JP2005109278A - Solid electrolytic capacitor - Google Patents

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JP2005109278A
JP2005109278A JP2003342695A JP2003342695A JP2005109278A JP 2005109278 A JP2005109278 A JP 2005109278A JP 2003342695 A JP2003342695 A JP 2003342695A JP 2003342695 A JP2003342695 A JP 2003342695A JP 2005109278 A JP2005109278 A JP 2005109278A
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foil
solid electrolytic
electrolytic capacitor
electrode foil
capacitor
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Norihito Fukui
典仁 福井
Katsunori Nogami
勝憲 野上
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Nippon Chemi Con Corp
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a solid electrolytic capacitor having proper electrostatic capacitance characteristics. <P>SOLUTION: The solid electrolytic capacitor is provided with a capacitor element constituted by winding an anode foil and a cathode foil with a separator holding a conductive polymer in between. Since an etching foil having a chemically converted coating film on its surface and a coating film composed of carbon on the film or planar foil having a chemically converted coating film on its surface and a coating film composed of carbon on the film is used as the cathode foil, the electrostatic capacitance and ESR characteristics of the capacitor are satisfactory. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

この発明は、固体電解コンデンサにかかり、特に導電性ポリマーを電解質に用いた固体電解コンデンサに関する。   The present invention relates to a solid electrolytic capacitor, and more particularly to a solid electrolytic capacitor using a conductive polymer as an electrolyte.

電解コンデンサは、タンタル、アルミニウム等の弁作用金属からなるとともに微細孔やエッチングピットを備える陽極電極の表面に、誘電体となる酸化皮膜層を形成し、この酸化皮膜層から電極を引き出した構成からなる。そして、酸化皮膜層からの電極の引出しは、導電性を有する電解質層により行っている。したがって、電解コンデンサにおいては電解質層が真の陰極を担うことになる。このような真の陰極として機能する電解質層は、酸化皮膜層との密着性、緻密性、均一性などが求められる。特に、陽極電極の微細孔やエッチングピットの内部における密着性が電気的な特性に大きな影響を及ぼしており、従来数々の電解質層が提案されている。   An electrolytic capacitor is made of a valve action metal such as tantalum or aluminum, and has a structure in which an oxide film layer serving as a dielectric is formed on the surface of an anode electrode having fine holes and etching pits, and an electrode is drawn from the oxide film layer. Become. And extraction of the electrode from an oxide film layer is performed by the electrolyte layer which has electroconductivity. Therefore, in the electrolytic capacitor, the electrolyte layer serves as a true cathode. Such an electrolyte layer functioning as a true cathode is required to have adhesion, denseness, and uniformity with the oxide film layer. In particular, the adhesion within the fine holes of the anode electrode and the etching pits has a great influence on the electrical characteristics, and a number of electrolyte layers have been proposed in the past.

ところで、近年、電子機器のデジタル化、高周波化に伴い、小型大容量で高周波領域でのインピーダンスの低いコンデンサが要求されている。   By the way, in recent years, with the digitization and high frequency of electronic equipment, a capacitor having a small size and a large capacity and a low impedance in a high frequency region is required.

これらの要求に対して、陰極箔と陽極箔をセパレータを介して巻回したコンデンサ素子を金属ケースに収納し、封口ゴムによって封止する巻回型の電解コンデンサによって、小型大容量を実現することができる。そして、低インピーダンスに対しては、電解質として固体電解質を用いることで対応することができる。このような固体電解質としては、7、7、8、8−テトラシアノキノジメタン(TCNQ)錯体、ポリピロール、ポリチオフエン等の高導電性を有する導電性ポリマーが知られている。そして、現在では反応速度が緩やかで、かつ陽極電極の酸化皮膜層との密着性に優れたポリエチレンジオキシチオフェン(PEDT)に着目し(特許文献1参照)、その結果、陽極電極箔と陰極電極箔とを、セパレータを介して巻回したコンデンサ素子に、モノマーと酸化剤とを含浸し、その後緩やかに起きるモノマーと酸化剤との化学重合反応で固体電解質であるポリエチレンジオキシチオフェンをコンデンサ素子内部で生成させる固体電解コンデンサが実現されている(特許文献2参照)。
特開平2−15611号公報 特開平10−340829号公報
In response to these requirements, a capacitor element in which a cathode foil and an anode foil are wound through a separator is housed in a metal case, and a small and large capacity is realized by a wound type electrolytic capacitor that is sealed with a sealing rubber. Can do. And it can respond to low impedance by using a solid electrolyte as an electrolyte. As such a solid electrolyte, conductive polymers having high conductivity such as 7,7,8,8-tetracyanoquinodimethane (TCNQ) complex, polypyrrole, polythiophene and the like are known. Attention is now focused on polyethylenedioxythiophene (PEDT), which has a slow reaction rate and excellent adhesion to the oxide film layer of the anode electrode (see Patent Document 1), and as a result, the anode electrode foil and the cathode electrode Capacitor element wound with foil through a separator is impregnated with monomer and oxidant, and then polyethylenedioxythiophene, which is a solid electrolyte, is generated by a chemical polymerization reaction between the monomer and oxidant that occurs slowly. (See Patent Document 2).
JP-A-2-15611 Japanese Patent Laid-Open No. 10-340829

ところで、近年、電子情報機器はデジタル化され、さらにこれらの電子情報機器の心臓部であるマイクロプロセッサの駆動周波数の高速化が進んでいる。これに伴って、消費電力の増大化が進み、発熱による信頼性の問題が顕在化してきたため、その対策として駆動電圧の低減化が図られてきた。   By the way, in recent years, electronic information devices have been digitized, and the driving frequency of the microprocessor which is the heart of these electronic information devices has been increased. Along with this, the power consumption has been increasing and the problem of reliability due to heat generation has become obvious. Therefore, the drive voltage has been reduced as a countermeasure.

上記駆動電圧の低減化を図るため、マイクロプロセッサに高精度な電力を供給する電源の出力側コンデンサには、ESRの低いコンデンサが多数用いられている。このような低ESR特性を有するコンデンサとして、上述したような固体電解コンデンサが用いられている。   In order to reduce the drive voltage, a large number of capacitors having low ESR are used as output-side capacitors of a power supply that supplies highly accurate power to the microprocessor. As the capacitor having such a low ESR characteristic, the solid electrolytic capacitor as described above is used.

しかしながら、マイクロプロセッサの駆動周波数の高速化は著しく、それに伴って消費電力がさらに増大し、コンデンサからの供給電力のさらなる増大化が求められ、このために固体電解コンデンサには大容量化が要求されている。   However, the increase in the driving frequency of the microprocessor is remarkable, and accordingly, the power consumption further increases, and further increase in the power supplied from the capacitor is required. For this reason, the solid electrolytic capacitor is required to have a large capacity. ing.

そこで、本発明は、前述のような問題点を解決するために、静電容量の高い固体電解コンデンサを提供することを目的とする。   Accordingly, an object of the present invention is to provide a solid electrolytic capacitor having a high capacitance in order to solve the above-described problems.

本発明は、陽極電極箔と陰極電極箔とをセパレータを介して巻回するとともに、導電性ポリマーをセパレータで保持したコンデンサ素子を備えた固体電解コンデンサにおいて、陰極電極箔として表面に化成皮膜を形成し、さらにその上にカーボンからなる皮膜を形成したエッチング箔、または表面に化成皮膜を形成し、さらにその上にカーボンからなる皮膜を形成したプレーン箔を用いている。     The present invention forms a chemical conversion film on the surface as a cathode electrode foil in a solid electrolytic capacitor having a capacitor element in which an anode electrode foil and a cathode electrode foil are wound via a separator and a conductive polymer is held by the separator. Moreover, an etching foil having a carbon film formed thereon or a plain foil having a chemical film formed on the surface and a carbon film formed thereon is used.

本発明の固体電解コンデンサについて説明する。アルミニウム等の弁作用金属からなり表面に酸化皮膜層が形成された陽極電極箔と、陰極電極箔とを、セパレータを介して巻回してコンデンサ素子を形成する。そして、このコンデンサ素子のセパレータに導電性ポリマーを保持している。   The solid electrolytic capacitor of the present invention will be described. An anode electrode foil made of a valve action metal such as aluminum and having an oxide film layer formed on the surface thereof and a cathode electrode foil are wound through a separator to form a capacitor element. The conductive polymer is held in the separator of the capacitor element.

陽極電極箔は、アルミニウム等の弁作用金属からなり、陽極電極箔の表面には、アジピン酸アンモニウム等の水溶液中で電圧を印加して誘電体となる酸化皮膜層を形成している。陰極電極箔は、陽極電極箔と同様にアルミニウム等からなり、表面にエッチング処理が施されているものを用いる。   The anode electrode foil is made of a valve action metal such as aluminum, and an oxide film layer serving as a dielectric is formed on the surface of the anode electrode foil by applying a voltage in an aqueous solution of ammonium adipate or the like. The cathode electrode foil is made of aluminum or the like like the anode electrode foil, and the surface is subjected to etching treatment.

陽極電極箔及び陰極電極箔にはそれぞれの電極を外部に接続するための陽極引出し手段、陰極引出し手段が、ステッチ、超音波溶接等の公知の手段により接続されている。これらの電極引出し手段は、巻回したコンデンサ素子の端面から導出される。   Anode extraction means and cathode extraction means for connecting the respective electrodes to the outside are connected to the anode electrode foil and the cathode electrode foil by known means such as stitching and ultrasonic welding. These electrode lead-out means are led out from the end face of the wound capacitor element.

コンデンサ素子は、上記の陽極電極箔と陰極電極箔とを、セパレータを間に挟むようにして巻き取って形成している。両極電極箔の寸法は、製造する固体電解コンデンサの仕様に応じて任意であり、セパレータも両極電極箔の寸法に応じてこれよりやや大きい幅寸法のものを用いればよい。   The capacitor element is formed by winding the anode electrode foil and the cathode electrode foil with a separator interposed therebetween. The dimensions of the bipolar electrode foil are arbitrary depending on the specifications of the solid electrolytic capacitor to be manufactured, and the separator having a slightly larger width may be used depending on the dimensions of the bipolar electrode foil.

このコンデンサ素子内に導電性ポリマーを形成するが、導電性ポリマーとしてポリエチレンジオキシチオフェン(PEDT)を用いると、大容量、低ESR特性を有する固体電解コンデンサを得ることができるので好適である。このPEDTは、モノマーである3,4−エチレンジオキシチオフェン(EDT)を酸化剤であるp−トルエンスルホン酸第二鉄で重合させて得ることができる。重合はEDTまたはEDT溶液と酸化剤溶液をコンデンサ素子に注入して加熱して行うこともできるし、EDTと酸化剤の混合液をコンデンサ素子に注入、または混合液にコンデンサ素子を浸漬して含浸し加熱して行うこともできる。   A conductive polymer is formed in this capacitor element. When polyethylenedioxythiophene (PEDT) is used as the conductive polymer, a solid electrolytic capacitor having a large capacity and low ESR characteristics can be obtained. This PEDT can be obtained by polymerizing 3,4-ethylenedioxythiophene (EDT) as a monomer with ferric p-toluenesulfonate as an oxidizing agent. Polymerization can be performed by injecting EDT or an EDT solution and an oxidant solution into a capacitor element and heating, or by injecting a mixed liquid of EDT and an oxidant into the capacitor element, or immersing the capacitor element in a mixed solution. It can also be performed by heating.

そして、この導電性ポリマーを形成したコンデンサ素子を有底筒状の金属ケースに収納し、封口ゴムで加締め封止して固体電解コンデンサが形成される。   Then, the capacitor element in which the conductive polymer is formed is housed in a bottomed cylindrical metal case, and is swaged and sealed with a sealing rubber to form a solid electrolytic capacitor.

ここで、本発明においては、陰極電極箔として、表面に化成皮膜を形成し、さらにその上にカーボンからなる皮膜を形成したエッチング箔、または表面に化成皮膜を形成し、さらにその上にカーボンからなる皮膜を形成したプレーン箔を用いる。また、カーボンの皮膜の厚みは、0.01〜3μmとすることが好ましく、さらに0.03〜2μmとすることが好ましい。この範囲未満ではESR低減効果が少なく、この範囲を越えると皮膜の接合強度が低下する。また、プレーン箔を用いた場合、エッチング箔に比べてエッチング部がない分、箔厚を小さくすることができ、箔面積を拡大して静電容量を増大することができる。   Here, in the present invention, as the cathode electrode foil, a chemical conversion film is formed on the surface, and an etching foil in which a film made of carbon is further formed thereon, or a chemical conversion film is formed on the surface, and carbon is further formed thereon. A plain foil on which a film is formed is used. The thickness of the carbon film is preferably 0.01 to 3 μm, and more preferably 0.03 to 2 μm. If it is less than this range, the effect of reducing ESR is small, and if it exceeds this range, the bonding strength of the film is lowered. In addition, when a plain foil is used, the thickness of the foil can be reduced as much as there is no etching portion compared to the etching foil, and the capacitance can be increased by increasing the foil area.

化成したエッチング箔、または化成したプレーン箔へのカーボンからなる皮膜の形成方法としては、蒸着法が好ましい。蒸着法としては、真空蒸着法、イオンプレーティング法、スパッタリング法、イオンビームスパッタ法、イオンビームアシスト蒸着法等を挙げることができる。なかでも、イオンプレーティング法が好ましく、さらにこの中でアークイオンプレーティング法(陰極アークプラズマ蒸着法)が好ましい。このアークプラズマ蒸着法の条件は、カーボンをターゲットとして、電流値は60〜300A、電圧値は15〜25Vである。そして、全圧が1×10-1〜1×10-4Torrのアルゴン雰囲気で行う。   As a method of forming a film made of carbon on the formed etching foil or the formed plain foil, a vapor deposition method is preferable. Examples of the vapor deposition method include a vacuum vapor deposition method, an ion plating method, a sputtering method, an ion beam sputtering method, and an ion beam assisted vapor deposition method. Of these, the ion plating method is preferable, and the arc ion plating method (cathode arc plasma deposition method) is more preferable. The conditions of this arc plasma deposition method are that carbon is a target, the current value is 60 to 300 A, and the voltage value is 15 to 25V. The total pressure is 1 × 10 −1 to 1 × 10 −4 Torr.

以上の固体電解コンデンサにおいては、化成皮膜の表面に形成したカーボンの比電気抵抗が低いので、導電性ポリマーと陰極箔が導通状態となって、コンデンサの合成容量が最大となり、静電容量が増大となる。さらに、カーボンと導電性ポリマーとの接着性が良好なので、ESRが低減する。   In the above solid electrolytic capacitor, the specific electric resistance of carbon formed on the surface of the chemical conversion film is low, so that the conductive polymer and the cathode foil are in a conductive state, the combined capacitance of the capacitor is maximized, and the capacitance is increased. It becomes. Further, since the adhesion between carbon and the conductive polymer is good, ESR is reduced.

本発明は、陽極電極箔と陰極電極箔とをセパレータを介して巻回するとともに、導電性ポリマーをセパレータで保持したコンデンサ素子を備えた固体電解コンデンサにおいて、陰極電極箔として表面に化成皮膜を形成し、さらにその上にカーボンからなる皮膜を形成したエッチング箔、または表面に化成皮膜を形成し、さらにその上にカーボンからなる皮膜を形成したプレーン箔を用いているので、静電容量特性、ESR特性が良好である。
The present invention forms a chemical conversion film on a surface as a cathode electrode foil in a solid electrolytic capacitor having a capacitor element in which an anode electrode foil and a cathode electrode foil are wound via a separator and a conductive polymer is held by the separator. In addition, an etching foil having a carbon film formed thereon or a plain foil having a chemical film formed on the surface and a carbon film formed thereon is used. Good characteristics.

次に本発明の固体電解コンデンサについて具体的に説明する。
陽極電極箔及び陰極電極箔は、弁作用金属、例えばアルミニウム、タンタルからなり、その表面には予めエッチング処理が施されて表面積が拡大されている。陽極電極箔については、更に化成処理が施され、表面に酸化アルミニウムからなる酸化皮膜層が形成されている。この陽極電極箔及び陰極電極箔を、セパレータを介して巻回し、コンデンサ素子を得る。
Next, the solid electrolytic capacitor of the present invention will be specifically described.
The anode electrode foil and the cathode electrode foil are made of a valve metal, such as aluminum or tantalum, and the surface thereof is preliminarily etched to increase the surface area. The anode electrode foil is further subjected to chemical conversion treatment, and an oxide film layer made of aluminum oxide is formed on the surface. The anode electrode foil and the cathode electrode foil are wound through a separator to obtain a capacitor element.

次いで、コンデンサ素子に、EDTと酸化剤とを含浸する。酸化剤は、p−トルエンスルホン酸第二鉄のブタノール溶液を用い、150℃、1時間加熱重合して、導電性ポリマーであるPEDTを生成する。   Next, the capacitor element is impregnated with EDT and an oxidizing agent. As the oxidizing agent, a butanol solution of ferric p-toluenesulfonate is used and polymerized by heating at 150 ° C. for 1 hour to produce PEDT which is a conductive polymer.

このようにして陽極電極箔と陰極電極箔の間に介在したセパレータに導電性ポリマー層が形成されたコンデンサ素子は、有底筒状のケースに収納され、ブチルゴムからなる封口ゴムで封止して固体電解コンデンサを形成する。定格は2.5WV−820μFである。   Thus, the capacitor element in which the conductive polymer layer is formed on the separator interposed between the anode electrode foil and the cathode electrode foil is housed in a bottomed cylindrical case and sealed with a sealing rubber made of butyl rubber. A solid electrolytic capacitor is formed. The rating is 2.5 WV-820 μF.

ここで、実施例1として、0.3μmのカーボン皮膜を形成した50μmの2V化成エッチング箔を陰極箔として用いた。また、実施例2として、0.3μmのカーボン皮膜を形成した30μmの2V化成プレーン箔を陰極箔として用いた。   Here, as Example 1, a 50 μm 2V chemical etching foil having a 0.3 μm carbon film formed thereon was used as a cathode foil. Further, as Example 2, a 30 μm 2V chemical conversion plain foil on which a 0.3 μm carbon film was formed was used as a cathode foil.

また、比較例1として、0.3μmの窒化チタン皮膜を形成した50μmのエッチング箔、比較例2として、0.3μmの窒化チタン皮膜を形成した50μmの2V化成エッチング箔を用いた。   Further, as Comparative Example 1, a 50 μm etching foil formed with a 0.3 μm titanium nitride film was used, and as Comparative Example 2, a 50 μm 2V chemical conversion etching foil formed with a 0.3 μm titanium nitride film was used.

次に、これらの固体電解コンデンサの初期特性を(表1)に示す。   Next, initial characteristics of these solid electrolytic capacitors are shown in (Table 1).

Figure 2005109278
Figure 2005109278

以上のように、実施例は比較例に比べて、静電容量、ESR共に良好である。
As described above, the example has better electrostatic capacity and ESR than the comparative example.

Claims (2)

陽極電極箔と陰極電極箔とをセパレータを介して巻回するとともに、導電性ポリマーをセパレータで保持したコンデンサ素子を備えた固体電解コンデンサにおいて、陰極電極箔として表面に化成皮膜を形成し、さらにその上にカーボンからなる皮膜を形成したエッチング箔、または表面に化成皮膜を形成し、さらにその上にカーボンからなる皮膜を形成したプレーン箔を用いた固体電解コンデンサ。 In a solid electrolytic capacitor having a capacitor element in which an anode electrode foil and a cathode electrode foil are wound via a separator and a conductive polymer is held by the separator, a chemical conversion film is formed on the surface as the cathode electrode foil, and A solid electrolytic capacitor using an etching foil having a carbon film formed thereon, or a plain foil having a chemical film formed on the surface and a carbon film formed thereon. 導電性ポリマーが3,4−エチレンジオキシチオフェンと酸化剤の化学重合によって形成したポリエチレンジオキシチオフェンである請求項1記載の固体電解コンデンサ。



The solid electrolytic capacitor according to claim 1, wherein the conductive polymer is polyethylene dioxythiophene formed by chemical polymerization of 3,4-ethylenedioxythiophene and an oxidizing agent.



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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05159984A (en) * 1991-12-06 1993-06-25 Nobuki Mutsukura Electrolytic capacitor
JPH09293639A (en) * 1996-04-26 1997-11-11 Nippon Chemicon Corp Solid electrolytic capacitor and manufacture thereof
JPH11219861A (en) * 1997-06-20 1999-08-10 Matsushita Electric Ind Co Ltd Electrolytic capacitor and manufacture thereof
JP2001307962A (en) * 2001-03-27 2001-11-02 Nippon Chemicon Corp Solid electrolytic capacitor and the manufacturing method

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05159984A (en) * 1991-12-06 1993-06-25 Nobuki Mutsukura Electrolytic capacitor
JPH09293639A (en) * 1996-04-26 1997-11-11 Nippon Chemicon Corp Solid electrolytic capacitor and manufacture thereof
JPH11219861A (en) * 1997-06-20 1999-08-10 Matsushita Electric Ind Co Ltd Electrolytic capacitor and manufacture thereof
JP2001307962A (en) * 2001-03-27 2001-11-02 Nippon Chemicon Corp Solid electrolytic capacitor and the manufacturing method

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