JP6061096B2 - Polymer electrolyte and lithium polymer battery - Google Patents
Polymer electrolyte and lithium polymer battery Download PDFInfo
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- JP6061096B2 JP6061096B2 JP2013507383A JP2013507383A JP6061096B2 JP 6061096 B2 JP6061096 B2 JP 6061096B2 JP 2013507383 A JP2013507383 A JP 2013507383A JP 2013507383 A JP2013507383 A JP 2013507383A JP 6061096 B2 JP6061096 B2 JP 6061096B2
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- monomer
- polymer electrolyte
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- polymer
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- 239000005518 polymer electrolyte Substances 0.000 title claims description 68
- 229920000642 polymer Polymers 0.000 title claims description 41
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title description 13
- 229910052744 lithium Inorganic materials 0.000 title description 13
- 239000000178 monomer Substances 0.000 claims description 80
- -1 acryl group Chemical group 0.000 claims description 56
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 54
- 239000003792 electrolyte Substances 0.000 claims description 31
- 239000002904 solvent Substances 0.000 claims description 30
- 150000001875 compounds Chemical class 0.000 claims description 27
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 26
- 150000003839 salts Chemical class 0.000 claims description 22
- 239000002243 precursor Substances 0.000 claims description 18
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- 239000003505 polymerization initiator Substances 0.000 claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 229910003002 lithium salt Inorganic materials 0.000 claims description 10
- 159000000002 lithium salts Chemical class 0.000 claims description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 9
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 claims description 9
- 229910013063 LiBF 4 Inorganic materials 0.000 claims description 7
- 229910052731 fluorine Chemical group 0.000 claims description 7
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 7
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 6
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 6
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 6
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 5
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 5
- 239000007869 azo polymerization initiator Substances 0.000 claims description 5
- 125000001153 fluoro group Chemical group F* 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
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- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 5
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- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 4
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 4
- 229910015015 LiAsF 6 Inorganic materials 0.000 claims description 4
- 229910013684 LiClO 4 Inorganic materials 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- WPKWPKDNOPEODE-UHFFFAOYSA-N bis(2,4,4-trimethylpentan-2-yl)diazene Chemical compound CC(C)(C)CC(C)(C)N=NC(C)(C)CC(C)(C)C WPKWPKDNOPEODE-UHFFFAOYSA-N 0.000 claims description 4
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- 229910013392 LiN(SO2CF3)(SO2C4F9) Inorganic materials 0.000 claims description 3
- 229910012424 LiSO 3 Inorganic materials 0.000 claims description 3
- IPTNXMGXEGQYSY-UHFFFAOYSA-N acetic acid;1-methoxybutan-1-ol Chemical compound CC(O)=O.CCCC(O)OC IPTNXMGXEGQYSY-UHFFFAOYSA-N 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 claims description 3
- 229940102396 methyl bromide Drugs 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 2
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 claims description 2
- IUONGRITOBFQAX-UHFFFAOYSA-N C1(CCCCC1)=O.C(CCC)C(=O)CCCC Chemical compound C1(CCCCC1)=O.C(CCC)C(=O)CCCC IUONGRITOBFQAX-UHFFFAOYSA-N 0.000 claims description 2
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical group ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 2
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 claims description 2
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 2
- 229910013385 LiN(SO2C2F5)2 Inorganic materials 0.000 claims 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims 1
- 229920000587 hyperbranched polymer Polymers 0.000 description 32
- 239000000243 solution Substances 0.000 description 19
- 239000007784 solid electrolyte Substances 0.000 description 16
- 238000000034 method Methods 0.000 description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 12
- 229910001416 lithium ion Inorganic materials 0.000 description 12
- 229920001223 polyethylene glycol Polymers 0.000 description 12
- 150000002500 ions Chemical class 0.000 description 9
- 229920002554 vinyl polymer Polymers 0.000 description 9
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 8
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 8
- 229920000570 polyether Polymers 0.000 description 8
- 239000008151 electrolyte solution Substances 0.000 description 7
- 239000012528 membrane Substances 0.000 description 7
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 6
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
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- 230000006872 improvement Effects 0.000 description 4
- UCUUFSAXZMGPGH-UHFFFAOYSA-N penta-1,4-dien-3-one Chemical compound C=CC(=O)C=C UCUUFSAXZMGPGH-UHFFFAOYSA-N 0.000 description 4
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- URQQDYIVGXOEDA-UHFFFAOYSA-N 2-(2-ethenoxyethoxy)ethyl prop-2-enoate Chemical compound C=COCCOCCOC(=O)C=C URQQDYIVGXOEDA-UHFFFAOYSA-N 0.000 description 3
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/122—Ionic conductors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Description
本発明は、高分子電解質、およびこの電解質を備えた固体型リチウムポリマー電池に関する。 The present invention relates to a polymer electrolyte and a solid-state lithium polymer battery provided with the electrolyte.
有機電解液を使用するリチウム二次電池も近年市販され、急激に市場が伸びている。
その電池構成材料や組立については多くの提案がなされ、例えば、正極活物質としてＬｉＣｏＯ2，ＬｉＮｉＯ2，ＬｉＭｎ2Ｏ4，Ｖ2Ｏ5，Ｖ6Ｏ13，ＴｉＳ2等を用い、負極活物質としてリチウム、リチウム−アルミニウム合金、カーボン（ハードカーボン、天然黒鉛、メソフェーズカーボンマイクロビーズ、メソフェーズカーボンファイバー）等を用いる二次電池が提案されている。Lithium secondary batteries that use organic electrolytes are also commercially available in recent years, and the market is growing rapidly.
Many proposals have been made for battery constituent materials and assembly. For example, LiCoO 2 , LiNiO 2 , LiMn 2 O 4 , V 2 O 5 , V 6 O 13 , TiS 2 or the like is used as the positive electrode active material, and the negative electrode active material is used. Secondary batteries using lithium, lithium-aluminum alloy, carbon (hard carbon, natural graphite, mesophase carbon microbeads, mesophase carbon fiber) or the like have been proposed.
これらのリチウム電池では、電解液としてリチウムイオンが移動可能なプロピレンカーボネート、エチレンカーボネート、１，２−ジメトキシエタン、ジエチルカーボネート等の非プロトン性有機溶媒に、ＬｉＣｌＯ4，ＬｉＢＦ4，ＬｉＡｓＦ6，ＬｉＰＦ6，ＬｉＣＦ3ＳＯ3，ＬｉＮ（ＣＦ3ＳＯ2）2等のリチウム塩を溶解させた電解液が一般に使用されている。
しかし、電解液に用いられる非プロトン性溶媒は、可燃性を有しているため発火や爆発の危険性がある。
また、リチウムやリチウム合金負極を使用した場合は、負極上で生成するリチウムデンドライトが正極に達して短絡する危険性もある。In these lithium batteries, LiClO 4 , LiBF 4 , LiAsF 6 , LiPF 6 can be used as an electrolytic solution in an aprotic organic solvent such as propylene carbonate, ethylene carbonate, 1,2-dimethoxyethane, diethyl carbonate or the like that can move lithium ions. , LiCF 3 SO 3 , LiN (CF 3 SO 2 ) 2 and other electrolytes in which lithium salts are dissolved are generally used.
However, since the aprotic solvent used for the electrolyte solution is flammable, there is a risk of ignition or explosion.
Moreover, when lithium or a lithium alloy negative electrode is used, there is a risk that the lithium dendrite produced on the negative electrode reaches the positive electrode and is short-circuited.
これらの問題点を解決するため、電解液をポリマーでゲル化したリチウムポリマー電池の開発が進められており、高イオン伝導性を有するゲル型高分子固体電解質について報告されている（特許文献１）。
しかし、溶媒の揮発を完全には抑制できない、高温環境下での使用条件に耐えられない、形状保持性や機械的強度に難があるなどの問題がある。In order to solve these problems, a lithium polymer battery in which an electrolytic solution is gelled with a polymer has been developed, and a gel type polymer solid electrolyte having high ionic conductivity has been reported (Patent Document 1). .
However, there are problems such that the volatilization of the solvent cannot be completely suppressed, the solvent cannot withstand the use conditions in a high temperature environment, and the shape retainability and mechanical strength are difficult.
そこで近年、完全固体電解質ポリマーを用いた固体型リチウム電池の研究が進められている。
固体電解質としては、無機材料固体電解質および高分子材料固体電解質が一般的に知られている。
中でも、高分子固体電解質は、大面積の加工が容易であることから、スパッタ法等の真空プロセスによって作製される無機固体電解質よりも高容量化が可能であり、製造コストの低減も期待できる。
また、高分子固体電解質は、液漏れの心配がないため金属缶が不要となる結果、フィルム等の種々の形状に加工することが可能となり、電池の薄型化、小型化に繋がるという利点もある。In recent years, therefore, research on solid-state lithium batteries using completely solid electrolyte polymers has been underway.
As solid electrolytes, inorganic material solid electrolytes and polymer material solid electrolytes are generally known.
Among these, since the solid polymer electrolyte can be easily processed in a large area, it can have a higher capacity than an inorganic solid electrolyte produced by a vacuum process such as a sputtering method, and a reduction in manufacturing cost can also be expected.
In addition, since the polymer solid electrolyte does not have to worry about liquid leakage, a metal can is not required. As a result, the polymer solid electrolyte can be processed into various shapes such as a film, which leads to reduction in the thickness and size of the battery. .
このような特徴を有する高分子固体電解質に関しては、世界中で様々な検討が行われている。
例えば、全固体型高分子固体電解質としては、ポリエチレンオキシド等のポリエーテル類が盛んに研究されている。当該ポリエーテル類では、エーテル官能基でリチウムイオンが包接されることによってリチウムイオンが高度に解離し、高分子鎖のセグメント運動によって、イオン移動が生じるメカニズムが考えられている（非特許文献１）。
しかし、ポリエーテル類を用いた場合は室温付近での高分子鎖のセグメント運動に限界があるため、イオン伝導能は乏しい。実際に、直鎖のポリエチレンオキシドでは、伝導度が１０-6Ｓ／ｃｍ程度であり、現在、これを大きく上回ることはできていない（特許文献２および３）。Various studies have been conducted all over the world regarding polymer solid electrolytes having such characteristics.
For example, as all solid-type polymer solid electrolytes, polyethers such as polyethylene oxide have been actively studied. In the polyethers, a mechanism is considered in which lithium ions are highly dissociated by inclusion of lithium ions with an ether functional group, and ion movement is caused by segment movement of a polymer chain (Non-patent Document 1). ).
However, when polyethers are used, the ionic conductivity is poor because there is a limit to the segmental motion of the polymer chain near room temperature. Actually, the linear polyethylene oxide has a conductivity of about 10 −6 S / cm, and it cannot be greatly exceeded at present (Patent Documents 2 and 3).
高分子鎖のセグメント運動を大きくさせるためには、分子量を低下させる必要があるが、この場合は固体電解質の良好な機械的強度を実現することが困難となり、膜の結晶化や亀裂が生じてイオン伝導能は大きく低下する。
また、ポリエチレンオキシドのみからなるポリエーテル類は、電解質塩添加時に機械的強度が低下し易く、多量の電解質塩を加えると、同様に膜の結晶化や亀裂が生じる。そのため、電解質塩を高濃度で含有する固体電解質を作製することができず、イオン伝導度の向上には限界がある。In order to increase the segment motion of the polymer chain, it is necessary to reduce the molecular weight. In this case, however, it becomes difficult to achieve a good mechanical strength of the solid electrolyte, resulting in film crystallization and cracking. The ionic conductivity is greatly reduced.
In addition, polyethers composed only of polyethylene oxide tend to have low mechanical strength when an electrolyte salt is added, and when a large amount of electrolyte salt is added, crystallization and cracking of the film occur similarly. For this reason, a solid electrolyte containing an electrolyte salt at a high concentration cannot be produced, and there is a limit to improving the ionic conductivity.
本発明は、このような事情に鑑みてなされたものであり、電解質溶液を含浸させなくとも、良好なイオン伝導能を有するとともに、溶媒を含浸させた電解質と比較して、形状保持性や機械的強度に優れる高分子電解質およびそれを用いたリチウムポリマー電池を提供することを目的とする。 The present invention has been made in view of such circumstances, and has good ionic conductivity without impregnation with an electrolyte solution, and has shape retention and mechanical properties as compared with an electrolyte impregnated with a solvent. It is an object of the present invention to provide a polymer electrolyte excellent in mechanical strength and a lithium polymer battery using the polymer electrolyte.
一般的に、高分岐ポリマーは、内部に多くの空隙を有することにより、直鎖状ポリマーと比較すると、例えばリチウムイオンのような十分に小さいイオンがより多く入り込むことが可能となる。この効果により、リチウムイオン電池やリチウム電池等の電解質としてそれを用いた場合に、キャリア密度の向上による電池の内部抵抗の抑制が期待できる。
上記のような観点から本発明者は鋭意検討を重ね、電解質塩のマトリックスポリマーとして、所定の高分岐ポリマーを用いることで、有機溶媒を用いなくとも良好なイオン伝導能を発揮し、形状保持性や機械的強度に優れた高分子電解質が得られることを見出し、本発明を完成した。In general, a hyperbranched polymer has a large number of voids inside, so that a sufficiently small ion such as lithium ion can enter more than a linear polymer. Due to this effect, when the electrolyte is used as an electrolyte such as a lithium ion battery or a lithium battery, it can be expected that the internal resistance of the battery is suppressed by improving the carrier density.
From the viewpoints described above, the present inventors have conducted intensive studies, and by using a predetermined hyperbranched polymer as a matrix polymer for the electrolyte salt, it exhibits good ion conductivity without using an organic solvent, and has shape retention. The inventors have found that a polymer electrolyte excellent in mechanical strength can be obtained and completed the present invention.
すなわち、本発明は、
１．分子内に２個以上のラジカル重合性二重結合を有するモノマーＡを含むモノマー成分を、このモノマー成分に対して５〜２００モル％の重合開始剤の存在下で重合させて得られる高分岐ポリマーと、電解質塩とを含み、前記モノマーＡが、ビニル基または（メタ）アクリル基のいずれか一方、または両方を有する化合物であることを特徴とする高分子電解質、
２．前記モノマーＡが、ジビニル化合物またはジ（メタ）アクリレート化合物である１の高分子電解質、
３．前記モノマーＡが、ジ（メタ）アクリレート化合物と、ビニル基および（メタ）アクリル基の両方を有する化合物との組み合わせである１の高分子電解質、
４．前記モノマーＡが、エチレングリコールジ（メタ）アクリレートである１または２の高分子電解質、
５．前記モノマー成分が、分子内にフルオロアルキル基および少なくとも１個のラジカル重合性二重結合を有するモノマーＢを含む１〜４のいずれかの高分子電解質、
６．前記モノマーＢが、前記モノマーＡ １ｍｏｌに対して０．０５〜３ｍｏｌ含まれる５の高分子電解質、
７．前記モノマーＢが、ビニル基または（メタ）アクリル基を有する化合物である５または６の高分子電解質、
８．前記モノマーＢが、下記式（１）で表される化合物である７の高分子電解質、
９．前記モノマーＢが、下記式（２）で表される化合物である８の高分子電解質、
１０．前記モノマー成分が、分子内にエーテル結合を含む置換基を有し、かつ少なくとも１個のラジカル重合性二重結合を有するモノマーＣを含む１〜９のいずれかの高分子電解質、
１１．前記重合開始剤が、アゾ系重合開始剤である１〜１０のいずれかの高分子電解質、
１２．前記重合開始剤が、２，２’−アゾビスイソ酪酸ジメチルおよび２，２’−アゾビス（２，４，４−トリメチルペンタン）から選ばれる少なくとも１種である１１の高分子電解質、
１３．前記電解質塩が、ＬｉＰＦ6、ＬｉＢＦ4、ＬｉＣｌＯ4およびＬｉＡｓＦ6からなる群から選ばれる無機リチウム塩およびその誘導体、並びに、ＬｉＳＯ3ＣＦ3、ＬｉＮ（ＳＯ2ＣＦ3）2、ＬｉＮ（ＳＯ2Ｃ2Ｆ5）2およびＬｉＮ（ＳＯ2ＣＦ3）（ＳＯ2Ｃ4Ｆ9）からなる群から選ばれる有機リチウム塩およびその誘導体からなる群から選ばれる少なくとも１種である１〜１２のいずれかの高分子電解質、
１４．前記電解質塩が、ＬｉＮ（ＳＯ2ＣＦ3）2またはＬｉＢＦ4である１３の高分子電解質、
１５．分子内に２個以上のラジカル重合性二重結合を有し、ビニル基または（メタ）アクリル基のいずれか一方または両方を有するモノマーＡを含むモノマー成分を、このモノマー成分に対して５〜２００モル％の重合開始剤の存在下で重合させて得られる高分岐ポリマーと、電解質塩とが、溶媒に溶解してなる高分子電解質前駆体溶液、
１６．前記溶媒が、ベンゼン、トルエン、キシレン、エチルベンゼン、テトラリン、ｎ−ヘキサン、ｎ−ヘプタン、ミネラルスピリット、シクロヘキサン、塩化メチル、臭化メチル、ヨウ化メチル、メチレンジクロライド、クロロホルム、四塩化炭素、トリクロロエチレン、パークロロエチレン、オルトジクロロベンゼン、酢酸エチル、酢酸ブチル、メトキシブチルアセテート、メチルセロソルブアセテート、エチルセロソルブアセテート、プロピレングリコールモノメチルエーテルアセテート、ジエチルエーテル、テトラヒドロフラン、１，４−ジオキサン、メチルセロソルブ、エチルセロソルブ、ブチルセロソルブ、プロピレングリコールモノメチルエーテル、アセトン、メチルエチルケトン、メチルイソブチルケトン、ジ−ｎ−ブチルケトン、シクロヘキサノン、メタノール、エタノール、ｎ−プロパノール、イソプロパノール、ｎ−ブタノール、イソブタノール、ｔｅｒｔ−ブタノール、２−エチルヘキシルアルコール、ベンジルアルコール、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、ジメチルスルホキシド、およびＮ−メチル−２−ピロリドンから選ばれる少なくとも１種である１５の高分子電解質前駆体溶液、
１７．前記有機溶媒が、メチルイソブチルケトンおよびテトラヒドロフランから選ばれる少なくとも１種である１６の高分子電解質前駆体溶液、
１８．１５〜１７のいずれかの高分子電解質前駆体溶液から、前記溶媒を除去して得られる高分子電解質
を提供する。That is, the present invention
1. Hyperbranched polymer obtained by polymerizing monomer component containing monomer A having two or more radically polymerizable double bonds in the molecule in the presence of 5 to 200 mol% of a polymerization initiator based on this monomer component A polymer electrolyte, wherein the monomer A is a compound having either a vinyl group or a (meth) acryl group, or both,
2. 1. The polymer electrolyte, wherein the monomer A is a divinyl compound or a di (meth) acrylate compound,
3. The polymer electrolyte according to 1, wherein the monomer A is a combination of a di (meth) acrylate compound and a compound having both a vinyl group and a (meth) acryl group,
4). 1 or 2 polymer electrolyte, wherein the monomer A is ethylene glycol di (meth) acrylate,
5. The polymer electrolyte according to any one of 1 to 4, wherein the monomer component comprises a monomer B having a fluoroalkyl group and at least one radical polymerizable double bond in the molecule;
6). 5 polymer electrolytes in which the monomer B is contained in an amount of 0.05 to 3 mol with respect to 1 mol of the monomer A,
7). 5 or 6 polymer electrolyte, wherein the monomer B is a compound having a vinyl group or a (meth) acryl group,
8). The polymer electrolyte of 7, wherein the monomer B is a compound represented by the following formula (1):
9. 8 polymer electrolyte, wherein the monomer B is a compound represented by the following formula (2):
10. The polymer electrolyte according to any one of 1 to 9, wherein the monomer component contains a monomer C having a substituent containing an ether bond in the molecule and having at least one radical polymerizable double bond,
11 The polymer electrolyte according to any one of 1 to 10, wherein the polymerization initiator is an azo polymerization initiator,
12 11 polymer electrolytes, wherein the polymerization initiator is at least one selected from dimethyl 2,2′-azobisisobutyrate and 2,2′-azobis (2,4,4-trimethylpentane);
13. The electrolyte salt is an inorganic lithium salt selected from the group consisting of LiPF 6 , LiBF 4 , LiClO 4 and LiAsF 6 and derivatives thereof, and LiSO 3 CF 3 , LiN (SO 2 CF 3 ) 2 , LiN (SO 2 C 1 to 12, which is at least one selected from the group consisting of an organic lithium salt selected from the group consisting of 2 F 5 ) 2 and LiN (SO 2 CF 3 ) (SO 2 C 4 F 9 ) and derivatives thereof Polymer electrolyte,
14 13 polymer electrolytes in which the electrolyte salt is LiN (SO 2 CF 3 ) 2 or LiBF 4 ;
15. A monomer component containing a monomer A having two or more radically polymerizable double bonds in the molecule and having either one or both of a vinyl group and a (meth) acryl group is used in an amount of 5 to 200 with respect to this monomer component. A polymer electrolyte precursor solution in which a hyperbranched polymer obtained by polymerization in the presence of a mol% polymerization initiator and an electrolyte salt are dissolved in a solvent;
16. The solvent is benzene, toluene, xylene, ethylbenzene, tetralin, n-hexane, n-heptane, mineral spirit, cyclohexane, methyl chloride, methyl bromide, methyl iodide, methylene dichloride, chloroform, carbon tetrachloride, trichlorethylene, Chloroethylene, orthodichlorobenzene, ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, diethyl ether, tetrahydrofuran, 1,4-dioxane, methyl cellosolve, ethyl cellosolve, butyl cellosolve, Propylene glycol monomethyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone Cyclohexanone, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, 2-ethylhexyl alcohol, benzyl alcohol, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, and N 15 polyelectrolyte precursor solutions that are at least one selected from methyl-2-pyrrolidone,
17. 16 polymer electrolyte precursor solutions in which the organic solvent is at least one selected from methyl isobutyl ketone and tetrahydrofuran;
18. A polymer electrolyte obtained by removing the solvent from the polymer electrolyte precursor solution of any one of 15.15 to 17 is provided.
本発明の高分子電解質では、所定の高分岐ポリマーを用いているため、例えば、室温で１．０×１０-5Ｓ／ｃｍを超えるような、優れたイオン伝導性を発揮し得る。したがって、リチウム電池等の電解液部位にこの高分子電解質を用いることで、内部抵抗の低い全固体電池を与え得る。
本発明の高分子電解質に含まれる高分岐ポリマーは、単独のポリマーによって直径１μｍ以下の微粒子を形成させることが可能であり、直鎖状のポリマーと比較して分子鎖の絡み合いが少ない。そのため、ポリマーの粘度が低く、加えられる電解質イオン、例えばリチウムイオンの自由エネルギーを向上させ易い。また、分子鎖の絡み合いが抑制されることからポリマー内部に多くの空隙を生じさせることが可能であり、ポリマー内部でのイオン移動も容易に行われる。
さらに、本発明で用いる高分岐ポリマーは、エステル基やエーテル基等の高極性官能基を含有しているために、電解質塩として用いられるリチウム塩との相溶性が高く、高濃度の電解質塩を均一に混合させることができる結果、高濃度の電解質塩を含む電解質層を形成することが可能である。
例えば、本発明で用いる高分岐ポリマーを合成する際に、モノマーＡとしてエチレングリコールジ（メタ）アクリレートを使用した場合、高分岐ポリマー内に−Ｃ（Ｏ）−Ｏ−ＣＨ2ＣＨ2−Ｏ−Ｃ（Ｏ）−ユニットが構築される。このユニットではエーテル酸素原子上の不対電子が非局在化するため、通常のポリエーテルユニット（−ＣＨ2ＣＨ2−Ｏ−ＣＨ2ＣＨ2−Ｏ−ＣＨ2ＣＨ2−）と比較してリチウムイオンと錯形成をし難いと推測されるが、本発明の高分子電解質は優れたイオン伝導性を発揮する。In the polymer electrolyte of the present invention, since a predetermined hyperbranched polymer is used, it is possible to exhibit excellent ionic conductivity, for example, exceeding 1.0 × 10 −5 S / cm at room temperature. Therefore, an all solid state battery having a low internal resistance can be provided by using this polymer electrolyte in an electrolyte solution site of a lithium battery or the like.
The hyperbranched polymer contained in the polymer electrolyte of the present invention can form fine particles having a diameter of 1 μm or less with a single polymer, and there is less entanglement of molecular chains than a linear polymer. Therefore, the viscosity of the polymer is low, and it is easy to improve the free energy of added electrolyte ions such as lithium ions. In addition, since entanglement of molecular chains is suppressed, many voids can be generated inside the polymer, and ion movement inside the polymer is also easily performed.
Furthermore, since the highly branched polymer used in the present invention contains a highly polar functional group such as an ester group or an ether group, it is highly compatible with a lithium salt used as an electrolyte salt, and a high concentration electrolyte salt is used. As a result of uniform mixing, it is possible to form an electrolyte layer containing a high concentration of electrolyte salt.
For example, when ethylene glycol di (meth) acrylate is used as monomer A when synthesizing the highly branched polymer used in the present invention, —C (O) —O—CH 2 CH 2 —O— is included in the highly branched polymer. C (O) -units are built. In this unit, unpaired electrons on the ether oxygen atom are delocalized, so compared with the usual polyether unit (—CH 2 CH 2 —O—CH 2 CH 2 —O—CH 2 CH 2 —). Although it is estimated that complex formation with lithium ions is difficult, the polymer electrolyte of the present invention exhibits excellent ionic conductivity.
また、当該高分岐ポリマーを合成する際に、フッ素官能基を含むモノマーを使用することによって、容易にフッ素官能基を含む高分岐ポリマーを形成することが可能であり、耐電圧特性の向上、ＳＥＩ厚膜化の抑制、集電体との結着性向上、電極活物質および導電助材の分散性向上、難燃性の向上に寄与する。
さらに、エーテル基やエチレンオキシド基を含むモノマーを使用することによって、リチウムイオンの解離度を向上させ、イオン伝導能をさらに向上させることが可能である。
なお、分子内にエチレンオキシド鎖等の−Ｏ−ＣＨ2ＣＨ2−Ｏ−ユニットを有している高分岐ポリマーでは、リチウムイオンが下記式（３）で表されるように錯形成することができる。これにより、ポリマーにリチウム塩が内包された場合も、イオン化状態が維持されるため、高リチウムイオン伝導性となり、この効果でも電池の内部抵抗抑制が期待できる。Further, when the hyperbranched polymer is synthesized, it is possible to easily form a hyperbranched polymer containing a fluorine functional group by using a monomer containing a fluorine functional group. This contributes to suppression of thickening, improvement of binding properties with the current collector, improvement of dispersibility of the electrode active material and conductive additive, and improvement of flame retardancy.
Further, by using a monomer containing an ether group or an ethylene oxide group, it is possible to improve the degree of dissociation of lithium ions and further improve the ion conductivity.
In the hyperbranched polymer having —O—CH 2 CH 2 —O— units such as ethylene oxide chains in the molecule, lithium ions can be complexed as represented by the following formula (3). . Thereby, even when lithium salt is encapsulated in the polymer, the ionized state is maintained, so that high lithium ion conductivity is obtained, and the internal resistance of the battery can also be suppressed by this effect.
また、本発明で用いる高分岐ポリマーは、ガラス転移温度が低く、柔軟性を有するガラス状ポリマー、あるいはゴム状のポリマーの形成が可能である。これによって、高分子鎖のセグメント運動の向上、イオン伝導経路の向上によるイオン伝導能向上がなされ、電極の増肉、減肉への追随を可能として接触抵抗の増加を抑制し、電池のサイクル特性向上にも寄与する。
以上の効果により、本発明の高分岐ポリマーを含む電解質を、リチウムイオン二次電池をはじめとする二次電池用の電解質として用いた場合に、高イオン伝導度を示す電解質層を形成して高レート特性を発現し、高サイクル特性を有し、溶媒揮発や発火の虞の無い安全な二次電池を作製することが可能となる。
さらに、本発明の高分子電解質は、リチウム塩を含有した状態で薄膜作製が可能であるため、電解液の含浸などの処理を必要としない。
本発明の高分子電解質は、電解液を用いない、すなわち有機溶媒を含んでいないことにより、溶媒揮発の問題や、溶媒を含むことによる形状保持性の低下および機械的強度の低下などを懸念する必要がないという利点がある。Further, the hyperbranched polymer used in the present invention has a low glass transition temperature and can form a flexible glassy polymer or rubbery polymer. As a result, the segment motion of the polymer chain is improved and the ion conductivity is improved by improving the ion conduction path, and the increase in contact resistance can be suppressed by increasing the thickness of the electrode, and the cycle characteristics of the battery. Contributes to improvement.
Due to the above effects, when the electrolyte containing the hyperbranched polymer of the present invention is used as an electrolyte for a secondary battery such as a lithium ion secondary battery, an electrolyte layer exhibiting a high ion conductivity is formed to increase the electrolyte layer. It is possible to produce a safe secondary battery that exhibits rate characteristics, has high cycle characteristics, and does not cause solvent volatilization or ignition.
Furthermore, since the polymer electrolyte of the present invention can produce a thin film in a state containing a lithium salt, it does not require treatment such as impregnation with an electrolytic solution.
Since the polymer electrolyte of the present invention does not use an electrolytic solution, that is, does not contain an organic solvent, there are concerns about a problem of solvent volatilization, a decrease in shape retention and a decrease in mechanical strength due to the inclusion of a solvent, etc. There is an advantage that it is not necessary.
以下、本発明についてさらに詳しく説明する。
本発明に係る高分子電解質は、分子内に２個以上のラジカル重合性二重結合を有するモノマーＡを含むモノマー成分を、このモノマー成分に対して５〜２００モル％の重合開始剤の存在下で重合させて得られる高分岐ポリマーと、電解質塩とを含み、モノマーＡが、ビニル基または（メタ）アクリル基のいずれか一方、または両方を有する化合物であることを特徴とする。Hereinafter, the present invention will be described in more detail.
The polymer electrolyte according to the present invention comprises a monomer component containing monomer A having two or more radically polymerizable double bonds in the molecule in the presence of 5 to 200 mol% of a polymerization initiator based on the monomer component. And the monomer A is a compound having either one or both of a vinyl group and a (meth) acryl group.
[高分岐ポリマー]
高分岐ポリマーは、一般に、デンドリマーとハイパーブランチポリマーに大別されるが、本発明で用いる高分岐ポリマーとしてはハイパーブランチポリマーが好ましい。
なお、本発明で用いる高分岐ポリマーは、いわゆる開始剤断片組込型高分岐ポリマーであり、その末端に重合に使用した重合開始剤の断片を有している。
上記モノマーＡは、ビニル基または（メタ）アクリル基のいずれか一方、または両方を有するものであれば、特に限定されるものではないが、特にジビニル化合物またはジ（メタ）アクリレート化合物が好ましい。
また、モノマーＡは複数種を組み合わせて用いてもよく、例えば、ジ（メタ）アクリレート化合物と、ビニル基および（メタ）アクリル基の両方を有する化合物との組み合わせも好適である。
なお、（メタ）アクリレート化合物とは、アクリレート化合物とメタクリレート化合物の両方をいう。例えば（メタ）アクリル酸は、アクリル酸とメタクリル酸をいう。[Highly branched polymer]
Hyperbranched polymers are generally roughly classified into dendrimers and hyperbranched polymers, but hyperbranched polymers are preferred as the hyperbranched polymers used in the present invention.
The hyperbranched polymer used in the present invention is a so-called initiator fragment-embedded hyperbranched polymer, and has a polymerization initiator fragment used for polymerization at its terminal.
The monomer A is not particularly limited as long as it has either one or both of a vinyl group and a (meth) acryl group, but a divinyl compound or a di (meth) acrylate compound is particularly preferable.
Moreover, the monomer A may be used in combination of a plurality of types. For example, a combination of a di (meth) acrylate compound and a compound having both a vinyl group and a (meth) acryl group is also suitable.
The (meth) acrylate compound refers to both an acrylate compound and a methacrylate compound. For example, (meth) acrylic acid refers to acrylic acid and methacrylic acid.
モノマーＡの具体例としては、以下の（Ａ１）〜（Ａ８）に示した有機化合物が挙げられる。
（Ａ１）ビニル系炭化水素：
（Ａ１−１）脂肪族ビニル系炭化水素類；イソプレン、ブタジエン、３−メチル−１，２−ブタジエン、２，３−ジメチル−１，３−ブタジエン、１，２−ポリブタジエン、ペンタジエン、ヘキサジエン、オクタジエン等
（Ａ１−２）脂環式ビニル系炭化水素類；シクロペンタジエン、シクロヘキサジエン、シクロオクタジエン、ノルボルナジエン等
（Ａ１−３）芳香族ビニル系炭化水素類；ジビニルベンゼン、ジビニルトルエン、ジビニルキシレン、トリビニルベンゼン、ジビニルビフェニル、ジビニルナフタレン、ジビニルフルオレン、ジビニルカルバゾール、ジビニルピリジン等Specific examples of the monomer A include organic compounds shown in the following (A1) to (A8).
(A1) Vinyl hydrocarbon:
(A1-1) Aliphatic vinyl hydrocarbons; isoprene, butadiene, 3-methyl-1,2-butadiene, 2,3-dimethyl-1,3-butadiene, 1,2-polybutadiene, pentadiene, hexadiene, octadiene (A1-2) Alicyclic vinyl hydrocarbons; cyclopentadiene, cyclohexadiene, cyclooctadiene, norbornadiene, etc. (A1-3) aromatic vinyl hydrocarbons; divinylbenzene, divinyltoluene, divinylxylene, tri Vinylbenzene, divinylbiphenyl, divinylnaphthalene, divinylfluorene, divinylcarbazole, divinylpyridine, etc.
（Ａ２）ビニルエステル、アリルエステル、ビニルエーテル、アリルエーテル、ビニルケトン：
（Ａ２−１）ビニルエステル；アジピン酸ジビニル、マレイン酸ジビニル、フタル酸ジビニル、イソフタル酸ジビニル、イタコン酸ジビニル、ビニル（メタ）アクリレート等
（Ａ２−２）アリルエステル；マレイン酸ジアリル、フタル酸ジアリル、イソフタル酸ジアリル、アジピン酸ジアリル、アリル（メタ）アクリレート等
（Ａ２−３）ビニルエーテル；ジビニルエーテル、ジエチレングリコールジビニルエーテル、トリエチレングリコールジビニルエーテル等
（Ａ２−４）アリルエーテル；ジアリルエーテル、ジアリルオキシエタン、トリアリルオキシエタン、テトラアリルオキシエタン、テトラアリルオキシプロパン、テトラアリルオキシブタン、テトラメタリルオキシエタン等
（Ａ２−５）ビニルケトン；ジビニルケトン、ジアリルケトン等(A2) Vinyl ester, allyl ester, vinyl ether, allyl ether, vinyl ketone:
(A2-1) vinyl ester; divinyl adipate, divinyl maleate, divinyl phthalate, divinyl isophthalate, divinyl itaconate, vinyl (meth) acrylate, etc. (A2-2) allyl ester; diallyl maleate, diallyl phthalate, Diallyl isophthalate, diallyl adipate, allyl (meth) acrylate, etc. (A2-3) vinyl ether; divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, etc. (A2-4) allyl ether; diallyl ether, diallyloxyethane, tri Allyloxyethane, tetraallyloxyethane, tetraallyloxypropane, tetraallyloxybutane, tetramethallyloxyethane, etc. (A2-5) vinyl ketone; divinyl ketone, diallyl Tons, etc.
（Ａ３）（メタ）アクリル酸エステル：エチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート、ノナエチレングリコールジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、グリセロールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、アルコキシチタントリ（メタ）アクリレート、１，６−ヘキサンジオールジ（メタ）アクリレート、２−メチル−１，８−オクタンジオールジ（メタ）アクリレート、１，９−ノナンジオールジ（メタ）アクリレート、１，１０−デカンジオールジ（メタ）アクリレート、トリシクロデカンジメタノールジ（メタ）アクリレート、ジオキサングリコールジ（メタ）アクリレート、２−ヒドロキシ−１−アクリロイルオキシ−３−メタクリロイルオキシプロパン、２−ヒドロキシ−１，３−ジ（メタ）アクリロイルオキシプロパン、９，９−ビス［４−（２−（メタ）アクリロイルオキシエトキシ）フェニル］フルオレン、ウンデシレノキシエチレングリコールジ（メタ）アクリレート、ビス［４−（メタ）アクリロイルチオフェニル］スルフィド、ビス［２−（メタ）アクリロイルチオエチル］スルフィド、１，３−アダマンタンジオールジ（メタ）アクリレート、１，３−アダマンタンジメタノールジ（メタ）アクリレート等 (A3) (Meth) acrylic acid ester: ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, nonaethylene glycol di (meth) acrylate, propylene glycol di (meth) ) Acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, alkoxy titanium tri (meth) acrylate, 1,6-hexanediol Di (meth) acrylate, 2-methyl-1,8-octanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di ( Acrylate), tricyclodecane dimethanol di (meth) acrylate, dioxane glycol di (meth) acrylate, 2-hydroxy-1-acryloyloxy-3-methacryloyloxypropane, 2-hydroxy-1,3-di (meth) Acryloyloxypropane, 9,9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene, undecylenoxyethylene glycol di (meth) acrylate, bis [4- (meth) acryloylthiophenyl] sulfide Bis [2- (meth) acryloylthioethyl] sulfide, 1,3-adamantanediol di (meth) acrylate, 1,3-adamantane dimethanol di (meth) acrylate, etc.
（Ａ４）ポリアルキレングリコール鎖を有するビニル系化合物：
ポリエチレングリコール（分子量３００）ジ（メタ）アクリレート、ポリプロピレングリコール（分子量５００）ジ（メタ）アクリレート等
（Ａ５）含窒素ビニル系化合物：ジアリルアミン、ジアリルイソシアヌレート、ジアリルシアヌレート、メチレンビス（メタ）アクリルアミド、ビスマレイミド等
（Ａ６）含ケイ素ビニル系化合物：ジメチルジビニルシラン、ジビニルメチルフェニルシラン、ジフェニルジビニルシラン、１，３−ジビニル−１，１，３，３−テトラメチルジシラザン、１，３−ジビニル−１，１，３，３−テトラフェニルジシラザン、ジエトキジビニルシラン等
（Ａ７）含フッ素ビニル系化合物：１，４−ジビニルパーフルオロブタン、１，６−ジビニルパーフルオロヘキサン、１，８−ジビニルパーフルオロオクタン等
（Ａ８）ビニルエーテル基含有（メタ）アクリレート化合物：２−（２−ビニルオキシエトキシ）エチルアクリレート等(A4) Vinyl compound having a polyalkylene glycol chain:
Polyethylene glycol (molecular weight 300) di (meth) acrylate, polypropylene glycol (molecular weight 500) di (meth) acrylate, etc. (A5) Nitrogen-containing vinyl compounds: diallylamine, diallyl isocyanurate, diallyl cyanurate, methylenebis (meth) acrylamide, bis (A6) silicon-containing vinyl compounds such as maleimide: dimethyldivinylsilane, divinylmethylphenylsilane, diphenyldivinylsilane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, 1,3-divinyl-1 , 1,3,3-tetraphenyldisilazane, dietodivinylsilane, etc. (A7) Fluorine-containing vinyl compounds: 1,4-divinylperfluorobutane, 1,6-divinylperfluorohexane, 1,8-divinylperfluoro Octa Etc. (A8) vinyl ether group-containing (meth) acrylate compound: 2- (2-vinyloxyethoxy) ethyl acrylate
これらの中でも、上記（Ａ１−３）群の芳香族ビニル系炭化水素類、（Ａ２）群のビニルエステル、アリルエステル、ビニルエーテル、アリルエーテルおよびビニルケトン、（Ａ３）群の（メタ）アクリル酸エステル、（Ａ４）群のポリアルキレングリコール鎖を有するビニル系化合物、並びに（Ａ５）群の含窒素ビニル系化合物が好ましく、（Ａ１−３）群のジビニルベンゼン、（Ａ２）群のフタル酸ジアリル、（Ａ３）群のエチレングリコールジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート、ノナエチレングリコールジ（メタ）アクリレート、１，３−アダマンタンジメタノールジ（メタ）アクリレート、トリシクロデカンジメタノールジ（メタ）アクリレート並びに（Ａ５）群の属するメチレンビス（メタ）アクリルアミドがより好ましい。
特に、ジビニルベンゼン、エチレングリコールジ（メタ）アクリレート、トリシクロデカンジメタノールジ（メタ）アクリレートが好ましく、特にエチレングリコールジ（メタ）アクリレートがより好ましい。
また、上記各化合物と、（Ａ８）群の２−（２−ビニルオキシエトキシ）エチルアクリレートとの組み合わせが好適である。Among these, (A1-3) group aromatic vinyl hydrocarbons, (A2) group vinyl esters, allyl esters, vinyl ethers, allyl ethers and vinyl ketones, (A3) group (meth) acrylic acid esters, A vinyl compound having a polyalkylene glycol chain of (A4) group and a nitrogen-containing vinyl compound of (A5) group are preferred, (A1-3) group divinylbenzene, (A2) group diallyl phthalate, (A3 ) Group of ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, nonaethylene glycol di (meth) acrylate, 1,3-adamantane dimethanol di (meth) acrylate, tricyclodecane dimethanol di (meta) ) Acrylate and methylene bis (me ) Acrylamide is more preferable.
In particular, divinylbenzene, ethylene glycol di (meth) acrylate, and tricyclodecane dimethanol di (meth) acrylate are preferable, and ethylene glycol di (meth) acrylate is more preferable.
Moreover, the combination of each said compound and 2- (2-vinyloxy ethoxy) ethyl acrylate of the (A8) group is suitable.
また、本発明で用いる高分岐ポリマーの合成において用いられるモノマー成分は、上記モノマーＡに加えて分子内にフルオロアルキル基および少なくとも１個のラジカル重合性二重結合を有するモノマーＢを混合してもよい。
この場合、モノマーＢとしては、ビニル基または（メタ）アクリル基のいずれか一方を少なくとも１つ有することが好ましい。
このようなモノマーＢとしては、式（１）で表される化合物が好ましく、式（２）で示される化合物がより好ましい。In addition to the monomer A, the monomer component used in the synthesis of the hyperbranched polymer used in the present invention may be a mixture of a monomer B having a fluoroalkyl group and at least one radical polymerizable double bond in the molecule. Good.
In this case, the monomer B preferably has at least one of either a vinyl group or a (meth) acryl group.
As such a monomer B, the compound represented by Formula (1) is preferable, and the compound represented by Formula (2) is more preferable.
上記式（１）または式（２）で示されるモノマーＢの具体例としては、２，２，２−トリフルオロエチル（メタ）アクリレート、２，２，３，３，３−ペンタフルオロプロピル（メタ）アクリレート、２−（パーフルオロブチル）エチル（メタ）アクリレート、２−（パーフルオロヘキシル）エチル（メタ）アクリレート、２−（パーフルオロオクチル）エチル（メタ）アクリレート、２−（パーフルオロデシル）エチル（メタ）アクリレート、２−（パーフルオロ−３−メチルブチル）エチル（メタ）アクリレート、２−（パーフルオロ−５−メチルヘキシル）エチル（メタ）アクリレート、２−（パーフルオロ−７−メチルオクチル）エチル（メタ）アクリレート、１Ｈ，１Ｈ，３Ｈ−テトラフルオロプロピル（メタ）アクリレート、１Ｈ，１Ｈ，５Ｈ−オクタフルオロペンチル（メタ）アクリレート、１Ｈ，１Ｈ，７Ｈ−ドデカフルオロヘプチル（メタ）アクリレート、１Ｈ，１Ｈ，９Ｈ−ヘキサデカフルオロノニル（メタ）アクリレート、１Ｈ−１−（トリフオロメチル）トリフルオロエチル（メタ）アクリレート、１Ｈ，１Ｈ，３Ｈ−ヘキサフルオロブチル（メタ）アクリレート、３−パーフルオロブチル−２−ヒドロキシプロピル（メタ）アクリレート、３−パーフルオロヘキシル−２−ヒドロキシプロピル（メタ）アクリレート、３−パーフルオロオクチル−２−ヒドロキシプロピル（メタ）アクリレート、３−（パーフルオロ−３−メチルブチル）−２−ヒドロキシプロピル（メタ）アクリレート、３−（パーフルオロ−５−メチルヘキシル）−２−ヒドロキシプロピル（メタ）アクリレート、および３−（パーフルオロ−７−メチルオクチル）−２−ヒドロキシプロピル（メタ）アクリレート等が挙げられる。 Specific examples of the monomer B represented by the above formula (1) or formula (2) include 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3,3-pentafluoropropyl (meth) ) Acrylate, 2- (perfluorobutyl) ethyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, 2- (perfluorooctyl) ethyl (meth) acrylate, 2- (perfluorodecyl) ethyl (Meth) acrylate, 2- (perfluoro-3-methylbutyl) ethyl (meth) acrylate, 2- (perfluoro-5-methylhexyl) ethyl (meth) acrylate, 2- (perfluoro-7-methyloctyl) ethyl (Meth) acrylate, 1H, 1H, 3H-tetrafluoropropyl (meth) acrylate, 1 , 1H, 5H-octafluoropentyl (meth) acrylate, 1H, 1H, 7H-dodecafluoroheptyl (meth) acrylate, 1H, 1H, 9H-hexadecafluorononyl (meth) acrylate, 1H-1- (trifluoromethyl ) Trifluoroethyl (meth) acrylate, 1H, 1H, 3H-hexafluorobutyl (meth) acrylate, 3-perfluorobutyl-2-hydroxypropyl (meth) acrylate, 3-perfluorohexyl-2-hydroxypropyl (meth) ) Acrylate, 3-perfluorooctyl-2-hydroxypropyl (meth) acrylate, 3- (perfluoro-3-methylbutyl) -2-hydroxypropyl (meth) acrylate, 3- (perfluoro-5-methylhexyl)- 2-hydroxyp Pill (meth) acrylate, and 3- (perfluoro-7-methyl-octyl) -2-hydroxypropyl (meth) acrylate.
なお、本発明で用いる高分岐ポリマーの合成において用いられるモノマー成分にモノマーＢを混合する場合、モノマーＡが、ジ（メタ）アクリレート化合物であり、かつ、モノマーＢが、分子内にフルオロアルキル基および少なくとも１個のラジカル重合性二重結合を有するモノマーであることが好ましく、モノマーＡが、エチレングリコールジ（メタ）アクリレートであり、かつ、モノマーＢが上記式（２）で示される化合物であることがより好ましい。 In addition, when the monomer B is mixed with the monomer component used in the synthesis of the hyperbranched polymer used in the present invention, the monomer A is a di (meth) acrylate compound, and the monomer B has a fluoroalkyl group and It is preferable that the monomer has at least one radical polymerizable double bond, the monomer A is ethylene glycol di (meth) acrylate, and the monomer B is a compound represented by the above formula (2). Is more preferable.
本発明において、モノマーＡとモノマーＢとを共重合させる割合は、反応性や表面改質効果等を考慮すると、モノマーＡ １ｍｏｌに対してモノマーＢ ０．０５〜３．０ｍｏｌが好ましく、０．１〜１．５ｍｏｌがより好ましい。 In the present invention, the ratio of the monomer A and the monomer B to be copolymerized is preferably 0.05 to 3.0 mol of the monomer B with respect to 1 mol of the monomer A in consideration of the reactivity and the surface modification effect. -1.5 mol is more preferable.
本発明で用いる高分岐ポリマーの合成において用いられるモノマー成分は、上記モノマーＡに加えて分子内にエーテル結合を含む置換基を有し、かつ少なくとも１個のラジカル重合性二重結合を有するモノマーＣを混合してもよい。
このようなモノマーＣとしては、ビニル基または（メタ）アクリル基のいずれか一方を少なくとも１つ有する化合物や、マレイミド化合物が好ましい。
また、モノマーＡおよびモノマーＢとともに、モノマーＣを用いてもよい。
エーテル結合を含む置換基としては、エチレンオキシド（−ＣＨ2−ＣＨ2−Ｏ−）基が挙げられる。The monomer component used in the synthesis of the hyperbranched polymer used in the present invention is a monomer C having a substituent containing an ether bond in the molecule in addition to the monomer A and having at least one radical polymerizable double bond. May be mixed.
As such a monomer C, a compound having at least one of either a vinyl group or a (meth) acryl group or a maleimide compound is preferable.
In addition to monomer A and monomer B, monomer C may be used.
Examples of the substituent containing an ether bond include an ethylene oxide (—CH 2 —CH 2 —O—) group.
モノマーＣの具体例としては、２−（２−ビニルオキシエトキシ）エチルアクリレートなどのビニルエーテル基含有（メタ）アクリレート化合物；グリシジルメタクリレートなどのエポキシ基含有（メタ）アクリレート化合物；３−メタクリルオキシプロピルトリエトキシシランなどのアルコキシシリル基含有（メタ）アクリレート化合物；シクロヘキシルマレイミド、Ｎ−ベンジルマレイミドなどのマレイミド化合物等が挙げられる。
本発明において、モノマーＣを共重合させる割合は、反応性や表面改質効果の観点から好ましくはモノマーＡ １ｍｏｌに対して０．０５〜３．０ｍｏｌが好ましく、０．１〜１．５ｍｏｌがより好ましい。Specific examples of the monomer C include vinyl ether group-containing (meth) acrylate compounds such as 2- (2-vinyloxyethoxy) ethyl acrylate; epoxy group-containing (meth) acrylate compounds such as glycidyl methacrylate; 3-methacryloxypropyltriethoxy Examples thereof include alkoxysilyl group-containing (meth) acrylate compounds such as silane; maleimide compounds such as cyclohexylmaleimide and N-benzylmaleimide.
In the present invention, the proportion of monomer C to be copolymerized is preferably 0.05 to 3.0 mol, more preferably 0.1 to 1.5 mol with respect to 1 mol of monomer A from the viewpoint of reactivity and surface modification effect. preferable.
高分岐ポリマーの合成に用いられる重合開始剤としては、特に限定されるものではないが、本発明においては、アゾ系重合開始剤が好ましい。
アゾ系重合開始剤としては、例えば、以下の（１）〜（５）に示す化合物が挙げられ、これらは単独で用いても、２種以上組み合わせて用いてもよい。The polymerization initiator used for the synthesis of the hyperbranched polymer is not particularly limited, but an azo polymerization initiator is preferred in the present invention.
Examples of the azo polymerization initiator include the compounds shown in the following (1) to (5), and these may be used alone or in combination of two or more.
（１）アゾニトリル化合物：２，２’−アゾビスイソブチロニトリル、２，２’−アゾビス（２−メチルブチロニトリル）、２，２’−アゾビス（２，４−ジメチルバレロニトリル）、１，１’−アゾビス（１−シクロヘキサンカルボニトリル）、２，２’−アゾビス（４−メトキシ−２，４−ジメチルバレロニトリル）、２−（カルバモイルアゾ）イソブチロニトリル等
（２）アゾアミド化合物：２，２’−アゾビス｛２−メチル−Ｎ−［１，１−ビス（ヒドロキシメチル）−２−ヒドロキシエチル］プロピオンアミド｝、２，２’−アゾビス｛２−メチル−Ｎ−［２−（１−ヒドロキシブチル）］プロピオンアミド｝、２，２’−アゾビス［２−メチル−Ｎ−（２−ヒドロキシエチル）プロピオンアミド］、２，２’−アゾビス［Ｎ−（２−プロペニル）−２−メチルプロピオンアミド］、２，２’−アゾビス（Ｎ−ブチル−２−メチルプロピオンアミド）、２，２’−アゾビス（Ｎ−シクロヘキシル−２−メチルプロピオンアミド）等
（３）環状アゾアミジン化合物：２，２’−アゾビス［２−（２−イミダゾリン−２−イル）プロパン］ジヒドロクロリド、２，２’−アゾビス［２−（２−イミダゾリン−２−イル）プロパン］ジスルフェートジヒドレート、２，２’−アゾビス［２−［１−（２−ヒドロキシエチル）−２−イミダゾリン−２−イル］プロパン］ジヒドロクロリド、２，２’−アゾビス［２−（２−イミダゾリン−２−イル）プロパン］、２，２’−アゾビス（１−イミノ−１−ピロリジノ−２−メチルプロパン）ジヒドロクロリド等
（４）アゾアミジン化合物：２，２’−アゾビス（２−メチルプロピオンアミジン）ジヒドロクロリド、２，２’−アゾビス［Ｎ−（２−カルボキシエチル）−２−メチルプロピオンアミジン］テトラヒドレート等
（５）その他：２，２’−アゾビスイソ酪酸ジメチル、４，４’−アゾビス（４−シアノバレリン酸）、２，２’−アゾビス（２，４，４−トリメチルペンタン）、１，１’−アゾビス（１−アセトキシ−１−フェニルエタン）等(1) Azonitrile compound: 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 1 1,2′-azobis (1-cyclohexanecarbonitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2- (carbamoylazo) isobutyronitrile, etc. (2) Azoamide compounds: 2,2′-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, 2,2′-azobis {2-methyl-N- [2- ( 1-hydroxybutyl)] propionamide}, 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2′-azobis [N- (2-propeni ) -2-Methylpropionamide], 2,2′-azobis (N-butyl-2-methylpropionamide), 2,2′-azobis (N-cyclohexyl-2-methylpropionamide), etc. (3) Cyclic azoamidine Compounds: 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] disulfate dihydride 2,2'-azobis [2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane] dihydrochloride, 2,2'-azobis [2- (2-imidazoline-2- Yl) propane], 2,2′-azobis (1-imino-1-pyrrolidino-2-methylpropane) dihydrochloride, etc. (4) Azoamidine compounds: 2,2′-azobi (2-Methylpropionamidine) dihydrochloride, 2,2′-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] tetrahydrate, etc. (5) Others: Dimethyl 2,2′-azobisisobutyrate 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2,4,4-trimethylpentane), 1,1′-azobis (1-acetoxy-1-phenylethane), etc.
上記アゾ系重合開始剤の中でも、得られる高分岐ポリマーの表面エネルギーを考慮すると、極性の比較的低い置換基を有するものが好ましく、特に、２，２’−アゾビスイソ酪酸ジメチルおよび／または２，２’−アゾビス（２，４，４−トリメチルペンタン）が好ましい。
上記重合開始剤は、モノマー成分中のモノマーＡのモル数に対して５〜２００ｍｏｌ％の量で用いられる。好ましくは１５〜２００ｍｏｌ％、より好ましくは１５〜１７０ｍｏｌ％、より一層好ましくは５０〜１００ｍｏｌ％の量である。
なお、モノマーＢおよびモノマーＣを、前記モノマーＡと混合して用いる場合でも、重合開始剤は、モノマーＡに対して、上記の比率で用いられる。Among the azo polymerization initiators, those having a relatively low polarity substituent are preferable in consideration of the surface energy of the resulting hyperbranched polymer, and in particular, dimethyl 2,2′-azobisisobutyrate and / or 2,2 '-Azobis (2,4,4-trimethylpentane) is preferred.
The polymerization initiator is used in an amount of 5 to 200 mol% with respect to the number of moles of monomer A in the monomer component. The amount is preferably 15 to 200 mol%, more preferably 15 to 170 mol%, still more preferably 50 to 100 mol%.
Even when monomer B and monomer C are used in combination with monomer A, the polymerization initiator is used in the above ratio with respect to monomer A.
具体的な高分岐ポリマーの合成は、国際公開第２０１０／１３７７２４号や、Macromol. Chem. Phys. 206, 860(2005)記載の方法に従って行えばよい。 A specific hyperbranched polymer may be synthesized according to the methods described in International Publication No. 2010/137724 and Macromol. Chem. Phys. 206, 860 (2005).
［電解質塩］
本発明の高分子電解質で使用される電解質塩としては、リチウムイオン二次電池に使用可能な従来公知の各種電解質塩が挙げられる。
電解質塩の具体例としては、ＬｉＰＦ6、ＬｉＢＦ4、ＬｉＣｌＯ4、およびＬｉＡｓＦ6から選ばれる無機リチウム塩およびその誘導体、並びに、ＬｉＳＯ3ＣＦ3、ＬｉＮ（ＳＯ2ＣＦ3）2［ＬｉＴＦＳＩ］、ＬｉＮ（ＳＯ2Ｃ2Ｆ5）2［ＬｉＢＥＳＩ］、ＬｉＮ（ＳＯ2ＣＦ3）（ＳＯ2Ｃ4Ｆ9）、およびリチウムビス（オキサレート）ボレート［Ｌｉ（ＢＯＢ）］から選ばれる有機リチウム塩およびその誘導体からなる群から選ばれる少なくとも１種が好ましく、汎用性や伝導性の面から、ＬｉＰＦ6、ＬｉＢＦ4、ＬｉＴＦＳＩが好ましく、この中でも特に、伝導性の面からＬｉＴＦＳＩが好ましい。
上記電解質塩の添加量は、高分岐ポリマー１ｋｇに対して、０．５〜５．０ｍｏｌが好ましく、１．０〜４．０ｍｏｌがより好ましく、２．０〜３．０ｍｏｌが最適である。[Electrolyte salt]
Examples of the electrolyte salt used in the polymer electrolyte of the present invention include various conventionally known electrolyte salts that can be used in lithium ion secondary batteries.
Specific examples of the electrolyte salt include inorganic lithium salt selected from LiPF 6 , LiBF 4 , LiClO 4 , and LiAsF 6 and derivatives thereof, and LiSO 3 CF 3 , LiN (SO 2 CF 3 ) 2 [LiTFSI], LiN An organic lithium salt selected from (SO 2 C 2 F 5 ) 2 [LiBESI], LiN (SO 2 CF 3 ) (SO 2 C 4 F 9 ), and lithium bis (oxalate) borate [Li (BOB)] At least one selected from the group consisting of derivatives is preferable, and LiPF 6 , LiBF 4 , and LiTFSI are preferable from the viewpoint of versatility and conductivity, and among these, LiTFSI is particularly preferable from the viewpoint of conductivity.
The amount of the electrolyte salt added is preferably 0.5 to 5.0 mol, more preferably 1.0 to 4.0 mol, and most preferably 2.0 to 3.0 mol with respect to 1 kg of the hyperbranched polymer.
［高分子電解質前駆体および高分子電解質］
本発明の高分子電解質を製造するにあたって、上述した高分岐ポリマーおよび電解質塩を溶解し、かつ、両成分と反応しない溶媒を用いることが好ましい。
このような溶媒を用い、一旦、溶液状の高分子電解質前駆体を調製し、この前駆体溶液を金属やガラス等の基板に塗布し、これを、例えば、３０〜２００℃で１０分〜６時間程度、加熱・乾燥して本発明の高分子電解質を作製することができるが、本発明の高分子電解質の作製方法はこれに限定されるものではない。
本発明において、上記溶媒は高分子電解質の形成時に加熱等によって除去される。このため、上記溶媒は、高分子電解質にはほとんど含まれていない。[Polymer electrolyte precursor and polymer electrolyte]
In producing the polymer electrolyte of the present invention, it is preferable to use a solvent that dissolves the hyperbranched polymer and the electrolyte salt described above and does not react with both components.
Using such a solvent, a polymer electrolyte precursor in the form of a solution is once prepared, and this precursor solution is applied to a substrate such as metal or glass, and this is applied, for example, at 30 to 200 ° C. for 10 minutes to 6 The polymer electrolyte of the present invention can be produced by heating and drying for about an hour, but the method for producing the polymer electrolyte of the present invention is not limited to this.
In the present invention, the solvent is removed by heating or the like during the formation of the polymer electrolyte. For this reason, the said solvent is hardly contained in the polymer electrolyte.
高分子電解質前駆体を調製する際に用いられる溶媒の割合は、特に限定されるものではないが、得られる高分子電解質の総質量の５〜９５質量％が好ましく、３０〜７０質量％がより好ましく、４０〜６０質量％がより一層好ましい。 The ratio of the solvent used in preparing the polymer electrolyte precursor is not particularly limited, but is preferably 5 to 95% by mass, more preferably 30 to 70% by mass of the total mass of the obtained polymer electrolyte. Preferably, 40 to 60% by mass is even more preferable.
上記高分子電解質前駆体調製に用いられる溶媒としては、上述のとおり、高分岐ポリマーおよび電解質塩を溶解可能、かつ、両成分と反応しない限り、特に限定されることはない。
その具体例としては、ベンゼン、トルエン、キシレン、エチルベンゼン、テトラリン等の芳香族炭化水素系溶媒；ｎ−ヘキサン、ｎ−ヘプタン、ミネラルスピリット、シクロヘキサン等の脂肪族または脂環式炭化水素系溶媒；塩化メチル、臭化メチル、ヨウ化メチル、メチレンジクロライド、クロロホルム、四塩化炭素、トリクロロエチレン、パークロロエチレン、オルトジクロロベンゼン等のハロゲン系溶媒；酢酸エチル、酢酸ブチル、メトキシブチルアセテート、メチルセロソルブアセテート、エチルセロソルブアセテート、プロピレングリコールモノメチルエーテルアセテート等のエステル系またはエステルエーテル系溶媒；ジエチルエーテル、テトラヒドロフラン、１，４−ジオキサン、メチルセロソルブ、エチルセロソルブ、ブチルセロソルブ、プロピレングリコールモノメチルエーテル等のエーテル系溶媒；アセトン、メチルエチルケトン、メチルイソブチルケトン、ジ−ｎ−ブチルケトン、シクロヘキサノン等のケトン系溶媒；メタノール、エタノール、ｎ−プロパノール、イソプロパノール、ｎ−ブタノール、イソブタノール、ｔｅｒｔ−ブタノール、２−エチルヘキシルアルコール、ベンジルアルコール等のアルコール系溶媒；Ｎ，Ｎ−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系溶媒；ジメチルスルホキシド等のスルホキシド系溶媒、Ｎ−メチル−２−ピロリドン等の複素環式化合物系溶媒、およびこれらの２種以上の混合溶媒が挙げられる。As described above, the solvent used for the preparation of the polymer electrolyte precursor is not particularly limited as long as it can dissolve the hyperbranched polymer and the electrolyte salt and does not react with both components.
Specific examples include aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and tetralin; aliphatic or alicyclic hydrocarbon solvents such as n-hexane, n-heptane, mineral spirit, and cyclohexane; Halogen solvents such as methyl, methyl bromide, methyl iodide, methylene dichloride, chloroform, carbon tetrachloride, trichloroethylene, perchloroethylene, orthodichlorobenzene; ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve Ester or ester ether solvents such as acetate and propylene glycol monomethyl ether acetate; diethyl ether, tetrahydrofuran, 1,4-dioxane, methyl cellosolve, ethyl cellosolve, buty Ether solvents such as cellosolve and propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone and cyclohexanone; methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, alcohol solvents such as tert-butanol, 2-ethylhexyl alcohol and benzyl alcohol; amide solvents such as N, N-dimethylformamide and N, N-dimethylacetamide; sulfoxide solvents such as dimethyl sulfoxide, N-methyl-2- Examples include heterocyclic compound solvents such as pyrrolidone, and mixed solvents of two or more of these.
中でも、芳香族炭化水素系溶媒、ハロゲン系溶媒、エステル系溶媒、エーテル系溶媒、ケトン系溶媒、アルコール系溶媒、アミド系溶媒、スルホキシド系溶媒が好ましく、特にトルエン、キシレン、オルトジクロロベンゼン、酢酸ブチル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノメチルエーテル、１，４−ジオキサン、メチルセロソルブ、メチルイソブチルケトン、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミドがより好ましい。 Among them, aromatic hydrocarbon solvents, halogen solvents, ester solvents, ether solvents, ketone solvents, alcohol solvents, amide solvents, sulfoxide solvents are preferable, and toluene, xylene, orthodichlorobenzene, butyl acetate are particularly preferable. , Propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 1,4-dioxane, methyl cellosolve, methyl isobutyl ketone, N, N-dimethylformamide, and N, N-dimethylacetamide are more preferable.
本発明のリチウムポリマー電池は、上述した高分子電解質を用いることに特徴があるため、その他の電池構成部材は任意であり、従来公知の材料や部材から適宜選択して用いればよい。 Since the lithium polymer battery of the present invention is characterized by using the above-described polymer electrolyte, other battery constituent members are arbitrary, and may be appropriately selected from conventionally known materials and members.
以下、実施例および比較例を挙げて、本発明をより具体的に説明するが、本発明は下記の実施例に限定されるものではない。
なお、ポリマーの分子量は下記手法によって測定した。
［ゲル浸透クロマトグラフィー（ＧＰＣ）］
装置：東ソー（株）製 ＨＬＣ−８２２０ＧＰＣ
カラム：Ｓｈｏｄｅｘ ＫＦ−８０４Ｌ、ＫＦ−８０５Ｌ
カラム温度：４０℃
溶媒：テトラヒドロフラン
検出器：ＲＩEXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to the following Example.
The molecular weight of the polymer was measured by the following method.
[Gel permeation chromatography (GPC)]
Device: HLC-8220GPC manufactured by Tosoh Corporation
Column: Shodex KF-804L, KF-805L
Column temperature: 40 ° C
Solvent: Tetrahydrofuran Detector: RI
［１］高分子電解質膜の作製
［実施例１］
国際公開第２０１０／１３７７２４号の実施例８記載の方法で合成した含フッ素高分岐（ハイパーブランチ）ポリマー（Ｍｗ１７，０００，Ｍｗ／Ｍｎ＝２．２、以下、化合物１という）３．０ｇとメチルイソブチルケトン（ＭＩＢＫ）３．０ｇとをサンプル瓶中に秤量し、超音波洗浄器（ＦＵ−６Ｈ、東京硝子機械（株）製）で６０分超音波照射して高分岐ポリマーのＭＩＢＫ溶液を調製した。得られた溶液にＬｉＴＦＳＩ（東京化成工業（株）製）２．６ｇを添加し、ミックスローター（ＭＲＣ−５、ＡＺＯＮＥ社製）で６０分撹拌して溶解させて高分子固体電解質前駆体溶液を得た。得られた前駆体溶液を、ドクターブレード法でアルミニウム板に塗布し、６０℃で３０分加熱した後、１５０℃で３０分再加熱し、高分子固体電解質膜を作製した。
なお、この組成では、ＬｉＴＦＳＩが含フッ素高分岐ポリマー１ｋｇ当たり３．０ｍｏｌ含まれている。[1] Preparation of polymer electrolyte membrane [Example 1]
3.0 g of fluorine-containing highly branched (hyperbranched) polymer (Mw 17,000, Mw / Mn = 2.2, hereinafter referred to as Compound 1) synthesized by the method described in Example 8 of International Publication No. 2010/137724 and methyl Weigh 3.0 g of isobutyl ketone (MIBK) in a sample bottle and prepare a highly branched polymer MIBK solution by ultrasonic irradiation for 60 minutes with an ultrasonic cleaner (FU-6H, manufactured by Tokyo Glass Machinery Co., Ltd.). did. 2.6 g LiTFSI (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the obtained solution, and the mixture was stirred for 60 minutes with a mix rotor (MRC-5, manufactured by AZONE) to dissolve the polymer solid electrolyte precursor solution. Obtained. The obtained precursor solution was applied to an aluminum plate by the doctor blade method, heated at 60 ° C. for 30 minutes, and then reheated at 150 ° C. for 30 minutes to produce a solid polymer electrolyte membrane.
In this composition, LiTFSI is contained in an amount of 3.0 mol per kg of the fluorine-containing highly branched polymer.
［実施例２〜６］
表１に従って、各添加剤、またはその添加量を変更した以外は実施例１と同様の検討を行った。[Examples 2 to 6]
According to Table 1, the same examination as in Example 1 was performed except that each additive or its addition amount was changed.
［比較例１］
ハイパーブランチポリマー３．０ｇの代わりにポリエチレングリコール（ＰＥＧ，平均分子量２０，０００、純正化学（株）製）０．５ｇを用い、ＭＩＢＫの使用量を０．５ｇとして、実施例１の方法に従ってＰＥＧ（平均分子量２０，０００）のＭＩＢＫ溶液を調製した。得られた溶液にＬｉＴＦＳＩ０．３ｇを添加し、ミックスローターで撹拌をしたところ、均一分散（溶解）した段階でゲル化してドクターブレード法でアルミニウム板に塗布可能な前駆体溶液を調製できず、薄膜を作製できなかった。[Comparative Example 1]
In place of 3.0 g of hyperbranched polymer, 0.5 g of polyethylene glycol (PEG, average molecular weight 20,000, manufactured by Junsei Chemical Co., Ltd.) was used, and the amount of MIBK used was 0.5 g. A MIBK solution (average molecular weight 20,000) was prepared. When 0.3g LiTFSI was added to the resulting solution and stirred with a mix rotor, it was gelled when uniformly dispersed (dissolved) and a precursor solution that could be applied to an aluminum plate by the doctor blade method could not be prepared. Could not be made.
［比較例２］
ハイパーブランチポリマー３．０ｇの代わりにＰＥＧ（平均分子量６，０００、純正化学株式会社製）５．０ｇを用い、ＭＩＢＫの使用量を５．０ｇとし、実施例１の方法に従ってＰＥＧ（平均分子量６，０００）のＭＩＢＫ溶液を調製し、さらに、ＬｉＴＦＳＩの使用量を２．９ｇとして、実施例１の方法に従って高分子電解質前駆体溶液を得た。得られた前駆体溶液を用いて、実施例１と同様の方法により、高分子固体電解質膜の作製を試みたが、加熱後も液状のままであり、薄膜を作製できなかった。[Comparative Example 2]
Instead of 3.0 g of hyperbranched polymer, 5.0 g of PEG (average molecular weight 6,000, manufactured by Junsei Chemical Co., Ltd.) was used, the amount of MIBK used was 5.0 g, and PEG (average molecular weight 6) was determined according to the method of Example 1. , 000) MIBK solution was prepared, and the amount of LiTFSI used was 2.9 g. According to the method of Example 1, a polymer electrolyte precursor solution was obtained. Using the obtained precursor solution, an attempt was made to produce a solid polymer electrolyte membrane by the same method as in Example 1. However, the polymer solution remained liquid after heating, and a thin film could not be produced.
※１：国際公開第２０１０／１３７７２４号の実施例４５記載の方法で合成した含フッ素高分岐（ハイパーブランチ）ポリマー（Ｍｗ８，４００，Ｍｗ／Ｍｎ＝２．５、以下、化合物２という）
※２：Macromol. Chem. Phys. 2005, 206, 860−868記載の方法を参考に合成した高分岐（ハイパーブランチ）ポリマー（Ｍｗ１７，０００，Ｍｗ／Ｍｎ＝４．８、以下、化合物３という）
※３：ｍｏｌ／ｋｇ−Ｐは高分岐ポリマー１ｋｇ当たりに含有するＬｉ塩のモル数を示す。* 1: Fluorine-containing hyperbranched polymer (Mw8,400, Mw / Mn = 2.5, hereinafter referred to as Compound 2) synthesized by the method described in Example 45 of International Publication No. 2010/137724
* 2: Hyperbranched polymer synthesized with reference to the method described in Macromol. Chem. Phys. 2005, 206, 860-868 (Mw 17,000, Mw / Mn = 4.8, hereinafter referred to as Compound 3)
* 3: mol / kg-P represents the number of moles of Li salt contained per kg of hyperbranched polymer.
［２］イオン伝導度測定
［実施例７〜１２］
上記実施例１〜６で作製した高分子電解質のイオン伝導度を、下記手法によって測定した。結果を表２に示す。
得られた塗膜の塗布面が互いに接触するように挟み、交流インピーダンス法（ＰＡＲＳＴＡＴ〔登録商標〕２２７３ Ａｄｖａｎｃｅｄ Ｅｌｅｃｔｒｏｃｈｅｍｉｃａｌ Ｓｙｓｔｅｍ、Ｐｒｉｎｃｅｔｏｎ Ａｐｐｌｉｅｄ Ｒｅｓｅａｒｃｈ社製）を用いて、室温（２５℃）でイオン伝導度を測定した。[2] Ionic conductivity measurement [Examples 7 to 12]
The ionic conductivity of the polymer electrolyte prepared in Examples 1-6 was measured by the following method. The results are shown in Table 2.
Using the AC impedance method (PARSTAT (registered trademark) 2273 Advanced Electrochemical System, manufactured by Princeton Applied Research), the ionic conductivity was measured at room temperature (25 ° C.) by sandwiching the coated surfaces of the obtained coating films so as to contact each other. It was measured.
表２に示されるように、平均分子量６，０００のＰＥＧを用いて、実施例１と同様の方法により薄膜の作製を試みたが、焼成しても薄膜を得ることができなかった。また、平均分子量２０，０００のＰＥＧを用いて、実施例１と同様の方法により薄膜の作製を試みたが、そのＭＩＢＫ溶液とＬｉＴＦＳＩとを混合した後の撹拌中に、溶液がゲル化してしまった。これらの結果から、平均分子量６，０００のような低分子量のポリエーテル化合物（平均分子量６，０００のＰＥＧ）を用いても、化合物１〜３を用いた場合と同様の高分子固体電解質膜を作製できず、また、高分子量のポリエーテル化合物（平均分子量２０，０００のＰＥＧ）や分子量２０，０００のＰＥＧよりもさらにゲル化し易いと考えられるポリエーテル化合物（ＰＥＯ）を用いても、化合物１〜３を用いた場合と同様の高分子固体電解質膜を作製できないことが示唆された。
これに対し、化合物１〜３を用いることで、高分子固体電解質膜を作製でき、得られた膜は、１．０×１０-5Ｓ／ｃｍ以上の高イオン伝導度を示した。As shown in Table 2, an attempt was made to produce a thin film by the same method as in Example 1 using PEG having an average molecular weight of 6,000, but the thin film could not be obtained even when baked. In addition, an attempt was made to produce a thin film by the same method as in Example 1 using PEG having an average molecular weight of 20,000, but the solution gelled during the stirring after mixing the MIBK solution and LiTFSI. It was. From these results, even when a low molecular weight polyether compound having an average molecular weight of 6,000 (PEG having an average molecular weight of 6,000) is used, the same polymer solid electrolyte membrane as that in the case of using compounds 1 to 3 is obtained. Even if a polyether compound (PEO) that cannot be prepared and is considered to be more easily gelled than a high molecular weight polyether compound (PEG having an average molecular weight of 20,000) or PEG having a molecular weight of 20,000, compound 1 It was suggested that the same polymer solid electrolyte membrane as in the case of using ~ 3 could not be produced.
On the other hand, a polymer solid electrolyte membrane can be produced by using compounds 1 to 3, and the obtained membrane showed a high ionic conductivity of 1.0 × 10 −5 S / cm or more.
Claims (18)
前記モノマーＡが、ビニル基または（メタ）アクリル基のいずれか一方、または両方を有する化合物であることを特徴とする高分子電解質。 A highly branched polymer, which is a polymer of a monomer component containing monomer A having two or more radically polymerizable double bonds in the molecule, and a polymerization initiator of 5 to 200 mol% with respect to the monomer component; Salt (but not including organic solvent),
The polymer electrolyte, wherein the monomer A is a compound having either one or both of a vinyl group and a (meth) acryl group.
（式中、Ｒ１は、水素原子またはメチル基を表し、Ｒ２は、水酸基で置換されていてもよい、炭素数２〜１２のフルオロアルキル基を表す。） The polymer electrolyte according to claim 7, wherein the monomer B is a compound represented by the following formula (1).
(In the formula, R 1 represents a hydrogen atom or a methyl group, and R 2 represents a C 2-12 fluoroalkyl group which may be substituted with a hydroxyl group.)
（式中、Ｘは、水素原子またはフッ素原子を表し、ｍは、１または２を表し、ｎは、０〜５の整数を表す。Ｒ１は前記と同じ。） The polymer electrolyte according to claim 8, wherein the monomer B is a compound represented by the following formula (2).
(In the formula, X represents a hydrogen atom or a fluorine atom, m represents 1 or 2, n represents an integer of 0 to 5. R 1 is the same as above.)
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| JPH11329064A (en) * | 1998-05-08 | 1999-11-30 | Ricoh Co Ltd | Ion conductive polymer solid electrolyte and battery using the solid electrolyte |
| JP2000030530A (en) * | 1998-07-10 | 2000-01-28 | Toyota Motor Corp | Ion conductive solid electrolyte |
| JP2001181352A (en) * | 1999-12-27 | 2001-07-03 | Kansai Research Institute | Multi-branched polymer, its production method, solid electrolyte and electrochemical element |
| JP2002279827A (en) * | 2001-03-16 | 2002-09-27 | Nippon Polyurethane Ind Co Ltd | Conductive crosslinked body |
| JP2003142160A (en) * | 2001-08-20 | 2003-05-16 | Sumitomo Bakelite Co Ltd | Lithium ion conductive gel-form electrolyte and polymer lithium ion secondary battery |
| WO2010137724A1 (en) * | 2009-05-29 | 2010-12-02 | 日産化学工業株式会社 | Highly branched fluorinated polymer and resin composition containing same |
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| JPH11329064A (en) * | 1998-05-08 | 1999-11-30 | Ricoh Co Ltd | Ion conductive polymer solid electrolyte and battery using the solid electrolyte |
| JP2000030530A (en) * | 1998-07-10 | 2000-01-28 | Toyota Motor Corp | Ion conductive solid electrolyte |
| JP2001181352A (en) * | 1999-12-27 | 2001-07-03 | Kansai Research Institute | Multi-branched polymer, its production method, solid electrolyte and electrochemical element |
| JP2002279827A (en) * | 2001-03-16 | 2002-09-27 | Nippon Polyurethane Ind Co Ltd | Conductive crosslinked body |
| JP2003142160A (en) * | 2001-08-20 | 2003-05-16 | Sumitomo Bakelite Co Ltd | Lithium ion conductive gel-form electrolyte and polymer lithium ion secondary battery |
| WO2010137724A1 (en) * | 2009-05-29 | 2010-12-02 | 日産化学工業株式会社 | Highly branched fluorinated polymer and resin composition containing same |
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