WO1999060586A1 - Condensateur electrolytique solide et son procede de preparation - Google Patents
Condensateur electrolytique solide et son procede de preparation Download PDFInfo
- Publication number
- WO1999060586A1 WO1999060586A1 PCT/JP1999/002647 JP9902647W WO9960586A1 WO 1999060586 A1 WO1999060586 A1 WO 1999060586A1 JP 9902647 W JP9902647 W JP 9902647W WO 9960586 A1 WO9960586 A1 WO 9960586A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- solid electrolytic
- electrolytic capacitor
- anion
- solution containing
- capacitor according
- Prior art date
Links
- 239000003990 capacitor Substances 0.000 title claims abstract description 186
- 239000007787 solid Substances 0.000 title claims abstract description 115
- 238000000034 method Methods 0.000 title claims abstract description 86
- -1 heterocyclic sulfonic acid anion Chemical class 0.000 claims abstract description 146
- 229920000642 polymer Polymers 0.000 claims abstract description 55
- 239000000203 mixture Substances 0.000 claims abstract description 45
- 150000001450 anions Chemical class 0.000 claims abstract description 44
- 239000002019 doping agent Substances 0.000 claims abstract description 43
- 229910052751 metal Inorganic materials 0.000 claims abstract description 43
- 239000002184 metal Substances 0.000 claims abstract description 43
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical class C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims description 88
- 150000002891 organic anions Chemical class 0.000 claims description 80
- 239000007784 solid electrolyte Substances 0.000 claims description 73
- 238000004519 manufacturing process Methods 0.000 claims description 72
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical group [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 62
- 238000006116 polymerization reaction Methods 0.000 claims description 61
- 239000011888 foil Substances 0.000 claims description 57
- 239000007800 oxidant agent Substances 0.000 claims description 55
- 239000000178 monomer Substances 0.000 claims description 51
- 239000002253 acid Substances 0.000 claims description 45
- 229920001940 conductive polymer Polymers 0.000 claims description 42
- 125000004432 carbon atom Chemical group C* 0.000 claims description 30
- 229920006395 saturated elastomer Polymers 0.000 claims description 27
- 125000001424 substituent group Chemical group 0.000 claims description 27
- 238000005406 washing Methods 0.000 claims description 26
- 125000003545 alkoxy group Chemical group 0.000 claims description 24
- 230000001590 oxidative effect Effects 0.000 claims description 24
- 239000000126 substance Substances 0.000 claims description 22
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 18
- 238000007598 dipping method Methods 0.000 claims description 18
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 14
- 125000004957 naphthylene group Chemical class 0.000 claims description 14
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 12
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 11
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 150000002391 heterocyclic compounds Chemical class 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 9
- 125000000623 heterocyclic group Chemical group 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 9
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 8
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 8
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 8
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 8
- 125000002373 5 membered heterocyclic group Chemical group 0.000 claims description 7
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 7
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 6
- 125000004070 6 membered heterocyclic group Chemical group 0.000 claims description 6
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 6
- 239000012964 benzotriazole Substances 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 239000003638 chemical reducing agent Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 125000004953 trihalomethyl group Chemical group 0.000 claims description 5
- 125000002030 1,2-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([*:2])C([H])=C1[H] 0.000 claims description 4
- AUFNSMKSGOXOLN-UHFFFAOYSA-N 3-(1,3-benzothiazol-2-ylsulfanyl)-1,2-benzoxazole Chemical compound S1C(=NC2=C1C=CC=C2)SC2=NOC1=C2C=CC=C1 AUFNSMKSGOXOLN-UHFFFAOYSA-N 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- 125000003341 7 membered heterocyclic group Chemical group 0.000 claims description 3
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 3
- 125000005842 heteroatom Chemical group 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 4
- 125000004429 atom Chemical group 0.000 claims 1
- 229910052711 selenium Inorganic materials 0.000 claims 1
- 230000009471 action Effects 0.000 abstract description 5
- 239000011248 coating agent Substances 0.000 abstract description 4
- 238000000576 coating method Methods 0.000 abstract description 4
- 239000003792 electrolyte Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 115
- 239000010410 layer Substances 0.000 description 91
- 239000000758 substrate Substances 0.000 description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 28
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 27
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 27
- 238000006243 chemical reaction Methods 0.000 description 27
- 239000007864 aqueous solution Substances 0.000 description 26
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 21
- 229930192474 thiophene Natural products 0.000 description 18
- 229910052782 aluminium Inorganic materials 0.000 description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 16
- 229910052708 sodium Inorganic materials 0.000 description 16
- 239000011734 sodium Substances 0.000 description 16
- 239000002904 solvent Substances 0.000 description 15
- 238000007654 immersion Methods 0.000 description 14
- 238000012360 testing method Methods 0.000 description 13
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 12
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 229910052742 iron Inorganic materials 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 9
- 150000002430 hydrocarbons Chemical group 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 8
- MWEMXEWFLIDTSJ-UHFFFAOYSA-M sodium;3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CCCN1CCOCC1 MWEMXEWFLIDTSJ-UHFFFAOYSA-M 0.000 description 8
- 150000003577 thiophenes Chemical class 0.000 description 8
- 230000002950 deficient Effects 0.000 description 7
- FLDCSPABIQBYKP-UHFFFAOYSA-N 5-chloro-1,2-dimethylbenzimidazole Chemical compound ClC1=CC=C2N(C)C(C)=NC2=C1 FLDCSPABIQBYKP-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 239000001741 Ammonium adipate Substances 0.000 description 6
- 235000019293 ammonium adipate Nutrition 0.000 description 6
- 229920000547 conjugated polymer Polymers 0.000 description 6
- 238000004255 ion exchange chromatography Methods 0.000 description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 125000000542 sulfonic acid group Chemical group 0.000 description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 5
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 5
- 229910000358 iron sulfate Inorganic materials 0.000 description 5
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 5
- 229920000123 polythiophene Polymers 0.000 description 5
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 5
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 150000007524 organic acids Chemical class 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- KVGOXGQSTGQXDD-UHFFFAOYSA-N 1-decane-sulfonic-acid Chemical compound CCCCCCCCCCS(O)(=O)=O KVGOXGQSTGQXDD-UHFFFAOYSA-N 0.000 description 3
- LDMOEFOXLIZJOW-UHFFFAOYSA-N 1-dodecanesulfonic acid Chemical compound CCCCCCCCCCCCS(O)(=O)=O LDMOEFOXLIZJOW-UHFFFAOYSA-N 0.000 description 3
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- QDHFHIQKOVNCNC-UHFFFAOYSA-N butane-1-sulfonic acid Chemical compound CCCCS(O)(=O)=O QDHFHIQKOVNCNC-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 229920000128 polypyrrole Polymers 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- COBAWKLKIXVBOA-UHFFFAOYSA-N 1h-pyrrole;thiophene Chemical compound C=1C=CNC=1.C=1C=CSC=1.C=1C=CSC=1 COBAWKLKIXVBOA-UHFFFAOYSA-N 0.000 description 2
- LYTMVABTDYMBQK-UHFFFAOYSA-N 2-benzothiophene Chemical compound C1=CC=CC2=CSC=C21 LYTMVABTDYMBQK-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 235000011054 acetic acid Nutrition 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-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
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229940098779 methanesulfonic acid Drugs 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 125000001624 naphthyl group Chemical class 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- MHYFEEDKONKGEB-UHFFFAOYSA-N oxathiane 2,2-dioxide Chemical compound O=S1(=O)CCCCO1 MHYFEEDKONKGEB-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- KATWGOIXXDLFBD-UHFFFAOYSA-M sodium;6-methoxynaphthalene-2-sulfonate Chemical compound [Na+].C1=C(S([O-])(=O)=O)C=CC2=CC(OC)=CC=C21 KATWGOIXXDLFBD-UHFFFAOYSA-M 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 229910021653 sulphate ion Inorganic materials 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- XNMVAVGXJZFTEH-BUYFANAVSA-N (1r,2s,4r)-4,7,7-trimethyl-3-oxobicyclo[2.2.1]heptane-2-carboxylic acid Chemical compound C1C[C@@]2(C)C(=O)[C@@H](C(O)=O)[C@@H]1C2(C)C XNMVAVGXJZFTEH-BUYFANAVSA-N 0.000 description 1
- AVXBCNFAWJPVFX-UHFFFAOYSA-N (4,7-dimethyl-3-oxo-7-bicyclo[2.2.1]heptanyl)methanesulfonic acid Chemical compound C1CC2(C)C(=O)CC1C2(CS(O)(=O)=O)C AVXBCNFAWJPVFX-UHFFFAOYSA-N 0.000 description 1
- 125000004815 1,2-dimethylethylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([*:2])C([H])([H])[H] 0.000 description 1
- UJWKDKCAAAMUCW-UHFFFAOYSA-N 1,4-dioxan-2-ylmethanesulfonic acid Chemical compound OS(=O)(=O)CC1COCCO1 UJWKDKCAAAMUCW-UHFFFAOYSA-N 0.000 description 1
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 description 1
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- 125000004173 1-benzimidazolyl group Chemical group [H]C1=NC2=C([H])C([H])=C([H])C([H])=C2N1* 0.000 description 1
- YCROCUGZWSEFIZ-UHFFFAOYSA-N 1-benzofuran-3-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=COC2=C1 YCROCUGZWSEFIZ-UHFFFAOYSA-N 0.000 description 1
- VKRRXIIHBJZRQP-UHFFFAOYSA-N 1-benzofuran-3-ylmethanesulfonic acid Chemical compound C1=CC=C2C(CS(=O)(=O)O)=COC2=C1 VKRRXIIHBJZRQP-UHFFFAOYSA-N 0.000 description 1
- 125000004973 1-butenyl group Chemical group C(=CCC)* 0.000 description 1
- ZESVFZAOAIZMEO-UHFFFAOYSA-N 10-(1-benzofuran-3-yl)decane-1-sulfonic acid Chemical compound C1=CC=C2C(CCCCCCCCCCS(=O)(=O)O)=COC2=C1 ZESVFZAOAIZMEO-UHFFFAOYSA-N 0.000 description 1
- UMSJDYWSEAKCBX-UHFFFAOYSA-N 10-(1h-imidazol-2-yl)decane-1-sulfonic acid Chemical compound OS(=O)(=O)CCCCCCCCCCC1=NC=CN1 UMSJDYWSEAKCBX-UHFFFAOYSA-N 0.000 description 1
- ULJUHJSWHYQBJU-UHFFFAOYSA-N 10-(benzimidazol-1-yl)decane-1-sulfonic acid Chemical compound C1=CC=C2N(CCCCCCCCCCS(=O)(=O)O)C=NC2=C1 ULJUHJSWHYQBJU-UHFFFAOYSA-N 0.000 description 1
- IGYFPJPPWGHMFD-UHFFFAOYSA-N 10-(benzotriazol-2-yl)decane-1-sulfonic acid Chemical compound C1=CC=CC2=NN(CCCCCCCCCCS(=O)(=O)O)N=C21 IGYFPJPPWGHMFD-UHFFFAOYSA-N 0.000 description 1
- YQYPSKOKTSHTKR-UHFFFAOYSA-N 10-(furan-2-yl)decane-1-sulfonic acid Chemical compound OS(=O)(=O)CCCCCCCCCCC1=CC=CO1 YQYPSKOKTSHTKR-UHFFFAOYSA-N 0.000 description 1
- KCVJUSRSCOIVEA-UHFFFAOYSA-N 12-(benzimidazol-1-yl)dodecane-1-sulfonic acid Chemical compound C1=CC=C2N(CCCCCCCCCCCCS(=O)(=O)O)C=NC2=C1 KCVJUSRSCOIVEA-UHFFFAOYSA-N 0.000 description 1
- HLTVVLNUTMUNAX-UHFFFAOYSA-N 12-(benzotriazol-2-yl)dodecane-1-sulfonic acid Chemical compound C1=CC=CC2=NN(CCCCCCCCCCCCS(=O)(=O)O)N=C21 HLTVVLNUTMUNAX-UHFFFAOYSA-N 0.000 description 1
- DSDZDLUBTMTHRO-UHFFFAOYSA-N 12-(furan-2-yl)dodecane-1-sulfonic acid Chemical compound OS(=O)(=O)CCCCCCCCCCCCC1=CC=CO1 DSDZDLUBTMTHRO-UHFFFAOYSA-N 0.000 description 1
- SQZQNWMQZWIIBH-UHFFFAOYSA-N 12-morpholin-4-yldodecane-1-sulfonic acid Chemical compound OS(=O)(=O)CCCCCCCCCCCCN1CCOCC1 SQZQNWMQZWIIBH-UHFFFAOYSA-N 0.000 description 1
- GWXQTTKUYBEZBP-UHFFFAOYSA-N 1h-benzimidazol-1-ium-2-sulfonate Chemical compound C1=CC=C2NC(S(=O)(=O)O)=NC2=C1 GWXQTTKUYBEZBP-UHFFFAOYSA-N 0.000 description 1
- LYLDIIUFTYRPPK-UHFFFAOYSA-N 1h-imidazole-2-sulfonic acid Chemical compound OS(=O)(=O)C1=NC=CN1 LYLDIIUFTYRPPK-UHFFFAOYSA-N 0.000 description 1
- ATOMRBXZTFKKKN-UHFFFAOYSA-N 2-(1,4-dioxan-2-yl)-2-methylpropane-1-sulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)C1COCCO1 ATOMRBXZTFKKKN-UHFFFAOYSA-N 0.000 description 1
- VYQVBHQAHSGRAC-UHFFFAOYSA-N 2-(1-benzofuran-3-yl)ethanesulfonic acid Chemical compound C1=CC=C2C(CCS(=O)(=O)O)=COC2=C1 VYQVBHQAHSGRAC-UHFFFAOYSA-N 0.000 description 1
- XTWMMJIFYHQBTQ-UHFFFAOYSA-N 2-(1h-imidazol-2-yl)-2-methylpropane-1-sulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)C1=NC=CN1 XTWMMJIFYHQBTQ-UHFFFAOYSA-N 0.000 description 1
- FYBBTSFTBSCONS-UHFFFAOYSA-N 2-(1h-imidazol-2-yl)ethanesulfonic acid Chemical compound OS(=O)(=O)CCC1=NC=CN1 FYBBTSFTBSCONS-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- KQULCOMMPRXGOY-UHFFFAOYSA-N 2-(benzimidazol-1-yl)-2-methylpropane-1-sulfonic acid Chemical compound C1=CC=C2N(C(C)(CS(O)(=O)=O)C)C=NC2=C1 KQULCOMMPRXGOY-UHFFFAOYSA-N 0.000 description 1
- VUJQDMOOWYTYRE-UHFFFAOYSA-N 2-(benzimidazol-1-yl)ethanesulfonic acid Chemical compound C1=CC=C2N(CCS(=O)(=O)O)C=NC2=C1 VUJQDMOOWYTYRE-UHFFFAOYSA-N 0.000 description 1
- UMONZQPLCRZXDB-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-2-methylpropane-1-sulfonic acid Chemical compound C1=CC=CC2=NN(C(C)(CS(O)(=O)=O)C)N=C21 UMONZQPLCRZXDB-UHFFFAOYSA-N 0.000 description 1
- AJWKCNXGEGUCMZ-UHFFFAOYSA-N 2-(benzotriazol-2-yl)ethanesulfonic acid Chemical compound C1=CC=CC2=NN(CCS(=O)(=O)O)N=C21 AJWKCNXGEGUCMZ-UHFFFAOYSA-N 0.000 description 1
- QYQIJSKJFRARHD-UHFFFAOYSA-N 2-(furan-2-yl)-2-methylpropane-1-sulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)C1=CC=CO1 QYQIJSKJFRARHD-UHFFFAOYSA-N 0.000 description 1
- LUZDYPLAQQGJEA-UHFFFAOYSA-N 2-Methoxynaphthalene Chemical compound C1=CC=CC2=CC(OC)=CC=C21 LUZDYPLAQQGJEA-UHFFFAOYSA-N 0.000 description 1
- BHQSVJXGDBRUCA-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid;methanesulfonic acid Chemical compound CS(O)(=O)=O.CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O BHQSVJXGDBRUCA-UHFFFAOYSA-N 0.000 description 1
- 125000002941 2-furyl group Chemical group O1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- MOPVFLJSAFTAPN-UHFFFAOYSA-N 2-methyl-2-morpholin-4-ylpropane-1-sulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)N1CCOCC1 MOPVFLJSAFTAPN-UHFFFAOYSA-N 0.000 description 1
- TWBSTLBDZZBDEP-UHFFFAOYSA-N 2-methyl-2-piperidin-1-ylpropane-1-sulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)N1CCCCC1 TWBSTLBDZZBDEP-UHFFFAOYSA-N 0.000 description 1
- UEXFDEKTELCPNF-UHFFFAOYSA-N 2-propoxynaphthalene Chemical compound C1=CC=CC2=CC(OCCC)=CC=C21 UEXFDEKTELCPNF-UHFFFAOYSA-N 0.000 description 1
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 description 1
- IKRGFMJRHFKXDS-UHFFFAOYSA-N 3-(1-benzofuran-3-yl)propane-1-sulfonic acid Chemical compound C1=CC=C2C(CCCS(=O)(=O)O)=COC2=C1 IKRGFMJRHFKXDS-UHFFFAOYSA-N 0.000 description 1
- DHVSTSTYEQLHDL-UHFFFAOYSA-N 3-(1h-imidazol-2-yl)propane-1-sulfonic acid Chemical compound OS(=O)(=O)CCCC1=NC=CN1 DHVSTSTYEQLHDL-UHFFFAOYSA-N 0.000 description 1
- DVLFYONBTKHTER-UHFFFAOYSA-N 3-(N-morpholino)propanesulfonic acid Chemical compound OS(=O)(=O)CCCN1CCOCC1 DVLFYONBTKHTER-UHFFFAOYSA-N 0.000 description 1
- GNNBEYIWUCEZOM-UHFFFAOYSA-N 3-(benzimidazol-1-yl)propane-1-sulfonic acid Chemical compound C1=CC=C2[N+](CCCS(=O)(=O)[O-])=CNC2=C1 GNNBEYIWUCEZOM-UHFFFAOYSA-N 0.000 description 1
- FIVKIETYHZKFAG-UHFFFAOYSA-N 3-(benzotriazol-2-yl)propane-1-sulfonic acid Chemical compound C1=CC=CC2=NN(CCCS(=O)(=O)O)N=C21 FIVKIETYHZKFAG-UHFFFAOYSA-N 0.000 description 1
- XWUMUMCJRVGHSK-UHFFFAOYSA-N 3-(furan-2-yl)propane-1-sulfonic acid Chemical compound OS(=O)(=O)CCCC1=CC=CO1 XWUMUMCJRVGHSK-UHFFFAOYSA-N 0.000 description 1
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 1
- CSIFGMFVGDBOQC-UHFFFAOYSA-N 3-iminobutanenitrile Chemical compound CC(=N)CC#N CSIFGMFVGDBOQC-UHFFFAOYSA-N 0.000 description 1
- ALDBKVFJKDDXNP-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1-sulfonic acid Chemical compound OS(=O)(=O)CCCN1CCCCC1 ALDBKVFJKDDXNP-UHFFFAOYSA-N 0.000 description 1
- LKTRVKICUSKZGA-UHFFFAOYSA-N 4,7,7-trimethyl-3-oxobicyclo[2.2.1]heptane-2-sulfonic acid Chemical compound C1CC2(C)C(=O)C(S(O)(=O)=O)C1C2(C)C LKTRVKICUSKZGA-UHFFFAOYSA-N 0.000 description 1
- XMYNCBDKIQFEDB-UHFFFAOYSA-N 4-(1-benzofuran-3-yl)butane-1-sulfonic acid Chemical compound C1=CC=C2C(CCCCS(=O)(=O)O)=COC2=C1 XMYNCBDKIQFEDB-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- SKISEDDHMMVXAQ-UHFFFAOYSA-N 4-(benzimidazol-1-yl)butane-1-sulfonic acid Chemical compound C1=CC=C2N(CCCCS(=O)(=O)O)C=NC2=C1 SKISEDDHMMVXAQ-UHFFFAOYSA-N 0.000 description 1
- ADALQMHBRNGNOU-UHFFFAOYSA-N 4-(benzotriazol-2-yl)butane-1-sulfonic acid Chemical compound C1=CC=CC2=NN(CCCCS(=O)(=O)O)N=C21 ADALQMHBRNGNOU-UHFFFAOYSA-N 0.000 description 1
- BWKZFZWLPOTPFG-UHFFFAOYSA-N 4-(furan-2-yl)butane-1-sulfonic acid Chemical compound OS(=O)(=O)CCCCC1=CC=CO1 BWKZFZWLPOTPFG-UHFFFAOYSA-N 0.000 description 1
- ZZLCFHIKESPLTH-UHFFFAOYSA-N 4-Methylbiphenyl Chemical compound C1=CC(C)=CC=C1C1=CC=CC=C1 ZZLCFHIKESPLTH-UHFFFAOYSA-N 0.000 description 1
- LMRKVKPRHROQRR-UHFFFAOYSA-N 4-butylmorpholine Chemical compound CCCCN1CCOCC1 LMRKVKPRHROQRR-UHFFFAOYSA-N 0.000 description 1
- RNSRXTIJUWXWCA-UHFFFAOYSA-N 5-(1,4-dioxan-2-yl)pentane-1-sulfonic acid Chemical compound OS(=O)(=O)CCCCCC1COCCO1 RNSRXTIJUWXWCA-UHFFFAOYSA-N 0.000 description 1
- YNAWTDHPOINMAE-UHFFFAOYSA-N 5-(1-benzofuran-3-yl)pentane-1-sulfonic acid Chemical compound C1=CC=C2C(CCCCCS(=O)(=O)O)=COC2=C1 YNAWTDHPOINMAE-UHFFFAOYSA-N 0.000 description 1
- GRRBNBMMYWSNTF-UHFFFAOYSA-N 5-(1h-imidazol-2-yl)pentane-1-sulfonic acid Chemical compound OS(=O)(=O)CCCCCC1=NC=CN1 GRRBNBMMYWSNTF-UHFFFAOYSA-N 0.000 description 1
- BIDLCWGYDDZSFY-UHFFFAOYSA-N 5-(furan-2-yl)pentane-1-sulfonic acid Chemical compound OS(=O)(=O)CCCCCC1=CC=CO1 BIDLCWGYDDZSFY-UHFFFAOYSA-N 0.000 description 1
- SDTHIDMOBRXVOQ-UHFFFAOYSA-N 5-[bis(2-chloroethyl)amino]-6-methyl-1h-pyrimidine-2,4-dione Chemical compound CC=1NC(=O)NC(=O)C=1N(CCCl)CCCl SDTHIDMOBRXVOQ-UHFFFAOYSA-N 0.000 description 1
- 125000006043 5-hexenyl group Chemical group 0.000 description 1
- STKQCNWGEAGMAZ-UHFFFAOYSA-N 6-(1,4-dioxan-2-yl)hexane-1-sulfonic acid Chemical compound OS(=O)(=O)CCCCCCC1COCCO1 STKQCNWGEAGMAZ-UHFFFAOYSA-N 0.000 description 1
- FZIHIXSQAGBJSE-UHFFFAOYSA-N 6-(1-benzofuran-3-yl)hexane-1-sulfonic acid Chemical compound C1=CC=C2C(CCCCCCS(=O)(=O)O)=COC2=C1 FZIHIXSQAGBJSE-UHFFFAOYSA-N 0.000 description 1
- YSIYXBSPHPWZHH-UHFFFAOYSA-N 6-(benzimidazol-1-yl)hexane-1-sulfonic acid Chemical compound C1=CC=C2N(CCCCCCS(=O)(=O)O)C=NC2=C1 YSIYXBSPHPWZHH-UHFFFAOYSA-N 0.000 description 1
- XIVUQQNZRHFJJP-UHFFFAOYSA-N 6-(benzotriazol-2-yl)hexane-1-sulfonic acid Chemical compound C1=CC=CC2=NN(CCCCCCS(=O)(=O)O)N=C21 XIVUQQNZRHFJJP-UHFFFAOYSA-N 0.000 description 1
- DGZSRBSXRCBBSC-UHFFFAOYSA-N 6-morpholin-4-ylhexane-1-sulfonic acid Chemical compound OS(=O)(=O)CCCCCCN1CCOCC1 DGZSRBSXRCBBSC-UHFFFAOYSA-N 0.000 description 1
- AFFNOMVTYNVSKZ-UHFFFAOYSA-N 6-piperidin-1-ylhexane-1-sulfonic acid Chemical compound OS(=O)(=O)CCCCCCN1CCCCC1 AFFNOMVTYNVSKZ-UHFFFAOYSA-N 0.000 description 1
- USJDSKCDHFDERO-UHFFFAOYSA-N 6-propoxynaphthalene-2-sulfonic acid Chemical compound C1=C(S(O)(=O)=O)C=CC2=CC(OCCC)=CC=C21 USJDSKCDHFDERO-UHFFFAOYSA-N 0.000 description 1
- YHNXCYRUIMOLJT-UHFFFAOYSA-N 7-(1,4-dioxan-2-yl)heptane-1-sulfonic acid Chemical compound OS(=O)(=O)CCCCCCCC1COCCO1 YHNXCYRUIMOLJT-UHFFFAOYSA-N 0.000 description 1
- GDOXNGCVIZSAFV-UHFFFAOYSA-N 7-(1h-imidazol-2-yl)heptane-1-sulfonic acid Chemical compound OS(=O)(=O)CCCCCCCC1=NC=CN1 GDOXNGCVIZSAFV-UHFFFAOYSA-N 0.000 description 1
- HMAKWHSGBSTDKI-UHFFFAOYSA-N 7-(benzimidazol-1-yl)heptane-1-sulfonic acid Chemical compound C1=CC=C2N(CCCCCCCS(=O)(=O)O)C=NC2=C1 HMAKWHSGBSTDKI-UHFFFAOYSA-N 0.000 description 1
- HGFIYFDKRMVUEW-UHFFFAOYSA-N 7-(benzotriazol-2-yl)heptane-1-sulfonic acid Chemical compound C1=CC=CC2=NN(CCCCCCCS(=O)(=O)O)N=C21 HGFIYFDKRMVUEW-UHFFFAOYSA-N 0.000 description 1
- RFFCPPRVPSEPRD-UHFFFAOYSA-N 7-morpholin-4-ylheptane-1-sulfonic acid Chemical compound OS(=O)(=O)CCCCCCCN1CCOCC1 RFFCPPRVPSEPRD-UHFFFAOYSA-N 0.000 description 1
- PMPJNHKXCXMHQU-UHFFFAOYSA-N 8-(1-benzofuran-3-yl)octane-1-sulfonic acid Chemical compound C1=CC=C2C(CCCCCCCCS(=O)(=O)O)=COC2=C1 PMPJNHKXCXMHQU-UHFFFAOYSA-N 0.000 description 1
- PPYKZFNGCYKEFL-UHFFFAOYSA-N 8-(1h-imidazol-2-yl)octane-1-sulfonic acid Chemical compound OS(=O)(=O)CCCCCCCCC1=NC=CN1 PPYKZFNGCYKEFL-UHFFFAOYSA-N 0.000 description 1
- ULIWZHKQAMZBTJ-UHFFFAOYSA-N 8-(benzimidazol-1-yl)octane-1-sulfonic acid Chemical compound C1=CC=C2N(CCCCCCCCS(=O)(=O)O)C=NC2=C1 ULIWZHKQAMZBTJ-UHFFFAOYSA-N 0.000 description 1
- ZXALEGRMDIYWCF-UHFFFAOYSA-N 8-(benzotriazol-2-yl)octane-1-sulfonic acid Chemical compound C1=CC=CC2=NN(CCCCCCCCS(=O)(=O)O)N=C21 ZXALEGRMDIYWCF-UHFFFAOYSA-N 0.000 description 1
- TUXSAQOCNHWDDW-UHFFFAOYSA-N 8-(furan-2-yl)octane-1-sulfonic acid Chemical compound OS(=O)(=O)CCCCCCCCC1=CC=CO1 TUXSAQOCNHWDDW-UHFFFAOYSA-N 0.000 description 1
- PGYACNBOYDCLCD-UHFFFAOYSA-N 8-morpholin-4-yloctane-1-sulfonic acid Chemical compound OS(=O)(=O)CCCCCCCCN1CCOCC1 PGYACNBOYDCLCD-UHFFFAOYSA-N 0.000 description 1
- BCGSRNAZAFSCAD-UHFFFAOYSA-N 8-piperidin-1-yloctane-1-sulfonic acid Chemical compound OS(=O)(=O)CCCCCCCCN1CCCCC1 BCGSRNAZAFSCAD-UHFFFAOYSA-N 0.000 description 1
- BYBBCJHZXNHGQX-UHFFFAOYSA-N 9-(1h-imidazol-2-yl)nonane-1-sulfonic acid Chemical compound OS(=O)(=O)CCCCCCCCCC1=NC=CN1 BYBBCJHZXNHGQX-UHFFFAOYSA-N 0.000 description 1
- HCGDNHAUNDTGCD-UHFFFAOYSA-N 9-(furan-2-yl)nonane-1-sulfonic acid Chemical compound OS(=O)(=O)CCCCCCCCCC1=CC=CO1 HCGDNHAUNDTGCD-UHFFFAOYSA-N 0.000 description 1
- GBNUQYYPQKDKDD-UHFFFAOYSA-N 9-piperidin-1-ylnonane-1-sulfonic acid Chemical compound OS(=O)(=O)CCCCCCCCCN1CCCCC1 GBNUQYYPQKDKDD-UHFFFAOYSA-N 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- WTDRDQBEARUVNC-LURJTMIESA-N L-DOPA Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C(O)=C1 WTDRDQBEARUVNC-LURJTMIESA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- GZEBOGSPYPQJKM-UHFFFAOYSA-K N1(CCOCC1)CCCS(=O)(=O)[O-].[Fe+3].N1(CCOCC1)CCCS(=O)(=O)[O-].N1(CCOCC1)CCCS(=O)(=O)[O-] Chemical compound N1(CCOCC1)CCCS(=O)(=O)[O-].[Fe+3].N1(CCOCC1)CCCS(=O)(=O)[O-].N1(CCOCC1)CCCS(=O)(=O)[O-] GZEBOGSPYPQJKM-UHFFFAOYSA-K 0.000 description 1
- BXUKUAYGHSRQDF-UHFFFAOYSA-N N1(CCOCC1)S(=O)(=O)O.[Na] Chemical compound N1(CCOCC1)S(=O)(=O)O.[Na] BXUKUAYGHSRQDF-UHFFFAOYSA-N 0.000 description 1
- JZZJBNHYAFUYOA-UHFFFAOYSA-N N1C(=NC=C1)CCCCCCCCCCCCS(=O)(=O)O Chemical compound N1C(=NC=C1)CCCCCCCCCCCCS(=O)(=O)O JZZJBNHYAFUYOA-UHFFFAOYSA-N 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- VBVUSAQKOCTWOK-UHFFFAOYSA-N OS(=O)(=O)CCCCCCCCCCCCN1CCCCC1 Chemical compound OS(=O)(=O)CCCCCCCCCCCCN1CCCCC1 VBVUSAQKOCTWOK-UHFFFAOYSA-N 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- JTMZBRWRXFAITF-UHFFFAOYSA-N azane;(7,7-dimethyl-3-oxo-4-bicyclo[2.2.1]heptanyl)methanesulfonic acid Chemical compound [NH4+].C1CC2(CS([O-])(=O)=O)C(=O)CC1C2(C)C JTMZBRWRXFAITF-UHFFFAOYSA-N 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- QGGSWEDJFFDTIQ-UHFFFAOYSA-N benzo[f][2]benzothiole Chemical compound C1=CC=CC2=CC3=CSC=C3C=C21 QGGSWEDJFFDTIQ-UHFFFAOYSA-N 0.000 description 1
- ATCZEUOZUCQIPX-UHFFFAOYSA-N benzotriazol-2-ylmethanesulfonic acid Chemical compound C1=CC=CC2=NN(CS(=O)(=O)O)N=C21 ATCZEUOZUCQIPX-UHFFFAOYSA-N 0.000 description 1
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000002933 cyclohexyloxy group Chemical group C1(CCCCC1)O* 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000006612 decyloxy group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000009189 diving Effects 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- OKSYMZKKVJYKKJ-UHFFFAOYSA-N furan-2-sulfonic acid Chemical compound OS(=O)(=O)C1=CC=CO1 OKSYMZKKVJYKKJ-UHFFFAOYSA-N 0.000 description 1
- OOKRBYZEGGSVIW-UHFFFAOYSA-N furan-3-sulfonic acid Chemical compound OS(=O)(=O)C=1C=COC=1 OOKRBYZEGGSVIW-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- AKRQHOWXVSDJEF-UHFFFAOYSA-N heptane-1-sulfonic acid Chemical compound CCCCCCCS(O)(=O)=O AKRQHOWXVSDJEF-UHFFFAOYSA-N 0.000 description 1
- FYAQQULBLMNGAH-UHFFFAOYSA-N hexane-1-sulfonic acid Chemical compound CCCCCCS(O)(=O)=O FYAQQULBLMNGAH-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical group [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- TUYCHXRSVYZXBL-UHFFFAOYSA-N morpholin-4-ylmethanesulfonic acid Chemical compound OS(=O)(=O)CN1CCOCC1 TUYCHXRSVYZXBL-UHFFFAOYSA-N 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
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- MCSAJNNLRCFZED-UHFFFAOYSA-N nitroethane Chemical compound CC[N+]([O-])=O MCSAJNNLRCFZED-UHFFFAOYSA-N 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- WLGDAKIJYPIYLR-UHFFFAOYSA-M octane-1-sulfonate Chemical compound CCCCCCCCS([O-])(=O)=O WLGDAKIJYPIYLR-UHFFFAOYSA-M 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005447 octyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- RJQRCOMHVBLQIH-UHFFFAOYSA-M pentane-1-sulfonate Chemical compound CCCCCS([O-])(=O)=O RJQRCOMHVBLQIH-UHFFFAOYSA-M 0.000 description 1
- 125000004115 pentoxy group Chemical group [*]OC([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- XPZWNIXACVBLAK-UHFFFAOYSA-N piperidin-1-ylmethanesulfonic acid Chemical compound OS(=O)(=O)CN1CCCCC1 XPZWNIXACVBLAK-UHFFFAOYSA-N 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000553 poly(phenylenevinylene) Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- XTUSEBKMEQERQV-UHFFFAOYSA-N propan-2-ol;hydrate Chemical compound O.CC(C)O XTUSEBKMEQERQV-UHFFFAOYSA-N 0.000 description 1
- IDOVRTFKNWXHFC-UHFFFAOYSA-M propane-1-sulfonate;tetrabutylazanium Chemical compound CCCS([O-])(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC IDOVRTFKNWXHFC-UHFFFAOYSA-M 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229940100890 silver compound Drugs 0.000 description 1
- 150000003379 silver compounds Chemical class 0.000 description 1
- HDZKJHHVJMAMBQ-UHFFFAOYSA-M sodium;6,7-dimethoxynaphthalene-2-sulfonate Chemical compound [Na+].C1=C(S([O-])(=O)=O)C=C2C=C(OC)C(OC)=CC2=C1 HDZKJHHVJMAMBQ-UHFFFAOYSA-M 0.000 description 1
- KKVTYAVXTDIPAP-UHFFFAOYSA-M sodium;methanesulfonate Chemical compound [Na+].CS([O-])(=O)=O KKVTYAVXTDIPAP-UHFFFAOYSA-M 0.000 description 1
- NPAWNPCNZAPTKA-UHFFFAOYSA-M sodium;propane-1-sulfonate Chemical compound [Na+].CCCS([O-])(=O)=O NPAWNPCNZAPTKA-UHFFFAOYSA-M 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/008—Terminals
- H01G9/012—Terminals specially adapted for solid capacitors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/48—Conductive polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/56—Solid electrolytes, e.g. gels; Additives therein
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/022—Electrolytes; Absorbents
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/022—Electrolytes; Absorbents
- H01G9/025—Solid electrolytes
- H01G9/028—Organic semiconducting electrolytes, e.g. TCNQ
Definitions
- the present invention relates to a solid electrolytic capacitor and a method for manufacturing the same. More specifically, the solid electrolyte is selected from (1) alkoxy-substituted naphthylene monosulfonic acid anion, (2) heterocyclic compound sulfonate anion, and (3) aliphatic polycyclic compound anion.
- the present invention relates to a solid electrolytic capacitor provided with a conductive polymer having a 7T electron conjugate structure containing at least one kind of organic anion as a dopant, and a method for manufacturing the capacitor.
- the present invention relates to a solid electrolytic capacitor provided with a conductive polymer containing, as a dopant, anion having another dopant function in addition to the organic anion dopant in the solid electrolyte, and a method for manufacturing the capacitor.
- a dielectric oxide film layer is formed on an anode substrate of an etched metal foil, and a solid semiconductive layer (hereinafter abbreviated as a solid electrolyte) is formed on the outside of the dielectric film as an opposing electrode.
- the element further comprises a conductive layer such as a conductive paste.
- the entire device It is completely sealed with epoxy resin and used.
- the solid electrolyte for example a conventional, non-machine semiconductor material such as manganese dioxide or lead dioxide, tetra Xia eaves diacetic methane (TCNQ) complex salt or range electric conductivity of 1 0 one 3 ⁇ 5 X 1 0 3 SZ cm, Intrinsic conductive polymers (JP-A-1-169914 (US Pat. No. 4,803,596)), ⁇ -conjugated polyaniline (JP-A-61-239617), polypyrrole (JP-A-6-239617) No. 240625), polythiophene derivatives (Japanese Patent Application Laid-Open No. 2-15611 (US Pat. No.
- Conventional methods for forming a solid electrolyte include a method for forming a solid electrolyte by melting such a solid electrolyte on a dielectric layer on a valve metal surface having a fine void structure, and a method for forming a solid electrolyte on a dielectric layer.
- Methods for producing a conductive polymer and the like are known. Specifically, for example, when a polymer of a five-membered heterocyclic compound such as pyrrole dithiophene is used, the anode foil is immersed in a lower alcohol aqueous solution of the five-membered heterocyclic compound, and then an oxidizing agent and an electrolyte are used.
- aromatic polysulfonic acid having a plurality of sulfonic acid groups in a molecular structure for example, naphthalenedisulfonic acid
- pyropropyl, thiophene, furan, aniline A polymer selected from the derivatives thereof is disclosed.
- a method for producing the polymer a polymerizable monomer is introduced and then a polymerizable monomer is introduced after coating and drying or introducing the oxidizing agent. Is disclosed.
- Japanese Patent Application Laid-Open No. 10-32145 discloses a production method using a dopant of the aromatic polysulfonic acid as a component of an oxidizing agent (a ferric salt), and as a result, a characteristic of a solid electrolytic capacitor provided with the same. Is described as a capacitor which is excellent in high temperature resistance and prevention of deterioration of capacitance.
- Japanese Patent Publication No. Hei 6-82590 discloses a solid electrolytic condenser containing, as a dopant, an alkylnaphthylene sulfonate anion in which one or more alkyl groups are substituted. And that it has excellent leakage current characteristics.
- the solid electrolyte capacitor using manganese dioxide has a drawback that the oxide film layer is destroyed during the thermal decomposition of manganese nitrate, and the impedance characteristics are also insufficient.
- lead dioxide environmental considerations are also required.
- Solid electrolyte capacitors using TCNQ complex salts Although excellent in melt processability and conductivity, it is said that the reliability of solder heat resistance is poor due to the problem of heat resistance of the TCNQ complex salt itself.
- conductive polymers such as polypyrrole are applied to the solid electrolyte on the dielectric surface by electrolytic polymerization or chemical polymerization, but the uniformity of the film, hang, heat resistance and impedance characteristics Etc. are not enough.
- an object of the present invention is to provide a solid electrolytic capacitor excellent in light weight, minimum capacity, high frequency characteristics, tan ⁇ 5, leakage current, heat resistance (reflow property), durability and the like. It is in.
- an object of the present invention is to provide a heat-resistant solid electrolytic capacitor having excellent low impedance characteristics and durable in a spark voltage test.
- the present inventors have conducted intensive studies on the type, combination, content, and the like of the dopant anion in the conductive polymer of the solid electrolyte in order to solve the above problems.
- an opposing electrode and one electrode are provided with a microstructured dielectric layer composed of a metal oxide on the surface of the valve metal foil, and a solid electrolyte composed of a conductive polymer formed on the dielectric layer.
- the above problem was solved by including a specific organic anion as a dopant in the solid electrolyte.
- the present invention provides, as an organic anion, (1) at least one or more linear or branched saturated or unsaturated alkoxy groups having 1 to 12 carbon atoms.
- a solid electrolytic capacitor in which a conductive polymer composition layer having a ⁇ -electron conjugate structure is provided on a dielectric oxide film, (1) a linear chain having 1 to 12 carbon atoms is added to the polymer composition layer. Alkoxy-substituted naphthalene monosulfonic acid anion substituted with at least one or more saturated or unsaturated alkoxy groups in a branched or branched state; (2) Anionic sulfonate of a heterocyclic compound having a 5- or 6-membered heterocyclic ring (compound (3) A solid electrolytic capacitor comprising, as a dopant, at least one kind of organic anion selected from aliphatic polycyclic compound anions.
- the organic anion as a dopant is an alkoxy-substituted naphthylene monosulfonic acid anion in which at least one linear or branched saturated or unsaturated alkoxy group having 1 to 12 carbon atoms is substituted.
- the heterocyclic skeleton of the heterocyclic sulfonic acid anion is morpholine, piberidine, piperazine, imidazole, furan, 1,4-dioxane, benzimidazole, benzothiazolylthio, benzisoxazole, Item 5.
- the solid electrolytic capacitor according to item 4 wherein the capacitor is selected from the group consisting of compounds having a chemical structure of benzotriazole and benzofuran.
- the substituents R 1 and R 2 each independently represent hydrogen or a linear or branched saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms, or 1 A linear or branched saturated or unsaturated alkoxy group, a hydroxyl group, a halogen atom, a nitro group, a cyano group, a trihalomethyl group, a phenyl group, and a substituted phenyl group.
- the substituents R 1 and R 2 may be bonded to each other at any position to form at least one or more divalent chains forming a 5- to 7-membered saturated or unsaturated cyclic structure. It may be formed.
- X is S, 0, S e, T e , or NR 3 represents a heteroatom.
- R 3 is H, a linear or branched saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms, a phenyl group, or a linear or branched saturated or unsaturated, having 1 to 6 carbon atoms.
- the chain of the alkyl group or the alkoxy group of R 1 , R 2 and R 3 may optionally contain a carbonyl bond, an ether bond, an ester bond, an amide bond, and an imino bond.
- ⁇ 5 ranges from 0 to 1.
- the substituents R 4 and R 5 are each independently hydrogen or a linear or branched saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms, or a hydrocarbon group having 1 to 6 carbon atoms. Are bonded to each other at any position to form a substituent that forms at least one or more 5- to 7-membered heterocyclic ring structure containing two oxygen atoms described in the formula.
- the range includes the chemical structure of a substituted vinylene group or a substituted o-phenylene group, etc.
- ⁇ is in the range of 0 to 1.
- a method for producing a solid electrolytic capacitor having a conductive polymer composition layer provided on a dielectric oxide film comprising polymerizing a polymerizable monomer compound with an oxidizing agent on the dielectric oxide film,
- the polymerizable monomer compound has the following general formula (III)
- the polymerization reaction is (1) an alkoxy-substituted naphthylene monosulfonic acid anion substituted with at least one linear or branched saturated or unsaturated alkoxy group having 1 to 12 carbon atoms. (2) at least one selected from the group consisting of a sulfonate anion of a heterocyclic compound having a 5- or 6-membered heterocyclic ring (referred to as a heterocyclic sulfonate anion) and (3) anion of an aliphatic polycyclic compound.
- a sulfonate anion of a heterocyclic compound having a 5- or 6-membered heterocyclic ring referred to as a heterocyclic sulfonate anion
- anion of an aliphatic polycyclic compound 2.
- the preceding item 13 or 14 comprising a step of immersing the valve-acting metal anode foil on which the dielectric oxide film layer is formed in a solution containing an oxidizing agent and a step of immersing it in a solution containing a polymerizable monomer compound and the organic anion.
- the preceding item 13 or 14 including a step of immersing the valve-acting metal anode foil having the dielectric oxide film layer formed thereon in a solution containing an oxidizing agent and then immersing it in a solution containing a polymerizable monomer compound and the organic anion.
- the preceding item 13 or 14 including a step of immersing the valve-acting metal anode foil having the dielectric oxide film layer formed thereon in a solution containing a polymerizable monomer compound and then immersing it in a solution containing an oxidizing agent and the organic anion. Manufacturing method of solid electrolytic capacitors.
- the preceding item 13 or 14 including a step of immersing the valve-acting metal anode foil on which the dielectric oxide film layer is formed in a solution containing an oxidizing agent and the organic anion, and then immersing it in a solution containing a polymerizable monomer compound. Manufacturing method of solid electrolytic capacitors.
- the preceding item 13 or 14 including a step of immersing the valve-acting metal anode foil on which the dielectric oxide film layer is formed in a solution containing a polymerizable monomer compound and the organic anion, and then immersing it in a solution containing an oxidizing agent.
- Manufacturing method of solid electrolytic capacitors including a step of immersing the valve-acting metal anode foil on which the dielectric oxide film layer is formed in a solution containing a polymerizable monomer compound and the organic anion, and then immersing it in a solution containing an oxidizing agent.
- a valve-acting metal anode foil having a dielectric oxide film layer formed thereon is immersed in a solution containing an oxidizing agent and the organic anion, and then immersed in a solution containing a polymerizable monomer compound. 13.
- a step of immersing the valve-acting metal anode foil on which the dielectric oxide film layer was formed in a solution containing an oxidizing agent and the organic anion and then immersing it in a solution containing a polymerizable monomer compound was repeated several times. 13.
- a step of immersing the valve-acting metal anode foil on which the dielectric oxide film layer was formed in a solution containing a polymerizable monomer compound and the organic anion and then immersing it in a solution containing an oxidizing agent was repeated several times. 13.
- valve-acting metal anode foil having the dielectric oxide film layer formed thereon is immersed in a solution containing an oxidizing agent, and then immersed in a solution containing a polymerizable monomer compound and the organic anion.
- the heterocyclic skeleton of the heterocyclic sulfonic acid anion is morpholine, piperidine, piperazine, imidazole, furan, 1,4-dioxane, benzimidazole, benzothiazolylthio, benzisoxazole 31.
- each layer of the solid electrolyte having the layered structure is in the range of 0.01 to 5 / zm, and the total thickness of the solid electrolyte layer is in the range of 1 to 200 / m.
- Solid electrolytic capacitors BRIEF DESCRIPTION OF THE FIGURES
- FIG. 1 is a vertical sectional view of a typical capacitor according to the present invention using a valve metal foil.
- FIG. 2 is a scanning electron micrograph (magnification: 5,000) of a cross section of an aluminum foil having a fine structure with a conductive polymer layer formed thereon in Example 32. Detailed description of the invention
- the conductive polymer layer contains (1) a C 1 to C 12 linear or Is an alkoxy-substituted naphthalene monosulfonic acid anion substituted with at least one or more branched saturated or unsaturated alkoxy groups, (2) a sulfonate anion of a heterocyclic compound having a 5- or 6-membered heterocyclic ring (heterocyclic (3) At least one kind of organic anion selected from aliphatic polycyclic compound anions is contained as a major anion having a dopant function, so that a heat-resistant and preferable conductive material can be obtained.
- a conductive polymer layer charge transfer complex
- a high-performance solid electrolytic capacitor having excellent durability in low impedance characteristics, spark voltage tests, and the like, and a method for producing the same can be provided. .
- the performance can be improved in the performance by including other anions as dopants in addition to the organic anion dopant.
- the T-electron conjugated polymer in the conductive polymer layer suitable for the capacitor of the present invention is a polymer having a ⁇ -electron conjugated structure in the polymer main chain structure, and specific examples thereof include polyaniline, polyparaphenylene, Examples include polyparaphenylenevinylene, polyphenylenevinylene, polyheterocyclic polymers and substituted derivatives thereof.
- Specific examples of the preferably used polyheterocyclic polymer include a ⁇ -electron conjugated polymer containing a structural unit represented by the general formula (I), and more preferably a structural unit represented by the general formula (II) Is a ⁇ -electron conjugated polymer.
- useful linear or branched saturated or unsaturated hydrocarbon groups having 1 to 6 carbon atoms represented by the substituents R 1 , R 2 and R 3 are useful. Examples include methyl, ethyl, vinyl, propyl, aryl, isopropyl, butyl, and 1-butenyl. Also, useful examples of linear or branched saturated or unsaturated alkoxy groups having 1 to 6 carbon atoms include Examples include methoxy, ethoxy, propoxy, isopropoxy, butoxy.
- substituents other than the hydrocarbon group and the alkoxy group include nitro group, cyano group, phenyl and substituted phenyl (halogen group-substituted phenyl such as CBr and F).
- the alkyl or alkoxy groups of R 1 and R may optionally contain a carbonyl bond, an ether bond, an ester bond, an amide bond, or an imino bond.
- Particularly useful examples of the substituent containing such a bond in the chain include methoxyethoxy and methoxyethoxyethoxy.
- substituents R 1 and R 2 are bonded to each other at an arbitrary position to form at least one or more divalent chains forming a saturated or unsaturated cyclic structure of one or more 5- to 7-membered rings. It may be formed.
- specific examples of the structure represented by the general formula (I) or (III) include a 3,4-monopropylene-substituted structure (V), a 3,4-butylene-substituted structure (VI), and a 3,4-butenylene Substituted structure (VII), 3,4-butene genylene substituted structure (VIII), and naphtho [2,3-c] condensed structure (IX).
- X represents a heteroatom
- examples, S, 0, S e, include T e or NR 3.
- the 3,4-butene genylene substituted structure in which X is S is also called an isothianaphthenylene structure in the repeating structural unit structure of the general formula (I), and a polymerizable monomer compound structure in the general formula (III). It is called isothianaphthene.
- the naphtho [2,3-c] condensed and substituted structure is a naphtho [2,3-c] chenylene structural unit in the case of the general formula (I), and is a polymerizable monomer represented by the general formula (II).
- ⁇ 5 represents the number of charges per repeating structural unit, and is a value in the range of 0 to 1.
- useful substituents for R 4 and R 5 in general formula (II) or general formula (IV) include methyl, ethyl, propyl, isopropyl, vinyl, and aryl.
- the hydrocarbon group having 1 to 6 carbon atoms of R 4 and R 5 is bonded to each other at an arbitrary position to contain two oxygen elements described in the general formula (II) or the general formula (IV).
- R 4 and R 5 are each a cyclic structure of an unsaturated hydrocarbon such as a substituted vinylene group or a substituted o-phenylene group, wherein the C 1 to C 6 hydrocarbon groups are bonded to each other at an arbitrary position.
- the conductive polymer of the capacitor disclosed in the above-mentioned Japanese Patent Application Laid-Open No. 10-32145 is an aromatic polysulfonic acid compound having a plurality of sulfonic acid groups in the molecular structure as a dopant (for example, naphthene disulfonic acid).
- a dopant for example, naphthene disulfonic acid.
- Anion is only disclosed a polymer selected from pyrrole, thiophene, furan, aniline and derivatives thereof doped therein, and the above-described (1) to (3) used in the capacitor of the present application is disclosed. No organic anion is disclosed.
- the excellent effects of the inclusion of a dopant other than the organic anion described in (1) to (3) above were not known.
- the dopa constituting the solid electrolyte of the solid electrolytic capacitor of the present invention is contained in a range of 0.1 to 50 mol% with respect to all repeating units of the ⁇ -conjugated polymer, and more preferably, A capacitor provided with a solid electrolyte containing a dopant other than an organic anion in a range of 0.1 to 10 mol%, and in addition to the above-mentioned problems, particularly heat resistance and durability by low impedance characteristics and spark voltage test. No high-performance, high-performance solid electrolytic capacitors have been known so far.
- the capacitor of the present invention is preferably provided with a solid electrolyte capable of providing a capacitor having particularly excellent low impedance characteristics and excellent withstand voltage characteristics. Is in the range of 1 to 30 mol%.
- the dopant content other than the organic anion is preferably included in the range of 0.1 to 5 mol% with respect to all the repeating units of the ⁇ -conjugated polymer.
- the other dopant is contained as a reductant anion of the oxidizing agent in order to use the oxidizing agent during the polymerization of the polymerizable monomer compound in the production method of the present invention, but may be added separately by another method, There are no restrictions on the inclusion method.
- the solid electrolyte is manufactured (formed).
- the method is important.
- the combination of a ⁇ -electron conjugate structure and a dopant that constitute the solid electrolyte and a conductive polymer layer are densely formed on a fine dielectric layer to improve or improve the uniformity of the conductive path. It is important that the configuration of the conductive polymer greatly affects the capacitor characteristics.
- One of the solid electrolytic capacitors of the present invention has a thermal stress relaxation property and the like.
- at least a part of the solid electrolyte layer has a layered structure.
- the solid electrolyte layer is formed in the micropore portion on the dielectric layer on the valve metal surface and on the outer surface thereof.
- the thickness of this outer surface layer is in the range 1 to 200, preferably in the range 1 to 100 zm.
- the above-mentioned layered structure is formed in a large amount on the outer surface, but it is preferable that the layered structure is also formed in the fine pore portion.
- the arrangement direction of the layers is mostly formed substantially parallel to the valve metal surface.
- a space is formed at least in part between adjacent layers.
- the thickness of each layer in the layered structure is in the range of 0.01 to 5 // m, preferably in the range of 0.01 to 1 m, and more preferably in the range of 0.1 to 0.3 // m. Range.
- the method for producing a solid electrolyte according to the present invention is characterized by a production method in which the organic anion or another anion is also contained as a dopant of the polymer of the polymerizable monomer compound.
- a process for producing a polymer as the solid electrolyte on a dielectric surface Then, by repeating the above-mentioned manufacturing process for one anode substrate at least once, preferably 3 to 30 times, a dense solid electrolyte layer can be easily formed.
- the method may include a step of immersing the anode foil in a solution containing an oxidizing agent and the organic anion (solution 3) and a step of immersing it in a solution containing a polymerizable monomer compound (solution 4).
- a manufacturing method including a step of dipping the anode foil in the solution 4 and then dipping in the solution 3 or a step of dipping in the solution 3 and then dipping in the solution 4 may be adopted.
- Each of the solutions 1 to 4 may be used in a suspended state.
- Solvents 1-4 can be the same or different solvent systems as needed, depending on the type of solvent, between solution 1 and solution 2 or between solution 3 and solution 4.
- a drying step may be separately provided.
- a step of washing the device with an organic solvent or water may be added.
- the washing organic solvent it is preferable to use the solvent used in Solutions 1 to 4 simply and preferably, but it is preferable to simply use a polymerizable monomer compound or the organic anion or a compound holding an anion having another dopant function. Any solvent that dissolves may be used.
- the content of the dopant other than the organic anion in the polymer can be reduced.
- at least the content of the organic anion is not included. It may also contribute to the characteristics.
- the repetitive treatment of the oxidative polymerization operation facilitates the production of a solid electrolyte having excellent solder heat resistance (thermal stability).
- a capacitor using a known solid electrolyte made of polypyrrole or the like has a large fluctuation in the capacitor characteristics at high temperature and high humidity, and has deteriorated the reliability.
- the solid electrolyte of the conductive composition according to the present invention has Capacitors with excellent thermal stability and good stability in the doped state.
- the polymer containing the organic anion or doping derived from the oxidizing agent as the dopan has a dielectric surface and pores. Filling the inside well and analyzing in steps This makes it possible to provide a capacitor excellent in thermal stability, in which the polymer does not damage the dielectric film.
- the organic Anion used in the present invention conventionally known dopants (eg if, C 1 0 4 -, BF 4 -, CI-, S_ ⁇ 4 2 -, benzenesulfonic acid Anion, alkyl-substituted naphthyl evening sulfone Compared to acid anion, etc.), it is a dopant compound that shows excellent thermal stability and conductive state stability in the formation of a charge transfer complex with a ⁇ -conjugated polymer, resulting in low impedance characteristics and spark voltage tests. It is understood that high performance capacitor characteristics with excellent heat resistance and durability can be obtained.
- dopants eg if, C 1 0 4 -, BF 4 -, CI-, S_ ⁇ 4 2 -, benzenesulfonic acid Anion, alkyl-substituted naphthyl evening sulfone Compared to acid anion, etc.
- the organic anions (1) when an alkoxy-substituted naphthylene monosulfonic acid anion is used, the high aromaticity and the aromatic ring-substituted sulfonic acid group of the naphthylene skeleton have From the contribution of the electron-withdrawing property and the water-solubility, and the electron-donating property of the alkoxy group to the naphthalene ring, a capacitor characteristic having the above performance is provided.
- the alkoxy-substituted naphthalene monosulfonic acid used in the present invention is a general term for an alkoxy-substituted naphthalene monosulfonic acid compound in which one sulfonic acid group is substituted on a naphthylene skeleton and another substituted naphthalene monosulfonic acid compound. .
- hydrogen of the naphthylene ring of naphthylene monosulfonic acid is a linear or branched saturated or unsaturated alkoxy group having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms. At least one substituted compound.
- Specific examples of the compound that provides the alkoxy-substituted naphthalene monosulfonic acid anion include naphthylene-11-sulfonic acid and naphthalene-12-sulfonic acid.
- a compound skeleton of an alkali metal salt, an ammonium salt, an organic quaternary ammonium salt, or the like having a chemical structure in which one or more hydrogens of a naphthylene ring are replaced with an alkoxy group.
- it is a substituted compound of a linear or branched saturated or unsaturated alkoxy group having 1 to 12 carbon atoms
- useful substituents include methoxy, ethoxy, bieroxy, propyloxy, aryloxy
- Examples include isopropyloxy, butyloxy, 1-butenyloxy, pentyloxy, hexyloxy, octyloxy, nonyloxy, decyloxy, and the like, and may also contain an alkoxy group substituted with a cyclic hydrocarbon group such as cyclohexyloxy or phenoxy.
- alkoxy-substituted naphthalene monosulfonic acid compounds include, for example, mono-sulfonic acid compounds substituted with 2- to 8-positions of 1-alkoxynaphthalene ring and 1- and 3- to 8-position-substituted 2-alkoxynaphthylene rings.
- Monosulfonic acid compound anion is effectively used.
- a hydrogen atom may be substituted on the alkoxynaphthylene ring by a halogen atom such as F, Cl, Br, and I, CF 3 , a nitro group, a cyano group, and the like.
- heterocyclic sulfonic acid anion includes at least one sulfonic acid group directly or via an alkylene group on the heterocyclic ring.
- a general term for anion of a heterocyclic sulfonic acid compound having a chemical structure in which the compound is indirectly substituted and a preferable skeleton of the heterocyclic compound is morpholine, piperidine, piperazin, imidazole, furan, 1, 2, or 3. 4-dioxane, benzimidazole, benzothiazolylthio, benzisoxazole, benzotriazole, and benzofuran-substituted skeleton.
- a heterocyclic compound anion in which the sulfonic acid anion is indirectly substituted is provided.
- Preferred examples of the morpholine-based compound include 1-morpholinomethanesulfonic acid, 2-morpholinoenesulfonic acid, 3-morpholinoppanpansulfonic acid, 2-methyl-2-morpholinopropanesulfonic acid, and 4-morpholinobutane.
- Sulfonic acid 5-morpholinopenesulfonic acid, 6-morpholinohexanesulfonic acid, 7-morpholinoheptanesulfonic acid, 8-morpholinooctanesulfonic acid, 9-morpholinonanesulfonic acid, 10-morpholinic acid Nodecanesulfonic acid, 12-morpholinododecanesulfonic acid and the like.
- 1-piperidinomethanesulfonic acid 2-piperidinoenesulfonic acid, 3-piperidinopropanesulfonic acid, 2-methyl-2-piperidinopropanesulfonic acid, 4- Piberdinobonesulfonic acid, 5-piperidinopenonesulfonic acid, 6-piperidinohexanesulfonic acid, 7-piperidinoheptonesulfonic acid, 8-piperidinooctanesulfonic acid, 9-piperidinononanesulfonic acid, 10-piperidi Nodecanesulfonic acid, 12-piperidinododecanesulfonic acid and the like.
- piperazine-1,4-bis (1-sulfomethyl), piperazine-1,4-bis (2-sulfoethyl), piperazine-1,4-bis ( 3-sulfopropyl), piperazine-1,4-bis (4-sulfobutyl), piperazine-1,4-bis (5-sulfopentyl), piperazine-1,4-bis (6-sulfopropyl) Hexyl), piperazine-1,4-bis (7-sulfoheptyl), piperazine-1,4-bis (8-sulfoctyl), piperazine-1,4-bis (9-sulfononyl) , Piperazine-11,4-bis (10-sulfodecyl) acid, and piperazine-1,4-bis (12-sulfododecyl) acid.
- 1,4-dioxane-based skeletal compounds 1- (1,4-dioxane-2-yl) methanesulfonic acid, 2- (1,4-dioxane-2-yl) enesulfonic acid, 3 — (1,4-Dioxane—2— ⁇ ⁇ ) Propanesulfonic acid, 2-methyl—2- (1,4-dioxane-2-yl) Propanesulfonic acid, 4- (1,4,1-dioxane—2 —Yl) Butanesulfonic acid, 5- (1,4-dioxane-2-yl) pentanesulfonic acid, 6— (1,4-dioxane-2-yl) hexanesulfonic acid, 7— (1 , 4-dioxane-2-yl) heptanesulfonic acid, 8- (1,4-dioxane-2-yl) octanesulfo Acid
- Benzothiazolylthio skeleton compounds include 1- (2-benzothiazolylthioyl) methanesulfonic acid, 2- (2-benzothiazolylthioyl) ethanesulfonic acid, and 3- (2-benzothiazolylthiol).
- 2-benzothiazolylthioyl methanesulfonic acid
- 2-benzothiazolylthioyl ethanesulfonic acid
- 3- (2-benzothiazolylthiol 2-benzothiazolylthiol
- Benzotriazole skeletal compounds include 1- (2-benzotriazolyl) methanesulfonic acid, 2- (2-benzotriazolyl) ethanesulfonic acid, 3- (2-benzotriazolyl) propanesulfonic acid, 2-methyl — 2 -— (2-benzotriazolyl) propanesulfonic acid, 4- (2-benzotriazolyl) butanesulfonic acid, 5- (2-benzotriazolyl) pentasulfonic acid, 6— (2-benzotriazolyl) Hexanesulfonic acid, 7- (2-benzotriazolyl) heptanesulfonic acid, 8- (2-benzotriazolyl) octanesulfonic acid, 9_ (2_benzotriazolyl) nonanesulfonic acid, 10- (2 —Benzotriazolyl) decanesulfonic acid, and 12— (2-benzotriazolyl) dodecanesulfonic acid.
- Benzofuran-based skeletal compounds include 1- (3-benzofuranyl) methanesulfonic acid, 2- (3-benzofuranyl) ethanesulfonic acid, 3- (3-benzofuranyl) propanesulfonic acid, 2-methyl-2- (3-benzofuranyl) two Le) Propanesulfonic acid, 4- (3-benzofuranyl) butanesulfonic acid, 5- (3-benzofuranyl) pentanesulfonic acid, 6- (3-benzofuranyl) hexanesulfonic acid, 7— (3-benzofuranyl) heptane Even sulfonic acid, 8- (3-benzofuranyl) octanesulfonic acid, 91- (3-benzofuranyl) nonanesulfonic acid, 10- (3-benzofuranyl) decanesulfonic acid, 12- (3-benzofuranyl) dodecanesulfone Acids and the like.
- a quaternary nitrogen compound salt such as an alkali metal salt such as a sodium salt or a potassium salt of these sulfonic acid compounds, or a gammonium salt can also be preferably used.
- heterocyclic compound in which the sulfonic acid group is directly substituted with a heterocyclic skeleton include 2 imidazole sulfonic acid, furan-2-sulfonic acid, furan-3-sulfonic acid, _ Benzimidazolesulfonic acid, benzofuran-3-sulfonic acid, alkaline metal salts such as sodium salt of these compounds, ammonium salts and quaternary ammonium salts.
- the hydrogen of the heterocyclic skeleton is a straight-chain or branched saturated or unsaturated hydrocarbon group or alkoxy group having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms. Derivatives with one or more substitutions are also preferred. Specific examples of the substituent include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group and a dodecyl group.
- Anion of aliphatic polycyclic compound is a compound having a bicyclic or more polycyclic aliphatic anion having a Bronsted acid group such as sulfonic acid, carboxylic acid, phosphoric acid, and boric acid, and is preferable.
- Useful examples include d-camphorsulfonic acid (XVI I) (also known as 10-camphorsulfonic acid), 2-camphorsulfonic acid (XVI II), 3-camphorsulfonic acid, and 8-camphorsulfonic acid. , D-camphorcarboxylic acid and their derivatives, which are used in the form of ammonium salts or alkali metal salts.
- the oxidizing agent used in the present invention may be any oxidizing agent suitable for the oxidative polymerization of pyrrole-dithiophenes, such as iron chloride (111), Fe (C) described in JP-A-2-15611. 1 0 4) 3 or an organic iron (111), inorganic iron (iota [pi), alkyl persulfates, persulfate Anmoniumu, hydrogen peroxide, K 2 C r 2 0 7 and the like can widely be used.
- Examples of the organic acid of the organic acid iron (III) include an alkylsulfonic acid having 1 to 20 carbon atoms such as methanesulfonic acid-dodecylbenzenesulfonic acid and an aliphatic carboxylic acid.
- the range of use of the oxidizing agent The box may be restricted by the chemical structure of the polymerizable monomer compound represented by the general formula (I11), the oxidizing agent, the reaction conditions, and the like.
- the oxidation (polymerization) of thiophenes is described in the Handbook of Conducting Polymers magazine (Marcel Dekker, Inc., 1987, p. 99, FIG. 5).
- a measure of the likelihood of polymerization can vary greatly and influence the polymerization reaction (the oxidation potential is widely spread from about 1.8 to about 2.7V). Therefore, specifically, the combination of the polymerizable monomer compound used, the oxidizing agent, and the reaction conditions is important.
- the organic Examples Anion such other de one dopant the changing Motokarada Anion after the reaction of the oxidizing agent, specifically chloride ion, C 10 4 primary, Anion aliphatic organic carboxylic acid having 1 to 12 carbon atoms, sulfate Ion, phosphoric acid anion, aliphatic organic phosphoric acid anion having 1 to 12 carbon atoms, and boric acid anion.
- N N +, N0 2 salt for example, N ⁇ BF 4 , NOPF 6 , NOSbF 6 , NOAs F 6 , N OCH 3 S ⁇ 3 , N0 2 BF 4 , N ⁇ 2 PF 6 , N ⁇ 2 CF 3 an electron acceptor dopant of S_ ⁇ 3 may be used.
- the chemical polymerization of thiophenes represented by the general formula (IV) is particularly preferably performed using persulfate.
- the reaction temperature is determined by the reaction method and is not particularly limited, but is generally in the range of ⁇ 70 to 250 ° C., preferably 0 ° C. to 15 ° C. It is preferably 0 ° C., and more preferably in a temperature range of 15 to 100 ° C.
- Examples of the solution used in the production method of the present invention or a solvent for washing after polymerization include ethers such as tetrahydrofuran (THF), dioxane, and dimethyl ether; ketones such as acetone and methylethyl ketone; and dimethylformamide.
- ethers such as tetrahydrofuran (THF), dioxane, and dimethyl ether
- ketones such as acetone and methylethyl ketone
- dimethylformamide dimethylformamide
- Aprotic polar solvents such as diacetonitrile, benzonitrile, N-methylpyrrolidone (NMP) and dimethylsulfoxide (DMSO); esters such as ethyl acetate and butyl acetate; non-aromatics such as chloroform and methylene chloride Chlorinated solvents, nitro compounds such as nitromethane, nitroethane, and nitrobenzene; alcohols such as methanol, ethanol, and propanol; organic acids such as formic acid, acetic acid, and propionic acid; and acid anhydrides of the organic acids (eg, anhydrous Acetic acid, etc.), water, or It can be used a mixed solvent of these.
- water, alcohols, ketones and a mixture thereof are used.
- FIG. 1 an outline of the configuration of the solid electrolytic capacitor of the present invention is shown.
- One electrode (anode) 1 having pores 2 connected to the connection terminals 7 on the entire surface is made of aluminum, titanium, tantalum, niobium or a substrate of these Known materials such as metal foils and rods having valve action, such as alloys, and sintered bodies containing these as main components are used.
- the surface of these metal electrodes is subjected to an etching treatment or a chemical conversion treatment by a known method for the purpose of forming a dielectric layer and increasing the specific surface area, and a metal oxide film layer 3 formed on a metal foil is used.
- the solid electrolyte (conductive polymer composition) 4 is preferably formed by a method in which a monomer compound is polymerized on a dielectric layer. A method of chemically depositing on a dielectric layer having a hole or void structure is preferable.
- the solid electrolytic capacitor manufactured by the manufacturing method of the present invention further includes a resin mold on the conductive layer, or a resin case, a metal outer case, and an outer case 6 formed by resin diving.
- An aluminum conversion foil processed to a specified area was subjected to 13 V conversion with a 10% by weight aqueous solution of ammonium adipate to prepare a dielectric.
- An aqueous solution (solution 3) prepared so that ammonium persulfate (hereinafter abbreviated as APS) was 20% by weight and sodium 2-propoxynaphthylene-6-sodium sulfonate was 0.3% by weight was impregnated. It was immersed in a 1.2mo 1/1 isopropanol (hereinafter abbreviated as IPA) solution (solution 4) in which 5 g of 4,4-dioxyethylene-thiophene was dissolved.
- IPA isopropanol
- the substrate was taken out and left under an environment of 60 ° C. for 10 minutes to complete oxidative polymerization, and washed with water. This polymerization reaction treatment and the washing step were repeated 10 times each.
- the content of sulfonic acid sulfate and 2-propyloxynaphthalene-16-sulfonate ion in the polymer was determined by first carefully reducing the polymer by hydrazine reduction in water ZIPA solvent, and performing ion chromatography. As a result, the content of sulfate ion was 1.6 mol% based on all repeating structural units of the polymer, and the content of 2-propyloxynaphthalene-16-sulfonate ion was 13.6 mol%.
- the conductivity of the solid electrolyte layer was 75 S / cm.
- the aluminum foil on which the polythiophene polymer was accumulated was treated in a 10% by weight aqueous solution of ammonium adipate, and the spark voltage was examined.
- current collection from the anode is performed by welding the aluminum core to the positive lead terminal, and current collection from the cathode is connected to the negative lead terminal via carbon paste and silver paste. Was encapsulated with an epoxy resin to produce a capacitor element.
- the dielectric surface prepared by the method described in Example 1 was impregnated with an aqueous solution (solution 1) in which APS was adjusted to 20% by weight, and then 5 g of 3,4-dioxyethylene-thiophene was dissolved in 1.2mo1Z1.
- aqueous solution solution 1 in which APS was adjusted to 20% by weight
- 5 g of 3,4-dioxyethylene-thiophene was dissolved in 1.2mo1Z1.
- 2-propyloxynaphthalene-16-sulfonic acid tetrabutylammonium salt was added to the IPA solution of Example 1, and the resultant was immersed in an IPAZ water mixed solution (solution 2) prepared to have a concentration of 0.1% by weight.
- Example 3 The dielectric prepared by the method described in Example 1 was immersed in an IPA solution (solution 4) of 1.2mo1Z1 in which 5 g of 3,4-dioxyethylene-thiophene was dissolved.
- the content of sulfate ion was 1.8 mol% and that of 2-methoxynaphthalene-6-
- the sulfonic acid ion content was 0.8 mol%.
- the conductivity of the solid electrolyte layer was 60 SZcm.
- a dielectric prepared by the method described in Example 1 was prepared.
- the dielectric surface was impregnated with an aqueous solution (solution 3) prepared so that 10% by weight of potassium persulfate and 1% by weight of sodium 2-methoxynaphthalene-6-sulfonate were obtained. It was immersed in a 1.2 mol / l IPA solution (solution 4) in which 5 g of dioxyethylene monothiophene was dissolved.
- the substrate was taken out and left for 10 minutes in a 6 O: environment to complete oxidative polymerization. After repeating this immersion step 10 times, each was washed with water and dried. When the capacitor element was evaluated, the results shown in Tables 1 and 2 were obtained.
- Example 5 the content of sulfate ion and 2-methoxynaphthalene-1-sulfonate ion in the polymer was determined by the method described in Example 1.
- the content of sulfate ion was 5.9 mol%, and that of 2-methoxynaphthalene.
- the 1-sulfonate ion content was 15.5 mol%.
- the conductivity of the solid electrolyte layer was 73 S / cm.
- a dielectric prepared by the method described in Example 1 was prepared.
- the dielectric surface was impregnated with an aqueous solution (solution 1) adjusted to an APS concentration of 35% by weight, and then 5 g of 3,4-dioxyethylene-thiophene was dissolved in a 1.2 mO 1 Z1 IPA solution.
- solution 2 3-Dimethoxynaphthalene-6-sulfonic acid tetrabutylammonium salt was added thereto, and the mixture was immersed in an IPA-water mixed solution (solution 2) prepared to have a concentration of 0.04% by weight.
- 2,3-dimethoxynaphthylene-6-sulfonic acid tetrabutylammonium salt was recrystallized from a mixed reaction of sodium 2,3-dimethoxynaphthalene-6-sulfonate and tetrabutylammonium bromide. One used.
- Example 6 the substrate was taken out and allowed to stand at 60 ° C. for 10 minutes to complete oxidative polymerization. This immersion step was repeated 10 times and then washed with water and dried. When the capacitor element was evaluated, the results shown in Tables 1 and 2 were obtained. However, the content of sulfate ion and 2,3-dimethoxynaphthalene-16-sulfonate ion in the polymer was determined by the method described in Example 1. The content of sulfate ion was 5.2 mol%, 2, 3 —Dimethoxynaphthalene-6-sulfonate ion content was 7.8 mol%. The conductivity of the solid electrolyte layer was 4 OS / cm. Example 6
- a dielectric prepared by the method described in Example 1 was prepared. This dielectric is disclosed in After immersion in a degassed IPA solution (solution 4) at a concentration of 1.2mo 1/1 of 5,6-dimethoxy-isothianaphthene synthesized and sublimated by the method described in JP-A-2-242816, 20 An aqueous solution of APS having a concentration of 1% by weight was impregnated with an aqueous solution (solution 3) prepared to be 0.1% by weight of 2-propyloxynaphthylene-6-sodium sulfonate. Then, the substrate was taken out and left in an environment of 60 ° C. for 10 minutes to complete oxidative polymerization.
- the capacitor element was the same as that described in Example 1 except that a solution of the same concentration of N-methyl was used instead of 3,4-dioxyethylene-thiophene used in Example 1. Was evaluated. The results are shown in Tables 1 and 2. However, the content of sulfate ion and 2-methoxynaphthalene-16-sulfonate ion in the polymer was determined by the method described in Example 1. The content of sulfate ion was 7.8 mol%, and that of 2-methoxynaphthalene-6 —Sulfonate ion content was 12.3 mol%. The conductivity of the solid electrolyte layer was 7 S / cm. Example 8
- the dielectric was prepared by 13 V conversion with a monium aqueous solution. This dielectric was prepared with 30% DMF prepared so that the concentration of 2-methoxynaphthylene-6-sodium sulfonate was 0.1% by weight and the concentration of 3,4-dioxyethylene-thiophene was 1.2mo1Z1.
- IPA solution Solution 2
- APS aqueous solution Solution 1
- the substrate was taken out and allowed to stand in a 6 Ot: environment for 10 minutes to complete oxidative polymerization. This immersion step was repeated 10 times and then washed with water and dried. When the capacitor element was evaluated, the results shown in Tables 1 and 2 were obtained.
- the sulfate ion content was 1.5 mol% and the 2-methoxynaphthalene-6-sulfonate ion content was 3.2 mol% based on all repeating structural units of the polymer.
- the conductivity of the solid electrolyte layer was 71 S / cm.
- the capacitor element was evaluated in the same manner as in Example 1 except that the APS of 20% by weight used in Example 1 was changed to 12% by weight. The results are shown in Tables 1 and 2. However, the content of sulfate ion and 2-methoxynaphthylene-6-sulfonate ion in the polymer was determined by the method described in Example 1. The content of ion sulfate was 0.2 mol% and that of 2-methoxynaphthalene- The 6-sulfonate ion content was 20 mol%. The conductivity of the solid electrolyte layer was 28 SZcm.
- Example 10 Example 10
- a dielectric formed as in Example 1 was prepared, immersed in a 12% IPA solution of 2-methoxynaphthalene-6-iron (III) sulfonate, and then 5 g of 3,4-dioxyethylene-thiophene. 1.2mo 1 Z 1 IPA solution dissolved Immersion.
- the substrate was left standing at 60 ° C. for 10 minutes to complete oxidative polymerization, and washed with water. This polymerization reaction treatment and the washing step were each repeated 10 times.
- the content of 2-methoxynaphthalene-6-sulfonate ion in the polymer was determined by carefully extracting the polymer by hydrazine reduction in water PA solvent and extracting it by ion chromatography.
- Example 1 1 The len-6-sulfonate ion content was 17 mol% per total repeating structural unit of the polymer.
- the conductivity of the solid electrolyte layer was 30 SZ cm.
- a capacitor element was fabricated, and the spark voltage and other capacitor characteristics were examined in the same manner as in Example 1. The results described in Tables 1 and 2 were obtained.
- Example 1 1
- Example 2 Example 1 was repeated except that the APS used in Example 1 was replaced with a solution prepared with 10% by weight of iron sulfate and 0.1% by weight of sodium 2-methoxynaphthalene-6-sulfonate. As described, the capacitor element was evaluated. The results are shown in Tables 1 and 2. However, the content of sulfate ion and 2-methoxynaphthylene-1-6-sulfonate ion in the polymer was determined by the method described in Example 1. The content of sulfate ion was 24.5 mol%, Even-lens-6-sulfonate ion content was 33.8 mol%. However, the capacitor characteristics were poor due to the presence of 8 mol% of iron ions and the sulfate ion content of more than 10 mol%.
- Example 1 2 Example 1 2
- Example 1 The 3,4-dioxyethylene-thiophene used in Example 1 was replaced by thiophene and, instead of APS, by 10% by weight of iron chloride, 2-methoxynaphtha
- the capacitor element was evaluated in the same manner as described in Example 1, except that the solution was adjusted to 0.1% by weight of sodium 6-sulfonate. The results are shown in Tables 1 and 2. However, the content of 2-methoxynaphthylene-6-sulfonate ion in the polymer was 3.1 mol% as determined by the method described in Example 1. Capacitor characteristics were poor because sulfate ions were not included.
- Reference example 1 The 3,4-dioxyethylene-thiophene used in Example 1 was replaced by thiophene and, instead of APS, by 10% by weight of iron chloride, 2-methoxynaphtha
- the capacitor element was evaluated in the same manner as described in Example 1, except that the solution was adjusted to 0.1% by weight of sodium 6-sulfonate
- a process for producing a capacitor element was performed under the same conditions as in Example 1 except that 3,4-dioxyethylene-thiophene described in Example 1 was replaced with thiophene. However, no black-blue polythiophene polymer was formed, and no thiophene polymerization occurred under the action of the APS. In other words, oxidative polymerization of thiophenes by APS occurred specifically for 3,4-dioxy-substituted thiophenes.
- Example 2 The procedure is the same as that described in Example 1, except that sodium 2-propyloxynaphthylene-6-sulfonate used in Example 1 is replaced by sodium 2-hydroxynaphthylene-6-sodium sulfonate.
- the capacitor element was evaluated. The results are shown in Tables 1 and 2. However, the content of sulfate ion and 2-hydroxynaphthalene-6-sulfonate ion in the polymer was determined by the method described in Example 1, and the sulfate ion content was 4.3 mol% and 2-hydroxynaphate was The content of 1-6-sulfonate ion was 12.1 mol%.
- the conductivity of the solid electrolyte layer was 10 S / cm.
- the aluminum conversion foil processed to a specified area was subjected to 13 V conversion with a 10% by weight aqueous solution of ammonium adipate to form a dielectric layer on the foil surface.
- the aluminum conversion foil (substrate) was immersed in an aqueous solution (solution 3) prepared to have 20% by weight of APS and 0.125% by weight of sodium 4-morpholine sodium pansulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.) It was immersed in a 1.2 molZ1 IPA solution (solution 4) in which 5 g of 4-dioxyethylene-thiophene was dissolved.
- the substrate was taken out and allowed to stand at 60 ° C. for 10 minutes to complete oxidative polymerization, and the substrate was washed with water. This polymerization reaction treatment and washing step were each repeated 10 times.
- the content of sulfate ion and 41-morpholinepropanesulfonate ion in the conductive polymer composition was first determined by hydrazine reduction of the polymerized substrate in water / IPA solvent and carefully extracted, followed by ion chromatography. Where The sulfate ion content is based on the total repeating structural units of the polymer in the conductive polymer composition.
- the content of 1.5 mol% and 4-morpholinepropanesulfonic acid ion was 14.0 mol%.
- the conductivity of the solid electrolyte layer was 73 SZ cm.
- the aluminum foil substrate on which the poly-1,4-dioxyethylene-thiophene polymer composition was accumulated was treated in a 10% by weight aqueous solution of ammonium adipate, and the spark voltage was examined.
- current collection from the anode is performed by welding the aluminum core of the substrate to the positive lead terminal, and current collection from the cathode is negative through the power cylinder and silver paste. It was connected to the side lead terminal and finally sealed with epoxy resin to produce a capacitor element. After aging the capacitor element thus obtained at 125 for 2 hours, the initial characteristics were measured. Table 4 summarizes these results.
- C in the initial characteristics in the table represents the capacitance
- DF represents the tangent of the loss angle (t an ⁇ ). All were measured at 12 mm.
- the impedance shows the value at the resonance frequency.
- LC leakage current
- LC was measured one minute after applying the rated voltage. Each measured value is the average value of 30 samples. For LC, 1% or more is indicated as defective, and 10A or more is indicated as short, and the LC value is averaged excluding this.
- solution 1 On the dielectric surface prepared by the method described in Example 13, 3 was impregnated with an aqueous solution (solution 1) prepared to 20% by weight, and then 3,4-dioxyethylene I-PAZ was prepared by adding 4-morpholine propanesulfonate tetrabutylammonium salt (hereinafter abbreviated as MOPSTB) to a 1.2 mol liter IPA solution in which 5 g of fenfen was dissolved, and adjusting the concentration to 0.1% by weight. It was immersed in a mixed solution of water (solution 2).
- MOPSTB 4-morpholine propanesulfonate tetrabutylammonium salt
- the MOPSTB salt used was recrystallized from 41-morpholine sodium propanesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.) through a mixed reaction with tetrabutylammonium bromide.
- the substrate was taken out and left at 60 ° C. for 10 minutes to complete oxidative polymerization, and the substrate was washed with water. This polymerization reaction treatment and the washing step were repeated 10 times, respectively, to evaluate the capacitor element.
- the measurement was performed in the same manner as in Example 13, and the results are shown in Tables 3 and 4.
- the content of sulfate ion and 41-morpholinepropanesulfonic acid ion in the polymer composition was determined by the same method as described in Example 13.
- the sulfate ion content was 1.6 mol%
- the 4-morpholinepropanesulfonic acid ion content. was 8.1 mol%
- the conductivity of the solid electrolyte layer was 56 SZcm.
- An aluminum chemically converted foil formed with a dielectric material prepared in the same manner as described in Example 13 was dissolved in 5 g of 3,4-dioxyethylene-thiophene in a 1.2 mol / L IPA solution ( After immersion in solution 4), the substrate was impregnated with an aqueous solution (solution 3) prepared so that the APS concentration was 20% by weight and the concentration of sodium 4-morpholinepropanesulfonate was 0.1% by weight. Was left in an environment of 60 ° C. for 10 minutes to complete oxidative polymerization, and then washed with water.
- the content of sulfate ion and 41-morpholinepropanesulfonic acid ion in the polymer composition was determined by the method described in Example 13.
- the sulfate ion content was 2.0 mol%
- the 4-morpholinepropanesulfonic acid ion content was 0.6 mol%
- the conductivity of the solid electrolyte layer was 60 SZcm.
- a dielectric formed aluminum foil prepared in the same manner as described in Example 13 was treated with a 1.2 molnoliter IPA solution in which 5 g of 3,4-dioxyethylene-thiophene was dissolved ( After immersion in solution 4), the substrate was impregnated with an aqueous solution (solution 3) prepared so that the APS concentration was 20% by weight and the sodium 4-morpholinesulfonic acid concentration was 0.3% by weight.
- solution 3 aqueous solution
- a capacitor element obtained by repeating the polymerization reaction treatment and the washing step 10 times was evaluated in the same manner as in Example 13. The results are shown in Tables 3 and 4.
- the contents of sulfate ion and 41-morpholine sulfonic acid ion in the polymer composition were determined by the method described in Example 13.
- the sulfate ion content was 2.1 mol%, and 4-morpholine ethane sulfonic acid ion.
- the content was 0.8 mol%.
- the conductivity of the solid electrolyte layer was 68 SZcm.
- An aluminum conversion foil on which a dielectric was formed in the same manner as described in Example 13 was prepared. 10% by weight of potassium persulfate, 4 mol An aqueous solution (solution 3) prepared so that sodium holinpropanesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.) was 0.1% by weight was impregnated, and then 1.2 g of 1.2 mol liter of 5 g of 3,4-dioxoxetren-lenthiophene was dissolved. It was immersed in an IPA solution (solution 4). The substrate was taken out and allowed to stand at 60 ° C. for 10 minutes to complete oxidative polymerization. After repeating this immersion step 10 times, the capacitor element was washed with water and dried, and evaluated in the same manner as in Example 13. The results are shown in Tables 3 and 4.
- the contents of sulfate ion and 41-morpholinepropanesulfonic acid ion in the polymer composition were determined by the method described in Example 13.
- the sulfate ion content was 6.2 mol%
- the 4-morpholinepropanesulfonic acid ion content was 15 mol%
- the electric conductivity of the solid electrolyte layer was 74 SZ cm.
- An aluminum conversion foil on which a dielectric was formed in the same manner as described in Example 13 was prepared.
- the aluminum conversion foil was immersed in a degassed IPA solution (solution 4) of 5, 6-dimethoxy-isothianaphthene synthesized and sublimated by using the method described in Japanese Patent Application Laid-Open No. 2-242816 at a concentration of 1 mol Z liter.
- aqueous solution of APS solution 3 prepared to be 0.1% by weight of sodium 4-morpholinepropanesulfonate was impregnated with an aqueous solution of APS having a concentration of 20% by weight.
- the substrate was taken out and left for 10 minutes in an environment of 60 to complete oxidative polymerization.
- the capacitor element obtained by repeating this immersion step 10 times, washing with water and drying was evaluated in the same manner as in Example 13. The results shown in Tables 3 and 4 were obtained.
- a capacitor element obtained by treating in the same manner as described in Example 13 was used, except that a solution of the same concentration of N-methylpyrrole was used in place of 3,4-dioxyethylene-thiophene used in Example 13. Evaluation was performed in the same manner as in Example 13. Tables 3 and 4 show the results.
- the contents of sulfate ion and 41-morpholinepropanesulfonic acid ion in the polymerization composition were determined by the method described in Example 13.
- the sulfate ion content was 6.8 mol%
- the 41-morpholinepropanesulfonic acid ion content was 16.8 mol%.
- the conductivity of the solid electrolyte layer was 7 S / cm.
- the capacitor element was evaluated in the same manner as described in Example 13 except that 20% by weight of APS used in Example 13 was changed to 12% by weight. The results are shown in Tables 3 and 4.
- the content of sulfate ion and 4-morpholinepropanesulfonate ion in the polymer composition was determined by the method described in Example 13.
- the sulfate ion content was 0.16 mol%, and 41-morpholinepropanesulfonate ion.
- the content was 25 mol%.
- the conductivity of the solid electrolyte layer was 34 S / cm.
- Example 13 The same procedure as described in Example 13 was carried out, except that sodium 4-benzimidazolepropanesulfonate was used in place of sodium 4-morpholinepropanesulfonate used in Example 13 to obtain a solution having the same concentration.
- the evaluated capacitor elements were evaluated, and the results are shown in Tables 3 and 4.
- the content of sulphate ion and 2-benzimidazolepropanesulfonate ion in the polymerization composition was determined by the method of Example 13; the sulfate ion content was 1.8 mol%, and the 2_benzimidazolesulfonate content was 2 mol%. , 14.5 mol%, and the electric conductivity of the solid electrolyte layer was 70 SZ cm.
- Example 23 The procedure was as described in Example 13 except that a solution of the same concentration of 4-methyl-1-piperazine sodium methanesulfonate was used instead of sodium 4-morpholinepropanesulfonate used in Example 13 to obtain the product.
- the evaluated capacitor elements were evaluated, and the results are shown in Tables 3 and 4.
- the contents of sulfate ion and 4-methyl-1-piperazine methanesulfonate ion in the polymerization composition were determined by the method of Example 13 to find that the sulfate ion content was 2.0 mol%, and that the 4-methyl-1 —The content of piperazine methanesulfonate ion was 16.5 mol%, and the conductivity of the solid electrolyte layer was 65 SZ cm.
- Example 13 was obtained in the same manner as in Example 13 except that sodium 4-morpholinepropanesulfonate used in Example 13 was replaced with a solution of sodium 2,3-benzofuran-13-sulfonate having the same concentration.
- the evaluated capacitor elements were evaluated, and the results are shown in Tables 3 and 4.
- the content of sulfate ion and 2,3-benzofuran-3-sulfonate ion in the polymer composition was determined by the method of Example 13 to find that the sulfate ion content was 1.9 mol%, 2,3- The benzofuran-3-sulfonic acid ion content was 15.8 mol%, and the conductivity of the solid electrolyte layer was 61 SZ cm. Comparative Example 1
- Example 13 Sodium 4-morpholinepropanesulfonate was prepared using thiophene instead of 3,4-dioxyethylene-thiophene of the monomer compound used in Example 13 and 10% by weight of iron chloride instead of APS.
- a solid electrolytic capacitor was prepared in the same manner as in Example 13 except that the solution was adjusted to 1% by weight. The capacitor element was manufactured, and the capacitor element was evaluated in the same manner as in Example 13. The results are shown in Tables 3 and 4.
- a dielectric formed in the same manner as in Example 13 was prepared, immersed in a 12% IPA solution of iron (III) 4-morpholinepropanesulfonate, and then treated with 3,4-dioxyethylene-thiophene. It was immersed in a 1.2-moulder solution of IPA dissolved in 5 g. The substrate was left in an environment of 60 for 10 minutes to complete oxidative polymerization, and washed with water. This polymerization reaction treatment and the washing step were each repeated 10 times.
- the content of 4_morpholinepropanesulfonate ion in the polymer composition was determined by carefully extracting the polymer composition by hydrazine reduction in aqueous 1PA solvent and extracting it by ion chromatography. The sulfonic acid ion content was 15 mol% per total repeating structural units of the polymer.
- the conductivity of the solid electrolyte layer was 35 S / cm.
- a capacitor element was prepared from the aluminum conversion foil coated with the conductive polymer composition obtained here, and the spark voltage and other capacitor characteristics were examined in the same manner as in Example 13.Table 3 and Table 4 show that The results described were obtained. Comparative Example 3
- Iron sulfate was changed to 10% by weight in place of the APS used in Example 13 and changed to a solution prepared to 0.1% by weight of sodium 4-morpholinepropanesulfonate.
- a solid electrolytic capacitor was manufactured in the same manner as described in Example 13 except that the capacitor element was evaluated, and the capacitor element was evaluated. The results are shown in Tables 3 and 4.
- the contents of sulfate ion and 41-morpholinepropanesulfonic acid ion in the polymerization composition were determined by the method described in Example 13.
- the sulfate ion content was 19.6% by mole, and the 4-morpholinepropanesulfonic acid ion
- the content was 31.8 mol%.
- due to the presence of 8 mol% of iron ions and the content of sulphate higher than 10 mol% the defective rate of the capacitor was high.
- a process for producing a capacitor element was performed under the same conditions as in Example 13 except that 3,4 dioxyethylene-thiophene described in Example 13 was replaced with thiophene. However, no black-blue polythiophene polymer was formed, and no thiophene polymerization occurred under the action of APS. That is, the oxidative polymerization of thiophenes by APS occurred specifically for 3,4-dioxy-substituted thiophenes. ⁇ 3 spark voltage (unit iV, number of elements n:: 5)
- Example 13 8.0 0.6 60 0.02 0/30 0
- Example 14 8.2 0.7 60 0.02 0/30 0
- Example 15 7.9 0.8 60 0.03 0/30 0
- Example 16 7.2 0.8 60 0.03 0/30 0
- Example 17 7.0 0.9 60 0.05 1/30 0
- Example 18 7.0 0.9 60 0.05 1/30 0
- Example 19 4.0 1.3 60 0.09 1/30 0
- Example 20 7.9 0.8 60 0.03 1/30 0
- Example 21 7.0 0.7 60 0.08 1/30 0
- Example 22 7.9 0.6 60 0.03 0/30 0
- Example 23 7.9 0.7 60 0.03 0/30 0
- Example 24 7.8 0.8 60 0.02 0/30 0
- Comparative example 1 5.8 3.2 90 0.44 27/30 19
- Comparative example 2 7.1 1.2 60 0.16 11/30 9
- Comparative Example 3 6.0 3.2 83 0.40 14/30 10
- Example 25 Comparative example 25
- An aluminum conversion foil processed to a specified area was subjected to 13 V conversion with a 10% by weight aqueous solution of ammonium adipate to prepare a dielectric.
- the dielectric surface was impregnated with an aqueous solution (solution 1) prepared to be 20% by weight of APS and 0.2% by weight of ammonium camphorsulfonic acid, and then IPA in which 5 g of 3,4-dioxyethylene-thiophene was dissolved. It was immersed in the solution (solution 2).
- the substrate was allowed to stand at 60 ° C for 10 minutes to complete oxidative polymerization, and the substrate was washed with water. This polymerization reaction treatment and the washing step were repeated 10 times each.
- the content of sulfate ion and d-camphorsulfonate ion in the polymer composition was determined by first carefully extracting the polymer composition by hydrazine reduction in water ZIPA solvent and determining the content by the ion chromatography method.
- the ion content was 1.5 mol% with respect to all the repeating structural units of the conductive polymer, and the d_camphorsulfonic acid ion content was 17 mol%.
- the conductivity of the solid electrolyte layer was 70 S / cm.
- Capacitor elements were fabricated by sealing with epoxy resin. After aging the capacitor element at 125 ° C for 2 hours, the initial characteristics were measured. Table 5 summarizes these results.
- C in Table 5 represents the capacitance
- DF represents the tangent value (t an 6) of the loss angle. Each was measured at 120 Hz. The impedance shows the value at the resonance frequency.
- LC leakage current
- LC For LC, 1 or more is indicated as a short (defective) product, and the average of the LC value is calculated excluding this.
- Moisture resistance performance test Table 6 shows the results.
- the LC value is the same as the initial value except that 10 zA or more is indicated as a short (defective) product.
- the moisture resistance performance test was carried out under a high temperature and high humidity of 85 t :, 85 RH% for 500 hours.
- Example 25 The same procedure as described in Example 25 was performed, except that the d-camphorsulfonic acid ammonium used in Example 25 was changed to 2-camphorsulfonic acid ammonium, and the capacitor element was evaluated in the same manner. The results are shown in Tables 5 and 6. However, the content of sulfate ion and 2-camphorsulfonate ion in the polymerization composition was determined by the method described in Example 25. The sulfate ion content was 1.9 mol%, and the 2-sulfonic acid sulfonate content was 14%. Mole%. The conductivity of the solid electrolyte layer was 45 SZcm.
- Example 2 7 The same procedure as described in Example 25 was performed, except that the d-camphorsulfonic acid ammonium used in Example 25 was changed to 2-camphorsulfonic acid ammonium, and the capacitor element was evaluated in the same manner. The results are shown in Tables 5 and 6. However, the content of sulfate ion and
- Example 28 The same procedure as described in Example 25 was carried out except that the d-camphorsulfonic acid ammonium used in Example 25 was changed to sodium d-camphorcarboxylate, and the capacitor element was evaluated in the same manner. The results are shown in Tables 5 and 6.
- the content of sulfate ion was 4.7 mol%, and the content of d-camphorcarboxylate ion was 4.3 mol%. Met.
- the conductivity of the solid electrolyte layer was 10 S / cm.
- Example 28 The same procedure as described in Example 25 was carried out except that the d-camphorsulfonic acid ammonium used in Example 25 was changed to sodium d-camphorcarboxylate, and the capacitor element was evaluated in the same manner. The results are shown in Tables 5 and 6.
- Example 2 9 APS used in Example 25 was replaced with potassium persulfate and 3,4-dioxeti
- the capacitor element was evaluated in the same manner as described in Example 25 except that N-methylvirol was used instead of len-thiophene. The results are shown in Tables 5 and 6. However, the content of sulfate ion and d-camphorsulfonic acid ion in the polymerization composition was determined by the method described in Example 1. The sulfate ion content was 6.8 mol%, and the d-camphorsulfonic acid ion content was It was 11 mol%. The electric conductivity of the solid electrolyte layer was 20 S / cm.
- Example 2 10% by weight of 2,3-dichloro-5,6-dicyanobenzoquinone (hereinafter abbreviated as DDQ) and 10% by weight of ⁇ 1-camphorsulfonic acid ammonium were applied to the surface of a dielectric material prepared in the same manner as described in Example 5.
- DDQ 2,3-dichloro-5,6-dicyanobenzoquinone
- ⁇ 1-camphorsulfonic acid ammonium were applied to the surface of a dielectric material prepared in the same manner as described in Example 5.
- a dioxane solution (solution 1) adjusted to 0.1% by weight was impregnated, and then immersed in an IPA solution (solution 2) in which 5 g of isothianaphthene was dissolved.
- This substrate was allowed to stand for 30 minutes in an environment at 80 ° C. to complete oxidative polymerization, and each was washed with dioxane and water. This polymerization reaction treatment and the washing step were each repeated 10 times.
- the content of d-camphorsulfonic acid ion in the polymerization composition was determined by hydrazine reduction of the above polymerization composition in water ZIPA solvent and careful extraction, and the content was determined by ion chromatography. Was 11.5 mol% with respect to all the repeating structural units of the conductive polymer.
- the conductivity of the solid electrolyte layer was 18 SZ cm.
- Example 30 The capacitor element was evaluated in the same manner as described in Example 25 except that the solution prepared by adjusting iron sulfate to 10% by weight was used instead of the APS used in Example 25. The results are shown in Tables 5 and 6. However, the content of sulfonate and d-camphorsulfonic acid ion in the polymer composition was determined by the method described in Example 25. The sulfate ion content was 23 mol%, and the content of d-camphorsulfonic acid ion was 23%. The ON content was 14 mol%. However, since the iron element was present at 11% by weight, the capacitor characteristics were not favorable.
- Example 3 1 Example 2 was repeated except that the APS used in Example 5 was replaced with a solution prepared with 10% by weight of iron chloride and 0.1% by weight of sodium d-phosphorus sulfonate. This was the same as described in 25, and the capacitor element was evaluated. The results are shown in Tables 5 and 6. However, the content of d-camphorsulfonic acid ion in the polymer composition was 2.3 mol% as determined by the method described in Example 25. Since the sulfate ion was not contained in combination, the capacitor characteristics were not so favorable.
- Example 27 5.0 1.0 32 0.05 1/30 0
- Example 30 5.4 0.6 25 0.08 1/30 0
- Example 26 0/30 0 0.16 0/30 0
- Example 27 0/29 0 0.20 0/29 0
- Example 1 a cross-sectional photograph observed in Example 1 is shown in FIG.
- the thickness of the conductive polymer layer formed on the outer surface of the microporous structure is about 5 jm
- the thickness per layer forming the layered structure is about 0.1 to 0.5 m. Range.
- the conductive polymer covered the surface of the micropores, but there was also a space in this portion.
- an alkoxy-substituted naphthalene monosulfonic acid anion (2) a heterocyclic ring are contained in a solid electrolyte containing a conductive polymer having a ⁇ -electron conjugated structure.
- Formula sulfonic acid anion (3) It is characterized by containing at least one kind of organic anion selected from anions of aliphatic polycyclic compounds as a dopant and also containing anion having another dopant function, and is small in size, low impedance and Z or fire resistance.
- Flower A high-performance solid electrolytic capacitor having excellent voltage characteristics can be provided.
- the solid electrolytic capacitor of the present invention by using a specific polyheterocyclic compound, particularly a conductive polythiophene substituted with a dioxymethylene group for the solid electrolyte, the withstand voltage characteristics (spark voltage test), the high frequency characteristics, It has been found that tan ⁇ , impedance characteristics, leakage current, heat resistance (reflow properties), etc. are significantly improved.
- the content of the organic anion is in the range of 0.1 to 50 mol% and the content of sulfate ion is in the range of 0.1 to 10 mol% in the conductive polymer.
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU37329/99A AU3732999A (en) | 1998-05-21 | 1999-05-20 | Solid electrolytic capacitor and method for preparing the same |
JP2000550115A JP4267825B2 (ja) | 1998-05-21 | 1999-05-20 | 固体電解コンデンサ及びその製造方法 |
AT99919660T ATE435497T1 (de) | 1998-05-21 | 1999-05-20 | Festelektrolytkondensator und herstellungsverfahren |
DE69941050T DE69941050D1 (de) | 1998-05-21 | 1999-05-20 | Festelektrolytkondensator und herstellungsverfahren |
EP99919660A EP1085540B1 (en) | 1998-05-21 | 1999-05-20 | Solid electrolytic capacitor and method for preparing the same |
US09/487,329 US6466421B1 (en) | 1998-05-21 | 2000-01-19 | Solid electrolytic capacitor and method for producing the same |
Applications Claiming Priority (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP10/140062 | 1998-05-21 | ||
JP14006298 | 1998-05-21 | ||
JP25364498 | 1998-09-08 | ||
JP10/253644 | 1998-09-08 | ||
US12398599P | 1999-03-11 | 1999-03-11 | |
US12398699P | 1999-03-11 | 1999-03-11 | |
US60/123,985 | 1999-03-11 | ||
US60/123,986 | 1999-03-11 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/369,419 Continuation-In-Part US6344966B1 (en) | 1998-05-21 | 1999-08-06 | Solid electrolytic capacitor and method for producing the same |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1999060586A1 true WO1999060586A1 (fr) | 1999-11-25 |
Family
ID=27472278
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP1999/002647 WO1999060586A1 (fr) | 1998-05-21 | 1999-05-20 | Condensateur electrolytique solide et son procede de preparation |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP1085540B1 (ja) |
JP (1) | JP4267825B2 (ja) |
AU (1) | AU3732999A (ja) |
WO (1) | WO1999060586A1 (ja) |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2006025262A1 (ja) * | 2004-08-30 | 2006-03-09 | Shin-Etsu Polymer Co., Ltd. | 導電性組成物及び導電性架橋体、コンデンサ及びその製造方法、並びに帯電防止塗料、帯電防止膜、帯電防止フィルム、光学フィルタ、及び光情報記録媒体 |
JP2006096975A (ja) * | 2004-08-30 | 2006-04-13 | Shin Etsu Polymer Co Ltd | 導電性組成物及び導電性架橋体 |
JP2006100774A (ja) * | 2004-08-30 | 2006-04-13 | Shin Etsu Polymer Co Ltd | コンデンサ及びその製造方法 |
JP2006117906A (ja) * | 2004-09-24 | 2006-05-11 | Shin Etsu Polymer Co Ltd | 帯電防止塗料、帯電防止膜及び帯電防止フィルム、光学フィルタ、光情報記録媒体 |
JP2008156636A (ja) * | 1999-04-06 | 2008-07-10 | Cambridge Display Technol Ltd | ポリマーのドーピング方法 |
JP2011097035A (ja) * | 2009-09-30 | 2011-05-12 | Semiconductor Energy Lab Co Ltd | 蓄電デバイス |
KR101108815B1 (ko) * | 2003-08-11 | 2012-01-31 | 데이카 가부시키가이샤 | 도전성 고분자와 이를 이용한 고체 전해 콘덴서 |
JP2012070013A (ja) * | 2004-08-30 | 2012-04-05 | Shin Etsu Polymer Co Ltd | コンデンサ |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02130906A (ja) * | 1988-11-11 | 1990-05-18 | Matsushita Electric Ind Co Ltd | 固体電解コンデンサおよびその製造方法 |
JPH1032145A (ja) * | 1996-07-16 | 1998-02-03 | Nec Corp | 固体電解コンデンサ及びその製造方法 |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3425511A1 (de) * | 1984-07-11 | 1986-01-16 | Basf Ag, 6700 Ludwigshafen | Verfahren zur herstellung von p-gedopten polyheterocyclen |
JPH06232009A (ja) * | 1993-02-03 | 1994-08-19 | Elna Co Ltd | アルミニウム電解コンデンサ駆動用電解液 |
JP2536458B2 (ja) * | 1994-08-16 | 1996-09-18 | 日本電気株式会社 | ジスルホン酸化合物、それをド―パントとする導電性高分子、導電材およびそれを用いた固体電解コンデンサ |
-
1999
- 1999-05-20 JP JP2000550115A patent/JP4267825B2/ja not_active Expired - Lifetime
- 1999-05-20 WO PCT/JP1999/002647 patent/WO1999060586A1/ja active Application Filing
- 1999-05-20 EP EP99919660A patent/EP1085540B1/en not_active Expired - Lifetime
- 1999-05-20 AU AU37329/99A patent/AU3732999A/en not_active Abandoned
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02130906A (ja) * | 1988-11-11 | 1990-05-18 | Matsushita Electric Ind Co Ltd | 固体電解コンデンサおよびその製造方法 |
JPH1032145A (ja) * | 1996-07-16 | 1998-02-03 | Nec Corp | 固体電解コンデンサ及びその製造方法 |
Non-Patent Citations (1)
Title |
---|
See also references of EP1085540A4 * |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008156636A (ja) * | 1999-04-06 | 2008-07-10 | Cambridge Display Technol Ltd | ポリマーのドーピング方法 |
KR101108815B1 (ko) * | 2003-08-11 | 2012-01-31 | 데이카 가부시키가이샤 | 도전성 고분자와 이를 이용한 고체 전해 콘덴서 |
US8388866B2 (en) | 2004-08-30 | 2013-03-05 | Shin-Etsu Polymer Co., Ltd. | Conductive composition and conductive cross-linked product, capacitor and production method thereof, and antistatic coating material, antistatic coating, antistatic film, optical filter, and optical information recording medium |
JP2006096975A (ja) * | 2004-08-30 | 2006-04-13 | Shin Etsu Polymer Co Ltd | 導電性組成物及び導電性架橋体 |
JP2006100774A (ja) * | 2004-08-30 | 2006-04-13 | Shin Etsu Polymer Co Ltd | コンデンサ及びその製造方法 |
WO2006025262A1 (ja) * | 2004-08-30 | 2006-03-09 | Shin-Etsu Polymer Co., Ltd. | 導電性組成物及び導電性架橋体、コンデンサ及びその製造方法、並びに帯電防止塗料、帯電防止膜、帯電防止フィルム、光学フィルタ、及び光情報記録媒体 |
US7666326B2 (en) | 2004-08-30 | 2010-02-23 | Shin-Etsu Polymer Co., Ltd. | Conductive composition and conductive cross-linked product, capacitor and production method thereof, and antistatic coating material, antistatic coating, antistatic film, optical filter, and optical information recording medium |
US8551366B2 (en) | 2004-08-30 | 2013-10-08 | Shin-Etsu Polymer Co., Ltd. | Conductive composition and conductive cross-linked product, capacitor and production method thereof, and antistatic coating material, antistatic coating, antistatic film, optical filter, and optical information recording medium |
US8097184B2 (en) | 2004-08-30 | 2012-01-17 | Shin-Etsu Polymer Co., Ltd. | Conductive composition and conductive cross-linked product, capacitor and production method thereof, and antistatic coating material, antistatic coating, antistatic film, optical filter, and optical information recording medium |
JP2012070013A (ja) * | 2004-08-30 | 2012-04-05 | Shin Etsu Polymer Co Ltd | コンデンサ |
JP2006117906A (ja) * | 2004-09-24 | 2006-05-11 | Shin Etsu Polymer Co Ltd | 帯電防止塗料、帯電防止膜及び帯電防止フィルム、光学フィルタ、光情報記録媒体 |
JP2011097035A (ja) * | 2009-09-30 | 2011-05-12 | Semiconductor Energy Lab Co Ltd | 蓄電デバイス |
JP2015079985A (ja) * | 2009-09-30 | 2015-04-23 | 株式会社半導体エネルギー研究所 | 蓄電デバイス |
Also Published As
Publication number | Publication date |
---|---|
AU3732999A (en) | 1999-12-06 |
EP1085540A4 (en) | 2007-05-02 |
EP1085540B1 (en) | 2009-07-01 |
EP1085540A1 (en) | 2001-03-21 |
JP4267825B2 (ja) | 2009-05-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR101144526B1 (ko) | 도전성 고분자용 도판트 용액, 도전성 고분자용 산화제겸도판트 용액, 도전성 조성물 및 고체 전해 컨덴서 | |
JP4908672B2 (ja) | 固体電解コンデンサ | |
US20020039274A1 (en) | Solid electrolytic capacitor and method for producing the same | |
JP4978827B2 (ja) | 固体電解コンデンサ及びその製造方法 | |
JP2012244077A (ja) | 固体電解コンデンサの製造方法 | |
US6344966B1 (en) | Solid electrolytic capacitor and method for producing the same | |
US20090225499A1 (en) | Conductive polymer and solid electrolytic capacitor using the same | |
JP4267825B2 (ja) | 固体電解コンデンサ及びその製造方法 | |
JP4736009B2 (ja) | 固体電解コンデンサ及びその製造方法 | |
US6466421B1 (en) | Solid electrolytic capacitor and method for producing the same | |
JP4236719B2 (ja) | 固体電解コンデンサ及びその製造方法 | |
WO2011052237A1 (ja) | 固体電解コンデンサおよびその製造方法 | |
JP3846760B2 (ja) | 固体電解コンデンサ及びその製造方法 | |
DE60035047T2 (de) | Festelektrolytkondensator und herstellungsverfahren | |
JP4925144B2 (ja) | 固体電解コンデンサの製造方法 | |
WO2007074869A1 (ja) | 固体電解コンデンサおよびその製造方法 | |
TW434602B (en) | Solid electrolytic capacitor and method for preparing the same | |
KR100590986B1 (ko) | 알루미늄 고체 전해 콘덴서의 제조방법 | |
CN114974902A (zh) | 一种气相法制备固态阀金属电解电容器固态阴极的方法 | |
JPWO2007074869A1 (ja) | 固体電解コンデンサおよびその製造方法 | |
JP2010143996A (ja) | 導電性高分子とそれを用い固体電解コンデンサ及びその製造方法 | |
JPH06325984A (ja) | 固体電解コンデンサおよびその製造方法 | |
JP2011108835A (ja) | 固体電解コンデンサ及びその製造方法 | |
JPH0682589B2 (ja) | 固体電解コンデンサ |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AE AL AM AT AU AZ BA BB BG BR BY CA CH CN CU CZ DE DK EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT UA UG US UZ VN YU ZA ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): GH GM KE LS MW SD SL SZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG |
|
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
NENP | Non-entry into the national phase |
Ref country code: KR |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1999919660 Country of ref document: EP |
|
WWP | Wipo information: published in national office |
Ref document number: 1999919660 Country of ref document: EP |
|
REG | Reference to national code |
Ref country code: DE Ref legal event code: 8642 |