JP6820727B2 - Capacitors and their manufacturing methods - Google Patents
Capacitors and their manufacturing methods Download PDFInfo
- Publication number
- JP6820727B2 JP6820727B2 JP2016227185A JP2016227185A JP6820727B2 JP 6820727 B2 JP6820727 B2 JP 6820727B2 JP 2016227185 A JP2016227185 A JP 2016227185A JP 2016227185 A JP2016227185 A JP 2016227185A JP 6820727 B2 JP6820727 B2 JP 6820727B2
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- Prior art keywords
- mass
- capacitor
- poly
- solid electrolyte
- conductive polymer
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- 239000003990 capacitor Substances 0.000 title claims description 90
- 238000004519 manufacturing process Methods 0.000 title claims description 24
- -1 azine compound Chemical class 0.000 claims description 86
- 229920001940 conductive polymer Polymers 0.000 claims description 59
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 48
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 33
- 229920000447 polyanionic polymer Polymers 0.000 claims description 29
- 239000002131 composite material Substances 0.000 claims description 26
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 26
- 229920000877 Melamine resin Polymers 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 18
- 239000004815 dispersion polymer Substances 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 12
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 claims description 9
- 229940005642 polystyrene sulfonic acid Drugs 0.000 claims description 9
- 230000001590 oxidative effect Effects 0.000 claims description 8
- JTTIOYHBNXDJOD-UHFFFAOYSA-N 2,4,6-triaminopyrimidine Chemical compound NC1=CC(N)=NC(N)=N1 JTTIOYHBNXDJOD-UHFFFAOYSA-N 0.000 claims description 4
- NJYZCEFQAIUHSD-UHFFFAOYSA-N acetoguanamine Chemical compound CC1=NC(N)=NC(N)=N1 NJYZCEFQAIUHSD-UHFFFAOYSA-N 0.000 claims description 4
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 3
- 239000004020 conductor Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- NUKYPUAOHBNCPY-UHFFFAOYSA-N 4-aminopyridine Chemical compound NC1=CC=NC=C1 NUKYPUAOHBNCPY-UHFFFAOYSA-N 0.000 claims 2
- 229960004979 fampridine Drugs 0.000 claims 2
- 239000007784 solid electrolyte Substances 0.000 description 85
- 239000000243 solution Substances 0.000 description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 31
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 24
- 239000007864 aqueous solution Substances 0.000 description 19
- 125000001424 substituent group Chemical group 0.000 description 13
- 239000002253 acid Substances 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 10
- 239000000654 additive Substances 0.000 description 10
- 230000000996 additive effect Effects 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 10
- 239000011888 foil Substances 0.000 description 10
- 125000003277 amino group Chemical group 0.000 description 9
- 238000000108 ultra-filtration Methods 0.000 description 9
- 239000006096 absorbing agent Substances 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 125000000129 anionic group Chemical group 0.000 description 6
- 239000003963 antioxidant agent Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000008151 electrolyte solution Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 229920000123 polythiophene Polymers 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 4
- 229920000767 polyaniline Polymers 0.000 description 4
- 229920000128 polypyrrole Polymers 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 150000003512 tertiary amines Chemical class 0.000 description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- FLDCSPABIQBYKP-UHFFFAOYSA-N 5-chloro-1,2-dimethylbenzimidazole Chemical compound ClC1=CC=C2N(C)C(C)=NC2=C1 FLDCSPABIQBYKP-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 239000001741 Ammonium adipate Substances 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical class C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000007983 Tris buffer Substances 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 235000019293 ammonium adipate Nutrition 0.000 description 3
- 150000001450 anions Chemical group 0.000 description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- 239000010955 niobium Substances 0.000 description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 3
- 150000003141 primary amines Chemical class 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 150000003335 secondary amines Chemical class 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 229910052715 tantalum Inorganic materials 0.000 description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 3
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical compound C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 description 2
- HXVNBWAKAOHACI-UHFFFAOYSA-N 2,4-dimethyl-3-pentanone Chemical compound CC(C)C(=O)C(C)C HXVNBWAKAOHACI-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 description 2
- QENGPZGAWFQWCZ-UHFFFAOYSA-N 3-Methylthiophene Chemical compound CC=1C=CSC=1 QENGPZGAWFQWCZ-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000005456 alcohol based solvent Substances 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- LIWAQLJGPBVORC-UHFFFAOYSA-N ethylmethylamine Chemical compound CCNC LIWAQLJGPBVORC-UHFFFAOYSA-N 0.000 description 2
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 2
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 2
- 238000007602 hot air drying Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000007603 infrared drying Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 2
- AUAAZFHKQJVSFA-UHFFFAOYSA-N pyridin-4-amine Chemical compound NC1=CC=NC=C1.NC1=CC=NC=C1 AUAAZFHKQJVSFA-UHFFFAOYSA-N 0.000 description 2
- LJXQPZWIHJMPQQ-UHFFFAOYSA-N pyrimidin-2-amine Chemical compound NC1=NC=CC=N1 LJXQPZWIHJMPQQ-UHFFFAOYSA-N 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 2
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical class CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 2
- OSBSFAARYOCBHB-UHFFFAOYSA-N tetrapropylammonium Chemical class CCC[N+](CCC)(CCC)CCC OSBSFAARYOCBHB-UHFFFAOYSA-N 0.000 description 2
- 125000005369 trialkoxysilyl group Chemical group 0.000 description 2
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 description 1
- SILNNFMWIMZVEQ-UHFFFAOYSA-N 1,3-dihydrobenzimidazol-2-one Chemical compound C1=CC=C2NC(O)=NC2=C1 SILNNFMWIMZVEQ-UHFFFAOYSA-N 0.000 description 1
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 description 1
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 description 1
- FBHPRUXJQNWTEW-UHFFFAOYSA-N 1-benzyl-2-methylimidazole Chemical compound CC1=NC=CN1CC1=CC=CC=C1 FBHPRUXJQNWTEW-UHFFFAOYSA-N 0.000 description 1
- MCMFEZDRQOJKMN-UHFFFAOYSA-N 1-butylimidazole Chemical compound CCCCN1C=CN=C1 MCMFEZDRQOJKMN-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- XDFZKQJLNGNJAN-UHFFFAOYSA-N 1-methylbenzimidazol-2-amine Chemical compound C1=CC=C2N(C)C(N)=NC2=C1 XDFZKQJLNGNJAN-UHFFFAOYSA-N 0.000 description 1
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Images
Description
本発明は、π共役系導電性高分子を含む固体電解質層を備えたキャパシタ及びその製造方法に関する。 The present invention relates to a capacitor provided with a solid electrolyte layer containing a π-conjugated conductive polymer and a method for producing the same.
キャパシタにおいては、誘電体層と陰極との間に配置される電解質として、導電性高分子を含む固体電解質層を用いて、等価直列抵抗を小さくしたものが知られている。
導電性高分子を含む固体電解質層としては、ポリ（３，４−エチレンジオキシチオフェン）とポリスチレンスルホン酸を含む導電性高分子分散液から形成したものが使用されることがある（例えば、特許文献１）。
In a capacitor, a solid electrolyte layer containing a conductive polymer is used as an electrolyte arranged between a dielectric layer and a cathode to reduce the equivalent series resistance.
As the solid electrolyte layer containing the conductive polymer, a layer formed from a conductive polymer dispersion containing poly (3,4-ethylenedioxythiophene) and polystyrene sulfonic acid may be used (for example, a patent). Document 1).
導電性高分子分散液を用いて製造された従来のキャパシタには、その等価直列抵抗をさらに小さくすることが求められている。
本発明は、等価直列抵抗が従来よりも小さいキャパシタ及びその製造方法を提供する。
Conventional capacitors manufactured using a conductive polymer dispersion are required to further reduce their equivalent series resistance.
The present invention provides a capacitor having a smaller equivalent series resistance than the conventional one and a method for manufacturing the same.
［１］ 弁金属の多孔質体からなる陽極と、前記弁金属の酸化物からなる誘電体層と、前記誘電体層の、前記陽極と反対側に設けられた導電物質製の陰極と、前記誘電体層及び前記陰極の間に設けられた少なくとも１層の固体電解質層とを具備し、前記固体電解質層が、π共役系導電性高分子及びポリアニオンを含む導電性複合体と、下記式（１）で表されるアジン化合物とを含有する、キャパシタ。 [1] An electrode made of a porous body of a valve metal, a dielectric layer made of an oxide of the valve metal, a cathode made of a conductive material provided on the opposite side of the dielectric layer to the anode, and the above. It is provided with at least one solid electrolyte layer provided between the dielectric layer and the cathode, and the solid electrolyte layer is a conductive composite containing a π-conjugated conductive polymer and a polyanion, and the following formula ( A capacitor containing an azine compound represented by 1).
［２］ 前記固体電解質層は、前記誘電体層の少なくとも一部を覆う第一の固体電解質層と、前記第一の固体電解質層の少なくとも一部を覆う第二の固体電解質層と、を有する、［１］に記載のキャパシタ。
［３］ 前記第一の固体電解質層は前記アジン化合物を含み、前記第二の固体電解質層は前記導電性複合体を含む、［２］に記載のキャパシタ。
［４］ 前記固体電解質層が、前記式（１）に該当しない含窒素化合物をさらに含有する、［１］〜［３］の何れか一項に記載のキャパシタ。
［５］ 前記式（１）に該当しない前記含窒素化合物が、イミダゾール、トリエチルアミン、及びトリプロピルアミンから選ばれる何れか１つ以上である、［４］に記載のキャパシタ。
［６］ 前記式（１）中、Ｒ１，Ｒ２，Ｒ３のうち少なくとも何れか１つはアミノ基である、［１］〜［５］の何れか一項に記載のキャパシタ。
［７］ 前記π共役系導電性高分子が、ポリ（３，４−エチレンジオキシチオフェン）である、［１］〜［６］の何れか一項に記載のキャパシタ。
［８］ 前記ポリアニオンが、ポリスチレンスルホン酸である、［１］〜［７］の何れか一項に記載のキャパシタ。
［９］ 弁金属の多孔質体からなる陽極の表面を酸化して誘電体層を形成する工程と、前記誘電体層に対向する位置に陰極を配置する工程と、前記誘電体層の表面の少なくとも一部に、前記式（１）で表されるアジン化合物を含む溶液を塗布し、乾燥させて、第一の固体電解質層を形成する工程と、前記第一の固体電解質層の表面の少なくとも一部に、π共役系導電性高分子及びポリアニオンを含む導電性複合体が分散された導電性高分子分散液を塗布し、乾燥させて、第二の固体電解質層を形成する工程と、を有するキャパシタの製造方法。
［１０］ 前記溶液及び前記導電性高分子分散液のうち少なくとも一方が、前記式（１）に該当しない含窒素化合物を含む、［９］に記載のキャパシタの製造方法。
［１１］ 前記式（１）に該当しない前記含窒素化合物が、イミダゾール、トリエチルアミン、及びトリプロピルアミンから選ばれる何れか１つ以上である、［１０］に記載のキャパシタの製造方法。
［１２］ 前記式（１）中、Ｒ１，Ｒ２，Ｒ３のうち少なくとも何れか１つはアミノ基である、［９］〜［１１］の何れか一項に記載のキャパシタの製造方法。
［１３］ 前記π共役系導電性高分子が、ポリ（３，４−エチレンジオキシチオフェン）である、［９］〜［１２］の何れか一項に記載のキャパシタの製造方法。
［１４］ 前記ポリアニオンが、ポリスチレンスルホン酸である、［９］〜［１３］の何れか一項に記載のキャパシタの製造方法。
[2] The solid electrolyte layer includes a first solid electrolyte layer that covers at least a part of the dielectric layer, and a second solid electrolyte layer that covers at least a part of the first solid electrolyte layer. , [1].
[3] The capacitor according to [2], wherein the first solid electrolyte layer contains the azine compound, and the second solid electrolyte layer contains the conductive composite.
[4] The capacitor according to any one of [1] to [3], wherein the solid electrolyte layer further contains a nitrogen-containing compound that does not correspond to the formula (1).
[5] The capacitor according to [4], wherein the nitrogen-containing compound that does not correspond to the formula (1) is any one or more selected from imidazole, triethylamine, and tripropylamine.
[6] The capacitor according to any one of [1] to [5], wherein at least one of R 1 , R 2 , and R 3 in the above formula (1) is an amino group.
[7] The capacitor according to any one of [1] to [6], wherein the π-conjugated conductive polymer is poly (3,4-ethylenedioxythiophene).
[8] The capacitor according to any one of [1] to [7], wherein the polyanion is polystyrene sulfonic acid.
[9] A step of forming a dielectric layer by oxidizing the surface of an anode made of a porous body of a valve metal, a step of arranging a cathode at a position facing the dielectric layer, and a step of arranging a cathode on the surface of the dielectric layer. A step of applying a solution containing an azine compound represented by the formula (1) to at least a part thereof and drying it to form a first solid electrolyte layer, and at least a surface of the first solid electrolyte layer. A step of applying a conductive polymer dispersion liquid in which a conductive composite containing a π-conjugated conductive polymer and a polyanion is dispersed and drying the mixture to form a second solid electrolyte layer. A method for manufacturing a dielectric having a capacitor.
[10] The method for producing a capacitor according to [9], wherein at least one of the solution and the conductive polymer dispersion contains a nitrogen-containing compound that does not correspond to the formula (1).
[11] The method for producing a capacitor according to [10], wherein the nitrogen-containing compound that does not correspond to the formula (1) is any one or more selected from imidazole, triethylamine, and tripropylamine.
[12] The method for producing a capacitor according to any one of [9] to [11], wherein at least one of R 1 , R 2 , and R 3 in the formula (1) is an amino group. ..
[13] The method for producing a capacitor according to any one of [9] to [12], wherein the π-conjugated conductive polymer is poly (3,4-ethylenedioxythiophene).
[14] The method for producing a capacitor according to any one of [9] to [13], wherein the polyanion is polystyrene sulfonic acid.
本発明のキャパシタの等価直列抵抗は従来よりも小さく、電子機器の高性能化に資する。
本発明のキャパシタの製造方法によれば、等価直列抵抗が小さいキャパシタを容易に製造することができる。
The equivalent series resistance of the capacitor of the present invention is smaller than that of the conventional one, which contributes to higher performance of electronic devices.
According to the capacitor manufacturing method of the present invention, a capacitor having a small equivalent series resistance can be easily manufactured.
《キャパシタ》
本発明のキャパシタの一実施形態について説明する。図１に示すように、本実施形態のキャパシタ１０は、弁金属の多孔質体からなる陽極１１と、弁金属の酸化物からなる誘電体層１２と、誘電体層１２の表面に形成された固体電解質層１４と、最も表側に設けられた陰極１３とを具備する。
《Capacitor》
An embodiment of the capacitor of the present invention will be described. As shown in FIG. 1, the
陽極１１を構成する弁金属としては、例えば、アルミニウム、タンタル、ニオブ、チタン、ハフニウム、ジルコニウム、亜鉛、タングステン、ビスマス、アンチモンなどが挙げられる。これらのうち、アルミニウム、タンタル、ニオブが好適である。
陽極１１の具体例としては、アルミニウム箔をエッチングして表面積を増加させた後、その表面を酸化処理したものや、タンタル粒子やニオブ粒子の焼結体表面を酸化処理してペレットにしたものが挙げられる。このように処理されたものは表面に凹凸が形成された多孔質体となる。
Examples of the valve metal constituting the anode 11 include aluminum, tantalum, niobium, titanium, hafnium, zirconium, zinc, tungsten, bismuth, and antimony. Of these, aluminum, tantalum, and niobium are preferable.
Specific examples of the anode 11 include etching an aluminum foil to increase the surface area and then oxidizing the surface thereof, and oxidizing the surface of a sintered body of tantalum particles and niobium particles to form pellets. Can be mentioned. The product treated in this way becomes a porous body having irregularities formed on its surface.
本実施形態における誘電体層１２は、陽極１１の表面が酸化されて形成された層であり、例えば、アジピン酸アンモニウム水溶液などの電解液中にて、金属体の陽極１１の表面を陽極酸化することで形成されたものである。よって、図１に示すように、陽極１１と同様に誘電体層１２にも凹凸が形成されている。
The
本実施形態における陰極１３としては、導電性ペーストから形成した導電層やアルミニウム箔など、導電物質製の金属層を使用することができる。
As the
本実施形態における固体電解質層１４は、第一の固体電解質層と、第二の固体電解質層とがこの順で誘電体層１２の表面に積層された構造を有する。第一の固体電解質層は、誘電体層１２の表面の少なくとも一部を覆っており、誘電体層１２の表面の全部を覆っていてもよい。第二の固体電解質層は、第一の固体電解質層の少なくとも一部を覆っており、第一の固体電解質層の全部を覆っていてもよい。第一の固体電解質層が誘電体層１２の一部を覆い、第二の固体電解質層が第一の固体電解質層を覆う構成において、第二の固体電解質層は、第一の固体電解質層に覆われていない誘電体層１２の残部も覆うことが好ましい。
本実施形態では第一の固体電解質層と第二の固体電解質層との境界が明確に分かれている場合について説明するが、その境界が明確に分かれていなくても構わない。
The
In the present embodiment, the case where the boundary between the first solid electrolyte layer and the second solid electrolyte layer is clearly separated will be described, but the boundary may not be clearly separated.
固体電解質層１４の厚さは、一定でもよいし、一定でなくてもよく、例えば、１μｍ以上１００μｍ以下の範囲内の厚さが挙げられる。
第一の固体電解質層の厚さｔ１と第二の固体電解質層の厚さｔ２の相対比（ｔ１／ｔ２）は、特に限定されず、例えば、１０／１〜１／１０が挙げられる。
The thickness of the
The relative ratio (t1 / t2) of the thickness t1 of the first solid electrolyte layer and the thickness t2 of the second solid electrolyte layer is not particularly limited, and examples thereof include 10/1 to 1/10.
第一の固体電解質層は、後述する式（１）で表されるアジン化合物を含有している。
第二の固体電解質層は、後で詳述するπ共役系導電性高分子及びポリアニオンを含む導電性複合体を含有している。
第一の固体電解質層は、前記導電性複合体を含有してもよいし、含有しなくてもよい。
第二の固体電解質層は、後述する式（１）で表されるアジン化合物を含有してもよいし、含有しなくてもよい。
The first solid electrolyte layer contains an azine compound represented by the formula (1) described later.
The second solid electrolyte layer contains a conductive composite containing a π-conjugated conductive polymer and a polyanion, which will be described in detail later.
The first solid electrolyte layer may or may not contain the conductive composite.
The second solid electrolyte layer may or may not contain the azine compound represented by the formula (1) described later.
本実施形態の固体電解質層は、下記式（１）で表されるアジン化合物を含有している。 The solid electrolyte layer of the present embodiment contains an azine compound represented by the following formula (1).
前記Ｘ１，Ｘ２，Ｘ３のうち、何れか１つがＮであってもよいし、何れか２つがＮであってもよいし、３つ全てがＮであってもよい。 Of the above X 1 , X 2 , and X 3 , any one may be N, any two may be N, or all three may be N.
前記Ｒ１，Ｒ２，Ｒ３の何れかが任意の置換基である場合、その任意の置換基としては、例えば、アルキル基（例えば、メチル基、エチル基、プロピル基、ブチル基等）、アルケニル基（例えば、ビニル基、アリル基等）、アルコキシ基（例えば、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基、等）、アリール基（例えば、フェニル基等）等が挙げられる。これらの置換基は、さらに別の置換基（例えば、アリルオキシ基、（メタ）アクリロイルオキシ基、カルボキシ基、ヒドロキシ基、メルカプト基、エポキシ基、アミノ基、トリアルコキシシリル基等）を有してもよい。 When any of the above R 1 , R 2 , and R 3 is an arbitrary substituent, the optional substituent includes, for example, an alkyl group (for example, a methyl group, an ethyl group, a propyl group, a butyl group, etc.). Examples thereof include an alkenyl group (for example, vinyl group, allyl group, etc.), an alkoxy group (for example, methoxy group, ethoxy group, propoxy group, butoxy group, etc.), an aryl group (for example, phenyl group, etc.) and the like. These substituents may have yet another substituent (eg, allyloxy group, (meth) acryloyloxy group, carboxy group, hydroxy group, mercapto group, epoxy group, amino group, trialkoxysilyl group, etc.). Good.
前記Ｒ１，Ｒ２，Ｒ３の何れかが窒素を有する置換基である場合、その置換基はアミノ基であることが好ましい。前記アミノ基を構成する水素原子は、さらに別の置換基によって置換されていてもよい。前記別の置換基としては、例えば、メチル基、エチル基、プロピル基、ブチル基等のアルキル基；アリル基などのアルケニル基；メトキシメチル基、エトキシメチル基、メトキシエチル基、エトキシエチル基等のアルコキシアルキル基；（メタ）アクリロイルオキシ基、カルボキシ基、ヒドロキシ基、エポキシ基、アミノ基、トリアルコキシシリル基等が挙げられる。 When any of the above R 1 , R 2 and R 3 is a substituent having nitrogen, the substituent is preferably an amino group. The hydrogen atom constituting the amino group may be substituted with yet another substituent. Examples of the other substituent include an alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group; an alkenyl group such as an allyl group; a methoxymethyl group, an ethoxymethyl group, a methoxyethyl group and an ethoxyethyl group. Alkoxyalkyl group; (meth) acryloyloxy group, carboxy group, hydroxy group, epoxy group, amino group, trialkoxysilyl group and the like can be mentioned.
前記式（１）で表されるアジン化合物の好適な具体例として、例えば、メラミン、アセトグアナミン、２，４，６−［トリス(ビスメトキシメチル) アミノ］−１，３，５−トリアジン、２，４，６−トリアミノピリミジン、２−アミノピリミジン、ｐ−アミノピリジン（４−アミノピリジン）、Ｎ，Ｎ−ジメチル−４−アミノピリジン（ＤＭＡＰ）等が挙げられる。これらのアジン化合物が固体電解質層に含有されていると、キャパシタの等価直列抵抗がより低下し易くなるので好ましい。 Suitable specific examples of the azine compound represented by the above formula (1) include, for example, melamine, acetoguanamine, 2,4,6- [tris (bismethoxymethyl) amino] -1,3,5-triazine, 2 , 4,6-Triaminopyrimidine, 2-aminopyrimidine, p-aminopyridine (4-aminopyridine), N, N-dimethyl-4-aminopyridine (DMAP) and the like. It is preferable that these azine compounds are contained in the solid electrolyte layer because the equivalent series resistance of the capacitor is more likely to decrease.
第一の固体電解質層の総質量に対するアジン化合物の含有量は、８０質量％以上１００質量％以下が好ましく、９０質量％以上１００質量％以下がより好ましく、９５質量％以上１００質量％以下がさらに好ましい。上記の範囲であると、キャパシタの等価直列抵抗がより低下し易くなるので好ましい。 The content of the azine compound with respect to the total mass of the first solid electrolyte layer is preferably 80% by mass or more and 100% by mass or less, more preferably 90% by mass or more and 100% by mass or less, and further preferably 95% by mass or more and 100% by mass or less. preferable. The above range is preferable because the equivalent series resistance of the capacitor is more likely to decrease.
次に、第二の固体電解質層に含有されるπ共役系導電性高分子及びポリアニオンを含む導電性複合体について説明する。
π共役系導電性高分子としては、主鎖がπ共役系で構成されている有機高分子であれば特に制限されず、例えば、ポリピロール系導電性高分子、ポリチオフェン系導電性高分子、ポリアセチレン系導電性高分子、ポリフェニレン系導電性高分子、ポリフェニレンビニレン系導電性高分子、ポリアニリン系導電性高分子、ポリアセン系導電性高分子、ポリチオフェンビニレン系導電性高分子、及びこれらの共重合体等が挙げられる。空気中での安定性の点からは、ポリピロール系導電性高分子、ポリチオフェン類及びポリアニリン系導電性高分子が好ましく、ポリチオフェン系導電性高分子がより好ましい。
Next, a conductive composite containing a π-conjugated conductive polymer and a polyanion contained in the second solid electrolyte layer will be described.
The π-conjugated conductive polymer is not particularly limited as long as it is an organic polymer whose main chain is composed of a π-conjugated system. For example, a polypyrrole-based conductive polymer, a polythiophene-based conductive polymer, or a polyacetylene-based polymer Conductive polymer, polyphenylene-based conductive polymer, polyphenylene vinylene-based conductive polymer, polyaniline-based conductive polymer, polyacene-based conductive polymer, polythiophene vinylene-based conductive polymer, and copolymers thereof, etc. Can be mentioned. From the viewpoint of stability in air, polypyrrole-based conductive polymers, polythiophenes and polyaniline-based conductive polymers are preferable, and polythiophene-based conductive polymers are more preferable.
ポリチオフェン系導電性高分子としては、例えば、ポリチオフェン、ポリ（３−メチルチオフェン）、ポリ（３−エチルチオフェン）、ポリ（３−プロピルチオフェン）、ポリ（３−ブチルチオフェン）、ポリ（３−ヘキシルチオフェン）、ポリ（３−ヘプチルチオフェン）、ポリ（３−オクチルチオフェン）、ポリ（３−デシルチオフェン）、ポリ（３−ドデシルチオフェン）、ポリ（３−オクタデシルチオフェン）、ポリ（３−ブロモチオフェン）、ポリ（３−クロロチオフェン）、ポリ（３−ヨードチオフェン）、ポリ（３−シアノチオフェン）、ポリ（３−フェニルチオフェン）、ポリ（３，４−ジメチルチオフェン）、ポリ（３，４−ジブチルチオフェン）、ポリ（３−ヒドロキシチオフェン）、ポリ（３−メトキシチオフェン）、ポリ（３−エトキシチオフェン）、ポリ（３−ブトキシチオフェン）、ポリ（３−ヘキシルオキシチオフェン）、ポリ（３−ヘプチルオキシチオフェン）、ポリ（３−オクチルオキシチオフェン）、ポリ（３−デシルオキシチオフェン）、ポリ（３−ドデシルオキシチオフェン）、ポリ（３−オクタデシルオキシチオフェン）、ポリ（３，４−ジヒドロキシチオフェン）、ポリ（３，４−ジメトキシチオフェン）、ポリ（３，４−ジエトキシチオフェン）、ポリ（３，４−ジプロポキシチオフェン）、ポリ（３，４−ジブトキシチオフェン）、ポリ（３，４−ジヘキシルオキシチオフェン）、ポリ（３，４−ジヘプチルオキシチオフェン）、ポリ（３，４−ジオクチルオキシチオフェン）、ポリ（３，４−ジデシルオキシチオフェン）、ポリ（３，４−ジドデシルオキシチオフェン）、ポリ（３，４−エチレンジオキシチオフェン）、ポリ（３，４−プロピレンジオキシチオフェン）、ポリ（３，４−ブチレンジオキシチオフェン）、ポリ（３−メチル−４−メトキシチオフェン）、ポリ（３−メチル−４−エトキシチオフェン）、ポリ（３−カルボキシチオフェン）、ポリ（３−メチル−４−カルボキシチオフェン）、ポリ（３−メチル−４−カルボキシエチルチオフェン）、ポリ（３−メチル−４−カルボキシブチルチオフェン）が挙げられる。 Examples of the polythiophene-based conductive polymer include polythiophene, poly (3-methylthiophene), poly (3-ethylthiophene), poly (3-propylthiophene), poly (3-butylthiophene), and poly (3-hexyl). Thiophene), poly (3-heptylthiophene), poly (3-octylthiophene), poly (3-decylthiophene), poly (3-dodecylthiophene), poly (3-octadecylthiophene), poly (3-bromothiophene) , Poly (3-chlorothiophene), poly (3-iodothiophene), poly (3-cyanothiophene), poly (3-phenylthiophene), poly (3,4-dimethylthiophene), poly (3,4-dibutyl) Thiophene), poly (3-hydroxythiophene), poly (3-methoxythiophene), poly (3-ethoxythiophene), poly (3-butoxythiophene), poly (3-hexyloxythiophene), poly (3-heptyloxy) Thiophene), poly (3-octyloxythiophene), poly (3-decyloxythiophene), poly (3-dodecyloxythiophene), poly (3-octadecyloxythiophene), poly (3,4-dihydroxythiophene), poly (3,4-dimethoxythiophene), poly (3,4-diethoxythiophene), poly (3,4-dipropoxythiophene), poly (3,4-dibutoxythiophene), poly (3,4-dihexyloxy) Thiophene), poly (3,4-diheptyloxythiophene), poly (3,4-dioctyloxythiophene), poly (3,4-didecyloxythiophene), poly (3,4-didodecyloxythiophene), Poly (3,4-ethylenedioxythiophene), poly (3,4-propylenedioxythiophene), poly (3,4-butylenedioxythiophene), poly (3-methyl-4-methoxythiophene), poly (3-methyl-4-methoxythiophene) 3-Methyl-4-ethoxythiophene), poly (3-carboxythiophene), poly (3-methyl-4-carboxythiophene), poly (3-methyl-4-carboxyethylthiophene), poly (3-methyl-4) -Carboxybutylthiophene).
ポリピロール系導電性高分子としては、例えば、ポリピロール、ポリ（Ｎ−メチルピロール）、ポリ（３−メチルピロール）、ポリ（３−エチルピロール）、ポリ（３−ｎ−プロピルピロール）、ポリ（３−ブチルピロール）、ポリ（３−オクチルピロール）、ポリ（３−デシルピロール）、ポリ（３−ドデシルピロール）、ポリ（３，４−ジメチルピロール）、ポリ（３，４−ジブチルピロール）、ポリ（３−カルボキシピロール）、ポリ（３−メチル−４−カルボキシピロール）、ポリ（３−メチル−４−カルボキシエチルピロール）、ポリ（３−メチル−４−カルボキシブチルピロール）、ポリ（３−ヒドロキシピロール）、ポリ（３−メトキシピロール）、ポリ（３−エトキシピロール）、ポリ（３−ブトキシピロール）、ポリ（３−ヘキシルオキシピロール）、ポリ（３−メチル−４−ヘキシルオキシピロール）が挙げられる。 Examples of the polypyrrole-based conductive polymer include polypyrrole, poly (N-methylpyrrole), poly (3-methylpyrrole), poly (3-ethylpyrrole), poly (3-n-propylpyrrole), and poly (3). -Butylpyrrole), poly (3-octylpyrrole), poly (3-decylpyrrole), poly (3-dodecylpyrrole), poly (3,4-dimethylpyrrole), poly (3,4-dibutylpyrrole), poly (3-carboxypyrrole), poly (3-methyl-4-carboxypyrrole), poly (3-methyl-4-carboxyethylpyrrole), poly (3-methyl-4-carboxybutylpyrrole), poly (3-hydroxy) Pyrrole), poly (3-methoxypyrrole), poly (3-ethoxypyrrole), poly (3-butoxypyrrole), poly (3-hexyloxypyrrole), poly (3-methyl-4-hexyloxypyrrole). Be done.
ポリアニリン系導電性高分子としては、例えば、ポリアニリン、ポリ（２−メチルアニリン）、ポリ（３−イソブチルアニリン）、ポリ（２−アニリンスルホン酸）、ポリ（３−アニリンスルホン酸）が挙げられる。
以上で例示したπ共役系導電性高分子の中でも、導電性、耐熱性の点から、ポリ（３，４−エチレンジオキシチオフェン）が特に好ましい。
π共役系導電性高分子は１種を単独で使用してもよいし、２種以上を併用してもよい。
Examples of the polyaniline-based conductive polymer include polyaniline, poly (2-methylaniline), poly (3-isobutylaniline), poly (2-aniline sulfonic acid), and poly (3-aniline sulfonic acid).
Among the π-conjugated conductive polymers exemplified above, poly (3,4-ethylenedioxythiophene) is particularly preferable from the viewpoint of conductivity and heat resistance.
One type of π-conjugated conductive polymer may be used alone, or two or more types may be used in combination.
ポリアニオンとは、アニオン基を有するモノマー単位を、分子内に２つ以上有する重合体である。このポリアニオンのアニオン基は、π共役系導電性高分子に対するドーパントとして機能して、π共役系導電性高分子の導電性を向上させることができる。
ポリアニオンのアニオン基は、スルホ基またはカルボキシ基であることが好ましい。
ポリアニオンの具体例としては、ポリスチレンスルホン酸、ポリビニルスルホン酸、ポリアリルスルホン酸、ポリアクリルスルホン酸、ポリメタクリルスルホン酸、ポリ（２−アクリルアミド−２−メチルプロパンスルホン酸）、ポリイソプレンスルホン酸、ポリスルホエチルメタクリレート、ポリ（４−スルホブチルメタクリレート）、ポリメタクリルオキシベンゼンスルホン酸等のスルホン酸基を有する高分子や、ポリビニルカルボン酸、ポリスチレンカルボン酸、ポリアリルカルボン酸、ポリアクリルカルボン酸、ポリメタクリルカルボン酸、ポリ（２−アクリルアミド−２−メチルプロパンカルボン酸）、ポリイソプレンカルボン酸、ポリアクリル酸等のカルボン酸基を有する高分子が挙げられる。これらの単独重合体であってもよいし、２種以上の共重合体であってもよい。
これらのポリアニオンのなかでも、導電性をより高くできることから、スルホン酸基を有する高分子が好ましく、ポリスチレンスルホン酸がより好ましい。
ポリアニオンは１種を単独で使用してもよいし、２種以上を併用してもよい。
ポリアニオンの質量平均分子量は２万以上１００万以下であることが好ましく、１０万以上５０万以下であることがより好ましい。
本明細書における質量平均分子量は、ゲルパーミエーションクロマトグラフィで測定し、標準物質をポリスチレンとして求めた値である。
The polyanion is a polymer having two or more monomer units having an anionic group in the molecule. The anionic group of this polyanion functions as a dopant for the π-conjugated conductive polymer, and can improve the conductivity of the π-conjugated conductive polymer.
The anionic group of the polyanion is preferably a sulfo group or a carboxy group.
Specific examples of the polyanion include polystyrene sulfonic acid, polyvinyl sulfonic acid, polyallyl sulfonic acid, polyacrylic sulfonic acid, polymethacrylsulfonic acid, poly (2-acrylamide-2-methylpropanesulfonic acid), polyisoprenesulfonic acid, and poly. Polymers with sulfonic acid groups such as sulfoethyl methacrylate, poly (4-sulfobutyl methacrylate), polymethacryloxybenzenesulfonic acid, polyvinylcarboxylic acid, polystyrene carboxylic acid, polyallylcarboxylic acid, polyacryliccarboxylic acid, polymethacryl Examples thereof include polymers having a carboxylic acid group such as carboxylic acid, poly (2-acrylamide-2-methylpropanecarboxylic acid), polyisoprenecarboxylic acid, and polyacrylic acid. These homopolymers may be used, or two or more kinds of copolymers may be used.
Among these polyanions, a polymer having a sulfonic acid group is preferable, and polystyrene sulfonic acid is more preferable, because the conductivity can be made higher.
One type of polyanion may be used alone, or two or more types may be used in combination.
The mass average molecular weight of the polyanion is preferably 20,000 or more and 1 million or less, and more preferably 100,000 or more and 500,000 or less.
The mass average molecular weight in the present specification is a value obtained by measuring by gel permeation chromatography and using polystyrene as a standard substance.
導電性複合体中の、ポリアニオンの含有割合は、π共役系導電性高分子１００質量部に対して１質量部以上１０００質量部以下の範囲であることが好ましく、１０質量部以上７００質量部以下の範囲であることがより好ましく、１００質量部以上５００質量部以下の範囲であることがさらに好ましい。ポリアニオンの含有割合が前記下限値未満であると、π共役系導電性高分子へのドーピング効果が弱くなる傾向にあり、導電性が不足することがあり、また、導電性高分子分散液における導電性複合体の分散性が低くなる。一方、ポリアニオンの含有量が前記上限値を超えると、π共役系導電性高分子の含有量が少なくなり、やはり充分な導電性が得られにくい。 The content ratio of the polyanion in the conductive composite is preferably in the range of 1 part by mass or more and 1000 parts by mass or less with respect to 100 parts by mass of the π-conjugated conductive polymer, and is 10 parts by mass or more and 700 parts by mass or less. The range is more preferably 100 parts by mass or more and 500 parts by mass or less. If the content ratio of the polyanion is less than the above lower limit value, the doping effect on the π-conjugated conductive polymer tends to be weakened, the conductivity may be insufficient, and the conductivity in the conductive polymer dispersion is also reduced. The dispersibility of the sex complex is low. On the other hand, when the content of the polyanion exceeds the upper limit value, the content of the π-conjugated conductive polymer decreases, and it is also difficult to obtain sufficient conductivity.
ポリアニオンがπ共役系導電性高分子に配位してドープすることによって導電性複合体が形成される。
ただし、本実施形態におけるポリアニオンにおいては、全てのアニオン基がπ共役系導電性高分子にドープすることはなく、ドープに寄与しない余剰のアニオン基を有するようになっている。
A conductive composite is formed by coordinating and doping a π-conjugated conductive polymer with a polyanion.
However, in the polyanion in the present embodiment, not all the anion groups are doped into the π-conjugated conductive polymer, and the polyanion has a surplus anion group that does not contribute to the doping.
第二の固体電解質層の総質量に対する導電性複合体の含有量は、８０質量％以上１００質量％以下が好ましく、９０質量％以上１００質量％以下がより好ましく、９５質量％以上１００質量％以下がさらに好ましい。上記の範囲であると、キャパシタの等価直列抵抗がより低下し易くなるので好ましい。 The content of the conductive composite with respect to the total mass of the second solid electrolyte layer is preferably 80% by mass or more and 100% by mass or less, more preferably 90% by mass or more and 100% by mass or less, and 95% by mass or more and 100% by mass or less. Is even more preferable. The above range is preferable because the equivalent series resistance of the capacitor is more likely to decrease.
前記固体電解質層の第一の固体電解質層及び第二の固体電解質層のうち少なくとも一方には、前記式（１）に該当しない含窒素化合物の１種以上がさらに含有されていてもよい。この含窒素化合物が固体電解質層に含まれることによって、キャパシタの等価直列抵抗をさらに低減できることがある。 At least one of the first solid electrolyte layer and the second solid electrolyte layer of the solid electrolyte layer may further contain one or more nitrogen-containing compounds that do not correspond to the formula (1). By including this nitrogen-containing compound in the solid electrolyte layer, the equivalent series resistance of the capacitor may be further reduced.
前記含窒素化合物として、以下のアミン化合物及び窒素含有芳香族性化合物を例示できる。これらのアミン化合物及び窒素含有芳香族性化合物の少なくともどちらか一方が固体電解質層に含まれると、キャパシタの等価直列抵抗をさらに低減できることがある。
アミン化合物は、アミノ基を有する化合物であり、アミノ基が、ポリアニオンのアニオン基と反応する。
アミン化合物としては、１級アミン、２級アミン、３級アミン、４級アンモニウム塩のいずれであってもよい。また、アミン化合物は１種を単独で使用してもよいし、２種以上を併用してもよい。
アミン化合物は、炭素数２以上１２以下の直鎖、もしくは分岐鎖のアルキル基、炭素数６以上１２以下のアリール基、炭素数７以上１２以下のアラルキル基、炭素数２以上１２以下のアルキレン基、炭素数６以上１２以下のアリーレン基、炭素数７以上１２以下のアラルキレン基、及び炭素数２以上１２以下のオキシアルキレン基から選択される置換基を有していてもよい。
具体的な１級アミンとしては、例えば、アニリン、トルイジン、ベンジルアミン、エタノールアミン等が挙げられる。
具体的な２級アミンとしては、例えば、ジエタノールアミン、ジメチルアミン、ジエチルアミン、ジプロピルアミン、ジフェニルアミン、ジベンジルアミン、ジナフチルアミン等が挙げられる。
具体的な３級アミンとしては、例えば、トリエタノールアミン、トリメチルアミン、トリエチルアミン、トリプロピルアミン、トリブチルアミン、トリオクチルアミン、トリフェニルアミン、トリベンジルアミン、トリナフチルアミン等が挙げられる。
具体的な４級アンモニウム塩としては、例えば、テトラメチルアンモニウム塩、テトラエチルアンモニウム塩、テトラプロピルアンモニウム塩、テトラフェニルアンモニウム塩、テトラベンジルアンモニウム塩、テトラナフチルアンモニウム塩等が挙げられる。アンモニウムの対となる陰イオンとしてはヒドロキシドイオンが挙げられる。
これらアミン化合物のうち、３級アミンが好ましく、トリエチルアミン、トリプロピルアミンがより好ましい。
窒素含有芳香族性化合物としては、例えば、アニリン、ベンジルアミン、ピロール、イミダゾール、２−メチルイミダゾール、２−プロピルイミダゾール、Ｎ−メチルイミダゾール、Ｎ−プロピルイミダゾール、Ｎ−ブチルイミダゾール、１−（２−ヒドロキシエチル）イミダゾール、２−エチル−４−メチルイミダゾール、１，２−ジメチルイミダゾール、１−ベンジル−２−メチルイミダゾール、１−シアノエチル−２−メチルイミダゾール、１−シアノエチル−２−エチル−４−メチルイミダゾール、２−フェニル−４，５−ジヒドロキシメチルイミダゾール、１−アセチルイミダゾール、２−アミノベンズイミダゾール、２−アミノ−１−メチルベンズイミダゾール、２−ヒドロキシベンズイミダゾール、２−（２−ピリジル）ベンズイミダゾール、ピリジン等が挙げられる。
これら窒素含有芳香族性化合物のうち、イミダゾールがより好ましい。
Examples of the nitrogen-containing compound include the following amine compounds and nitrogen-containing aromatic compounds. When at least one of these amine compounds and nitrogen-containing aromatic compounds is contained in the solid electrolyte layer, the equivalent series resistance of the capacitor may be further reduced.
Amine compounds are compounds that have an amino group, and the amino group reacts with the anionic group of the polyanion.
The amine compound may be any of a primary amine, a secondary amine, a tertiary amine, and a quaternary ammonium salt. In addition, one type of amine compound may be used alone, or two or more types may be used in combination.
The amine compound is a linear or branched alkyl group having 2 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, and an alkylene group having 2 to 12 carbon atoms. , It may have a substituent selected from an arylene group having 6 to 12 carbon atoms, an aralkylene group having 7 to 12 carbon atoms, and an oxyalkylene group having 2 to 12 carbon atoms.
Specific primary amines include, for example, aniline, toluidine, benzylamine, ethanolamine and the like.
Specific examples of the secondary amine include diethanolamine, dimethylamine, diethylamine, dipropylamine, diphenylamine, dibenzylamine, dinaphthylamine and the like.
Specific examples of the tertiary amine include triethanolamine, trimethylamine, triethylamine, tripropylamine, tributylamine, trioctylamine, triphenylamine, tribenzylamine, and trinaphthylamine.
Specific examples of the quaternary ammonium salt include tetramethylammonium salt, tetraethylammonium salt, tetrapropylammonium salt, tetraphenylammonium salt, tetrabenzylammonium salt, and tetranaphthylammonium salt. Hydroxide ions are examples of anions that are paired with ammonium.
Of these amine compounds, tertiary amines are preferable, and triethylamine and tripropylamine are more preferable.
Examples of the nitrogen-containing aromatic compound include aniline, benzylamine, pyrrole, imidazole, 2-methylimidazole, 2-propylimidazole, N-methylimidazole, N-propylimidazole, N-butylimidazole, 1- (2-). Hydroxyethyl) imidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methyl Imidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 1-acetylimidazole, 2-aminobenzimidazole, 2-amino-1-methylbenzimidazole, 2-hydroxybenzimidazole, 2- (2-pyridyl) benzimidazole , Pyridine and the like.
Of these nitrogen-containing aromatic compounds, imidazole is more preferable.
前記固体電解質層には、電解液用溶媒中に電解質を溶解させた電解液が含まれてもよい。電解液の電気伝導度は高いほど好ましい。
電解液用溶媒としては、例えば、エチレングリコール、ジエチレングリコール、プロピレングリコール、１，４−ブタンジオール、グリセリン等のアルコール系溶媒、γ−ブチロラクトン、γ−バレロラクトン、δ−バレロラクトン等のラクトン系溶媒、Ｎ−メチルホルムアミド、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ−メチルアセトアミド、Ｎ−メチルピロリジノン等のアミド系溶媒、アセトニトリル、３−メトキシプロピオニトリル等のニトリル系溶媒、水等が挙げられる。
電解質としては、例えば、アジピン酸、グルタル酸、コハク酸、安息香酸、イソフタル酸、フタル酸、テレフタル酸、マレイン酸、トルイル酸、エナント酸、マロン酸、蟻酸、１，６−デカンジカルボン酸、５，６−デカンジカルボン酸等のデカンジカルボン酸、１，７−オクタンジカルボン酸等のオクタンジカルボン酸、アゼライン酸、セバシン酸等の有機酸；あるいは、硼酸、硼酸と多価アルコールより得られる硼酸の多価アルコール錯化合物；リン酸、炭酸、ケイ酸等の無機酸などをアニオン成分とし、１級アミン（メチルアミン、エチルアミン、プロピルアミン、ブチルアミン、エチレンジアミン等）、２級アミン（ジメチルアミン、ジエチルアミン、ジプロピルアミン、メチルエチルアミン、ジフェニルアミン等）、３級アミン（トリメチルアミン、トリエチルアミン、トリプロピルアミン、トリフェニルアミン、１，８−ジアザビシクロ（５，４，０）−ウンデセン−７等）、テトラアルキルアンモニウム（テトラメチルアンモニウム、テトラエチルアンモニウム、テトラプロピルアンモニウム、テトラブチルアンモニウム、メチルトリエチルアンモニウム、ジメチルジエチルアンモニウム等）などをカチオン成分とした電解質；等が挙げられる。
The solid electrolyte layer may contain an electrolytic solution in which an electrolyte is dissolved in a solvent for an electrolytic solution. The higher the electrical conductivity of the electrolytic solution, the more preferable.
Examples of the solvent for the electrolytic solution include alcohol solvents such as ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol and glycerin, and lactone solvents such as γ-butyrolactone, γ-valerolactone and δ-valerolactone. Examples thereof include amide solvents such as N-methylformamide, N, N-dimethylformamide, N-methylacetamide and N-methylpyrrolidinone, nitrile solvents such as acetonitrile and 3-methoxypropionitrile, and water.
Examples of the electrolyte include adipic acid, glutaric acid, succinic acid, benzoic acid, isophthalic acid, phthalic acid, terephthalic acid, maleic acid, toluic acid, enanthic acid, ammonium acid, formic acid, 1,6-decandicarboxylic acid, 5 , Decandycarboxylic acid such as 6-decandicarboxylic acid, octanedicarboxylic acid such as 1,7-octanedicarboxylic acid, organic acid such as azelaic acid, sebacic acid; or a large amount of boric acid obtained from boric acid, boric acid and polyvalent alcohol. Hyvalent alcohol complex compounds; primary amines (methylamine, ethylamine, propylamine, butylamine, ethylenediamine, etc.) and secondary amines (dimethylamine, diethylamine, diamine, etc.) with inorganic acids such as phosphoric acid, carbonic acid, and silicic acid as anionic components. Propylamine, methylethylamine, diphenylamine, etc.), tertiary amine (trimethylamine, triethylamine, tripropylamine, triphenylamine, 1,8-diazabicyclo (5,4,0) -undecene-7, etc.), tetraalkylammonium (tetraalkylammonium) An electrolyte containing methylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, methyltriethylammonium, dimethyldiethylammonium, etc.) as a cation component; and the like.
＜作用効果＞
本発明のキャパシタの固体電解質層に前記式（１）で表されるアジン化合物が含有されることによって、静電容量を低下させることなく、キャパシタの等価直列抵抗を従来よりも低減することができる。このメカニズムは未解明であるが、前記アジン化合物が固体電解質層の導電性を向上させることによって、その等価直列抵抗が小さくなったと推測される。
<Effect>
By containing the azine compound represented by the above formula (1) in the solid electrolyte layer of the capacitor of the present invention, the equivalent series resistance of the capacitor can be reduced as compared with the conventional case without lowering the capacitance. .. Although this mechanism has not been elucidated, it is presumed that the equivalent series resistance of the azine compound was reduced by improving the conductivity of the solid electrolyte layer.
《キャパシタの製造方法》
本発明にかかるキャパシタは、弁金属の多孔質体からなる陽極の表面を酸化して誘電体層を形成する工程（誘電体形成工程）と、前記誘電体層に対向する位置に陰極を配置する工程（陰極形成工程）と、前記誘電体層の表面の少なくとも一部に、前記式（１）で表されるアジン化合物を含む溶液を塗布し、乾燥させて、第一の固体電解質層を形成する工程（第一の固体電解質層形成工程）と、前記第一の固体電解質層の表面の少なくとも一部に、π共役系導電性高分子及びポリアニオンを含む導電性複合体が分散された導電性高分子分散液を塗布し、乾燥させて、第二の固体電解質層を形成する工程（第二の固体電解質層形成工程）と、によって製造することができる。
<< Capacitor manufacturing method >>
In the capacitor according to the present invention, a step of forming a dielectric layer by oxidizing the surface of an anode made of a porous body of a valve metal (a dielectric forming step) and a step of arranging a cathode at a position facing the dielectric layer. In the step (electrode forming step), a solution containing the azine compound represented by the formula (1) is applied to at least a part of the surface of the dielectric layer and dried to form a first solid electrolyte layer. (First solid electrolyte layer forming step) and conductivity in which a conductive composite containing a π-conjugated conductive polymer and a polyanion is dispersed on at least a part of the surface of the first solid electrolyte layer. It can be produced by a step of applying a polymer dispersion liquid and drying it to form a second solid electrolyte layer (second solid electrolyte layer forming step).
誘電体層形成工程は、弁金属の多孔質体からなる陽極１１の表面を酸化して誘電体層１２を形成する工程である。
誘電体層１２を形成する方法としては、例えば、アジピン酸アンモニウム水溶液、ホウ酸アンモニウム水溶液、リン酸アンモニウム水溶液などの化成処理用電解液中にて、陽極１１の表面を陽極酸化する方法が挙げられる。
The dielectric layer forming step is a step of oxidizing the surface of the anode 11 made of the porous body of the valve metal to form the
Examples of the method for forming the
陰極形成工程は、誘電体層１２に対向する位置に陰極１３を配置する工程である。
陰極１３を配置する方法としては、例えば、カーボンペースト、銀ペースト等の導電性ペーストを用いて陰極１３を形成する方法、アルミニウム箔等の金属箔を誘電体層１２に対向配置させる方法などが挙げられる。
The cathode forming step is a step of arranging the
Examples of the method of arranging the
第一の固体電解質層形成工程は、誘電体層１２の表面の少なくとも一部に、前記式（１）で表されるアジン化合物を含む溶液を塗布し、乾燥させて、第一の固体電解質層を形成する工程である。
前記溶液には、前記式（１）に該当しない前記含窒素化合物、後述する添加剤を含有させてもよい。
In the first solid electrolyte layer forming step, at least a part of the surface of the
The solution may contain the nitrogen-containing compound that does not correspond to the formula (1) and an additive described later.
前記アジン化合物を含む前記溶液を構成する溶媒は、前記アジン化合物を溶解又は分散させ得るもので、前記アジン化合物と反応しないものであれば特に限定されず、例えば、水、有機溶剤、又は、水と有機溶剤との混合液が挙げられる。前記有機溶剤の具体例としては、後述する導電性高分子分散液を構成する有機溶剤と同じものが挙げられる。それらの中でも、前記アジン化合物を安定に塗布できることから、水又は酢酸水溶液が好ましい。
前記酢酸水溶液の酢酸濃度は、例えば、０．０１Ｍ以上１Ｍ以下が好ましく、０．０５Ｍ以上０．５Ｍ以下がより好ましく、０．１Ｍ以上０．３Ｍ以下がさらに好ましい。
The solvent constituting the solution containing the azine compound is not particularly limited as long as it can dissolve or disperse the azine compound and does not react with the azine compound. For example, water, an organic solvent, or water. A mixed solution of and an organic solvent can be mentioned. Specific examples of the organic solvent include the same organic solvents as those constituting the conductive polymer dispersion liquid described later. Among them, water or an aqueous acetic acid solution is preferable because the azine compound can be stably applied.
The acetic acid concentration of the acetic acid aqueous solution is, for example, preferably 0.01 M or more and 1 M or less, more preferably 0.05 M or more and 0.5 M or less, and further preferably 0.1 M or more and 0.3 M or less.
前記溶液の総質量に対する前記アジン化合物の含有量は特に限定されず、塗布することが容易な粘度となる含有量が好ましい。具体的には、例えば、０．１質量％以上１０質量％以下が好ましく、０．３質量％以上５質量％以下がより好ましく、０．５質量％以上３質量％以下がさらに好ましい。
前記溶液が後述する添加剤を含有する場合、その含有量は、添加剤の種類に応じて適宜決められる。具体的には、例えば、前記溶液の総質量に対して、０．０１質量％以上１０質量％以下とすることができる。
The content of the azine compound with respect to the total mass of the solution is not particularly limited, and a content having a viscosity that makes it easy to apply is preferable. Specifically, for example, 0.1% by mass or more and 10% by mass or less is preferable, 0.3% by mass or more and 5% by mass or less is more preferable, and 0.5% by mass or more and 3% by mass or less is further preferable.
When the solution contains an additive described later, the content thereof is appropriately determined according to the type of the additive. Specifically, for example, it can be 0.01% by mass or more and 10% by mass or less with respect to the total mass of the solution.
前記溶液は常法により調製され、例えば、溶媒に前記アジン化合物及び任意の添加剤を投入して、撹拌及び混合することにより調製される。 The solution is prepared by a conventional method, for example, by adding the azine compound and any additive to a solvent, stirring and mixing.
前記溶液の塗布方法としては、例えば、浸漬（ディップコーティング）、コンマコーティング、リバースコーティング、リップコーティング、マイクログラビアコーティング等を適用することができる。これらの中でも、誘電体層１２と陰極１３との間に第一の固体電解質層を容易に形成できる観点から、浸漬が好ましい。
乾燥方法としては、例えば、室温乾燥、熱風乾燥、遠赤外線乾燥等が挙げられる。
As a method for applying the solution, for example, dipping (dip coating), comma coating, reverse coating, lip coating, microgravure coating and the like can be applied. Among these, immersion is preferable from the viewpoint that the first solid electrolyte layer can be easily formed between the
Examples of the drying method include room temperature drying, hot air drying, far infrared drying and the like.
第二の固体電解質層形成工程は、第一の固体電解質層の表面の少なくとも一部に、π共役系導電性高分子及びポリアニオンを含む導電性複合体が分散された導電性高分子分散液を塗布し、乾燥させて、第二の固体電解質層を形成する工程である。
前段の工程において誘電体１２の表面の一部のみが第一の固体電解質層によって覆われている場合には、第一の固体電解質層に覆われずに残った誘電体１２の表面が第二の固体電解質層によって覆われてもよい。
前記導電性高分子分散液には、前記式（１）に該当しない前記含窒素化合物、後述する添加剤を含有させてもよい。一方、前記導電性高分子分散液に前記式（１）で表されるアジン化合物を添加すると、凝集が発生して塗布し難い状態になる場合があるので、前記アジン化合物を前記導電性高分子分散液に添加しない方がよい。
In the second solid electrolyte layer forming step, a conductive polymer dispersion liquid in which a conductive composite containing a π-conjugated conductive polymer and a polyanion is dispersed on at least a part of the surface of the first solid electrolyte layer is applied. It is a step of applying and drying to form a second solid electrolyte layer.
When only a part of the surface of the dielectric 12 is covered by the first solid electrolyte layer in the previous step, the surface of the dielectric 12 remaining without being covered by the first solid electrolyte layer is the second. It may be covered with a solid electrolyte layer of.
The conductive polymer dispersion may contain the nitrogen-containing compound that does not correspond to the formula (1) and an additive described later. On the other hand, when the azine compound represented by the formula (1) is added to the conductive polymer dispersion liquid, aggregation may occur and it may be difficult to apply the azine compound. Therefore, the azine compound is added to the conductive polymer. It is better not to add it to the dispersion.
導電性高分子分散液を構成する分散媒は、前記導電性複合体を分散させ得る液体であれば特に限定されず、例えば、水、有機溶剤、又は、水と有機溶剤との混合液が挙げられる。
有機溶剤としては、例えば、アルコール系溶媒、エーテル系溶媒、ケトン系溶媒、エステル系溶媒、芳香族炭化水素系溶媒等が挙げられる。これら有機溶剤は１種を単独で使用してもよいし、２種以上を併用してもよい。
アルコール系溶媒としては、例えば、メタノール、エタノール、イソプロパノール、ｎ−ブタノール、ｔ−ブタノール、アリルアルコール等が挙げられる。
エーテル系溶媒としては、例えば、ジエチルエーテル、ジメチルエーテル、エチレングリコール、プロピレングリコール、プロプレングリコールモノメチルエーテル等のプロピレングリコールモノアルキルエーテル、プロピレングリコールジアルキルエーテル等が挙げられる。
ケトン系溶媒としては、例えば、ジエチルケトン、メチルプロピルケトン、メチルブチルケトン、メチルイソプロピルケトン、メチルイソブチルケトン、メチルアミルケトン、ジイソプロピルケトン、メチルエチルケトン、アセトン、ジアセトンアルコール等が挙げられる。
エステル系溶媒としては、例えば、酢酸エチル、酢酸プロピル、酢酸ブチル等が挙げられる。
芳香族炭化水素系溶媒としては、例えば、ベンゼン、トルエン、キシレン、エチルベンゼン、プロピルベンゼン、イソプロピルベンゼン等が挙げられる。
The dispersion medium constituting the conductive polymer dispersion is not particularly limited as long as it is a liquid capable of dispersing the conductive composite, and examples thereof include water, an organic solvent, or a mixed solution of water and an organic solvent. Be done.
Examples of the organic solvent include alcohol solvents, ether solvents, ketone solvents, ester solvents, aromatic hydrocarbon solvents and the like. One of these organic solvents may be used alone, or two or more of them may be used in combination.
Examples of the alcohol solvent include methanol, ethanol, isopropanol, n-butanol, t-butanol, allyl alcohol and the like.
Examples of the ether solvent include propylene glycol monoalkyl ethers such as diethyl ether, dimethyl ether, ethylene glycol, propylene glycol, and propylene glycol monomethyl ether, and propylene glycol dialkyl ethers.
Examples of the ketone solvent include diethyl ketone, methyl propyl ketone, methyl butyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, methyl amyl ketone, diisopropyl ketone, methyl ethyl ketone, acetone, diacetone alcohol and the like.
Examples of the ester solvent include ethyl acetate, propyl acetate, butyl acetate and the like.
Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, ethylbenzene, propylbenzene, isopropylbenzene and the like.
添加剤としては、例えば、界面活性剤、無機導電剤、消泡剤、カップリング剤、酸化防止剤、紫外線吸収剤などが挙げられる。ただし、添加剤は、前記導電性複合体、前記式（１）で表されるアジン化合物及び前記アジン化合物に該当しない前記含窒素化合物以外の化合物である。
界面活性剤としては、ノニオン系、アニオン系、カチオン系の界面活性剤が挙げられるが、保存安定性の面からノニオン系が好ましい。また、ポリビニルアルコール、ポリビニルピロリドンなどのポリマー系界面活性剤を添加してもよい。
無機導電剤としては、金属イオン類、導電性カーボン等が挙げられる。金属イオンは、金属塩を水に溶解させることにより生成させることができる。
消泡剤としては、シリコーン樹脂、ポリジメチルシロキサン、シリコーンオイル等が挙げられる。
カップリング剤としては、ビニル基、アミノ基、エポキシ基等を有するシランカップリング剤等が挙げられる。
酸化防止剤としては、フェノール系酸化防止剤、アミン系酸化防止剤、リン系酸化防止剤、硫黄系酸化防止剤、糖類等が挙げられる。
紫外線吸収剤としては、ベンゾトリアゾール系紫外線吸収剤、ベンゾフェノン系紫外線吸収剤、サリシレート系紫外線吸収剤、シアノアクリレート系紫外線吸収剤、オキサニリド系紫外線吸収剤、ヒンダードアミン系紫外線吸収剤、ベンゾエート系紫外線吸収剤等が挙げられる。
Examples of the additive include a surfactant, an inorganic conductive agent, a defoaming agent, a coupling agent, an antioxidant, an ultraviolet absorber and the like. However, the additive is a compound other than the conductive complex, the azine compound represented by the formula (1), and the nitrogen-containing compound which does not correspond to the azine compound.
Examples of the surfactant include nonionic, anionic and cationic surfactants, and nonionic surfactants are preferable from the viewpoint of storage stability. Further, a polymer-based surfactant such as polyvinyl alcohol or polyvinylpyrrolidone may be added.
Examples of the inorganic conductive agent include metal ions and conductive carbon. Metal ions can be generated by dissolving a metal salt in water.
Examples of the defoaming agent include silicone resin, polydimethylsiloxane, silicone oil and the like.
Examples of the coupling agent include a silane coupling agent having a vinyl group, an amino group, an epoxy group and the like.
Examples of the antioxidant include phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, and sugars.
Examples of UV absorbers include benzotriazole-based UV absorbers, benzophenone-based UV absorbers, salicylate-based UV absorbers, cyanoacrylate-based UV absorbers, oxanilide-based UV absorbers, hindered amine-based UV absorbers, benzoate-based UV absorbers, etc. Can be mentioned.
導電性高分子分散液の総質量に対する前記導電性複合体の含有量は特に限定されず、塗布することが容易な粘度となる含有量が好ましい。具体的には、例えば、０．０１質量％以上１０質量％以下が好ましく、０．１質量％以上５質量％以下がより好ましく、０．１質量％以上３質量％以下がさらに好ましい。
導電性高分子分散液が前記添加剤を含有する場合、その含有割合は、添加剤の種類に応じて適宜決められるが、例えば、導電性複合体の固形分１００質量部に対して、０．１質量部以上５００質量部以下の範囲内とすることができる。
The content of the conductive composite with respect to the total mass of the conductive polymer dispersion is not particularly limited, and a content having a viscosity that makes it easy to apply is preferable. Specifically, for example, 0.01% by mass or more and 10% by mass or less is preferable, 0.1% by mass or more and 5% by mass or less is more preferable, and 0.1% by mass or more and 3% by mass or less is further preferable.
When the conductive polymer dispersion liquid contains the additive, the content ratio thereof is appropriately determined according to the type of the additive. For example, it is 0. 0 parts by mass of the solid content of the conductive composite. It can be in the range of 1 part by mass or more and 500 parts by mass or less.
導電性高分子分散液の調製方法としては、ポリアニオン及び分散媒の存在下、π共役系導電性高分子を形成する前駆体モノマーを酸化重合する方法が挙げられる。前記式（１）に該当しない含窒素化合物及び添加剤の一方又は両方を添加する場合、それらの添加タイミングに特に制限はない。 Examples of the method for preparing the conductive polymer dispersion include a method of oxidatively polymerizing a precursor monomer forming a π-conjugated conductive polymer in the presence of a polyanion and a dispersion medium. When one or both of the nitrogen-containing compound and the additive that do not correspond to the above formula (1) are added, the timing of their addition is not particularly limited.
導電性高分子分散液の塗布方法は、前述した溶液の塗布方法と同様の方法が挙げられる。それらの中でも、第一の固体電解質層と陰極１３との間に第二の固体電解質層を容易に形成できる観点から、浸漬が好ましい。
乾燥方法としては、例えば、室温乾燥、熱風乾燥、遠赤外線乾燥等が挙げられる。
Examples of the method for applying the conductive polymer dispersion liquid include the same method as the above-mentioned solution application method. Among them, immersion is preferable from the viewpoint that a second solid electrolyte layer can be easily formed between the first solid electrolyte layer and the
Examples of the drying method include room temperature drying, hot air drying, far infrared drying and the like.
本発明のキャパシタ及びその製造方法は上記の実施形態の例に限定されない。
本発明のキャパシタでは、誘電体層と陰極との間に、セパレータが設けられてもよい。誘電体層と陰極との間にセパレータが設けられたキャパシタとしては、巻回型キャパシタが挙げられる。
セパレータとしては、例えば、ポリビニルアルコール、ポリエステル、ポリエチレン、ポリスチレン、ポリプロピレン、ポリイミド、ポリアミド、ポリフッ化ビニリデンなどからなるシート（不織布を含む）、ガラス繊維の不織布などが挙げられる。
セパレータの密度は、０．１ｇ／ｃｍ３以上１．０ｇ／ｃｍ３以下の範囲であることが好ましく、０．２ｇ／ｃｍ３以上０．８ｇ／ｃｍ３以下の範囲であることがより好ましい。
セパレータを設ける場合には、セパレータにカーボンペーストあるいは銀ペーストを含浸させて陰極を形成する方法を適用することもできる。
The capacitor of the present invention and the method for producing the same are not limited to the examples of the above embodiments.
In the capacitor of the present invention, a separator may be provided between the dielectric layer and the cathode. Examples of the capacitor in which the separator is provided between the dielectric layer and the cathode include a wound capacitor.
Examples of the separator include a sheet (including a non-woven fabric) made of polyvinyl alcohol, polyester, polyethylene, polystyrene, polypropylene, polyimide, polyamide, polyvinylidene fluoride and the like, a non-woven fabric made of glass fiber, and the like.
The density of the separator is preferably in the range of 0.1 g / cm 3 or more and 1.0 g / cm 3 or less, and more preferably in the range of 0.2 g / cm 3 or more and 0.8 g / cm 3 or less.
When the separator is provided, a method of impregnating the separator with carbon paste or silver paste to form a cathode can also be applied.
（製造例１）
１０００ｍｌのイオン交換水に２０６ｇのスチレンスルホン酸ナトリウムを溶解し、８０℃で攪拌しながら、予め１０ｍｌの水に溶解した１．１４ｇの過硫酸アンモニウム酸化剤溶液を２０分間滴下し、この溶液を１２時間攪拌した。
得られたスチレンスルホン酸ナトリウム含有溶液に１０質量％に希釈した硫酸を１０００ｍｌ添加し、限外ろ過法によりポリスチレンスルホン酸含有溶液の約１０００ｍｌ溶液を除去し、残液に２０００ｍｌのイオン交換水を加え、限外ろ過法により約２０００ｍｌ溶液を除去した。上記の限外ろ過操作を３回繰り返した。さらに、得られたろ液に約２０００ｍｌのイオン交換水を添加し、限外ろ過法により約２０００ｍｌの溶液を除去した。この限外ろ過操作を３回繰り返した。
得られた溶液中の水を減圧除去して、無色の固形状のポリスチレンスルホン酸を得た。
(Manufacturing Example 1)
206 g of sodium styrene sulfonate was dissolved in 1000 ml of ion-exchanged water, and 1.14 g of ammonium persulfate oxidant solution previously dissolved in 10 ml of water was added dropwise for 20 minutes while stirring at 80 ° C., and this solution was added dropwise for 12 hours. Stirred.
To the obtained sodium styrene sulfonate-containing solution, 1000 ml of sulfuric acid diluted to 10% by mass was added, about 1000 ml of the polystyrene sulfonate-containing solution was removed by an ultrafiltration method, and 2000 ml of ion-exchanged water was added to the residual solution. , About 2000 ml of solution was removed by ultrafiltration. The above ultrafiltration operation was repeated 3 times. Further, about 2000 ml of ion-exchanged water was added to the obtained filtrate, and about 2000 ml of the solution was removed by an ultrafiltration method. This ultrafiltration operation was repeated 3 times.
Water in the obtained solution was removed under reduced pressure to obtain colorless solid polystyrene sulfonic acid.
（製造例２）
３，４−エチレンジオキシチオフェン１４．２ｇと、製造例１で得たポリスチレンスルホン酸３６．７ｇとを２０００ｍｌのイオン交換水に溶かした溶液とを２０℃で混合させた。
これにより得られた混合溶液を２０℃に保ち、掻き混ぜながら、２００ｍｌのイオン交換水に溶かした２９．６４ｇの過硫酸アンモニウムと８．０ｇの硫酸第二鉄の酸化触媒溶液とをゆっくり添加し、３時間攪拌して反応させた。
得られた反応液に２０００ｍｌのイオン交換水を加え、限外ろ過法により約２０００ｍｌ溶液を除去した。この操作を３回繰り返した。
そして、得られた溶液に２００ｍｌの１０質量％に希釈した硫酸と２０００ｍｌのイオン交換水とを加え、限外ろ過法により約２０００ｍｌの溶液を除去し、これに２０００ｍｌのイオン交換水を加え、限外ろ過法により約２０００ｍｌ溶液を除去した。この操作を３回繰り返した。
さらに、得られた溶液に２０００ｍｌのイオン交換水を加え、限外ろ過法により約２０００ｍｌの溶液を除去した。この操作を５回繰り返したのち、高圧分散機を用い、１４０ＭＰａの圧力で分散処理を施して、１．４質量％のポリスチレンスルホン酸ドープポリ（３，４−エチレンジオキシチオフェン）水分散液（ＰＥＤＯＴ−ＰＳＳ水分散液）を得た。
(Manufacturing Example 2)
A solution prepared by dissolving 14.2 g of 3,4-ethylenedioxythiophene and 36.7 g of polystyrene sulfonic acid obtained in Production Example 1 in 2000 ml of ion-exchanged water was mixed at 20 ° C.
The mixed solution thus obtained was kept at 20 ° C., and while stirring, 29.64 g of ammonium persulfate dissolved in 200 ml of ion-exchanged water and 8.0 g of a ferric sulfate oxidation catalyst solution were slowly added. The reaction was carried out with stirring for 3 hours.
2000 ml of ion-exchanged water was added to the obtained reaction solution, and about 2000 ml of the solution was removed by an ultrafiltration method. This operation was repeated 3 times.
Then, 200 ml of sulfuric acid diluted to 10% by mass and 2000 ml of ion-exchanged water were added to the obtained solution, about 2000 ml of the solution was removed by an ultrafiltration method, and 2000 ml of ion-exchanged water was added thereto. About 2000 ml of the solution was removed by ultrafiltration. This operation was repeated 3 times.
Further, 2000 ml of ion-exchanged water was added to the obtained solution, and about 2000 ml of the solution was removed by an ultrafiltration method. After repeating this operation 5 times, dispersion treatment was performed at a pressure of 140 MPa using a high-pressure disperser to obtain a 1.4 mass% polystyrene sulfonate-doped poly (3,4-ethylenedioxythiophene) aqueous dispersion (PEDOT). -PSS aqueous dispersion) was obtained.
（製造例３）
エッチドアルミニウム箔（陽極箔）に陽極リード端子を接続した後、アジピン酸アンモニウム１０質量％水溶液中で８０Ｖの電圧を印加し、化成（酸化処理）して、アルミニウム箔の両面に誘電体層を形成して陽極箔を得た。
次に、陽極箔の両面に、陰極リード端子を溶接させた対向アルミニウム陰極箔を、セルロース製のセパレータを介して積層し、これを円筒状に巻き取ってキャパシタ用素子を得た。
(Manufacturing Example 3)
After connecting the anode lead terminal to the etched aluminum foil (anode foil), a voltage of 80 V is applied in a 10 mass% aqueous solution of ammonium adipate and chemical conversion (oxidation treatment) is performed to form dielectric layers on both sides of the aluminum foil. It was formed to obtain an anode foil.
Next, an opposed aluminum cathode foil in which cathode lead terminals were welded was laminated on both sides of the anode foil via a cellulose separator, and this was wound into a cylindrical shape to obtain a capacitor element.
（実施例１）
イオン交換水９９．７質量部にメラミン０．３質量部を溶かしてアジン化合物の水溶液を得た。この水溶液を、製造例３で得たキャパシタ用素子に減圧下で浸漬した後、１２５℃の熱風乾燥機により１５分間乾燥し、誘電体層表面上にアジン化合物を含む固体電解質層（第一の固体電解質層）を形成させた。
次いで、アジン化合物を含む固体電解質層を形成させたキャパシタ用素子を製造例２で得たＰＥＤＯＴ−ＰＳＳ水分散液に減圧下で浸漬した後、１２５℃の熱風乾燥機により１５分間乾燥し、誘電体層表面上及び第一の固体電解質層上に導電性複合体を含む第二の固体電解質層を形成させた。
さらに、アルミニウム製のケースに、第一及び第二の固体電解質層を形成したキャパシタ用素子を装填し、封口ゴムで封止して、キャパシタを得た。
(Example 1)
An aqueous solution of an azine compound was obtained by dissolving 0.3 part by mass of melamine in 99.7 parts by mass of ion-exchanged water. This aqueous solution is immersed in the capacitor element obtained in Production Example 3 under reduced pressure, dried by a hot air dryer at 125 ° C. for 15 minutes, and the solid electrolyte layer containing an azine compound on the surface of the dielectric layer (first). A solid electrolyte layer) was formed.
Next, the capacitor element on which the solid electrolyte layer containing the azine compound was formed was immersed in the PEDOT-PSS aqueous dispersion obtained in Production Example 2 under reduced pressure, and then dried in a hot air dryer at 125 ° C. for 15 minutes to obtain a dielectric. A second solid electrolyte layer containing a conductive composite was formed on the surface of the body layer and on the first solid electrolyte layer.
Further, a capacitor element on which the first and second solid electrolyte layers were formed was loaded in an aluminum case and sealed with a sealing rubber to obtain a capacitor.
（実施例２）
イオン交換水を０．１Ｍ酢酸水溶液に変更した他は、実施例１と同様にして、キャパシタを得た。
(Example 2)
A capacitor was obtained in the same manner as in Example 1 except that the ion-exchanged water was changed to a 0.1 M aqueous acetic acid solution.
（実施例３）
イオン交換水９９．７質量部を０．１Ｍ酢酸水溶液９９．０質量部に、メラミン０．３質量部を１．０質量部に変更した他は、実施例１と同様にして、キャパシタを得た。
(Example 3)
A capacitor was obtained in the same manner as in Example 1 except that 99.7 parts by mass of ion-exchanged water was changed to 99.0 parts by mass of a 0.1 M acetic acid aqueous solution and 0.3 parts by mass of melamine was changed to 1.0 parts by mass. It was.
（実施例４）
イオン交換水９９．７質量部を０．１Ｍ酢酸水溶液９８．７質量部に、メラミン０．３質量部を１．３質量部に変更した他は、実施例１と同様にして、キャパシタを得た。
(Example 4)
A capacitor was obtained in the same manner as in Example 1 except that 99.7 parts by mass of ion-exchanged water was changed to 98.7 parts by mass of a 0.1 M acetic acid aqueous solution and 0.3 parts by mass of melamine was changed to 1.3 parts by mass. It was.
（実施例５）
イオン交換水９９．７質量部を９９．９質量部に、メラミン０．３質量部を０．１質量部に変更した他は、実施例１と同様にして、キャパシタを得た。
(Example 5)
A capacitor was obtained in the same manner as in Example 1 except that 99.7 parts by mass of ion-exchanged water was changed to 99.9 parts by mass and 0.3 parts by mass of melamine was changed to 0.1 parts by mass.
（実施例６）
イオン交換水を０．１Ｍ酢酸水溶液に、メラミンをアセトグアナミンに変更した他は、実施例１と同様にして、キャパシタを得た。
(Example 6)
A capacitor was obtained in the same manner as in Example 1 except that the ion-exchanged water was changed to a 0.1 M aqueous acetic acid solution and the melamine was changed to acetguanamine.
（実施例７）
イオン交換水９９．７質量部を０．１Ｍ酢酸水溶液９９．９質量部に、メラミン０．３質量部をアセトグアナミン０．１質量部に変更した他は、実施例１と同様にして、キャパシタを得た。
(Example 7)
Capacitors in the same manner as in Example 1 except that 99.7 parts by mass of ion-exchanged water was changed to 99.9 parts by mass of a 0.1 M acetic acid aqueous solution and 0.3 parts by mass of melamine was changed to 0.1 parts by mass of acetoguanamine. Got
（実施例８）
メラミン０．３質量部を２，４，６−［トリス（ビスメトキシメチル）アミノ］１，３，５−トリアジン０．３質量部に変更した他は、実施例１と同様にして、キャパシタを得た。
(Example 8)
The capacitor was changed in the same manner as in Example 1 except that 0.3 parts by mass of melamine was changed to 0.3 parts by mass of 2,4,6- [tris (bismethoxymethyl) amino] 1,3,5-triazine. Obtained.
（実施例９）
イオン交換水９９．７質量部を９９．０質量部に、メラミン０．３質量部を２，４，６−［トリス（ビスメトキシメチル）アミノ］１，３，５−トリアジン１．０質量部に変更した他は、実施例１と同様にして、キャパシタを得た。
(Example 9)
99.7 parts by mass of ion-exchanged water is 99.0 parts by mass, 0.3 parts by mass of melamine is 2,4,6- [tris (bismethoxymethyl) amino] 1,3,5-triazine 1.0 parts by mass. A capacitor was obtained in the same manner as in Example 1 except that it was changed to.
（実施例１０）
メラミン０．３質量部を２，４，６−トリアミノピリミジン０．３質量部に変更した他は、実施例１と同様にして、キャパシタを得た。
(Example 10)
A capacitor was obtained in the same manner as in Example 1 except that 0.3 parts by mass of melamine was changed to 0.3 parts by mass of 2,4,6-triaminopyrimidine.
（実施例１１）
メラミン０．３質量部を２−アミノピリミジン０．３質量部に変更した他は、実施例１と同様にして、キャパシタを得た。
(Example 11)
A capacitor was obtained in the same manner as in Example 1 except that 0.3 parts by mass of melamine was changed to 0.3 parts by mass of 2-aminopyrimidine.
（実施例１２）
メラミン０．３質量部をｐ−アミノピリジン（４−アミノピリジン）０．３質量部に変更した他は、実施例１と同様にして、キャパシタを得た。
(Example 12)
A capacitor was obtained in the same manner as in Example 1 except that 0.3 part by mass of melamine was changed to 0.3 part by mass of p-aminopyridine (4-aminopyridine).
（実施例１３）
メラミン０．３質量部をＮ，Ｎ−ジメチル−４−アミノピリジン（ＤＭＡＰ）０．３質量部に変更した他は、実施例１と同様にして、キャパシタを得た。
(Example 13)
A capacitor was obtained in the same manner as in Example 1 except that 0.3 part by mass of melamine was changed to 0.3 part by mass of N, N-dimethyl-4-aminopyridine (DMAP).
（実施例１４）
アジン化合物の水溶液を、イオン交換水９９．６質量部にメラミン０．３質量部及びイミダゾール０．１質量部を溶かして得たアジン化合物の水溶液に変更した他は、実施例１と同様にして、キャパシタを得た。
(Example 14)
The same as in Example 1 except that the aqueous solution of the azine compound was changed to an aqueous solution of the azine compound obtained by dissolving 0.3 part by mass of melamine and 0.1 part by mass of imidazole in 99.6 parts by mass of ion-exchanged water. , Obtained a capacitor.
（実施例１５）
アジン化合物の水溶液を、イオン交換水９９．６質量部にメラミン０．３質量部及びトリエチルアミン０．１質量部を溶かして得たアジン化合物の水溶液に変更した他は、実施例１と同様にして、キャパシタを得た。
(Example 15)
The same as in Example 1 except that the aqueous solution of the azine compound was changed to an aqueous solution of the azine compound obtained by dissolving 0.3 part by mass of melamine and 0.1 part by mass of triethylamine in 99.6 parts by mass of ion-exchanged water. , Obtained a capacitor.
（実施例１６）
アジン化合物の水溶液を、イオン交換水９９．６質量部にメラミン０．３質量部及びトリプロピルアミン０．１質量部を溶かして得たアジン化合物の水溶液に変更した他は、実施例１と同様にして、キャパシタを得た。
(Example 16)
The same as in Example 1 except that the aqueous solution of the azine compound was changed to an aqueous solution of the azine compound obtained by dissolving 0.3 part by mass of melamine and 0.1 part by mass of tripropylamine in 99.6 parts by mass of ion-exchanged water. And obtained a capacitor.
（比較例１）
メラミン０．３質量部をイミダゾール０．３質量部に変更した他は、実施例１と同様にして、キャパシタを得た。
(Comparative Example 1)
A capacitor was obtained in the same manner as in Example 1 except that 0.3 parts by mass of melamine was changed to 0.3 parts by mass of imidazole.
（比較例２）
イオン交換水９９．７質量部を９９．９質量部に、トリエチルアミン０．１質量部に変更した他は、実施例１と同様にして、キャパシタを得た。
(Comparative Example 2)
A capacitor was obtained in the same manner as in Example 1 except that 99.7 parts by mass of ion-exchanged water was changed to 99.9 parts by mass and 0.1 parts by mass of triethylamine.
（比較例３）
メラミンを含まなかった以外は、実施例１と同様にして、キャパシタを得た。
(Comparative Example 3)
Capacitors were obtained in the same manner as in Example 1 except that they did not contain melamine.
（比較例４）
メラミンを含まなかった以外は、実施例２と同様にして、キャパシタを得た。
(Comparative Example 4)
Capacitors were obtained in the same manner as in Example 2 except that they did not contain melamine.
（実施例１７）
イオン交換水９９．７質量部にメラミン０．３質量部を溶かしてアジン化合物の水溶液を得た。この水溶液を、製造例３で得たキャパシタ用素子に減圧下で浸漬した後、１２５℃の熱風乾燥機により１５分間乾燥し、誘電体層表面上にアジン化合物を含む固体電解質層（第一の固体電解質層）を形成させた。
次いで、製造例２で得たＰＥＤＯＴ−ＰＳＳ水分散液１００質量部にイミダゾール０．０５質量部を加えて含窒素化合物を含むＰＥＤＯＴ−ＰＳＳ水分散液を調製した。
アジン化合物を含む固体電解質層を形成させたキャパシタ用素子に、含窒素化合物を含むＰＥＤＯＴ−ＰＳＳ水分散液を減圧下で浸漬した後、１２５℃の熱風乾燥機により１５分間乾燥し、誘電体層表面上及び第一の固体電解質層上に導電性複合体を含む第二の固体電解質層を形成させた。
さらに、アルミニウム製のケースに、第一及び第二の固体電解質層を形成したキャパシタ用素子を装填し、封口ゴムで封止して、キャパシタを得た。
(Example 17)
An aqueous solution of the azine compound was obtained by dissolving 0.3 part by mass of melamine in 99.7 parts by mass of ion-exchanged water. This aqueous solution is immersed in the capacitor element obtained in Production Example 3 under reduced pressure, dried by a hot air dryer at 125 ° C. for 15 minutes, and the solid electrolyte layer containing an azine compound on the surface of the dielectric layer (first). A solid electrolyte layer) was formed.
Next, 0.05 parts by mass of imidazole was added to 100 parts by mass of the PEDOT-PSS aqueous dispersion obtained in Production Example 2 to prepare a PEDOT-PSS aqueous dispersion containing a nitrogen-containing compound.
A PEDOT-PSS aqueous dispersion containing a nitrogen-containing compound is immersed under reduced pressure in a capacitor element having a solid electrolyte layer containing an azine compound, and then dried with a hot air dryer at 125 ° C. for 15 minutes to form a dielectric layer. A second solid electrolyte layer containing a conductive composite was formed on the surface and on the first solid electrolyte layer.
Further, a capacitor element on which the first and second solid electrolyte layers were formed was loaded in an aluminum case and sealed with a sealing rubber to obtain a capacitor.
（実施例１８）
イミダゾール０．０５質量部を０．１質量部に変更した他は、実施例１７と同様にして、キャパシタを得た。
(Example 18)
A capacitor was obtained in the same manner as in Example 17, except that 0.05 parts by mass of imidazole was changed to 0.1 parts by mass.
（実施例１９）
イミダゾール０．０５質量部を０．２５質量部に変更した他は、実施例１７と同様にして、キャパシタを得た。
(Example 19)
A capacitor was obtained in the same manner as in Example 17, except that 0.05 parts by mass of imidazole was changed to 0.25 parts by mass.
（実施例２０）
イミダゾール０．０５質量部をトリエチルアミン０．０５質量部に変更した他は、実施例１７と同様にして、キャパシタを得た。
(Example 20)
A capacitor was obtained in the same manner as in Example 17, except that 0.05 parts by mass of imidazole was changed to 0.05 parts by mass of triethylamine.
（実施例２１）
イミダゾール０．０５質量部をトリエチルアミン０．１質量部に変更した他は、実施例１７と同様にして、キャパシタを得た。
(Example 21)
A capacitor was obtained in the same manner as in Example 17, except that 0.05 parts by mass of imidazole was changed to 0.1 parts by mass of triethylamine.
（実施例２２）
イミダゾール０．０５質量部をトリプロピルアミン０．０５質量部に変更した他は、実施例１７と同様にして、キャパシタを得た。
(Example 22)
A capacitor was obtained in the same manner as in Example 17, except that 0.05 parts by mass of imidazole was changed to 0.05 parts by mass of tripropylamine.
（実施例２３）
イミダゾール０．０５質量部をトリプロピルアミン０．１質量部に変更した他は、実施例１７と同様にして、キャパシタを得た。
(Example 23)
A capacitor was obtained in the same manner as in Example 17, except that 0.05 parts by mass of imidazole was changed to 0.1 parts by mass of tripropylamine.
＜評価＞
得られた各例のキャパシタについて、ＬＣＲメータＺＭ２３７６（（株）エヌエフ回路設計ブロック製）を用いて、１２０Ｈｚでの静電容量、及び１００ｋＨｚでの等価直列抵抗を測定した。１２０Ｈｚでの静電容量、及び１００ｋＨｚでの等価直列抵抗（ＥＳＲ）の測定結果を表１に示す。
<Evaluation>
For each of the obtained capacitors, the capacitance at 120 Hz and the equivalent series resistance at 100 kHz were measured using an LCR meter ZM2376 (manufactured by NF Circuit Design Block Co., Ltd.). Table 1 shows the measurement results of the capacitance at 120 Hz and the equivalent series resistance (ESR) at 100 kHz.
前記式（１）で表されるアジン化合物を含む第一の固体電解質層をキャパシタ素子の誘電体表面に形成した実施例１〜１３では、得られたキャパシタが充分な静電容量を有しつつ、等価直列抵抗が充分に小さかった。
上記アジン化合物を含有しない第一の固体電解質層をキャパシタ素子の誘電体表面に形成した比較例１〜４では、得られたキャパシタの等価直列抵抗が大きかった。
In Examples 1 to 13 in which the first solid electrolyte layer containing the azine compound represented by the formula (1) was formed on the dielectric surface of the capacitor element, the obtained capacitor had a sufficient capacitance. , The equivalent series resistance was small enough.
In Comparative Examples 1 to 4 in which the first solid electrolyte layer containing no azine compound was formed on the dielectric surface of the capacitor element, the equivalent series resistance of the obtained capacitor was large.
実施例１４〜１６では、前記式（１）で表されるアジン化合物だけでなく、前記式（１）に該当しない含窒素化合物も合わせて含む第一の固体電解質層をキャパシタ素子の誘電体表面に形成した。その結果、得られたキャパシタの静電容量が増加し、等価直列抵抗がより小さくなる傾向が確認された。
実施例１７〜２３では、導電性複合体のＰＥＤＯＴ−ＰＳＳだけでなく、前記式（１）に該当しない含窒素化合物を添加した第二の固体電解質層を、誘電体層を覆う第一の固体電解質層の上に形成した。その結果、得られたキャパシタの静電容量が増加し、等価直列抵抗がより小さくなる傾向が確認された。
なお、本明細書において、第一の固体電解質層をアジン化合物含有層と称してもよく、第二の固体電解質層を導電性複合体含有層と称してもよい。
また、上記の実施例１１は比較例である。
In Examples 14 to 16, the dielectric surface of the capacitor element includes a first solid electrolyte layer containing not only the azine compound represented by the formula (1) but also a nitrogen-containing compound not corresponding to the formula (1). Formed in. As a result, it was confirmed that the capacitance of the obtained capacitor increased and the equivalent series resistance tended to become smaller.
In Examples 17 to 23, not only the conductive composite PEDOT-PSS but also the second solid electrolyte layer to which the nitrogen-containing compound not corresponding to the above formula (1) is added is provided with the first solid covering the dielectric layer. It was formed on the electrolyte layer. As a result, it was confirmed that the capacitance of the obtained capacitor increased and the equivalent series resistance tended to become smaller.
In the present specification, the first solid electrolyte layer may be referred to as an azine compound-containing layer, and the second solid electrolyte layer may be referred to as a conductive composite-containing layer.
Further, the above-mentioned Example 11 is a comparative example.
１０ キャパシタ
１１ 陽極
１２ 誘電体層
１３ 陰極
１４ 固体電解質層
10 Capacitor 11
Claims (9)
前記アジン化合物含有層は、前記誘電体層の少なくとも一部を覆い、アジン化合物を含有し、π共役系導電性高分子及びポリアニオンを含む導電性複合体を含有しない層であり、
前記導電性複合体含有層は、前記アジン化合物含有層の少なくとも一部を覆い、π共役系導電性高分子及びポリアニオンを含む導電性複合体を含有する層であり、
前記アジン化合物は、メラミン、アセトグアナミン、２，４，６−トリアミノピリミジン、４−アミノピリジン、又はＮ，Ｎ−ジメチル−４−アミノピリジンである、キャパシタ。 An anode made of a porous body of a valve metal, a dielectric layer made of an oxide of the valve metal, a cathode made of a conductive material provided on the opposite side of the dielectric layer to the anode, and the dielectric layer. A capacitor provided between the cathode and the azine compound-containing layer and the conductive composite-containing layer .
The azine compound-containing layer is a layer that covers at least a part of the dielectric layer, contains an azine compound, and does not contain a conductive composite containing a π-conjugated conductive polymer and a polyanion.
The conductive composite-containing layer is a layer that covers at least a part of the azine compound-containing layer and contains a conductive composite containing a π-conjugated conductive polymer and a polyanion.
A capacitor in which the azine compound is melamine, acetoguanamine, 2,4,6-triaminopyrimidine, 4-aminopyridine, or N, N-dimethyl-4-aminopyridine .
前記誘電体層に対向する位置に陰極を配置する工程と、
前記誘電体層の表面の少なくとも一部に、メラミン、アセトグアナミン、２，４，６−トリアミノピリミジン、４−アミノピリジン、又はＮ，Ｎ−ジメチル−４−アミノピリジンを含み、π共役系導電性高分子及びポリアニオンを含む導電性複合体を含有しない、アジン化合物の溶液を塗布し、乾燥させて、アジン化合物含有層を形成する工程と、
前記アジン化合物含有層の表面の少なくとも一部に、π共役系導電性高分子及びポリアニオンを含む導電性複合体が分散された導電性高分子分散液を塗布し、乾燥させて、導電性複合体含有層を形成する工程と、を有するキャパシタの製造方法。 The process of oxidizing the surface of the anode made of the porous body of the valve metal to form a dielectric layer,
The step of arranging the cathode at a position facing the dielectric layer and
Wherein at least a part of the surface of the dielectric layer, melamine, acetoguanamine, 2,4,6-triaminopyrimidine, 4-aminopyridine, or N, viewing including the N- dimethyl-4-aminopyridine, [pi conjugated system A step of applying a solution of an azine compound, which does not contain a conductive composite containing a conductive polymer and a polyanion , and drying the solution to form an azine compound-containing layer .
A conductive polymer dispersion liquid in which a conductive composite containing a π-conjugated conductive polymer and a polyanion is dispersed is applied to at least a part of the surface of the azine compound-containing layer , dried, and the conductive composite is dried. A method for manufacturing a capacitor, comprising a step of forming a containing layer .
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