JPH0474853B2 - - Google Patents
Info
- Publication number
- JPH0474853B2 JPH0474853B2 JP62004053A JP405387A JPH0474853B2 JP H0474853 B2 JPH0474853 B2 JP H0474853B2 JP 62004053 A JP62004053 A JP 62004053A JP 405387 A JP405387 A JP 405387A JP H0474853 B2 JPH0474853 B2 JP H0474853B2
- Authority
- JP
- Japan
- Prior art keywords
- conductive polymer
- film
- mol
- electrolytic
- capacitor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000003990 capacitor Substances 0.000 claims description 33
- 229920001940 conductive polymer Polymers 0.000 claims description 27
- 238000006116 polymerization reaction Methods 0.000 claims description 25
- 229920000128 polypyrrole Polymers 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 15
- 230000003647 oxidation Effects 0.000 claims description 11
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- 239000007784 solid electrolyte Substances 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- 239000007800 oxidant agent Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 229910052715 tantalum Inorganic materials 0.000 claims description 6
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 5
- 239000012528 membrane Substances 0.000 claims description 4
- 239000010408 film Substances 0.000 description 35
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 12
- 230000001590 oxidative effect Effects 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- -1 difluorosulfonyl peroxide Chemical class 0.000 description 10
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 10
- 239000010409 thin film Substances 0.000 description 10
- 239000000178 monomer Substances 0.000 description 9
- 239000011888 foil Substances 0.000 description 8
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 239000010407 anodic oxide Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 5
- 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 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000003115 supporting electrolyte Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 150000002391 heterocyclic compounds Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000615 nonconductor Substances 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 2
- WFMGQHBNGMIKCM-UHFFFAOYSA-M phenylmethanesulfonate;tetrabutylazanium Chemical compound [O-]S(=O)(=O)CC1=CC=CC=C1.CCCC[N+](CCCC)(CCCC)CCCC WFMGQHBNGMIKCM-UHFFFAOYSA-M 0.000 description 2
- OBCUTHMOOONNBS-UHFFFAOYSA-N phosphorus pentafluoride Chemical compound FP(F)(F)(F)F OBCUTHMOOONNBS-UHFFFAOYSA-N 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- 229920000414 polyfuran Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920000123 polythiophene Polymers 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- XTHPWXDJESJLNJ-UHFFFAOYSA-N sulfurochloridic acid Chemical compound OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 2
- 229910001936 tantalum oxide Inorganic materials 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- HWTDMFJYBAURQR-UHFFFAOYSA-N 80-82-0 Chemical class OS(=O)(=O)C1=CC=CC=C1[N+]([O-])=O HWTDMFJYBAURQR-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910021630 Antimony pentafluoride Inorganic materials 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- VBVBHWZYQGJZLR-UHFFFAOYSA-I antimony pentafluoride Chemical compound F[Sb](F)(F)(F)F VBVBHWZYQGJZLR-UHFFFAOYSA-I 0.000 description 1
- YBGKQGSCGDNZIB-UHFFFAOYSA-N arsenic pentafluoride Chemical compound F[As](F)(F)(F)F YBGKQGSCGDNZIB-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
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- PYRZPBDTPRQYKG-UHFFFAOYSA-N cyclopentene-1-carboxylic acid Chemical compound OC(=O)C1=CCCC1 PYRZPBDTPRQYKG-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- ZRZKFGDGIPLXIB-UHFFFAOYSA-N fluoroform;sulfuric acid Chemical compound FC(F)F.OS(O)(=O)=O ZRZKFGDGIPLXIB-UHFFFAOYSA-N 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- CBEQRNSPHCCXSH-UHFFFAOYSA-N iodine monobromide Chemical compound IBr CBEQRNSPHCCXSH-UHFFFAOYSA-N 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 description 1
- KVBGVZZKJNLNJU-UHFFFAOYSA-N naphthalene-2-sulfonic acid Chemical compound C1=CC=CC2=CC(S(=O)(=O)O)=CC=C21 KVBGVZZKJNLNJU-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- PVGBHEUCHKGFQP-UHFFFAOYSA-N sodium;n-[5-amino-2-(4-aminophenyl)sulfonylphenyl]sulfonylacetamide Chemical compound [Na+].CC(=O)NS(=O)(=O)C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 PVGBHEUCHKGFQP-UHFFFAOYSA-N 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003481 tantalum Chemical class 0.000 description 1
- 125000005207 tetraalkylammonium group Chemical group 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
Classifications
-
- 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
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Oscillators With Electromechanical Resonators (AREA)
- Glass Compositions (AREA)
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は導電性高分子を固体電解質として用い
たコンデンサに関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a capacitor using a conductive polymer as a solid electrolyte.
（従来の技術）
近年デジタル機器の発展に伴ない、高周波領域
においてインピーダンスの低い高周特性の優れた
大容量のコンデンサの出現が待たれ、この分野の
研究が盛んになつている。現在知られている高周
波特性の優れたコンデンサには、フイルム、マイ
カ、セラミツクス等のコンデンサがあるが、1μF
以上の静電容量を得ようとすると、サイズが大き
くなり、価格も非常に高くなる。(Prior Art) In recent years, with the development of digital equipment, the emergence of large-capacity capacitors with low impedance and excellent high-frequency characteristics in the high-frequency region has been awaited, and research in this field has become active. Currently known capacitors with excellent high frequency characteristics include capacitors made of film, mica, ceramics, etc.
Attempting to obtain a larger capacitance would result in a larger size and a significantly higher price.
また大容量のコンデンサとして知られている電
解コンデンサには電解液式と固体式とがある。前
者の電解コンデンサは液状の電解質を用いている
のでイオン伝導であるため、高周波領域において
著しく抵抗が増大し、コンデンサのインピーダン
スが増大する。後者の電解コンデンサには、固体
電解質として、二酸化マンガンを使用するもの
と、７，７，８，８−テトラシアノキノジメタン
（TCNQと略す）錯体を使用するものがある。二
酸化マンガンを固体電解質として用いたコンデン
サにおいては、二酸化マンガンが不溶の固体であ
るため、硝酸マンガンを熱分解して得られる二酸
化マンガンが固体電解質として用いられている。
この熱分解は、通常数回繰り返して行なわれてい
る。二酸化マンガンは比抵抗が比較的高く、また
繰り返して熱分解する際に誘電体である酸化皮膜
を損傷しやすいなどの理由によりインピーダンス
が高く、漏れ電流が大きいなどの欠点がある。
TCNQ錯体を固体電解質として用いたコンデン
サ（特開昭58−191414号、特開昭58−17609号な
ど）では、TCNQ錯体は高い導電性を示すが、
熱安定性に乏しいため、コンデンサ製造過程にお
いて分解し、絶縁体になることがあり、コンデン
サの熱特性などに欠点がある。 Furthermore, electrolytic capacitors, which are known as large-capacity capacitors, include electrolyte type and solid type. The former electrolytic capacitor uses a liquid electrolyte and is ionic conductive, so the resistance increases significantly in the high frequency range and the impedance of the capacitor increases. The latter electrolytic capacitors include those that use manganese dioxide and those that use 7,7,8,8-tetracyanoquinodimethane (abbreviated as TCNQ) complex as a solid electrolyte. In capacitors using manganese dioxide as a solid electrolyte, since manganese dioxide is an insoluble solid, manganese dioxide obtained by thermally decomposing manganese nitrate is used as the solid electrolyte.
This thermal decomposition is usually repeated several times. Manganese dioxide has drawbacks such as high impedance and large leakage current due to its relatively high resistivity and its tendency to damage the dielectric oxide film during repeated thermal decomposition.
In capacitors using TCNQ complexes as solid electrolytes (JP-A-58-191414, JP-A-58-17609, etc.), the TCNQ complex shows high conductivity.
Due to its poor thermal stability, it may decompose during the capacitor manufacturing process and become an insulator, which has disadvantages in the capacitor's thermal characteristics.
まだ実用の域には達していないが電解重合によ
る複素環式化合物の重合体を固体電解質としたコ
ンデンサの製造法が提案された（特開昭60−
244017、特開昭61−2315など）。上記方法は、陽
極酸化皮膜上に電解酸化により複素環式化合物の
ポリマー薄膜層を形成する方法である。この方法
では、陽極酸化皮膜層が絶縁化されているので、
電解酸化により陽極酸化皮膜層上に複素環式化合
物を電解重合させることは不可能か、又は非常に
困難である。また陽極酸化皮膜層のピンホールか
ら電解酸化重合が起こつたとしても不均一な膜と
なり、実用上大きな問題となる。 Although it has not yet reached the level of practical use, a method for manufacturing capacitors using electrolytic polymerization of a polymer of a heterocyclic compound as a solid electrolyte has been proposed (Japanese Patent Application Laid-Open No. 1989-1999).
244017, JP-A-61-2315, etc.). The above method is a method of forming a polymer thin film layer of a heterocyclic compound on an anodic oxide film by electrolytic oxidation. In this method, the anodic oxide film layer is insulated, so
It is impossible or very difficult to electrolytically polymerize a heterocyclic compound onto an anodic oxide film layer by electrolytic oxidation. Further, even if electrolytic oxidation polymerization occurs through pinholes in the anodic oxide film layer, the film will be non-uniform, which poses a serious problem in practice.
（発明が解決しようとする問題点）
導電性高分子の合成法は化学的酸化重合法およ
び電解酸化重合法があるが、化学的酸化重合法で
は陽極酸化皮膜層上に強度の強い膜が形成でき
ず、また電解酸化重合法法では陽極酸化皮膜層が
電気絶縁体であるため、電流を通さず、その上に
強靭な導電性高分子膜を形成することができなか
つた。本発明の目的は電解重合法により得られた
導電性高分子膜を固体電解質として使用し、静電
容量が大きくかつ電気的特性、温度特性の優れた
固体電解コンデンサを提供することにある。(Problem to be solved by the invention) There are two methods for synthesizing conductive polymers: chemical oxidative polymerization and electrolytic oxidative polymerization. However, in chemical oxidative polymerization, a strong film is formed on the anodic oxide film layer. Moreover, in the electrolytic oxidation polymerization method, since the anodic oxide film layer is an electrical insulator, it does not conduct current, and it was not possible to form a strong conductive polymer film thereon. An object of the present invention is to provide a solid electrolytic capacitor that uses a conductive polymer membrane obtained by an electrolytic polymerization method as a solid electrolyte and has a large capacitance and excellent electrical characteristics and temperature characteristics.
（問題点を解決するための手段）
本発明者らは上記問題点を解決するため種々検
討した結果、皮膜形成金属に誘電体酸化皮膜を形
成し、該誘電体酸化皮膜上に、酸化剤を用いて化
学酸化重合した導電性高分子膜を形成し、更に該
導電性高分子膜の上に、電解重合法により得られ
る導電性高分子膜を積層して、二重に形成された
導電性高分子膜を固体電解質として用いることに
より、静電容量の大きくかつ電気特性、温度特性
の優れた固体電解コンデンサを提供することがで
きた。(Means for Solving the Problems) As a result of various studies to solve the above problems, the present inventors formed a dielectric oxide film on the film-forming metal, and applied an oxidizing agent on the dielectric oxide film. A conductive polymer film obtained by chemical oxidation polymerization is formed using a conductive polymer film, and then a conductive polymer film obtained by an electrolytic polymerization method is laminated on top of the conductive polymer film to form a double-formed conductive polymer film. By using a polymer membrane as a solid electrolyte, it was possible to provide a solid electrolytic capacitor with large capacitance and excellent electrical and temperature characteristics.
本発明を本発明の構成を示す第１図により更に
詳しく説明すると、エツチングして表面を粗した
皮膜形成金属１を電解酸化または空気酸化により
該金属の酸化物を生成させ、誘電体酸化皮膜２を
形成する。ついで誘電体酸化皮膜２上に、酸化剤
を0.001mol／１〜〜2mol／１含む溶液を塗布ま
たは噴霧などの方法により均一に分散した後導電
性高分子の単量体を少なくとも0.01mol／１含む
溶液または無溶媒で接触させるか、または逆に導
電性高分子の単量体を誘電体表面上に均一に分散
した後酸化剤を接触させて、誘電体酸化皮膜２上
に化学酸化重合による導電性高分子膜３を形成
し、表面を導電化する。ついで形成した導電性高
分子膜３を陽極とし、支持電解質を0.01mol／１
〜2mol／１および導電性高分子単量体を
0.01mol／１〜5mol／１含む電解液中にて電解酸
化重合を行なうと、酸化剤を用いて重合した導電
性高分子膜３の上に、電解酸化重合された強靭な
導電性高分子膜４が得られる。更に一般的に用い
られている銀ペーストなどにより対極リードを取
り出し、エポキシ樹脂などにより外装すると本発
明のコンデンサとなる。 To explain the present invention in more detail with reference to FIG. 1 showing the structure of the present invention, a film-forming metal 1 whose surface has been roughened by etching is electrolytically oxidized or air oxidized to generate an oxide of the metal, and a dielectric oxide film 2 is formed. form. Next, a solution containing 0.001 mol/1 to 2 mol/1 of an oxidizing agent is uniformly dispersed on the dielectric oxide film 2 by a method such as coating or spraying, and then at least 0.01 mol/1 of a conductive polymer monomer is applied to the dielectric oxide film 2. The conductive polymer monomer is uniformly dispersed on the dielectric surface, and then an oxidizing agent is brought into contact with the dielectric oxide film 2 by chemical oxidation polymerization. A conductive polymer film 3 is formed to make the surface conductive. Next, the formed conductive polymer film 3 was used as an anode, and the supporting electrolyte was 0.01 mol/1.
~2mol/1 and conductive polymer monomer
When electrolytic oxidative polymerization is performed in an electrolytic solution containing 0.01 mol/1 to 5 mol/1, a strong conductive polymer film that has been electrolytically oxidized and polymerized is formed on the conductive polymer film 3 that has been polymerized using an oxidizing agent. 4 is obtained. Furthermore, the counter electrode lead is taken out using commonly used silver paste or the like, and then covered with epoxy resin or the like to obtain the capacitor of the present invention.
本発明の皮膜形成金属はアルミニウムまたはタ
ンタルを用いる。本発明の化学的酸化重合に用い
られる酸化剤は、ヨウ素、臭素、ヨウ化臭素など
のハロゲン、五フツ化ヒ素、五フツ化アンチモ
ン、四フツ化ケイ素、五塩化リン、五フツ化リ
ン、塩化アルミニウム、塩化モリブデンなどの金
属ハロゲン化物、硫酸、硝酸、フルオロ硫酸、ト
リフルオロメタン硫酸、クロロ硫酸などのプロト
ン酸、三酸化イオウ、二酸化窒素などの含酸素化
合物、過硫酸ナトリウム、過硫酸カリウム、過硫
酸アンモニウムなどの過硫酸塩、過酸化水素、過
酢酸、ジフルオロスルホニルパーオキサイドなど
の過酸化物などの酸化剤を用いる。本発明の化学
的酸化重合により形成される導電性高分子膜は、
ポリピロール、ポリチオフエン、ポリアニリン、
ポリフランを用い、特に好ましくはポリピロール
を用いる。 The film-forming metal of the present invention is aluminum or tantalum. The oxidizing agents used in the chemical oxidative polymerization of the present invention include halogens such as iodine, bromine, and bromine iodide, arsenic pentafluoride, antimony pentafluoride, silicon tetrafluoride, phosphorus pentafluoride, phosphorus pentafluoride, and chloride. Metal halides such as aluminum and molybdenum chloride, protic acids such as sulfuric acid, nitric acid, fluorosulfuric acid, trifluoromethanesulfuric acid, and chlorosulfuric acid, oxygenated compounds such as sulfur trioxide and nitrogen dioxide, sodium persulfate, potassium persulfate, and ammonium persulfate. Oxidizing agents such as persulfates, hydrogen peroxide, peracetic acid, difluorosulfonyl peroxide, and other peroxides are used. The conductive polymer film formed by chemical oxidative polymerization of the present invention is
polypyrrole, polythiophene, polyaniline,
Polyfuran is used, particularly preferably polypyrrole.
本発明における支持電解質は陰イオンがヘキサ
フロロリン、ヘキサフロロヒ素、テトラフロロホ
ウ素などのハロゲン化物アニオワ、ヨウ素、臭
素、塩素などのハロゲンアニオン、過塩素酸アニ
オン、アルキルベンゼンスルホン酸、ニトロベン
ゼンスルホン酸、アミノベンゼンスルホン酸、ベ
ンゼンスルホン酸、β−ナフタレンスルホン酸等
のスルホン酸アニオンであり、好ましくはスルホ
ン酸アニオンである。また陽イオンがリチウム、
ナトリウム、カリウムなどのアルカリ金属カチオ
ン、アンモニウム、テトラアルキルアンモニウム
などの四級アンモニウムカチオンである。化合物
としては、LiPF6、LiAsF6、LiCIO4、NaI、
NaPF6、NaCIO、KI、KPF6、KASF6、
KCIO4、LiBF4、トルエンスルホン酸ナトリウ
ム、トルエンスルホン酸テトラブチルアンモニウ
ムなどを掲げることができる。 The supporting electrolyte in the present invention includes anions such as halides such as hexafluoroline, hexafluoroarsenic, and tetrafluoroborine, halogen anions such as iodine, bromine, and chlorine, perchlorate anions, alkylbenzenesulfonic acids, nitrobenzenesulfonic acids, and aminobenzenes. Sulfonic acid anions such as sulfonic acid, benzenesulfonic acid, and β-naphthalenesulfonic acid, preferably sulfonic acid anions. Also, the cation is lithium,
These are alkali metal cations such as sodium and potassium, and quaternary ammonium cations such as ammonium and tetraalkylammonium. Compounds include LiPF 6 , LiAsF 6 , LiCIO 4 , NaI,
NaPF 6 , NaCIO, KI, KPF 6 , KASF 6 ,
Examples include KCIO 4 , LiBF 4 , sodium toluenesulfonate, and tetrabutylammonium toluenesulfonate.
本発明の電解酸化重合により得られる導電性高
分子はポリピロール、ポリチオフエン、ポリアニ
リン、ポリフランを用い、好ましくはポリピロー
ルを用いる。 The conductive polymer obtained by electrolytic oxidative polymerization of the present invention includes polypyrrole, polythiophene, polyaniline, and polyfuran, preferably polypyrrole.
以下実施例により本発明を具体的に説明する
が、本発明はこれらの実施例に限定されるもので
はない。 EXAMPLES The present invention will be specifically explained below with reference to Examples, but the present invention is not limited to these Examples.
実施例 １
電解酸化により化成処理を施して表面に酸化ア
ルミニウム誘電体を形成させた厚さ60μmのアル
ミニウム箔を、過硫酸アンモニウム0.04mol／ｌ
の水溶液に減圧下で10分間浸漬した後、乾燥し
た。これをピロール単量体2mol／ｌを含むアセ
トニトリル溶液に減圧下で10分間浸漬して、酸化
アルミニウム誘電体上にポリピロール薄膜を化学
酸化重合法により形成させた。ついで上記処理を
行なつたアルミニウム箔をピロール単量体
0.2mol／ｌ、シユウ酸0.02mol／ｌおよび支持電
解質としてトルエンスルホン酸テトラブチルアン
モニウム0.05mol／ｌを含む水溶液中に浸漬し
た。該アルミニウム箔上に形成したポリピロール
薄膜を陽極とし、ステンレス板を陰極として電流
密度0.5mA／cm2の条件下で150分間定電流電解を
行なつた結果、均一な黒色のポリピロールの薄膜
が表面に生成した。ついでこの表面に銀ペースト
を用いて対極リードを取り出し、エポキシ樹脂に
より外装しコンデンサを完成させた。得られたコ
ンデンサは120Hzにおいて静電容量2.2μF／cm2で損
失角の正接（tanδ）は1.5％であつた。なおこの
箔の液中容量は2.0μF／cm2であるので110％の容量
達成率であつた。Example 1 A 60 μm thick aluminum foil that had been chemically treated by electrolytic oxidation to form an aluminum oxide dielectric on its surface was treated with 0.04 mol/l of ammonium persulfate.
After being immersed in an aqueous solution of for 10 minutes under reduced pressure, it was dried. This was immersed in an acetonitrile solution containing 2 mol/l of pyrrole monomer under reduced pressure for 10 minutes to form a polypyrrole thin film on the aluminum oxide dielectric by chemical oxidative polymerization. Then, the aluminum foil subjected to the above treatment is treated with pyrrole monomer.
0.2 mol/l, 0.02 mol/l of oxalic acid, and 0.05 mol/l of tetrabutylammonium toluenesulfonate as a supporting electrolyte. Using the polypyrrole thin film formed on the aluminum foil as an anode and the stainless steel plate as a cathode, constant current electrolysis was performed for 150 minutes at a current density of 0.5 mA/cm 2 , resulting in a uniform black polypyrrole thin film on the surface. generated. Next, silver paste was applied to this surface to take out the counter electrode lead, which was then covered with epoxy resin to complete the capacitor. The capacitor obtained had a capacitance of 2.2 μF/cm 2 at 120 Hz and a loss angle tangent (tan δ) of 1.5%. Note that since the liquid capacity of this foil was 2.0 μF/cm 2 , the capacity achievement rate was 110%.
比較例 １
アルミニウム箔上に化学酸化重合法によるポリ
ピロール薄膜を形成せずに実施例１に準じて電解
を行なつたが、酸化アルミニウム誘電体上の一部
にしかポリピロールが得られず、膜を形成するこ
とができなかつた。Comparative Example 1 Electrolysis was carried out according to Example 1 without forming a polypyrrole thin film by chemical oxidation polymerization on aluminum foil, but polypyrrole was obtained only on a part of the aluminum oxide dielectric, and the film was not formed. could not be formed.
実施例 ２
ヨウ素0.1mol／ｌを含むエチルエーテル溶液
を調製し、電解酸化により化成処理を施して表面
に酸化アルミニウム誘電体皮膜を形成させた厚さ
60μmのアルミニウム箔上に、先に調製したエチ
ルエーテル溶液を噴霧して乾燥した。上記処理を
行なつたアルミニウム箔をピロール単量体中に30
分間減圧下で浸漬し、化学酸化重合法により黒色
のポリピロール薄膜を形成した。以下実施例１に
準じてコンデンサを完成した。得られたコンデン
サは120Hzにおいて、静電容量2.0μF／cm2、tanδは
1.3％であつた。Example 2 An ethyl ether solution containing 0.1 mol/l of iodine was prepared, and a chemical conversion treatment was performed by electrolytic oxidation to form an aluminum oxide dielectric film on the surface.
The previously prepared ethyl ether solution was sprayed onto a 60 μm aluminum foil and dried. The aluminum foil treated above is placed in pyrrole monomer for 30 minutes.
A black polypyrrole thin film was formed by a chemical oxidative polymerization method by immersing the sample under reduced pressure for a minute. A capacitor was then completed according to Example 1. The obtained capacitor has a capacitance of 2.0μF/cm 2 at 120Hz, and tanδ is
It was 1.3%.
実施例 ３
電解酸化により化成処理を施して表面を酸化ア
ルミニウム誘電体皮膜を形成させた厚さ60μmの
アルミニウム箔を塩化第二鉄0.02mol／ｌを含む
水溶液に減圧下で２分間浸漬した後、乾燥した。
これをピロール単量体0.1mol／ｌを含む水溶液
に30分間浸漬し、化学酸化重合法により黒色のポ
リピロール薄膜を形成した。以下実施例１に準じ
てコンデンサを完成した。得られたコンデンサは
120Hzにおいて、静電容量2.1μF／cm2、tanδは1.8
％であつた。Example 3 A 60 μm thick aluminum foil that had been chemically treated by electrolytic oxidation to form an aluminum oxide dielectric film on its surface was immersed in an aqueous solution containing 0.02 mol/l of ferric chloride for 2 minutes under reduced pressure. Dry.
This was immersed in an aqueous solution containing 0.1 mol/l of pyrrole monomer for 30 minutes, and a black polypyrrole thin film was formed by chemical oxidative polymerization. A capacitor was then completed according to Example 1. The resulting capacitor is
At 120Hz, capacitance is 2.1μF/cm 2 and tanδ is 1.8
It was %.
実施例 ４
化成処理を施して表面に酸化タンタル誘電体皮
膜を形成させたタンタル焼結体を過硫酸アンモニ
ウム塩0.04mol／ｌの水溶液に減圧下で５分間浸
漬した後、乾燥した。これをピロール単量体
0.2mol／ｌおよびアジピン酸0.02mol／ｌを含む
水溶液に減圧下で10分間浸漬して、酸化タンタル
誘電体上にポリピロール薄膜を化学酸化重合法に
より形成させた。ついで上記処理を行なつたタン
タル焼結体をピロール単量体0.2mol／ｌ、シユ
ウ酸0.02mol／ｌおよび支持電解質として過塩素
酸リチウム0.05mol／ｌを含む水溶液中に浸漬し
た。該タンタル焼結体上に形成したポリピロール
薄膜を陽極とし、ステンレス板を陰極として、電
流密度0.5mA／cm2の条件下で150分間、定電流電
解を行なつた結果、均一な黒色のポリピロールの
薄膜が表面に生成した。ついでこの表面に銀ペー
ストを用いて対極リードを取り出し、エポキシ樹
脂により外装しコンデンサを完成させた。得られ
たコンデンサは120Hzにおいて、静電容量は
1.2μF／cm2であり、損失角の正接（tanδ）は1.0％
であつた。尚このタンタル焼結体の液中容量は
1.0μF／cm2であるので容量達成率は120％であつ
た。Example 4 A tantalum sintered body that had been subjected to a chemical conversion treatment to form a tantalum oxide dielectric film on its surface was immersed in an aqueous solution of ammonium persulfate salt of 0.04 mol/l under reduced pressure for 5 minutes, and then dried. This is pyrrole monomer
A polypyrrole thin film was formed on the tantalum oxide dielectric by a chemical oxidative polymerization method by immersing it in an aqueous solution containing 0.2 mol/l and adipic acid 0.02 mol/l under reduced pressure for 10 minutes. The tantalum sintered body subjected to the above treatment was then immersed in an aqueous solution containing 0.2 mol/l of pyrrole monomer, 0.02 mol/l of oxalic acid, and 0.05 mol/l of lithium perchlorate as a supporting electrolyte. Using the polypyrrole thin film formed on the tantalum sintered body as an anode and a stainless steel plate as a cathode, constant current electrolysis was performed for 150 minutes at a current density of 0.5 mA/cm 2 . As a result, uniform black polypyrrole was formed. A thin film formed on the surface. Next, silver paste was applied to this surface to take out the counter electrode lead, which was then covered with epoxy resin to complete the capacitor. The capacitance of the obtained capacitor at 120Hz is
1.2μF/cm 2 , and the loss angle tangent (tanδ) is 1.0%
It was hot. The liquid capacity of this tantalum sintered body is
Since it was 1.0 μF/cm 2 , the capacity achievement rate was 120%.
（発明の効果）
先に述べたように固体電解コンデンサの固体電
解質に有機半導体であるTCNQ錯体を用いると
電気特性とくに高周波特性の優れたコンデンサが
得られることがすでに知られているが、その熱安
定性および溶解性が悪いため製造上大きな問題と
なつている。また電気絶縁体である誘電体酸化皮
膜上に直接電解重合によつて得られる強靭な導電
性高分子膜を重合することは不可能であつたが本
発明により可能となり、導電性高分子膜を固体電
解質として用いた温度特性、電気特性の優れた固
体電解コンデンサを提供することができた。(Effects of the Invention) As mentioned above, it is already known that when a TCNQ complex, which is an organic semiconductor, is used as the solid electrolyte of a solid electrolytic capacitor, a capacitor with excellent electrical properties, especially high frequency properties, can be obtained. It poses a major manufacturing problem due to its poor stability and solubility. In addition, it has been impossible to polymerize a strong conductive polymer film obtained by direct electrolytic polymerization on a dielectric oxide film, which is an electrical insulator, but this invention has made it possible. We were able to provide a solid electrolytic capacitor that was used as a solid electrolyte and had excellent temperature and electrical characteristics.
第１図は本発明の固体電解コンデンサの構成を
示す概略断面図である。
１……皮膜形成金属、２……誘電体酸化皮膜、
３……化学酸化重合により形成した導電性高分子
膜、４……電解重合により得られた導電性高分子
膜。
FIG. 1 is a schematic sectional view showing the structure of a solid electrolytic capacitor of the present invention. 1...Film forming metal, 2...Dielectric oxide film,
3... Conductive polymer membrane formed by chemical oxidative polymerization, 4... Conductive polymer membrane obtained by electrolytic polymerization.
Claims (1)
誘電体酸化皮膜上に酸化剤を用いて化学酸化重合
した導電性高分子膜を形成し、更に該導電性高分
子膜上に電解重合により得られる導電性高分子膜
を積層して、二重に形成された導電性高分子膜を
固体電解質として用いることを特徴とする固体電
解コンデンサ。 ２ 皮膜形成金属がアルミニウムまたはタンタル
である特許請求の範囲第１項記載の固体電解コン
デンサ。 ３ 酸化剤を用いて化学酸化重合した導電性高分
子膜がポリピロールである特許請求の範囲第１項
記載の固体電解コンデンサ。 ４ 電解重合により得られる導電性高分子膜がポ
リピロールである特許請求の範囲第１項記載の固
体電解コンデンサ。[Scope of Claims] 1. A dielectric oxide film is formed on a film-forming metal, a conductive polymer film is formed on the dielectric oxide film by chemical oxidation polymerization using an oxidizing agent, and the conductive polymer A solid electrolytic capacitor characterized in that a conductive polymer film obtained by electrolytic polymerization is laminated on a membrane, and the double-formed conductive polymer film is used as a solid electrolyte. 2. The solid electrolytic capacitor according to claim 1, wherein the film-forming metal is aluminum or tantalum. 3. The solid electrolytic capacitor according to claim 1, wherein the conductive polymer film chemically oxidized and polymerized using an oxidizing agent is polypyrrole. 4. The solid electrolytic capacitor according to claim 1, wherein the conductive polymer film obtained by electrolytic polymerization is polypyrrole.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62004053A JPS63173313A (en) | 1987-01-13 | 1987-01-13 | Solid electrolytic capacitor |
| US07/138,591 US4780796A (en) | 1987-01-13 | 1987-12-28 | Solid electrolytic capacitor |
| DE8787119399T DE3773166D1 (en) | 1987-01-13 | 1987-12-30 | FIXED ELECTROLYTE CAPACITOR. |
| KR1019870015438A KR910009477B1 (en) | 1987-01-13 | 1987-12-30 | Solid electrolytic capacitor |
| EP87119399A EP0274755B1 (en) | 1987-01-13 | 1987-12-30 | Solid electrolytic capacitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62004053A JPS63173313A (en) | 1987-01-13 | 1987-01-13 | Solid electrolytic capacitor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63173313A JPS63173313A (en) | 1988-07-16 |
| JPH0474853B2 true JPH0474853B2 (en) | 1992-11-27 |
Family
ID=11574142
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62004053A Granted JPS63173313A (en) | 1987-01-13 | 1987-01-13 | Solid electrolytic capacitor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63173313A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012049574A (en) * | 2007-03-15 | 2012-03-08 | Sanyo Electric Co Ltd | Manufacturing method for solid electrolytic capacitor and solid electrolytic capacitor |
Families Citing this family (28)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0232521A (en) * | 1988-07-22 | 1990-02-02 | Marcon Electron Co Ltd | Solid electrolytic capacitor |
| JP2764938B2 (en) * | 1988-09-01 | 1998-06-11 | 松下電器産業株式会社 | Method for manufacturing solid electrolytic capacitor |
| JPH0297008A (en) * | 1988-10-04 | 1990-04-09 | Marcon Electron Co Ltd | Solid electrolytic capacitor and manufacture thereof |
| JPH02234410A (en) * | 1989-03-07 | 1990-09-17 | Shinei Tsushin Kogyo Kk | Manufacture of solid electrolytic capacitor |
| JP2826341B2 (en) * | 1989-05-13 | 1998-11-18 | 日本ケミコン株式会社 | Method for manufacturing solid electrolytic capacitor |
| JPH077740B2 (en) * | 1989-12-29 | 1995-01-30 | 松下電器産業株式会社 | Capacitor |
| JPH0736375B2 (en) * | 1991-04-05 | 1995-04-19 | 松下電器産業株式会社 | Method for manufacturing solid electrolytic capacitor |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6037114A (en) * | 1983-08-09 | 1985-02-26 | 昭和電工株式会社 | Solid electrolytic condenser |
| JPS60245209A (en) * | 1984-05-21 | 1985-12-05 | 日本ケミコン株式会社 | Capacitor |
| JPS6122613A (en) * | 1984-07-10 | 1986-01-31 | 昭和電工株式会社 | Solid electrolytic condenser |
| JPS6147625A (en) * | 1984-08-14 | 1986-03-08 | 昭和電工株式会社 | Solid electrolytic condenser |
| JPS62118511A (en) * | 1985-11-19 | 1987-05-29 | 昭和電工株式会社 | Manufacture of solid electrolytic capacitor |
-
1987
- 1987-01-13 JP JP62004053A patent/JPS63173313A/en active Granted
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6037114A (en) * | 1983-08-09 | 1985-02-26 | 昭和電工株式会社 | Solid electrolytic condenser |
| JPS60245209A (en) * | 1984-05-21 | 1985-12-05 | 日本ケミコン株式会社 | Capacitor |
| JPS6122613A (en) * | 1984-07-10 | 1986-01-31 | 昭和電工株式会社 | Solid electrolytic condenser |
| JPS6147625A (en) * | 1984-08-14 | 1986-03-08 | 昭和電工株式会社 | Solid electrolytic condenser |
| JPS62118511A (en) * | 1985-11-19 | 1987-05-29 | 昭和電工株式会社 | Manufacture of solid electrolytic capacitor |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012049574A (en) * | 2007-03-15 | 2012-03-08 | Sanyo Electric Co Ltd | Manufacturing method for solid electrolytic capacitor and solid electrolytic capacitor |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63173313A (en) | 1988-07-16 |
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