JP2016199428A - Composition having ionic conductivity - Google Patents
Composition having ionic conductivity Download PDFInfo
- Publication number
- JP2016199428A JP2016199428A JP2015080731A JP2015080731A JP2016199428A JP 2016199428 A JP2016199428 A JP 2016199428A JP 2015080731 A JP2015080731 A JP 2015080731A JP 2015080731 A JP2015080731 A JP 2015080731A JP 2016199428 A JP2016199428 A JP 2016199428A
- Authority
- JP
- Japan
- Prior art keywords
- composition
- group
- salts
- ionic liquid
- mass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 111
- 239000002608 ionic liquid Substances 0.000 claims abstract description 90
- 150000001875 compounds Chemical class 0.000 claims description 46
- 238000005259 measurement Methods 0.000 claims description 28
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 13
- 238000003860 storage Methods 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical class NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 125000005392 carboxamide group Chemical group NC(=O)* 0.000 claims description 5
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical class NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical class C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical class C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 4
- 150000003863 ammonium salts Chemical class 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 150000004693 imidazolium salts Chemical class 0.000 claims description 4
- 150000004714 phosphonium salts Chemical class 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical class NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical group OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 3
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 description 31
- 125000000524 functional group Chemical group 0.000 description 28
- -1 halide ions Chemical class 0.000 description 26
- 230000002378 acidificating effect Effects 0.000 description 20
- 238000002156 mixing Methods 0.000 description 14
- 239000000126 substance Substances 0.000 description 14
- 238000002474 experimental method Methods 0.000 description 13
- 239000007787 solid Substances 0.000 description 12
- 239000007788 liquid Substances 0.000 description 11
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 10
- DFPAKSUCGFBDDF-UHFFFAOYSA-N Nicotinamide Chemical group NC(=O)C1=CC=CN=C1 DFPAKSUCGFBDDF-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 230000002441 reversible effect Effects 0.000 description 8
- 230000009974 thixotropic effect Effects 0.000 description 8
- JFZKOODUSFUFIZ-UHFFFAOYSA-N trifluoro phosphate Chemical compound FOP(=O)(OF)OF JFZKOODUSFUFIZ-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 7
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 6
- 239000007983 Tris buffer Substances 0.000 description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 6
- 238000013329 compounding Methods 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 239000003973 paint Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 4
- UYRFPODVSLYSCO-UHFFFAOYSA-N 4-phosphonobutanoic acid Chemical compound OC(=O)CCCP(O)(O)=O UYRFPODVSLYSCO-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- 239000011244 liquid electrolyte Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000003115 supporting electrolyte Substances 0.000 description 4
- 229910021642 ultra pure water Inorganic materials 0.000 description 4
- 239000012498 ultrapure water Substances 0.000 description 4
- YWHZQHRLNXKZNA-UHFFFAOYSA-M 1-ethyl-3-methylimidazol-3-ium;2-(2-methoxyethoxy)ethyl sulfate Chemical compound CC[N+]=1C=CN(C)C=1.COCCOCCOS([O-])(=O)=O YWHZQHRLNXKZNA-UHFFFAOYSA-M 0.000 description 3
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 230000001588 bifunctional effect Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910052809 inorganic oxide Inorganic materials 0.000 description 3
- 230000033001 locomotion Effects 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 235000011837 pasties Nutrition 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- POWFTOSLLWLEBN-UHFFFAOYSA-N tetrasodium;silicate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-][Si]([O-])([O-])[O-] POWFTOSLLWLEBN-UHFFFAOYSA-N 0.000 description 3
- RVEJOWGVUQQIIZ-UHFFFAOYSA-N 1-hexyl-3-methylimidazolium Chemical compound CCCCCCN1C=C[N+](C)=C1 RVEJOWGVUQQIIZ-UHFFFAOYSA-N 0.000 description 2
- 229910018512 Al—OH Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-L Oxalate Chemical compound [O-]C(=O)C([O-])=O MUBZPKHOEPUJKR-UHFFFAOYSA-L 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004455 differential thermal analysis Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(iii) oxide Chemical compound O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229920000592 inorganic polymer Polymers 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000002071 nanotube Substances 0.000 description 2
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000005518 polymer electrolyte Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000012719 thermal polymerization Methods 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- ZIKATJAYWZUJPY-UHFFFAOYSA-N thulium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Tm+3].[Tm+3] ZIKATJAYWZUJPY-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- PYVOHVLEZJMINC-UHFFFAOYSA-N trihexyl(tetradecyl)phosphanium Chemical compound CCCCCCCCCCCCCC[P+](CCCCCC)(CCCCCC)CCCCCC PYVOHVLEZJMINC-UHFFFAOYSA-N 0.000 description 2
- GWENLLRIMBJBRA-NSCUHMNNSA-N (e)-4-amino-3-methyl-4-oxobut-2-enoic acid Chemical compound NC(=O)C(/C)=C/C(O)=O GWENLLRIMBJBRA-NSCUHMNNSA-N 0.000 description 1
- FSQQTNAZHBEJLS-OWOJBTEDSA-N (e)-4-amino-4-oxobut-2-enoic acid Chemical compound NC(=O)\C=C\C(O)=O FSQQTNAZHBEJLS-OWOJBTEDSA-N 0.000 description 1
- GWENLLRIMBJBRA-IHWYPQMZSA-N (z)-4-amino-3-methyl-4-oxobut-2-enoic acid Chemical compound NC(=O)C(/C)=C\C(O)=O GWENLLRIMBJBRA-IHWYPQMZSA-N 0.000 description 1
- WLQRTXOOEGUPJY-UHFFFAOYSA-M 1,3-dimethylimidazol-1-ium;trifluoromethanesulfonate Chemical compound CN1C=C[N+](C)=C1.[O-]S(=O)(=O)C(F)(F)F WLQRTXOOEGUPJY-UHFFFAOYSA-M 0.000 description 1
- PXELHGDYRQLRQO-UHFFFAOYSA-N 1-butyl-1-methylpyrrolidin-1-ium Chemical compound CCCC[N+]1(C)CCCC1 PXELHGDYRQLRQO-UHFFFAOYSA-N 0.000 description 1
- XHCDOFZBVYGCFK-UHFFFAOYSA-M 1-butyl-1-methylpyrrolidin-1-ium;2,2,2-trifluoroacetate Chemical compound [O-]C(=O)C(F)(F)F.CCCC[N+]1(C)CCCC1 XHCDOFZBVYGCFK-UHFFFAOYSA-M 0.000 description 1
- BOOXKGZZTBKJFE-UHFFFAOYSA-M 1-butyl-1-methylpyrrolidin-1-ium;chloride Chemical compound [Cl-].CCCC[N+]1(C)CCCC1 BOOXKGZZTBKJFE-UHFFFAOYSA-M 0.000 description 1
- WZJDNKTZWIOOJE-UHFFFAOYSA-M 1-butyl-1-methylpyrrolidin-1-ium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.CCCC[N+]1(C)CCCC1 WZJDNKTZWIOOJE-UHFFFAOYSA-M 0.000 description 1
- BKBMVPFAQIFUHM-UHFFFAOYSA-M 1-butyl-3,4-dimethylpyridin-1-ium;chloride Chemical compound [Cl-].CCCC[N+]1=CC=C(C)C(C)=C1 BKBMVPFAQIFUHM-UHFFFAOYSA-M 0.000 description 1
- WMAXAGIQZLTOTA-UHFFFAOYSA-M 1-butyl-3,5-dimethylpyridin-1-ium;chloride Chemical compound [Cl-].CCCC[N+]1=CC(C)=CC(C)=C1 WMAXAGIQZLTOTA-UHFFFAOYSA-M 0.000 description 1
- QPDGLRRWSBZCHP-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;2,2,2-trifluoroacetate Chemical compound [O-]C(=O)C(F)(F)F.CCCC[N+]=1C=CN(C)C=1 QPDGLRRWSBZCHP-UHFFFAOYSA-M 0.000 description 1
- KYCQOKLOSUBEJK-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;bromide Chemical compound [Br-].CCCCN1C=C[N+](C)=C1 KYCQOKLOSUBEJK-UHFFFAOYSA-M 0.000 description 1
- FHDQNOXQSTVAIC-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;chloride Chemical compound [Cl-].CCCCN1C=C[N+](C)=C1 FHDQNOXQSTVAIC-UHFFFAOYSA-M 0.000 description 1
- MEMNKNZDROKJHP-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;methyl sulfate Chemical compound COS([O-])(=O)=O.CCCCN1C=C[N+](C)=C1 MEMNKNZDROKJHP-UHFFFAOYSA-M 0.000 description 1
- KIDIBVPFLKLKAH-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;octyl sulfate Chemical compound CCCCN1C=C[N+](C)=C1.CCCCCCCCOS([O-])(=O)=O KIDIBVPFLKLKAH-UHFFFAOYSA-M 0.000 description 1
- PHCASOSWUQOQAG-UHFFFAOYSA-M 1-butyl-3-methylpyridin-1-ium;chloride Chemical compound [Cl-].CCCC[N+]1=CC=CC(C)=C1 PHCASOSWUQOQAG-UHFFFAOYSA-M 0.000 description 1
- UWVZAZVPOZTKNM-UHFFFAOYSA-M 1-butyl-4-methylpyridin-1-ium;bromide Chemical compound [Br-].CCCC[N+]1=CC=C(C)C=C1 UWVZAZVPOZTKNM-UHFFFAOYSA-M 0.000 description 1
- YTSDTJNDMGOTFN-UHFFFAOYSA-M 1-butyl-4-methylpyridin-1-ium;chloride Chemical compound [Cl-].CCCC[N+]1=CC=C(C)C=C1 YTSDTJNDMGOTFN-UHFFFAOYSA-M 0.000 description 1
- POKOASTYJWUQJG-UHFFFAOYSA-M 1-butylpyridin-1-ium;chloride Chemical compound [Cl-].CCCC[N+]1=CC=CC=C1 POKOASTYJWUQJG-UHFFFAOYSA-M 0.000 description 1
- BEFWDPZVLOCGRP-UHFFFAOYSA-M 1-butylpyridin-1-ium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.CCCC[N+]1=CC=CC=C1 BEFWDPZVLOCGRP-UHFFFAOYSA-M 0.000 description 1
- IRGDPGYNHSIIJJ-UHFFFAOYSA-N 1-ethyl-2,3-dimethylimidazol-3-ium Chemical compound CCN1C=C[N+](C)=C1C IRGDPGYNHSIIJJ-UHFFFAOYSA-N 0.000 description 1
- GITMVCYKHULLDM-UHFFFAOYSA-M 1-ethyl-2,3-dimethylimidazol-3-ium;bromide Chemical compound [Br-].CCN1C=C[N+](C)=C1C GITMVCYKHULLDM-UHFFFAOYSA-M 0.000 description 1
- NUJYCYLTUXYHQU-UHFFFAOYSA-M 1-ethyl-2,3-dimethylimidazol-3-ium;chloride Chemical compound [Cl-].CCN1C=C[N+](C)=C1C NUJYCYLTUXYHQU-UHFFFAOYSA-M 0.000 description 1
- IBZJNLWLRUHZIX-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole Chemical compound CCN1CN(C)C=C1 IBZJNLWLRUHZIX-UHFFFAOYSA-N 0.000 description 1
- JOKVYNJKBRLDAT-UHFFFAOYSA-M 1-ethyl-3-methylimidazol-3-ium;2,2,2-trifluoroacetate Chemical compound [O-]C(=O)C(F)(F)F.CC[N+]=1C=CN(C)C=1 JOKVYNJKBRLDAT-UHFFFAOYSA-M 0.000 description 1
- HXMUPILCYSJMLQ-UHFFFAOYSA-M 1-ethyl-3-methylimidazol-3-ium;4-methylbenzenesulfonate Chemical compound CC[N+]=1C=CN(C)C=1.CC1=CC=C(S([O-])(=O)=O)C=C1 HXMUPILCYSJMLQ-UHFFFAOYSA-M 0.000 description 1
- GWQYPLXGJIXMMV-UHFFFAOYSA-M 1-ethyl-3-methylimidazol-3-ium;bromide Chemical compound [Br-].CCN1C=C[N+](C)=C1 GWQYPLXGJIXMMV-UHFFFAOYSA-M 0.000 description 1
- BXSDLSWVIAITRQ-UHFFFAOYSA-M 1-ethyl-3-methylimidazol-3-ium;methyl sulfate Chemical compound COS([O-])(=O)=O.CCN1C=C[N+](C)=C1 BXSDLSWVIAITRQ-UHFFFAOYSA-M 0.000 description 1
- VASPYXGQVWPGAB-UHFFFAOYSA-M 1-ethyl-3-methylimidazol-3-ium;thiocyanate Chemical compound [S-]C#N.CCN1C=C[N+](C)=C1 VASPYXGQVWPGAB-UHFFFAOYSA-M 0.000 description 1
- ZPTRYWVRCNOTAS-UHFFFAOYSA-M 1-ethyl-3-methylimidazol-3-ium;trifluoromethanesulfonate Chemical compound CC[N+]=1C=CN(C)C=1.[O-]S(=O)(=O)C(F)(F)F ZPTRYWVRCNOTAS-UHFFFAOYSA-M 0.000 description 1
- BMQZYMYBQZGEEY-UHFFFAOYSA-M 1-ethyl-3-methylimidazolium chloride Chemical compound [Cl-].CCN1C=C[N+](C)=C1 BMQZYMYBQZGEEY-UHFFFAOYSA-M 0.000 description 1
- ABFDKXBSQCTIKH-UHFFFAOYSA-M 1-ethylpyridin-1-ium;bromide Chemical compound [Br-].CC[N+]1=CC=CC=C1 ABFDKXBSQCTIKH-UHFFFAOYSA-M 0.000 description 1
- AMFMJCAPWCXUEI-UHFFFAOYSA-M 1-ethylpyridin-1-ium;chloride Chemical compound [Cl-].CC[N+]1=CC=CC=C1 AMFMJCAPWCXUEI-UHFFFAOYSA-M 0.000 description 1
- NJRCNTQXAQBYBY-UHFFFAOYSA-M 1-hexadecyl-2,3-dimethylimidazol-3-ium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCN1C=C[N+](C)=C1C NJRCNTQXAQBYBY-UHFFFAOYSA-M 0.000 description 1
- ZCPPLZJPPBIWRU-UHFFFAOYSA-M 1-hexadecyl-3-methylimidazol-3-ium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCN1C=C[N+](C)=C1 ZCPPLZJPPBIWRU-UHFFFAOYSA-M 0.000 description 1
- NUTXZTVTZOEIEY-UHFFFAOYSA-M 1-hexyl-1-methylpyrrolidin-1-ium;chloride Chemical compound [Cl-].CCCCCC[N+]1(C)CCCC1 NUTXZTVTZOEIEY-UHFFFAOYSA-M 0.000 description 1
- NCTQEXWJEPRHLV-UHFFFAOYSA-M 1-hexyl-2,3-dimethylimidazol-3-ium;chloride Chemical compound [Cl-].CCCCCCN1C=C[N+](C)=C1C NCTQEXWJEPRHLV-UHFFFAOYSA-M 0.000 description 1
- NKRASMXHSQKLHA-UHFFFAOYSA-M 1-hexyl-3-methylimidazolium chloride Chemical compound [Cl-].CCCCCCN1C=C[N+](C)=C1 NKRASMXHSQKLHA-UHFFFAOYSA-M 0.000 description 1
- QFAUKQKOJVLHEL-UHFFFAOYSA-M 1-hexylpyridin-1-ium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.CCCCCC[N+]1=CC=CC=C1 QFAUKQKOJVLHEL-UHFFFAOYSA-M 0.000 description 1
- LNMCPMPHEHNPRY-UHFFFAOYSA-M 1-methyl-1-octylpyrrolidin-1-ium;chloride Chemical compound [Cl-].CCCCCCCC[N+]1(C)CCCC1 LNMCPMPHEHNPRY-UHFFFAOYSA-M 0.000 description 1
- MMJMYYUZGLJBST-UHFFFAOYSA-N 1-methyl-3-octadecylimidazol-1-ium Chemical compound CCCCCCCCCCCCCCCCCCN1C=C[N+](C)=C1 MMJMYYUZGLJBST-UHFFFAOYSA-N 0.000 description 1
- IDXFCXOPTUHTKE-UHFFFAOYSA-M 1-methyl-3-octylimidazol-1-ium;octyl sulfate Chemical compound CCCCCCCCOS([O-])(=O)=O.CCCCCCCC[N+]=1C=CN(C)C=1 IDXFCXOPTUHTKE-UHFFFAOYSA-M 0.000 description 1
- WGHMGICKLQSEIA-UHFFFAOYSA-M 1-methyl-3-octylimidazol-1-ium;trifluoroborane;fluoride Chemical compound [F-].FB(F)F.CCCCCCCCN1C=C[N+](C)=C1 WGHMGICKLQSEIA-UHFFFAOYSA-M 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- OVIYAWWBKPWUOH-UHFFFAOYSA-M 1-octylpyridin-1-ium;chloride Chemical compound [Cl-].CCCCCCCC[N+]1=CC=CC=C1 OVIYAWWBKPWUOH-UHFFFAOYSA-M 0.000 description 1
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- 238000001704 evaporation Methods 0.000 description 1
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- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
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- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 1
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- FSQQTNAZHBEJLS-UPHRSURJSA-N maleamic acid Chemical compound NC(=O)\C=C/C(O)=O FSQQTNAZHBEJLS-UPHRSURJSA-N 0.000 description 1
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- 150000002739 metals Chemical class 0.000 description 1
- OEDJAKMCWJUAHH-UHFFFAOYSA-M methyl(trioctyl)azanium;2,2,2-trifluoroacetate Chemical compound [O-]C(=O)C(F)(F)F.CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC OEDJAKMCWJUAHH-UHFFFAOYSA-M 0.000 description 1
- WYNCDLDEWVNKJX-UHFFFAOYSA-M methyl(trioctyl)azanium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC WYNCDLDEWVNKJX-UHFFFAOYSA-M 0.000 description 1
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- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- UZLYXNNZYFBAQO-UHFFFAOYSA-N oxygen(2-);ytterbium(3+) Chemical compound [O-2].[O-2].[O-2].[Yb+3].[Yb+3] UZLYXNNZYFBAQO-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- PTMHPRAIXMAOOB-UHFFFAOYSA-N phosphoramidic acid Chemical compound NP(O)(O)=O PTMHPRAIXMAOOB-UHFFFAOYSA-N 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 1
- UKDIAJWKFXFVFG-UHFFFAOYSA-N potassium;oxido(dioxo)niobium Chemical compound [K+].[O-][Nb](=O)=O UKDIAJWKFXFVFG-UHFFFAOYSA-N 0.000 description 1
- 229910003447 praseodymium oxide Inorganic materials 0.000 description 1
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- 230000008569 process Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium oxide Chemical compound O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- JDVPQXZIJDEHAN-UHFFFAOYSA-N succinamic acid Chemical compound NC(=O)CCC(O)=O JDVPQXZIJDEHAN-UHFFFAOYSA-N 0.000 description 1
- RVKZDIDATLDTNR-UHFFFAOYSA-N sulfanylideneeuropium Chemical compound [Eu]=S RVKZDIDATLDTNR-UHFFFAOYSA-N 0.000 description 1
- 125000000565 sulfonamide group Chemical group 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- 229910003451 terbium oxide Inorganic materials 0.000 description 1
- SCRZPWWVSXWCMC-UHFFFAOYSA-N terbium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Tb+3].[Tb+3] SCRZPWWVSXWCMC-UHFFFAOYSA-N 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- JCQGIZYNVAZYOH-UHFFFAOYSA-M trihexyl(tetradecyl)phosphanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[P+](CCCCCC)(CCCCCC)CCCCCC JCQGIZYNVAZYOH-UHFFFAOYSA-M 0.000 description 1
- LAGQNGWYNLUQRI-UHFFFAOYSA-N trioctylmethylammonium bis(trifluoromethylsulfonyl)imide Chemical compound FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F.CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC LAGQNGWYNLUQRI-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 229910003454 ytterbium oxide Inorganic materials 0.000 description 1
- 229940075624 ytterbium oxide Drugs 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
Description
本発明は、イオン伝導性を有する組成物に関する。 The present invention relates to a composition having ion conductivity.
イオン伝導素材は電池を始めとする幅広い工業技術に関わっている。広く用いられているイオン伝導素材としては、例えば、特許文献１に開示されるような液体系電解質が挙げられる。しかし、液体系電解質は、その多くが有機溶媒を用いているため、電池等への応用の際に、引火・爆発などが懸念される。また、液状であるため、金属等での封止が必要となり加工性が低く軽量化も困難であった。このような液体系電解質に代わり、固体系電解質が開発されつつある。その例としては、特許文献２及び非特許文献１に開示されるような高分子電解質が挙げられる。係る高分子電解質は、引火・漏えいしにくく加工性も高いという一方で、液体系電解質に比較してイオン伝導度は必ずしも十分でない。 Ion conductive materials are involved in a wide range of industrial technologies, including batteries. Examples of widely used ion conductive materials include liquid electrolytes as disclosed in Patent Document 1. However, since many liquid electrolytes use an organic solvent, there is a concern about ignition, explosion, etc. when applied to batteries. Moreover, since it is liquid, sealing with a metal etc. was needed, and workability was low and weight reduction was difficult. Instead of such liquid electrolytes, solid electrolytes are being developed. Examples thereof include polymer electrolytes as disclosed in Patent Document 2 and Non-Patent Document 1. Such a polymer electrolyte is not easily ignited or leaked and has high workability, but its ionic conductivity is not always sufficient as compared with a liquid electrolyte.
近年、高いイオン伝導性を持つイオン伝導素材として、イオン液体（以下ＩＬと略する場合がある。）が注目されている（特許文献３及び非特許文献２参照）。イオン液体は、イオンのみから成る塩の一種でありながら、分子の大きさ及び弱いイオン間相互作用のため、室温付近でも液体の状態をとる物質である。さらに、イオン液体は、（１）不揮発性、（２）高いイオン伝導性、（３）広い液相温度域を有する、という特徴を有しており、イオン伝導素材として期待されている。イオン液体においても、液体であるが故、加工性等は十分でなく、係る観点から、固体化が望まれている。固体化を試みた例として、例えば、特許文献４及び非特許文献３等に、構成イオンそのものを高分子化することが開示されている。 In recent years, an ionic liquid (hereinafter sometimes abbreviated as IL) has been attracting attention as an ion conductive material having high ion conductivity (see Patent Document 3 and Non-Patent Document 2). An ionic liquid is a kind of salt composed only of ions, but is a substance that takes a liquid state even near room temperature due to the size of molecules and the interaction between weak ions. Furthermore, the ionic liquid has the characteristics of (1) non-volatility, (2) high ionic conductivity, and (3) a wide liquidus temperature range, and is expected as an ionic conductive material. Since the ionic liquid is also a liquid, the processability and the like are not sufficient, and solidification is desired from this viewpoint. As an example of attempts to solidify, for example, Patent Document 4 and Non-Patent Document 3 disclose that constituent ions themselves are polymerized.
しかしながら、特許文献４等に開示された技術によって、イオン液体を構成するイオンを高分子化すると、液体としての流動性は抑制できるものの、構成イオンの分子運動が阻害されてしまい、イオン伝導性が低下するという課題があった。 However, if the ions constituting the ionic liquid are polymerized by the technique disclosed in Patent Document 4 and the like, the fluidity as the liquid can be suppressed, but the molecular motion of the constituent ions is inhibited, and the ionic conductivity is reduced. There was a problem of a decrease.
ところで、発明者らは、イモゴライト（以下ＩＧと記すことがある。）を、水及び水溶性モノマーを含む溶媒中に分散させて、係る水溶性モノマーを重合させて得られる重合体であって、イモゴライトに網目構造を取らせることにより、重合体の力学的強度が向上できることを見出している（特開２０１３−２１３０８６号公報等）。 By the way, the inventors are a polymer obtained by dispersing imogolite (hereinafter sometimes referred to as IG) in a solvent containing water and a water-soluble monomer, and polymerizing the water-soluble monomer, It has been found that the mechanical strength of a polymer can be improved by allowing imogolite to take a network structure (JP 2013-213086 A, etc.).
イモゴライトは、アルミニウムとケイ素からなるナノチューブ状無機高分子である。イモゴライト（ＩＧ）の外形形状は、長さが数十ｎｍ〜数μｍ、外径が２ｎｍ〜３ｎｍと、高いアスペクト比を有している。また、ＩＧの表面には、多数の水酸基が存在するため、水を始めとした溶媒に容易に分散することができる。 Imogolite is a nanotube-like inorganic polymer made of aluminum and silicon. The outer shape of imogolite (IG) has a high aspect ratio with a length of several tens nm to several μm and an outer diameter of 2 nm to 3 nm. Moreover, since many hydroxyl groups exist on the surface of IG, it can be easily dispersed in a solvent such as water.
このようなイモゴライトは、媒体中で分散された場合に、可逆的な網目構造を取ることができる。そのため、液体中で網目構造を取る場合には、粘度を上昇させたり、擬塑性（チクソトロピー性）を付与することができ、例えば、流動時の流動性を確保したまま、静置時の液体の流動性を低下させることを期待できる。 Such imogolite can take a reversible network structure when dispersed in a medium. Therefore, when taking a network structure in the liquid, the viscosity can be increased or pseudoplasticity (thixotropic property) can be imparted. For example, while the fluidity at the time of fluidization is secured, It can be expected to reduce the fluidity.
本発明の幾つかの態様に係る目的の一つは、イオン液体の高いイオン伝導性を維持するとともに優れた流動特性を有する、イオン伝導性の組成物を提供することにある。 One of the objects according to some embodiments of the present invention is to provide an ion conductive composition that maintains high ionic conductivity of the ionic liquid and has excellent flow characteristics.
本発明は、上記課題の少なくとも一部を解決するために為されたものであり、以下の態様又は適用例として実現することができる。 SUMMARY An advantage of some aspects of the invention is to solve at least a part of the problems described above, and the invention can be implemented as the following aspects or application examples.
［適用例１］本発明に係る組成物の一態様は、
平均長さが１μｍ以上１０μｍ以下のイモゴライトと、
イオン液体と、
を含み、イオン伝導性を有する。
[Application Example 1] One aspect of the composition according to the present invention is:
Imogolite having an average length of 1 μm to 10 μm;
An ionic liquid,
And has ion conductivity.
本適用例の組成物によれば、イモゴライトの平均長さが１μｍ以上１０μｍ以下であるため、イオン液体中で複数のイモゴライトが接触しやすく、及び／又は、絡み合いやすい。これにより、イモゴライトの可逆的な網目構造が組成物中に形成される結果、本適用例の組成物は、イオン液体の高いイオン伝導性を維持できるとともに、静置時の流動性が低く、かつ、流動時の流動性が高いという、優れた流動特性を呈することができる。したがって、電池や導電塗料等への適用の際に、加工性が良好である。 According to the composition of this application example, since the average length of imogolite is 1 μm or more and 10 μm or less, a plurality of imogolites are easily contacted and / or easily entangled in the ionic liquid. As a result, a reversible network structure of imogolite is formed in the composition. As a result, the composition of this application example can maintain the high ionic conductivity of the ionic liquid, and has low fluidity during standing, and The fluidity at the time of fluidity is high, and excellent fluidity can be exhibited. Therefore, workability is good when applied to batteries, conductive paints, and the like.
［適用例２］適用例１において、
前記組成物は、動的粘弾性測定において、損失弾性率Ｇ”が貯蔵弾性率Ｇ’よりも小さくなるせん断ひずみの領域を有してもよい。
[Application Example 2] In Application Example 1,
The composition may have a shear strain region in which the loss elastic modulus G ″ is smaller than the storage elastic modulus G ′ in the dynamic viscoelasticity measurement.
本適用例の組成物は、損失弾性率Ｇ”が貯蔵弾性率Ｇ’よりも小さくなるせん断ひずみの領域を有する結果、成型時の良好な流動性と、成形後の良好な粘性を示すことができる。したがって、電池や導電塗料等への適用の際に、加工性が良好である。 The composition of this application example has a shear strain region in which the loss elastic modulus G ″ is smaller than the storage elastic modulus G ′, and as a result, exhibits good fluidity during molding and good viscosity after molding. Therefore, the processability is good when applied to batteries, conductive paints, and the like.
［適用例３］本発明に係る組成物の一態様は、
平均長さが５０ｎｍ以上１０μｍ以下のイモゴライトと、
イオン液体と、
多官能性化合物と、
を含み、イオン伝導性を有する。
[Application Example 3] One aspect of the composition according to the present invention is:
Imogolite having an average length of 50 nm to 10 μm,
An ionic liquid,
A polyfunctional compound;
And has ion conductivity.
本適用例の組成物によれば、イモゴライトの平均長さが５０ｎｍ以上１０μｍ以下であり、かつ、多官能性化合物を含むため、イオン液体中で複数のイモゴライト間を可逆的に架橋することができる。これにより、イモゴライト及び多官能性化合物により、可逆的な網目構造が組成物中に形成される結果、本適用例の組成物は、イオン液体の高いイオン伝導性を維持できるとともに、擬塑性（チクソトロピー性）を呈することができ、優れた流動特性を有する。したがって、電池や導電塗料等への適用の際に、加工性が良好である。 According to the composition of this application example, since the average length of imogolite is 50 nm or more and 10 μm or less and contains a polyfunctional compound, a plurality of imogolites can be reversibly crosslinked in an ionic liquid. . As a result, a reversible network structure is formed in the composition by the imogolite and the polyfunctional compound. As a result, the composition of this application example can maintain high ionic conductivity of the ionic liquid, and is also pseudoplastic (thixotropic). Property) and excellent flow characteristics. Therefore, workability is good when applied to batteries, conductive paints, and the like.
［適用例４］適用例３において、
前記組成物は、動的粘弾性測定において、損失弾性率Ｇ”の値と貯蔵弾性率Ｇ’の値とが、逆転するせん断ひずみの領域を有してもよい。
[Application Example 4] In Application Example 3,
In the dynamic viscoelasticity measurement, the composition may have a shear strain region in which the value of the loss modulus G ″ and the value of the storage modulus G ′ are reversed.
本適用例の組成物は、損失弾性率Ｇ”の値と貯蔵弾性率Ｇ’の値とが、逆転するせん断ひずみの領域を有する結果、良好なチクソトロピー性を示すことができる。したがって、電池や導電塗料等への適用の際に、加工性が良好である。 The composition of this application example can exhibit good thixotropy as a result of having a shear strain region in which the value of the loss elastic modulus G ″ and the value of the storage elastic modulus G ′ are reversed. Workability is good when applied to conductive paints.
［適用例５］適用例３又は適用例４において、
前記多官能性化合物は、二官能性有機酸であってもよい。
[Application Example 5] In Application Example 3 or Application Example 4,
The polyfunctional compound may be a bifunctional organic acid.
本適用例の組成物によれば、イオン液体中で複数のイモゴライト間を、より効率的に可逆的に架橋することができる。 According to the composition of this application example, a plurality of imogolites can be more efficiently and reversibly cross-linked in the ionic liquid.
［適用例６］適用例３ないし適用例５のいずれか一例において、
前記多官能性化合物は、
炭素数２以上６以下の化合物であって、
カルボキシル基、リン酸基、リン酸基、亜リン酸基、ホスホン酸基、スルホン酸基及び硫酸基から選択される少なくとも一種の基と、
アミノ基及びカルボキサミド基から選択される少なくとも一種の基と、
を含んでもよい。
[Application Example 6] In any one of Application Examples 3 to 5,
The polyfunctional compound is
A compound having 2 to 6 carbon atoms,
At least one group selected from a carboxyl group, a phosphoric acid group, a phosphoric acid group, a phosphorous acid group, a phosphonic acid group, a sulfonic acid group, and a sulfuric acid group;
At least one group selected from an amino group and a carboxamide group;
May be included.
本適用例の組成物によれば、イオン液体中で複数のイモゴライト間を、より効率的に可逆的に架橋することができる。 According to the composition of this application example, a plurality of imogolites can be more efficiently and reversibly cross-linked in the ionic liquid.
［適用例７］適用例３ないし適用例６のいずれか一例において、
前記多官能性化合物は、全質量に対して０．５質量％以上４．２質量％以下含まれてもよい。
[Application Example 7] In any one of Application Examples 3 to 6,
The polyfunctional compound may be contained in an amount of 0.5% by mass to 4.2% by mass with respect to the total mass.
本適用例の組成物によれば、イオン液体中で複数のイモゴライト間を、より効率的に可逆的に架橋することができる。 According to the composition of this application example, a plurality of imogolites can be more efficiently and reversibly cross-linked in the ionic liquid.
［適用例８］適用例１ないし適用例７のいずれか一例において、
前記イモゴライトは、全質量に対して２質量％以上１０質量％以下含まれてもよい。
[Application Example 8] In any one of Application Examples 1 to 7,
The imogolite may be contained in an amount of 2% by mass to 10% by mass with respect to the total mass.
本適用例の組成物によれば、イオン液体中で複数のイモゴライトがより接触しやすく、又は、複数のイモゴライト間を可逆的により架橋しやすい。これにより、さらに優れた流動特性を示すことができる。 According to the composition of this application example, the plurality of imogolites are more likely to come into contact with each other in the ionic liquid, or the plurality of imogolites are easily reversibly crosslinked. Thereby, the further outstanding flow characteristic can be shown.
［適用例９］適用例１ないし適用例８のいずれか一例において、
前記イオン液体は、イミダゾリウム塩、ピリジニウム塩、ピロリジニウム塩、ホスホニウム塩、アンモニウム塩、グアニジニウム塩、イソウロニウム塩及びイソチオウロニウム塩から選択される少なくとも一種であってもよい。
[Application Example 9] In any one of Application Examples 1 to 8,
The ionic liquid may be at least one selected from imidazolium salts, pyridinium salts, pyrrolidinium salts, phosphonium salts, ammonium salts, guanidinium salts, isouronium salts, and isothiouronium salts.
本適用例の組成物によれば、さらに優れたイオン伝導性を呈することができる。 According to the composition of this application example, further excellent ion conductivity can be exhibited.
以下に本発明の幾つかの実施形態について説明する。以下に説明する実施形態は、本発明の例を説明するものである。本発明は以下の実施形態になんら限定されるものではなく、本発明の要旨を変更しない範囲において実施される各種の変形形態も含む。なお以下に説明される構成の全てが本発明の必須の構成であるとは限らない。 Several embodiments of the present invention will be described below. The embodiments described below illustrate examples of the present invention. The present invention is not limited to the following embodiments, and includes various modified embodiments that are implemented within a range that does not change the gist of the present invention. Note that not all of the configurations described below are essential configurations of the present invention.
本発明に係る組成物は、イオン伝導性を有する。本発明に係る組成物の第１の実施形態では、平均長さが１μｍ以上１０μｍ以下のイモゴライトと、イオン液体と、を含む。また、本発明に係る組成物の第２の実施形態では、平均長さが５０ｎｍ以上１０μｍ以下のイモゴライトと、イオン液体と、多官能性化合物と、を含む。以下、本発明の実施形態の例として、第１実施形態及び第２実施形態について順に説明する。 The composition according to the present invention has ionic conductivity. In the first embodiment of the composition according to the present invention, imogolite having an average length of 1 μm or more and 10 μm or less and an ionic liquid are included. Moreover, in 2nd Embodiment of the composition based on this invention, the average length contains 50 nm or more and 10 micrometer or less imogolite, an ionic liquid, and a polyfunctional compound. Hereinafter, as an example of an embodiment of the present invention, a first embodiment and a second embodiment will be described in order.
１．第１実施形態
本実施形態の組成物は、平均長さが１μｍ以上１０μｍ以下のイモゴライトと、イオン液体と、を含む。
1. 1st Embodiment The composition of this embodiment contains the imogolite whose average length is 1 micrometer or more and 10 micrometers or less, and an ionic liquid.
１．１．イモゴライト
イモゴライト（Imogolite）（以下「ＩＧ」と記すことがある。)は、基本単位（ＯＨ）３Ａｌ２Ｏ３ＳｉＯで構成される円筒状無機高分子であり、塩化アルミニウムとオルトケイ酸ナトリウムとを、適当なｐＨ条件下において熱重合することにより得ることができる（図１；V.C.Farmeretal.,J.Chem.Soc.Chem.Comm.,1977,13,462）。なお、ＩＧの化学組成式は、Ａｌ２ＳｉＯ３（ＯＨ）４とも表され得るが、分析等により測定される組成は、係る組成式から多少ずれる場合もある。
1.1. Imogolite Imogolite (hereinafter sometimes referred to as “IG”) is a cylindrical inorganic polymer composed of the basic unit (OH) 3 Al 2 O 3 SiO, and contains aluminum chloride and sodium orthosilicate. It can be obtained by thermal polymerization under suitable pH conditions (FIG. 1; VCFarmeretal., J. Chem. Soc. Chem. Comm., 1977, 13, 462). The chemical composition formula of IG can also be expressed as Al 2 SiO 3 (OH) 4 , but the composition measured by analysis or the like may deviate somewhat from the composition formula.
ＩＧは、円筒の長さは百ｎｍ〜数十μｍ、円筒の外径は２ｎｍ〜２．５ｎｍ、円筒の内径は約１ｎｍの剛直円筒状分子であることが報告されている（N.Donkaietal.,Macromol.Chem.1985,186,2623）。すなわち、ＩＧは、非常に高いアスペクト比を有している。また、ＩＧの円筒の外側の面には、Ａｌ−ＯＨ基が、円筒の内側の面には、Ｓｉ−ＯＨ基がそれぞれ配置されている。このようなＩＧは、水系溶媒に分散される際、水系溶媒のｐＨに依存してその分散性が変化する。例えば、酸性及び中性の条件では、単一フィラメント状や細い束状に分散する。また、塩基性の条件では、太い束状に分散する場合や、ネットワークを形成する場合があることが報告されている（J.Karube,ClaysClayMiner.1998,46(5),583）。 It is reported that IG is a rigid cylindrical molecule having a cylinder length of 100 nm to several tens of μm, a cylinder outer diameter of 2 nm to 2.5 nm, and a cylinder inner diameter of about 1 nm (N. Donkaietal. Macromol. Chem. 1985, 186, 2623). That is, IG has a very high aspect ratio. Further, an Al—OH group is arranged on the outer surface of the cylinder of the IG, and an Si—OH group is arranged on the inner surface of the cylinder. When such IG is dispersed in an aqueous solvent, its dispersibility changes depending on the pH of the aqueous solvent. For example, under acidic and neutral conditions, it is dispersed in the form of a single filament or a thin bundle. In addition, it has been reported that, under basic conditions, a thick bundle may be dispersed or a network may be formed (J. Karube, ClaysClayMiner. 1998, 46 (5), 583).
本実施形態におけるＩＧは、平均長さが１μｍ以上１０μｍ以下である。ＩＧの平均長さは、例えば、ボールミル、ビーズミル、ジェットミル及び／又は超音波破砕等により、調節することができる。これらの中でも、ＩＧを適宜の溶媒や後述するイオン液体に分散させて、超音波を照射することによって調節すると、ＩＧの長さの分布を比較的小さくできるため、より好ましい。なおここで、ＩＧの平均長さとは、数平均長さであり、長さの分布は特に限定されず、長さが１μｍ以下のＩＧを含んでもよいし、長さが１０μｍ以上
のＩＧを含んでもよい。
The IG in the present embodiment has an average length of 1 μm or more and 10 μm or less. The average length of IG can be adjusted by, for example, a ball mill, a bead mill, a jet mill and / or ultrasonic crushing. Among these, it is more preferable to disperse IG in an appropriate solvent or an ionic liquid to be described later and adjust by irradiating ultrasonic waves because the distribution of IG length can be made relatively small. Here, the average length of the IG is the number average length, and the length distribution is not particularly limited, and may include an IG having a length of 1 μm or less, or including an IG having a length of 10 μm or more. But you can.
本実施形態の組成物におけるＩＧの平均長さは、１μｍ以上１０μｍ以下であるが、好ましくは１．３μｍ以上１０μｍ以下、より好ましくは１．５μｍ以上１０μｍ以下、さらに好ましくは１．６μｍ以上１０μｍ以下である。 The average length of IG in the composition of the present embodiment is 1 μm or more and 10 μm or less, preferably 1.3 μm or more and 10 μm or less, more preferably 1.5 μm or more and 10 μm or less, and further preferably 1.6 μm or more and 10 μm or less. It is.
また、ＩＧは、天然に産出する鉱物を原料としてもよいが、上記のように化学合成によって得るほうが、平均長さを調節しやすい、不純物が少ない、コストが低い、等の理由により有利である。 In addition, IG may be produced from a naturally occurring mineral, but it is more advantageous to obtain it by chemical synthesis as described above for reasons such as easier adjustment of the average length, fewer impurities, and lower costs. .
本実施形態で使用するＩＧは、平均長さが１μｍ以上であるため、後述のイオン液体中に分散されると、互いに接触したり絡み合ったりしやすい。複数のＩＧが接触及び／又は絡み合うことにより、イオン液体中で網目構造が形成される。このような網目構造が形成されると、組成物の粘性が高まり、ペースト状又は固体状の性状となる。 Since the IG used in the present embodiment has an average length of 1 μm or more, when it is dispersed in an ionic liquid described later, it is likely to contact or entangle with each other. A network structure is formed in the ionic liquid by contacting and / or entwining a plurality of IGs. When such a network structure is formed, the viscosity of the composition increases, and a paste or solid property is obtained.
このようにＩＧは、網目構造をイオン液体中で形成することができるが、組成物全体に対するＩＧの添加量は、例えば、０．１質量％以上である。網目構造の形成のしやすさは、ＩＧの平均長さに依存し、平均長さが長いほどより少ない添加量とすることができる。例えば、ＩＧの平均長さが１μｍ程度である場合には、組成物全体に対するＩＧの添加量は、０．０１質量％以上１０質量％以下、好ましくは０．１質量％以上８質量％以下、より好ましくは１質量％以上７質量％以下である。また例えば、ＩＧの平均長さが１０μｍ程度である場合には、組成物全体に対するＩＧの添加量は、０．００１質量％以上８質量％以下、好ましくは０．０５質量％以上７質量％以下、より好ましくは０．１質量％以上５質量％以下である。 Thus, although IG can form network structure in an ionic liquid, the addition amount of IG with respect to the whole composition is 0.1 mass% or more, for example. The ease of forming a network structure depends on the average length of IG, and the longer the average length, the smaller the addition amount. For example, when the average length of IG is about 1 μm, the amount of IG added to the entire composition is 0.01% by mass to 10% by mass, preferably 0.1% by mass to 8% by mass, More preferably, it is 1 mass% or more and 7 mass% or less. For example, when the average length of IG is about 10 μm, the amount of IG added to the whole composition is 0.001% by mass to 8% by mass, preferably 0.05% by mass to 7% by mass. More preferably, it is 0.1 mass% or more and 5 mass% or less.
組成物におけるＩＧの配合量は、一般的な化学分析、機器分析の手法により求めることができる。また、ＩＧであることの同定は、例えば、透過型電子顕微鏡（ＴＥＭ）、フーリエ変換赤外分光法（ＦＴ−ＩＲ）、熱重量測定−示差熱分析（ＴＧ−ＤＴＡ）、Ｘ線回折（ＸＲＤ）等により同定することができる。 The compounding quantity of IG in a composition can be calculated | required by the method of a general chemical analysis and an instrumental analysis. The identification of IG is, for example, transmission electron microscope (TEM), Fourier transform infrared spectroscopy (FT-IR), thermogravimetry-differential thermal analysis (TG-DTA), X-ray diffraction (XRD) ) And the like.
１．２．イオン液体
本実施形態の組成物は、イオン液体を含む。イオン液体（以下、「ＩＬ」と記すことがある。）は、イオンのみから成る塩の一種でありながら、分子の大きさ及び弱いイオン間相互作用のため、温度に応じて液体又は固体の状態をとる物質である。さらに、イオン液体は、（１）不揮発性、（２）高いイオン伝導性、（３）広い液相温度域を有する、という特徴を有している。
1.2. Ionic liquid The composition of this embodiment contains an ionic liquid. An ionic liquid (hereinafter sometimes referred to as “IL”) is a kind of salt composed of only ions, but it is in a liquid or solid state depending on temperature due to molecular size and weak ionic interaction. It is a substance that takes Furthermore, the ionic liquid has the characteristics of (1) non-volatility, (2) high ionic conductivity, and (3) a wide liquidus temperature range.
温度を調整し液状にしたイオン液体を含む、本実施形態の組成物においては、上述の平均長さが１μｍ以上１０μｍ以下のイモゴライトの存在により増粘し、又は、ペースト固体状の性状となる。 In the composition of this embodiment containing an ionic liquid whose temperature is adjusted to be liquid, the above-mentioned average length increases due to the presence of imogolite having a size of 1 μm or more and 10 μm or less, or becomes a paste solid property.
本実施形態の組成物に配合されるイオン液体は、特に限定されず、公知のイオン液体を用いることができる。イオン液体の例としては、イミダゾリウム塩、ピリジニウム塩、ピロリジニウム塩、ホスホニウム塩、アンモニウム塩、グアニジニウム塩、イソウロニウム塩及びイソチオウロニウム塩から選択される少なくとも一種を挙げることができる。これらの塩は、複数種を混合して用いてもよい。これらの塩のアニオン種も特に限定されず、例えば、ハロゲン化物イオン（Ｉ−、Ｃｌ−、Ｂｒ−等）、ＳＣＮ−、ＢＦ４ −、ＰＦ６ −、ＣｌＯ４ −、ＳｂＦ６ −、（ＣＦ３ＳＯ２）２Ｎ−、（ＣＦ３ＣＦ２ＳＯ２）２Ｎ−、Ｐｈ４Ｂ−、（Ｃ２Ｈ４Ｏ２）２Ｂ−、（ＣＦ３ＳＯ２）３Ｃ−、ＣＦ３ＣＯＯ−、ＣＦ３ＳＯ３ −、Ｃ６Ｆ５ＳＯ３ −、ＭｅＯ（ＥｔＯ）２ＳＯ３ −等が挙げられる。 The ionic liquid blended in the composition of the present embodiment is not particularly limited, and a known ionic liquid can be used. Examples of the ionic liquid include at least one selected from imidazolium salts, pyridinium salts, pyrrolidinium salts, phosphonium salts, ammonium salts, guanidinium salts, isouronium salts, and isothiouronium salts. These salts may be used as a mixture of plural kinds. The anion species of these salts are not particularly limited, and examples thereof include halide ions (I − , Cl − , Br − etc.), SCN − , BF 4 − , PF 6 − , ClO 4 − , SbF 6 − , (CF 3 SO 2) 2 N -, (CF 3 CF 2 SO 2) 2 N -, Ph 4 B -, (C 2 H 4 O 2) 2 B -, (CF 3 SO 2) 3 C -, CF 3 COO -, CF 3 SO 3 -, C 6 F 5 SO 3 -, MeO (EtO) 2 SO 3 - , and the like.
イミダゾリウム塩のイオン液体の具体例としては、１，３−ジメチルイミダゾリウムトリフルオロメタンスルホネート、１−エチル−３−メチルイミダゾリウムビス［オキサレート（２−）］ボレート、１−エチル−３−メチルイミダゾリウムテトラフルオロボレート、１−エチル−３−メチルイミダゾリウムブロミド、１−エチル−３−メチルイミダゾリウムクロリド、１−エチル−３−メチルイミダゾリウムヘキサフルオロフォスフェイト、１−エチル−３−メチルイミダゾリウムトリフルオロメタンスルホネート、１−エチル−３−メチルイミダゾリウムトリフルオロアセテート、１−エチル−３−メチルイミダゾリウムメチルサルフェート、１−エチル−３−メチルイミダゾリウムｐ−トルエンスルホネート、１−エチル−３−メチルイミダゾリウムチオシアネート、１−エチル−３−メチルイミダゾリウム２−（２−メトキシエトキシ）エチルサルフェート、１−エチル−３−メチルイミダゾリウムビス（トリフルオロメチルスルホニル）イミド、１−ブチル−３−メチルイミダゾリウムトリフルオロメタンスルホネート、１−ブチル−３−メチルイミダゾリウムテトラフルオロボレート、１−ブチル−３−メチルイミダゾリウムヘキサフルオロフォスフェイト、１−ブチル−３−メチルイミダゾリウムメチルサルフェート、１−ブチル−３−メチルイミダゾリウムクロリド、１−ブチル−３−メチルイミダゾリウムブロミド、１−ブチル−３−メチルイミダゾリウムトリフルオロアセテート、１−ブチル−３−メチルイミダゾリウムオクチルサルフェート、１−ヘキシル−３−メチルイミダゾリウムビス（トリフルオロメチルスルホニル）イミド、１−ヘキシル−３−メチルイミダゾリウムクロリド、１−ヘキシル−３−メチルイミダゾリウムテトラフルオロボレート、１−ヘキシル−３−メチルイミダゾリウムヘキサフルオロフォスフェイト、１−ヘキシル−３−メチルイミダゾリウムトリス（ペンタフルオロエチル）トリフルオロフォスフェイト、３−メチル−１−オクチルイミダゾリウムヘキサフルオロフォスフェイト、３−メチル−１−オクチルイミダゾリウムクロリド、３−メチル−１−オクチルイミダゾリウムテトラフルオロボレート、３−メチル−１−オクチルイミダゾリウムビス（トリフルオロメチルスルホニル）イミド、３−メチル−１−オクチルイミダゾリウムオクチルサルフェート、３−メチル−１−テトラデシルイミダゾリウムテトラフルオロボレート、１−ヘキサデシル−３−メチルイミダゾリウムクロリド、３−メチル−１−オクタデシルイミダゾリウムヘキサフルオロフォスフェイト、３−メチル−１−オクタデシルイミダゾリウムビス（トリフルオロメチルスルホニル）イミド、３−メチル−１−オクタデシルイミダゾリウムトリ（ペンタフルオロエチル）トリフルオロフォスフェイト、１−エチル−２，３−ジメチルイミダゾリウムブロミド、１−エチル−２，３−ジメチルイミダゾリウムテトラフルオロボレート、１−エチル−２，３−ジメチルイミダゾリウムヘキサフルオロフォスフェイト、１−エチル−２，３−ジメチルイミダゾリウムクロリド、１−エチル−２，３−ジメチルイミダゾリウムｐ−トルエンスルホネート、１−ブチル−２，３−ジメチルイミダゾリウムテトラフルオロボレート、１−ブチル−２，３−ジメチルイミダゾリウムクロリド、１−ブチル−２，３−ジメチルイミダゾリウムヘキサフルオロフォスフェイト、１−ブチル−２，３−ジメチルイミダゾリウムオクチルサルフェート、１−ヘキシル−２，３−ジメチルイミダゾリウムクロリド、１−ヘキサデシル−２，３−ジメチルイミダゾリウムクロリド等が挙げられる。 Specific examples of the ionic liquid of the imidazolium salt include 1,3-dimethylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium bis [oxalate (2-)] borate, 1-ethyl-3-methylimidazole. 1-ethyl-3-methylimidazolium bromide, 1-ethyl-3-methylimidazolium chloride, 1-ethyl-3-methylimidazolium hexafluorophosphate, 1-ethyl-3-methylimidazolium Trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium trifluoroacetate, 1-ethyl-3-methylimidazolium methylsulfate, 1-ethyl-3-methylimidazolium p-toluenesulfonate, 1-ethyl-3-methyl Imidazolium thiocyanate, 1-ethyl-3-methylimidazolium 2- (2-methoxyethoxy) ethyl sulfate, 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide, 1-butyl-3-methylimidazole 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium methyl sulfate, 1-butyl-3- Methyl imidazolium chloride, 1-butyl-3-methyl imidazolium bromide, 1-butyl-3-methyl imidazolium trifluoroacetate, 1-butyl-3-methyl imidazolium octyl sulfate, 1-hex -3-Methylimidazolium bis (trifluoromethylsulfonyl) imide, 1-hexyl-3-methylimidazolium chloride, 1-hexyl-3-methylimidazolium tetrafluoroborate, 1-hexyl-3-methylimidazolium hexafluoro Phosphate, 1-hexyl-3-methylimidazolium tris (pentafluoroethyl) trifluorophosphate, 3-methyl-1-octylimidazolium hexafluorophosphate, 3-methyl-1-octylimidazolium chloride, 3-methyl -1-octylimidazolium tetrafluoroborate, 3-methyl-1-octylimidazolium bis (trifluoromethylsulfonyl) imide, 3-methyl-1-octylimidazolium octyl sulfate, 3 -Methyl-1-tetradecylimidazolium tetrafluoroborate, 1-hexadecyl-3-methylimidazolium chloride, 3-methyl-1-octadecylimidazolium hexafluorophosphate, 3-methyl-1-octadecylimidazolium bis (tri Fluoromethylsulfonyl) imide, 3-methyl-1-octadecylimidazolium tri (pentafluoroethyl) trifluorophosphate, 1-ethyl-2,3-dimethylimidazolium bromide, 1-ethyl-2,3-dimethylimidazolium tetra Fluoroborate, 1-ethyl-2,3-dimethylimidazolium hexafluorophosphate, 1-ethyl-2,3-dimethylimidazolium chloride, 1-ethyl-2,3-dimethylimidazolium p-tolue Sulfonate, 1-butyl-2,3-dimethylimidazolium tetrafluoroborate, 1-butyl-2,3-dimethylimidazolium chloride, 1-butyl-2,3-dimethylimidazolium hexafluorophosphate, 1-butyl- Examples include 2,3-dimethylimidazolium octyl sulfate, 1-hexyl-2,3-dimethylimidazolium chloride, 1-hexadecyl-2,3-dimethylimidazolium chloride and the like.
ピリジニウム塩のイオン液体の具体例としては、Ｎ−エチルピリジニウムクロリド、Ｎ−エチルピリジニウムブロミド、Ｎ−ブチルピリジニウムクロリド、Ｎ−ブチルピリジニウムテトラフルオロボレート、Ｎ−ブチルピリジニウムヘキサフルオロフォスフェイト、Ｎ−ブチルピリジニウムトリフルオロメタンスルホネート、Ｎ−ヘキシルピリジニウムテトラフルオロボレート、Ｎ−ヘキシルピリジニウムヘキサフルオロフォスフェイト、Ｎ−ヘキシルピリジニウムビス（トリフルオロメチルスルホニル）イミド、Ｎ−ヘキシルピリジニウムトリフルオロメタンスルホネート、Ｎ−オクチルピリジニウムクロリド、４−メチル−Ｎ−ブチルピリジニウムクロリド、４−メチル−Ｎ−ブチルピリジニウムテトラフルオロボレート、４−メチル−Ｎ−ブチルピリジニウムヘキサフルオロフォスフェイト、
３−メチル−Ｎ−ブチルピリジニウムクロリド、４−メチル−Ｎ−ブチルピリジニウムブロミド、３，４−ジメチル−Ｎ−ブチルピリジニウムクロリド、３，５−ジメチル−Ｎ−ブチルピリジニウムクロリド等が挙げられる。
Specific examples of the ionic liquid of the pyridinium salt include N-ethylpyridinium chloride, N-ethylpyridinium bromide, N-butylpyridinium chloride, N-butylpyridinium tetrafluoroborate, N-butylpyridinium hexafluorophosphate, N-butylpyridinium Trifluoromethanesulfonate, N-hexylpyridinium tetrafluoroborate, N-hexylpyridinium hexafluorophosphate, N-hexylpyridinium bis (trifluoromethylsulfonyl) imide, N-hexylpyridinium trifluoromethanesulfonate, N-octylpyridinium chloride, 4- Methyl-N-butylpyridinium chloride, 4-methyl-N-butylpyridinium tetrafluoroborate, 4-methyl- - butyl pyridinium hexafluorophosphate,
Examples include 3-methyl-N-butylpyridinium chloride, 4-methyl-N-butylpyridinium bromide, 3,4-dimethyl-N-butylpyridinium chloride, 3,5-dimethyl-N-butylpyridinium chloride.
ピロリジニウム塩のイオン液体の具体例としては、）１−ブチル−１−メチルピロリジニウムクロリド、１−ブチル−１−メチルピロリジニウムトリフルオロメタンスルホネート、１−ブチル−１−メチルピロリジニウムビス（トリフルオロメチルスルホニル）イミド、１−ブチル−１−メチルピロリジニウムテトラフルオロボレート、１−ブチル−１−メチルピロリジニウムヘキサフルオロフォスフェイト、１−ブチル−１−メチルピロリジニウムトリス（ペンタフルオロエチル）トリフルオロフォスフェイト、１−ブチル−１−メチルピロリジニウムトリフルオロアセテート、１−ヘキシル−１−メチルピロリジニウムクロリド、１−メチル−１−オクチルピロリジニウムクロリド等が挙げられる。 Specific examples of pyrrolidinium salt ionic liquids include: 1-butyl-1-methylpyrrolidinium chloride, 1-butyl-1-methylpyrrolidinium trifluoromethanesulfonate, 1-butyl-1-methylpyrrolidinium bis ( Trifluoromethylsulfonyl) imide, 1-butyl-1-methylpyrrolidinium tetrafluoroborate, 1-butyl-1-methylpyrrolidinium hexafluorophosphate, 1-butyl-1-methylpyrrolidinium tris (pentafluoro) Ethyl) trifluorophosphate, 1-butyl-1-methylpyrrolidinium trifluoroacetate, 1-hexyl-1-methylpyrrolidinium chloride, 1-methyl-1-octylpyrrolidinium chloride and the like.
ホスホニウム塩のイオン液体の具体例としては、トリヘキシル（テトラデシル）ホスホニウムクロリド、トリヘキシル（テトラデシル）ホスホニウムトリス（ペンタフルオロエチル）トリフルオロフォスフェイト、トリヘキシル（テトラデシル）ホスホニウムテトラフルオロボレート、トリヘキシル（テトラデシル）ホスホニウムビス（トリフルオロメチルスルホニル）イミド、トリヘキシル（テトラデシル）ホスホニウムヘキサフルオロフォスフェイト、トリヘキシル（テトラデシル）ホスホニウムビス［オキサレート（２−）］ボレート等が挙げられる。 Specific examples of ionic liquids of phosphonium salts include trihexyl (tetradecyl) phosphonium chloride, trihexyl (tetradecyl) phosphonium tris (pentafluoroethyl) trifluorophosphate, trihexyl (tetradecyl) phosphonium tetrafluoroborate, trihexyl (tetradecyl) phosphonium bis (tri Fluoromethylsulfonyl) imide, trihexyl (tetradecyl) phosphonium hexafluorophosphate, trihexyl (tetradecyl) phosphonium bis [oxalate (2-)] borate and the like.
アンモニウム塩のイオン液体の具体例としては、メチルトリオクチルアンモニウムトリフルオロアセテート、メチルトリオクチルアンモニウムトリフルオロメタンスルホネート、メチルトリオクチルアンモニウムビス（トリフルオロメチルスルホニル）イミド等が挙げられる。 Specific examples of the ionic liquid of the ammonium salt include methyl trioctyl ammonium trifluoroacetate, methyl trioctyl ammonium trifluoromethanesulfonate, methyl trioctyl ammonium bis (trifluoromethylsulfonyl) imide and the like.
グアニジニウム塩のイオン液体の具体例としては、）Ｎ”−エチル−Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルグアニジニウムトリス（ペンタフルオロエチル）トリフルオロフォスフェイト、グアニジニウムトリス（ペンタフルオロエチル）トリフルオロフォスフェイト、グアニジニウムトリフルオロメタンスルホネート、Ｎ”−エチル−Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルグアニジニウムトリフルオロメタンスルホネートが挙げられる。 Specific examples of ionic liquids of guanidinium salts include: N) -ethyl-N, N, N ′, N′-tetramethylguanidinium tris (pentafluoroethyl) trifluorophosphate, guanidinium tris (pentafluoroethyl) ) Trifluorophosphate, guanidinium trifluoromethanesulfonate, N ″ -ethyl-N, N, N ′, N′-tetramethylguanidinium trifluoromethanesulfonate.
イソウロニウム塩のイオン液体の具体例としては、Ｏ−エチル−Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルイソウロニウムトリフルオロメタンスルホネート、Ｏ−エチル−Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルイソウロニウムトリ（ペンタフルオロエチル）トリフルオロフォスフェイトが挙げられる。 Specific examples of ionic liquids of isouronium salts include O-ethyl-N, N, N ′, N′-tetramethylisouronium trifluoromethanesulfonate, O-ethyl-N, N, N ′, N′-tetramethyl. An isouronium tri (pentafluoroethyl) trifluorophosphate may be mentioned.
イソチオウロニウム塩のイオン液体の具体例としては、Ｓ−エチル−Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルイソチオウロニウムトリフルオロメタンスルホネート、Ｓ−エチル−Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルイソチオウロニウムトリス（ペンタフルオロエチル）トリフルオロフォスフェイトが挙げられる。 Specific examples of the ionic liquid of isothiouronium salt include S-ethyl-N, N, N ′, N′-tetramethylisothiouronium trifluoromethanesulfonate, S-ethyl-N, N, N ′, N′— Examples include tetramethylisothiouronium tris (pentafluoroethyl) trifluorophosphate.
既に述べたように、ＩＧの円筒の外側の面には、Ａｌ−ＯＨ基が存在していることから、組成物中でＩＧがより分散しやすくなるという観点から、イオン液体は、親水性の高いものを用いることが好ましい。そのようなイオン液体としては、例えば、１−エチル−３−メチルイミダゾリウム２−（２−メトキシエトキシ）エチルサルフェート、１−ブチル−３−メチルイミダゾリウムテトラフルオロボレート、１−エチル−３−メチルイミダゾリウムテトラフルオロボラート等を挙げることができる。
本実施形態の組成物におけるイオン液体の含有量は、特に限定されない。
As already described, since the Al—OH group is present on the outer surface of the IG cylinder, the ionic liquid is hydrophilic from the viewpoint that IG is more easily dispersed in the composition. It is preferable to use a high one. Examples of such ionic liquids include 1-ethyl-3-methylimidazolium 2- (2-methoxyethoxy) ethyl sulfate, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methyl. Examples thereof include imidazolium tetrafluoroborate.
The content of the ionic liquid in the composition of the present embodiment is not particularly limited.
１．３．その他の成分
本実施形態の組成物は、上述のＩＧ及びＩＬの他に、流動性やイオン伝導性を阻害しない範囲で各種の物質を含むことができる。そのような物質としては、例えば、無機酸化物粒子、支持電解質塩、界面活性剤、水等が挙げられ、目的に応じて適宜に配合することができる。また、これらの物質は、不純物として含まれていてもよい。
1.3. Other Components The composition of the present embodiment can contain various substances in addition to the above-described IG and IL as long as the fluidity and ion conductivity are not impaired. Examples of such substances include inorganic oxide particles, supporting electrolyte salts, surfactants, water, and the like, which can be appropriately blended depending on the purpose. Moreover, these substances may be contained as impurities.
無機酸化物粒子としては、Ｌｉ、Ｎａ、Ｍｇ、Ａｌ、Ｓｉ、Ｋ、Ｃａ、Ｓｃ、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚｎ、Ｒｂ、Ｓｒ、Ｙ、Ｎｂ、Ｚｒ、Ｍｏ、Ａｇ、Ｃｄ、Ｉｎ、Ｓｎ、Ｓｂ、Ｃｓ、Ｂａ、Ｌａ、Ｔａ、Ｈｆ、Ｗ、Ｉｒ、Ｔｌ、Ｐｂ、Ｂｉ及び希土類金属からなる群より選ばれる１種または２種以上の金属の酸化物からなる粒子を挙げることができ、具体的には、例えば、酸化チタン、酸化亜鉛、酸化アルミニウム、酸化ジルコニウム、酸化ハフニウム、酸化ニオブ、酸化タンタル、酸化マグネシウム、酸化カルシウム、酸化ストロンチウム、酸化バリウム、酸化インジウム、酸化錫、酸化鉛、酸化スカンジウム、酸化イットリウム、酸化ランタン、酸化セリウム、酸化プラセオジム、酸化ネオジム、酸化サマリウム、酸化ユウロピウム、酸化ガドリニウム、酸化テルビウム、酸化ジスプロシウム、酸化ホルミウム、酸化エルビウム、酸化ツリウム、酸化イッテルビウム、酸化ルテチウム、並びに、これら酸化物より構成される複合酸化物であるニオブ酸リチウム、ニオブ酸カリウム、タンタル酸リチウム、アルミニウム・マグネシウム酸化物（ＭｇＡｌ２Ｏ４）等が挙げられ、これらの複数種を用いてもよい。 As inorganic oxide particles, Li, Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Rb, Sr, Y, Nb, Zr Of one or more metals selected from the group consisting of Mo, Ag, Cd, In, Sn, Sb, Cs, Ba, La, Ta, Hf, W, Ir, Tl, Pb, Bi and rare earth metals Examples of the particles include oxides, and specific examples include titanium oxide, zinc oxide, aluminum oxide, zirconium oxide, hafnium oxide, niobium oxide, tantalum oxide, magnesium oxide, calcium oxide, strontium oxide, and barium oxide. , Indium oxide, tin oxide, lead oxide, scandium oxide, yttrium oxide, lanthanum oxide, cerium oxide, praseodymium oxide, neodymium oxide, summer Au, europium oxide, gadolinium oxide, terbium oxide, dysprosium oxide, holmium oxide, erbium oxide, thulium oxide, ytterbium oxide, lutetium oxide, and complex oxides composed of these oxides, lithium niobate and potassium niobate , Lithium tantalate, aluminum / magnesium oxide (MgAl 2 O 4 ), and the like, and a plurality of these may be used.
また、支持電解質塩としては、周期律表Ｉａ族またはＩＩａ族に属する金属イオンの塩を用いてもよい。周期律表Ｉａ族またはＩＩａ族に属する金属イオンとしては、リチウム、ナトリウム、カリウムのイオンが好ましい。金属イオンの塩のアニオンとしては、上述のイオン液体の項で例示したアニオンを用いることができる。代表的な支持電解質塩としては、ＬｉＣＦ３ＳＯ３、ＬｉＰＦ６、ＬｉＣｌＯ４、ＬｉＩ、ＬｉＢＦ４、ＬｉＣＦ３ＣＯ２、ＬｉＳＣＮ、ＬｉＮ（ＳＯ２ＣＦ３）２、ＮａＩ、ＮａＣＦ３ＳＯ３、ＮａＣｌＯ４、ＮａＢＦ４、ＮａＡｓＦ６、ＫＣＦ３ＳＯ３、ＫＳＣＮ、ＫＰＦ６、ＫＣｌＯ４、ＫＡｓＦ６などが挙げられる。 Further, as the supporting electrolyte salt, a salt of a metal ion belonging to Group Ia or Group IIa of the periodic table may be used. As the metal ions belonging to Group Ia or Group IIa of the periodic table, ions of lithium, sodium and potassium are preferable. As the anion of the metal ion salt, the anions exemplified in the section of the ionic liquid described above can be used. Typical supporting electrolyte salts include LiCF 3 SO 3 , LiPF 6 , LiClO 4 , LiI, LiBF 4 , LiCF 3 CO 2 , LiSCN, LiN (SO 2 CF 3 ) 2 , NaI, NaCF 3 SO 3 , NaClO 4. , NaBF 4 , NaAsF 6 , KCF 3 SO 3 , KSCN, KPF 6 , KClO 4 , KAsF 6 and the like.
１．４．組成物の流動特性及びイオン伝導性
本実施形態の組成物は、非ニュートン性を示す。すなわち、ＩＧがＩＬ中で接触、及び／又は、絡み合う結果、ＩＬ単独の場合に比較して、特にせん断速度が低い領域において粘度が高まる。換言すると、本実施形態の組成物は、動的粘弾性測定において、損失弾性率Ｇ”が貯蔵弾性率Ｇ’よりも小さくなるせん断ひずみの領域を有する。なお、動的粘弾性測定は、公知の方法により行うことができる。
1.4. Flow characteristics and ionic conductivity of the composition The composition of the present embodiment exhibits non-Newtonian properties. That is, as a result of the contact and / or entanglement of IG in IL, the viscosity increases particularly in a region where the shear rate is low as compared with the case of IL alone. In other words, the composition of the present embodiment has a shear strain region in which the loss elastic modulus G ″ is smaller than the storage elastic modulus G ′ in the dynamic viscoelasticity measurement. The method can be used.
このため、本実施形態の組成物は、静置された際には、ペースト状、ゲル状ないし固体状の高粘度の粘弾性体として振る舞うが、変形、流動させたり、対象に塗布したりする際には、低粘度の粘弾性体として振る舞うことができる。これにより、例えば、適宜の容器に導入する際には液体状態であり、容器中で静置された際には増粘した状態を形成することができる。 For this reason, the composition of this embodiment behaves as a pasty, gel-like or solid high-viscosity viscoelastic body when left standing, but is deformed, fluidized, or applied to an object. In some cases, it can behave as a low-viscosity viscoelastic body. Thereby, for example, when introduced into a suitable container, it is in a liquid state, and when left in the container, a thickened state can be formed.
また、本実施形態の組成物においては、イオン液体のイオンは、ＩＧによりほとんど拘束されず、移動の自由度の高い状態で存在することができる。このような状態は、組成物が静置され、ペースト状ないし固体状の高粘度の粘弾性体となっている場合でも維持することができる。 Moreover, in the composition of this embodiment, the ion of an ionic liquid is hardly restrained by IG and can exist in a state with a high freedom degree of movement. Such a state can be maintained even when the composition is allowed to stand and becomes a pasty or solid high-viscosity viscoelastic body.
本実施形態の組成物のイオン伝導度は、例えば、複素インピーダンスを測定することにより算出することができる。具体的な測定としては、例えば、ＳＵＳ製の電極に挟んだ試料に対し、Potentiostat/Galvanostat SP-150（BioLogic製）を用いて乾燥アルゴン雰囲
気の循環精製装置付グローブボックス中にて行うことができる。また、測定周波数範囲は限定されないが例えば１００Ｈｚ〜１ＭＨｚである。
The ionic conductivity of the composition of the present embodiment can be calculated, for example, by measuring complex impedance. As a specific measurement, for example, a sample sandwiched between electrodes made of SUS can be performed in a glove box with a circulation purifier in a dry argon atmosphere using Potentiostat / Galvanostat SP-150 (manufactured by BioLogic). . The measurement frequency range is not limited, but is, for example, 100 Hz to 1 MHz.
本実施形態の組成物のイオン伝導度の値としては、３０℃以上１００℃以下程度の温度範囲において、１×１０−４（Ｓ／ｃｍ）以上であり、好ましくは２×１０−４（Ｓ／ｃｍ）以上、より好ましくは１×１０−３（Ｓ／ｃｍ）以上である。本実施形態の組成物のイオン伝導度がこの範囲であれば、良好なイオン伝導性を有すると言える。 The value of ionic conductivity of the composition of the present embodiment is 1 × 10 −4 (S / cm) or more, preferably 2 × 10 −4 (S) in a temperature range of about 30 ° C. or more and 100 ° C. or less. / Cm) or more, more preferably 1 × 10 −3 (S / cm) or more. If the ionic conductivity of the composition of this embodiment is in this range, it can be said that it has good ionic conductivity.
１．５．作用効果
本実施形態（第１実施形態）の組成物によれば、配合されるイモゴライトの平均長さが１μｍ以上１０μｍ以下である。そのため、イオン液体中で複数のイモゴライトが接触しやすく、及び／又は、絡み合いやすい。これにより、イモゴライトの可逆的な網目構造が組成物中に形成される結果、イオン液体の高いイオン伝導性を維持できるとともに、静置時の流動性が低く、かつ、流動時の流動性が高いという、優れた流動特性を呈することができる。したがって、イオン伝導性及び加工性が良好な組成物として、電池や導電塗料等への応用に好適である。
1.5. Effects According to the composition of the present embodiment (first embodiment), the average length of imogolite to be blended is 1 μm or more and 10 μm or less. Therefore, a plurality of imogolites are likely to contact and / or easily entangle with each other in the ionic liquid. As a result, a reversible network structure of imogolite is formed in the composition. As a result, the high ionic conductivity of the ionic liquid can be maintained, the flowability at the time of standing is low, and the flowability at the time of flow is high. It can exhibit excellent flow characteristics. Therefore, the composition having good ion conductivity and processability is suitable for application to batteries, conductive paints, and the like.
２．第２実施形態
本実施形態の組成物は、平均長さが５０ｎｍ以上１０μｍ以下のイモゴライトと、イオン液体と、多官能性化合物と、を含む。
2. Second Embodiment The composition of the present embodiment includes imogolite having an average length of 50 nm to 10 μm, an ionic liquid, and a polyfunctional compound.
２．１．イモゴライト
第２実施形態の組成物に配合されるイモゴライト（ＩＧ）は、平均長さが５０ｎｍ以上１０μｍ以下である。ＩＧの平均長さの調節、分布、合成等については、第１実施形態で述べた同様であり、説明を省略する。
2.1. Imogolite (IG) blended in the composition of the second embodiment has an average length of 50 nm to 10 μm. The adjustment, distribution, synthesis, and the like of the average length of IG are the same as described in the first embodiment, and a description thereof is omitted.
本実施形態の組成物におけるＩＧの平均長さは、５０ｎｍ以上１０μｍ以下であるが、好ましくは８０ｎｍ以上１０μｍ以下、より好ましくは１００ｎｍ以上１０μｍ以下、さらに好ましくは１３０ｎｍ以上１０μｍ以下である。 The average length of IG in the composition of the present embodiment is from 50 nm to 10 μm, preferably from 80 nm to 10 μm, more preferably from 100 nm to 10 μm, and still more preferably from 130 nm to 10 μm.
本実施形態で使用するＩＧは、後述する多官能性化合物とともにイオン液体中に分散されると、多官能性化合物によって、非共有結合を介して互いに連結しやすい。複数のＩＧが可逆的に結合されることにより、組成物中でＩＧ及び多官能性化合物によって、分子レベルの網目構造が形成される。このような網目構造が形成されると、組成物が擬塑性（チクソトロピー性）を呈することになる。 When the IG used in the present embodiment is dispersed in an ionic liquid together with a polyfunctional compound described later, the IG is easily linked to each other via a non-covalent bond by the polyfunctional compound. By reversibly bonding a plurality of IGs, a network structure at a molecular level is formed by IGs and polyfunctional compounds in the composition. When such a network structure is formed, the composition exhibits pseudoplasticity (thixotropic properties).
本実施形態の組成物で用いられるＩＧは、第１実施形態の組成物で用いられるＩＧよりも平均長さは小さくてもよい。これは、多官能性化合物によって、複数のＩＧ間が多官能性化合物によって非共有結合するからである。非共有結合としては、例えば、イオン結合であり、ＩＧ表面の水酸基と、多官能性化合物のカルボキシル基との電気的な引力による結合が挙げられる。ここで、水酸基とカルボキシル基とは、エステル結合等の共有結合を形成しないため、可逆的な結合であり、例えば、せん断等による流動が生じた際に、分子の位置が固定されることはない。 The IG used in the composition of the present embodiment may have a smaller average length than the IG used in the composition of the first embodiment. This is because a plurality of IGs are non-covalently bonded by a polyfunctional compound by the polyfunctional compound. Examples of the non-covalent bond include ionic bonds, and include a bond by an electric attractive force between a hydroxyl group on the IG surface and a carboxyl group of a polyfunctional compound. Here, the hydroxyl group and the carboxyl group are reversible bonds because they do not form a covalent bond such as an ester bond. For example, when a flow due to shearing occurs, the position of the molecule is not fixed. .
本実施形態では、ＩＧは、多官能性化合物とともに網目構造を組成物中で形成することができるが、組成物全体に対するＩＧの添加量は、例えば、０．０１質量％以上である。本実施形態においても網目構造の形成のしやすさは、ＩＧの平均長さに依存し、平均長さが長いほどより少ない添加量とすることができる。例えば、ＩＧの平均長さが１μｍ程度である場合には、組成物全体に対するＩＧの添加量は、０．０１質量％以上８質量％以下、好ましくは０．１質量％以上７質量％以下、より好ましくは１質量％以上６質量％以下
である。また例えば、ＩＧの平均長さが１００ｎｍ程度である場合には、組成物全体に対するＩＧの添加量は、１質量％以上７質量％以下、好ましくは１．５質量％以上６質量％以下、より好ましくは２質量％以上５質量％以下である。
In this embodiment, although IG can form a network structure in a composition with a polyfunctional compound, the addition amount of IG with respect to the whole composition is 0.01 mass% or more, for example. Also in this embodiment, the ease of forming a network structure depends on the average length of IG, and the smaller the amount added, the longer the average length. For example, when the average length of IG is about 1 μm, the amount of IG added to the entire composition is 0.01% by mass or more and 8% by mass or less, preferably 0.1% by mass or more and 7% by mass or less, More preferably, it is 1 mass% or more and 6 mass% or less. For example, when the average length of IG is about 100 nm, the amount of IG added to the entire composition is 1% by mass or more and 7% by mass or less, preferably 1.5% by mass or more and 6% by mass or less. Preferably they are 2 mass% or more and 5 mass% or less.
本実施形態の組成物におけるＩＧや多官能性化合物の配合量は、一般的な化学分析、機器分析の手法により求めることができる。 The compounding quantity of IG and a polyfunctional compound in the composition of this embodiment can be calculated | required by the method of a general chemical analysis and an instrumental analysis.
２．２．イオン液体
本実施形態の組成物で使用されるイオン液体は、第１実施形態と同様であるため、詳細な説明を省略する。本実施形態の組成物におけるイオン液体の含有量は、特に限定されない。
2.2. Ionic liquid The ionic liquid used in the composition of the present embodiment is the same as that of the first embodiment, and thus detailed description thereof is omitted. The content of the ionic liquid in the composition of the present embodiment is not particularly limited.
２．３．多官能性化合物
本実施形態（第２実施形態）の組成物は、多官能性化合物を含有する。多官能性化合物の官能基の数は、複数であれば特に限定されないが、ＩＧ間を可逆的に架橋する際の架橋密度が高くなりすぎない点で、好ましくは、二つであり、二官能性化合物であることが好ましい。
2.3. Polyfunctional compound The composition of this embodiment (2nd Embodiment) contains a polyfunctional compound. The number of functional groups of the polyfunctional compound is not particularly limited as long as it is plural, but it is preferably two and bifunctional in that the crosslinking density when reversibly crosslinking between IGs is not too high. It is preferable that it is an ionic compound.
多官能性化合物としては、２つの酸性官能基を有する化合物、１つの酸性官能基と１つの非酸性官能基とを有する化合物を挙げることができる。ここで、酸性官能基とは、当該化合物中において水素イオンを放出し得る官能基を指す。酸性官能基としては、例えば、カルボキシル基、リン酸基、リン酸基、亜リン酸基、ホスホン酸基、スルホン酸基及び硫酸基等が挙げられ、なかでもカルボキシル基及びホスホン酸基が好ましい。 Examples of the polyfunctional compound include a compound having two acidic functional groups, a compound having one acidic functional group, and one non-acidic functional group. Here, the acidic functional group refers to a functional group capable of releasing hydrogen ions in the compound. Examples of the acidic functional group include a carboxyl group, a phosphoric acid group, a phosphoric acid group, a phosphorous acid group, a phosphonic acid group, a sulfonic acid group, and a sulfuric acid group. Among them, a carboxyl group and a phosphonic acid group are preferable.
好ましくは、２つの酸性官能基を有する化合物は、第１の官能基（酸性官能基）としてカルボキシル基を有し、第２の官能基（酸性官能基）としてカルボキシル基又はホスホン酸基を有する化合物である。第１の官能基としてカルボキシル基を有し、第２の官能基としてカルボキシル基を有する化合物としては、例えば、マレイン酸、フマル酸、コハク酸、グルタル酸、アジピン酸、シトラコン酸、メサコン酸等が挙げられる。また、第１の官能基としてカルボキシル基を有し、第２の官能基としてホスホン酸基を有する化合物としては、例えば、４−ホスホノブタン酸（ＰＢＡ）等が挙げられる。 Preferably, the compound having two acidic functional groups has a carboxyl group as the first functional group (acidic functional group) and has a carboxyl group or a phosphonic acid group as the second functional group (acidic functional group). It is. Examples of the compound having a carboxyl group as the first functional group and a carboxyl group as the second functional group include maleic acid, fumaric acid, succinic acid, glutaric acid, adipic acid, citraconic acid, and mesaconic acid. Can be mentioned. Moreover, as a compound which has a carboxyl group as a 1st functional group and has a phosphonic acid group as a 2nd functional group, 4-phosphonobutanoic acid (PBA) etc. are mentioned, for example.
１つの酸性官能基と１つの非酸性官能基とを有する化合物における酸性官能基は上述の酸性官能基とすることができる。また、非酸性官能基としては、アミノ基、酸アミド基等を例示することができる。なお、酸アミド基とは、酸（オキソ酸）とアンモニア又はアミンとが反応して生成する基を指し、上記例示した酸性官能基における−ＯＨ（個数は特に限定されないが、好ましくは１個）がアミノ基に置換された基を指す。酸アミド基としては、例えば、カルボキサミド基（−ＣＯＮＨ２）、スルホンアミド基（−ＳＯ２ＮＨ２）、リン酸アミド（−ＰＯ（ＯＨ）ＮＨ２）等が挙げられる。これらのうち、酸アミド基としては、カルボキサミド基が好ましく、カルボキシル基から誘導されるものが好ましい。１つの酸性官能基と１つの酸アミド基とを有する化合物としては、例えば、マレイン酸モノアミド、フマル酸モノアミド、コハク酸モノアミド、グルタル酸モノアミド、アジピン酸モノアミド、シトラコン酸モノアミド、メサコン酸モノアミド等が挙げられる。１つの酸性官能基と１つの酸アミド基とを有する化合物は、酸性官能基としてカルボキシル基を有し、酸アミド基としてカルボキサミド基を有することが好ましい。 The acidic functional group in the compound having one acidic functional group and one non-acidic functional group can be the above-described acidic functional group. Examples of non-acidic functional groups include amino groups and acid amide groups. The acid amide group refers to a group formed by a reaction between an acid (oxo acid) and ammonia or an amine, and —OH (number is not particularly limited, but preferably 1) in the acidic functional groups exemplified above. Refers to a group substituted with an amino group. Examples of the acid amide group include a carboxamide group (—CONH 2 ), a sulfonamide group (—SO 2 NH 2 ), and a phosphoric acid amide (—PO (OH) NH 2 ). Among these, as the acid amide group, a carboxamide group is preferable, and those derived from a carboxyl group are preferable. Examples of the compound having one acidic functional group and one acid amide group include maleic acid monoamide, fumaric acid monoamide, succinic acid monoamide, glutaric acid monoamide, adipic acid monoamide, citraconic acid monoamide, and mesaconic acid monoamide. It is done. The compound having one acidic functional group and one acid amide group preferably has a carboxyl group as the acidic functional group and a carboxamide group as the acid amide group.
また、２つの酸性官能基を有する化合物、又は、１つの酸性官能基と１つの酸アミド基とを有する化合物（以下、二官能性化合物と称する）は、炭素数が２以上６以下であることがより好ましい。なお、炭素数には、上記官能基に含まれる炭素原子も含まれる。主鎖は、炭素−炭素の単結合又は二重結合で構成されることが好ましく、二重結合が含まれる
場合は、その個数は１個又は２個であることが好ましい。
In addition, the compound having two acidic functional groups or the compound having one acidic functional group and one acid amide group (hereinafter referred to as a bifunctional compound) has 2 to 6 carbon atoms. Is more preferable. The carbon number includes carbon atoms contained in the functional group. The main chain is preferably composed of a carbon-carbon single bond or a double bond, and when a double bond is included, the number is preferably 1 or 2.
本実施形態の組成物における多官能性化合物の配合量は、特に限定されず、組成物全体に対して、例えば、０．１質量％以上である。多官能性化合物の配合量は、例えば、ＩＧの平均長さや、ＩＧの配合量により調節してもよい。例えば、組成物全体に対するＩＧの添加量が小さい場合には、これを補うように配合量を大きくしてもよい。また、ＩＧの平均長さが長い場合には、配合量を小さくしてもよい。 The compounding quantity of the polyfunctional compound in the composition of this embodiment is not specifically limited, For example, it is 0.1 mass% or more with respect to the whole composition. You may adjust the compounding quantity of a polyfunctional compound with the average length of IG, and the compounding quantity of IG, for example. For example, when the amount of IG added to the entire composition is small, the blending amount may be increased to compensate for this. Moreover, when the average length of IG is long, you may make a compounding quantity small.
具体的には、例えば、ＩＧの平均長さが５０ｎｍ〜１．５μｍ程度であって、ＩＧの含有量が０．０１質量％〜５質量％程度である場合には、多官能性化合物の配合量は、０．１質量％以上１５質量％以下、好ましくは０．３質量％以上１０質量％以下、より好ましくは０．５質量％以上５質量％以下、さらに好ましくは０．５質量％以上４．２質量％以下である。 Specifically, for example, when the average length of IG is about 50 nm to 1.5 μm and the content of IG is about 0.01% by mass to 5% by mass, blending of a multifunctional compound The amount is from 0.1% by weight to 15% by weight, preferably from 0.3% by weight to 10% by weight, more preferably from 0.5% by weight to 5% by weight, and even more preferably from 0.5% by weight. It is 4.2 mass% or less.
２．４．その他の成分
本実施形態（第２実施形態）の組成物において、上述のＩＧ、ＩＬ、多官能性化合物の他に、流動性やイオン伝導性を阻害しない範囲で各種の物質を含むことができる。そのような物質としては、例えば、無機酸化物粒子、支持電解質塩、界面活性剤、水等が挙げられ、目的に応じて適宜に配合することができる。また、これらの物質は、不純物として含まれていてもよい。これらの詳細は、第１実施形態と同様であるため、説明を省略する。
2.4. Other components In the composition of the present embodiment (second embodiment), in addition to the above-described IG, IL, and multifunctional compound, various substances can be included as long as fluidity and ion conductivity are not inhibited. . Examples of such substances include inorganic oxide particles, supporting electrolyte salts, surfactants, water, and the like, which can be appropriately blended depending on the purpose. Moreover, these substances may be contained as impurities. Since these details are the same as those in the first embodiment, description thereof will be omitted.
２．５．組成物の流動特性及びイオン伝導性
本実施形態の組成物は、チクソトロピー性（擬塑性）を示す。すなわち、ＩＧが多官能性化合物とともにＩＬ中で可逆的な非共有結合をする結果、ＩＬ単独の場合に比較して、特にせん断速度が大きい領域において粘度が低下する。換言すると、本実施形態の組成物は、動的粘弾性測定において、損失弾性率Ｇ”の値と貯蔵弾性率Ｇ’の値とが、逆転するせん断ひずみの領域を有する。なお、動的粘弾性測定は、公知の方法により行うことができる。
2.5. Flow characteristics and ionic conductivity of the composition The composition of the present embodiment exhibits thixotropic properties (pseudoplasticity). That is, as a result of IG reversible non-covalent bonding in the IL together with the polyfunctional compound, the viscosity is lowered particularly in a region where the shear rate is large as compared with the case of IL alone. In other words, the composition of the present embodiment has a shear strain region in which the value of the loss elastic modulus G ″ and the value of the storage elastic modulus G ′ are reversed in the dynamic viscoelasticity measurement. Elasticity measurement can be performed by a known method.
このため、本実施形態の組成物は、静置された際には、ゲル状ないし固体状の高粘度の粘弾性体として振る舞い、変形、流動させたり、対象に塗布したりする際のせん断速度の大きい領域では、低粘度の粘弾性体として振る舞うことができる。これにより、例えば、適宜の容器に導入する際には液体状態であり、容器中で静置された際には増粘した状態を形成することができる。 For this reason, the composition of this embodiment behaves as a gel-like or solid high-viscosity viscoelastic body when allowed to stand, and is deformed, fluidized, or sheared when applied to an object. In a large area, it can behave as a low-viscosity viscoelastic body. Thereby, for example, when introduced into a suitable container, it is in a liquid state, and when left in the container, a thickened state can be formed.
また、本実施形態の組成物においても、イオン液体のイオンは、ＩＧによりほとんど拘束されず、移動の自由度の高い状態で存在することができる。このような状態は、組成物が静置され、固体状の高粘度の粘弾性体となっている場合でも維持することができる。 Moreover, also in the composition of this embodiment, the ion of an ionic liquid is hardly restrained by IG and can exist in a state with a high freedom degree of movement. Such a state can be maintained even when the composition is allowed to stand and is a solid high-viscosity viscoelastic body.
本実施形態の組成物のイオン伝導度は、第１実施形態で述べたと同様にして測定することができる。本実施形態の組成物のイオン伝導度の値としては、３０℃以上１００℃以下程度の温度範囲において、２×１０−４（Ｓ／ｃｍ）以上であり、好ましくは５×１０−４（Ｓ／ｃｍ）以上、より好ましくは１×１０−３（Ｓ／ｃｍ）以上である。本実施形態の組成物のイオン伝導度がこの範囲であれば、良好なイオン伝導性を有すると言える。 The ionic conductivity of the composition of the present embodiment can be measured in the same manner as described in the first embodiment. The value of the ionic conductivity of the composition of the present embodiment is 2 × 10 −4 (S / cm) or more, preferably 5 × 10 −4 (S) in a temperature range of about 30 ° C. to 100 ° C. / Cm) or more, more preferably 1 × 10 −3 (S / cm) or more. If the ionic conductivity of the composition of this embodiment is in this range, it can be said that it has good ionic conductivity.
２．６．作用効果
本実施形態（第２実施形態）の組成物によれば、イモゴライトの平均長さが５０ｎｍ以上１０μｍ以下であり、かつ、多官能性化合物を含むため、組成物中で複数のイモゴライト間を可逆的に架橋することができる。これにより、イモゴライト及び多官能性化合物により、可逆的な網目構造が組成物中に形成される結果、イオン液体の高いイオン伝導性を
維持できるとともに、擬塑性（チクソトロピー性）を呈することができ、優れた流動特性を有する。イオン伝導性及び加工性が良好な組成物として、電池や導電塗料等への応用に好適である。
2.6. Effects According to the composition of the present embodiment (second embodiment), the average length of imogolite is 50 nm or more and 10 μm or less, and contains a polyfunctional compound. It can crosslink reversibly. As a result, a reversible network structure is formed in the composition by the imogolite and the polyfunctional compound. As a result, high ionic conductivity of the ionic liquid can be maintained, and pseudoplasticity (thixotropic property) can be exhibited. Excellent flow characteristics. As a composition having good ion conductivity and workability, it is suitable for application to batteries, conductive paints and the like.
３．実験例
以下に実験例を示し、本発明をさらに説明するが、本発明は以下の例によってなんら限定されるものではない。
3. Experimental Examples The experimental examples are shown below to further explain the present invention, but the present invention is not limited to the following examples.
３．１．イモゴライト（ＩＧ）の合成およびＩＧの水分散液の調製
本項で使用した試薬は和光純薬より購入した。塩化アルミニウム水溶液（０．１０Ｍ、３６９ｍＬ）とオルトケイ酸ナトリウム水溶液（０．１１Ｍ、３６２ｍＬ）を混合後、ＮａＯＨ（１Ｍ）水溶液をゆっくりと滴下して、ｐＨ＝６に調整した。室温で１時間撹拌し白色のＩＧ前駆体水溶液を得た。
3.1. Synthesis of imogolite (IG) and preparation of aqueous dispersion of IG Reagents used in this section were purchased from Wako Pure Chemical. After mixing an aluminum chloride aqueous solution (0.10 M, 369 mL) and a sodium orthosilicate aqueous solution (0.11 M, 362 mL), an aqueous NaOH (1 M) solution was slowly added dropwise to adjust to pH = 6. The mixture was stirred at room temperature for 1 hour to obtain a white IG precursor aqueous solution.
ＩＧ前駆体水溶液に対し、遠心分離（５０００×ｇ、１５分×３＋３０分×１）を行い、得られたペレットを４００ｍＬの超純水で洗浄して系中から塩化物イオンを取り除いた。遠心で得られた残渣を２８００ｍＬの超純水に分散させ、ＨＣｌ（１Ｍ）水溶液をゆっくりと滴下しｐＨ＝４．５に調整した。１００℃で９６時間、加熱環流を行いＩＧ分散液
（ＬＩＧａｑ．；平均長さ１．６μｍ、以下この時点のＩＧを「ＬＩＧ」（ＬｏｎｇＩＧ）ということがある。）を得た。係る分散液にＮａＣｌを加えてＩＧを凝集させ、遠心分離（５０００×ｇ）によりＩＧをペレットとして単離した。係るペレットを１６００ｍＬの超純水で洗浄・吸引ろ過し、ＮａＣｌを除去したゲル状のＩＧを得た。
The IG precursor aqueous solution was centrifuged (5000 × g, 15 minutes × 3 + 30 minutes × 1), and the resulting pellet was washed with 400 mL of ultrapure water to remove chloride ions from the system. The residue obtained by centrifugation was dispersed in 2800 mL of ultrapure water, and an aqueous HCl (1M) solution was slowly added dropwise to adjust the pH to 4.5. The mixture was heated to reflux at 100 ° C. for 96 hours to obtain an IG dispersion (LIGaq .; average length 1.6 μm, hereinafter, IG at this point may be referred to as “LIG” (Long IG)). IG was aggregated by adding NaCl to the dispersion, and IG was isolated as a pellet by centrifugation (5000 × g). The pellet was washed and suction filtered with 1600 mL of ultrapure water to obtain a gel-like IG from which NaCl was removed.
その後テトラヒドロフラン（ＴＨＦ）を貧溶媒として再沈殿した後、室温で８時間真空乾燥してＩＧ粉末を得た。所定量のＩＧ粉末を超純水と混合し４時間超音波処理することによりＩＧ分散液（ＩＧ−１３１ａｑ．；平均長さ１３１ｎｍ、以下このＩＧを「ＩＧ−１３１」ということがある。）を得た。ＩＧ−１３１は透過型電子顕微鏡（ＴＥＭ）、フーリエ変換赤外分光法（ＦＴ−ＩＲ）、熱重量測定−示差熱分析（ＴＧ−ＤＴＡ）、Ｘ線回折（ＸＲＤ）により同定した。 Then, after reprecipitation using tetrahydrofuran (THF) as a poor solvent, IG powder was obtained by vacuum drying at room temperature for 8 hours. A predetermined amount of IG powder was mixed with ultrapure water and subjected to ultrasonic treatment for 4 hours to obtain an IG dispersion (IG-131aq .; average length of 131 nm; hereinafter, this IG may be referred to as “IG-131”). Obtained. IG-131 was identified by transmission electron microscope (TEM), Fourier transform infrared spectroscopy (FT-IR), thermogravimetry-differential thermal analysis (TG-DTA), and X-ray diffraction (XRD).
ＴＥＭはＪＥＭ−２１００（日本電子株式会社製により加速電圧２００ｋＶで観察した。フォルムバール膜を張った銅メッシュ（１５０ｍｅｓｈ）に水分散液を滴下、余分な分散液をろ紙で吸い取り乾燥させ、観察試料とした。ＩＧ−１３１の観察結果を図２に示す。 TEM was observed with an acceleration voltage of 200 kV by JEM-2100 (manufactured by JEOL Ltd.). An aqueous dispersion was dropped onto a copper mesh (150 mesh) with a formval film, and the excess dispersion was blotted with a filter paper and dried. The observation result of IG-131 is shown in FIG.
ＦＴ−ＩＲはＦＴ／ＩＲ−４１００（日本分光株式会社製）により測定した。臭化カリウム微粉末にＩＧ紛体を混合後、圧をかけ作成したペレットを測定試料とした。ＩＧ−１３１の測定結果を図３に示す。 FT-IR was measured by FT / IR-4100 (manufactured by JASCO Corporation). After mixing the IG powder with the potassium bromide fine powder, the pellet formed by applying pressure was used as a measurement sample. The measurement result of IG-131 is shown in FIG.
ＴＧ−ＤＴＡは、Rigaku Thermo Plus TG8129（株式会社リガク製）により測定した。室温から１０００℃の範囲で昇温レート１０℃／ｍｉｎとし乾燥窒素下で重量変化を測定した。ＩＧ−１３１の測定結果を図４に示す。 TG-DTA was measured by Rigaku Thermo Plus TG8129 (manufactured by Rigaku Corporation). The change in weight was measured under dry nitrogen at a heating rate of 10 ° C./min in the range of room temperature to 1000 ° C. The measurement result of IG-131 is shown in FIG.
ＸＲＤは、SmartLab（株式会社リガク製）により測定した。室温でガラス板に乗せたＩＧ粉末に対し３°〜７０°の範囲で測定した。ＩＧ−１３１の測定結果を図５に示す。 XRD was measured by SmartLab (manufactured by Rigaku Corporation). It measured in the range of 3 degrees-70 degrees with respect to the IG powder put on the glass plate at room temperature. The measurement result of IG-131 is shown in FIG.
上記測定それぞれの結果より円筒状のＩＧが合成されたことを確認した。 From the results of the above measurements, it was confirmed that cylindrical IG was synthesized.
３．２．イモゴライト（ＩＧ）−イオン液体（ＩＬ）複合物の調製及び評価
ＩＧ−１３１ａｑ．及びＬＩＧａｑ．を、それぞれイオン液体（ＩＬ）と混合した。Ｉ
Ｌは、1-Ethyl-3-methylimidazolium 2-(2-Methoxyethoxy)ethyl Sulfate （[EmIm][MeSO3]と略することがある。）及び1-Butyl-3-methylimidazolium Tetrafluoroborate （[BmIm][BF4]と略することがある。）（いずれも東京化成工業株式会社製）を用いた。混合物より水を除去するために６０℃で３時間エバポレーションし、さらに６０℃で１２時間の真空加熱乾燥をおこなった。その結果、均一にＩＧとＩＬが混和した組成物（ＩＧ−ＩＬ）が得られた。
3.2. Preparation and evaluation of imogolite (IG) -ionic liquid (IL) complex IG-131aq. And LIGaq. Were each mixed with ionic liquid (IL). I
L may be abbreviated as 1-Ethyl-3-methylimidazolium 2- (2-Methoxyethoxy) ethyl Sulfate ([EmIm] [MeSO 3 ]) and 1-Butyl-3-methylimidazolium Tetrafluoroborate ([BmIm] [BF 4 ] may be abbreviated.) (Both manufactured by Tokyo Chemical Industry Co., Ltd.). In order to remove water from the mixture, the mixture was evaporated at 60 ° C. for 3 hours, and further dried under vacuum heating at 60 ° C. for 12 hours. As a result, a composition (IG-IL) in which IG and IL were uniformly mixed was obtained.
超音波照射の時間を１時間、２時間と変更した以外は、ＩＧ−１３１と同様にして、ＩＧ−１１００；平均長さ１．１μｍ、ＩＧ−８００；平均長さ０．８μｍを作成した。各実験例におけるＩＧ及びＩＬの種類及び配合量は、表１に示した。 IG-1100; average length 1.1 μm, IG-800; average length 0.8 μm were prepared in the same manner as IG-131 except that the time of ultrasonic irradiation was changed to 1 hour and 2 hours. The types and blending amounts of IG and IL in each experimental example are shown in Table 1.
ＩＧ−１３１及び[EmIm][MeSO3]を原料としたＩＧ−ＩＬ（実験例１）をスクリューバ
イアルに入れた状態の外観写真（図６（ａ））、並びに、ＬＩＧ及び[EmIm][MeSO3]を原料としたＩＧ−ＩＬ（実験例２）をスライドガラスに載せた状態の外観写真（図６（ｂ））を示す。図６（ａ）に示すように、実験例１では、ほぼ透明でオパレーセントな液体となることが判明した。一方図６（ｂ）に示すように、実験例２では、白色のペースト状固体となることが判明した。
External appearance photograph (FIG. 6 (a)) of IG-IL (Experimental Example 1) using IG-131 and [EmIm] [MeSO 3 ] as raw materials, and LIG and [EmIm] [MeSO 3 3 ] shows an external view photograph (Fig. 6 (b)) of a state where IG-IL (Experimental example 2) made from a raw material is placed on a slide glass. As shown in FIG. 6 (a), it was found that in Experimental Example 1, the liquid was almost transparent and operative. On the other hand, as shown in FIG. 6 (b), in Experimental Example 2, it was found to be a white pasty solid.
次に、ＴＥＭ観察を行った。図７（ａ）、図７（ｂ）及び図７（ｃ）は、それぞれ実験例１、実験例２及び実験例３のＴＥＭ観察結果を示す図である。図７において、いずれのＩＧ−ＩＬでも一部束状に凝集したナノチューブ構造が確認された。このことから、実験例１ないし実験例３のＩＧ−ＩＬ（組成物）中ではＩＧが網目構造を保って存在していることが判明した。 Next, TEM observation was performed. FIGS. 7A, 7B, and 7C are diagrams showing TEM observation results of Experimental Example 1, Experimental Example 2, and Experimental Example 3, respectively. In FIG. 7, any IG-IL confirmed a nanotube structure that was partly aggregated in a bundle. From this, it was found that IG was present in the IG-IL (composition) of Experimental Examples 1 to 3 while maintaining the network structure.
３．３．イモゴライト（ＩＧ）−イオン液体（ＩＬ）−二官能化合物（ＤＡ）の複合物の調製及び評価
上記で得られたＩＧ−１３１ａｑ．をイオン液体（ＩＬ）と混合した。ＩＬは、[EmIm]及び[BmIm][BF4]を用いた。混合物より水を除去するために６０℃３時間のエバポレーション及び６０℃１２時間の真空加熱乾燥を行って、均一にＩＧとＩＬが混和した組成物（ＩＧ−ＩＬ）を得た。ＩＧ−ＩＬをＩＬに溶解した二塩基酸（マレイン酸（ＭＡ）又は４−ホスホノブタン酸（ＰＢＡ）、いずれも和光純薬工業株式会社製）と混合し、ゲル状の組成物（複合物）（ＩＧ−ＩＬ−ＤＡ）を得た。なお、超音波照射の時間を１２時間と変更した以外は、ＩＧ−１３１と同様にして、ＩＧ−５０；平均長さ５０ｎｍを作成した。
3.3. Preparation and Evaluation of Imogolite (IG) -Ionic Liquid (IL) -Bifunctional Compound (DA) Composite IG-131aq. Was mixed with ionic liquid (IL). [EmIm] and [BmIm] [BF 4 ] were used for IL. In order to remove water from the mixture, evaporation at 60 ° C. for 3 hours and vacuum heat drying at 60 ° C. for 12 hours were performed to obtain a composition (IG-IL) in which IG and IL were uniformly mixed. A dibasic acid (maleic acid (MA) or 4-phosphonobutanoic acid (PBA), both manufactured by Wako Pure Chemical Industries, Ltd.) in which IG-IL is dissolved in IL is mixed, and a gel-like composition (composite) ( IG-IL-DA) was obtained. In addition, except having changed the time of ultrasonic irradiation to 12 hours, IG-50; average length 50nm was created like IG-131.
各実験例におけるＩＧ、ＩＬ及びＤＡの種類及び配合量は、表２に示した。 The types and blending amounts of IG, IL and DA in each experimental example are shown in Table 2.
図８は、ＩＧ−１３１[EmIm][MeSO3]、及びＭＡを原料としたＩＧ−ＩＬ−ＤＡ（実験例１３）を流動状態でスクリューバイアルに入れて正立させ、その状態で１時間静置し、静かに上下を反転させてスクリューバイアルを倒立させた際の外観写真（図８（ａ））、及び、同実験例１３のＩＧ−ＩＬ−ＤＡのＴＥＭ観察結果（図８（ｂ））である。
FIG. 8 shows that IG-131 [EmIm] [MeSO 3 ] and IG-IL-DA (Experimental Example 13) made of MA as raw materials are put in a screw vial in a fluidized state and left standing for one hour. And externally photographed when the screw vial is inverted by gently reversing the top and bottom (FIG. 8 (a)), and TEM observation result of IG-IL-DA of the experimental example 13 (FIG. 8 (b)) ).
図８（ａ）に示すとおり、実験例１３のＩＧ−ＩＬ−ＤＡは、優れた可逆的ゲル／ゾル転移（チクソトロピー性）を示すことが判明した。また、図８（ｂ）において、ナノチューブが作るネットワーク（網目構造）が確認された。このことからＩＧ−ＩＬ−ＤＡの組成物は、ＩＧが組成物中で網目構造を形成し、ゲル化していると考えられる。 As shown to Fig.8 (a), it turned out that IG-IL-DA of Experimental example 13 shows the outstanding reversible gel / sol transition (thixotropic property). Moreover, in FIG.8 (b), the network (network structure) which a nanotube makes was confirmed. From this, the composition of IG-IL-DA is considered that IG forms the network structure in the composition and is gelatinized.
３．４．イオン伝導度の測定
上述の実験例について、イオン伝導度を測定した。イオン伝導度は、複素インピーダンスから算出した。試料は、測定前に１２時間常温で真空乾燥を施した。測定はＳＵＳ製の電極に挟んだ試料に対し、Potentiostat/Galvanostat SP-150（BioLogic製）を用いて乾燥アルゴン雰囲気の循環精製装置付グローブボックス中にて実施した。測定周波数範囲は１００Ｈｚ〜１ＭＨｚとした。また、測定温度は、３０℃〜１００℃の範囲で７点測定した。
3.4. Measurement of ion conductivity Ion conductivity was measured for the above experimental example. The ionic conductivity was calculated from the complex impedance. The sample was vacuum dried at room temperature for 12 hours before measurement. The measurement was carried out on a sample sandwiched between SUS electrodes in a glove box with a circulation purifier in a dry argon atmosphere using Potentiostat / Galvanostat SP-150 (manufactured by BioLogic). The measurement frequency range was 100 Hz to 1 MHz. Moreover, the measurement temperature measured 7 points | pieces in the range of 30 to 100 degreeC.
図９は、実験例１、実験例２、及び、これらに使用したＩＬ（[EmIm][MeSO3]）のみの場合のイオン伝導度の測定結果のアレニウスプロットである。 FIG. 9 is an Arrhenius plot of the measurement results of ion conductivity in the case of Experiment 1, Experiment 2, and only IL ([EmIm] [MeSO 3 ]) used therein.
図１０は、実験例３、実験例５、及び、これらに使用したＩＬ（[BmIm][BF4]）のみの場合のイオン伝導度の測定結果のアレニウスプロットである。 FIG. 10 is an Arrhenius plot of the measurement results of ion conductivity in the case of Experimental Example 3, Experimental Example 5, and only IL ([BmIm] [BF 4 ]) used in these.
図１１は、実験例１３、実験例１６、及び、これらに使用したＩＬ（[EmIm][MeSO3]）のみの場合のイオン伝導度の測定結果のアレニウスプロットである。 FIG. 11 is an Arrhenius plot of measurement results of ion conductivity in the case of Experimental Example 13, Experimental Example 16, and only IL ([EmIm] [MeSO 3 ]) used therein.
図９〜図１１に示すように、各実験例の組成物は、広い温度範囲で高いイオン伝導度を呈することが判明した。 As shown in FIGS. 9 to 11, it was found that the composition of each experimental example exhibited high ionic conductivity over a wide temperature range.
また、表１及び表２に記載した各実験例について、ＩＧ−ＩＬに関しては、目視による性状観察を行い、固体（ペースト）状となったものをＡ、液体状ではあるが増粘効果が認められるものをＢとし、ＩＧ−ＩＬ−ＤＡに関しては、明確にチクソトロピー性が観察されたものをＡ、チクソトロピー性を示さないものをＢとして、各表に併記した。さらに、各実験例において、３０℃におけるイオン伝導度が、１×１０−３以上であるものをＡ、１×１０−３未満であるものをＢとして各表に併記した。 Moreover, about each experiment example described in Table 1 and Table 2, regarding IG-IL, the property observation by visual observation is performed, and what became solid (paste) form is A, and although it is a liquid form, the thickening effect is recognized. The IG-IL-DA is shown in each table as IG-IL-DA, where A is clearly observed thixotropy and B is not thixotropy. Furthermore, in each experimental example, those having an ionic conductivity at 30 ° C. of 1 × 10 −3 or more are shown in each table as A and those having an ion conductivity of less than 1 × 10 −3 as B.
表１をみると、いずれの実験例についても、増粘効果及び良好なイオン伝導性を示すことが分かった。また、ＩＧの平均長さが長いほど固体状となりやすい傾向があることが分かった。また、ＩＬの種類にかかわらず、高いイオン伝導度を示し、係るイオン伝導度は、ＩＧの配合量に大きく依存しないことが分かった。さらに、ＩＧの含有量が少なくても、平均長さが大きいと、十分に固体状となり得ることが分かった。 When Table 1 was seen, about any experimental example, it turned out that a thickening effect and favorable ion conductivity are shown. It was also found that the longer the average IG length, the more likely it becomes solid. Moreover, regardless of the type of IL, high ionic conductivity was exhibited, and it was found that such ionic conductivity did not greatly depend on the blending amount of IG. Furthermore, even if there was little content of IG, when the average length was large, it turned out that it can become solid state sufficiently.
また、表２をみると、いずれの実験例についても、良好なイオン伝導性を示すことが分かった。一方、チクソトロピー性については、ＩＧの平均長さ及び配合量、並びに、ＤＡの種類及び配合量等と、明確な相関は見られなかった。このことからチクソトロピー性は、ＩＧの平均長さ及び配合量、並びに、ＤＡの種類及び配合量のバランスによって発現すると考えられる。また、イオン伝導性については、ＩＬの種類が[BmIm][BF4]の場合には、[EmIm][MeSO3]の場合よりも少ない配合量で良好となる傾向が見られるが、[EmIm][MeSO3]を用いた実験例同士で比較すると、明確な傾向は認められなかった。このことから、イオン伝導性についても、ＩＧの平均長さ及び配合量、ＤＡの種類及び配合量、ＩＬの種類のバランスによって発現しているものと考えられる。 Moreover, when Table 2 was seen, about any experimental example, it turned out that favorable ion conductivity is shown. On the other hand, regarding thixotropy, there was no clear correlation with the average length and blending amount of IG, the type and blending amount of DA, and the like. From this, it is considered that thixotropic properties are manifested by the balance between the average length and blending amount of IG, and the type and blending amount of DA. In addition, regarding the ionic conductivity, when the type of IL is [BmIm] [BF 4 ], there is a tendency that it becomes better with a smaller amount than in the case of [EmIm] [MeSO 3 ], but [EmIm ] When comparing experimental examples using [MeSO 3 ], no clear tendency was observed. From this, it is considered that the ion conductivity is also expressed by the balance of the average length and blending amount of IG, the type and blending amount of DA, and the type of IL.
本発明は、本願に記載の特徴や効果を有する範囲で一部の構成を省略したり、各実施形態や変形例を組み合わせたりしてもよい。また本発明は、実施の形態で説明した構成と実質的に同一の構成（機能、方法及び結果が同一の構成、あるいは目的及び効果が同一の構成）を含む。また、本発明は、実施の形態で説明した構成の本質的でない部分を置き換えた構成を含む。また、本発明は、実施の形態で説明した構成と同一の作用効果を奏する構成又は同一の目的を達成することができる構成を含む。また、本発明は、実施の形態で説明した構成に公知技術を付加した構成を含む。 In the present invention, a part of the configuration may be omitted within a range having the characteristics and effects described in the present application, or each embodiment or modification may be combined. In addition, the invention includes substantially the same configuration (the configuration having the same function, method, and result, or the configuration having the same purpose and effect) as the configuration described in the embodiment. In addition, the invention includes a configuration in which a non-essential part of the configuration described in the embodiment is replaced. In addition, the present invention includes a configuration that exhibits the same operational effects as the configuration described in the embodiment or a configuration that can achieve the same object. Further, the invention includes a configuration in which a known technique is added to the configuration described in the embodiment.
本発明によれば、「チクソトロピー性／固体性状に由来する優れた加工性」と「イオン液体に由来する高いイオン伝導性」を併せ持つ電解質素材として有用な組成物が得られる。したがって本発明に係る組成物は、産業的・学術的に大きな意義がある。また、本発明に係る組成物は、各構成の混合ないし乾燥という簡便な工程で実施できる。そのため、電池を始めとした幅広い工業分野への応用が期待される。さらに、イモゴライトは塩化アルミニウムとオルトケイ酸ナトリウムの熱重合により合成できることから、例えばイオン液
体に分散し、イオン液体を固体化させるカーボンナノチューブ等の素材に比べて、安価かつ簡便に製造（合成）できるとともに、製造の大スケール化も可能であるため、この点においても産業的・工業的に有利である。
According to the present invention, a composition useful as an electrolyte material having both “excellent processability derived from thixotropic / solid properties” and “high ionic conductivity derived from an ionic liquid” can be obtained. Therefore, the composition according to the present invention has significant industrial and academic significance. Moreover, the composition according to the present invention can be carried out by a simple process of mixing or drying each component. Therefore, application to a wide range of industrial fields including batteries is expected. Furthermore, since imogolite can be synthesized by thermal polymerization of aluminum chloride and sodium orthosilicate, it can be produced (synthesized) cheaply and easily compared to materials such as carbon nanotubes that are dispersed in an ionic liquid and solidify the ionic liquid. Further, since it is possible to increase the scale of production, this point is also advantageous industrially and industrially.
Claims (9)
イオン液体と、
を含み、イオン伝導性を有する、組成物。 Imogolite having an average length of 1 μm to 10 μm;
An ionic liquid,
And a composition having ionic conductivity.
前記組成物は、動的粘弾性測定において、損失弾性率Ｇ”が貯蔵弾性率Ｇ’よりも小さくなるせん断ひずみの領域を有する、組成物。 In claim 1,
The composition has a shear strain region in which the loss elastic modulus G ″ is smaller than the storage elastic modulus G ′ in the dynamic viscoelasticity measurement.
イオン液体と、
多官能性化合物と、
を含み、イオン伝導性を有する、組成物。 Imogolite having an average length of 50 nm to 10 μm,
An ionic liquid,
A polyfunctional compound;
And a composition having ionic conductivity.
前記組成物は、動的粘弾性測定において、損失弾性率Ｇ”の値と貯蔵弾性率Ｇ’の値とが、逆転するせん断ひずみの領域を有する、組成物。 In claim 3,
The composition has a shear strain region in which the value of the loss modulus G ″ and the value of the storage modulus G ′ are reversed in the dynamic viscoelasticity measurement.
前記多官能性化合物は、二官能性有機酸である、組成物。 In claim 3 or claim 4,
The composition wherein the polyfunctional compound is a difunctional organic acid.
前記多官能性化合物は、
炭素数２以上６以下の化合物であって、
カルボキシル基、リン酸基、リン酸基、亜リン酸基、ホスホン酸基、スルホン酸基及び硫酸基から選択される少なくとも一種の基と、
アミノ基及びカルボキサミド基から選択される少なくとも一種の基と、
を含む、組成物。 In any one of Claims 3 thru | or 5,
The polyfunctional compound is
A compound having 2 to 6 carbon atoms,
At least one group selected from a carboxyl group, a phosphoric acid group, a phosphoric acid group, a phosphorous acid group, a phosphonic acid group, a sulfonic acid group, and a sulfuric acid group;
At least one group selected from an amino group and a carboxamide group;
A composition comprising:
前記多官能性化合物は、全質量に対して０．５質量％以上４．２質量％以下含まれる、組成物。 In any one of Claims 3 thru | or 6,
The polyfunctional compound is a composition comprising 0.5% by mass to 4.2% by mass with respect to the total mass.
前記イモゴライトは、全質量に対して２質量％以上１０質量％以下含まれる、組成物。 In any one of Claims 1 thru | or 7,
The imogolite is a composition containing 2% by mass to 10% by mass with respect to the total mass.
前記イオン液体は、イミダゾリウム塩、ピリジニウム塩、ピロリジニウム塩、ホスホニウム塩、アンモニウム塩、グアニジニウム塩、イソウロニウム塩及びイソチオウロニウム塩から選択される少なくとも一種である、組成物。 In any one of Claims 1 thru | or 8,
The composition, wherein the ionic liquid is at least one selected from imidazolium salts, pyridinium salts, pyrrolidinium salts, phosphonium salts, ammonium salts, guanidinium salts, isouronium salts, and isothiouronium salts.
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