JP4762587B2 - Manufacturing method of solid electrolytic capacitor - Google Patents
Manufacturing method of solid electrolytic capacitor Download PDFInfo
- Publication number
- JP4762587B2 JP4762587B2 JP2005096599A JP2005096599A JP4762587B2 JP 4762587 B2 JP4762587 B2 JP 4762587B2 JP 2005096599 A JP2005096599 A JP 2005096599A JP 2005096599 A JP2005096599 A JP 2005096599A JP 4762587 B2 JP4762587 B2 JP 4762587B2
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- JP
- Japan
- Prior art keywords
- poly
- conductive polymer
- dielectric layer
- electron donating
- donating compound
- Prior art date
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- 239000003990 capacitor Substances 0.000 title claims description 53
- 238000004519 manufacturing process Methods 0.000 title claims description 20
- 239000007787 solid Substances 0.000 title claims description 18
- 229920001940 conductive polymer Polymers 0.000 claims description 49
- 150000001875 compounds Chemical class 0.000 claims description 47
- 229920000447 polyanionic polymer Polymers 0.000 claims description 20
- -1 alkylphosphines Chemical class 0.000 claims description 19
- 239000007784 solid electrolyte Substances 0.000 claims description 19
- 230000001590 oxidative effect Effects 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 150000004982 aromatic amines Chemical class 0.000 claims description 3
- 150000002540 isothiocyanates Chemical class 0.000 claims description 3
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 3
- 150000003568 thioethers Chemical class 0.000 claims description 3
- 150000003573 thiols Chemical class 0.000 claims description 3
- 239000000243 solution Substances 0.000 description 27
- 238000000034 method Methods 0.000 description 24
- 239000002904 solvent Substances 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 229910052782 aluminium Inorganic materials 0.000 description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 13
- 238000006116 polymerization reaction Methods 0.000 description 13
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 125000000217 alkyl group Chemical group 0.000 description 10
- 239000000178 monomer Substances 0.000 description 10
- 229910052717 sulfur Inorganic materials 0.000 description 10
- 125000004093 cyano group Chemical group *C#N 0.000 description 9
- 239000002243 precursor Substances 0.000 description 9
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 8
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 8
- 239000011888 foil Substances 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 125000001424 substituent group Chemical group 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 7
- 125000003118 aryl group Chemical group 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 229930192474 thiophene Natural products 0.000 description 7
- QENGPZGAWFQWCZ-UHFFFAOYSA-N 3-Methylthiophene Chemical compound CC=1C=CSC=1 QENGPZGAWFQWCZ-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 239000002019 doping agent Substances 0.000 description 6
- 239000007800 oxidant agent Substances 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 150000001450 anions Chemical class 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 5
- 229910052758 niobium Inorganic materials 0.000 description 5
- 239000010955 niobium Substances 0.000 description 5
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 5
- 229920000128 polypyrrole Polymers 0.000 description 5
- 229920000123 polythiophene Polymers 0.000 description 5
- 229910052709 silver Inorganic materials 0.000 description 5
- 239000004332 silver Substances 0.000 description 5
- 229910052715 tantalum Inorganic materials 0.000 description 5
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 5
- 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 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 4
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000004185 ester group Chemical group 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 229920000767 polyaniline Polymers 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 125000004434 sulfur atom Chemical group 0.000 description 4
- FLDCSPABIQBYKP-UHFFFAOYSA-N 5-chloro-1,2-dimethylbenzimidazole Chemical compound ClC1=CC=C2N(C)C(C)=NC2=C1 FLDCSPABIQBYKP-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 239000001741 Ammonium adipate Substances 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 235000019293 ammonium adipate Nutrition 0.000 description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 229910003472 fullerene Inorganic materials 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 150000003233 pyrroles Chemical class 0.000 description 3
- 150000003577 thiophenes Chemical class 0.000 description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical class C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 229920002292 Nylon 6 Polymers 0.000 description 2
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
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- 239000005456 alcohol based solvent Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 238000007743 anodising Methods 0.000 description 2
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- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
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- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical group CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 2
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- 238000010438 heat treatment Methods 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
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- 239000011574 phosphorus Substances 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 229920002850 poly(3-methoxythiophene) polymer Polymers 0.000 description 2
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- 239000002685 polymerization catalyst Substances 0.000 description 2
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- 238000002360 preparation method Methods 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
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- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- ZMCHBSMFKQYNKA-UHFFFAOYSA-N 2-aminobenzenesulfonic acid Chemical compound NC1=CC=CC=C1S(O)(=O)=O ZMCHBSMFKQYNKA-UHFFFAOYSA-N 0.000 description 1
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- LGPVKMIWERPYIJ-UHFFFAOYSA-N 3,4-dibutyl-1h-pyrrole Chemical compound CCCCC1=CNC=C1CCCC LGPVKMIWERPYIJ-UHFFFAOYSA-N 0.000 description 1
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- GPSFYJDZKSRMKZ-UHFFFAOYSA-N 3,4-dimethylthiophene Chemical compound CC1=CSC=C1C GPSFYJDZKSRMKZ-UHFFFAOYSA-N 0.000 description 1
- FYMPIGRRSUORAR-UHFFFAOYSA-N 3-(4-methyl-1h-pyrrol-3-yl)propanoic acid Chemical compound CC1=CNC=C1CCC(O)=O FYMPIGRRSUORAR-UHFFFAOYSA-N 0.000 description 1
- JCOLSHCVCITSFG-UHFFFAOYSA-N 3-(4-methylthiophen-3-yl)propanoic acid Chemical compound CC1=CSC=C1CCC(O)=O JCOLSHCVCITSFG-UHFFFAOYSA-N 0.000 description 1
- ZAJAQTYSTDTMCU-UHFFFAOYSA-N 3-aminobenzenesulfonic acid Chemical compound NC1=CC=CC(S(O)(=O)=O)=C1 ZAJAQTYSTDTMCU-UHFFFAOYSA-N 0.000 description 1
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- 150000003512 tertiary amines Chemical class 0.000 description 1
- RKHXQBLJXBGEKF-UHFFFAOYSA-M tetrabutylphosphanium;bromide Chemical compound [Br-].CCCC[P+](CCCC)(CCCC)CCCC RKHXQBLJXBGEKF-UHFFFAOYSA-M 0.000 description 1
- NLDYACGHTUPAQU-UHFFFAOYSA-N tetracyanoethylene Chemical group N#CC(C#N)=C(C#N)C#N NLDYACGHTUPAQU-UHFFFAOYSA-N 0.000 description 1
- PCCVSPMFGIFTHU-UHFFFAOYSA-N tetracyanoquinodimethane Chemical compound N#CC(C#N)=C1C=CC(=C(C#N)C#N)C=C1 PCCVSPMFGIFTHU-UHFFFAOYSA-N 0.000 description 1
- LIXPXSXEKKHIRR-UHFFFAOYSA-M tetraethylphosphanium;bromide Chemical compound [Br-].CC[P+](CC)(CC)CC LIXPXSXEKKHIRR-UHFFFAOYSA-M 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- HERSKCAGZCXYMC-UHFFFAOYSA-N thiophen-3-ol Chemical compound OC=1C=CSC=1 HERSKCAGZCXYMC-UHFFFAOYSA-N 0.000 description 1
- GSXCEVHRIVLFJV-UHFFFAOYSA-N thiophene-3-carbonitrile Chemical compound N#CC=1C=CSC=1 GSXCEVHRIVLFJV-UHFFFAOYSA-N 0.000 description 1
- YNVOMSDITJMNET-UHFFFAOYSA-N thiophene-3-carboxylic acid Chemical compound OC(=O)C=1C=CSC=1 YNVOMSDITJMNET-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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Classifications
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- 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
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- 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)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、アルミ電解コンデンサ、タンタル電解コンデンサ、ニオブ電解コンデンサなどの固体電解コンデンサ及びその製造方法に関する。 The present invention relates to a solid electrolytic capacitor such as an aluminum electrolytic capacitor, a tantalum electrolytic capacitor, and a niobium electrolytic capacitor, and a method for manufacturing the same.
近年、電子機器のデジタル化に伴い、電子機器に用いられるコンデンサは高周波領域におけるインピーダンス（ＥＳＲ）を低下させることが要求されている。従来から、この要求に対応すべく、アルミニウム、タンタル、ニオブなどの弁金属の酸化皮膜を誘電体とし、この表面に、ポリピロールやポリチオフェンなどのπ共役系導電性高分子を形成して陰極とした固体電解コンデンサが使用されている。 In recent years, with the digitization of electronic devices, capacitors used in electronic devices are required to reduce impedance (ESR) in a high frequency region. Conventionally, in order to meet this requirement, an oxide film of valve metal such as aluminum, tantalum, or niobium is used as a dielectric, and a π-conjugated conductive polymer such as polypyrrole or polythiophene is formed on this surface as a cathode. Solid electrolytic capacitors are used.
この固体電解コンデンサの構造は、特許文献１に示されるように、弁金属多孔質体からなる陽極と、陽極の表面を酸化して形成した誘電体層と、誘電体層に固体電解質層、カーボン層、銀層を積層した陰極とを有するものが一般的である。固体電解コンデンサの固体電解質層には、ピロール、チオフェンなどのπ共役系導電性高分子が用いられている。
π共役系導電性高分子の形成法としては、電解重合法（特許文献２参照）と化学酸化重合法（特許文献３参照）とが広く知られている。
しかし、電解重合法では、陽極表面にマンガン酸化物からなる導電層を誘電体層上にあらかじめ形成しておく必要があり、非常に煩雑である上に、マンガン酸化物は導電性が低く、高導電性のπ共役系導電性高分子を使用する効果が薄れるという問題があった。
一方、化学酸化重合法では、重合時間が長く、また、厚みを確保するために繰り返し重合しなければならず、固体電解コンデンサの生産効率が低かった上に、導電性も低かった。
As shown in Patent Document 1, the structure of this solid electrolytic capacitor includes an anode made of a valve metal porous body, a dielectric layer formed by oxidizing the surface of the anode, and a solid electrolyte layer and carbon on the dielectric layer. It is common to have a cathode having a laminated layer and a silver layer. A π-conjugated conductive polymer such as pyrrole or thiophene is used for the solid electrolyte layer of the solid electrolytic capacitor.
As a method for forming a π-conjugated conductive polymer, an electrolytic polymerization method (see Patent Document 2) and a chemical oxidation polymerization method (see Patent Document 3) are widely known.
However, in the electropolymerization method, it is necessary to previously form a conductive layer made of manganese oxide on the surface of the anode on the dielectric layer, which is very complicated, and manganese oxide has low conductivity and high conductivity. There is a problem that the effect of using a conductive π-conjugated conductive polymer is reduced.
On the other hand, in the chemical oxidative polymerization method, the polymerization time is long, and it is necessary to repeat the polymerization in order to ensure the thickness, so that the production efficiency of the solid electrolytic capacitor is low and the conductivity is also low.
このように、電解重合法、化学酸化重合法をコンデンサ製造工程内で行うことは、煩雑で、困難である。そこで、特許文献４では、スルホ基、カルボキシ基等を持つポリアニオンを共存させながらアニリンを重合して得たポリアニリン溶液を塗布、乾燥することにより、固体電解質層を形成することが提案されている。
しかしながら、特許文献４に記載の方法では、ポリアニリン溶液の弁金属多孔質体内部への浸透性が低いため、上記電解重合法や化学酸化重合法と同等のインピーダンスを得ることが困難であった。
本発明は、インピーダンスの低い固体電解コンデンサを提供することを目的とする。また、インピーダンスの低い固体電解コンデンサを簡便に製造できる固体電解コンデンサの製造方法を提供することを目的とする。
However, in the method described in Patent Document 4, since the permeability of the polyaniline solution into the valve metal porous body is low, it is difficult to obtain an impedance equivalent to the electrolytic polymerization method or the chemical oxidation polymerization method.
An object of the present invention is to provide a solid electrolytic capacitor with low impedance. Moreover, it aims at providing the manufacturing method of the solid electrolytic capacitor which can manufacture a solid electrolytic capacitor with low impedance simply.
本発明の固体電解コンデンサの製造方法は、弁金属の多孔質体からなる陽極の表面を酸化して誘電体層を形成する工程と、少なくとも該誘電体層の表面に、電子供与性元素を含む電子供与性化合物を塗布する工程と、電子供与性化合物が塗布された誘電体層表面に、π共役系導電性高分子およびポリアニオンを含む導電性高分子溶液を塗布して、π共役系導電性高分子を含む固体電解質層を形成する工程とを有し、
電子供与性化合物が、芳香族アミン、リン酸エステル類、アルキルホスフィン類、サルファイド類、チオール類、イソチオシアナート類から選ばれることを特徴とする。
The method for producing a solid electrolytic capacitor of the present invention includes a step of forming a dielectric layer by oxidizing the surface of an anode made of a porous body of valve metal, and an electron donating element at least on the surface of the dielectric layer. Applying an electron donating compound and applying a conductive polymer solution containing a π-conjugated conductive polymer and a polyanion to the surface of the dielectric layer coated with the electron-donating compound, thereby providing a π-conjugated conductive property. possess and forming a solid electrolyte layer comprising a polymer,
The electron donating compound is selected from aromatic amines, phosphate esters, alkylphosphines, sulfides, thiols, and isothiocyanates .
本発明の固体電解コンデンサは、インピーダンスが低いものである。
また、本発明の固体電解コンデンサの製造方法によれば、インピーダンスの低い固体電解コンデンサを簡便に製造できる。
The solid electrolytic capacitor of the present invention has a low impedance.
Moreover, according to the method for producing a solid electrolytic capacitor of the present invention, a solid electrolytic capacitor having a low impedance can be easily produced.
以下、本発明の固体電解コンデンサ（以下、コンデンサと略す。）の一実施形態例について説明する。
図１は、本実施形態例のコンデンサの構成を示す図である。このコンデンサ１０は、弁金属の多孔質体からなる陽極１１と、陽極１１の表面が酸化されて形成された誘電体層１２と、誘電体層１２上に配置された陰極１３とを有して概略構成されている。
Hereinafter, an embodiment of a solid electrolytic capacitor (hereinafter abbreviated as a capacitor) of the present invention will be described.
FIG. 1 is a diagram illustrating a configuration of a capacitor according to the present embodiment. The
＜陽極＞
陽極１１をなす弁金属としては、例えば、アルミニウム、タンタル、ニオブ、チタン、ハフニウム、ジルコニウム、亜鉛、タングステン、ビスマス、アンチモンなどが挙げられる。これらのうち、アルミニウム、タンタル、ニオブが好適である。
陽極１１の具体例としては、アルミニウム箔をエッチングして表面積を増加させた後、その表面を酸化処理したものや、タンタル粒子やニオブ粒子の焼結体表面を酸化処理してペレットにしたものが挙げられる。このように処理されたものは表面に凹凸が形成されている。
<Anode>
Examples of the valve metal forming the
Specific examples of the
＜誘電体層＞
誘電体層１２は、例えば、アジピン酸アンモニウム水溶液などの電解液中にて、陽極１１の表面を陽極酸化することで形成されたものである。よって、図１に示すように、陽極１１と同様に誘電体層１２の表面にも凹凸が形成されている。
<Dielectric layer>
The
＜陰極＞
陰極１３は、固体電解質層１３ａと、固体電解質層１３ａ上に形成されたカーボン、銀、アルミニウムなどの陰極導電層１３ｂとを備えるものであり、固体電解質層１３ａは、π共役系導電性高分子を含む層であり、誘電体層１２側に備えられている。
陰極導電層１３ｂがカーボン、銀等で構成される場合には、例えば、カーボン、銀等の導電体を含む導電性ペーストから形成することができる。また、陰極導電層１３ｂがアルミニウムで構成される場合には、例えば、アルミニウム箔から形成することができる。
また、固体電解質層１３ａと陽極１１との間には、必要に応じて、セパレータを設けることができる。
<Cathode>
The
When the cathode
Moreover, a separator can be provided between the
［π共役系導電性高分子］
π共役系導電性高分子は、主鎖がπ共役系で構成されている有機高分子であれば使用できる。例えば、ポリピロール類、ポリチオフェン類、ポリアセチレン類、ポリフェニレン類、ポリフェニレンビニレン類、ポリアニリン類、ポリアセン類、ポリチオフェンビニレン類、及びこれらの共重合体等が挙げられる。
[Π-conjugated conductive polymer]
The π-conjugated conductive polymer can be used as long as the main chain is an organic polymer having a π-conjugated system. Examples thereof include polypyrroles, polythiophenes, polyacetylenes, polyphenylenes, polyphenylene vinylenes, polyanilines, polyacenes, polythiophene vinylenes, and copolymers thereof.
このようなπ共役系導電性高分子の具体例としては、ポリピロール、ポリ（Ｎ−メチルピロール）、ポリ（３−メチルピロール）、ポリ（３−エチルピロール）、ポリ（３−ｎ−プロピルピロール）、ポリ（３−ブチルピロール）、ポリ（３−オクチルピロール）、ポリ（３−デシルピロール）、ポリ（３−ドデシルピロール）、ポリ（３，４−ジメチルピロール）、ポリ（３，４−ジブチルピロール）、ポリ（３−カルボキシピロール）、ポリ（３−メチル−４−カルボキシピロール）、ポリ（３−メチル−４−カルボキシエチルピロール）、ポリ（３−メチル−４−カルボキシブチルピロール）、ポリ（３−ヒドロキシピロール）、ポリ（３−メトキシピロール）、ポリ（３−エトキシピロール）、ポリ（３−ブトキシピロール）、ポリ（３−メチル−４−ヘキシルオキシピロール）、ポリチオフェン、ポリ（３−メチルチオフェン）、ポリ（３−エチルチオフェン）、ポリ（３−プロピルチオフェン）、ポリ（３−ブチルチオフェン）、ポリ（３−ヘキシルチオフェン）、ポリ（３−ヘプチルチオフェン）、ポリ（３−オクチルチオフェン）、ポリ（３−デシルチオフェン）、ポリ（３−ドデシルチオフェン）、ポリ（３−オクタデシルチオフェン）、ポリ（３−ブロモチオフェン）、ポリ（３−クロロチオフェン）、ポリ（３−ヨードチオフェン）、ポリ（３−シアノチオフェン）、ポリ（３−フェニルチオフェン）、ポリ（３，４−ジメチルチオフェン）、ポリ（３，４−ジブチルチオフェン）、ポリ（３−ヒドロキシチオフェン）、ポリ（３−メトキシチオフェン）、ポリ（３−エトキシチオフェン）、ポリ（３−ブトキシチオフェン）、ポリ（３−ヘキシルオキシチオフェン）、ポリ（３−ヘプチルオキシチオフェン）、ポリ（３−オクチルオキシチオフェン）、ポリ（３−デシルオキシチオフェン）、ポリ（３−ドデシルオキシチオフェン）、ポリ（３−オクタデシルオキシチオフェン）、ポリ（３−メチル−４−メトキシチオフェン）、ポリ（３，４−エチレンジオキシチオフェン）、ポリ（３−メチル−４−エトキシチオフェン）、ポリ（３−カルボキシチオフェン）、ポリ（３−メチル−４−カルボキシチオフェン）、ポリ（３−メチル−４−カルボキシエチルチオフェン）、ポリ（３−メチル−４−カルボキシブチルチオフェン）、ポリアニリン、ポリ（２−メチルアニリン）、ポリ（３−イソブチルアニリン）、ポリ（２−アニリンスルホン酸）、ポリ（３−アニリンスルホン酸）等が挙げられる。 Specific examples of such π-conjugated conductive polymers include polypyrrole, poly (N-methylpyrrole), poly (3-methylpyrrole), poly (3-ethylpyrrole), and poly (3-n-propylpyrrole). ), Poly (3-butylpyrrole), poly (3-octylpyrrole), poly (3-decylpyrrole), poly (3-dodecylpyrrole), poly (3,4-dimethylpyrrole), poly (3,4 Dibutylpyrrole), poly (3-carboxypyrrole), poly (3-methyl-4-carboxypyrrole), poly (3-methyl-4-carboxyethylpyrrole), poly (3-methyl-4-carboxybutylpyrrole), Poly (3-hydroxypyrrole), poly (3-methoxypyrrole), poly (3-ethoxypyrrole), poly (3-butoxypyrrole), poly 3-methyl-4-hexyloxypyrrole), polythiophene, poly (3-methylthiophene), poly (3-ethylthiophene), poly (3-propylthiophene), poly (3-butylthiophene), poly (3-hexyl) Thiophene), poly (3-heptylthiophene), poly (3-octylthiophene), poly (3-decylthiophene), poly (3-dodecylthiophene), poly (3-octadecylthiophene), poly (3-bromothiophene) , Poly (3-chlorothiophene), poly (3-iodothiophene), poly (3-cyanothiophene), poly (3-phenylthiophene), poly (3,4-dimethylthiophene), poly (3,4-dibutyl) Thiophene), poly (3-hydroxythiophene), poly (3-methoxythiophene), poly Li (3-ethoxythiophene), poly (3-butoxythiophene), poly (3-hexyloxythiophene), poly (3-heptyloxythiophene), poly (3-octyloxythiophene), poly (3-decyloxythiophene) ), Poly (3-dodecyloxythiophene), poly (3-octadecyloxythiophene), poly (3-methyl-4-methoxythiophene), poly (3,4-ethylenedioxythiophene), poly (3-methyl- 4-ethoxythiophene), poly (3-carboxythiophene), poly (3-methyl-4-carboxythiophene), poly (3-methyl-4-carboxyethylthiophene), poly (3-methyl-4-carboxybutylthiophene) ), Polyaniline, poly (2-methylaniline), poly (3-isobutene) Ruanirin), poly (2-aniline sulfonic acid), poly (3-aniline sulfonic acid), and the like.
これらの中でも、ポリピロール、ポリチオフェン、ポリ（Ｎ−メチルピロール）、ポリ（３−メチルチオフェン）、ポリ（３−メトキシチオフェン）、ポリ（３，４−エチレンジオキシチオフェン）から選ばれる１種又は２種からなる（共）重合体が抵抗値、反応性の点から好適に用いられる。さらには、ポリピロール、ポリ（３，４−エチレンジオキシチオフェン）は、導電性がより高い上に、耐熱性が向上する点から、より好ましい。
また、置換基に炭素数６以上のアルキル基を有するものは、後述するポリアニオンを用いることなく溶剤溶解性を付与することができる点で、好ましい。また、置換基としてアニオン基を分子内に持つπ共役系導電性高分子はそのもの自体が水に溶解する点で好ましい。
Among these, one or two selected from polypyrrole, polythiophene, poly (N-methylpyrrole), poly (3-methylthiophene), poly (3-methoxythiophene), and poly (3,4-ethylenedioxythiophene) A (co) polymer consisting of seeds is preferably used from the viewpoint of resistance and reactivity. Furthermore, polypyrrole and poly (3,4-ethylenedioxythiophene) are more preferable because they have higher conductivity and improved heat resistance.
Moreover, what has a C6 or more alkyl group in a substituent is preferable at the point which can provide solvent solubility, without using the polyanion mentioned later. In addition, a π-conjugated conductive polymer having an anionic group as a substituent in the molecule is preferable because it itself dissolves in water.
上記π共役系導電性高分子は、溶媒中、π共役系導電性高分子の前駆体モノマーを、酸化剤又は酸化重合触媒の存在下で化学酸化重合することによって容易に得ることができる。
その際、π共役系導電性高分子の前駆体モノマーとしては、ピロール類及びその誘導体、チオフェン類及びその誘導体、アニリン類及びその誘導体等を使用することができる。
酸化剤としては、ぺルオキソ二硫酸アンモニウム、ぺルオキソ二硫酸ナトリウム、ぺルオキソ二硫酸カリウム等のぺルオキソ二硫酸塩、塩化第二鉄、塩化第二銅等の遷移金属化合物、酸化銀、酸化セシウム等の金属酸化物、過酸化水素、オゾン等の過酸化物、過酸化ベンゾイル等の有機過酸化物、酸素、三フッ化ホウ素等が使用できる。
The π-conjugated conductive polymer can be easily obtained by chemical oxidative polymerization of a precursor monomer of the π-conjugated conductive polymer in a solvent in the presence of an oxidizing agent or an oxidation polymerization catalyst.
At that time, pyrroles and derivatives thereof, thiophenes and derivatives thereof, anilines and derivatives thereof, and the like can be used as precursor monomers for the π-conjugated conductive polymer.
As oxidizing agents, peroxodisulfates such as ammonium peroxodisulfate, sodium peroxodisulfate, potassium peroxodisulfate, transition metal compounds such as ferric chloride, cupric chloride, silver oxide, cesium oxide, etc. Metal oxides, peroxides such as hydrogen peroxide and ozone, organic peroxides such as benzoyl peroxide, oxygen, boron trifluoride and the like can be used.
化学酸化重合を行う際に用いる溶媒としては、特に制限されるものではなく、前記前駆体モノマー、酸化剤又は酸化重合触媒を溶解又は分散しうる溶媒であればよい。例えば、水、Ｎ−メチル−２−ピロリドン、Ｎ，Ｎ’−ジメチルホルムアミド、Ｎ，Ｎ’−ジメチルアセトアミド、ジメチルスルホキシド、ヘキサメチルホスホルトリアミド等の極性溶媒、クレゾール、フェノール、キシレノール等のフェノール類、メタノール、エタノール、プロパノール、ブタノール等のアルコール類、アセトン、メチルエチルケトン等のケトン類、ヘキサン、ベンゼン、トルエン等の炭化水素類、ギ酸、酢酸等のカルボン酸、エチレンカーボネート、プロピレンカーボネートなどのカーボネート化合物、ジオキサン、ジエチルエーテルなどのエーテル化合物、エチレングリコールジアルキルエーテル、プロピレングリコールジアルキルエーテル、ポリエチレングリコールジアルキルエーテル、ポリプロピレングリコールジアルキルエーテルなどの鎖状エーテル類、３−メチル−２−オキサゾリジノンなどの複素環化合物、アセトニトリル、グルタロジニトリル、メトキシアセトニトリル、プロピオニトリル、ベンゾニトリルなどのニトリル化合物等が挙げられる。これらの溶媒は、適宜、単独で用いてもよいし、２種以上の混合物としてもよいし、他の有機溶媒との混合物としてもよい。 The solvent used in performing the chemical oxidative polymerization is not particularly limited as long as it is a solvent that can dissolve or disperse the precursor monomer, the oxidizing agent, or the oxidative polymerization catalyst. For example, water, polar solvents such as N-methyl-2-pyrrolidone, N, N′-dimethylformamide, N, N′-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphortriamide, and phenols such as cresol, phenol, xylenol , Alcohols such as methanol, ethanol, propanol and butanol, ketones such as acetone and methyl ethyl ketone, hydrocarbons such as hexane, benzene and toluene, carboxylic acids such as formic acid and acetic acid, carbonate compounds such as ethylene carbonate and propylene carbonate, Ether compounds such as dioxane and diethyl ether, ethylene glycol dialkyl ether, propylene glycol dialkyl ether, polyethylene glycol dialkyl ether, polypropylene glycol Chain ethers such as alkyl ethers, 3-methyl-2-oxazolidinone heterocyclic compounds such as, acetonitrile, glutarodinitrile, methoxy acetonitrile, propionitrile, nitrile compounds such as benzonitrile and the like. These solvents may be used alone as appropriate, as a mixture of two or more kinds, or as a mixture with other organic solvents.
上記コンデンサ１０においては、誘電体層１２の陰極１３側表面に、電子供与性元素を含む電子供与性化合物が塗布されている。したがって、誘電体層１２の陰極１３側表面に電子供与性化合物が付着している。
In the
［電子供与性化合物］
本発明における電子供与性化合物とは、電子供与性元素を含む化合物のことであって、重合体ではない化合物のことである。
電子供与性化合物に含まれる電子供与性元素としては、誘電体層と、π共役導電性高分子を含む陰極との電気的親和性がより高くなることから、周期律表第１５属、第１６属の元素のうち、窒素、酸素、燐、硫黄から選ばれる少なくとも１種以上であることが好ましい。
[Electron donating compound]
The electron donating compound in the present invention is a compound containing an electron donating element and is not a polymer.
As the electron donating element contained in the electron donating compound, the electrical affinity between the dielectric layer and the cathode containing the π-conjugated conductive polymer becomes higher. Of the genus elements, at least one selected from nitrogen, oxygen, phosphorus, and sulfur is preferable.
窒素を含む電子供与性化合物としては、誘電体層と陰極との電気的親和性がより高くなることから、１級アミン、２級アミン、３級アミンなどのアミン類が好ましい。アミン類としては、具体的には、エチルアミン、ジエチルアミン、メチルエチルアミン、トリエチルアミンのような脂肪族アミン、アニリン、ベンジルアミン、ピロール、イミダゾール、ピリジン、ピリミジン、ピラジン、トリアジンのような芳香族アミンもしくはこれらの誘導体が挙げられる。 As the electron-donating compound containing nitrogen, amines such as primary amine, secondary amine, tertiary amine and the like are preferable because the electrical affinity between the dielectric layer and the cathode becomes higher. Specific examples of amines include aliphatic amines such as ethylamine, diethylamine, methylethylamine, and triethylamine, aromatic amines such as aniline, benzylamine, pyrrole, imidazole, pyridine, pyrimidine, pyrazine, and triazine, or these amines. Derivatives.
酸素を含む電子供与性化合物としては、例えば、アルコール類、エーテル類、ケトン類が挙げられ、具体的には、ラウリルアルコール、ヘキサデシルアルコール、ベンジルアルコール、エチレングリコール、プロピレングリコール、グリセリン、ジフェニルエーテル、シクロヘキサノン、ジアセトンアルコール、イソホロン、フラン及びその誘導体などが挙げられる。 Examples of the electron donating compound containing oxygen include alcohols, ethers, and ketones. Specifically, lauryl alcohol, hexadecyl alcohol, benzyl alcohol, ethylene glycol, propylene glycol, glycerin, diphenyl ether, cyclohexanone. , Diacetone alcohol, isophorone, furan and derivatives thereof.
燐を含む電子供与性化合物としては、例えば、リン酸エステル類、亜リン酸エステル類、ホスホン酸類、アルキルホスフィン類、アルキルホスホニウム塩類などが挙げられ、具体的には、リン酸トリメチル、リン酸トリフェニル、亜リン酸トリメチル、亜リン酸トリエチル、ホスホン酸ジメチル、ホスホン酸ジエチル、トリエチルホスフィン、トリ−ｎ−ブチルホスフィン、トリ−ｎ−ブチルホスフィンオキサイド、テトラエチルホスホニウムブロミド、テトラ−ｎ−ブチルホスホニウムブロミドなどが挙げられる。 Examples of the electron-donating compound containing phosphorus include phosphate esters, phosphites, phosphonic acids, alkylphosphines, alkylphosphonium salts, and the like. Specifically, trimethyl phosphate, triphosphate phosphate, and the like. Phenyl, trimethyl phosphite, triethyl phosphite, dimethyl phosphonate, diethyl phosphonate, triethylphosphine, tri-n-butylphosphine, tri-n-butylphosphine oxide, tetraethylphosphonium bromide, tetra-n-butylphosphonium bromide, etc. Is mentioned.
硫黄を含む電子供与性化合物としては、例えば、サルファイド類、チオール類、イソチオシアネート類、チオフェン及びその誘導体などが挙げられ、具体的には、ジメチルサルファイド、ジエチルサルファイド、メチルメルカプタン、エチルメルカプタン、フェニルイソチオシアネート、ｎ−ブチルイソチオシアネート、チオフェン、３−メチルチオフェンなどが挙げられる。 Examples of the electron-donating compound containing sulfur include sulfides, thiols, isothiocyanates, thiophene and derivatives thereof, and specifically, dimethyl sulfide, diethyl sulfide, methyl mercaptan, ethyl mercaptan, phenyl isopropene. Examples include thiocyanate, n-butylisothiocyanate, thiophene, and 3-methylthiophene.
これら電子供与性化合物の中でも、誘電体層に残存しても等価直列抵抗の低下を防止できることから、芳香環の中に窒素又は酸素又は硫黄を含む化合物が好ましい。芳香環の中に窒素を含む化合物としては、ピロールやその誘導体（ピロール類）、イミダゾール、ピリジン、ピリミジン、ピラジン、トリアジンやその誘導体などが挙げられ、芳香環の中に酸素を含む化合物としては、フランやその誘導体（フラン類）などが挙げられ、芳香環の中に硫黄を含む化合物としては、チオフェンやその誘導体（チオフェン類）が挙げられる。中でも、誘電体層と陰極との電気的親和性がより高くなることから、ピロール類、チオフェン類、フラン類から選ばれる少なくとも１種が好ましい。 Among these electron donating compounds, a compound containing nitrogen, oxygen, or sulfur in the aromatic ring is preferable because the equivalent series resistance can be prevented from being lowered even if it remains in the dielectric layer. Examples of the compound containing nitrogen in the aromatic ring include pyrrole and derivatives thereof (pyrroles), imidazole, pyridine, pyrimidine, pyrazine, triazine and derivatives thereof. As the compound containing oxygen in the aromatic ring, Examples include furan and derivatives thereof (furans), and examples of the compound containing sulfur in the aromatic ring include thiophene and derivatives thereof (thiophenes). Among them, at least one selected from pyrroles, thiophenes, and furans is preferable because the electrical affinity between the dielectric layer and the cathode is higher.
芳香環中に窒素、酸素、硫黄を含む電子供与性化合物では、窒素原子、酸素原子、硫黄原子に非共有電子対が存在しているため、これらの原子上に置換基又はプロトンが配位又は結合されやすい。窒素原子、酸素原子、硫黄原子上に置換基又はプロトンが配位又は結合された場合には、これらの原子上にカチオン電荷を帯びる傾向がある。また、窒素原子、酸素原子、硫黄原子と他の原子とは共役関係を有しているため、これらの原子上に置換基又はプロトンが配位又は結合されたことによって生じたカチオン電荷は芳香環中に拡散されて、安定した形で存在するようになる。
このようなことから、上記のような芳香環中に窒素、酸素、硫黄を含む電子供与性化合物は、窒素、酸素、硫黄原子に置換基が導入されてカチオンを形成していてもよい。さらに、そのカチオンとアニオンとが組み合わされて塩が形成されていてもよい。塩であっても、カチオンでない電子供与性化合物と同様の効果を発揮する。
In an electron-donating compound containing nitrogen, oxygen, and sulfur in the aromatic ring, since a non-shared electron pair exists in the nitrogen atom, oxygen atom, and sulfur atom, a substituent or a proton is coordinated on these atoms. Easy to be combined. When a substituent or proton is coordinated or bonded to a nitrogen atom, oxygen atom or sulfur atom, it tends to have a cationic charge on these atoms. In addition, since the nitrogen atom, oxygen atom, sulfur atom and other atoms have a conjugated relationship, the cation charge generated by the coordination or bonding of a substituent or proton on these atoms is an aromatic ring. It diffuses in and becomes stable.
For this reason, the electron donating compound containing nitrogen, oxygen, and sulfur in the aromatic ring as described above may form a cation by introducing a substituent into the nitrogen, oxygen, or sulfur atom. Further, a salt may be formed by combining the cation and the anion. Even a salt exhibits the same effect as an electron donating compound that is not a cation.
以上説明したコンデンサは、誘電体層表面に電子供与性化合物が塗布されており、誘電体層表面の電荷が中和されているため、該誘電体層と、π共役系導電性高分子を含む固体電解質層との電気的親和性が高くなっている。その結果、誘電体層と陰極との界面の抵抗が小さくなっているため、コンデンサのインピーダンスが低いとともに、容量が高い。 The capacitor described above includes the dielectric layer and the π-conjugated conductive polymer because the surface of the dielectric layer is coated with an electron donating compound and the charge on the surface of the dielectric layer is neutralized. The electrical affinity with the solid electrolyte layer is high. As a result, since the resistance at the interface between the dielectric layer and the cathode is reduced, the impedance of the capacitor is low and the capacitance is high.
（コンデンサの製造方法）
次に、本発明のコンデンサの製造方法の一実施形態例に付いて説明する。
本実施形態例のコンデンサの製造方法は、弁金属の多孔質体からなる陽極の表面を酸化して誘電体層を形成する工程と、該誘電体層の表面に電子供与性化合物を塗布する工程と、電子供与性化合物が塗布された誘電体層表面に、π共役系導電性高分子を含む層（固体電解質層）を形成する工程と、固体電解質層上に陰極導電層を設けて陰極を形成する工程とを有する方法である。
(Capacitor manufacturing method)
Next, an embodiment of a capacitor manufacturing method according to the present invention will be described.
The method of manufacturing a capacitor according to this embodiment includes a step of oxidizing a surface of an anode made of a porous body of a valve metal to form a dielectric layer, and a step of applying an electron donating compound to the surface of the dielectric layer. Forming a layer containing a π-conjugated conductive polymer (solid electrolyte layer) on the surface of the dielectric layer coated with the electron donating compound, and providing a cathode conductive layer on the solid electrolyte layer to form a cathode Forming the method.
このコンデンサの製造方法において、陽極表面を酸化する方法としては、例えば、アジピン酸アンモニウム水溶液などの電解液中にて、陽極表面を陽極酸化する方法が挙げられる。 In this method of manufacturing a capacitor, examples of a method for oxidizing the anode surface include a method for anodizing the anode surface in an electrolytic solution such as an aqueous solution of ammonium adipate.
誘電体層表面に電子供与性化合物を塗布する方法としては、コーティング、浸漬、スプレーなどの公知の塗布方法を採ることができる。電子供与性化合物が固体である場合には、電子供与性化合物を溶媒で溶解した溶液を塗布すればよい。その場合、塗布後、乾燥して溶媒を除去することが好ましい。また、液体の電子供与性化合物を希釈した場合にも溶媒を除去することが好ましい。
電子供与性化合物を含む溶液の濃度は特に限定されないが、薄すぎると効果が発現しにくく、濃すぎると塗布しにくくなったり、ＥＳＲが低下したりする恐れがあるので、１〜８０質量％であることが好ましく、５〜５０質量％であることがより好ましい。
As a method for applying the electron donating compound to the surface of the dielectric layer, a known application method such as coating, dipping or spraying can be employed. When the electron donating compound is a solid, a solution in which the electron donating compound is dissolved in a solvent may be applied. In that case, it is preferable to remove the solvent by drying after coating. It is also preferable to remove the solvent when the liquid electron donating compound is diluted.
The concentration of the solution containing the electron-donating compound is not particularly limited. However, if it is too thin, the effect is difficult to express, and if it is too thick, it may be difficult to apply or ESR may be reduced. It is preferable that it is 5 to 50% by mass.
π共役系導電性高分子を含む層を形成するには、簡便である上に誘電体層と陰極との電気的親和性をより向上させやすいことから、誘電体層表面に、π共役系導電性高分子を溶媒に溶解した導電性高分子溶液を塗布する方法が好ましい。また、誘電体層上で、π共役系導電性高分子を構成する前駆体モノマーを化学酸化重合や電解重合を直接行うことによって形成しても構わない。 In order to form a layer containing a π-conjugated conductive polymer, it is easy and the electrical affinity between the dielectric layer and the cathode can be improved more easily. A method of applying a conductive polymer solution in which a conductive polymer is dissolved in a solvent is preferable. Alternatively, the precursor monomer constituting the π-conjugated conductive polymer may be formed on the dielectric layer by directly performing chemical oxidative polymerization or electrolytic polymerization.
導電性高分子溶液は、ポリアニオン存在下でπ共役系導電性高分子の前駆体モノマーを重合することにより得られる。または、溶媒溶解性を有するπ共役系導電性高分子を溶媒に溶解することにより得られる。
ポリアニオン存在下でπ共役系導電性高分子の前駆体モノマーを重合して導電性高分子溶液を調製する方法の具体例としては、まず、ポリアニオンを、これを溶解可能な溶媒に溶解し、これにより得られた溶液に、π共役系導電性高分子の前駆体モノマーを添加する。次いで、酸化剤を添加して前駆体モノマーを重合させ、その後、余剰の酸化剤や前駆体モノマーを分離、精製して導電性高分子溶液を得る。
The conductive polymer solution is obtained by polymerizing a precursor monomer of a π-conjugated conductive polymer in the presence of a polyanion. Alternatively, it can be obtained by dissolving a π-conjugated conductive polymer having solvent solubility in a solvent.
As a specific example of a method for preparing a conductive polymer solution by polymerizing a precursor monomer of a π-conjugated conductive polymer in the presence of a polyanion, first, a polyanion is dissolved in a solvent capable of dissolving it. A precursor monomer of a π-conjugated conductive polymer is added to the solution obtained by the above. Next, an oxidizing agent is added to polymerize the precursor monomer, and then the excess oxidizing agent and precursor monomer are separated and purified to obtain a conductive polymer solution.
ここで用いられるポリアニオンとしては、例えば、置換若しくは未置換のポリアルキレン、置換若しくは未置換のポリアルケニレン、置換若しくは未置換のポリイミド、置換若しくは未置換のポリアミド、置換若しくは未置換のポリエステルから選ばれ、アニオン基を有する構成単位のみからなるポリマーであっても、アニオン基を有する構成単位とアニオン基を有さない構成単位とからなるポリマーであってもよい。
なお、ポリアニオンは、π共役系導電性高分子を溶媒に可溶化させるだけでなく、π共役系導電性高分子のドーパントしても機能する。
The polyanion used here is selected from, for example, substituted or unsubstituted polyalkylene, substituted or unsubstituted polyalkenylene, substituted or unsubstituted polyimide, substituted or unsubstituted polyamide, substituted or unsubstituted polyester, Even if it is a polymer which consists only of the structural unit which has an anion group, the polymer which consists of the structural unit which has an anion group, and the structural unit which does not have an anion group may be sufficient.
The polyanion not only solubilizes the π-conjugated conductive polymer in a solvent, but also functions as a dopant for the π-conjugated conductive polymer.
ここで、ポリアルキレンとは、主鎖がメチレンの繰り返しで構成されているポリマーである。ポリアルケニレンとしては、主鎖にビニル基が１個含まれる構成単位からなるポリマーを挙げることができ、不飽和結合と導電性高分子化合物との相互作用があること、置換若しくは未置換のブタジエンを出発物質として合成しやすいことから、置換若しくは未置換のブテニレン等を例示できる。
ポリイミドとしては、ピロメリット酸二無水物、ビフェニルテトラカルボン酸二無水物、ベンゾフェノンテトラカルボン酸二無水物、２，２，３，３−テトラカルボキシジフェニルエーテル二無水物、２，２−［４，４’−ジ（ジカルボキシフェニルオキシ）フェニル］プロパン二無水物等の酸無水物と、オキシジアニリン、パラフェニレンジアミン、メタフェニレンジアミン、ベンゾフェノンジアミン等のジアミンとからのポリイミドを例示できる。
ポリアミドとしては、ポリアミド６、ポリアミド６，６、ポリアミド６, １０等を例示できる。
ポリエステルとしては、ポリエチレンテレフタレート、ポリブチレンテレフタレート等を例示できる。
Here, polyalkylene is a polymer whose main chain is composed of repeating methylene. Examples of polyalkenylene include a polymer composed of structural units containing one vinyl group in the main chain, and there is an interaction between an unsaturated bond and a conductive polymer compound, and substituted or unsubstituted butadiene. Since it is easy to synthesize as a starting material, substituted or unsubstituted butenylene can be exemplified.
As polyimide, pyromellitic dianhydride, biphenyltetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, 2,2,3,3-tetracarboxydiphenyl ether dianhydride, 2,2- [4,4 Examples include polyimides from acid anhydrides such as' -di (dicarboxyphenyloxy) phenyl] propane dianhydride and diamines such as oxydianiline, paraphenylenediamine, metaphenylenediamine, and benzophenonediamine.
Examples of the polyamide include polyamide 6, polyamide 6,6,
Examples of the polyester include polyethylene terephthalate and polybutylene terephthalate.
ポリアニオンを構成するポリマーが有する置換基としては、アルキル基、ヒドロキシ基、カルボキシ基、シアノ基、フェニル基、フェノール基、エステル基、アルコキシ基、カルボニル基等が挙げられる。アルキル基は、極性溶媒又は非極性溶媒への溶解性及び分散性、樹脂への相溶性及び分散性等を高くすることができ、ヒドロキシ基は、他の水素原子等との水素結合を形成しやすくでき、有機溶媒への溶解性、樹脂への相溶性、分散性、接着性を高くすることができる。また、シアノ基及びヒドロキシフェニル基は、極性樹脂への相溶性、溶解性を高くすることができ、しかも、耐熱性も高くすることができる。上記置換基の中ではアルキル基、ヒドロキシ基、エステル基、シアノ基が好ましい。 Examples of the substituent of the polymer constituting the polyanion include an alkyl group, a hydroxy group, a carboxy group, a cyano group, a phenyl group, a phenol group, an ester group, an alkoxy group, and a carbonyl group. Alkyl groups can increase solubility and dispersibility in polar or nonpolar solvents, compatibility and dispersibility in resins, and hydroxy groups form hydrogen bonds with other hydrogen atoms. This makes it easy to increase solubility in organic solvents, compatibility with resins, dispersibility, and adhesion. In addition, the cyano group and the hydroxyphenyl group can increase the compatibility and solubility in the polar resin, and can also increase the heat resistance. Among the above substituents, an alkyl group, a hydroxy group, an ester group, and a cyano group are preferable.
アルキル基としては、メチル、エチル、プロピル、ブチル、イソブチル、ｔ−ブチル、ペンチル、へキシル、オクチル、デシル、ドデシル等のアルキル基と、シクロプロピル、シクロペンチル及びシクロヘキシル等のシクロアルキル基が挙げられる。有機溶剤への溶解性、樹脂への分散性、立体障害等を考慮すると、炭素数１〜１２のアルキル基がより好ましい。
ヒドロキシ基としては、ポリアニオンの主鎖に直接結合したヒドロキシ基、ポリアニオンの主鎖に結合した炭素数１〜７のアルキル基の末端に結合したヒドロキシ基、ポリアニオンの主鎖に結合した炭素数２〜７のアルケニル基の末端に結合したヒドロキシ基等が挙げられる。これらの中では樹脂への相溶及び有機溶剤への溶解性から、主鎖に結合した炭素数１〜６のアルキル基の末端に結合したヒドロキシ基がより好ましい。
エステル基としては、ポリアニオンの主鎖に直接結合したアルキル系エステル基、芳香族系エステル基、他の官能基を介在してなるアルキル系エステル基又は芳香族系エステル基を挙げることができる。
シアノ基としては、ポリアニオンの主鎖に直接結合したシアノ基、ポリアニオンの主鎖に結合した炭素数１〜７のアルキル基の末端に結合したシアノ基、ポリアニオンの主鎖に結合した炭素数２〜７のアルケニル基の末端に結合したシアノ基等を挙げることができる。
Examples of the alkyl group include alkyl groups such as methyl, ethyl, propyl, butyl, isobutyl, t-butyl, pentyl, hexyl, octyl, decyl, and dodecyl, and cycloalkyl groups such as cyclopropyl, cyclopentyl, and cyclohexyl. In consideration of solubility in an organic solvent, dispersibility in a resin, steric hindrance, and the like, an alkyl group having 1 to 12 carbon atoms is more preferable.
Examples of the hydroxy group include a hydroxy group directly bonded to the main chain of the polyanion, a hydroxy group bonded to the terminal of the alkyl group having 1 to 7 carbon atoms bonded to the main chain of the polyanion, and 2 to 2 carbon atoms bonded to the main chain of the polyanion. And a hydroxy group bonded to the terminal of 7 alkenyl group. Among these, a hydroxy group bonded to the terminal of an alkyl group having 1 to 6 carbon atoms bonded to the main chain is more preferable from the viewpoint of compatibility with a resin and solubility in an organic solvent.
Examples of the ester group include an alkyl ester group directly bonded to the main chain of the polyanion, an aromatic ester group, and an alkyl ester group or an aromatic ester group having another functional group interposed therebetween.
The cyano group includes a cyano group directly bonded to the main chain of the polyanion, a cyano group bonded to the terminal of the alkyl group having 1 to 7 carbon atoms bonded to the main chain of the polyanion, and 2 to 2 carbon atoms bonded to the main chain of the polyanion. And a cyano group bonded to the terminal of 7 alkenyl group.
ポリアニオンにおけるアニオン基としては、π共役導電性高分子への化学酸化ドープが起こりうる官能基であればよいが、中でも、製造の容易さ及び安定性の観点からは、一置換硫酸エステル基、一置換リン酸エステル基、カルボン酸基、スルホン酸基等が好ましい。さらに、官能基の導電性高分子化合物へのドープ効果の観点より、スルホン酸基及び一置換硫酸エステル基がより好ましい。
ポリアニオンの具体例としては、ポリビニルスルホン酸、ポリスチレンスルホン酸、ポリアリルスルホン酸、ポリアクリルスルホン酸、ポリメタクリルスルホン酸、ポリ−２−アクリルアミド−２−メチルプロパンスルホン酸、ポリイソプレンスルホン酸、ポリアクリル酸等が挙げられる。
これらのうち、ポリアクリルスルホン酸、ポリメタクリルスルホン酸は、熱エネルギーを吸収して自ら分解することにより、導電性高分子成分の熱分解が緩和されるため、耐熱性、耐環境性に優れ、さらに、エステル基を有することから、バインダー樹脂との相溶性、分散性に優れるので、特に好ましい。
The anion group in the polyanion may be any functional group that can undergo chemical oxidation doping to the π-conjugated conductive polymer. Among them, from the viewpoint of ease of production and stability, a mono-substituted sulfate group, A substituted phosphate group, carboxylic acid group, sulfonic acid group and the like are preferred. Furthermore, a sulfonic acid group and a monosubstituted sulfate group are more preferable from the viewpoint of the doping effect of the functional group on the conductive polymer compound.
Specific examples of polyanions include polyvinyl sulfonic acid, polystyrene sulfonic acid, polyallyl sulfonic acid, polyacryl sulfonic acid, polymethacryl sulfonic acid, poly-2-acrylamido-2-methylpropane sulfonic acid, polyisoprene sulfonic acid, polyacrylic. An acid etc. are mentioned.
Of these, polyacrylsulfonic acid and polymethacrylsulfonic acid absorb heat energy and decompose by themselves, so that thermal decomposition of the conductive polymer component is alleviated, so heat resistance and environmental resistance are excellent. Furthermore, since it has an ester group, it is particularly preferable because it has excellent compatibility and dispersibility with the binder resin.
導電性高分子溶液には、π共役系導電性高分子の導電性を向上させるために、ポリアニオン以外のドーパントを添加してもよい。通常、ドーパントとしてはハロゲン化合物、ルイス酸、プロトン酸などが用いられ、具体的には、例えば、有機カルボン酸、有機スルホン酸等の有機酸、有機シアノ化合物、フラーレン、水素化フラーレン、水酸化フラーレン、カルボン酸化フラーレン、スルホン酸化フラーレンなどが挙げられる。 In order to improve the conductivity of the π-conjugated conductive polymer, a dopant other than the polyanion may be added to the conductive polymer solution. Usually, halogen compounds, Lewis acids, proton acids and the like are used as dopants. Specifically, for example, organic acids such as organic carboxylic acids and organic sulfonic acids, organic cyano compounds, fullerenes, hydrogenated fullerenes, and fullerene hydroxides. Carboxylic acid fullerene, sulfonated fullerene and the like.
有機酸としては、アルキルベンゼンスルホン酸、アルキルナフタレンスルホン酸、アルキルナフタレンジスルホン酸、ナフタレンスルホン酸ホルマリン重縮合物、メラミンスルホン酸ホルマリン重縮合物、ナフタレンジスルホン酸、ナフタレントリスルホン酸、ジナフチルメタンジスルホン酸、アントラキノンスルホン酸、アントラキノンジスルホン酸、アントラセンスルホン酸、ピレンスルホン酸などが挙げられる。また、これらの金属塩も使用できる。
有機シアノ化合物としては、共役結合に二つ以上のシアノ基を含む化合物が使用できる。例えば、テトラシアノエチレン、テトラシアノエチレンオキサイド、テトラシアノベンゼン、ジクロロジシアノベンゾキノン（ＤＤＱ）、テトラシアノキノジメタン、テトラシアノアザナフタレン等が挙げられる。
Examples of organic acids include alkylbenzene sulfonic acid, alkyl naphthalene sulfonic acid, alkyl naphthalene disulfonic acid, naphthalene sulfonic acid formalin polycondensate, melamine sulfonic acid formalin polycondensate, naphthalene disulfonic acid, naphthalene trisulfonic acid, dinaphthylmethane disulfonic acid, Anthraquinone sulfonic acid, anthraquinone disulfonic acid, anthracene sulfonic acid, pyrene sulfonic acid and the like can be mentioned. These metal salts can also be used.
As the organic cyano compound, a compound containing two or more cyano groups in a conjugated bond can be used. Examples include tetracyanoethylene, tetracyanoethylene oxide, tetracyanobenzene, dichlorodicyanobenzoquinone (DDQ), tetracyanoquinodimethane, and tetracyanoazanaphthalene.
π共役系導電性高分子とドーパントとの割合は、モル比としてπ共役系導電性高分子：ドーパントが９７：３〜１０：９０であることが好ましい。ドーパントがこれより多くても少なくても導電性が低下する傾向にある。 The ratio of the π-conjugated conductive polymer to the dopant is preferably 97: 3 to 10:90 as a molar ratio of π-conjugated conductive polymer: dopant. Even if there are more or less dopants, the conductivity tends to decrease.
導電性高分子溶液に使用できる溶媒としては特に限定されず、メタノール、エタノール、イソプロピルアルコール（ＩＰＡ）などのアルコール系溶媒、Ｎ−メチルピロリドン（ＮＭＰ）、ジメチルアセトアミド（ＤＭＡｃ）、ジメチルホルムアミド（ＤＭＦ）などのアミド系溶媒、メチルエチルケトン（ＭＥＫ）、アセトン、シクロヘキサノンなどのケトン系溶媒、酢酸エチル、酢酸ブチルのようなエステル系溶媒、トルエン、キシレン、水などが挙げられ、これらを単独で使用してもよいし混合して使用してもよい。中でも、近年の環境保護の観点から、環境負荷の小さい水やアルコール系溶媒が好ましい。 The solvent that can be used in the conductive polymer solution is not particularly limited, and alcohol solvents such as methanol, ethanol, isopropyl alcohol (IPA), N-methylpyrrolidone (NMP), dimethylacetamide (DMAc), dimethylformamide (DMF) Examples include amide solvents such as methyl ethyl ketone (MEK), ketone solvents such as acetone and cyclohexanone, ester solvents such as ethyl acetate and butyl acetate, toluene, xylene, water, and the like. They may be used or mixed. Among these, from the viewpoint of environmental protection in recent years, water and alcohol solvents having a low environmental load are preferable.
上記導電性高分子溶液を塗布する方法としては、例えば、コーティング、浸漬、スプレーなどの公知の手法が挙げられる。また、溶媒を除去するための乾燥方法としては、熱風乾燥など公知の手法が挙げられる。 Examples of the method for applying the conductive polymer solution include known methods such as coating, dipping, and spraying. Moreover, well-known methods, such as hot air drying, are mentioned as a drying method for removing a solvent.
固体電解質層を形成した後には、必要に応じて電解液を浸透させ、次いで、カーボンペースト、銀ペーストを塗布して陰極導電層を形成する方法や、セパレータを介してアルミニウム箔などの陰極導電層を配置する公知の手法により陰極を形成して、コンデンサを得ることができる。
セパレータを用いる場合には、セパレータとして、例えば、セルロース繊維、ガラス繊維、ポリプロピレン繊維、ポリエステル繊維、ポリアミド繊維などの単一又は混合不織布、これらを炭化した炭化不織布などが用いられる。
After forming the solid electrolyte layer, a method of forming a cathode conductive layer by impregnating an electrolytic solution as necessary and then applying a carbon paste or a silver paste, or a cathode conductive layer such as an aluminum foil via a separator A capacitor can be obtained by forming a cathode by a known method of arranging
When using a separator, as the separator, for example, a single or mixed nonwoven fabric such as cellulose fiber, glass fiber, polypropylene fiber, polyester fiber, polyamide fiber, carbonized nonwoven fabric obtained by carbonizing these, or the like is used.
上述したコンデンサの製造方法では、誘電体層表面に電子供与性化合物を塗布することにより、誘電体層と固体電解質層との電気的親和性を向上させることができ、コンデンサのインピーダンスを低くすることができる。しかも、電子供与性化合物の塗布は簡便である。したがって、上述したコンデンサの製造方法は、インピーダンスの低いコンデンサを簡便に製造できる。
さらに、この製造方法により得られたコンデンサは、容量が高く、耐熱性にも優れる。
In the capacitor manufacturing method described above, by applying an electron donating compound to the surface of the dielectric layer, the electrical affinity between the dielectric layer and the solid electrolyte layer can be improved, and the impedance of the capacitor can be lowered. Can do. Moreover, the application of the electron donating compound is simple. Therefore, the capacitor manufacturing method described above can easily manufacture a capacitor with low impedance.
Furthermore, the capacitor obtained by this manufacturing method has a high capacity and excellent heat resistance.
なお、本発明は、上述した実施形態例に限定されない。上述した実施形態例では、電子供与性化合物を誘電体層の表面に塗布し、固体電解質層を形成した後、導電陰極層を設けて陰極を形成してコンデンサを得たが、本発明では、陰極導電層を設けるタイミングは限定されない。例えば、陰極導電層を誘電体層に対向するように配置した後に、誘電体層の表面に電子供与性化合物を塗布し、次いで、固体電解質層を形成してもよい。その場合、陰極導電層と誘電体層との間に、セパレータを配置することが好ましい。
また、電子供与性化合物は誘電体層表面のみならず、陰極導電層の誘電体層側の表面、セパレータにも塗布されていても構わない。
Note that the present invention is not limited to the above-described embodiments. In the embodiment described above, an electron donating compound was applied to the surface of the dielectric layer, and after forming a solid electrolyte layer, a conductive cathode layer was provided to form a cathode to obtain a capacitor. The timing for providing the cathode conductive layer is not limited. For example, after disposing the cathode conductive layer so as to face the dielectric layer, an electron donating compound may be applied to the surface of the dielectric layer, and then the solid electrolyte layer may be formed. In that case, it is preferable to arrange a separator between the cathode conductive layer and the dielectric layer.
The electron donating compound may be applied not only to the surface of the dielectric layer, but also to the surface of the cathode conductive layer on the dielectric layer side and the separator.
以下、実施例により本発明をさらに詳しく説明する。
（実施例１）
（１）導電性高分子溶液の調製
１４．２ｇ（０．１ｍｏｌ）の３，４−エチレンジオキシチオフェンと、２７．５ｇ（０．１５ｍｏｌ）のポリスチレンスルホン酸（分子量；約１５０，０００）を２０００ｍｌのイオン交換水に溶かした溶液とを２０℃で混合した。
これにより得られた混合溶液を２０℃に保ち、掻き混ぜながら、２００ｍｌのイオン交換水に溶かした２９．６４ｇ（０．１３ｍｏｌ）の過硫酸アンモニウムと８．０ｇ（０．０２ｍｏｌ）の硫酸第二鉄の酸化触媒溶液とを添加し、３時間攪拌して反応させた。
得られた反応液を透析して、未反応モノマー、酸化剤を除去して約１．５質量％の青色のポリスチレンスルホン酸ドープポリ（３，４−エチレンジオキシチオフェン）を含む導電性高分子溶液を得た。
（２）電子供与性化合物溶液の調製
蒸留水１００ｍｌに７．７９ｇのイミダゾールを溶解させて電子供与性化合物溶液を得た。
Hereinafter, the present invention will be described in more detail with reference to examples.
Example 1
(1) Preparation of conductive polymer solution 14.2 g (0.1 mol) of 3,4-ethylenedioxythiophene and 27.5 g (0.15 mol) of polystyrene sulfonic acid (molecular weight; about 150,000) A solution dissolved in 2000 ml of ion-exchanged water was mixed at 20 ° C.
29.64 g (0.13 mol) of ammonium persulfate and 8.0 g (0.02 mol) of ferric sulfate dissolved in 200 ml of ion-exchanged water were kept at 20 ° C. while stirring the mixed solution thus obtained. The oxidation catalyst solution was added and stirred for 3 hours to react.
The resulting reaction solution is dialyzed to remove unreacted monomers and oxidants, and a conductive polymer solution containing about 1.5% by weight of blue polystyrenesulfonic acid-doped poly (3,4-ethylenedioxythiophene). Got.
(2) Preparation of electron donating compound solution 7.79 g of imidazole was dissolved in 100 ml of distilled water to obtain an electron donating compound solution.
（３）コンデンサの製造
エッチドアルミニウム箔に陽極リード端子を接続した後、アジピン酸アンモニウム１０質量％水溶液中で化成（酸化処理）して、アルミニウム箔表面に誘電体層を形成して陽極箔を得た。
次に、この陽極箔と、陰極リード端子を溶接させた対向アルミ陰極箔との間に、セルロール製のセパレータを挟み、円筒状に巻き取ってコンデンサ素子を得た。
次いで、（２）で調製した電子供与性化合物溶液にコンデンサ素子を、減圧下で浸漬した後、１２０℃の熱風乾燥機で２分間乾燥し、続いて、（１）で調製した導電性高分子溶液にコンデンサ素子を減圧下で浸漬した後、１５０℃の熱風乾燥機で１０分間乾燥した。そして、導電性高分子溶液への浸漬を５回繰り返して、誘電体層表面にπ共役系導電性高分子を含む固体電解質層を形成させた。
次いで、アルミニウム製のケースに、固体電解質層が形成されたコンデンサ素子を装填し、封口ゴムで封止して、コンデンサを作製した。
作製したコンデンサについて、ＬＣＺメータ２３５３（エヌエフ回路設計ブロック社製）を用いて、１２０Ｈｚでの静電容量、１００ｋＨｚでの等価直列抵抗（ＥＳＲ）の初期値、１２５℃、１０００時間後のＥＳＲを測定した。それらの結果を表１に示す。なお、ＥＳＲはインピーダンスの指標となる。
(3) Manufacture of capacitor After connecting the anode lead terminal to the etched aluminum foil, it was formed (oxidized) in an aqueous solution of 10% by weight of ammonium adipate to form a dielectric layer on the surface of the aluminum foil to form the anode foil. Obtained.
Next, a separator made of cell roll was sandwiched between the anode foil and the opposed aluminum cathode foil to which the cathode lead terminal was welded, and wound into a cylindrical shape to obtain a capacitor element.
Next, after immersing the capacitor element in the electron donating compound solution prepared in (2) under reduced pressure, the capacitor element is dried for 2 minutes in a hot air dryer at 120 ° C., and then the conductive polymer prepared in (1). The capacitor element was immersed in the solution under reduced pressure, and then dried for 10 minutes with a hot air dryer at 150 ° C. Then, immersion in the conductive polymer solution was repeated five times to form a solid electrolyte layer containing a π-conjugated conductive polymer on the surface of the dielectric layer.
Next, a capacitor element on which a solid electrolyte layer was formed was loaded into an aluminum case and sealed with a sealing rubber to produce a capacitor.
Using the LCZ meter 2353 (manufactured by NF Circuit Design Block Co., Ltd.), measured the capacitance at 120 Hz, the initial value of the equivalent series resistance (ESR) at 100 kHz, and the ESR after 1000 hours at 125 ° C. did. The results are shown in Table 1. Note that ESR is an index of impedance.
（実施例２）
電子供与性化合物溶液として、蒸留水１００ｍｌに７．７９ｇのイミダゾールを溶解させた溶液の代わりに、メチルエチルケトン１００ｍｌに１０ｇのピロールを溶解させて得た溶液を用いたこと以外は実施例１と同様にしてコンデンサを得た。そして、実施例１と同様にして評価した。評価結果を表１に示す。
(Example 2)
The same procedure as in Example 1 was used except that a solution obtained by dissolving 10 g of pyrrole in 100 ml of methyl ethyl ketone was used as an electron donating compound solution instead of a solution obtained by dissolving 7.79 g of imidazole in 100 ml of distilled water. To obtain a capacitor. And it evaluated similarly to Example 1. FIG. The evaluation results are shown in Table 1.
（比較例１）
実施例１のコンデンサの作製において、電子供与性化合物溶液にコンデンサ素子を浸漬しなかったこと以外は実施例１と同様にしてコンデンサを作製した。そして、実施例１と同様にして評価した。評価結果を表１に示す。
(Comparative Example 1)
A capacitor was produced in the same manner as in Example 1 except that the capacitor element was not immersed in the electron donating compound solution in the production of the capacitor of Example 1. And it evaluated similarly to Example 1. FIG. The evaluation results are shown in Table 1.
誘電体層表面に電子供与性化合物を塗布した実施例１，２のコンデンサは、静電容量が高く、ＥＳＲが低かった（インピーダンスが低かった）。しかも、加熱後のＥＳＲの低下が防止されており、耐熱性にも優れていた。
これに対し、誘電体層表面に電子供与性化合物を塗布しなかった比較例１のコンデンサは、静電容量が低く、ＥＳＲが高かった（インピーダンスが高かった）。また、加熱後、ＥＳＲが大幅に上昇しており、耐熱性が低かった。
The capacitors of Examples 1 and 2 in which the electron donating compound was applied to the surface of the dielectric layer had high capacitance and low ESR (impedance was low). In addition, a decrease in ESR after heating was prevented, and heat resistance was excellent.
On the other hand, the capacitor of Comparative Example 1 in which the electron donating compound was not applied to the surface of the dielectric layer had a low capacitance and a high ESR (high impedance). Moreover, after heating, ESR was significantly increased and the heat resistance was low.
１０ コンデンサ（固体電解コンデンサ）
１１ 陽極
１２ 誘電体層
１３ 陰極
１３ａ 固体電解質層（π共役系導電性高分子を含む層）
10 Capacitor (solid electrolytic capacitor)
11
Claims (1)
少なくとも該誘電体層の表面に、電子供与性元素を含む電子供与性化合物を塗布する工程と、
電子供与性化合物が塗布された誘電体層表面に、π共役系導電性高分子およびポリアニオンを含む導電性高分子溶液を塗布して、π共役系導電性高分子を含む固体電解質層を形成する工程とを有し、
電子供与性化合物が、芳香族アミン、リン酸エステル類、アルキルホスフィン類、サルファイド類、チオール類、イソチオシアナート類から選ばれることを特徴とする固体電解コンデンサの製造方法。 Oxidizing the surface of the anode made of a porous body of valve metal to form a dielectric layer;
Applying an electron donating compound containing an electron donating element to at least the surface of the dielectric layer;
A conductive polymer solution containing a π-conjugated conductive polymer and a polyanion is applied to the surface of the dielectric layer coated with the electron-donating compound to form a solid electrolyte layer containing the π-conjugated conductive polymer. It possesses a step,
A method for producing a solid electrolytic capacitor, wherein the electron donating compound is selected from aromatic amines, phosphate esters, alkylphosphines, sulfides, thiols, and isothiocyanates .
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005096599A JP4762587B2 (en) | 2005-03-30 | 2005-03-30 | Manufacturing method of solid electrolytic capacitor |
| PCT/JP2005/015482 WO2006025262A1 (en) | 2004-08-30 | 2005-08-25 | Conductive composition and conductive crosslinked material, capacitor and method for manufacturing same, antistatic coating composition, antistatic coat, antistatic film, optical filter and optical information recording medium |
| TW094129034A TWI303832B (en) | 2004-08-30 | 2005-08-25 | Conductive composition and conductive cross-linked product, capacitor and production method thereof, and antistatic coating material, antistatic coating, antistatic film, optical filter, bnd optical information recording medium |
| US11/211,557 US7666326B2 (en) | 2004-08-30 | 2005-08-25 | 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 |
| CN2005800345932A CN101040002B (en) | 2004-08-30 | 2005-08-25 | Conductive composition and conductive crosslinked material, capacitor and method for manufacturing same, antistatic coating composition, antistatic coat, antistatic film, optical filter and optical information recording medium |
| US12/645,022 US8097184B2 (en) | 2004-08-30 | 2009-12-22 | 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 |
| US12/644,858 US8551366B2 (en) | 2004-08-30 | 2009-12-22 | 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 |
| US13/296,456 US8388866B2 (en) | 2004-08-30 | 2011-11-15 | 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 |
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| US7515396B2 (en) * | 2007-03-21 | 2009-04-07 | Avx Corporation | Solid electrolytic capacitor containing a conductive polymer |
| JP2009009998A (en) * | 2007-06-26 | 2009-01-15 | Shin Etsu Polymer Co Ltd | Capacitor and manufacturing method thereof |
| JP5305774B2 (en) * | 2007-09-21 | 2013-10-02 | 三洋電機株式会社 | Solid electrolytic capacitor |
| WO2014136796A1 (en) * | 2013-03-05 | 2014-09-12 | 昭和電工株式会社 | Solid electrolyte capacitor and method for producing same |
| JP2015023123A (en) * | 2013-07-18 | 2015-02-02 | カーリットホールディングス株式会社 | Method for manufacturing solid electrolytic capacitor |
| JP6462255B2 (en) * | 2014-07-14 | 2019-01-30 | テイカ株式会社 | Electrolytic capacitor and manufacturing method thereof |
| JP7445875B2 (en) * | 2019-02-28 | 2024-03-08 | パナソニックＩｐマネジメント株式会社 | Electrode foil for electrolytic capacitors, electrolytic capacitors and their manufacturing method |
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| JP3068430B2 (en) * | 1995-04-25 | 2000-07-24 | 富山日本電気株式会社 | Solid electrolytic capacitor and method of manufacturing the same |
| JP3551108B2 (en) * | 1999-09-14 | 2004-08-04 | 松下電器産業株式会社 | Conductive composition precursor, conductive composition, and method for producing solid electrolytic capacitor |
| JP2003289016A (en) * | 2002-03-28 | 2003-10-10 | Nippon Chemicon Corp | Manufacturing method for solid electrolytic capacitor |
| JP2004253537A (en) * | 2003-02-19 | 2004-09-09 | Matsushita Electric Ind Co Ltd | Solid electrolytic capacitor |
| DK1524678T3 (en) * | 2003-10-17 | 2009-11-02 | Starck H C Gmbh | Electrolyte capacitors with polymeric outer layers |
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