JP3551098B2 - Manufacturing method of capacitor - Google Patents

Description

【００９１】
（比較例１）
次に比較のため、比較例１として本実施の形態では、実施の形態１のポリピロール層を形成する替わりに電解液を充填した以外、実施の形態１と同様にして５個のコンデンサを完成させた。
【００９２】
電解液としては、フタル酸モノメチルトリエチルアンモニウムを２０％含むγ―ブチロラクトン溶液を用いた。
コンデンサ完成後、実施の形態１と同様の評価を行い、その結果を（表１）に示した。
【００９３】
（表１）より理解されるように、本実施の形態本実施の形態において、容量達成率（液中容量との比率）に優れたコンデンサが得られ、さらに損失係数の小さくなっていることが分かる。
【００９４】
高い容量達成率が得られるのは、重合反応が比較的緩やかに進むため、素子深部まで液が浸透するための効果と考えられる。
【００９５】
また損失係数が小さいのは、ポリピロールの電気伝導度が従来使用されている電解液のそれより格段に高いことに起因したものである。
【００９６】
すなわち、本実施の形態によるコンデンサは優れた初期特性を有することが実証された。
【００９７】
（実施の形態２）
本実施の形態においては、アルミニウム箔電極捲回型コンデンサ素子に替えてタンタル焼結体素子を用いて、これに実施の形態１と同様にしてポリピロールで対極層を形成してコンデンサを作製した。
【００９８】
タンタル焼結体のジメンジョン及び化成方法を以下に述べる。
【００９９】
０．３ｍｍのタンタル線リードを埋め込んだ１．３ｍｍ×３．０ｍｍ×３．８ｍｍのタンタル焼結体を用意し、燐酸５ｍｌを１０００ｍｌの水に溶解した溶液を用い、約９０℃で４０Ｖを印加して、陽極酸化により酸化皮膜誘電体被膜を形成した。
【０１００】
この構成をコンデンサと見立て、化成液中の容量を測定したところ、１２０Ｈｚで２３０μＦであった。
【０１０１】
上記コンデンサ素子を用いて実施の形態１と同様にしてポリピロール層を形成し、さらにコロイダルグラファイト、銀ペイントで対極を形成して、て５個のコンデンサを得、１２０Ｈｚにおける容量、損失係数を各々測定し、それらの平均値を（表１）に示した。
【０１０２】
（比較例２）
次に比較のため、比較例２として、実施の形態２において、ポリピロール層を形成する替わりに、従来のタンタルコンデンサの製法に準じてコンデンサを作製した。
【０１０３】
すなわち、３０％濃度の硝酸マンガン水溶液に、素子を浸漬後２５０℃で熱分解二酸化マンガン層を対極として形成した以外、実施の形態２と同様にして５個のコンデンサを完成させた。
【０１０４】
得られたコンデンサの初期特性を実施の形態１と同様に評価し、その結果を（表１）に示した。
【０１０５】
比較例２との比較から本実施の形態においても、容量達成率が高く、損失係数の小さいタンタルコンデンサが得られていること明らかであり、本発明の優れた効果が実証された。
【０１０６】
（実施の形態３）
本実施の形態では、実施の形態１において過炭酸ナトリウムを用いる替わりに０．５Ｍの過ホウ酸ナトリウム（ＮａＢＯ_３・４Ｈ_２Ｏ）を用いた以外、実施の形態１と同様にして５個のコンデンサを作製し、やはり実施の形態１と同様の評価を行い、その結果を（表１）に示した。
【０１０７】
（表１）から、本発明によるコンデンサは、容量達成率が高くかつ損失係数の小さいことが明らかであり、本発明の優れた効果が実証された。
【０１０８】
（実施の形態４）
本実施の形態では、実施の形態１において０．５Ｍのテトラアセチルエチレンジアミンを用いる替わりに、（Ａ）０．５Ｍのオクタノイルオキシベンゼンスルホン酸ナトリウム（（Ｃ８Ｈ１７Ｃ（＝Ｏ）Ｏ（Ｃ６Ｈ６）ＳＯ３Ｎａ）、（Ｂ）０．５Ｍのデカノイルオキシ安息香酸（（Ｃ９Ｈ１９Ｃ（＝Ｏ）Ｏ（Ｃ６Ｈ６）ＣＯＯＨ）、（Ｃ）０．５Ｍのペンタアセチルグルコース（Ｃ_１６Ｈ_２２Ｏ_１１）、（Ｄ）０．５Ｍのトリアセチルグリセリド（（ＣＨ_３ＣＯＯ）_３Ｃ_３Ｈ_５）をそれぞれ用いた以外、実施の形態４と同様にして５個ずつコンデンサを作製し、実施の形態１と同様の評価を行ってその結果を（表１）に示した。
【０１０９】
（表１）から、本発明によるコンデンサは、いずれも容量達成率が高くかつ損失係数の小さいことが明らかであり、本発明の優れた効果が実証された。
【０１１０】
（実施の形態５）
本実施の形態では、実施の形態４において過炭酸ナトリウムの替わりに同濃度の過ホウ酸ナトリウム塩を用いた以外、実施の形態４と同様にして（Ａ）から（Ｄ）の各有機過酸前駆体を含む系で５個ずつコンデンサを作製した。
（Ａ）０．５Ｍ濃度のオクタノイルオキシベンゼンスルホン酸ナトリウム
（Ｂ）０．５Ｍ濃度のデカノイルオキシ安息香酸
（Ｃ）０．５Ｍ濃度のペンタアセチルグルコース
（Ｄ）０．５Ｍ濃度のトリアセチルグリセリド
作製したコンデンサについて実施の形態１と同様にして特性評価を行い、その結果を（表１）に示した。
【０１１１】
（表１）から、本発明によるコンデンサは、いずれも容量達成率が高くかつ損失係数の小さいことが明らかであり、本発明の優れた効果が実証された。
【０１１２】
（実施の形態６）
本実施の形態では、エッチドアルミニウム箔表面に（Ａ）アクリル酸とメタクリル酸とスチレンの共重合体ならびに（Ｂ）ポリイミドからなる誘電体を形成した電極箔を用い、さらにテトラアセチルエチレンジアミンを除去した以外実施の形態１で用いたものと同じ重合溶液を用いて５個のコンデンサを作製した。
【０１１３】
本実施の形態におけるアクリル酸とメタクリル酸とスチレンの共重合体からなる誘電体の形成法の一例を次に示す。
【０１１４】
電極箔として厚さ約０．１ｍｍ、平均細孔径が約２μｍ、表面積が約３０倍に拡面化されたエッチドアルミニウム箔を実施の形態１と同様の寸法に切断してアルミニウムリードを取り付けた。
【０１１５】
対極は、実施の形態１と同じものを用いた。
【０１１６】
先ず、前者の電極箔に電着によりアクリル酸とメタクリル酸とスチレンの共重合体からなる誘電体薄膜を形成した。
【０１１７】
用いた電着液組成は、固形分が１０重量％、イオン交換水８６重量％、ブチルセロソルブ４重量％である。
【０１１８】
ここで固形分として、分子量約３万のアクリル酸とメタクリル酸とスチレンの共重合体とベンゾグアナミン系樹脂が重量比で７：３で混合したものを用いた。
【０１１９】
この固形分を液中に分散させるため、カルボン酸基の５０％をトリメチルアミンにより中和した。
【０１２０】
上記電着液に、電極箔を浸し、０．３ｍＡ／ｃｍ２の電流密度で１０Ｖに達するまで定電流電着を行い、さらに１０Ｖで１５分間定電圧電着を行った。
次に、アクリル酸系の高分子薄膜が形成された電極箔を水洗後８０℃で２０分間、１８０℃で３０分間熱処理することにより、ベンゾグアナミン系樹脂との間で架橋反応させた。
【０１２１】
以上述べた一連の処理を３回繰り返した後、洗浄乾燥し、さらに実施の形態１と同様にセパレータを介して対極と捲回してコンデンサ素子を用意した。
この素子を電解液中で容量を測定したところ、１２０Ｈｚで２１．５μＦを示した。
【０１２２】
次にポリイミド電着膜形成の１例を以下に示す。
【０１２３】
ビフェニルテトラカルボン酸二無水物とｐ―フェニレンジアミンをＮ−メチルピロリドン中で窒素還流下で反応させてポリアミック酸を得た。
【０１２４】
このポリアミック酸をＮ，Ｎ−ジメチルアミドに希釈し、トリエチルアミンを加えてポリアミック酸塩溶液を得た。
【０１２５】
上記溶液にメタノールを添加して最終的にポリアミック酸を０．１５％含むように調整を電着液とした。
【０１２６】
この溶液にコンデンサ素子を浸し、これを陽極として前記コンデンサ素子と離隔して設けた陰極間に３０Ｖの電圧を印可してポリアミック酸膜を析出させた。
【０１２７】
その後、２５０℃で１時間加熱してポリアミック酸をポリイミド化した。
【０１２８】
この電着並びに加熱を３回繰り返した後導電性高分子層形成を行った。
【０１２９】
その後、アクリル酸とメタクリル酸とスチレンの共重合体からなる誘電体が形成された電極箔の場合と同様に対極とセパレータを介して捲回してコンデンサ素子を完成させた。
【０１３０】
電解液中で得られた１２０Ｈｚにおける容量は、２２．１μＦであった。
【０１３１】
これらのコンデンサ素子に、実施の形態１と同様にして過炭酸ナトリウムを酸化剤としてポリピロール層を形成した。
【０１３２】
その後実施の形態１と同様にして特性を評価してその結果を（表１）に示した。（表１）から、本発明によるコンデンサは、いずれも容量達成率が高くかつ損失係数の小さいことが明らかであり、本発明の優れた効果が実証された。
【０１３３】
（実施の形態７）
本実施の形態では、実施の形態６（Ａ）において、過炭酸ナトリウムを過ホウ酸ナトリウムに替えた以外、実施の形態６（Ａ）と同様にして５個のコンデンサを作製した。
【０１３４】
これらのコンデンサについて、実施の形態１と同様にして特性評価を行い、その結果を（表１）に示した。
【０１３５】
（表１）から、本発明によるコンデンサは、いずれも容量達成率が高くかつ損失係数の小さいことが明らかであり、本発明の優れた効果が実証された。
【０１３６】
（実施の形態８）
本実施の形態では、実施の形態６において過炭酸ナトリウムを重合酸化剤として単独使用する替わりに以下に示す（Ａ）から（Ｅ）の有機過酸前駆体を組合せ使用した以外、実施の形態６と同様にして５個ずつコンデンサを作製した。
（Ａ）０．５Ｍ濃度のテトラアセチルエチレンジアミン
（Ｂ）０．５Ｍ濃度のオクタノイルオキシベンゼンスルホン酸ナトリウム
（Ｃ）０．５Ｍ濃度のデカノイルオキシ安息香酸
（Ｄ）０．５Ｍ濃度のペンタアセチルグルコース
（Ｅ）０．５Ｍ濃度のトリアセチルグリセリド
作製したコンデンサについて実施の形態１と同様にして特性評価を行い、その結果を（表１）に示した。
【０１３７】
（表１）から、本発明によるコンデンサは、いずれも容量達成率が高くかつ損失係数の小さいことが明らかであり、本発明の優れた効果が実証された。
【０１３８】
（実施の形態９）
本実施の形態では、実施の形態８において過炭酸ナトリウムを使用する替わりに０．５Ｍの過ホウ酸ナトリウムを使用した以外、実施の形態８と同様にして５個ずつコンデンサを作製した。
【０１３９】
なお、組合せ使用した有機過酸前駆体の種類濃度ともに実施の形態８と同様にした。
（Ａ）０．５Ｍ濃度のテトラアセチルエチレンジアミン
（Ｂ）０．５Ｍ濃度のオクタノイルオキシベンゼンスルホン酸ナトリウム
（Ｃ）０．５Ｍ濃度のデカノイルオキシ安息香酸
（Ｄ）０．５Ｍ濃度のペンタアセチルグルコース
（Ｅ）０．５Ｍ濃度のトリアセチルグリセリド
作製したコンデンサについて実施の形態１と同様にして特性評価を行い、その結果を（表１）に示した。
【０１４０】
（表１）から、本発明によるコンデンサは、いずれも容量達成率が高くかつ損失係数の小さいことが明らかであり、本発明の優れた効果が実証された。
なお、実施の形態では、過炭酸塩ならびに過ホウ酸塩として、ナトリウム塩を用いた場合のついてのみ述べたが、他のアルカリ金属塩またはアンモニウム塩を用いることもできる。
【０１４１】
なお、本実施の形態ではピロールモノマーを重合前駆体に用いた場合についてのみ述べたが、例えばＮ―メチルピロールなど他の重合可能なモノマーを用いることもでき、またアニリン、チオフェン誘導体を用いてもよく、本発明は重合前駆体の種類に限定されない。
【０１４２】
なお、有機過酸前駆体として、テトラアセチルエチレンジアミン、オクタノイルオキシベンゼンスルホン酸ナトリウム、デカノイルオキシ安息香酸、ペンタアセチルグルコース、トリアセチルグリセリドを用いた場合についてのみ述べたが、たの有機過酸前駆体を用いることもでき、本発明はその種類に限定されない。なお、実施の形態では、重合性モノマーに対して概略化学量論量の酸化剤を用いた場合についてのみ述べたが、化学量論量より過剰または過少に添加することもでき、本発明はその添加比率に限定されない。
【０１４３】
なお、テトラアセチルエチレンジアミンの替わりにテトラメチレンジアミンなど他のアルキレン基を有する同様に使用することが可能であり、さらにオクタノイルオキシベンゼンスルホン酸ナトリウム、デカノイルオキシ安息香酸において、炭素数の異なる他のアルキノイル基を有するものを用いることもできる。
【０１４４】
なお、有機過酸前駆体濃度は、過炭酸塩もしくは過ホウ酸塩との共存により有効に有機過酸を生成する量が含まれていればよく、その濃度は本発明の実施の形態に限定されない。
【０１４５】
なお、本実施の形態ではフィルムコンデンサの誘電体としてアクリル酸とメタクリル酸とスチレンの共重合体ならびにポリイミドを用いる場合についてのみ述べたが、本発明の趣旨から金属箔電極上に薄膜を形成できる高分子であれば他の共重合体または単独の重合体を用いることもできる。
【０１４６】
なお、実施の形態ではドーパントとなる基を含む塩として、トリイソプロピルナフタレンスルホン酸ナトリウムを用いた場合についてのみ述べたが、有効にドーパントになる基を含むものであれば、他のスルホン酸基を含む塩または含まない塩を用いることもでき、濃度もドーパントとして取り込まれる以上の量が重合液系内に存在していればよく、本発明はその種類及び添加量に限定されない。
【０１４７】
なお、実施の形態では箔状電極を用いたコンデンサにおいて捲回型構造のものについてのみ述べたが、電極箔を単板で用いてもよくまたそれを積層して用いた構造に適用することもできる。
【０１４８】
なお、実施の形態ではモノマーと酸化剤とドーパントのみもしくはモノマーと酸化剤と有機過酸とドーパントのみを含む重合水溶液を用いる場合についてのみ述べたが、有機過酸前駆体の溶解を助ける有機溶媒などを含んでもよい。
【０１４９】
なお、実施の形態では、液の水素イオン濃度を酸性にするために硫酸をもちいるばあいについてのみ述べたが、他の鉱酸を用いてもよくまたスルホン酸等の有機酸を用いることでき、その種類のよって本発明は限定されない。
【０１５０】
【発明の効果】
本発明の重合酸化剤を用いることにより、重合反応が緩やかに進むために、電解コンデンサおよび巻回したエッチドアルミニウム箔表面に設けた高分子フィルムを誘電体としたフィルムコンデンサ内部へ溶液の浸透を確実に行わせることが可能になり、容量達成率の高い電解コンデンサおよびフィルムコンデンサを容易に得ることができるという効果を奏する。
【０１５１】
また、対極導電層に電子伝導性の導電性高分子層を形成しているため、電解液を用いた場合よりも損失係数の小さい電解コンデンサが実現できるという効果も奏する。
【図面の簡単な説明】
【図１】本発明第１の実施の形態におけるコンデンサの構成を示す断面図
【符号の説明】
１、３ 金属箔電極
２ 誘電体皮膜
４ セパレータ
５ ポリピロール層[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for manufacturing a capacitor, and more particularly to a method for easily realizing a small and large-capacity solid electrolytic capacitor having excellent frequency characteristics and a small and large-capacity film capacitor.
[0002]
[Prior art]
2. Description of the Related Art In recent years, with the digitization of electric devices, a capacitor having a small size, a large capacity, and a low impedance in a high frequency region has been demanded.
[0003]
Conventionally, there are mica capacitors and multilayer ceramic capacitors as capacitors used in a high frequency region. However, these capacitors have a large shape and it is difficult to increase the capacitance.
[0004]
On the other hand, as a large-capacity capacitor, there is an electrolytic capacitor such as an aluminum dry electrolytic capacitor or an aluminum or tantalum solid electrolytic capacitor.
[0005]
In these capacitors, a large capacity can be realized because the oxide film serving as a dielectric is extremely thin.On the other hand, since the oxide film is easily damaged, it also serves as a true cathode for repairing the oxide film. It is necessary to provide an electrolyte.
[0006]
For example, in an aluminum dry capacitor, the etched anode and cathode aluminum foils are wound through a separator, and the separator is impregnated with a liquid electrolyte for use.
[0007]
This liquid electrolyte has a problem that it has a large loss due to ionic conductivity and a large specific resistance, and the frequency characteristics and the temperature characteristics of the impedance are extremely poor.
[0008]
In addition, there is a problem that liquid leakage, evaporation, and the like are inevitable, and the capacity is reduced and the loss is increased over time.
[0009]
Tantalum solid electrolytic capacitors use manganese oxide as the electrolyte, so that the problems of temperature characteristics and changes over time such as capacity and loss are improved, but the loss of loss due to the relatively high specific resistance of manganese oxide is improved. The frequency characteristics of the impedance were inferior to those of the multilayer ceramic capacitor or the film capacitor.
[0010]
In order to solve this problem, there has been proposed an aluminum and tantalum solid electrolytic capacitor using polypyrrole having high electric conductivity as a counter electrode.
[0011]
Polypyrrole is insoluble and infusible, and it has been practically impossible to take any other method than polymerizing it in situ using monomers to form it on the dielectric film.
[0012]
In particular, it is difficult to fill the polypyrrole layer by electrolytic polymerization in aluminum electrolytic capacitors with an etched aluminum foil structure and in tantalum capacitors using porous sintered bodies. There is.
[0013]
As an example of a method for forming a chemically polymerized polypyrrole, there is a method of immersing a capacitor element in a solution containing a pyrrole monomer and an oxidizing agent.
[0014]
As a liquid to be immersed, there are a method using one liquid in which a pyrrole monomer and an oxidizing agent coexist, and a method using two liquids separated separately.
[0015]
On the other hand, although the film capacitor has excellent frequency characteristics, the capacity per unit volume is small, and it has been difficult to realize a film capacitor having a small size and a large capacity.
[0016]
Accordingly, a large-capacity film capacitor has been proposed in which a dielectric made of an electrodeposited polyimide thin film is formed on an etched aluminum foil, and then a conductive polymer layer is formed by chemical polymerization and electrolytic polymerization to serve as a counter electrode. Proceedings of the 58th Annual Meeting of the Chemical Society, pp. 251-252 (1991)).
[0017]
Except for forming an electrodeposited polymer layer on the dielectric film, a structure similar to that of an aluminum solid electrolytic capacitor can realize a larger-capacity film capacitor. It is necessary to use legal methods.
[0018]
[Problems to be solved by the invention]
However, as described above, when chemical polymerization is to be used to form the counter electrode polypyrrole, a conventionally known oxidizing agent, persulfate, hydrogen peroxide, ferric salt, or the like is polymerized with an oxidizing agent. At a room temperature near the room temperature, the polymerization reaction takes place at the moment when the monomer and the oxidizing agent are mixed, and the pot life of the polymerization solution is extremely short, so that one solution cannot be used.
[0019]
Although this can be solved by lowering the mixing temperature, a cooling device is required, which causes a new problem that the polymerization process becomes complicated and the cost becomes high.
[0020]
In addition, it becomes difficult to use water that freezes at around 0 ° C. as a polymerization medium, and there is a problem that an expensive organic solvent must be used.
[0021]
Further, the above problem can be solved by lowering the concentration of the monomer and the oxidizing agent in the medium, but in this case, since the amount of polypyrrole formed in one treatment is small, a polypyrrole layer having a desired amount is formed. In order to do so, there is an undesirable problem that the number of times of immersion processing must be increased.
[0022]
Further, the problem of the pot life of the polymerization solution can be solved by mutually immersing the capacitor elements in the monomer solution and the oxidizing agent solution, but in this case, the polymerization reaction proceeds before the monomer and the oxidizing agent are sufficiently mixed. As a result, the formation of the polypyrrole layer in the etching pit or the deep portion of the sintered body is hindered, and a capacitor with a high capacity achievement ratio (the ratio of the capacity obtained in the electrolytic solution to the capacity obtained when coated with the conductive polymer) is obtained Another problem that cannot be obtained occurs.
[0023]
An object of the present invention is to solve the above-mentioned problems in the prior art, and to provide a method for efficiently manufacturing a small solid electrolytic capacitor having excellent high frequency characteristics and a film capacitor and a film capacitor.
[0024]
[Means for Solving the Problems]
The present invention relates to a method for manufacturing a solid electrolytic capacitor and a film capacitor using a polypyrrole layer obtained by chemical polymerization as a counter electrode.
[0025]
One example of the structure of the capacitor of the present invention is shown in FIG. 1. A metal foil electrode 1 on which a dielectric film 2 is formed and a metal foil counter electrode 3 are wound together with two separators 4 so that a true In this case, a chemically polymerized polypyrrole layer 5 serving as a counter electrode is formed.
[0026]
It is known that polypyrrole can be easily obtained by chemical polymerization.However, when a conventionally used oxidizing agent, persulfate, hydrogen peroxide, various types of ferric iron, etc. are used, the polymerization reaction occurs at around room temperature. There are a variety of issues that arise in a very short time and are difficult to control.
[0027]
That is, typically, the pot life of a polymerization solution in which a pyrrole monomer and an oxidizing agent coexist is short, and when a polymerization solution is impregnated into a capacitor element, a polymerization reaction occurs before the liquid penetrates deep into the element, and the void is closed. That is, the capacity that can be originally obtained cannot be obtained.
[0028]
In order to avoid the conventional problem, a percarbonate or perborate having low activity around room temperature is used as an oxidizing agent.
[0029]
Percarbonate and perborate are known to decompose rapidly at a temperature higher than room temperature to generate hydrogen peroxide, and are widely used as household bleaching agents.
[0030]
According to the present invention, a film capacitor can be obtained by polymerizing polypyrrole on the surface of a dielectric substance by utilizing the oxidizing action of hydrogen peroxide.
[0031]
As described above, since the decomposition reaction of the oxidizing agent is slow at around room temperature, the polymerization reaction does not occur immediately even when the oxidizing agent is brought into contact with the monomer in a solution as in the case of the conventional oxidizing agent.
[0032]
Therefore, even if the capacitor element is alternately immersed in the monomer solution and the oxidizing agent solution, the polymerization reaction is unlikely to occur in the process of penetrating deep into the capacitor element. Do not disturb.
[0033]
As the cation of percarbonate and perborate, any can be used, but an alkali metal ion or an ammonium ion is preferably used.
[0034]
Another solution of the present invention is to use the above-mentioned percarbonate or perborate and an organic peracid precursor together as a polymerization oxidizing agent when applied to an electrolytic capacitor or a film capacitor.
[0035]
For the decomposition of percarbonate and perborate, it is considered that a temperature higher than room temperature is desirable as described above.
[0036]
The combined use of organic peracid precursors produces a more active organic peracid by reaction with percarbonate and perborate, and by using this in the polymerization reaction, it is lower than in the case of using them alone. The inventors have found that the polymerization reaction of polypyrrole can proceed at a temperature and in a short time.
[0037]
This is based on the following reaction mechanism.
[0038]
RC (= O) -L + H ₂ O ₂ → RC (= O) OOH + HL
Here, RC (= O) -L is an organic peracid precursor, R is an alkyl group, and L is a leaving group.
[0039]
Alkyl having about 1 to 12 carbon atoms is desirable because it has solubility in water, and the leaving group is suitably selected from ethylene diamino group, glucose group, carboxylic acid phenolate, sulfonic acid phenolate and glyceride.
[0040]
In addition, other leaving groups such as a methylene diamino group can be used.
[0041]
When this organic peracid precursor is used in combination, polypyrrole can be produced in a shorter time at a lower temperature than in the case of using a percarbonate or perborate alone, and there is an advantage that the capacitor manufacturing time can be shortened.
[0042]
However, even in this case, since the polymerization reactivity of polypyrrole is much lower than conventionally used persulfate, hydrogen peroxide and various ferric salts, it is possible to polymerize after permeating the polymerization liquid into the capacitor element. Thus, a capacitor having a high capacity achievement ratio can be obtained.
[0043]
The polymerization solution may contain an organic peracid precursor used in combination with the pyrrole monomer, percarbonate or perborate, or a salt containing a group serving as a dopant.
[0044]
Various sulfonic acids are suitable as a substance containing the above-mentioned dopant group.
[0045]
Among them, aromatic sulfonic acids in which a sulfonic acid group is bonded to an aromatic ring are more preferable because a conductive polymer having high environmental stability can be obtained.
[0046]
Further, aromatic sulfonic acids having a substituent can also be suitably used.
[0047]
According to the present invention, polymerization is less likely to occur during the permeation process into the inside of the capacitor element because the generation of hydrogen peroxide is low around room temperature.
[0048]
Since the capacitor thus obtained is covered with polypyrrole to a deep portion, the capacity achievement ratio is easily improved.
[0049]
The capacity achievement rate is a value expressed by the ratio of the capacity obtained in a solution in which an appropriate electrolyte is dissolved after the formation of the dielectric film and the capacity obtained after the formation of polypyrrole. I have.
[0050]
As the capacitor, in addition to the above-mentioned wound aluminum electrolytic capacitor, a tantalum electrolytic capacitor using a porous tantalum sintered body as an electrode can be manufactured by the present invention.
[0051]
Further, a film capacitor which is a dielectric by forming a polyacrylic acid-based copolymer or polyimide on the surface of a metal electrode by, for example, electrodeposition can also be manufactured by the present invention.
[0052]
It is also possible to use other thin film production methods that can control the thickness of the polymer layer serving as the dielectric, and it is also possible to use other materials as the polymer serving as the dielectric.
[0053]
BEST MODE FOR CARRYING OUT THE INVENTION
According to the first aspect of the present invention, there is provided a method for manufacturing a solid electrolytic capacitor in which a valve metal electrode surface is provided with an anodic oxide film dielectric layer of the valve metal and a conductive polymer layer obtained by polymerizing a polymerizable monomer. A method for producing a solid electrolytic capacitor, wherein a percarbonate and an organic peracid precursor are used for the polymerization of the polymerizable monomer.
[0054]
Here, as described in claim 2, pyrrole or a derivative thereof can be used as the polymerizable monomer.
[0055]
Here, as described in claim 3, one kind selected from tetraacetylalkylenediamine, alkinoyloxybenzenesulfonate, phenolcarboxylic acid fatty acid ester, pentaacetylglucose, and triacetylglyceride is used as the organic peracid precursor. be able to.
[0056]
Here, as described in claim 4, a capacitor element having a structure in which an etched aluminum foil anode on which an anodic oxide film is formed and an etched aluminum foil cathode are wound via a separator may be used. it can.
[0057]
Further, a porous sintered body having an anodic oxide film formed thereon can be used as the capacitor element.
[0058]
According to a sixth aspect of the present invention, there is provided a method for manufacturing a solid electrolytic capacitor comprising a valve metal electrode, a surface of which is successively provided with a dielectric layer of an anodic oxide film of the valve metal and a conductive polymer layer obtained by polymerizing a polymerizable monomer. A method for producing a solid electrolytic capacitor, wherein a perborate and an organic peracid precursor are used for the polymerization of the polymerizable monomer.
[0059]
Here, as described in claim 7, pyrrole or a derivative thereof can be used as the polymerizable monomer.
[0060]
Here, as described in claim 8, one selected from tetraacetylalkylenediamine, alkinoyloxybenzenesulfonate, phenolcarboxylic acid fatty acid ester, pentaacetylglucose, and triacetylglyceride is used as the organic peracid precursor. be able to.
[0061]
In this case, as described in claim 9, a capacitor element having a structure in which an etched aluminum foil anode on which an anodic oxide film is formed and an etched aluminum foil cathode are wound via a separator may be used. it can.
[0062]
In addition, a porous sintered body having an anodic oxide film formed thereon can be used as the capacitor element.
[0071]
Claim 11 The present invention according to the present invention relates to a method for manufacturing a film capacitor comprising a metal electrode subjected to a surface-expansion treatment and a conductive polymer layer formed by polymerizing a dielectric layer of an electrodeposited polymer film and a polymerizable monomer in order on a surface of the metal electrode. And a method for producing a film capacitor using a percarbonate and an organic peracid precursor for the polymerization of the polymerizable monomer.
[0072]
here, Claim 12 As described, pyrrole or its derivatives can be used as the polymerizable monomer.
[0073]
Also here Claim 13 As described, one selected from tetraacetylalkylenediamine, alkinoyloxybenzenesulfonate, phenolcarboxylic acid fatty acid ester, pentaacetylglucose, and triacetylglyceride can be used as the organic peracid precursor.
[0074]
Also here Claim 14 As described, a copolymer or polyimide containing acrylic acid, methacrylic acid or styrene can be used for the polymer film dielectric layer.
[0075]
Also here Claim 15 As described, an etched aluminum foil can be used as the metal electrode.
[0076]
Claim 16 The present invention according to the present invention relates to a method for manufacturing a film capacitor comprising a metal electrode subjected to a surface enlargement treatment, and a conductive polymer layer formed by polymerizing an electrodeposited polymer film dielectric layer and a polymerizable monomer on a surface of the metal electrode. And a method for producing a film capacitor using a perborate and an organic peracid precursor for the polymerization of the polymerizable monomer.
[0077]
here, Claim 17 As described, pyrrole or its derivatives can be used as the polymerizable monomer.
[0078]
Also here Claim 18 As described, one selected from tetraacetylalkylenediamine, alkinoyloxybenzenesulfonate, phenolcarboxylic acid fatty acid ester, pentaacetylglucose, and triacetylglyceride can be used as the organic peracid precursor.
[0079]
Also here Claim 19 As described, the polymer film dielectric layer can use a copolymer or polyimide containing acrylic acid, methacrylic acid or styrene.
[0080]
Also here Claim 20 As described, an etched aluminum foil can be used as the metal electrode.
[0081]
Hereinafter, embodiments of the present invention will be described with reference to the drawings.
[0082]
(Embodiment 1)
In this embodiment, a 0.1 mm × 2.3 mm × 155 mm low-voltage etched aluminum electrode foil 1 having leads attached thereto through an aluminum tab and a 0.05 mm × As shown in FIG. 1, a 2.3 mm × 180 mm counter electrode etched aluminum electrode foil 2 was wound through a separator 3 made of manila paper, and the end of the winding was stopped with an adhesive tape (not shown). Obtained.
[0083]
The capacitor element was immersed in a 3% aqueous solution of ammonium adipate at 70 ° C., and the electrode foil 1 was used as an anode. Formed.
[0084]
After formation of the anodized film, the capacity obtained in the chemical conversion solution was 221 μF at 120 Hz.
[0085]
A counter-electrode conductive layer made of polypyrrole was formed on the capacitor element to produce five capacitors.
[0086]
An example of polypyrrole formation is shown below.
[0087]
An aqueous solution containing 0.5 M of a pyrrole monomer and 0.02 M of sodium triisopropylnaphthalenesulfonate, and sodium percarbonate (2Na ₂ CO ₃ ・ 3H ₂ O ₂ ) 0.17M, tetraacetylethylenediamine ((CH ₃ CO) ₂ NCH ₂ CH ₂ N (CCCH ₃ ) ₂ ), 0.34 M and 0.5 M sulfuric acid, the capacitor elements were alternately immersed at room temperature to form a polypyrrole layer, and the reaction residue was washed with water and dried.
[0088]
The above operation was repeated until the space between the electrode foils 1 and 3 was filled with the polypyrrole layer without any gap.
[0089]
With respect to these five capacitors, the capacitance and the loss coefficient at 120 Hz were measured, and their average values are shown in the following (Table 1).
[0090]
[Table 1]

[0091]
(Comparative Example 1)
Next, for comparison, in this embodiment as Comparative Example 1, five capacitors were completed in the same manner as in Embodiment 1 except that an electrolytic solution was filled instead of forming the polypyrrole layer of Embodiment 1. Was.
[0092]
As an electrolytic solution, a γ-butyrolactone solution containing 20% of monomethyltriethylammonium phthalate was used.
After the completion of the capacitor, the same evaluation as in the first embodiment was performed, and the results are shown in (Table 1).
[0093]
As can be understood from (Table 1), in the present embodiment, it is possible to obtain a capacitor having an excellent capacity achievement ratio (ratio with the liquid capacity) and to further reduce the loss coefficient. I understand.
[0094]
It is considered that the high capacity achievement rate is obtained because the polymerization reaction proceeds relatively slowly, and the liquid permeates deep into the element.
[0095]
Further, the low loss coefficient is due to the fact that the electric conductivity of polypyrrole is much higher than that of the conventionally used electrolyte.
[0096]
That is, it was proved that the capacitor according to the present embodiment had excellent initial characteristics.
[0097]
(Embodiment 2)
In the present embodiment, a capacitor was manufactured by using a tantalum sintered body element instead of the aluminum foil electrode wound type capacitor element and forming a counter electrode layer with polypyrrole in the same manner as in the first embodiment.
[0098]
The method of dimensioning and forming a tantalum sintered body will be described below.
[0099]
A 1.3 mm × 3.0 mm × 3.8 mm tantalum sintered body in which a 0.3 mm tantalum wire lead is embedded is prepared, and a solution obtained by dissolving 5 ml of phosphoric acid in 1000 ml of water is applied at 40 ° C. at about 90 ° C. Then, an oxide film dielectric film was formed by anodic oxidation.
[0100]
This configuration was regarded as a capacitor, and the capacity in the chemical conversion solution was 230 μF at 120 Hz.
[0101]
A polypyrrole layer was formed in the same manner as in Embodiment 1 using the above capacitor element, and further, a counter electrode was formed with colloidal graphite and silver paint to obtain five capacitors, and the capacitance and loss coefficient at 120 Hz were measured. The average values were shown in (Table 1).
[0102]
(Comparative Example 2)
Next, for comparison, as Comparative Example 2, a capacitor was manufactured according to the conventional method of manufacturing a tantalum capacitor instead of forming the polypyrrole layer in Embodiment 2.
[0103]
That is, five capacitors were completed in the same manner as in Embodiment 2, except that the element was immersed in a 30% manganese nitrate aqueous solution and then a pyrolytic manganese dioxide layer was formed at 250 ° C. as a counter electrode.
[0104]
The initial characteristics of the obtained capacitor were evaluated in the same manner as in the first embodiment, and the results are shown in (Table 1).
[0105]
From the comparison with Comparative Example 2, it is clear that also in the present embodiment, a tantalum capacitor having a high capacity achievement ratio and a small loss coefficient has been obtained, demonstrating the excellent effects of the present invention.
[0106]
(Embodiment 3)
In this embodiment, instead of using sodium percarbonate in the first embodiment, 0.5M sodium perborate (NaBO) is used. ₃ ・ 4H ₂ Except for using O), five capacitors were manufactured in the same manner as in the first embodiment, and the same evaluation as in the first embodiment was performed. The results are shown in (Table 1).
[0107]
From Table 1, it is clear that the capacitor according to the present invention has a high capacity achievement ratio and a small loss coefficient, and the excellent effect of the present invention has been demonstrated.
[0108]
(Embodiment 4)
In this embodiment, instead of using 0.5 M tetraacetylethylenediamine in Embodiment 1, (A) 0.5 M sodium octanoyloxybenzenesulfonate ((C8H17C (= O) O (C6H6) SO3Na) , (B) 0.5M decanoyloxybenzoic acid ((C9H19C (= O) O (C6H6) COOH), (C) 0.5M pentaacetylglucose (C ₁₆ H ₂₂ O ₁₁ ), (D) 0.5 M triacetylglyceride ((CH ₃ COO) ₃ C ₃ H ₅ 5) were produced in the same manner as in the fourth embodiment, except that each of the above was used, and the same evaluation as in the first embodiment was performed. The results are shown in (Table 1).
[0109]
From Table 1, it is clear that all of the capacitors according to the present invention have a high capacity achievement ratio and a small loss coefficient, demonstrating the excellent effects of the present invention.
[0110]
(Embodiment 5)
In this embodiment, each of the organic peracids (A) to (D) is the same as in Embodiment 4 except that sodium percarbonate of the same concentration is used instead of sodium percarbonate in Embodiment 4. Five capacitors were prepared in the system containing the precursor.
(A) 0.5M sodium octanoyloxybenzenesulfonate
(B) Decanoyloxybenzoic acid at a concentration of 0.5M
(C) 0.5M pentaacetylglucose
(D) 0.5 M concentration of triacetyl glyceride
The characteristics of the manufactured capacitor were evaluated in the same manner as in Embodiment 1, and the results are shown in (Table 1).
[0111]
From Table 1, it is clear that all of the capacitors according to the present invention have a high capacity achievement ratio and a small loss coefficient, demonstrating the excellent effects of the present invention.
[0112]
(Embodiment 6)
In the present embodiment, an electrode foil having a (A) a copolymer of acrylic acid, methacrylic acid, and styrene and a dielectric made of (B) polyimide on the surface of an etched aluminum foil was used, and tetraacetylethylenediamine was further removed. Except for this, five capacitors were produced using the same polymerization solution used in the first embodiment.
[0113]
An example of a method for forming a dielectric comprising a copolymer of acrylic acid, methacrylic acid and styrene in the present embodiment will be described below.
[0114]
An etched aluminum foil having a thickness of about 0.1 mm, an average pore diameter of about 2 μm, and a surface area of about 30 times as the electrode foil was cut into the same dimensions as in Embodiment 1, and an aluminum lead was attached. .
[0115]
The same counter electrode as in the first embodiment was used.
[0116]
First, a dielectric thin film made of a copolymer of acrylic acid, methacrylic acid and styrene was formed on the former electrode foil by electrodeposition.
[0117]
The composition of the electrodeposition solution used was such that the solid content was 10% by weight, ion-exchanged water 86% by weight, and butyl cellosolve 4% by weight.
[0118]
Here, as a solid content, a mixture of a copolymer of acrylic acid, methacrylic acid, and styrene having a molecular weight of about 30,000 and a benzoguanamine-based resin in a weight ratio of 7: 3 was used.
[0119]
To disperse this solid in the liquid, 50% of the carboxylic acid groups were neutralized with trimethylamine.
[0120]
The electrode foil was immersed in the electrodeposition solution, and was subjected to constant current electrodeposition at a current density of 0.3 mA / cm2 until the voltage reached 10 V, and further constant voltage electrodeposition was performed at 10 V for 15 minutes.
Next, the electrode foil on which the acrylic acid-based polymer thin film was formed was washed with water and then heat-treated at 80 ° C. for 20 minutes and at 180 ° C. for 30 minutes to cause a cross-linking reaction with the benzoguanamine-based resin.
[0121]
After repeating the series of processes described above three times, the substrate was washed and dried, and then wound with a counter electrode via a separator as in Embodiment 1, to prepare a capacitor element.
When the capacitance of this device was measured in an electrolytic solution, it showed 21.5 μF at 120 Hz.
[0122]
Next, an example of the formation of a polyimide electrodeposition film will be described below.
[0123]
Biphenyltetracarboxylic dianhydride and p-phenylenediamine were reacted in N-methylpyrrolidone under nitrogen reflux to obtain a polyamic acid.
[0124]
This polyamic acid was diluted with N, N-dimethylamide, and triethylamine was added to obtain a polyamic acid salt solution.
[0125]
Methanol was added to the above solution to prepare an electrodeposition solution so as to finally contain 0.15% of polyamic acid.
[0126]
A capacitor element was immersed in this solution, and a voltage of 30 V was applied between a cathode provided separately from the capacitor element as an anode to deposit a polyamic acid film.
[0127]
Thereafter, the mixture was heated at 250 ° C. for 1 hour to polyimide the polyamic acid.
[0128]
After repeating this electrodeposition and heating three times, a conductive polymer layer was formed.
[0129]
Thereafter, as in the case of the electrode foil on which a dielectric made of a copolymer of acrylic acid, methacrylic acid and styrene was formed, the resultant was wound via a counter electrode and a separator to complete a capacitor element.
[0130]
The capacity at 120 Hz obtained in the electrolytic solution was 22.1 μF.
[0131]
Polypyrrole layers were formed on these capacitor elements using sodium percarbonate as an oxidizing agent in the same manner as in the first embodiment.
[0132]
Thereafter, the characteristics were evaluated in the same manner as in Embodiment 1, and the results are shown in (Table 1). From Table 1, it is clear that all of the capacitors according to the present invention have a high capacity achievement ratio and a small loss coefficient, demonstrating the excellent effects of the present invention.
[0133]
(Embodiment 7)
In this embodiment, five capacitors were manufactured in the same manner as in Embodiment 6 (A) except that sodium percarbonate was replaced with sodium perborate in Embodiment 6 (A).
[0134]
The characteristics of these capacitors were evaluated in the same manner as in the first embodiment, and the results are shown in (Table 1).
[0135]
From Table 1, it is clear that all of the capacitors according to the present invention have a high capacity achievement ratio and a small loss coefficient, demonstrating the excellent effects of the present invention.
[0136]
(Embodiment 8)
In the present embodiment, except that sodium percarbonate is used alone as a polymerization oxidizing agent in the sixth embodiment, an organic peracid precursor (A) to (E) shown below is used in combination. In the same manner as in the above, five capacitors were produced.
(A) 0.5 M concentration of tetraacetylethylenediamine
(B) 0.5M sodium octanoyloxybenzenesulfonate
(C) 0.5M concentration of decanoyloxybenzoic acid
(D) 0.5M concentration of pentaacetylglucose
(E) 0.5M concentration of triacetylglyceride
The characteristics of the manufactured capacitor were evaluated in the same manner as in Embodiment 1, and the results are shown in (Table 1).
[0137]
From Table 1, it is clear that all of the capacitors according to the present invention have a high capacity achievement ratio and a small loss coefficient, demonstrating the excellent effects of the present invention.
[0138]
(Embodiment 9)
In this embodiment, five capacitors were manufactured in the same manner as in Embodiment 8, except that 0.5M sodium perborate was used instead of using sodium percarbonate in Embodiment 8.
[0139]
Note that the type and concentration of the organic peracid precursor used in combination were the same as in Embodiment 8.
(A) 0.5 M concentration of tetraacetylethylenediamine
(B) 0.5M sodium octanoyloxybenzenesulfonate
(C) 0.5M concentration of decanoyloxybenzoic acid
(D) 0.5M concentration of pentaacetylglucose
(E) 0.5M concentration of triacetylglyceride
The characteristics of the manufactured capacitor were evaluated in the same manner as in Embodiment 1, and the results are shown in (Table 1).
[0140]
From Table 1, it is clear that all of the capacitors according to the present invention have a high capacity achievement ratio and a small loss coefficient, demonstrating the excellent effects of the present invention.
In the embodiment, only the case where a sodium salt is used as the percarbonate and perborate has been described, but other alkali metal salts or ammonium salts can also be used.
[0141]
In this embodiment, only the case where a pyrrole monomer is used as a polymerization precursor has been described.However, other polymerizable monomers such as N-methylpyrrole can be used, and aniline and a thiophene derivative can be used. Often, the present invention is not limited to the type of polymerization precursor.
[0142]
In addition, only the case where tetraacetylethylenediamine, sodium octanoyloxybenzenesulfonate, decanoyloxybenzoic acid, pentaacetylglucose, and triacetylglyceride were used as the organic peracid precursor was described. A body can also be used, and the invention is not limited to that type. Note that, in the embodiment, only a case where an oxidizing agent having a roughly stoichiometric amount is used with respect to the polymerizable monomer has been described. It is not limited to the addition ratio.
[0143]
In addition, it is possible to use similarly having another alkylene group, such as tetramethylenediamine, instead of tetraacetylethylenediamine. Those having an alkinoyl group can also be used.
[0144]
The concentration of the organic peracid precursor may be an amount that effectively generates an organic peracid in the presence of a percarbonate or perborate, and the concentration is limited to the embodiment of the present invention. Not done.
[0145]
In this embodiment, only the case where a copolymer of acrylic acid, methacrylic acid, and styrene and polyimide are used as the dielectric of the film capacitor has been described. Other copolymers or homopolymers can be used as long as they are molecules.
[0146]
Note that, in the embodiment, only the case where sodium triisopropylnaphthalenesulfonate is used as the salt containing the group serving as the dopant is described. It is possible to use a salt containing or not containing a salt, and it is sufficient that the concentration of the salt is higher than that taken in as a dopant in the polymerization liquid system.
[0147]
In the embodiment, only the wound type structure in the capacitor using the foil electrode is described. However, the electrode foil may be used as a single plate or may be applied to a structure in which the electrode foil is laminated. it can.
[0148]
Note that, in the embodiment, only the case where a polymerization aqueous solution containing only a monomer, an oxidizing agent, and a dopant or only a monomer, an oxidizing agent, an organic peracid, and a dopant is used. May be included.
[0149]
In the embodiment, only the case where sulfuric acid is used to make the hydrogen ion concentration of the liquid acidic is described. However, other mineral acids may be used, and organic acids such as sulfonic acid may be used. The invention is not limited by the type.
[0150]
【The invention's effect】
By using the polymerization oxidizing agent of the present invention, in order for the polymerization reaction to proceed slowly, the permeation of the solution into the electrolytic capacitor and the inside of the film capacitor having a polymer film provided on the surface of the wound etched aluminum foil as a dielectric is used. As a result, it is possible to obtain an electrolytic capacitor and a film capacitor having a high capacity achievement ratio easily.
[0151]
In addition, since the conductive polymer layer having electron conductivity is formed on the counter electrode conductive layer, an effect that an electrolytic capacitor having a smaller loss coefficient than when an electrolytic solution is used can be realized.
[Brief description of the drawings]
FIG. 1 is a sectional view showing a configuration of a capacitor according to a first embodiment of the present invention.
[Explanation of symbols]
1,3 metal foil electrode
2 Dielectric film
4 separator
5 Polypyrrole layer

Claims (20)

A method for manufacturing a solid electrolytic capacitor, comprising a valve metal electrode and a conductive polymer layer obtained by polymerizing a polymerizable monomer and an anodic oxide film dielectric layer of the valve metal in order, wherein the polymerizable monomer is polymerized. A method for producing a solid electrolytic capacitor using a percarbonate and an organic peracid precursor for the method. 2. The method according to claim 1, wherein the polymerizable monomer is pyrrole or a derivative thereof. 3. The production of a solid electrolytic capacitor according to claim 1, wherein the organic peracid precursor contains one selected from tetraacetylalkylenediamine, alkinoyloxybenzenesulfonate, phenolcarboxylic acid fatty acid ester, pentaacetylglucose and triacetylglyceride. Method. The solid electrolytic capacitor according to any one of claims 1 to 3, wherein the capacitor element has a structure in which an etched aluminum foil anode on which an anodic oxide film is formed and an etched aluminum foil cathode are wound via a separator. Manufacturing method. 4. The method according to claim 1, wherein the capacitor element is a porous sintered body having an anodic oxide film formed thereon. A method for manufacturing a solid electrolytic capacitor, comprising a valve metal electrode and a conductive polymer layer obtained by polymerizing a polymerizable monomer and an anodic oxide film dielectric layer of the valve metal in order, wherein the polymerizable monomer is polymerized. A method for producing a solid electrolytic capacitor using a perborate and an organic peracid precursor for the method. 7. The method according to claim 6, wherein the polymerizable monomer is pyrrole or a derivative thereof. The production of a solid electrolytic capacitor according to claim 6 or 7, wherein the organic peracid precursor contains one selected from tetraacetylalkylenediamine, alkinoyloxybenzenesulfonate, phenolcarboxylic acid fatty acid ester, pentaacetylglucose or triacetylglyceride. . The solid electrolytic capacitor according to any one of claims 6 to 8, wherein the capacitor element has a structure in which an etched aluminum foil anode having an anodic oxide film formed thereon and an etched aluminum foil cathode are wound via a separator. Manufacturing method. 9. The method for manufacturing a solid electrolytic capacitor according to claim 6, wherein the capacitor element is a porous sintered body having an anodic oxide film formed thereon. A method for producing a film capacitor, comprising sequentially disposing an electrodeposited polymer film dielectric layer and a conductive polymer layer obtained by polymerizing a polymerizable monomer on the surface of a metal electrode that has been subjected to surface enlargement treatment, A method for producing a film capacitor using a percarbonate and an organic peracid precursor for polymerization. The method for producing a film capacitor according to claim 11 , wherein the polymerizable monomer is pyrrole or a derivative thereof. The production of a solid electrolytic capacitor according to claim 11 or 12 , wherein the organic peracid precursor contains one selected from tetraacetylalkylenediamine, alkinoyloxybenzenesulfonate, phenolcarboxylic acid fatty acid ester, pentaacetylglucose or triacetylglyceride. . 14. The method according to claim 11, wherein a copolymer or polyimide containing acrylic acid, methacrylic acid, or styrene is used for the polymer film dielectric layer. 15. The method for producing a film capacitor according to claim 11 , wherein an etched aluminum foil is used for the metal electrode. A method for producing a film capacitor, comprising sequentially disposing an electrodeposited polymer film dielectric layer and a conductive polymer layer obtained by polymerizing a polymerizable monomer on the surface of a metal electrode that has been subjected to surface enlargement treatment, A method for producing a film capacitor using a perborate and an organic peracid precursor for polymerization. 17. The method according to claim 16 , wherein the polymerizable monomer is pyrrole or a derivative thereof. 18. The production of a film capacitor according to claim 16 , wherein the organic peracid precursor contains one selected from tetraacetylalkylenediamine, alkinoyloxybenzenesulfonate, phenolcarboxylic acid fatty acid ester, pentaacetylglucose and triacetylglyceride. 19. The method for manufacturing a film capacitor according to claim 16 , wherein the polymer film dielectric layer uses a copolymer or polyimide containing acrylic acid, methacrylic acid, or styrene. 20. The method according to claim 16 , wherein an etched aluminum foil is used for the metal electrode.

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