JP4329299B2 - Manufacturing method of solid electrolytic capacitor - Google Patents
Manufacturing method of solid electrolytic capacitor Download PDFInfo
- Publication number
- JP4329299B2 JP4329299B2 JP2002073627A JP2002073627A JP4329299B2 JP 4329299 B2 JP4329299 B2 JP 4329299B2 JP 2002073627 A JP2002073627 A JP 2002073627A JP 2002073627 A JP2002073627 A JP 2002073627A JP 4329299 B2 JP4329299 B2 JP 4329299B2
- Authority
- JP
- Japan
- Prior art keywords
- conductive polymer
- electrolyte layer
- solid electrolyte
- electrolytic capacitor
- solid electrolytic
- 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 - Fee Related
Links
- 239000003990 capacitor Substances 0.000 title claims description 63
- 239000007787 solid Substances 0.000 title claims description 36
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 229920001940 conductive polymer Polymers 0.000 claims description 49
- 239000007784 solid electrolyte Substances 0.000 claims description 33
- 239000010419 fine particle Substances 0.000 claims description 28
- 239000011888 foil Substances 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 21
- 238000011282 treatment Methods 0.000 claims description 19
- 239000006185 dispersion Substances 0.000 claims description 17
- 239000007800 oxidant agent Substances 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 239000000178 monomer Substances 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 11
- 125000000623 heterocyclic group Chemical group 0.000 claims description 10
- 239000004094 surface-active agent Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 6
- 238000005530 etching Methods 0.000 claims description 6
- 229920000128 polypyrrole Polymers 0.000 claims description 6
- 229920000767 polyaniline Polymers 0.000 claims description 5
- 229920000123 polythiophene Polymers 0.000 claims description 5
- 238000004804 winding Methods 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 11
- 229910052782 aluminium Inorganic materials 0.000 description 11
- 229920000728 polyester Polymers 0.000 description 9
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 8
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 8
- -1 polyethylene Polymers 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 7
- 229920005549 butyl rubber Polymers 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- 239000005020 polyethylene terephthalate Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 5
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- YMMGRPLNZPTZBS-UHFFFAOYSA-N 2,3-dihydrothieno[2,3-b][1,4]dioxine Chemical compound O1CCOC2=C1C=CS2 YMMGRPLNZPTZBS-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000010008 shearing Methods 0.000 description 4
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 3
- FLDCSPABIQBYKP-UHFFFAOYSA-N 5-chloro-1,2-dimethylbenzimidazole Chemical compound ClC1=CC=C2N(C)C(C)=NC2=C1 FLDCSPABIQBYKP-UHFFFAOYSA-N 0.000 description 3
- 239000001741 Ammonium adipate Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 235000019293 ammonium adipate Nutrition 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000011256 inorganic filler Substances 0.000 description 3
- 229910003475 inorganic filler Inorganic materials 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- 239000004589 rubber sealant Substances 0.000 description 3
- 239000000565 sealant Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- FYMCOOOLDFPFPN-UHFFFAOYSA-K iron(3+);4-methylbenzenesulfonate Chemical compound [Fe+3].CC1=CC=C(S([O-])(=O)=O)C=C1.CC1=CC=C(S([O-])(=O)=O)C=C1.CC1=CC=C(S([O-])(=O)=O)C=C1 FYMCOOOLDFPFPN-UHFFFAOYSA-K 0.000 description 2
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- TUOBWFMODGQPRM-UHFFFAOYSA-N 1,4-dioxecane-5,10-dione;ethane-1,2-diol Chemical compound OCCO.O=C1CCCCC(=O)OCCO1 TUOBWFMODGQPRM-UHFFFAOYSA-N 0.000 description 1
- RSZXXBTXZJGELH-UHFFFAOYSA-N 2,3,4-tri(propan-2-yl)naphthalene-1-sulfonic acid Chemical compound C1=CC=CC2=C(C(C)C)C(C(C)C)=C(C(C)C)C(S(O)(=O)=O)=C21 RSZXXBTXZJGELH-UHFFFAOYSA-N 0.000 description 1
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- ACQYKVVPCCAWBZ-UHFFFAOYSA-K iron(3+);methanesulfonate Chemical compound [Fe+3].CS([O-])(=O)=O.CS([O-])(=O)=O.CS([O-])(=O)=O ACQYKVVPCCAWBZ-UHFFFAOYSA-K 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Images
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
- H01G11/52—Separators
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Description
【0001】
【発明の属する技術分野】
本発明は導電性高分子を固体電解質層に用いた固体電解コンデンサの製造方法に関するものである。
【0002】
【従来の技術】
電子機器の高周波化に伴って、電子部品である電解コンデンサにも従来よりも高周波領域でのインピーダンス特性に優れる大容量のコンデンサが求められてきている。最近では、この高周波領域でのインピーダンス低減のために電気伝導度の高い導電性高分子を電解質に用いた固体電解コンデンサが検討されてきており、また大容量化の要求に対しては電極箔を積層させる場合と比較して、構造的に大容量化が容易な巻回形(陽極箔と陰極箔をその間にセパレータを介して巻回した構造のもの)による導電性高分子を用いた固体電解コンデンサが製品化されてきている。
【0003】
この巻回形の固体電解コンデンサにおいて、導電性高分子の形成方法についてこれまで多くの発明がなされており、一般的には導電性高分子のモノマー溶液と酸化剤溶液で交互に電解重合または化学重合して固体電解質層を形成するか、導電性高分子のモノマー溶液と酸化剤溶液の混合溶液で電解重合または化学重合して固体電解質層を形成させていた。ここで用いられている導電性高分子のモノマーとしてはピロール、チオフェン、エチレンジオキシチオフェン、アニリンまたはその誘導体であり、酸化剤溶液としてはp−トルエンスルホン酸第二鉄塩、ドデシルベンゼンスルホン酸第二鉄塩、ナフタレンスルホン酸第二鉄塩、トリイソプロピルナフタレンスルホン酸第二鉄塩や長鎖脂肪族スルホン酸等の第二鉄塩を含有したアルコール(メタノール、エタノール、イソプロピルアルコール、n−ブタノール、エチレングリコール等)溶液が用いられている。
【0004】
【発明が解決しようとする課題】
しかしながら上記巻回形の固体電解コンデンサにおいて、導電性高分子を巻回形のコンデンサ素子の内部に均一かつ十分に含浸させることは困難であり、特にエチレンジオキシチオフェンを重合してなるポリエチレンジオキシチオフェンにおいては、種々の酸化剤や重合条件の微妙な変化、さらには酸化剤溶液を調合してから導電性高分子のモノマーを重合するまでの経過時間等によって、電気特性のバラツキ(特に導電性高分子の誘電体酸化皮膜層上への被覆率により決定される静電容量のバラツキや導電性高分子の充填率により決定される高周波域でのインピーダンスのバラツキ)が大きいという課題を有していた。
【0005】
また、導電性高分子のモノマー溶液は粘性が高いため、コンデンサ素子の陽極箔および陰極箔のピット内に充填させるには低温雰囲気や真空含浸などの工夫が必要であった。
【0006】
本発明はこのような従来の課題を解決し、巻回形のコンデンサ素子に導電性高分子の固体電解質層を比較的容易に形成させて、容量達成率の高い高周波特性に優れた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ものである。
【0007】
【課題を解決するための手段】
上記課題を解決するために本発明の請求項1に記載の発明は、誘電体酸化皮膜層を形成した陽極箔とエッチング処理あるいはエッチング後化成処理された陰極箔とをその間にセパレータを介在させて巻回することによりコンデンサ素子を形成する工程と、有機バインダーおよび界面活性剤を含む溶液にポリピロール、ポリチオフェン、ポリアニリンおよびそれらの誘導体のいずれかの微粒子を分散させ、粘度を5〜100cpに調整した導電性高分子微粒子分散水溶液をコンデンサ素子に含浸させて微粒子の導電性高分子を有した第1の固体電解質層を形成する工程と、この第1の固体電解質層の表面に複素環式モノマーを含有する溶液と酸化剤を含有する溶液を個々に含浸または複素環式モノマーと酸化剤を含有する混合溶液を含浸することにより第2の固体電解質層を形成する工程とを具備した製造方法としたもので、この方法により、誘電体酸化皮膜層上に微粒子の導電性高分子を有した第1の固体電解質層を比較的容易に形成することができ、この第1の固体電解質層の表面に形成される第2の固体電解質層との密着性を向上させることができるので、固体電解コンデンサの内部抵抗を低くし、容量達成率の高い高周波特性に優れた固体電解コンデンサを得ることができるという作用を有する。
【0008】
なお、上記有機バインダーとしては、ポリビニルアルコール、ポリ酢酸ビニル、ポリカーボネート、ポリアクリレート、ポリメタアクリレート、ポリスチレン、ポリウレタン、ポリアクリロニトリル、ポリブタジエン、ポリイソプレン、ポリエーテル、ポリエステル、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、ポリアミド、ポリイミド、ブチラール樹脂、シリコーン樹脂、メラミン樹脂、アルキッド樹脂、セルロース、ニトロセルロース、ビスフェノールA型エポキシ、ビスフェノールF型エポキシ、脂環式エポキシおよびこれらの誘導体よりなる群より選ばれる1つ以上を含有する高分子または共重合体の1つ以上からなるものが挙げられ、これらの高分子または共重合体は導電性の乏しい高分子であり、かつこれらの抵抗率を1.0×1010Ω/□を超える値に設定することが容易であるため、電子なだれ現象を局所的な範囲に止めるに十分な絶縁性能を有する誘電体酸化皮膜上の層を構成できるので、漏れ電流が非常に小さく、かつエージング中にショートの発生しにくい固体電解質層を得ることができる。
【0009】
請求項2に記載の発明は、導電性高分子微粒子分散水溶液の微粒子が200〜10000nmとした製造方法としたもので、上記請求項1に記載の発明により得られる作用と同様の作用を有する。
【0010】
上記導電性高分子微粒子分散水溶液を超音波、ホモジナイザー、ハイブリッドミキサー、ハイシェアミキサーの少なくとも1種で分散処理して粘度を調整することにより、流体せん断作用および機械的せん断作用により導電性高分子微粒子分散水溶液中の微粒子および有機バインダーの分散性を高めることができ、上記水溶液を低粘度にして誘電体酸化皮膜層上に第1の固体電解質層を緻密に形成することができるという作用を有する。
【0011】
なお、上記超音波は周波数40〜60kHz、出力50〜100Wを有する一般的な超音波処理装置で処理するもの、ホモジナイザーはポンプで液体をオリフィス機構を通過させることにより、高いせん断作用を液体に与えることができる装置で処理するもの、ハイブリッドミキサーは液体を公転および自転させながら攪拌することができる装置で処理するもの、ハイシェアミキサーはロータとスクリーンを高速で回転させ、ロータとスクリーンの間に液体を通過させることにより、高いせん断作用を液体に与えながら攪拌することができる装置で処理するもので、これらの各分散処理のいずれか、あるいはそれらの組み合わせで導電性高分子微粒子分散水溶液を分散処理することができる。
【0012】
上記複素環式モノマーがポリピロール、ポリチオフェン、ポリアニリンおよびそれらの誘導体のいずれかを用いるもので、これらの電子導電性高分子は導電率が非常に高いため、陽極誘電体酸化皮膜上に設けた層の電子導電性高分子の抵抗率を1.0×1010Ω/□以下に設定しやすい上、前記した第1の固体電解質層の有機バインダーであるグリシジル変性ポリエステル、スルホン酸変性ポリエステル、カルボン酸変性ポリエステル等との相溶性が極めて高いので、これらの非電子伝導性高分子との併用により誘電体酸化皮膜上へこれらの電子導電性高分子の被覆率が高められるという効果を有するので、漏れ電流が非常に小さく、かつエージング中にショートが発生しにくい上、容量引き出し率の高い大容量の固体電解コンデンサを構成することができるという作用を有する。
【0013】
上記ポリチオフェンとしてポリエチレンジオキシチオフェンを用いることができる。
【0014】
【発明の実施の形態】
次に、本発明の具体的な実施の形態について説明する。
【0015】
(実施の形態1)
誘電体酸化皮膜の耐電圧が30Vの陽極アルミニウム箔と陰極アルミニウム箔との間にポリエチレンテレフタレート製のセパレータ(厚さ50μm、秤量25g/m2)を介在させて巻回することにより巻回形のコンデンサ素子を作製した(このコンデンサ素子にアジピン酸アンモニウム10重量%エチレングリコール溶液を含浸させた際の周波数120Hzにおける静電容量は250μFであった)。
【0016】
次に、ポリエチレンジオキシチオフェンポリスチレンスルホン酸の微粒子(平均粒径200nm)の濃度が1.0重量%と、グリシジル変性ポリエステルの濃度が3.0重量%と界面活性剤を添加した導電性高分子微粒子分散水溶液に上記コンデンサ素子を浸漬して引き上げた後、150℃で5分間乾燥処理を行い、少なくとも誘電体酸化皮膜上に電子導電性高分子であるポリエチレンジオキシチオフェンポリスチレンスルホン酸とグリシジル変性ポリエステルを含有する第1の固体電解質層を形成した。
【0017】
続いて、このコンデンサ素子を複素環式モノマーであるエチレンジオキシチオフェン1部と酸化剤であるp−トルエンスルホン酸第二鉄2部と重合溶剤であるn−ブタノール4部を含む混合溶液に浸漬して引き上げた後、85℃で60分間放置することにより導電性高分子であるポリエチレンジオキシチオフェンの第2の固体電解質層を電極箔間に形成した。
【0018】
このコンデンサ素子を樹脂加硫ブチルゴム封口材(ブチルゴムポリマー30部、カーボン20部、無機充填剤50部から構成、封口体硬度:70IRHD[国際ゴム硬さ単位])と共にアルミニウム製の外装ケースに封入した後、カーリング処理により開口部を封止し固体電解コンデンサを作製した。
【0019】
(実施の形態2)
上記実施の形態1において、陰極アルミニウム箔を化成処理したアルミニウム箔(化成皮膜耐圧5.0V)を用いた以外は実施の形態1と同様にして固体電解コンデンサを作製した。
【0020】
(実施の形態3)
上記実施の形態1において、導電性高分子微粒子分散水溶液をポリエチレンジオキシチオフェンポリスチレンスルホン酸の微粒子(平均粒径500nm)の濃度が1.5重量%と、グリシジル変性ポリエステルの濃度が3.0重量%と界面活性剤を添加したものを用いた以外は実施の形態1と同様にして固体電解コンデンサを作製した。
【0021】
(実施の形態4)
上記実施の形態1において、導電性高分子微粒子分散水溶液を超音波装置(出力100W)により2時間処理を行った後に用いた以外は実施の形態1と同様にして固体電解コンデンサを作製した。
【0022】
(実施の形態5)
上記実施の形態1において、導電性高分子微粒子分散水溶液を超音波装置(出力100W)により4時間処理を行った後に用いた以外は実施の形態1と同様にして固体電解コンデンサを作製した。
【0023】
(実施の形態6)
上記実施の形態1において、導電性高分子微粒子分散水溶液をホモジナイザー(ヒスコトロン製NS−56)により1時間処理した後に用いた以外は実施の形態1と同様にして固体電解コンデンサを作製した。
【0024】
(実施の形態7)
上記実施の形態1において、導電性高分子微粒子分散水溶液をハイブリッドミキサー(キーエンス製HM−500)で3時間処理した後に用いた以外は実施の形態1と同様にして固体電解コンデンサを作製した。
【0025】
(実施の形態8)
上記実施の形態1において、導電性高分子微粒子分散水溶液をハイシェアミキサー(エム・テクニック製CLM−0.8S)で10分間処理した後に用いた以外は実施の形態1と同様にして固体電解コンデンサを作製した。
【0026】
(実施の形態9)
上記実施の形態1において、導電性高分子微粒子分散水溶液をポリアニリンの微粒子(平均粒径1000nm)の濃度が5.0重量%と、ポリエチレンテレフタレートの濃度が3.0重量%と界面活性剤を添加したものを、超音波装置により2時間処理を行った後に用いた以外は実施の形態1と同様にして固体電解コンデンサを作製した。
【0027】
(実施の形態10)
上記実施の形態1において、導電性高分子微粒子分散水溶液をポリピロールの微粒子(平均粒径800nm)の濃度が3.0重量%と、ポリエチレンテレフタレートの濃度が3.0重量%と界面活性剤を添加したものを、超音波装置により1時間処理を行った後に用いた以外は実施の形態1と同様にして固体電解コンデンサを作製した。
【0028】
(実施の形態11)
上記実施の形態1において、第1の固体電解質層を形成したコンデンサ素子を、複素環式モノマーであるピロール1部と酸化剤であるナフタレンスルホン酸第二鉄2部と重合溶剤であるn−ブタノール3部を含む混合溶液に浸漬して引き上げた後、85℃で60分間放置することにより導電性高分子であるポリピロールの第2の固体電解質層を電極箔間に形成した以外は実施の形態1と同様にして固体電解コンデンサを作製した。
【0029】
(実施の形態12)
上記実施の形態11において、酸化剤であるナフタレンスルホン酸第二鉄の代わりにメタンスルホン酸第二鉄塩を用いた以外は実施の形態11と同様にして固体電解コンデンサを作製した。
【0030】
(実施の形態13)
誘電体酸化皮膜の耐電圧が30Vの陽極アルミニウム箔と化成処理された陰極アルミニウム箔(化成皮膜耐圧5.0V)との間にポリエチレンテレフタレート製のセパレータ(厚さ50μm、秤量25g/m2)を介在させて巻回することにより巻回形のコンデンサ素子を作製した(このコンデンサ素子にアジピン酸アンモニウム10重量%エチレングリコール溶液を含浸させた際の周波数120Hzにおける静電容量は250μFであった)。
【0031】
次に、ポリエチレンジオキシチオフェンポリスチレンスルホン酸の微粒子(平均粒径500nm)の濃度が1.0重量%と、グリシジル変性ポリエステルの濃度が3.0重量%と界面活性剤を添加した導電性高分子微粒子分散水溶液に上記コンデンサ素子を浸漬して引き上げた後、150℃で5分間乾燥処理を行い、少なくとも誘電体酸化皮膜上に電子導電性高分子であるポリエチレンジオキシチオフェンポリスチレンスルホン酸とグリシジル変性ポリエステルを含有する第1の固体電解質層を形成した。
【0032】
続いて、第1の固体電解質層を形成したコンデンサ素子にアジピン酸アンモニウム10%を溶かしたエチレングリコール電解液を含浸した。
【0033】
このコンデンサ素子を樹脂加硫ブチルゴム封口材(ブチルゴムポリマー30部、カーボン20部、無機充填剤50部から構成、封口体硬度:70IRHD[国際ゴム硬さ単位])と共にアルミニウム製の外装ケースに封入した後、カーリング処理により開口部を封止して固体電解コンデンサを作製した。
【0034】
(比較例)
誘電体酸化皮膜の耐電圧が30Vの陽極アルミニウム箔と陰極アルミニウム箔との間にポリエチレンテレフタレート製のセパレータ(厚さ50μm、秤量25g/m2)を介在させて巻回することにより巻回形のコンデンサ素子を作製した(このコンデンサ素子にアジピン酸アンモニウム10重量%のエチレングリコール溶液を含浸させた際の周波数120Hzにおける静電容量は250μFであった)。
【0035】
このコンデンサ素子を複素環式モノマーであるエチレンジオキシチオフェン1部と酸化剤であるp−トルエンスルホン酸第二鉄2部と重合溶剤であるn−ブタノール4部を含む混合溶液に浸漬して引き上げた後、85℃で60分間放置することにより導電性高分子であるポリエチレンジオキシチオフェンを電極箔間に形成した。
【0036】
このコンデンサ素子を樹脂加硫ブチルゴム封口材(ブチルゴムポリマー30部、カーボン20部、無機充填剤50部から構成、封口体硬度:70IRHD[国際ゴム硬さ単位])と共にアルミニウム製の外装ケースに封入した後、カーリング処理により開口部を封止し固体電解コンデンサを作製した。
【0037】
上記実施の形態1〜13と比較例の固体電解コンデンサについて、その静電容量(測定周波数120Hz)、tanδ(測定周波数120Hz)、インピーダンス(測定周波数100kHz)を比較した結果を(表1)に示す。なお、試験個数はいずれも50個であり、静電容量、インピーダンスはショート品を除いたサンプルについての平均値で示した。
【0038】
【表1】
【0039】
(表1)より明らかなように、本発明の実施の形態1〜12の固体電解コンデンサは、誘電体酸化皮膜層上に導電性高分子の微粒子を有した第1の固体電解質層を比較的容易に形成することができ、この第1の固体電解質層の表面に形成される第2の固体電解質層との密着性も向上することができるので、固体電解コンデンサの内部抵抗を低くし、容量達成率の高い高周波特性に優れた固体電解コンデンサを得ることができる。
【0040】
また、導電性高分子微粒子分散水溶液を超音波処理(実施の形態4および5)、ホモジナイザー処理(実施の形態6)、ハイブリッドミキサー処理(実施の形態7)、ハイシェアミキサー処理(実施の形態8)することにより、第1の固体電解質層を緻密で均一に形成することができることから、容量およびインピーダンス特性に優れた固体電解コンデンサを得ることができる。
【0041】
特に実施の形態8の固体電解コンデンサは、導電性高分子微粒子分散水溶液の分散処理時間を短くしても分散効率を高めることができ、容量およびインピーダンス特性をさらに高めることができる。
【0042】
上記超音波処理およびハイシェアミキサー処理において、導電性高分子微粒子分散水溶液の分散処理時間と粘性の関係をBRANSON製のBRANSONIC220を用いて測定した結果を図1に示す。同図より超音波処理では1〜4時間処理することにより低粘性(100cp以下)にすることができ、また、ハイシェアミキサー処理では10分で低粘性になり、この低粘性(5〜100cp)の導電性高分子微粒子分散水溶液を用いることにより、緻密で均一な第1の固体電解質層を形成することができるものである。
【0043】
さらに、実施の形態13においては、導電性高分子微粒子分散水溶液により第1の固体電解質層を形成したコンデンサ素子に、エチレングリコール電解液を含浸した固体電解コンデンサで、比較的容易に高周波領域のインピーダンス特性の低い固体電解コンデンサを得ることができるものである。
【0044】
【発明の効果】
以上のように本発明によれば、誘電体酸化皮膜層を形成した陽極箔とエッチング処理あるいはエッチング後化成処理された陰極箔とをその間にセパレータを介在して巻回することによりコンデンサ素子を形成する工程と、有機バインダーおよび界面活性剤を含む溶液にポリピロール、ポリチオフェン、ポリアニリンおよびそれらの誘導体のいずれかの微粒子を分散させ、粘度を5〜100cpに調整した導電性高分子微粒子分散水溶液をコンデンサ素子に含浸させて微粒子の導電性高分子を有した第1の固体電解質層を形成する工程と、この第1の固体電解質層の表面に、複素環式モノマーを含有する溶液と酸化剤を含有する溶液を個々に含浸または複素環式モノマーと酸化剤を含有する混合溶液を含浸することにより第2の固体電解質層を形成する工程とを具備した製造方法としたもので、この方法により、誘電体酸化皮膜層上に微粒子の導電性高分子を有した第1の固体電解質層を比較的容易に形成することができ、この第1の固体電解質層の表面に形成される第2の固体電解質層との密着性を向上させることができるので、固体電解コンデンサの内部抵抗を低くし、容量達成率の高い高周波特性に優れた固体電解コンデンサを得ることができるものであり、その工業的な価値は大なるものである。
【図面の簡単な説明】
【図1】 本発明の実施の形態における超音波およびハイシェアミキサーで導電性高分子微粒子分散水溶液を分散処理したときの処理時間と粘性の関係を示すグラフ[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a solid electrolytic capacitor using a conductive polymer as a solid electrolyte layer.
[0002]
[Prior art]
With the increase in frequency of electronic equipment, electrolytic capacitors that are electronic components have been required to have a large capacity capacitor that is superior in impedance characteristics in a high frequency region than before. Recently, in order to reduce impedance in this high-frequency region, solid electrolytic capacitors using a conductive polymer with high electrical conductivity as an electrolyte have been studied. Solid electrolysis using a conductive polymer of a wound type (a structure in which an anode foil and a cathode foil are wound with a separator between them), which makes it easy to increase the capacity compared to the case of stacking Capacitors have been commercialized.
[0003]
In this wound-type solid electrolytic capacitor, many inventions have been made so far regarding a method for forming a conductive polymer. Generally, an electropolymerization or chemical reaction is alternately performed between a monomer solution and an oxidant solution of a conductive polymer. The solid electrolyte layer is formed by polymerization, or the solid electrolyte layer is formed by electrolytic polymerization or chemical polymerization using a mixed solution of a conductive polymer monomer solution and an oxidizing agent solution. The conductive polymer monomer used here is pyrrole, thiophene, ethylenedioxythiophene, aniline or a derivative thereof, and the oxidizing agent solution is p-toluenesulfonic acid ferric salt, dodecylbenzenesulfonic acid Alcohol (methanol, ethanol, isopropyl alcohol, n-butanol, ferric salt such as ferric salt, naphthalenesulfonic acid ferric salt, ferric salt of triisopropylnaphthalenesulfonic acid and long chain aliphatic sulfonic acid Ethylene glycol etc.) solution is used.
[0004]
[Problems to be solved by the invention]
However, in the above wound solid electrolytic capacitor, it is difficult to uniformly and sufficiently impregnate the conductive polymer inside the wound capacitor element, and in particular, polyethylene dioxypolymer formed by polymerizing ethylenedioxythiophene. In thiophene, there are variations in electrical properties (particularly conductivity) due to subtle changes in various oxidizing agents and polymerization conditions, and the elapsed time from the preparation of the oxidizing agent solution to the polymerization of the conductive polymer monomer. There is a problem that the capacitance variation determined by the coating rate of the polymer on the dielectric oxide film layer and the impedance variation in the high frequency range determined by the filling rate of the conductive polymer are large. It was.
[0005]
Further, since the monomer solution of the conductive polymer has a high viscosity, a device such as a low temperature atmosphere or vacuum impregnation is required to fill the pits of the anode foil and the cathode foil of the capacitor element.
[0006]
The present invention solves such a conventional problem, and a solid electrolytic layer of a conductive polymer is formed on a wound capacitor element relatively easily, so that a solid electrolytic capacitor excellent in high frequency characteristics with a high capacity achievement rate is obtained. An object of the present invention is to provide a manufacturing method.
[0007]
[Means for Solving the Problems]
In order to solve the above-mentioned problems, according to the first aspect of the present invention, an anode foil on which a dielectric oxide film layer is formed and a cathode foil that has been subjected to etching treatment or post-etching chemical conversion treatment are interposed between them. A step of forming a capacitor element by winding , and a conductive material in which fine particles of any of polypyrrole, polythiophene, polyaniline and their derivatives are dispersed in a solution containing an organic binder and a surfactant, and the viscosity is adjusted to 5 to 100 cp. A step of forming a first solid electrolyte layer having a conductive polymer fine particle by impregnating a capacitor element with an aqueous dispersion of fine polymer particles, and containing a heterocyclic monomer on the surface of the first solid electrolyte layer Impregnating with a solution containing an oxidizing agent and a solution containing an oxidizing agent individually or with a mixed solution containing a heterocyclic monomer and an oxidizing agent. And a step of forming a second solid electrolyte layer by the above method. By this method, the first solid electrolyte layer having a conductive polymer of fine particles on the dielectric oxide film layer is compared. Can be formed easily, and the adhesion with the second solid electrolyte layer formed on the surface of the first solid electrolyte layer can be improved, so that the internal resistance of the solid electrolytic capacitor is lowered, It has the effect that a solid electrolytic capacitor having a high capacity achievement rate and excellent high frequency characteristics can be obtained.
[0008]
Examples of the organic binder include polyvinyl alcohol, polyvinyl acetate, polycarbonate, polyacrylate, polymethacrylate, polystyrene, polyurethane, polyacrylonitrile, polybutadiene, polyisoprene, polyether, polyester, polyethylene terephthalate, polybutylene terephthalate, polyamide, High containing at least one selected from the group consisting of polyimide, butyral resin, silicone resin, melamine resin, alkyd resin, cellulose, nitrocellulose, bisphenol A type epoxy, bisphenol F type epoxy, alicyclic epoxy, and derivatives thereof And those consisting of one or more molecules or copolymers, these polymers or copolymers are polymers with poor conductivity, and these Since it is easy to set the anti-factor to a value greater than 1.0 × 10 10 Ω / □, a layer on the dielectric oxide film having a sufficient insulation performance in stopping the local range of the electron avalanche Since it can be configured, it is possible to obtain a solid electrolyte layer that has a very small leakage current and is less likely to cause a short circuit during aging.
[0009]
The invention according to claim 2 is a production method in which the fine particles of the aqueous dispersion of fine conductive polymer particles are 200 to 10,000 nm, and has the same action as that obtained by the invention according to claim 1 .
[0010]
The conductive polymer particles dispersed aqueous ultrasound homogenizer, a hybrid mixer, by adjusting the viscosity and dispersion treatment with at least one high shear mixer, conductive polymer particles by the fluid shearing action and mechanical shearing action The dispersibility of the fine particles and the organic binder in the dispersed aqueous solution can be enhanced, and the aqueous solution has a low viscosity so that the first solid electrolyte layer can be densely formed on the dielectric oxide film layer.
[0011]
The ultrasonic wave is processed by a general ultrasonic processing apparatus having a frequency of 40-60 kHz and an output of 50-100 W. The homogenizer gives a high shearing action to the liquid by passing the liquid through the orifice mechanism with a pump. That can be processed with a device that can handle, a hybrid mixer that processes with a device that can stir while revolving and rotating the liquid, a high shear mixer that rotates the rotor and the screen at high speed, and the liquid between the rotor and the screen Is processed with an apparatus that can stir while giving a high shearing action to the liquid, and the conductive polymer fine particle dispersion aqueous solution is dispersed by any of these dispersion treatments or a combination thereof. can do.
[0012]
The heterocyclic monomer uses any one of polypyrrole, polythiophene, polyaniline, and derivatives thereof , and these electronic conductive polymers have very high conductivity, so that the layer provided on the anode dielectric oxide film It is easy to set the resistivity of the electron conductive polymer to 1.0 × 10 10 Ω / □ or less, and the glycidyl-modified polyester, sulfonic acid-modified polyester, and carboxylic acid-modified organic binder for the first solid electrolyte layer described above. Since the compatibility with polyester, etc. is extremely high, the combined use of these non-electron conductive polymers has the effect of increasing the coverage of these electronic conductive polymers on the dielectric oxide film, so that leakage current This is a very small capacitor that does not easily cause a short circuit during aging, and has a large capacity solid electrolytic capacitor with a high capacity extraction rate. It has the effect that it is Rukoto.
[0013]
It can be used polyethylenedioxythiophene as the polythiophene.
[0014]
DETAILED DESCRIPTION OF THE INVENTION
Next, specific embodiments of the present invention will be described.
[0015]
(Embodiment 1)
The dielectric oxide film is wound by interposing a polyethylene terephthalate separator (thickness 50 μm, weighing 25 g / m 2 ) between an anode aluminum foil and a cathode aluminum foil having a withstand voltage of 30 V. A capacitor element was produced (the capacitance at a frequency of 120 Hz when this capacitor element was impregnated with an ammonium adipate 10 wt% ethylene glycol solution was 250 μF).
[0016]
Next, a conductive polymer in which the concentration of fine particles of polyethylenedioxythiophene polystyrene sulfonic acid (
[0017]
Subsequently, the capacitor element is immersed in a mixed solution containing 1 part of ethylenedioxythiophene as a heterocyclic monomer, 2 parts of ferric p-toluenesulfonate as an oxidizing agent and 4 parts of n-butanol as a polymerization solvent. After being pulled up, it was left at 85 ° C. for 60 minutes to form a second solid electrolyte layer of polyethylenedioxythiophene, which is a conductive polymer, between the electrode foils.
[0018]
This capacitor element was encapsulated in an aluminum outer case together with a resin vulcanized butyl rubber sealant (30 parts butyl rubber polymer, 20 parts carbon, 50 parts inorganic filler, sealant hardness: 70 IRHD [international rubber hardness unit]). Thereafter, the opening was sealed by curling treatment to produce a solid electrolytic capacitor.
[0019]
(Embodiment 2)
A solid electrolytic capacitor was produced in the same manner as in the first embodiment except that an aluminum foil (chemical conversion film withstand voltage 5.0 V) obtained by chemical conversion of the cathode aluminum foil was used.
[0020]
(Embodiment 3)
In the first embodiment, in the conductive polymer fine particle dispersion aqueous solution, the concentration of polyethylenedioxythiophene polystyrenesulfonic acid fine particles (
[0021]
(Embodiment 4)
A solid electrolytic capacitor was produced in the same manner as in the first embodiment except that the aqueous conductive polymer fine particle dispersion was used after being treated for 2 hours by an ultrasonic device (output 100 W).
[0022]
(Embodiment 5)
A solid electrolytic capacitor was produced in the same manner as in the first embodiment except that the aqueous conductive polymer fine particle dispersion was used after being treated for 4 hours by an ultrasonic device (output 100 W).
[0023]
(Embodiment 6)
A solid electrolytic capacitor was produced in the same manner as in Embodiment 1 except that the aqueous conductive polymer fine particle dispersion was used after being treated for 1 hour with a homogenizer (NS-56 manufactured by Hiscotron).
[0024]
(Embodiment 7)
A solid electrolytic capacitor was produced in the same manner as in Embodiment 1 except that the aqueous conductive polymer fine particle dispersion was used after being treated with a hybrid mixer (Keyence HM-500) for 3 hours.
[0025]
(Embodiment 8)
A solid electrolytic capacitor in the same manner as in the first embodiment except that the aqueous conductive polymer fine particle dispersion was used after being treated with a high shear mixer (CLM-0.8S manufactured by M Technique) for 10 minutes. Was made.
[0026]
(Embodiment 9)
In the first embodiment, a conductive polymer fine particle- dispersed aqueous solution is added with a surfactant having a polyaniline fine particle concentration (average particle size of 1000 nm) of 5.0% by weight and a polyethylene terephthalate concentration of 3.0% by weight. A solid electrolytic capacitor was produced in the same manner as in Embodiment 1 except that the obtained product was used after being treated with an ultrasonic device for 2 hours.
[0027]
(Embodiment 10)
In the first embodiment, a conductive polymer fine particle dispersed aqueous solution is added with a surfactant having a polypyrrole fine particle (average particle size of 800 nm) concentration of 3.0% by weight and a polyethylene terephthalate concentration of 3.0% by weight. A solid electrolytic capacitor was produced in the same manner as in Embodiment 1 except that the obtained product was used after being treated with an ultrasonic device for 1 hour.
[0028]
(Embodiment 11)
In the first embodiment, the capacitor element formed with the first solid electrolyte layer is composed of 1 part of pyrrole as a heterocyclic monomer, 2 parts of ferric naphthalene sulfonate as an oxidizing agent, and n-butanol as a polymerization solvent. Embodiment 1 Except that a second solid electrolyte layer of polypyrrole, which is a conductive polymer, was formed between electrode foils by dipping in a mixed solution containing 3 parts and pulling it up and then standing at 85 ° C. for 60 minutes. A solid electrolytic capacitor was produced in the same manner as described above.
[0029]
(Embodiment 12)
In the eleventh embodiment, a solid electrolytic capacitor was fabricated in the same manner as in the eleventh embodiment except that ferric methanesulfonate was used instead of ferric naphthalene sulfonate, which is an oxidizing agent.
[0030]
(Embodiment 13)
A separator made of polyethylene terephthalate (thickness 50 μm, weighing 25 g / m 2 ) between an anode aluminum foil with a dielectric oxide film with a withstand voltage of 30 V and a chemically treated cathode aluminum foil (chemical conversion film withstand voltage 5.0 V). A wound capacitor element was produced by interposing and winding (capacitance at a frequency of 120 Hz when this capacitor element was impregnated with a 10 wt% ethylene adipate ethylene glycol solution was 250 μF).
[0031]
Next, a conductive polymer in which the concentration of fine particles of polyethylenedioxythiophene polystyrene sulfonic acid (
[0032]
Subsequently, the capacitor element on which the first solid electrolyte layer was formed was impregnated with an ethylene glycol electrolytic solution in which 10% ammonium adipate was dissolved.
[0033]
This capacitor element was encapsulated in an aluminum outer case together with a resin vulcanized butyl rubber sealant (30 parts butyl rubber polymer, 20 parts carbon, 50 parts inorganic filler, sealant hardness: 70 IRHD [international rubber hardness unit]). Thereafter, the opening was sealed by curling treatment to produce a solid electrolytic capacitor.
[0034]
(Comparative example)
The dielectric oxide film is wound by interposing a polyethylene terephthalate separator (thickness 50 μm, weighing 25 g / m 2 ) between an anode aluminum foil and a cathode aluminum foil having a withstand voltage of 30 V. A capacitor element was produced (the capacitance at a frequency of 120 Hz when this capacitor element was impregnated with an ethylene glycol solution containing 10% by weight of ammonium adipate was 250 μF).
[0035]
Immerse this capacitor element in a mixed solution containing 1 part of ethylenedioxythiophene as a heterocyclic monomer, 2 parts of ferric p-toluenesulfonate as an oxidizing agent and 4 parts of n-butanol as a polymerization solvent, and pull it up. Then, the conductive polymer, polyethylenedioxythiophene, was formed between the electrode foils by leaving it at 85 ° C. for 60 minutes.
[0036]
This capacitor element was encapsulated in an aluminum outer case together with a resin vulcanized butyl rubber sealant (30 parts butyl rubber polymer, 20 parts carbon, 50 parts inorganic filler, sealant hardness: 70 IRHD [international rubber hardness unit]). Thereafter, the opening was sealed by curling treatment to produce a solid electrolytic capacitor.
[0037]
About the solid electrolytic capacitor of the said Embodiments 1-13 and a comparative example, the result of having compared the electrostatic capacitance (measuring frequency 120Hz), tan-delta (measuring frequency 120Hz), and impedance (measuring frequency 100kHz) is shown in (Table 1). . The number of tests was 50, and the capacitance and impedance were shown as average values for samples excluding short-circuited products.
[0038]
[Table 1]
[0039]
As is clear from Table 1, the solid electrolytic capacitors according to the first to twelfth embodiments of the present invention are obtained by relatively disposing the first solid electrolyte layer having conductive polymer fine particles on the dielectric oxide film layer. Since it can be easily formed and the adhesion to the second solid electrolyte layer formed on the surface of the first solid electrolyte layer can also be improved, the internal resistance of the solid electrolytic capacitor is reduced, and the capacitance A solid electrolytic capacitor having a high achievement rate and excellent high frequency characteristics can be obtained.
[0040]
In addition, the conductive polymer fine particle- dispersed aqueous solution is subjected to ultrasonic treatment (Embodiments 4 and 5), homogenizer treatment (Embodiment 6), hybrid mixer treatment (Embodiment 7), and high shear mixer treatment (Embodiment 8). ), The first solid electrolyte layer can be formed densely and uniformly, so that a solid electrolytic capacitor having excellent capacitance and impedance characteristics can be obtained.
[0041]
In particular, the solid electrolytic capacitor of Embodiment 8 can increase the dispersion efficiency even if the dispersion treatment time of the conductive polymer fine particle- dispersed aqueous solution is shortened, and can further increase the capacitance and impedance characteristics.
[0042]
FIG. 1 shows the results of measuring the relationship between the dispersion treatment time and the viscosity of the aqueous conductive polymer fine particle dispersion using the BRANSONIC 220 manufactured by BRANSON in the ultrasonic treatment and the high shear mixer treatment. From the figure, ultrasonic treatment can reduce the viscosity (100 cp or less) by processing for 1 to 4 hours, and high shear mixer treatment reduces the viscosity in 10 minutes. This low viscosity (5 to 100 cp) By using the aqueous conductive polymer fine particle dispersion aqueous solution, a dense and uniform first solid electrolyte layer can be formed.
[0043]
Further, in the thirteenth embodiment, a capacitor element in which the first solid electrolyte layer is formed with the conductive polymer fine particle dispersed aqueous solution is a solid electrolytic capacitor impregnated with an ethylene glycol electrolytic solution. A solid electrolytic capacitor having low characteristics can be obtained.
[0044]
【The invention's effect】
As described above, according to the present invention, the capacitor element is formed by winding the anode foil formed with the dielectric oxide film layer and the cathode foil subjected to etching treatment or post-etching chemical conversion treatment with a separator interposed therebetween. And a conductive polymer fine particle dispersed aqueous solution in which fine particles of any of polypyrrole, polythiophene, polyaniline and derivatives thereof are dispersed in a solution containing an organic binder and a surfactant and the viscosity is adjusted to 5 to 100 cp. a step of impregnating to form a first solid electrolyte layer having a conductive polymer fine particles, the surface of the first solid electrolyte layer, containing a solution with an oxidizing agent containing a heterocyclic monomer The second solid electrolyte layer is individually impregnated with a solution or impregnated with a mixed solution containing a heterocyclic monomer and an oxidizing agent. The first solid electrolyte layer having the fine conductive polymer on the dielectric oxide film layer can be formed relatively easily by this method. Since the adhesiveness with the second solid electrolyte layer formed on the surface of the first solid electrolyte layer can be improved, the internal resistance of the solid electrolytic capacitor is lowered, and the high frequency characteristics with a high capacity achievement rate are achieved. An excellent solid electrolytic capacitor can be obtained, and its industrial value is great.
[Brief description of the drawings]
FIG. 1 is a graph showing the relationship between the treatment time and viscosity when a conductive polymer fine particle- dispersed aqueous solution is dispersed using an ultrasonic wave and a high shear mixer according to an embodiment of the present invention.
Claims (2)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2002073627A JP4329299B2 (en) | 2001-07-16 | 2002-03-18 | Manufacturing method of solid electrolytic capacitor |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2001-214985 | 2001-07-16 | ||
JP2001214985 | 2001-07-16 | ||
JP2002073627A JP4329299B2 (en) | 2001-07-16 | 2002-03-18 | Manufacturing method of solid electrolytic capacitor |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2008099058A Division JP4831108B2 (en) | 2001-07-16 | 2008-04-07 | Manufacturing method of solid electrolytic capacitor |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2003100561A JP2003100561A (en) | 2003-04-04 |
JP4329299B2 true JP4329299B2 (en) | 2009-09-09 |
Family
ID=26618769
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2002073627A Expired - Fee Related JP4329299B2 (en) | 2001-07-16 | 2002-03-18 | Manufacturing method of solid electrolytic capacitor |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP4329299B2 (en) |
Families Citing this family (27)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE502004009915D1 (en) * | 2003-10-17 | 2009-10-01 | Starck H C Gmbh | Electrolytic capacitors with a polymer outer layer |
DE102005043829A1 (en) * | 2005-09-13 | 2007-04-05 | H.C. Starck Gmbh | Process for the production of electrolytic capacitors with high nominal voltage |
DE102005043828A1 (en) | 2005-09-13 | 2007-03-22 | H.C. Starck Gmbh | Process for the preparation of electrolytic capacitors |
TWI404090B (en) | 2006-02-21 | 2013-08-01 | Shinetsu Polymer Co | Capacitor and capacitor manufacturing method |
JP5305569B2 (en) * | 2006-06-29 | 2013-10-02 | 三洋電機株式会社 | Electrolytic capacitor manufacturing method and electrolytic capacitor |
JP2008066502A (en) * | 2006-09-07 | 2008-03-21 | Matsushita Electric Ind Co Ltd | Electrolytic capacitor |
JP5058633B2 (en) * | 2006-09-27 | 2012-10-24 | 信越ポリマー株式会社 | Capacitor |
JP4803741B2 (en) * | 2007-02-06 | 2011-10-26 | Necトーキン株式会社 | Manufacturing method of solid electrolytic capacitor |
JP4836887B2 (en) * | 2007-07-09 | 2011-12-14 | 三洋電機株式会社 | Electrolytic capacitor manufacturing method and electrolytic capacitor |
JP2009105171A (en) * | 2007-10-23 | 2009-05-14 | Nec Tokin Corp | Solid-state electrolytic capacitor and its method for manufacturing |
JP4916416B2 (en) * | 2007-10-30 | 2012-04-11 | サン電子工業株式会社 | Electrolytic capacitor manufacturing method and electrolytic capacitor |
DE102008005568A1 (en) | 2008-01-22 | 2009-07-23 | H.C. Starck Gmbh | Process for the preparation of conductive polymers |
DE102008024805A1 (en) * | 2008-05-23 | 2009-12-03 | H.C. Starck Gmbh | Process for the preparation of electrolytic capacitors |
JP2010087401A (en) * | 2008-10-02 | 2010-04-15 | Shin Etsu Polymer Co Ltd | Method for manufacturing capacitor |
JP5598897B2 (en) * | 2008-10-22 | 2014-10-01 | テイカ株式会社 | Manufacturing method of solid electrolytic capacitor |
JP2010129651A (en) * | 2008-11-26 | 2010-06-10 | Nichicon Corp | Method for producing solid electrolytic capacitor |
WO2011108255A1 (en) * | 2010-03-01 | 2011-09-09 | 日本ケミコン株式会社 | Process for producing solid electrolytic capacitor, and solid electrolytic capacitor |
JP2011216752A (en) * | 2010-03-31 | 2011-10-27 | Nippon Chemicon Corp | Solid-state electrolytic capacitor |
JP5327255B2 (en) * | 2011-03-29 | 2013-10-30 | パナソニック株式会社 | Electrolytic capacitor manufacturing method |
JP5259895B1 (en) | 2011-12-19 | 2013-08-07 | テイカ株式会社 | Electrolytic capacitor and manufacturing method thereof |
WO2014017098A1 (en) * | 2012-07-25 | 2014-01-30 | 昭和電工株式会社 | Method for producing conductive polymer and method for producing solid electrolyte capacitor |
CN105051847B (en) | 2013-04-05 | 2018-01-16 | 昭和电工株式会社 | The manufacture method of solid electrolytic capacitor |
US11183340B2 (en) | 2016-12-28 | 2021-11-23 | Showa Denko K.K. | Method for manufacturing solid electrolytic capacitor |
CN111052280B (en) | 2017-08-31 | 2022-08-23 | 昭和电工株式会社 | Method for manufacturing solid electrolytic capacitor |
WO2019130677A1 (en) | 2017-12-25 | 2019-07-04 | 昭和電工株式会社 | Liquid dispersion composition for solid electrolytic capacitor production, and production method for solid electrolytic capacitor |
JP6770217B2 (en) | 2018-03-30 | 2020-10-14 | 昭和電工株式会社 | A method for producing a solid electrolytic capacitor and a method for producing a dispersion containing a conjugated conductive polymer. |
TWI675389B (en) * | 2018-05-02 | 2019-10-21 | 鈺邦科技股份有限公司 | Wound type capacitor component with enhanced structural strength and method for manufacturing the same |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0494110A (en) * | 1990-08-09 | 1992-03-26 | Kao Corp | Manufacture of solid electrolytic capacitor |
JP3543526B2 (en) * | 1997-01-10 | 2004-07-14 | 松下電器産業株式会社 | Solid electrolytic capacitor and method of manufacturing the same |
JPH1145824A (en) * | 1997-07-24 | 1999-02-16 | Matsushita Electric Ind Co Ltd | Capacitor and its manufacture |
JP3459547B2 (en) * | 1997-10-17 | 2003-10-20 | 三洋電機株式会社 | Electrolytic capacitor and method for manufacturing the same |
JP4164911B2 (en) * | 1998-09-28 | 2008-10-15 | 日本ケミコン株式会社 | Solid electrolytic capacitor and manufacturing method thereof |
JP2001155966A (en) * | 1999-09-14 | 2001-06-08 | Matsushita Electric Ind Co Ltd | Method of manufacturing capacitor |
JP2001143968A (en) * | 1999-11-15 | 2001-05-25 | Matsushita Electric Ind Co Ltd | Solid electrolytic capacitor and its manufacturing method |
-
2002
- 2002-03-18 JP JP2002073627A patent/JP4329299B2/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
JP2003100561A (en) | 2003-04-04 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP4329299B2 (en) | Manufacturing method of solid electrolytic capacitor | |
CN101106021B (en) | Method of manufacturing electrolytic capacitor and electrolytic capacitor | |
JP4911509B2 (en) | Electrolytic capacitor and manufacturing method thereof | |
US9287053B2 (en) | Method of manufacturing solid electrolytic capacitor | |
JP3705306B2 (en) | Solid electrolytic capacitor and manufacturing method thereof | |
WO1997041577A1 (en) | Solid electrolyte capacitor and its manufacture | |
JP4831108B2 (en) | Manufacturing method of solid electrolytic capacitor | |
WO2001073801A1 (en) | Solid electrolytic capacitor | |
JP6803519B2 (en) | Manufacturing method of electrolytic capacitors | |
JP6868848B2 (en) | Electrolytic capacitor | |
JP2001102255A (en) | Tantalum solid electrolytic capacitor and manufacturing method therefor | |
JPH1145824A (en) | Capacitor and its manufacture | |
JP2001110683A (en) | Method of manufacturing capacitor | |
JP3671828B2 (en) | Manufacturing method of solid electrolytic capacitor | |
JP2000269070A (en) | Manufacturing of capacitor | |
TWI532783B (en) | Conductive material formulation and use thereof | |
JP2003173932A (en) | Solid-state capacitor and its manufacturing method | |
CN110189920B (en) | Conductive polymer electrode material, preparation method thereof and aluminum electrolytic capacitor | |
JP2001110685A (en) | Solid electrolytic capacitor | |
JP2696982B2 (en) | Solid electrolytic capacitors | |
KR102259541B1 (en) | Method for manufacturing hybrid aluminum polymer capacitor | |
JP2765440B2 (en) | Method for manufacturing solid electrolytic capacitor | |
JP3891304B2 (en) | Manufacturing method of solid electrolytic capacitor | |
JP2021073720A (en) | Electrolytic capacitor | |
JP2000106328A (en) | Capacitor and its manufacture |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20050303 |
|
RD01 | Notification of change of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7421 Effective date: 20050706 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20080125 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20080205 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20080407 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20090526 |
|
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20090608 |
|
R151 | Written notification of patent or utility model registration |
Ref document number: 4329299 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120626 Year of fee payment: 3 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120626 Year of fee payment: 3 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130626 Year of fee payment: 4 |
|
LAPS | Cancellation because of no payment of annual fees |