained latex was 21.0 wt%, and the particle size was 130 nm.
各実施例および各比較例における、フッ素ポリマー粒子の物性の測定方法について以下に記載する。 The method for measuring the physical properties of the fluoropolymer particles in each Example and each Comparative Example will be described below.
〔ＨＦＰ導入量〕
重合により調製した分散液中のフッ素ポリマー粒子に含まれるＨＦＰ導入量は、１９Ｆ−ＮＭＲ（ＢＵＲＵＫＡＲ社製）で測定した。塩析によって粉体化したフッ素ポリマー粒子４０ｍｇをアセトン−ｄ６ ９６０ｍｇに溶解させ測定用サンプルとした。ＨＦＰ単位に由来するＣＦ３部分のピークは−７０−〜８０ｐｐｍ付近の２本のピークに相当し、ＶＤＦおよびＨＦＰ単位（全単量体）に由来するＣＦ２部分のピークは−９０ｐｐｍ以下のピークに相当する。これらのピーク強度からＨＦＰ導入量を下記式によって求めた。
ＨＦＰ導入量［ｗｔ％］＝ＨＦＰピーク面積／全単量体ピーク面積×１００
[HFP introduction amount]
The amount of HFP introduced into the fluoropolymer particles in the dispersion prepared by polymerization was measured by 19 F-NMR (manufactured by BURUKAR). 40 mg of fluoropolymer particles pulverized by salting out were dissolved in 960 mg of acetone-d6 to prepare a sample for measurement. The peak of CF 3 part derived from HFP unit corresponds to two peaks around -70- to 80 ppm, and the peak of CF 2 part derived from VDF and HFP unit (all monomers) is -90 ppm or less. Corresponds to. From these peak intensities, the amount of HFP introduced was calculated by the following formula.
HFP introduction amount [wt%] = HFP peak area / total monomer peak area x 100
〔吸光度比（ＩＲ比）ＡＲ〕
各実施例および各比較例において得られたフッ素ポリマー粒子を含む分散液を０．５質量％の塩化カルシウムで塩析し、８０℃のオーブンで乾燥させることによって粉体化した。粉体化したフッ素ポリマー粒子を２００℃で熱プレスし、厚さ約０．０１μｍのプレスシートを作製した。作製したプレスシートのＩＲスペクトルを、赤外分光光度計ＦＴ−７３０（株式会社堀場製作所製）を用いて、１５００ｃｍ−１〜４０００ｃｍ−１の範囲で測定した。ＩＲ比ＡＲは、下記式によって求めた。
ＡＲ＝Ａ１７６０／Ａ３０２０
上記式において、Ａ１７６０は１７６０ｃｍ−１付近に検出されるカルボニル基の伸縮振動に由来の吸光度であり、１６００ｃｍ−１〜１８００ｃｍ−１に検出されるピークをカルボニル基の伸縮振動に由来の吸光度とした。Ａ３０２０は３０２０ｃｍ−１付近に検出されるＣＨの伸縮振動に由来の吸光度であり、２９００ｃｍ−１〜３１００ｃｍ−１に検出されるピークをカルボニル基の伸縮振動に由来の吸光度とした。
[Absorptance ratio (IR ratio) AR ]
The dispersion liquid containing the fluoropolymer particles obtained in each Example and each Comparative Example was salted out with 0.5% by mass of calcium chloride and pulverized by drying in an oven at 80 ° C. The powdered fluoropolymer particles were hot-pressed at 200 ° C. to prepare a press sheet having a thickness of about 0.01 μm. The IR spectrum of the press sheets produced, infrared spectrophotometer FT-730 (manufactured by Horiba Ltd.) was measured in the range of 1500cm -1 ~4000cm -1. IR ratio A R was determined by the following equation.
A R = A 1760 / A 3020
In the above formula, A 1760 is the absorbance derived from stretching vibration of the carbonyl group to be detected near 1760 cm -1, and the absorbance from the peak detected in 1600cm -1 ~1800cm -1 on the stretching vibration of the carbonyl group did. A 3020 was the absorbance derived from the expansion and contraction vibration of CH detected near 3020 cm -1 , and the peak detected at 2900 cm -1 to 3100 cm -1 was defined as the absorbance derived from the expansion and contraction vibration of the carbonyl group.
〔融点〕
重合により調製した分散液中のフッ素ポリマー粒子の融点は、フィルムの形態で測定した。フィルムは以下の操作によって作製した。剥離剤を噴霧した２枚のアルミ箔の間に、縦５ｃｍ×横５ｃｍ×厚み１５０μｍの鋳型と塩析によって粉体化したフッ素ポリマー粒子約１ｇを挟み、２００℃でプレスした。融点は、ＤＳＣ（ＭＥＴＴＬＥＲ社製「ＤＳＣ−１」）を用いてＡＳＴＭ ｄ ３４１８に準拠して測定した。
[Melting point]
The melting point of the fluoropolymer particles in the dispersion prepared by polymerization was measured in the form of a film. The film was prepared by the following operation. A mold having a length of 5 cm, a width of 5 cm, and a thickness of 150 μm and about 1 g of fluoropolymer particles powdered by salting out were sandwiched between two aluminum foils sprayed with a release agent, and pressed at 200 ° C. The melting point was measured using DSC (“DSC-1” manufactured by METTLER) according to ASTM d 3418.
〔剥離強度試験〕
各実施例および各比較例において得られたフッ素ポリマー粒子を用いてフッ素ポリマー粒子コーティングセパレータを作製し、電極（正極および負極）との剥離強度試験を行った。フッ素ポリマー粒子コーティングセパレータおよび電極の製造方法について、以下に詳細に記載する。
[Peeling strength test]
Fluoropolymer particle-coated separators were prepared using the fluoropolymer particles obtained in each Example and each Comparative Example, and a peel strength test with electrodes (positive electrode and negative electrode) was performed. The method for manufacturing the fluoropolymer particle-coated separator and the electrode will be described in detail below.
（コーティング組成物の作製）
フッ素ポリマー粒子１００重量部、ＣＭＣ（カルボキシメチルセルロース）（セロゲン４Ｈ、第一工業製薬製）２重量部に水を加えて固形分濃度１０質量％の組成物を調製し、これをコーティング組成物とした。
(Preparation of coating composition)
Water was added to 100 parts by weight of fluoropolymer particles and 2 parts by weight of CMC (carboxymethyl cellulose) (cellogen 4H, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) to prepare a composition having a solid content concentration of 10% by mass, which was used as a coating composition. ..
（剥離強度測定用フッ素ポリマー粒子コーティングセパレータの作製）
上記で得られたコーティング組成物をコロナ処理装置（春日電気社製）にてコロナ処理を施したセパレータ（ハイポアＮＤ４２０ 旭化成製）の片面に、ウェット塗布量２４μｍ（番手１２）でワイヤーバーを用いて逐次コートし、７０℃で３０分間乾燥した。さらに７０℃で２時間の熱処理を実施した。
(Preparation of fluoropolymer particle coating separator for peel strength measurement)
Using a wire bar with a wet coating amount of 24 μm (count 12) on one side of a separator (Hypore ND420, Asahi Kasei) in which the coating composition obtained above was corona-treated with a corona treatment device (manufactured by Kasuga Denki Co., Ltd.). It was coated sequentially and dried at 70 ° C. for 30 minutes. Further, heat treatment was carried out at 70 ° C. for 2 hours.
（剥離強度測定用正極の作製）
ＬｉＮｉＣｏＭｎＯ２（ＭＸ６ ユミコア製）９４重量部、導電助剤（ＳｕｐｅｒＰ ＴＩＭＣＡＬ製）３重量部、ＰＶＤＦ（ポリフッ化ビニリデン）（ＫＦ＃７２００、クレハ製）３重量部にＮ−メチル−２−ピロリドンを加えてスラリーを作製し、Ａｌ箔（厚さ１５μｍ）に塗布した。乾燥した後、プレスし、１２０℃で３時間熱処理を実施し、電極嵩密度が３．０［ｇ／ｃｍ３］、目付け量が１０３［ｇ／ｍ２］である正極を得た。
(Preparation of positive electrode for peel strength measurement)
Add N-methyl-2-pyrrolidone to 94 parts by weight of LiNiComnO 2 (made by MX6 Umicore), 3 parts by weight of conductive aid (made by SuperP TIMCAL), and 3 parts by weight of PVDF (polyvinylidene fluoride) (KF # 7200, made by Kureha). A slurry was prepared and applied to an Al foil (thickness: 15 μm). After drying, it was pressed and heat-treated at 120 ° C. for 3 hours to obtain a positive electrode having an electrode bulk density of 3.0 [g / cm 3 ] and a grain size of 103 [g / m 2].
（剥離強度測定用の負極の作製）
ＢＴＲ９１８（改質天然黒鉛 ＢＴＲ製）９５重量部、導電助剤（ＳｕｐｅｒＰ ＴＩＭＣＡＬ製）２重量部、ＳＢＲ（スチレンブタジエンゴム）ラテックス（ＢＭ−４００ 日本ゼオン製）２重量部、ＣＭＣ（カルボキシメチルセルロース）（セロゲン４Ｈ 第一工業製薬製）１重量部に水を加えてスラリーを作製し、Ｃｕ箔（厚さ１０μｍ）に塗布した。乾燥した後、プレスし、１５０℃で３時間熱処理を実施し、電極嵩密度が１．６［ｇ／ｃｍ３］、目付け量が５０［ｇ／ｍ２］である負極を得た。
(Preparation of negative electrode for peel strength measurement)
BTR918 (manufactured by modified natural graphite BTR) 95 parts by weight, conductive aid (manufactured by SuperP TIMCAL) 2 parts by weight, SBR (styrene butadiene rubber) latex (manufactured by BM-400 Nippon Zeon) 2 parts by weight, CMC (carboxymethyl cellulose) ( Cellogen 4H (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) Water was added to 1 part by weight to prepare a slurry, which was applied to a Cu foil (thickness: 10 μm). After drying, it was pressed and heat-treated at 150 ° C. for 3 hours to obtain a negative electrode having an electrode bulk density of 1.6 [g / cm 3 ] and a grain size of 50 [g / m 2].
（剥離強度測定用サンプルの作製）
上記により得られた正極および負極を２．５×５．０ｃｍに切り出し、フッ素ポリマー粒子コーティングセパレータを３．０×６．０ｃｍに切ってそれぞれ接合させ、電解液（エチレンカーボネート（ＥＣ）／エチルメチルカーボネート（ＥＭＣ）＝３／７、ＬｉＰＦ６１．２Ｍ、ＶＣ１ｗｔ％）を１２０μＬ浸み込ませた後、Ａｌラミネートセル中に真空脱気封入し、一晩静置した。
(Preparation of sample for peel strength measurement)
The positive electrode and the negative electrode obtained as described above are cut into 2.5 × 5.0 cm, and the fluoropolymer particle-coated separator is cut into 3.0 × 6.0 cm and bonded to each other, and the electrolytic solution (ethylene carbonate (EC) / ethylmethyl) is used. After soaking 120 μL of carbonate (EMC) = 3/7, LiPF 6 1.2 M, VC 1 wt%), the mixture was vacuum degassed and sealed in an Al laminate cell and allowed to stand overnight.
このＡｌラミネートセルを熱プレスすることによって、対正極の剥離強度測定用サンプルおよび対負極の剥離強度測定用サンプルを得た。具体的には、対正極の剥離強度測定用サンプルおよび対負極の剥離強度測定用サンプルは、１００℃において、１分間の余熱の後、２分間、面圧約４ＭＰaで熱プレスを行うことで作製した。この対正極の剥離強度測定用サンプルおよび対負極の剥離強度測定用サンプルでは、熱プレスによって、フッ素ポリマー粒子コーティングセパレータと電極（正極または負極）との界面にフッ素樹脂層を形成した。 By hot-pressing this Al laminate cell, a sample for measuring the peel strength of the positive electrode and a sample for measuring the peel strength of the negative electrode were obtained. Specifically, the sample for measuring the peel strength of the positive electrode and the sample for measuring the peel strength of the negative electrode were prepared by performing hot pressing at 100 ° C. for 1 minute of residual heat and then for 2 minutes at a surface pressure of about 4 MPa. .. In the sample for measuring the peel strength of the positive electrode and the sample for measuring the peel strength of the negative electrode, a fluororesin layer was formed at the interface between the fluoropolymer particle-coated separator and the electrode (positive electrode or negative electrode) by hot pressing.
（剥離強度の測定）
作製した対正極の剥離強度測定用サンプルおよび対負極の剥離強度測定用サンプルについて、それぞれ正極または負極を固定し、引張試験機（ＯＲＩＥＮＴＥＣ社製「ＳＴＡ−１１５０ ＵＮＩＶＥＲＳＡＬ ＴＥＳＴＩＮＧ ＭＡＣＨＩＮＥ」）を使用し、ヘッド速度２００ｍｍ／分で、１８０°剥離試験を行い、剥離強度を測定した。
(Measurement of peel strength)
For the prepared sample for measuring the peel strength of the positive electrode and the sample for measuring the peel strength of the negative electrode, fix the positive electrode or the negative electrode, respectively, and use a tensile tester (“STA-1150 UNIVERSAL TESTING MACHINE” manufactured by ORIENTEC) to head. A 180 ° peel test was performed at a speed of 200 mm / min, and the peel strength was measured.
〔ＳＥＭ観察による多孔性の評価〕
各実施例および各比較例において得られたフッ素ポリマー粒子を用いてフッ素ポリマー粒子コーティングセパレータを作製した。電極（負極）とＳＥＭ観察用フッ素樹脂コーティングセパレータを熱プレスし、熱プレス後のフッ素樹脂層コーティングセパレータのＳＥＭ観察を行った。フッ素ポリマー粒子コーティングセパレータおよび電極の製造方法について、以下に詳細に記載する。
[Evaluation of porosity by SEM observation]
A fluoropolymer particle-coated separator was prepared using the fluoropolymer particles obtained in each Example and each Comparative Example. The electrode (negative electrode) and the fluororesin-coated separator for SEM observation were heat-pressed, and the fluororesin layer-coated separator after heat pressing was observed by SEM. The method for manufacturing the fluoropolymer particle-coated separator and the electrode will be described in detail below.
（コーティング組成物の作製）
剥離強度試験で作製したコーティング組成物の作製方法と同様の方法で調製したものをコーティング組成物とした。
(Preparation of coating composition)
The coating composition was prepared by the same method as the method for producing the coating composition prepared in the peel strength test.
（ＳＥＭ観察用フッ素樹脂層コーティングセパレータの作製）
剥離強度試験で作製したコーティングセパレータと同様の方法で作製した。
(Preparation of fluororesin layer coating separator for SEM observation)
It was prepared in the same manner as the coating separator prepared in the peel strength test.
（ＳＥＭ観察用負極の作製）
剥離強度測定用負極と同様の方法で作製し、ＳＥＭ観察用負極とした。
(Preparation of negative electrode for SEM observation)
A negative electrode for SEM observation was prepared by the same method as the negative electrode for measuring peel strength.
（ＳＥＭ観察用サンプルの作製および多孔性の評価）
上記により得られた負極を４．０×４．０ｃｍに切り出し、フッ素ポリマー粒子コーティングセパレータを４．０×４．０ｃｍに切ってそれぞれ接合させ、電解液（エチレンカーボネート（ＥＣ）／エチルメチルカーボネート（ＥＭＣ）＝３／７、ＬｉＰＦ６ １．２Ｍ、ＶＣ１ｗｔ％）を１５０μＬ浸み込ませた後、Ａｌラミネートセル中に真空脱気封入し、一晩静置した。
(Preparation of SEM observation sample and evaluation of porosity)
The negative electrode obtained as described above was cut into 4.0 × 4.0 cm, and the fluoropolymer particle-coated separator was cut into 4.0 × 4.0 cm and bonded to each other, and an electrolytic solution (ethylene carbonate (EC) / ethylmethyl carbonate (ethylene carbonate (EC) / ethylmethyl carbonate) ( After impregnating 150 μL of EMC) = 3/7, LiPF6 1.2M, VC 1 wt%), the mixture was vacuum degassed and sealed in an Al laminate cell and allowed to stand overnight.
このＡｌラミネートセルを熱プレスした後、セパレータと負極を剥離し、セパレータを洗浄することによって、ＳＥＭ観察用サンプルを得た。具体的には、ＳＥＭ観察用サンプルは、１００℃において、１分間、面圧約３ＭＰaで熱プレスを行うことで、フッ素ポリマー粒子コーティングセパレータと電極（負極）との界面にフッ素樹脂層を形成した。続いて、フッ素樹脂層が形成されたコーティングセパレータと負極との界面を剥離し、セパレータをジメチルカーボネート（ＤＭＣ）洗浄し、７０℃で２時間乾燥処理を実施することで、ＳＥＭ観察用サンプルを得た。 After hot pressing this Al laminate cell, the separator and the negative electrode were peeled off, and the separator was washed to obtain a sample for SEM observation. Specifically, the SEM observation sample was hot-pressed at 100 ° C. for 1 minute at a surface pressure of about 3 MPa to form a fluororesin layer at the interface between the fluoropolymer particle-coated separator and the electrode (negative electrode). Subsequently, the interface between the coating separator on which the fluororesin layer was formed and the negative electrode was peeled off, the separator was washed with dimethyl carbonate (DMC), and dried at 70 ° C. for 2 hours to obtain a sample for SEM observation. It was.
作成したＳＥＭ観察用サンプルについて、走査電子顕微鏡（日本電子製「ＪＳＭ−６５１０ＬＡ型」）を用いて、フッ素樹脂層が形成されたコーティングセパレータと電極（負極）との界面画像を撮影した。加速電圧５ｋＶで倍率１０，０００倍撮影したＳＥＭ画像において、フッ素樹脂層に含まれる各粒子が粒子形状を維持していることが確認できたものを「多孔性あり」とし、粒子が熱プレスによって溶融して粒子形状を維持できていないものを「多孔性なし」とした。 For the prepared SEM observation sample, an interface image between the coating separator on which the fluororesin layer was formed and the electrode (negative electrode) was taken using a scanning electron microscope (“JSM-6510LA type” manufactured by JEOL Ltd.). In the SEM image taken at an acceleration voltage of 5 kV and a magnification of 10,000 times, it was confirmed that each particle contained in the fluororesin layer maintained the particle shape, which was regarded as "porous", and the particles were heat-pressed. Those that were melted and could not maintain the particle shape were defined as "no porosity".
＜結果＞
各実施例および各比較例における粒子径、ＩＲ比、融点、剥離強度、およびＳＥＭ画像による多孔性の評価結果を、各実施例および各比較例におけるフッ素ポリマー粒子の仕込み組成比と併せて表１〜３に示す。
<Result>
The evaluation results of particle size, IR ratio, melting point, peel strength, and porosity by SEM images in each example and each comparative example are shown in Table 1 together with the charged composition ratio of the fluoropolymer particles in each example and each comparative example. Shown in ~ 3.
本発明に係るコアシェル型粒子は、例えば、二次電池の製造において好適に利用することができる。 The core-shell type particles according to the present invention can be suitably used, for example, in the production of a secondary battery.
Claims (13)
当該コア部は、フッ化ビニリデンに由来する構成単位を主構成単位とする第１の重合体を含み、
当該シェル部は、フッ化ビニリデンに由来する構成単位を主構成単位とする第２の重合体を含み、
当該第２の重合体は、下記式（１）で表される化合物に由来する構成単位、下記式（２）で表される化合物に由来する構成単位および下記式（３）で表される化合物に由来する構成単位の少なくとも何れかをさらに含み、
当該第１の重合体の融点は、当該第２の重合体の融点よりも高いことを特徴とするコアシェル型粒子。
The core portion contains a first polymer having a structural unit derived from vinylidene fluoride as a main structural unit.
The shell portion contains a second polymer having a structural unit derived from vinylidene fluoride as a main structural unit.
The second polymer is a structural unit derived from a compound represented by the following formula (1), a structural unit derived from a compound represented by the following formula (2), and a compound represented by the following formula (3). further seen contains at least one constituent unit derived from,
A core-shell type particle characterized in that the melting point of the first polymer is higher than the melting point of the second polymer.
請求項１から５の何れか１項に記載のコアシェル型粒子を含む、コーティング組成物。 A coating composition for forming a porous fluororesin layer provided on at least one surface of a separator provided between a negative electrode layer and a positive electrode layer in a secondary battery.
A coating composition comprising the core-shell type particles according to any one of claims 1 to 5.
上記フッ素樹脂層は、上記負極層と上記正極層と上記セパレータとを熱プレスすることによって形成されてなる上記第２の重合体を含む層を有しており、
上記第２の重合体を含む層には、上記第１の重合体を含む粒子が含まれている、二次電池。 A secondary battery provided with a fluororesin layer formed from the coating composition according to any one of claims 7 to 9.
The fluororesin layer has a layer containing the second polymer formed by hot-pressing the negative electrode layer, the positive electrode layer, and the separator.
A secondary battery in which particles containing the first polymer are contained in the layer containing the second polymer.
請求項１から５の何れか１項に記載のコアシェル型粒子を含む、コーティング組成物。 Coating composition for forming a fluororesin layer provided on at least one surface of the negative electrode layer and the positive electrode layer so as to be in contact with a separator provided between the negative electrode layer and the positive electrode layer in the secondary battery. It ’s a thing,
A coating composition comprising the core-shell type particles according to any one of claims 1 to 5.
フッ化ビニリデンに由来する構成単位を主構成単位とする第１の重合体を含むコア部を形成するコア部形成工程と、
フッ化ビニリデンに由来する構成単位を主構成単位とする第２の重合体を含むシェル部を形成するシェル部形成工程と、を含み、
当該第１の重合体の融点は、当該第２の重合体の融点よりも高く、
当該シェル部形成工程では、当該コア部形成工程により形成されたコア部を含む分散液において、下記式（１）で表される化合物、下記式（２）で表される化合物および下記式（３）で表される化合物の少なくとも何れかと、フッ化ビニリデンとを含む、当該第２の重合体を構成するための単量体を重合反応させることにより当該コア部の周囲に当該シェル部を形成する、コアシェル型粒子の製造方法。
A core portion forming step of forming a core portion containing a first polymer having a constituent unit derived from vinylidene fluoride as a main constituent unit, and a core portion forming step.
Includes a shell portion forming step of forming a shell portion containing a second polymer having a constituent unit derived from vinylidene fluoride as a main constituent unit.
The melting point of the first polymer is higher than the melting point of the second polymer.
In the shell portion forming step, in the dispersion liquid containing the core portion formed by the core portion forming step, the compound represented by the following formula (1), the compound represented by the following formula (2), and the following formula (3). ) And vinylidene fluoride, a monomer for forming the second polymer, is polymerized to form the shell portion around the core portion. , A method for producing core-shell type particles.
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| JPWO2021241300A1 (en) * | 2020-05-27 | 2021-12-02 | ||
| CN111690092B (en) * | 2020-06-03 | 2022-04-19 | 乳源东阳光氟树脂有限公司 | Polyvinylidene fluoride surface-modified core-shell structure lithium battery binder and preparation method and application thereof |
| CN114163572A (en) * | 2020-09-10 | 2022-03-11 | 浙江蓝天环保高科技股份有限公司 | Polyvinylidene fluoride copolymer with core-shell structure and preparation method thereof |
| CN112724424B (en) * | 2020-12-02 | 2022-08-19 | 乐凯胶片股份有限公司 | Method for preparing hydrophilic modified fluoropolymer particles and use thereof |
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| JP2001023643A (en) * | 1999-07-05 | 2001-01-26 | Toshiba Battery Co Ltd | Polymer lithium secondary battery |
| JP2003231722A (en) * | 2002-02-13 | 2003-08-19 | Daikin Ind Ltd | Aqueous dispersion composition of fluororesin |
| JP5053073B2 (en) * | 2005-01-27 | 2012-10-17 | 株式会社クレハ | Vinylidene fluoride core / shell polymer and its use in non-aqueous electrochemical devices |
| WO2012090876A1 (en) * | 2010-12-28 | 2012-07-05 | 株式会社クレハ | Vinylidene-fluoride-based copolymer and application of said copolymer |
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| US9850394B2 (en) * | 2012-06-28 | 2017-12-26 | Kureha Corporation | Resin composition, filler-containing resin film for non-aqueous electrolyte secondary battery, and method for producing filler-containing resin film for non-aqueous electrolyte secondary battery |
| EP2869363B1 (en) * | 2012-10-05 | 2017-04-26 | LG Chem, Ltd. | Separator, and electrochemical device comprising same |
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