JP5522674B2 - Monomer composition for producing conductive polymer, conductive polymer, solid electrolytic capacitor using the same as solid electrolyte, and method for producing the same - Google Patents
Monomer composition for producing conductive polymer, conductive polymer, solid electrolytic capacitor using the same as solid electrolyte, and method for producing the same Download PDFInfo
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- JP5522674B2 JP5522674B2 JP2010087422A JP2010087422A JP5522674B2 JP 5522674 B2 JP5522674 B2 JP 5522674B2 JP 2010087422 A JP2010087422 A JP 2010087422A JP 2010087422 A JP2010087422 A JP 2010087422A JP 5522674 B2 JP5522674 B2 JP 5522674B2
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- 239000003990 capacitor Substances 0.000 title claims description 165
- 239000000203 mixture Substances 0.000 title claims description 144
- 239000000178 monomer Substances 0.000 title claims description 144
- 239000007787 solid Substances 0.000 title claims description 131
- 229920001940 conductive polymer Polymers 0.000 title claims description 46
- 238000004519 manufacturing process Methods 0.000 title claims description 24
- 239000007784 solid electrolyte Substances 0.000 title claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 91
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 91
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 84
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 83
- 239000007800 oxidant agent Substances 0.000 claims description 52
- 239000002019 doping agent Substances 0.000 claims description 50
- 229930192474 thiophene Natural products 0.000 claims description 42
- 230000001590 oxidative effect Effects 0.000 claims description 27
- 238000006116 polymerization reaction Methods 0.000 claims description 23
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 16
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 8
- 238000004804 winding Methods 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- LOWMYOWHQMKBTM-UHFFFAOYSA-N 1-butylsulfinylbutane Chemical compound CCCCS(=O)CCCC LOWMYOWHQMKBTM-UHFFFAOYSA-N 0.000 claims description 2
- VTRRCXRVEQTTOE-UHFFFAOYSA-N 1-methylsulfinylethane Chemical compound CCS(C)=O VTRRCXRVEQTTOE-UHFFFAOYSA-N 0.000 claims description 2
- CCAFPWNGIUBUSD-UHFFFAOYSA-N diethyl sulfoxide Chemical compound CCS(=O)CC CCAFPWNGIUBUSD-UHFFFAOYSA-N 0.000 claims description 2
- HLANOUYSOJLOPM-UHFFFAOYSA-N methoxy benzenesulfonate Chemical compound COOS(=O)(=O)C1=CC=CC=C1 HLANOUYSOJLOPM-UHFFFAOYSA-N 0.000 claims 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-M toluene-4-sulfonate Chemical compound CC1=CC=C(S([O-])(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-M 0.000 claims 3
- 150000007524 organic acids Chemical class 0.000 claims 2
- 125000003158 alcohol group Chemical group 0.000 claims 1
- 150000003460 sulfonic acids Chemical class 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 60
- 239000000243 solution Substances 0.000 description 51
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 description 40
- 150000001875 compounds Chemical class 0.000 description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 125000003375 sulfoxide group Chemical group 0.000 description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- YMMGRPLNZPTZBS-UHFFFAOYSA-N 2,3-dihydrothieno[2,3-b][1,4]dioxine Chemical class O1CCOC2=C1C=CS2 YMMGRPLNZPTZBS-UHFFFAOYSA-N 0.000 description 17
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 11
- 238000004817 gas chromatography Methods 0.000 description 10
- 239000011521 glass Substances 0.000 description 9
- 235000019441 ethanol Nutrition 0.000 description 8
- 239000000706 filtrate Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 7
- KVGZZAHHUNAVKZ-UHFFFAOYSA-N 1,4-Dioxin Chemical compound O1C=COC=C1 KVGZZAHHUNAVKZ-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 6
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 5
- 230000009931 harmful effect Effects 0.000 description 5
- 238000011065 in-situ storage Methods 0.000 description 5
- 229910052758 niobium Inorganic materials 0.000 description 5
- 239000010955 niobium Substances 0.000 description 5
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 229910052715 tantalum Inorganic materials 0.000 description 5
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 4
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 description 3
- -1 2-Ethyl Chemical group 0.000 description 3
- FQBAMYDJEQUGNV-UHFFFAOYSA-N 2-methoxybenzenesulfonic acid Chemical compound COC1=CC=CC=C1S(O)(=O)=O FQBAMYDJEQUGNV-UHFFFAOYSA-N 0.000 description 3
- JAJIPIAHCFBEPI-UHFFFAOYSA-N 9,10-dioxoanthracene-1-sulfonic acid Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)O JAJIPIAHCFBEPI-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
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229940044654 phenolsulfonic acid Drugs 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 3
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 2
- 229940092714 benzenesulfonic acid Drugs 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
- 239000004020 conductor Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- GPUMPJNVOBTUFM-UHFFFAOYSA-N naphthalene-1,2,3-trisulfonic acid Chemical compound C1=CC=C2C(S(O)(=O)=O)=C(S(O)(=O)=O)C(S(=O)(=O)O)=CC2=C1 GPUMPJNVOBTUFM-UHFFFAOYSA-N 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- CTOPCEPRAXJJEO-UHFFFAOYSA-N 2-butoxybenzenesulfonic acid Chemical compound CCCCOC1=CC=CC=C1S(O)(=O)=O CTOPCEPRAXJJEO-UHFFFAOYSA-N 0.000 description 1
- QFNSAOSWJSCHID-UHFFFAOYSA-N 2-butylbenzenesulfonic acid Chemical compound CCCCC1=CC=CC=C1S(O)(=O)=O QFNSAOSWJSCHID-UHFFFAOYSA-N 0.000 description 1
- BMRVLXHIZWDOOK-UHFFFAOYSA-N 2-butylnaphthalene-1-sulfonic acid Chemical compound C1=CC=CC2=C(S(O)(=O)=O)C(CCCC)=CC=C21 BMRVLXHIZWDOOK-UHFFFAOYSA-N 0.000 description 1
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
- SWDHKZPAUHBMHV-UHFFFAOYSA-N 2-ethoxybenzenesulfonic acid Chemical compound CCOC1=CC=CC=C1S(O)(=O)=O SWDHKZPAUHBMHV-UHFFFAOYSA-N 0.000 description 1
- JCRMBLKUFLUWPU-UHFFFAOYSA-N 2-ethylnaphthalene-1-sulfonic acid Chemical compound C1=CC=CC2=C(S(O)(=O)=O)C(CC)=CC=C21 JCRMBLKUFLUWPU-UHFFFAOYSA-N 0.000 description 1
- WODGMMJHSAKKNF-UHFFFAOYSA-N 2-methylnaphthalene-1-sulfonic acid Chemical compound C1=CC=CC2=C(S(O)(=O)=O)C(C)=CC=C21 WODGMMJHSAKKNF-UHFFFAOYSA-N 0.000 description 1
- UHUAIOVEACSXTN-UHFFFAOYSA-N 2-propoxybenzenesulfonic acid Chemical compound CCCOC1=CC=CC=C1S(O)(=O)=O UHUAIOVEACSXTN-UHFFFAOYSA-N 0.000 description 1
- ZQGPVVNVISOGEU-UHFFFAOYSA-N 2-propylbenzenesulfonic acid Chemical compound CCCC1=CC=CC=C1S(O)(=O)=O ZQGPVVNVISOGEU-UHFFFAOYSA-N 0.000 description 1
- FWMKPJYJDJSEHR-UHFFFAOYSA-N 2-propylnaphthalene-1-sulfonic acid Chemical compound C1=CC=CC2=C(S(O)(=O)=O)C(CCC)=CC=C21 FWMKPJYJDJSEHR-UHFFFAOYSA-N 0.000 description 1
- NNIKSVAOFGELNT-UHFFFAOYSA-N 3-butyl-2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1C(CCCC)COC2=CSC=C21 NNIKSVAOFGELNT-UHFFFAOYSA-N 0.000 description 1
- BZOVBIIWPDQIHF-UHFFFAOYSA-N 3-hydroxy-2-methylbenzenesulfonic acid Chemical compound CC1=C(O)C=CC=C1S(O)(=O)=O BZOVBIIWPDQIHF-UHFFFAOYSA-N 0.000 description 1
- MXLYDTCSOHXFFA-UHFFFAOYSA-N 3-methyl-2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1C(C)COC2=CSC=C21 MXLYDTCSOHXFFA-UHFFFAOYSA-N 0.000 description 1
- BRIXOPDYGQCZFO-UHFFFAOYSA-N 4-ethylphenylsulfonic acid Chemical compound CCC1=CC=C(S(O)(=O)=O)C=C1 BRIXOPDYGQCZFO-UHFFFAOYSA-N 0.000 description 1
- PDKNKWRYRJPPPO-UHFFFAOYSA-N 9,10-dioxoanthracene-1,2,3-trisulfonic acid Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=C(S(=O)(=O)O)C(S(O)(=O)=O)=C2S(O)(=O)=O PDKNKWRYRJPPPO-UHFFFAOYSA-N 0.000 description 1
- PTKWYSNDTXDBIZ-UHFFFAOYSA-N 9,10-dioxoanthracene-1,2-disulfonic acid Chemical compound C1=CC=C2C(=O)C3=C(S(O)(=O)=O)C(S(=O)(=O)O)=CC=C3C(=O)C2=C1 PTKWYSNDTXDBIZ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- MPIRVKMYLJPSOH-UHFFFAOYSA-N O1C=2C(OCC1)=CSC2.O2C=COC=C2 Chemical compound O1C=2C(OCC1)=CSC2.O2C=COC=C2 MPIRVKMYLJPSOH-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- VRAIHTAYLFXSJJ-UHFFFAOYSA-N alumane Chemical compound [AlH3].[AlH3] VRAIHTAYLFXSJJ-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- MIAUJDCQDVWHEV-UHFFFAOYSA-N benzene-1,2-disulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1S(O)(=O)=O MIAUJDCQDVWHEV-UHFFFAOYSA-N 0.000 description 1
- 150000008107 benzenesulfonic acids Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- YZMHQCWXYHARLS-UHFFFAOYSA-N naphthalene-1,2-disulfonic acid Chemical compound C1=CC=CC2=C(S(O)(=O)=O)C(S(=O)(=O)O)=CC=C21 YZMHQCWXYHARLS-UHFFFAOYSA-N 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000003577 thiophenes Chemical class 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Description
本発明は、チオフェンまたはその誘導体をモノマーとする導電性高分子製造用モノマー組成物、そのモノマー組成物中のチオフェンまたはその誘導体を酸化重合して製造した導電性高分子、その導電性高分子を固体電解質として用いた固体電解コンデンサおよびその製造方法に関する。 The present invention relates to a monomer composition for producing a conductive polymer using thiophene or a derivative thereof as a monomer, a conductive polymer produced by oxidative polymerization of thiophene or a derivative thereof in the monomer composition, The present invention relates to a solid electrolytic capacitor used as a solid electrolyte and a method for manufacturing the same.
導電性高分子は、その高い導電性により、例えば、アルミニウム固体電解コンデンサ、タンタル固体電解コンデンサ、ニオブ固体電解コンデンサなどの固体電解コンデンサの固体電解質として用いられている。 Conductive polymers are used as solid electrolytes for solid electrolytic capacitors such as aluminum solid electrolytic capacitors, tantalum solid electrolytic capacitors, and niobium solid electrolytic capacitors because of their high conductivity.
この用途における導電性高分子としては、チオフェンまたはその誘導体を酸化重合（化学酸化重合）することによって得られたものが、導電性および耐熱性のバランスがとれていて有用性が高いという理由から、多用されている（特許文献１〜２）。 As the conductive polymer in this application, what is obtained by oxidative polymerization (chemical oxidative polymerization) of thiophene or a derivative thereof has a good balance between conductivity and heat resistance, and is highly useful. Widely used (Patent Documents 1 and 2).
上記チオフェンまたはその誘導体などの化学酸化重合を行う際のドーパントとしては、有機スルホン酸が適し、酸化剤としては、遷移金属が適していて、その中でも特に第二鉄が適しているといわれていて、一般に有機スルホン酸の第二鉄塩がチオフェンまたはその誘導体の化学酸化重合にあたっての酸化剤兼ドーパントとして用いられている。 Organic sulfonic acid is suitable as a dopant when performing chemical oxidative polymerization of the above thiophene or its derivative, etc., and transition metal is suitable as an oxidizing agent, among which ferric iron is particularly suitable. In general, a ferric salt of an organic sulfonic acid is used as an oxidizing agent and a dopant in the chemical oxidative polymerization of thiophene or a derivative thereof.
そして、この導電性高分子を固体電解質として用いる固体電解コンデンサの製造にあたっては、例えば、コンデンサ素子をモノマー溶液に浸漬し、引き上げた後、該コンデンサ素子を酸化剤兼ドーパント溶液に浸漬し、引き上げて重合を行うか、コンデンサ素子を酸化剤兼ドーパント溶液に浸漬し、引き上げた後、該コンデンサ素子をモノマー溶液に浸漬し、引き上げて重合を行うか、あるいは酸化剤兼ドーパント溶液とモノマー溶液を混合して調製した溶液にコンデンサ素子を浸漬し、引き上げて重合することが行われている。 In manufacturing a solid electrolytic capacitor using the conductive polymer as a solid electrolyte, for example, the capacitor element is immersed in a monomer solution and pulled up, and then the capacitor element is immersed in an oxidant / dopant solution and pulled up. Polymerize or immerse the capacitor element in an oxidant / dopant solution and pull it up, then immerse the capacitor element in a monomer solution and pull it up for polymerization, or mix the oxidant / dopant solution and the monomer solution. The capacitor element is dipped in a solution prepared in the above manner, and then pulled up for polymerization.
その際、酸化剤兼ドーパント溶液の濃度が高い方が、得られる固体電解コンデンサのＥＳＲ（等価直列抵抗）が低く（小さく）なり、静電容量が高く（大きく）なるなど、コンデンサ特性が向上する傾向があるが、酸化剤兼ドーパント溶液の濃度が、ある濃度を超えると、かえってコンデンサ特性が悪くなる。 At that time, the higher the concentration of the oxidizing agent / dopant solution, the lower the ESR (equivalent series resistance) of the obtained solid electrolytic capacitor, and the higher the capacitance (higher), and the better the capacitor characteristics. There is a tendency, but if the concentration of the oxidizing agent / dopant solution exceeds a certain concentration, the capacitor characteristics are deteriorated.
これは、酸化剤兼ドーパント溶液の濃度が高くなるのに伴なって粘度が高くなり、かつ反応速度が速くなるため、コンデンサ素子の細部に酸化剤兼ドーパント溶液が行き渡らないうちに高分子化が進んでしまって、静電容量が出にくくなり、また、反応速度が速いが故に、副反応が起こり、導電性高分子の合成がうまくいかず、結果としてＥＳＲが大きくなっているものと考えられる。この傾向は、固体電解コンデンサの種類によって異なるが、巻回型アルミニウム固体電解コンデンサの場合は、酸化剤兼ドーパント溶液の濃度が５５質量％以上になると現われるようになる。 This is because the viscosity increases as the concentration of the oxidizer / dopant solution increases, and the reaction speed increases, so that the polymerization is performed before the oxidant / dopant solution reaches the details of the capacitor element. It is considered that the electrostatic capacity is difficult to be generated and the reaction rate is high, so that a side reaction occurs, the synthesis of the conductive polymer is not successful, and as a result, the ESR is increased. . This tendency varies depending on the type of the solid electrolytic capacitor, but in the case of a wound aluminum solid electrolytic capacitor, it appears when the concentration of the oxidizing agent / dopant solution is 55% by mass or more.
そこで、酸化剤兼ドーパント溶液にイミダゾールを添加することにより反応速度を遅くすることができるという可能性が示されている（特許文献３）。
しかし、この場合は、添加したイミダゾールが導電性高分子中に残留し、特性に悪影響を及ぼすことが考えられる。
Therefore, there is a possibility that the reaction rate can be slowed by adding imidazole to the oxidizing agent / dopant solution (Patent Document 3).
However, in this case, the added imidazole remains in the conductive polymer, which may adversely affect the characteristics.
また、それとは別に、酸化剤兼ドーパントとなるトルエンスルホン酸を、該トルエンスルホン酸と錯塩を形成する低沸点溶剤のテトラヒドロフランとトルエンスルホン酸と錯塩を形成しない高沸点溶剤のブタノールとの混合溶剤に溶解させて反応速度を遅くさせることができる可能性が示されている（特許文献４）。
しかし、それを固体電解コンデンサの製造にあたって応用した場合、充分な成果が得られなかった。
Separately, toluenesulfonic acid as an oxidizing agent and dopant is mixed with a mixed solvent of tetrahydrofuran, a low boiling point solvent that forms a complex salt with toluenesulfonic acid, and butanol, a high boiling point solvent that does not form a complex salt with toluenesulfonic acid. The possibility that the reaction rate can be slowed by dissolution is shown (Patent Document 4).
However, when it was applied in the production of solid electrolytic capacitors, sufficient results were not obtained.
本発明は、上記のような事情に鑑み、酸化剤兼ドーパント溶液の濃度が高くなっても、その高濃度化に伴なう弊害を抑制し、固体電解質として用いたときに、ＥＳＲが低く、かつ静電容量が大きい固体電解コンデンサを提供できる導電性高分子を製造するのに適したモノマー組成物を提供し、また、その導電性高分子を用いて、上記のようにＥＳＲが低く、かつ静電容量が大きい固体電解コンデンサを提供することを目的とする。 In view of the circumstances as described above, the present invention suppresses the harmful effects associated with the increase in concentration even when the concentration of the oxidizing agent / dopant solution is high, and when used as a solid electrolyte, the ESR is low, And a monomer composition suitable for producing a conductive polymer capable of providing a solid electrolytic capacitor having a large capacitance, and using the conductive polymer, the ESR is low as described above, and An object of the present invention is to provide a solid electrolytic capacitor having a large capacitance.
本発明は、導電性高分子の製造にあたってモノマーとなるチオフェンまたはその誘導体にスルホキシド基を有する化合物を特定比率で添加することによって、上記目的を達成し、それに基づいて完成したものである。 The present invention achieves the above object by adding a compound having a sulfoxide group to a thiophene or a derivative thereof as a monomer in the production of a conductive polymer at a specific ratio, and has been completed based on the object.
すなわち、本発明は、チオフェンまたはその誘導体をモノマーとする導電性高分子製造用モノマー組成物であって、スルホキシド基を有する化合物を、上記チオフェンまたはその誘導体に対して質量基準で１.５〜２０％添加したことを特徴とする導電性高分子製造用モノマー組成物に関する。 That is, the present invention is a monomer composition for producing a conductive polymer using thiophene or a derivative thereof as a monomer, and the compound having a sulfoxide group is 1.5 to 20 on a mass basis with respect to the thiophene or a derivative thereof. It is related with the monomer composition for electroconductive polymer manufacture characterized by adding%.
また、本発明は、上記導電性高分子製造用モノマー組成物中のチオフェンまたはその誘導体を酸化重合して製造したことを特徴とする導電性高分子に関する。 The present invention also relates to a conductive polymer produced by oxidative polymerization of thiophene or a derivative thereof in the monomer composition for producing a conductive polymer.
さらに、本発明は、上記導電性高分子製造用モノマー組成物中のチオフェンまたはその誘導体を酸化重合して製造した導電性高分子を固体電解質として用いたことを特徴とする固体電解コンデンサおよびその製造方法に関する。 Furthermore, the present invention provides a solid electrolytic capacitor characterized in that a conductive polymer produced by oxidative polymerization of thiophene or a derivative thereof in the monomer composition for producing a conductive polymer is used as a solid electrolyte, and the production thereof. Regarding the method.
本発明の導電性高分子製造用モノマー組成物（以下、簡略化して、「モノマー組成物」という）は、スルホキシド基を有する化合物を添加しているので、その酸化重合時に、モノマーのチオフェンまたはその誘導体に添加しておいたスルホキシド基を有する化合物が酸化剤の反応速度を低下させる。その結果、酸化剤兼ドーパントを高濃度化しても、その高濃度化に伴なう反応速度の増加を抑制できるので、その高濃度化した酸化剤兼ドーパントで酸化重合されたチオフェンまたはその誘導体の重合体をポリマー骨格とする導電性高分子は、固体電解コンデンサの固体電解質として用いたときに、ＥＳＲが低く、かつ静電容量が大きい固体電解コンデンサを提供することができる。 Since the monomer composition for producing a conductive polymer of the present invention (hereinafter simply referred to as “monomer composition”) is added with a compound having a sulfoxide group, the thiophene monomer or A compound having a sulfoxide group added to the derivative reduces the reaction rate of the oxidizing agent. As a result, even if the concentration of the oxidizing agent / dopant is increased, an increase in the reaction rate accompanying the increase in concentration can be suppressed, so that the thiophene or its derivative oxidized by the increased concentration of the oxidizing agent / dopant can be reduced. A conductive polymer having a polymer as a polymer skeleton can provide a solid electrolytic capacitor having a low ESR and a large capacitance when used as a solid electrolyte of a solid electrolytic capacitor.
本発明において、上記モノマー組成物の基材となるモノマーとしては、チオフェンまたはその誘導体を用いるが、これは、前記したように、チオフェンまたはその誘導体を重合して得られる導電性高分子が導電性および耐熱性のバランスがとれていて、他のモノマーに比べて、コンデンサの特性の優れた固体電解コンデンサが得られやすいという理由に基づいている。 In the present invention, thiophene or a derivative thereof is used as a monomer as a base material for the monomer composition. As described above, the conductive polymer obtained by polymerizing thiophene or a derivative thereof is conductive. Further, this is based on the reason that a solid electrolytic capacitor having a good balance of heat resistance and excellent capacitor characteristics as compared with other monomers is easily obtained.
そして、そのチオフェンまたはその誘導体におけるチオフェンの誘導体としては、例えば、３，４−エチレンジオキシチオフェン、３−アルキルチオフェン、３−アルコキシチオフェン、３−アルキル−４−アルコキシチオフェン、３，４−アルキルチオフェン、３，４−アルコキシチオフェンや、上記の３，４−エチレンジオキシチオフェンをアルキル基で修飾したアルキル化エチレンジオキシチオフェンなどが挙げられ、そのアルキル基やアルコキシ基の炭素数としては１〜１６が好ましく、特に１〜４が好ましい。 Examples of the thiophene derivative in the thiophene or the derivative thereof include 3,4-ethylenedioxythiophene, 3-alkylthiophene, 3-alkoxythiophene, 3-alkyl-4-alkoxythiophene, and 3,4-alkylthiophene. 3,4-alkoxythiophene, alkylated ethylenedioxythiophene obtained by modifying the above 3,4-ethylenedioxythiophene with an alkyl group, and the number of carbon atoms of the alkyl group or alkoxy group is 1-16. Are preferable, and 1-4 are especially preferable.
上記の３，４−エチレンジオキシチオフェンをアルキル基で修飾したアルキル化エチレンジオキシチオフェンについて詳しく説明すると、上記３，４−エチレンジオキシチオフェンやアルキル化３，４−エチレンジオキシチオフェンは、下記の一般式（１）で表される化合物に該当する。 The alkylated ethylenedioxythiophene obtained by modifying the 3,4-ethylenedioxythiophene with an alkyl group will be described in detail. The 3,4-ethylenedioxythiophene and the alkylated 3,4-ethylenedioxythiophene are as follows. It corresponds to the compound represented by the general formula (1).
そして、上記一般式（１）中のＲが水素の化合物が、３，４−エチレンジオキシチオフェンであり、これをＩＵＰＡＣ名称で表示すると、「２，３−ジヒドロ−チエノ〔３，４−ｂ〕〔１，４〕ジオキシン（２，３−Ｄｉｈｙｄｒｏ−ｔｈｉｅｎｏ〔３，４−ｂ〕〔１，４〕ｄｉｏｘｉｎｅ）」であるが、この化合物は、ＩＵＰＡＣ名称で表示されるよりも、一般名称の「３，４−エチレンジオキシチオフェン」で表示されることが多いので、本書では、この「２，３−ジヒドロ−チエノ〔３，４−ｂ〕〔１，４〕ジオキシン」を「３，４−エチレンジオキシチオフェン」と表示している。そして、上記一般式（１）中のＲがアルキル基の場合、該アルキル基としては、炭素数が１〜４のもの、つまり、メチル基、エチル基、プロピル基、ブチル基が好ましく、それらを具体的に例示すると、一般式（１）中のＲがメチル基の化合物は、ＩＵＰＡＣ名称で表示すると、「２−メチル−２，３−ジヒドロ−チエノ〔３，４−ｂ〕〔１，４〕ジオキシン（２−Ｍｅｔｈｙｌ−２，３−ｄｉｈｙｄｒｏ−ｔｈｉｅｎｏ〔３，４−ｂ〕〔１，４〕ｄｉｏｘｉｎｅ）」であるが、以下、これを簡略化して「メチル化エチレンジオキシチオフェン」と表示する。一般式（１）中のＲがエチル基の化合物は、ＩＵＰＡＣ名称で表示すると、「２−エチル−２，３−ジヒドロ−チエノ〔３，４−ｂ〕〔１，４〕ジオキシン（２−Ｅｔｈｙｌ−２，３−ｄｉｈｙｄｒｏ−ｔｈｉｅｎｏ〔３，４−ｂ〕〔１，４〕ｄｉｏｘｉｎｅ）」であるが、以下、これを簡略化して「エチル化エチレンジオキシチオフェン」と表示する。一般式（１）中のＲがプロピル基の化合物は、ＩＵＰＡＣ名称で表示すると、「２−プロピル−２，３−ジヒドロ−チエノ〔３，４−ｂ〕〔１，４〕ジオキシン（２−Ｐｒｏｐｙｌ−２，３−ｄｉｈｙｄｒｏ−ｔｈｉｅｎｏ〔３，４−ｂ〕〔１，４〕ｄｉｏｘｉｎｅ）」であるが、以下、これを簡略化して「プロピル化エチレンジオキシチオフェン」と表示する。そして、一般式（１）中のＲがブチル基の化合物は、ＩＵＰＡＣ名称で表示すると、「２−ブチル−２，３−ジヒドロ−チエノ〔３，４−ｂ〕〔１，４〕ジオキシン（２−Ｂｕｔｙｌ−２，３−ｄｉｈｙｄｒｏ−ｔｈｉｅｎｏ〔３，４−ｂ〕〔１，４〕ｄｉｏｘｉｎｅ）」であるが、以下、これを簡略化して「ブチル化エチレンジオキシチオフェン」と表示する。また、「２−アルキル−２，３−ジヒドロ−チエノ〔３，４−ｂ〕〔１，４〕ジオキシン」を、以下、簡略化して「アルキル化エチレンジオキシチオフェン」で表わす。そして、これらのアルキル化エチレンジオキシチオフェンの中でも、メチル化エチレンジオキシチオフェン、エチル化エチレンジオキシチオフェン、プロピル化エチレンジオキシチオフェン、ブチル化エチレンジオキシチオフェンが好ましく、特にエチル化エチレンジオキシチオフェン、プロピル化エチレンジオキシチオフェンが好ましい。 And the compound in which R in the general formula (1) is hydrogen is 3,4-ethylenedioxythiophene, which is expressed by the IUPAC name, “2,3-dihydro-thieno [3,4-b ] [1,4] dioxin (2,3-Dihydro-thieno [3,4-b] [1,4] dioxine) ", but this compound has a generic name rather than the IUPAC name. Since it is often expressed as “3,4-ethylenedioxythiophene”, in this document, “2,3-dihydro-thieno [3,4-b] [1,4] dioxin” is referred to as “3,4”. -"Ethylenedioxythiophene". And when R in the said General formula (1) is an alkyl group, as this alkyl group, a C1-C4 thing, ie, a methyl group, an ethyl group, a propyl group, a butyl group, is preferable, Specifically, a compound in which R in the general formula (1) is a methyl group is represented by IUPAC name, “2-methyl-2,3-dihydro-thieno [3,4-b] [1,4 Dioxin (2-Methyl-2,3-dihydro-thieno [3,4-b] [1,4] dioxine) ”, which is hereinafter simplified and displayed as“ methylated ethylenedioxythiophene ”. To do. A compound in which R in the general formula (1) is an ethyl group is represented by IUPAC name, “2-ethyl-2,3-dihydro-thieno [3,4-b] [1,4] dioxin (2-Ethyl). -2,3-dihydro-thieno [3,4-b] [1,4] dioxine) ", hereinafter, this is simplified and expressed as" ethylated ethylenedioxythiophene ". A compound in which R in the general formula (1) is a propyl group is represented by “IUPAC name”, “2-propyl-2,3-dihydro-thieno [3,4-b] [1,4] dioxin (2-Propyl). -2,3-dihydro-thieno [3,4-b] [1,4] dioxine) ", hereinafter, this is simplified and expressed as" propylated ethylenedioxythiophene ". A compound in which R in the general formula (1) is a butyl group is represented by “IUPAC name”, “2-butyl-2,3-dihydro-thieno [3,4-b] [1,4] dioxin (2 -Butyl-2,3-dihydro-thieno [3,4-b] [1,4] dioxine) ", hereinafter, this will be simplified and expressed as" butylated ethylenedioxythiophene ". Further, “2-alkyl-2,3-dihydro-thieno [3,4-b] [1,4] dioxin” is hereinafter simply expressed as “alkylated ethylenedioxythiophene”. Among these alkylated ethylenedioxythiophenes, methylated ethylenedioxythiophene, ethylated ethylenedioxythiophene, propylated ethylenedioxythiophene, and butylated ethylenedioxythiophene are preferable, and in particular ethylated ethylenedioxythiophene. Propylated ethylenedioxythiophene is preferred.
そして、３，４−エチレンジオキシチオフェン（すなわち、２，３−ジヒドロ−チエノ〔３，４−ｂ〕〔１，４〕ジオキシン）とアルキル化エチレンジオキシチオフェン（すなわち、２−アルキル−２，３−ジヒドロ−チエノ〔３，４−ｂ〕〔１，４〕ジオキシン）とは、混合して用いることが好ましく、その混合比は、モル比で０．１：１〜１：０．１、特に０．２：１〜１：０．２、とりわけ０．３：１〜１：０．３が好ましい。 And 3,4-ethylenedioxythiophene (ie 2,3-dihydro-thieno [3,4-b] [1,4] dioxin) and alkylated ethylenedioxythiophene (ie 2-alkyl-2, 3-dihydro-thieno [3,4-b] [1,4] dioxin) is preferably used as a mixture, and the mixing ratio is 0.1: 1 to 1: 0.1 in terms of molar ratio. In particular, 0.2: 1 to 1: 0.2, particularly 0.3: 1 to 1: 0.3 is preferable.
そして、スルホキシド基を有する化合物としては、例えば、ジメチルスルホキシド、メチルエチルスルホキシド、ジエチルスルホキシド、ジブチルスルホキシドなどを用いることができ、それらの中でも、特にジメチルスルホキシドが好ましい。 As the compound having a sulfoxide group, for example, dimethyl sulfoxide, methyl ethyl sulfoxide, diethyl sulfoxide, dibutyl sulfoxide and the like can be used, and among them, dimethyl sulfoxide is particularly preferable.
このスルホキシド基を有する化合物は、酸化剤兼ドーパントを構成する有機スルホン酸第二鉄の反応速度を低下させる作用があり、有機スルホン酸第二鉄の高濃度化に伴なう反応速度の増加を抑制できるので、反応速度の増加に伴なう弊害（固体電解コンデンサにしたときのＥＳＲの増加や静電容量の低下など）を招くことなく、酸化剤兼ドーパント溶液を高濃度化でき、それによって、固体電解コンデンサのＥＳＲの低減や静電容量の増加を達成でき、コンデンサ特性を向上させることができる。 This compound having a sulfoxide group has the effect of reducing the reaction rate of ferric organic sulfonate that constitutes an oxidizing agent and dopant, and increases the reaction rate accompanying the increase in concentration of ferric organic sulfonate. Since it can be suppressed, the concentration of the oxidant / dopant solution can be increased without causing adverse effects (increased ESR and decreased capacitance when the solid electrolytic capacitor is made) due to the increase in reaction rate, thereby In addition, the ESR of the solid electrolytic capacitor can be reduced and the capacitance can be increased, and the capacitor characteristics can be improved.
そして、このスルホキシド基を有する化合物は、一般に高沸点なので（例えば、ジメチルスルホキシドは沸点が１８９℃）、通常の乾燥では、除去されることなく、導電性高分子中に残る可能性があるが、たとえ残存したとしても、後記の実施例に示すように、ＥＳＲの増加や静電容量の低下を引き起こすことがない。 And since this compound having a sulfoxide group generally has a high boiling point (for example, dimethyl sulfoxide has a boiling point of 189 ° C.), it may remain in the conductive polymer without being removed by ordinary drying. Even if it remains, it does not cause an increase in ESR or a decrease in capacitance as shown in the examples described later.
そして、上記モノマー組成物を構成するにあたって、このスルホキシド基を有する化合物のモノマーのチオフェンまたはその誘導体に対する添加量は、質量基準で１.５〜２０％（すなわち、チオフェンまたはその誘導体１００質量部に対してスルホキシド基を有する化合物が１.５〜２０質量部）であり、スルホキシド基を有する化合物の添加量が上記より少ない場合は、反応速度を低下させる作用が充分に発揮されず、また、スルホキシド基を有する化合物の添加量が上記より多い場合は、反応速度の低下が大きくなりすぎ、生産性が低下する上に、得られる導電性高分子の導電性が低下するおそれがある。そして、このスルホキシド基を有する化合物のチオフェンまたはその誘導体に対する添加量は、上記範囲内で、質量基準で２％以上が好ましく、３％以上がより好ましく、また、１８％以下が好ましく、１５％以下がより好ましい。 And in comprising the said monomer composition, the addition amount with respect to the thiophene or its derivative of the monomer of the compound which has this sulfoxide group is 1.5-20% on the mass basis (namely, with respect to 100 mass parts of thiophene or its derivative). When the amount of the compound having a sulfoxide group is 1.5 to 20 parts by mass) and the addition amount of the compound having a sulfoxide group is less than the above, the effect of reducing the reaction rate is not sufficiently exhibited, and the sulfoxide group When the amount of the compound having an amount added is larger than the above, the reaction rate is excessively lowered, the productivity is lowered, and the conductivity of the obtained conductive polymer may be lowered. The addition amount of the compound having a sulfoxide group with respect to thiophene or a derivative thereof is preferably 2% or more, more preferably 3% or more, and more preferably 18% or less, and 15% or less within the above range on a mass basis. Is more preferable.
上記モノマー組成物中のチオフェンまたはその誘導体を酸化重合する酸化剤兼ドーパントは、有機スルホン酸第二鉄で構成されるものが最も適しているが、その有機スルホン酸第二鉄の有機スルホン酸としては、例えば、ベンゼンスルホン酸またはその誘導体、ナフタレンスルホン酸またはその誘導体、アントラキノンスルホン酸またはその誘導体などの芳香族系スルホン酸や、ポリスチレンスルホン酸、スルホン化ポリエステル、フェノールスルホン酸ノボラック樹脂などの高分子スルホン酸が好適に用いられる。 The oxidant / dopant that oxidizes and polymerizes thiophene or its derivative in the monomer composition is most preferably composed of ferric organic sulfonate, but as the organic sulfonic acid of ferric organic sulfonate. Are, for example, aromatic sulfonic acids such as benzene sulfonic acid or derivatives thereof, naphthalene sulfonic acid or derivatives thereof, anthraquinone sulfonic acid or derivatives thereof, and polymers such as polystyrene sulfonic acid, sulfonated polyester, phenol sulfonic acid novolak resin, etc. Sulfonic acid is preferably used.
上記ベンゼンスルホン酸またはその誘導体におけるベンゼンスルホン酸誘導体としては、例えば、トルエンスルホン酸、エチルベンゼンスルホン酸、プロピルベンゼンスルホン酸、ブチルベンゼンスルホン酸、ドデシルベンゼンスルホン酸、メトキシベンゼンスルホン酸、エトキシベンゼンスルホン酸、プロポキシベンゼンスルホン酸、ブトキシベンゼンスルホン酸、フェノールスルホン酸、クレゾールスルホン酸、ベンゼンジスルホン酸などが挙げられ、ナフタレンスルホン酸またはその誘導体におけるナフタレンスルホン酸誘導体としては、例えば、ナフタレンジスルホン酸、ナフタレントリスルホン酸、メチルナフタレンスルホン酸、エチルナフタレンスルホン酸、プロピルナフタレンスルホン酸、ブチルナフタレンスルホン酸などが挙げられ、アントラキノンスルホン酸またはその誘導体におけるアントラキノンスルホン酸誘導体としては、例えば、アントラキノンジスルホン酸、アントラキノントリスルホン酸などが挙げられる。これらの芳香族系スルホン酸の中でも、特に、トルエンスルホン酸、メトキシベンゼンスルホン酸、フェノールスルホン酸、ナフタレンスルホン酸、ナフタレントリスルホン酸などが好ましく、とりわけ、パラトルエンスルホン酸、メトキシベンゼンスルホン酸が好ましい。 Examples of the benzenesulfonic acid derivative in the benzenesulfonic acid or derivative thereof include toluenesulfonic acid, ethylbenzenesulfonic acid, propylbenzenesulfonic acid, butylbenzenesulfonic acid, dodecylbenzenesulfonic acid, methoxybenzenesulfonic acid, ethoxybenzenesulfonic acid, Examples thereof include propoxybenzene sulfonic acid, butoxybenzene sulfonic acid, phenol sulfonic acid, cresol sulfonic acid, and benzene disulfonic acid. Examples of naphthalene sulfonic acid derivatives in naphthalene sulfonic acid or its derivatives include naphthalene disulfonic acid and naphthalene trisulfonic acid. Methyl naphthalene sulfonic acid, ethyl naphthalene sulfonic acid, propyl naphthalene sulfonic acid, butyl naphthalene sulfonic acid, etc. Gerare, as the anthraquinone sulfonic acid derivatives in anthraquinone sulfonic acid or its derivatives, e.g., anthraquinone disulfonic acid, anthraquinone-trisulfonic acid. Among these aromatic sulfonic acids, toluenesulfonic acid, methoxybenzenesulfonic acid, phenolsulfonic acid, naphthalenesulfonic acid, naphthalenetrisulfonic acid and the like are particularly preferable, and paratoluenesulfonic acid and methoxybenzenesulfonic acid are particularly preferable. .
また、上記有機スルホン酸第二鉄は、その鉄に対する有機スルホン酸のモル比が１：３より有機スルホン酸が少ないものが好ましい。これは鉄に対する有機スルホン酸のモル比を、その化学量論的モル比である１：３より有機スルホン酸を少なくすることによって、その有機スルホン酸第二鉄の反応速度を若干低減できるからであり、鉄に対する有機スルホン酸のモル比が、１：２程度のものまでが好ましく、１：２．２程度、特に１：２．４程度のものまでがより好ましく、１：２．７５程度のものまでがさらに好ましい。 The ferric organic sulfonate is preferably one having a lower organic sulfonic acid ratio than the molar ratio of the organic sulfonic acid to the iron of 1: 3. This is because the reaction rate of the ferric organic sulfonate can be slightly reduced by making the organic sulfonic acid to iron molar ratio less than the stoichiometric molar ratio of 1: 3. The molar ratio of organic sulfonic acid to iron is preferably up to about 1: 2, more preferably about 1: 2.2, more preferably about 1: 2.4, and about 1: 2.75. Even more preferred is.
この酸化剤兼ドーパントは、使用にあたって、溶液状にされるが、その溶液化のための溶剤としては、ヒドロキシル基を有する有機溶剤が用いられる。このヒドロキシル基を有する有機溶剤としては、例えば、メタノール（メチルアルコール）、エタノール（エチルアルコール）、プロパノール（プロピルアルコール）、ブタノール（ブチルアルコール）、エチレングリコール、プロピレングリコール、ジエチレングリコール、トリエチレングリコール、ポリエチレングリコールなどを用いることができ、それらの中でも、メタノール、エタノール、プロパノール、ブタノールなどの炭素数が１〜４のアルコールが好ましい。 The oxidizer / dopant is used in the form of a solution in use, and an organic solvent having a hydroxyl group is used as a solvent for the solution. Examples of the organic solvent having a hydroxyl group include methanol (methyl alcohol), ethanol (ethyl alcohol), propanol (propyl alcohol), butanol (butyl alcohol), ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol. Among them, alcohols having 1 to 4 carbon atoms such as methanol, ethanol, propanol, and butanol are preferable.
導電性高分子製造用の酸化剤兼ドーパント溶液としては、これまで、溶剤としてブタノールを用いたブタノール系溶液では、有機スルホン酸第二鉄の濃度を５４質量％にすることが、高濃度化に伴なう弊害を招くことなく高濃度化できる限界であったが、上記のようにチオフェンまたはその誘導体にスルホキシド基を有する化合物を添加しておくことにより、有機スルホン酸第二鉄の濃度を５４質量％より高濃度にした酸化剤兼ドーパント溶液を使用しても、高濃度化に伴なう弊害の発生を抑制することができ、また、溶剤としてエタノールを用いたエタノール系溶液では、これまで、有機スルホン酸第二鉄の濃度を６０質量％にすることが、有機スルホン酸第二鉄の高濃度化に伴なう弊害を招くことなく高濃度化できる限界であったが、上記のようにチオフェンまたはその誘導体にスルホキシド基を有する化合物を添加しておくことにより、有機スルホン酸第二鉄の濃度を６０質量％より高濃度にした酸化剤兼ドーパント溶液を使用しても、高濃度化に伴なう弊害の発生を抑制できるので、チオフェンまたはその誘導体へのスルホキシド基を有する化合物の添加は、高濃度の酸化剤兼ドーパント溶液の使用を可能にし、それによって、特性の良い固体電解コンデンサを作製できるようにする。 As an oxidizing agent / dopant solution for producing a conductive polymer, so far, in a butanol-based solution using butanol as a solvent, it is possible to increase the concentration of ferric organic sulfonate to 54% by mass. However, the concentration of ferric organic sulfonate was reduced to 54 by adding a compound having a sulfoxide group to thiophene or a derivative thereof as described above. Even if an oxidizer / dopant solution with a concentration higher than mass% is used, it is possible to suppress the occurrence of harmful effects associated with the increase in concentration, and ethanol-based solutions using ethanol as a solvent have so far been used. In addition, the concentration of ferric organic sulfonate of 60% by mass was the limit that could increase the concentration without incurring the harmful effects of increasing the concentration of ferric organic sulfonate. As described above, by adding a compound having a sulfoxide group to thiophene or a derivative thereof, even if an oxidizing agent / dopant solution having a concentration of ferric organic sulfonate higher than 60% by mass is used, Since the occurrence of harmful effects due to concentration can be suppressed, the addition of a compound having a sulfoxide group to thiophene or a derivative thereof enables the use of a high-concentration oxidant / dopant solution, and thereby a solid with good characteristics. Enable to make electrolytic capacitors.
また、溶剤としてメタノールを用いたメタノール系の酸化剤兼ドーパント溶液や溶剤としてプロパノールを用いたプロパノール系の酸化剤兼ドーパント溶液においても、それぞれ、上記のようなチオフェンまたはその誘導体へのスルホキシド基を有する化合物の添加により、有機スルホン酸第二鉄の高濃度化に伴なう弊害の発生を抑制することができ、それによって、高濃度の酸化剤兼ドーパント溶液の使用が可能になり、特性が良い固体電解コンデンサが得られるようになる。このようなチオフェンまたはその誘導体へのスルホキシド基を有する化合物の添加は、これまでの限界濃度より高濃度化した酸化剤兼ドーパント溶液を使用したときに、その効果が顕著に発現するが、これまでの限界濃度やそれより若干濃度が低い酸化剤兼ドーパント溶液を使用する場合でも、重合反応を穏やかに進行させるので、これまでのものより特性の良い固体電解コンデンサの作製を可能にするものと考えられる。 Further, a methanol-based oxidant / dopant solution using methanol as a solvent and a propanol-based oxidant / dopant solution using propanol as a solvent each have a sulfoxide group to thiophene or a derivative thereof as described above. By adding a compound, it is possible to suppress the occurrence of harmful effects associated with increasing the concentration of ferric organic sulfonate, thereby enabling the use of a high concentration oxidizing agent / dopant solution and good characteristics. A solid electrolytic capacitor can be obtained. The addition of a compound having a sulfoxide group to such thiophene or a derivative thereof exhibits a remarkable effect when an oxidizing agent / dopant solution having a concentration higher than the limit concentration so far is used. Even when using an oxidizing agent / dopant solution whose concentration is slightly lower than that, it is considered that the polymerization reaction proceeds gently, so that it is possible to produce a solid electrolytic capacitor with better characteristics than before. It is done.
本発明のモノマー組成物を用いての導電性高分子の製造は、通常に導電性高分子を製造する場合と、固体電解コンデンサの製造時に導電性高分子を製造する、いわゆる「その場重合」による導電性高分子の製造との両方によって行うことができる。 The production of the conductive polymer using the monomer composition of the present invention is usually performed when the conductive polymer is produced, and when the solid electrolytic capacitor is produced, the conductive polymer is produced, so-called “in situ polymerization”. And can be carried out both by the production of the conductive polymer.
モノマーとなるチオフェンやその誘導体は、常温で液状であり、スルホキシド基を有する化合物も常温で液状であるので、重合にあたって、モノマー組成物は、そのまま用いることができるし、また、重合反応をよりスムーズに進行させるために、チオフェンまたはその誘導体を、例えば、メタノール、エタノール、プロパノール、ブタノール、アセトン、アセトニトリルなどの有機溶剤で希釈してモノマー組成物を有機溶剤溶液として用いてもよい。ただし、モノマー組成物を上記のような有機溶剤で希釈してしまうと、酸化剤兼ドーパント溶液を高濃度化した特色が損なわれてしまうので、モノマー組成物を酸化剤兼ドーパント溶液と混合して用いる場合には、モノマー組成物を溶剤で希釈することなく、そのまま用いることが好ましい。 The monomer thiophene and its derivatives are liquid at normal temperature, and the compound having a sulfoxide group is also liquid at normal temperature. Therefore, the monomer composition can be used as it is for polymerization, and the polymerization reaction is smoother. For example, thiophene or a derivative thereof may be diluted with an organic solvent such as methanol, ethanol, propanol, butanol, acetone, or acetonitrile, and the monomer composition may be used as an organic solvent solution. However, if the monomer composition is diluted with the organic solvent as described above, the feature of increasing the concentration of the oxidizing agent / dopant solution is impaired, so the monomer composition is mixed with the oxidizing agent / dopant solution. When used, it is preferable to use the monomer composition as it is without diluting it with a solvent.
通常に導電性高分子を製造する場合（この通常に導電性高分子を製造する場合とは、固体電解コンデンサの作製時に「その場重合」により導電性高分子を製造するのではないという意味である）、本発明のモノマー組成物と酸化剤兼ドーパントとを混合した混合物を用い（その混合割合は質量基準で、酸化剤兼ドーパント：モノマーのチオフェンまたはその誘導体が５：１〜１５：１が好ましい）、例えば、５〜９５℃で、１〜７２時間酸化重合することによって行われる。 When a conductive polymer is normally manufactured (this normal conductive polymer is manufactured means that the conductive polymer is not manufactured by “in-situ polymerization” at the time of production of the solid electrolytic capacitor. A mixture of the monomer composition of the present invention and an oxidizing agent / dopant (the mixing ratio is based on mass, and the oxidizing agent / dopant: monomer thiophene or its derivative is 5: 1 to 15: 1) Preferably), for example, by oxidative polymerization at 5 to 95 ° C. for 1 to 72 hours.
本発明のモノマー組成物は、特に固体電解コンデンサの作製時にモノマー組成物中のチオフェンまたはその誘導体をいわゆる「その場重合」で酸化重合して導電性高分子を製造するのに適するように開発したものであることから、これについて以下に詳しく説明する。 The monomer composition of the present invention was developed to be suitable for producing a conductive polymer by oxidative polymerization of thiophene or a derivative thereof in a monomer composition by so-called “in situ polymerization”, particularly when a solid electrolytic capacitor was produced. This will be described in detail below.
また、固体電解コンデンサも、アルミニウム固体電解コンデンサ、タンタル固体電解コンデンサ、ニオブ固体電解コンデンサなどがあり、そのアルミニウム固体電解コンデンサの中にも、巻回型アルミニウム固体電解コンデンサと積層型アルミニウム固体電解コンデンサがあるが、本発明のモノマー組成物は特に巻回型アルミニウム固体電解コンデンサの作製にあたって適するように開発したものであるから、これについて特に詳しく説明する。 In addition, solid electrolytic capacitors include aluminum solid electrolytic capacitors, tantalum solid electrolytic capacitors, niobium solid electrolytic capacitors, etc. Among these aluminum solid electrolytic capacitors, wound aluminum solid electrolytic capacitors and stacked aluminum solid electrolytic capacitors are also included. However, since the monomer composition of the present invention has been developed to be particularly suitable for the production of a wound aluminum solid electrolytic capacitor, this will be described in detail.
まず、巻回型アルミニウム固体電解コンデンサのコンデンサ素子としては、アルミニウム箔の表面をエッチング処理した後、化成処理して誘電体層を形成した陽極にリード端子を取り付け、また、アルミニウム箔からなる陰極にリード端子を取り付け、それらのリード端子付き陽極と陰極とをセパレータを介して巻回して作製したものを使用する。
First, the capacitor element of a wound-type aluminum solid electrolytic capacitor, after the surface of the aluminum foil was etched, attach the lead terminals to the anode forming the induction conductor layer by chemical conversion treatment, also made of an aluminum foil cathode A lead terminal is attached to the electrode, and those prepared by winding the anode and cathode with the lead terminal through a separator are used.
そして、上記コンデンサ素子を用いての巻回型アルミニウム固体電解コンデンサの作製は、例えば、次のように行われる。
すなわち、上記コンデンサ素子を本発明のモノマー組成物と酸化剤兼ドーパント溶液との混合物に浸漬し、引き上げた後、室温または加熱下でモノマー組成物中のチオフェンまたはその誘導体を重合させて、その重合体をポリマー骨格とする導電性高分子からなる固体電解質層を形成した後、水に浸漬し、引き上げた後、乾燥し、その固体電解質層を有するコンデンサ素子を外装材で外装して、巻回型アルミニウム固体電解コンデンサを作製する。
And manufacture of the winding type aluminum solid electrolytic capacitor using the said capacitor | condenser element is performed as follows, for example.
That is, the capacitor element is immersed in a mixture of the monomer composition of the present invention and an oxidizing agent / dopant solution, pulled up, and then polymerized with thiophene or a derivative thereof in the monomer composition at room temperature or under heating, After forming a solid electrolyte layer composed of a conductive polymer having a polymer skeleton as a polymer, it is immersed in water, pulled up, dried, and a capacitor element having the solid electrolyte layer is packaged with an exterior material and wound. Type aluminum solid electrolytic capacitor.
また、上記のように、コンデンサ素子を本発明のモノマー組成物と酸化剤兼ドーパント溶液との混合物に浸漬するのに代えて、モノマー組成物を前記したメタノールなどの有機溶剤で希釈しておき、そのモノマー組成物溶液にコンデンサ素子を浸漬し、引き上げて乾燥した後、該コンデンサ素子を酸化剤兼ドーパント溶液に浸漬し、引き上げた後、室温または加熱下でモノマー組成物中のチオフェンまたはその誘導体を重合させるか、または、コンデンサ素子を先に酸化剤兼ドーパント溶液に浸漬し、引き上げた後、該コンデンサ素子をモノマー組成物に浸漬し、引き上げた後、室温または加熱下でモノマー組成物中のチオフェンまたはその誘導体を重合させ、以後、前記と同様にして、巻回型アルミニウム固体電解コンデンサを作製する。 Further, as described above, instead of immersing the capacitor element in the mixture of the monomer composition of the present invention and the oxidant / dopant solution, the monomer composition is diluted with an organic solvent such as methanol described above, After immersing the capacitor element in the monomer composition solution, pulling it up and drying it, immersing the capacitor element in the oxidant / dopant solution and pulling it up, the thiophene or its derivative in the monomer composition is heated at room temperature or under heating. Polymerize or immerse the capacitor element in an oxidant / dopant solution and pull it up, then immerse the capacitor element in the monomer composition, pull it up, and then at room temperature or under heating, the thiophene in the monomer composition Alternatively, a derivative thereof is polymerized, and thereafter, a wound aluminum solid electrolytic capacitor is produced in the same manner as described above.
上記巻回型アルミニウム固体電解コンデンサ以外の固体電解コンデンサ、例えば、積層型アルミニウム固体電解コンデンサ、タンタル固体電解コンデンサ、ニオブ固体電解コンデンサなどの作製にあたっては、コンデンサ素子としてアルミニウム、タンタル、ニオブなどの弁金属の多孔体からなる陽極と、それらの弁金属の酸化皮膜からなる誘電体層を有するものを用い、そのコンデンサ素子を、前記巻回型アルミニウム固体電解コンデンサの場合と同様に、本発明のモノマー組成物と酸化剤兼ドーパント溶液との混合物に浸漬し、引き上げて、室温またが加熱下でモノマー組成物中のチオフェンまたはその誘導体を重合させるか、あるいは、コンデンサ素子を本発明のモノマー組成物の溶液に浸漬し、引き上げて乾燥した後、該コンデンサ素子を酸化剤兼ドーパント溶液に浸漬し、引き上げて、室温または加熱下でモノマー組成物中のチオフェンまたはその誘導体を重合させるか、もしくは、コンデンサ素子を酸化剤兼ドーパント溶液に浸漬し、引き上げた後、該コンデンサ素子を本発明のモノマー組成物中に浸漬し、引き上げた後、室温または加熱下で、モノマー組成物中のチオフェンまたはその誘導体を重合させ、これらの工程を繰り返して、チオフェンまたはその誘導体の重合体をポリマー骨格とする導電性高分子からなる固体電解質層を形成した後、カーボンペースト、銀ペーストを付け、乾燥した後、外装することによって、積層型アルミニウム固体電解コンデンサ、タンタル固体電解コンデンサ、ニオブ固体電解コンデンサなどが作製される。 In the production of solid electrolytic capacitors other than the above wound aluminum solid electrolytic capacitors, for example, laminated aluminum solid electrolytic capacitors, tantalum solid electrolytic capacitors, niobium solid electrolytic capacitors, etc., valve metals such as aluminum, tantalum, and niobium as capacitor elements of the anode made of a porous material, with those having induction conductor layer made of an oxide film of their valve metal, the capacitor element, as in the case of the winding type aluminum solid electrolytic capacitor, the monomers of the present invention It is immersed in a mixture of the composition and an oxidizing agent / dopant solution and pulled up to polymerize thiophene or a derivative thereof in the monomer composition at room temperature or under heating, or a capacitor element of the monomer composition of the present invention. After immersing in the solution, pulling up and drying, the capacitor After the child is immersed in the oxidizing agent / dopant solution and pulled up to polymerize the thiophene or its derivative in the monomer composition at room temperature or under heating, or the capacitor element is immersed in the oxidizing agent / dopant solution and pulled up After immersing the capacitor element in the monomer composition of the present invention and pulling it up, the thiophene or derivative thereof in the monomer composition is polymerized at room temperature or under heating, and these steps are repeated to obtain thiophene or derivative thereof. After forming a solid electrolyte layer made of a conductive polymer having a polymer skeleton of the polymer as described above, a carbon paste and a silver paste are applied, dried, and then packaged to form a laminated aluminum solid electrolytic capacitor, a tantalum solid electrolytic capacitor A niobium solid electrolytic capacitor or the like is manufactured.
上記のような導電性高分子の製造や固体電解コンデンサの作製時の「その場重合」による導電性高分子の製造にあたって、本発明のモノマー組成物中のチオフェンまたはその誘導体と酸化剤兼ドーパントとの使用比率は、チオフェンまたはその誘導体と酸化剤兼ドーパントの有機スルホン酸第二鉄とが質量比で２：１〜８：１が好ましく、「その場重合」は、例えば、１０〜３００℃、１〜１８０分で行われる。 In the production of a conductive polymer by “in-situ polymerization” at the time of production of the above-described conductive polymer or solid electrolytic capacitor, thiophene or a derivative thereof in the monomer composition of the present invention and an oxidizing agent / dopant The use ratio of thiophene or a derivative thereof and oxidizer / dopant organic ferric sulfonate is preferably 2: 1 to 8: 1 by mass ratio, and “in situ polymerization” is, for example, 10 to 300 ° C., It takes 1 to 180 minutes.
以下に実施例を挙げて本発明をより具体的に説明するが、本発明はそれらの実施例に限定されるものではない。なお、以下において添加量や溶液濃度などを示す％は、特にその基準を付記しないかぎり、質量基準による％である。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In the following, “%” indicating the addition amount, solution concentration, etc. is “%” based on mass unless otherwise indicated.
〔モノマー組成物の調製〕
以下に示す実施例１〜６および比較例１〜３では、モノマー組成物の調製について説明する。ただし、これら実施例１〜６および比較例１〜３のモノマー組成物の評価は、後記の〔固体電解コンデンサの評価（１）〕および〔固体電解コンデンサでの評価（２）〕における固体電解コンデンサの評価によって行う。
(Preparation of monomer composition)
In Examples 1 to 6 and Comparative Examples 1 to 3 shown below, preparation of the monomer composition will be described. However, the evaluation of the monomer compositions of Examples 1 to 6 and Comparative Examples 1 to 3 was performed in accordance with the solid electrolytic capacitors in [Evaluation of Solid Electrolytic Capacitors (1)] and [Evaluation with Solid Electrolytic Capacitors (2)] described later. It is done by evaluation.
実施例１
ガスクロマトグラフィ分析（以下、簡略化して、「ＧＣ分析」という）による純度が９９．９％の３，４−エチレンジオキシチオフェン（テイカ社製）１ｋｇに対しジメチルスルホキシド３０ｇを添加した後、６時間撹拌して混合し、アドバンテック東洋社製のガラスフィルターＧＦ７５（ＧＦ７５は品番であり、以下、社名を省略して表示する）で濾過し、濾過を実施例１のモノマー組成物とした。このモノマー組成物における３，４−エチレンジオキシチオフェンに対するジメチルスルホキシドの添加量は３％であった。
Example 1
6 hours after adding 30 g of dimethyl sulfoxide to 1 kg of 3,4-ethylenedioxythiophene (manufactured by Teika) having a purity of 99.9% by gas chromatography analysis (hereinafter simply referred to as “GC analysis”) The mixture was stirred and mixed, and filtered through a glass filter GF75 manufactured by Advantech Toyo Co., Ltd. (GF75 is a product number, hereinafter, the company name is omitted), and filtration was performed as the monomer composition of Example 1. The amount of dimethyl sulfoxide added to 3,4-ethylenedioxythiophene in this monomer composition was 3%.
実施例２
ＧＣ分析による純度が９９．９％の３，４−エチレンジオキシチオフェン（テイカ社製）１ｋｇに対しジメチルスルホキシド５０ｇを添加した後、６時間撹拌して混合し、ガラスフィルターＧＦ７５で濾過し、濾液を実施例２のモノマー組成物とした。このモノマー組成物における３，４−エチレンジオキシチオフェンに対するジメチルスルホキシドの添加量は５％であった。
Example 2
After adding 50 g of dimethyl sulfoxide to 1 kg of 3,4-ethylenedioxythiophene (manufactured by Teika) having a purity of 99.9% according to GC analysis, the mixture was stirred for 6 hours, mixed, filtered through a glass filter GF75, and the filtrate. Was used as the monomer composition of Example 2. The amount of dimethyl sulfoxide added to 3,4-ethylenedioxythiophene in this monomer composition was 5%.
実施例３
ＧＣ分析による純度が９９．９％の３，４−エチレンジオキシチオフェン（テイカ社製）１ｋｇに対しジメチルスルホキシド１００ｇを添加した後、６時間撹拌して混合し、ガラスフィルターＧＦ７５で濾過し、濾液を実施例３のモノマー組成物とした。このモノマー組成物における３，４−エチレンジオキシチオフェンに対するジメチルスルホキシドの添加量は１０％であった。
Example 3
After adding 100 g of dimethyl sulfoxide to 1 kg of 3,4-ethylenedioxythiophene (manufactured by Teika) having a purity of 99.9% according to GC analysis, the mixture was stirred for 6 hours, mixed, filtered through a glass filter GF75, and the filtrate. Was used as the monomer composition of Example 3. The amount of dimethyl sulfoxide added to 3,4-ethylenedioxythiophene in this monomer composition was 10%.
実施例４
ＧＣ分析による純度が９９．９％の３，４−エチレンジオキシチオフェン（テイカ社製）１ｋｇに対しジメチルスルホキシド１５０ｇを添加した後、６時間撹拌して混合し、ガラスフィルターＧＦ７５で濾過し、濾液を実施例４のモノマー組成物とした。このモノマー組成物における３，４−エチレンジオキシチオフェンに対するジメチルスルホキシドの添加量は１５％であった。
Example 4
After adding 150 g of dimethyl sulfoxide to 1 kg of 3,4-ethylenedioxythiophene (manufactured by Teika) having a purity of 99.9% according to GC analysis, the mixture was stirred for 6 hours, mixed, filtered through a glass filter GF75, and the filtrate. Was the monomer composition of Example 4. The amount of dimethyl sulfoxide added to 3,4-ethylenedioxythiophene in this monomer composition was 15%.
実施例５
ＧＣ分析による純度が９９．９％の３，４−エチレンジオキシチオフェン（テイカ社製）１ｋｇに対しジメチルスルホキシド２０ｇを添加した後、６時間撹拌して混合し、ガラスフィルターＧＦ７５で濾過し、濾液を実施例５のモノマー組成物とした。このモノマー組成物における３，４−エチレンジオキシチオフェンに対するジメチルスルホキシドの添加量は２％であった。
Example 5
After adding 20 g of dimethyl sulfoxide to 1 kg of 3,4-ethylenedioxythiophene (manufactured by Teica) having a purity of 99.9% according to GC analysis, the mixture was stirred for 6 hours, mixed, filtered through a glass filter GF75, and the filtrate. Was used as the monomer composition of Example 5. The amount of dimethyl sulfoxide added to 3,4-ethylenedioxythiophene in this monomer composition was 2%.
実施例６
ＧＣ分析による純度が９９．９％の３，４−エチレンジオキシチオフェン（テイカ社製）１ｋｇに対しジメチルスルホキシド１８０ｇを添加した後、６時間撹拌して混合し、ガラスフィルターＧＦ７５で濾過し、濾液を実施例６のモノマー組成物とした。このモノマー組成物における３，４−エチレンジオキシチオフェンに対するジメチルスルホキシドの添加量は１８％であった。
Example 6
After adding 180 g of dimethyl sulfoxide to 1 kg of 3,4-ethylenedioxythiophene (manufactured by Teika) having a purity of 99.9% according to GC analysis, the mixture was stirred for 6 hours and mixed, filtered through a glass filter GF75, and the filtrate. Was used as the monomer composition of Example 6. The amount of dimethyl sulfoxide added to 3,4-ethylenedioxythiophene in this monomer composition was 18%.
比較例１
ＧＣ分析による純度が９９．９％の３，４−エチレンジオキシチオフェン（テイカ社製）１ｋｇに対しジメチルスルホキシド１０ｇを添加した後、６時間撹拌して混合し、ガラスフィルターＧＦ７５で濾過し、濾液を比較例１のモノマー組成物とした。このモノマー組成物における３，４−エチレンジオキシチオフェンに対するジメチルスルホキシドの添加量は１％であった。
Comparative Example 1
After adding 10 g of dimethyl sulfoxide to 1 kg of 3,4-ethylenedioxythiophene (manufactured by Teika) having a purity of 99.9% according to GC analysis, the mixture was stirred for 6 hours and mixed, filtered through a glass filter GF75, and the filtrate. Was the monomer composition of Comparative Example 1. The amount of dimethyl sulfoxide added to 3,4-ethylenedioxythiophene in this monomer composition was 1%.
比較例２
ＧＣ分析による純度が９９．９％の３，４−エチレンジオキシチオフェン（テイカ社製）１ｋｇに対しジメチルスルホキシド２５０ｇを添加した後、６時間撹拌して混合し、ガラスフィルターＧＦ７５で濾過し、濾液を比較例２のモノマー組成物とした。このモノマー組成物における３，４−エチレンジオキシチオフェンに対するジメチルスルホキシドの添加量は２５％であった。
Comparative Example 2
After adding 250 g of dimethyl sulfoxide to 1 kg of 3,4-ethylenedioxythiophene (manufactured by Teika) having a purity of 99.9% according to GC analysis, the mixture was stirred for 6 hours, mixed, filtered through a glass filter GF75, and the filtrate. Was the monomer composition of Comparative Example 2. The amount of dimethyl sulfoxide added to 3,4-ethylenedioxythiophene in this monomer composition was 25%.
比較例３
ＧＣ分析による純度が９９．９％の３，４−エチレンジオキシチオフェン（テイカ社製）１ｋｇに対しスルホラン５０ｇを添加した後、６時間撹拌して混合し、ガラスフィルターＧＦ７５で濾過し、濾液を比較例３のモノマー組成物とした。このモノマー組成物における３，４−エチレンジオキシチオフェンに対するスルホランの添加量は５％であった。
Comparative Example 3
After adding 50 g of sulfolane to 1 kg of 3,4-ethylenedioxythiophene (manufactured by Teika) having a purity of 99.9% according to GC analysis, the mixture was stirred for 6 hours, mixed, filtered through a glass filter GF75, and the filtrate was filtered. The monomer composition of Comparative Example 3 was used. The amount of sulfolane added to 3,4-ethylenedioxythiophene in this monomer composition was 5%.
〔固体電解コンデンサでの評価（１）〕
以下に示す実施例７〜１１では、上記実施例１〜５のモノマー組成物を用いて設定静電容量が５０μＦ以上で、設定ＥＳＲが１２ｍΩ以下の巻回型アルミニウム固体電解コンデンサを作製し、それらとジメチルスルホキシドを添加していない３，４−エチレンジオキシチオフェンを用いて作製した比較例４の巻回型アルミニウム固体電解コンデンサ、ジメチルスルホキシドの添加量が少ない比較例１のモノマー組成物を用いて作製した比較例５の巻回型アルミニウム固体電解コンデンサ、ジメチルスルホキシドの添加量が多すぎる比較例２のモノマー組成物を用いて作製した比較例６の巻回型アルミニウム固体電解コンデンサおよびジメチルスルホキシドに代えてスルホキシド基を有しないスルホランを添加した比較例３のモノマー組成物を用いて作製した比較例７の巻回型アルミニウム固体電解コンデンサとのコンデンサ特性を比較するとともに、それらの作製にあたって用いたモノマー組成物の特性を評価する。
[Evaluation with solid electrolytic capacitor (1)]
In Examples 7 to 11 shown below, winding type aluminum solid electrolytic capacitors having a set capacitance of 50 μF or more and a set ESR of 12 mΩ or less using the monomer compositions of Examples 1 to 5 were prepared. And a wound aluminum aluminum electrolytic capacitor of Comparative Example 4 prepared using 3,4-ethylenedioxythiophene to which dimethyl sulfoxide is not added, and using the monomer composition of Comparative Example 1 with a small amount of dimethyl sulfoxide added In place of the wound aluminum solid electrolytic capacitor of Comparative Example 5 and the wound aluminum solid electrolytic capacitor and dimethyl sulfoxide of Comparative Example 6 prepared using the monomer composition of Comparative Example 2 in which the amount of dimethyl sulfoxide added is too large. The monomer composition of Comparative Example 3 to which sulfolane having no sulfoxide group was added was used. The capacitor characteristics of the wound aluminum solid electrolytic capacitor of Comparative Example 7 manufactured in comparison with the above were compared, and the characteristics of the monomer composition used in the preparation thereof were evaluated.
実施例７
アルミニウム箔の表面をエッチング処理した後、化成処理を行って誘電体層を形成した陽極にリード端子を取り付け、また、アルミニウム箔からなる陰極にリード端子を取り付け、それらのリード端子付き陽極と陰極とをセパレータを介して巻回して、設定静電容量が５０μＦ以上で、設定ＥＳＲが１２ｍΩ以下の巻回型アルミニウム固体電解コンデンサ作製用のコンデンサ素子を作製した。
Example 7
After etching the surface of the aluminum foil, a lead terminal is attached to the anode on which the dielectric layer is formed by performing a chemical conversion treatment, and the lead terminal is attached to the cathode made of aluminum foil. Was wound through a separator to produce a capacitor element for producing a wound aluminum solid electrolytic capacitor having a set capacitance of 50 μF or more and a set ESR of 12 mΩ or less.
これとは別に、濃度が４０％のパラトルエンスルホン酸第二鉄ブタノール溶液（テイカ社製）を蒸留により濃縮し、濃度を５８％に調整して、酸化剤兼ドーパント溶液とした。 Separately, a 40% concentration of para-toluenesulfonic acid ferric butanol solution (manufactured by Teika) was concentrated by distillation, and the concentration was adjusted to 58% to obtain an oxidizing agent / dopant solution.
そして、前記実施例１のモノマー組成物２０ｍｌにメタノール８０ｍｌを添加して含モノマー組成物溶液にし、この含モノマー組成物溶液に、上記のコンデンサ素子を浸漬し、引き上げた後、５０℃で１０分間放置して乾燥した。その後、該コンデンサ素子を上記濃度が５８％の酸化剤兼ドーパント溶液５００ｍｌに浸漬し、引き上げた後、６０℃で２時間、１８０℃で１時間加熱することによって、上記含モノマー組成物溶液中の３，４−エチレンジオキシチオフェンを上記酸化剤兼ドーパントの酸化剤で酸化重合してポリエチレンジオキシチオフェンをポリマー骨格とする導電性高分子からなる固体電解質層を形成し、それらを外装材で外装して、巻回型アルミニウム固体電解コンデンサを作製した。 Then, 80 ml of methanol was added to 20 ml of the monomer composition of Example 1 to obtain a monomer-containing composition solution. The capacitor element was immersed in this monomer-containing composition solution and pulled up, and then at 50 ° C. for 10 minutes. Leave to dry. Thereafter, the capacitor element is immersed in 500 ml of an oxidizing agent / dopant solution having a concentration of 58% and pulled up, and then heated at 60 ° C. for 2 hours and at 180 ° C. for 1 hour, whereby in the monomer-containing composition solution. 3,4-ethylenedioxythiophene is oxidatively polymerized with the above oxidizing agent / dopant oxidizing agent to form a solid electrolyte layer made of a conductive polymer having polyethylenedioxythiophene as a polymer skeleton, and these are packaged with an exterior material. Thus, a wound aluminum solid electrolytic capacitor was produced.
上記のようにして作製した巻回型アルミニウム固体電解コンデンサについて、ＨＥＷＬＥＴＴ ＰＡＣＫＡＲＤ社製のＬＳＲメーター（４２８４Ａ）を用い、２５℃の条件下で、ＥＳＲを１００ｋＨｚで測定し、静電容量を１２０Ｈｚで測定した。その結果を後記の表１に示す。 For the wound aluminum solid electrolytic capacitor produced as described above, the ESR is measured at 100 kHz and the capacitance is measured at 120 Hz using a LSR meter (4284A) manufactured by HEWLETT PACKARD under the condition of 25 ° C. did. The results are shown in Table 1 below.
実施例８
実施例１のモノマー組成物に代えて、実施例２のモノマー組成物を用いた以外は、すべて実施例７と同様の操作を行って、巻回型アルミニウム固体電解コンデンサを作製し、その巻回型アルミニウム固体電解コンデンサについて、実施例７と同様にＥＳＲおよび静電容量を測定した。その結果を後記の表１に示す。
Example 8
A wound aluminum solid electrolytic capacitor was produced by performing the same operation as in Example 7 except that the monomer composition of Example 2 was used instead of the monomer composition of Example 1. The ESR and capacitance of the type aluminum solid electrolytic capacitor were measured in the same manner as in Example 7. The results are shown in Table 1 below.
実施例９
実施例１のモノマー組成物に代えて、実施例３のモノマー組成物を用いた以外は、すべて実施例７と同様の操作を行って、巻回型アルミニウム固体電解コンデンサを作製し、その巻回型アルミニウム固体電解コンデンサについて、実施例７と同様にＥＳＲおよび静電容量を測定した。その結果を後記の表１に示す。
Example 9
A wound aluminum solid electrolytic capacitor was produced in the same manner as in Example 7 except that the monomer composition of Example 3 was used instead of the monomer composition of Example 1. The ESR and capacitance of the type aluminum solid electrolytic capacitor were measured in the same manner as in Example 7. The results are shown in Table 1 below.
実施例１０
実施例１のモノマー組成物に代えて、実施例４のモノマー組成物を用いた以外は、すべて実施例７と同様の操作を行って、巻回型アルミニウム固体電解コンデンサを作製し、その巻回型アルミニウム固体電解コンデンサについて、実施例７と同様にＥＳＲおよび静電容量を測定した。その結果を後記の表１に示す。
Example 10
A wound aluminum solid electrolytic capacitor was produced in the same manner as in Example 7 except that the monomer composition of Example 4 was used instead of the monomer composition of Example 1. The ESR and capacitance of the type aluminum solid electrolytic capacitor were measured in the same manner as in Example 7. The results are shown in Table 1 below.
実施例１１
実施例１のモノマー組成物に代えて、実施例５のモノマー組成物を用いた以外は、すべて実施例７と同様の操作を行って、巻回型アルミニウム固体電解コンデンサを作製し、その巻回型アルミニウム固体電解コンデンサについて、実施例７と同様にＥＳＲおよび静電容量を測定した。その結果を後記の表１に示す。
Example 11
A wound aluminum solid electrolytic capacitor was produced in the same manner as in Example 7 except that the monomer composition of Example 5 was used instead of the monomer composition of Example 1. The ESR and capacitance of the type aluminum solid electrolytic capacitor were measured in the same manner as in Example 7. The results are shown in Table 1 below.
比較例４
実施例１のモノマー組成物に代えて、ジメチルスルホキシドを添加していない純度が９９．９％の３，４−エチレンジオキシチオフェンをそのまま用いた以外は、すべて実施例７と同様の操作を行って、巻回型アルミニウム固体電解コンデンサを作製し、その巻回型アルミニウム固体電解コンデンサについて、実施例７と同様にＥＳＲおよび静電容量を測定した。その結果を後記の表１に示す。
Comparative Example 4
The same operation as in Example 7 was performed except that 3,4-ethylenedioxythiophene having a purity of 99.9% without addition of dimethyl sulfoxide was used as it was instead of the monomer composition of Example 1. Then, a wound aluminum solid electrolytic capacitor was produced, and the ESR and capacitance of the wound aluminum solid electrolytic capacitor were measured in the same manner as in Example 7. The results are shown in Table 1 below.
比較例５
実施例１のモノマー組成物に代えて、比較例１のモノマー組成物を用いた以外は、すべて実施例７と同様の操作を行って、巻回型アルミニウム固体電解コンデンサを作製し、その巻回型アルミニウム固体電解コンデンサについて、実施例７と同様にＥＳＲおよび静電容量を測定した。その結果を後記の表１に示す。
Comparative Example 5
A wound aluminum solid electrolytic capacitor was produced in the same manner as in Example 7 except that the monomer composition of Comparative Example 1 was used instead of the monomer composition of Example 1. The ESR and capacitance of the type aluminum solid electrolytic capacitor were measured in the same manner as in Example 7. The results are shown in Table 1 below.
比較例６
実施例１のモノマー組成物に代えて、比較例２のモノマー組成物を用いた以外は、すべて実施例７と同様の操作を行って、巻回型アルミニウム固体電解コンデンサを作製し、その巻回型アルミニウム固体電解コンデンサについて、実施例７と同様にＥＳＲおよび静電容量を測定した。その結果を後記の表１に示す。
Comparative Example 6
A wound aluminum solid electrolytic capacitor was produced in the same manner as in Example 7 except that the monomer composition of Comparative Example 2 was used instead of the monomer composition of Example 1. The ESR and capacitance of the type aluminum solid electrolytic capacitor were measured in the same manner as in Example 7. The results are shown in Table 1 below.
比較例７
実施例１のモノマー組成物に代えて、比較例３のモノマー組成物を用いた以外は、すべて実施例７と同様の操作を行って、巻回型アルミニウム固体電解コンデンサを作製し、その巻回型アルミニウム固体電解コンデンサについて、実施例７と同様にＥＳＲおよび静電容量を測定した。その結果を後記の表１に示す。
Comparative Example 7
A wound aluminum solid electrolytic capacitor was produced in the same manner as in Example 7 except that the monomer composition of Comparative Example 3 was used instead of the monomer composition of Example 1. The ESR and capacitance of the type aluminum solid electrolytic capacitor were measured in the same manner as in Example 7. The results are shown in Table 1 below.
表１に上記実施例７〜１１および比較例４〜７の巻回型アルミニウム固体電解コンデンサの静電容量およびＥＳＲを示す。 Table 1 shows the capacitance and ESR of the wound aluminum solid electrolytic capacitors of Examples 7 to 11 and Comparative Examples 4 to 7.
表１に示すように、実施例７〜１１の巻回型アルミニウム固体電解コンデンサは、静電容量が５０.３〜５２．１μＦ以上であって、設定静電容量の５０μＦ以上を満たし、ＥＳＲが１１ｍΩ台であって、設定ＥＳＲの１２ｍΩ以下を満たしていたが、比較例４〜７の巻回型アルミニウム固体電解コンデンサは、静電容量が５０μＦに達せず、設定静電容量の５０μＦ以上を満たさず、ＥＳＲが１２ｍΩより大きく、設定ＥＳＲの１２ｍΩ以下を満たさなかった。 As shown in Table 1, the wound aluminum solid electrolytic capacitors of Examples 7 to 11 have a capacitance of 50.3 to 52.1 μF or more, satisfy a set capacitance of 50 μF or more, and have an ESR of Although it was 11 mΩ and satisfied the set ESR of 12 mΩ or less, the wound aluminum solid electrolytic capacitors of Comparative Examples 4 to 7 did not reach the capacitance of 50 μF and satisfied the set capacitance of 50 μF or more. The ESR was larger than 12 mΩ and did not satisfy the set ESR of 12 mΩ or less.
すなわち、モノマーの３，４−エチレンジオキシチオフェンにジメチルスルホキシドを所定量添加した実施例１〜５のモノマー組成物を用いて作製した実施例７〜１１の巻回型アルミニウム固体電解コンデンサは、静電容量が５０μＦ以上と大きく、ＥＳＲが１１ｍΩ台で小さかったが、ジメチルスルホキシドを添加していない３，４−エチレンジオキシチオフェンを用いて作製した比較例４の巻回型アルミニウム固体電解コンデンサや、ジメチルスルホキシドの添加量が少ない比較例１のモノマー組成物を用いて作製した比較例５の巻回型アルミニウム固体電解コンデンサ、ジメチルスルホキシドの添加量が多すぎる比較例２のモノマー組成物を用いて作製した比較例５の巻回型アルミニウム固体電解コンデンサ、ジメチルスルホキシドに代えてスルホキシド基を有しないスルホランを添加した比較例３のモノマー組成物を用いて作製した比較例７の巻回型アルミニウム固体電解コンデンサは、静電容量が４０μＦ台と小さく、ＥＳＲが１２ｍΩを超えていて大きく、実施例７〜１１の巻回型アルミニウム固体電解コンデンサに比べて、コンデンサ特性が劣っていた。 That is, the wound aluminum solid electrolytic capacitors of Examples 7 to 11 produced using the monomer compositions of Examples 1 to 5 in which a predetermined amount of dimethyl sulfoxide was added to the monomer 3,4-ethylenedioxythiophene were static A winding type aluminum solid electrolytic capacitor of Comparative Example 4 produced using 3,4-ethylenedioxythiophene without adding dimethyl sulfoxide, although the capacitance was as large as 50 μF or more and the ESR was as small as 11 mΩ, Prepared using the wound aluminum solid electrolytic capacitor of Comparative Example 5 prepared using the monomer composition of Comparative Example 1 with a small amount of dimethyl sulfoxide added, and using the monomer composition of Comparative Example 2 with an excessive amount of dimethyl sulfoxide added. The wound aluminum solid electrolytic capacitor of Comparative Example 5 was replaced with dimethyl sulfoxide. The wound aluminum solid electrolytic capacitor of Comparative Example 7 produced using the monomer composition of Comparative Example 3 to which sulfolane having no sulfoxide group was added had a small capacitance of 40 μF and ESR exceeded 12 mΩ. Compared to the wound aluminum solid electrolytic capacitors of Examples 7 to 11, the capacitor characteristics were inferior.
そして、この結果から、実施例７〜１１の巻回型アルミニウム固体電解コンデンサの作製にあたって用いた実施例１〜５のモノマー組成物は、比較例４の巻回型アルミニウム固体電解コンデンサの作製にあたって用いた３，４−エチレンジオキシチオフェンそのもの（つまり、ジメチルスルホキシドを添加していない３，４−エチレンジオキシチオフェン）に対してはもとより、比較例５〜７の巻回型アルミニウム固体電解コンデンサの作製にあたって用いた比較例１〜３のモノマー組成物に比べて、導電性高分子製造用のモノマー組成物として優れていることがわかるし、また、実施例１〜５のモノマー組成物を用いて製造した導電性高分子が、特性が優れていることがわかる。 From these results, the monomer compositions of Examples 1 to 5 used in the production of the wound aluminum solid electrolytic capacitors of Examples 7 to 11 were used for the production of the wound aluminum solid electrolytic capacitor of Comparative Example 4. Preparation of wound aluminum solid electrolytic capacitors of Comparative Examples 5 to 7 as well as 3,4-ethylenedioxythiophene itself (that is, 3,4-ethylenedioxythiophene to which dimethyl sulfoxide is not added) Compared to the monomer compositions of Comparative Examples 1 to 3 used in the process, it can be seen that they are superior as a monomer composition for producing a conductive polymer, and are produced using the monomer compositions of Examples 1 to 5. It can be seen that the conductive polymer has excellent characteristics.
〔固体電解コンデンサの評価（２）〕
以下に示す実施例１２〜１６では実施例１〜４および実施例６のモノマー組成物を用いて設定静電容量が１００μＦ以上で、設定ＥＳＲが８ｍΩ以下の巻回型アルミニウム固体電解コンデンサを作製し、それらをジメチルスルホキシドを添加していない３，４−エチレンジオキシチオフェンを用いて作製した比較例８の巻回型アルミニウム固体電解コンデンサ、ジメチルスルホキシドの添加量が少ない比較例１のモノマー組成物を用いて作製した比較例９の巻回型アルミニウム固体電解コンデンサ、ジメチルスルホキシドの添加量が多すぎる比較例２のモノマー組成物を用いて作製した比較例１０の巻回型アルミニウム固体電解コンデンサ、ジメチルスルホキシドに代えてスルホキシド基を有しないスルホランを添加した比較例３のモノマー組成物を用いて作製した比較例１１の巻回型アルミニウム固体電解コンデンサとのコンデンサ特性を比較するとともに、それらの作製にあたって用いたモノマー組成物の特性を評価する。
[Evaluation of solid electrolytic capacitor (2)]
In Examples 12 to 16 shown below, a wound aluminum solid electrolytic capacitor having a set capacitance of 100 μF or more and a set ESR of 8 mΩ or less was prepared using the monomer compositions of Examples 1 to 4 and Example 6. The wound aluminum solid electrolytic capacitor of Comparative Example 8 prepared using 3,4-ethylenedioxythiophene to which dimethyl sulfoxide was not added, and the monomer composition of Comparative Example 1 with a small amount of dimethyl sulfoxide added. The wound aluminum solid electrolytic capacitor of Comparative Example 9 produced using the monomer composition of Comparative Example 2 prepared using the monomer composition of Comparative Example 2 in which the amount of dimethyl sulfoxide added is too large, and dimethyl sulfoxide The monomer set of Comparative Example 3 to which sulfolane having no sulfoxide group was added instead of While comparing the capacitor | condenser characteristic with the winding type aluminum solid electrolytic capacitor of the comparative example 11 produced using the composition, the characteristic of the monomer composition used in producing them is evaluated.
実施例１２
アルミニウム箔の表面をエッチング処理した後、化成処理を行って誘電体層を形成した陽極にリード端子を取り付け、また、アルミニウム箔からなる陰極にリード端子を取り付け、それらのリード端子付き陽極と陰極とをセパレータを介して巻回し、設定静電容量が１００μＦ以上で、設定ＥＳＲが８ｍΩ以下の巻回型アルミニウム固体電解コンデンサ作製用のコンデンサ素子を作製した。
Example 12
After etching the surface of the aluminum foil, a lead terminal is attached to the anode on which the dielectric layer is formed by performing a chemical conversion treatment, and the lead terminal is attached to the cathode made of aluminum foil. Was wound through a separator, and a capacitor element for producing a wound aluminum solid electrolytic capacitor having a set capacitance of 100 μF or more and a set ESR of 8 mΩ or less was produced.
これとは別に、濃度が４０％のパラトルエンスルホン酸第二鉄エタノール溶液（テイカ社製）を蒸留により濃縮し、濃度を６４％に調整し、この濃度が６４％の酸化剤兼ドーパント溶液１００ｍｌと実施例１のモノマー組成物２０ｍｌとを混合して、モノマー組成物と酸化剤兼ドーパント溶液との混合液を得た。 Separately, a 40% concentration of para-toluenesulfonic acid ferric ethanol solution (manufactured by Teika) was concentrated by distillation to adjust the concentration to 64%, and this concentration of 64% oxidant / dopant solution 100 ml. And 20 ml of the monomer composition of Example 1 were mixed to obtain a mixed solution of the monomer composition and the oxidizing agent / dopant solution.
このモノマー組成物と酸化剤兼ドーパント溶液との混合液に上記コンデンサ素子を浸漬し、引き上げた後、６０℃で２時間、１８０℃で１時間加熱することによって、モノマー組成物中の３，４−エチレンジオキシチオフェンを重合させてポリエチレンジオキシチオフェンをポリマー骨格とする導電性高分子からなる固体電解質層を形成した。これを外装材で外装して、巻回型アルミニウム固体電解コンデンサを作製した。 The capacitor element is immersed in a mixed solution of the monomer composition and the oxidizing agent / dopant solution, pulled up, and then heated at 60 ° C. for 2 hours and at 180 ° C. for 1 hour, whereby 3,4 in the monomer composition is obtained. -A solid electrolyte layer made of a conductive polymer having polyethylenedioxythiophene as a polymer skeleton was formed by polymerizing ethylenedioxythiophene. This was covered with an exterior material to produce a wound aluminum solid electrolytic capacitor.
上記のようにして作製した巻回型アルミニウム固体電解コンデンサについて、ＨＥＷＬＥＴＴ ＰＡＣＫＡＲＤ社製のＬＣＲメーター（４２８４Ａ）を用い、２５℃の条件下で、ＥＳＲを１００ｋＨｚで測定し、静電容量を１２０Ｈｚで測定を行った。その結果を後記の表２に示す。 For the wound aluminum solid electrolytic capacitor produced as described above, the ESR is measured at 100 kHz and the capacitance is measured at 120 Hz using a LCR meter (4284A) manufactured by HEWLETT PACKARD under the condition of 25 ° C. Went. The results are shown in Table 2 below.
実施例１３
実施例１のモノマー組成物に代えて、実施例２のモノマー組成物を用いた以外は、すべて実施例１２と同様の操作を行って、巻回型アルミニウム固体電解コンデンサを作製し、その巻回型アルミニウム固体電解コンデンサについて、実施例１２と同様にＥＳＲおよび静電容量を測定した。その結果を後記の表２に示す。
Example 13
A wound aluminum solid electrolytic capacitor was produced in the same manner as in Example 12 except that the monomer composition of Example 2 was used instead of the monomer composition of Example 1. The ESR and capacitance of the type aluminum solid electrolytic capacitor were measured in the same manner as in Example 12. The results are shown in Table 2 below.
実施例１４
実施例１のモノマー組成物に代えて、実施例３のモノマー組成物を用いた以外は、すべて実施例１２と同様の操作を行って、巻回型アルミニウム固体電解コンデンサを作製し、その巻回型アルミニウム固体電解コンデンサについて、実施例１２と同様にＥＳＲおよび静電容量を測定した。その結果を後記の表２に示す。
Example 14
A wound aluminum solid electrolytic capacitor was produced by performing the same operation as in Example 12 except that the monomer composition of Example 3 was used instead of the monomer composition of Example 1. The ESR and capacitance of the type aluminum solid electrolytic capacitor were measured in the same manner as in Example 12. The results are shown in Table 2 below.
実施例１５
実施例１のモノマー組成物に代えて、実施例４のモノマー組成物を用いた以外は、すべて実施例１２と同様の操作を行って、巻回型アルミニウム固体電解コンデンサを作製し、その巻回型アルミニウム固体電解コンデンサについて、実施例１２と同様にＥＳＲおよび静電容量を測定した。その結果を後記の表２に示す。
Example 15
A wound aluminum solid electrolytic capacitor was produced in the same manner as in Example 12 except that the monomer composition of Example 4 was used instead of the monomer composition of Example 1. The ESR and capacitance of the type aluminum solid electrolytic capacitor were measured in the same manner as in Example 12. The results are shown in Table 2 below.
実施例１６
実施例１のモノマー組成物に代えて、実施例６のモノマー組成物を用いた以外は、すべて実施例１２と同様の操作を行って、巻回型アルミニウム固体電解コンデンサを作製し、その巻回型アルミニウム固体電解コンデンサについて、実施例１２と同様にＥＳＲおよび静電容量を測定した。その結果を後記の表２に示す。
Example 16
A wound aluminum solid electrolytic capacitor was produced in the same manner as in Example 12 except that the monomer composition of Example 6 was used instead of the monomer composition of Example 1. The ESR and capacitance of the type aluminum solid electrolytic capacitor were measured in the same manner as in Example 12. The results are shown in Table 2 below.
比較例８
実施例１のモノマー組成物に代えて、ジメチルスルホキシド添加していない純度が９９．９％の３，４−エチレンジオキシチオフェンをそのまま用いた以外は、すべて実施例１２と同様の操作を行って、巻回型アルミニウム固体電解コンデンサを作製し、その巻回型アルミニウム固体電解コンデンサについて、実施例１２と同様にＥＳＲおよび静電容量を測定した。その結果を後記の表２に示す。
Comparative Example 8
The same operation as in Example 12 was performed except that 3,4-ethylenedioxythiophene having a purity of 99.9% without addition of dimethyl sulfoxide was used as it was instead of the monomer composition of Example 1. A wound aluminum solid electrolytic capacitor was prepared, and the ESR and capacitance of the wound aluminum solid electrolytic capacitor were measured in the same manner as in Example 12. The results are shown in Table 2 below.
比較例９
実施例１のモノマー組成物に代えて、比較例１のモノマー組成物を用いた以外は、すべて実施例１２と同様の操作を行って、巻回型アルミニウム固体電解コンデンサを作製し、その巻回型アルミニウム固体電解コンデンサについて、実施例１２と同様にＥＳＲおよび静電容量を測定した。その結果を後記の表２に示す。
Comparative Example 9
A wound aluminum solid electrolytic capacitor was produced by performing the same operation as in Example 12 except that the monomer composition of Comparative Example 1 was used instead of the monomer composition of Example 1. The ESR and capacitance of the type aluminum solid electrolytic capacitor were measured in the same manner as in Example 12. The results are shown in Table 2 below.
比較例１０
実施例１のモノマー組成物に代えて、比較例２のモノマー組成物を用いた以外は、すべて実施例１２と同様の操作を行って、巻回型アルミニウム固体電解コンデンサを作製し、その巻回型アルミニウム固体電解コンデンサについて、実施例１２と同様にＥＳＲおよび静電容量を測定した。その結果を後記の表２に示す。
Comparative Example 10
A wound aluminum solid electrolytic capacitor was produced in the same manner as in Example 12 except that the monomer composition of Comparative Example 2 was used in place of the monomer composition of Example 1. The ESR and capacitance of the type aluminum solid electrolytic capacitor were measured in the same manner as in Example 12. The results are shown in Table 2 below.
比較例１１
実施例１のモノマー組成物に代えて、比較例３のモノマー組成物を用いた以外は、すべて実施例１２と同様の操作を行って、巻回型アルミニウム固体電解コンデンサを作製し、その巻回型アルミニウム固体電解コンデンサについて、実施例１２と同様にＥＳＲおよび静電容量を測定した。その結果を後記の表２に示す。
Comparative Example 11
A wound aluminum solid electrolytic capacitor was produced in the same manner as in Example 12 except that the monomer composition of Comparative Example 3 was used instead of the monomer composition of Example 1. The ESR and capacitance of the type aluminum solid electrolytic capacitor were measured in the same manner as in Example 12. The results are shown in Table 2 below.
上記実施例１２〜１６および比較例８〜１１の巻回型アルミニウム固体電解コンデンサの静電容量およびＥＳＲを次の表２に示す。 The capacitance and ESR of the wound aluminum solid electrolytic capacitors of Examples 12 to 16 and Comparative Examples 8 to 11 are shown in Table 2 below.
表２に示すように、実施例１２〜１６の巻回型アルミニウム固体電解コンデンサは、静電容量が１００.８〜１０４．７μＦ以上であって、設定静電容量の１００μＦ以上を満たし、ＥＳＲが７ｍΩ台であって、設定ＥＳＲの８ｍΩ以下を満たしていたが、比較例８〜１１の巻回型アルミニウム固体電解コンデンサは、静電容量が１００μＦ以上に達せず、設定静電容量の１００μＦ以上を満たさず、ＥＳＲが８ｍΩより大きく、設定ＥＳＲの８ｍΩ以下を満たしていなかった。 As shown in Table 2, the wound aluminum solid electrolytic capacitors of Examples 12 to 16 have a capacitance of 100.8 to 104.7 μF or more, satisfy a set capacitance of 100 μF or more, and have an ESR of Although it was on the order of 7 mΩ and satisfied the set ESR of 8 mΩ or less, the wound aluminum solid electrolytic capacitors of Comparative Examples 8 to 11 did not reach the capacitance of 100 μF or more, and the set capacitance of 100 μF or more. Not satisfied, ESR was larger than 8 mΩ, and the set ESR of 8 mΩ or less was not satisfied.
すなわち、モノマーの３，４−エチレンジオキシチオフェンにジメチルスルホキシドを所定量添加した実施例１〜４および実施例６のモノマー組成物を用いて作製した実施例１２〜１６の巻回型アルミニウム固体電解コンデンサは、静電容量が１００μＦを超えていて大きく、ＥＳＲが７ｍΩ台と小さかったが、ジメチルスルホキシドを添加していない３，４−エチレンジオキシチオフェンを用いて作製した比較例８の巻回型アルミニウム固体電解コンデンサや、ジメチルスルホキシドの添加量が少ない比較例１のモノマー組成物を用いて作製した比較例９の巻回型アルミニウム固体電解コンデンサ、ジメチルスルホキシドの添加量が多すぎる比較例２のモノマー組成物を用いて作製した比較例１０の巻回型アルミニウム固体電解コンデンサ、ジメチルスルホキシドに代えてスルホキシド基を有しないスルホランを添加した比較例３のモノマー組成物を用いて作製した比較例１１の巻回型アルミニウム固体電解コンデンサは、静電容量が１００μＦに達せず、ＥＳＲも８ｍΩを超えていて、実施例１２〜１６の巻回型アルミニウム固体電解コンデンサに比べて、コンデンサ特性が劣っていた。 That is, the wound aluminum solid electrolysis of Examples 12 to 16 produced using the monomer compositions of Examples 1 to 4 and Example 6 in which a predetermined amount of dimethyl sulfoxide was added to the monomer 3,4-ethylenedioxythiophene. The capacitor had a capacitance exceeding 100 μF and was large, and the ESR was as small as 7 mΩ, but it was a wound type of Comparative Example 8 made using 3,4-ethylenedioxythiophene to which dimethyl sulfoxide was not added. Aluminum solid electrolytic capacitor, wound aluminum solid electrolytic capacitor of Comparative Example 9 prepared using the monomer composition of Comparative Example 1 with a small amount of dimethyl sulfoxide added, monomer of Comparative Example 2 with a large amount of dimethyl sulfoxide added A wound aluminum solid electrolytic capacitor of Comparative Example 10 produced using the composition, The wound aluminum solid electrolytic capacitor of Comparative Example 11 produced using the monomer composition of Comparative Example 3 to which sulfolane having no sulfoxide group was added instead of dimethyl sulfoxide had an electrostatic capacity of less than 100 μF, and ESR was It exceeded 8 mΩ, and the capacitor characteristics were inferior compared with the wound aluminum solid electrolytic capacitors of Examples 12-16.
そして、この結果から、実施例１２〜１６の巻回型アルミニウム固体電解コンデンサの作製にあたって用いた実施例１〜４および実施例６のモノマー組成物は、比較例８の巻回型アルミニウム固体電解コンデンサの作製にあたって用いた３，４−エチレンジオキシチオフェンそのもの（つまり、ジメチルスルホキシドを添加していない３，４−エチレンジオキシチオフェン）に対してはもとより、比較例９〜１１の巻回型アルミニウム固体電解コンデンサの作製にあたって用いた比較例１〜３のモノマー組成物に比べて、導電性高分子製造用のモノマー組成物として優れていることがわかるし、また、実施例１〜４および実施例６のモノマー組成物を用いて製造した導電性高分子が、特性が優れていることがわかる。 From these results, the monomer compositions of Examples 1 to 4 and Example 6 used in the production of the wound aluminum solid electrolytic capacitors of Examples 12 to 16 are the wound aluminum solid electrolytic capacitors of Comparative Example 8. In addition to the 3,4-ethylenedioxythiophene itself (that is, 3,4-ethylenedioxythiophene to which dimethyl sulfoxide is not added) used in the production of the present invention, the wound aluminum solids of Comparative Examples 9-11 It turns out that it is excellent as a monomer composition for electroconductive polymer manufacture compared with the monomer composition of Comparative Examples 1-3 used in preparation of an electrolytic capacitor. Moreover, Examples 1-4 and Example 6 are understood. It can be seen that the conductive polymer produced using this monomer composition has excellent characteristics.
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