JPH06267798A - Manufacture of capacitor - Google Patents
Manufacture of capacitorInfo
- Publication number
- JPH06267798A JPH06267798A JP5189993A JP5189993A JPH06267798A JP H06267798 A JPH06267798 A JP H06267798A JP 5189993 A JP5189993 A JP 5189993A JP 5189993 A JP5189993 A JP 5189993A JP H06267798 A JPH06267798 A JP H06267798A
- Authority
- JP
- Japan
- Prior art keywords
- capacitor
- electrolytic solution
- concentration
- dielectric film
- conductive polymer
- 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.)
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Links
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- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
- Organic Insulating Materials (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は誘電体皮膜を介して対向
している電極の、少なくとも一方の電極に導電性高分子
膜を用いるコンデンサの製造方法に関するものであり、
特に高性能、高信頼特性、高耐圧性に優れたコンデンサ
を提供するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of manufacturing a capacitor in which a conductive polymer film is used for at least one electrode of electrodes facing each other through a dielectric film,
In particular, the present invention provides a capacitor having high performance, high reliability, and high withstand voltage.
【０００２】[0002]
【従来の技術】最近、電気機器のディジタル化にともな
って、そこに使用されるコンデンサも高周波領域におい
てインピーダンスが低く、小型大容量化への要求が高ま
っている。2. Description of the Related Art Recently, with the digitalization of electric equipment, the capacitors used therein have low impedance in the high frequency region, and there is an increasing demand for miniaturization and large capacity.
【０００３】従来、高周波用のコンデンサとしてはプラ
スチックフィルムコンデンサ、マイカコンデンサ、積層
セラミックコンデンサなどが用いられている。Conventionally, plastic film capacitors, mica capacitors, laminated ceramic capacitors and the like have been used as high frequency capacitors.
【０００４】また、その他にアルミニウム乾式電解コン
デンサやアルミニウムまたはタンタル固体電解コンデン
サなどがある。Besides, there are aluminum dry electrolytic capacitors and aluminum or tantalum solid electrolytic capacitors.
【０００５】アルミニウム乾式電解コンデンサでは、エ
ッチングを施した陽、陰極アルミニウム箔を紙のセパレ
ータを介して巻取り、液状の電解質を用いている。In the aluminum dry electrolytic capacitor, the positive and negative aluminum foils subjected to etching are wound around a paper separator and a liquid electrolyte is used.
【０００６】又、アルミニウムやタンタル固体電解コン
デンサでは、前記アルミニウム電解コンデンサの特性改
良のため、電解質の固体化がなされている。In addition, in the aluminum or tantalum solid electrolytic capacitor, the electrolyte is solidified in order to improve the characteristics of the aluminum electrolytic capacitor.
【０００７】この固体電解質形成には、硝酸マンガン液
に陽極箔を浸漬し、３５０℃前後の高温炉中にて熱分解
し、二酸化マンガン層を作る。このコンデンサの場合、
電解質が固体のために高温における電解液の揮散、低温
域での凝固から生ずる機能低下などの欠点がなく、液状
電解質と比べて良好な周波数特性、温度特性を示す。To form this solid electrolyte, the anode foil is dipped in a manganese nitrate solution and pyrolyzed in a high temperature furnace at about 350 ° C. to form a manganese dioxide layer. For this capacitor,
Since the electrolyte is a solid, it has no defects such as volatilization of the electrolytic solution at high temperature and deterioration of function caused by solidification at low temperature, and shows better frequency characteristics and temperature characteristics than the liquid electrolyte.
【０００８】そして、アルミ電解コンデンサはタンタル
電解コンデンサと同様、誘電体となる酸化皮膜を非常に
薄くできるために大容量を実現できる。As with the tantalum electrolytic capacitor, the aluminum electrolytic capacitor can realize a large capacity because the oxide film serving as a dielectric can be made very thin.
【０００９】又、近年では７，７，８，８−テトラシア
ノキノジメタン（ＴＣＮＱ）塩等の有機半導体を固体電
解質として用いた固体電解コンデンサ（特開昭５８−１
７６０９号公報）が開発されている。In recent years, a solid electrolytic capacitor using an organic semiconductor such as 7,7,8,8-tetracyanoquinodimethane (TCNQ) salt as a solid electrolyte (Japanese Patent Laid-Open No. 58-1).
7609) has been developed.
【００１０】さらに、ピロール、チオフェン、フランな
どの重合性モノマーを電解重合させて導電性高分子と
し、これをコンデンサの電極の少なくとも一方に用いる
方法もあり、電極表面に誘電体となるポリイミド薄膜を
電着法によって形成し、化学重合導電性高分子膜を積層
してさらに電解重合導電性高分子膜を積層してなるコン
デンサを１９９１年春の電気化学協会第５８回大会で開
示された（講演要旨集Ｐ．２５１から２５２）。Further, there is also a method in which a polymerizable monomer such as pyrrole, thiophene, or furan is electrolytically polymerized to form a conductive polymer, which is used for at least one of the electrodes of a capacitor, and a polyimide thin film serving as a dielectric is formed on the electrode surface. A capacitor formed by the electrodeposition method, laminated with a chemically polymerized conductive polymer film, and further laminated with an electrolytic polymerized conductive polymer film was disclosed at the 58th Congress of the Electrochemical Society of Japan in the spring of 1991 (Abstract of Abstract) Vol. 251, 252).
【００１１】[0011]
【発明が解決しようとする課題】このように、種々のコ
ンデンサが使用されているが、フィルムコンデンサおよ
びマイカコンデンサでは、形状が大きくなってしまうた
めに大容量化が難しく、また積層セラミックコンデンサ
は小型大容量の要望から生まれたものであるが、価格が
非常に高くなるということと、温度特性が悪いことなど
の欠点を有している。As described above, various capacitors are used, but it is difficult to increase the capacity of the film capacitor and the mica capacitor due to their large size, and the monolithic ceramic capacitor is small in size. Although it was born from the demand for a large capacity, it has drawbacks such as a very high price and poor temperature characteristics.
【００１２】又、アルミ電解コンデンサは酸化皮膜の損
傷が起き易いために酸化皮膜と陰極の間に電解質を施し
随時損傷を修復する必要がある。Further, since the aluminum electrolytic capacitor is apt to be damaged by the oxide film, it is necessary to apply an electrolyte between the oxide film and the cathode to repair the damage at any time.
【００１３】このため、電解質に液状のものを使用して
いるものは、電解質の液漏れやイオン伝導性などの理由
から経時的に静電容量の減少や損失の増大をもたらす事
と高周波特性、低温領域での損失が大きい事などの欠点
を有している。For this reason, when a liquid electrolyte is used, it causes a decrease in capacitance and an increase in loss over time due to electrolyte leakage and ionic conductivity, and high frequency characteristics, It has drawbacks such as large loss in the low temperature range.
【００１４】次に、固体電解質のものについて述べる
と、高温で数回熱分解することによる酸化皮膜の損傷、
及び二酸化マンガンの比抵抗が高いことなどの理由から
高周波域での損失は十分に小さいとは言えない。Next, regarding the solid electrolyte, the oxide film is damaged by thermal decomposition at high temperature several times,
Also, due to the high specific resistance of manganese dioxide, the loss in the high frequency region cannot be said to be sufficiently small.
【００１５】又、ＴＣＮＱ塩などの有機半導体を用いた
固体電解コンデンサは、二酸化マンガンを用いたものに
比して優れた高周波特性を示すが、有機半導体を塗布す
る際の比抵抗の上昇、陽極箔への接着性が弱いことなど
が原因で、理想的な特性を示すとはいえない。Further, the solid electrolytic capacitor using an organic semiconductor such as TCNQ salt has excellent high frequency characteristics as compared with those using manganese dioxide, but the increase in the specific resistance when applying the organic semiconductor and the anode. It cannot be said to exhibit ideal characteristics due to weak adhesion to the foil.
【００１６】さらに導電性高分子薄膜をコンデンサの電
極として用いると、周波数特性，温度特性、寿命特性な
どが優れている。しかし、イオン伝導性のペ−スト状電
解質に比べ、損傷した誘電体皮膜の修復能力に欠点を有
している。Further, when a conductive polymer thin film is used as an electrode of a capacitor, frequency characteristics, temperature characteristics, life characteristics, etc. are excellent. However, it has a defect in the repair ability of a damaged dielectric film as compared with an ion conductive paste electrolyte.
【００１７】[0017]
【課題を解決するための手段】本発明によるコンデンサ
の製造方法は、アルキル燐酸エステルと芳香族スルフォ
ン酸塩、あるいはポリエチレンオキサイドと芳香族スル
フォン酸塩、あるいはアルキル燐酸エステルとフェノ−
ル誘導体と芳香族スルフォン酸塩、あるいは架橋型ポリ
アクリル酸ソ−ダと芳香族スルフォン酸塩、のいずれか
から選ばれる少なくとも一つと重合性モノマ−とを少な
くとも含有する電解液を用いる電解重合により得られる
導電性高分子を、誘電体皮膜上に形成される電極として
使用するものである。 なお本発明の芳香族スルフォン
酸塩としは、アルキル置換基を有するナフタレンスルフ
ォン酸塩が好適である。SUMMARY OF THE INVENTION A method of manufacturing a capacitor according to the present invention comprises an alkyl phosphate and an aromatic sulfonate, a polyethylene oxide and an aromatic sulfonate, or an alkyl phosphate and a phenol.
By using an electrolytic solution containing at least one selected from the group consisting of a vinyl derivative and an aromatic sulfonate, or a cross-linked polyacrylic acid soda and an aromatic sulfonate, and a polymerizable monomer. The obtained conductive polymer is used as an electrode formed on the dielectric film. As the aromatic sulfonate of the present invention, naphthalene sulfonate having an alkyl substituent is preferable.
【００１８】さらに具体的には、モノメチルナフタレン
スルフォン酸ナトリウム、トリイソプロピルナフタレン
スルフォン酸ナトリウム、モノイソプロピルナフタレン
スルフォン酸ナトリウム、ジブチルナフタレンスルフォ
ン酸ナトリウム等が挙げられる。More specifically, sodium monomethylnaphthalene sulfonate, sodium triisopropyl naphthalene sulfonate, sodium monoisopropyl naphthalene sulfonate, sodium dibutyl naphthalene sulfonate, and the like can be mentioned.
【００１９】なお本発明のアルキル燐酸エステルとはア
ルキル置換基を１個あるいは２個有する物であり、その
炭素数は３から１２が好適であり、請求項７記載の発明
のようにヘキシル燐酸エステルが最適である。The alkyl phosphate of the present invention is one having one or two alkyl substituents, and the number of carbon atoms thereof is preferably 3 to 12, and the hexyl phosphate ester according to the invention of claim 7 Is the best.
【００２０】なお本発明のフェノ−ル誘導体とはフェノ
−ルまたは置換基を有する芳香族ヒドロキシ化合物のこ
とであり、単独で用いても複数種混合して用いても良
い。The phenol derivative of the present invention is an aromatic hydroxy compound having phenol or a substituent, and may be used alone or in combination of two or more.
【００２１】さらに、置換基としては電子吸引性が大き
なものが好適であり、請求項１３記載の発明のようにニ
トロフェノ−ルが最適であるが、他に例えば、「シアノ
フェノ−ル、ヒドロキシアセトフェノン、ヒドロキシベ
ンズアルデヒド、ヒドロキシベンズアミド、ヒドロキシ
安息香酸」等でもよい。Further, as the substituent, those having a large electron withdrawing property are preferable, and nitrophenol is most suitable as in the invention of claim 13, but in addition, for example, "cyanophenol, hydroxyacetophenone, “Hydroxybenzaldehyde, hydroxybenzamide, hydroxybenzoic acid” and the like may also be used.
【００２２】なお本発明の重合性モノマ−としては、請
求項１５記載の発明のように、ピロ−ル、チオフェンま
たは、それらの誘導体（例えば、Ｎ−メチルピロ−ル）
の少なくとも一つが挙げられるが、例えば、フラン等で
もよい。As the polymerizable monomer of the present invention, pyrrole, thiophene or their derivatives (for example, N-methylpyrrole) can be used as in the invention of claim 15.
Although at least one of the above may be mentioned, for example, a franc or the like may be used.
【００２３】また、ピロ−ル、チオフェンをそれぞれの
誘導体と混合して用いるなど上記モノマ−も複数種併用
してもよい。Further, plural kinds of the above-mentioned monomers may be used in combination, such as a mixture of pyrrole and thiophene with each derivative.
【００２４】さらに、導電性高分子層を複合化するため
に、電解液に適当な添加剤を入れてもよい。Further, in order to form a composite of the conductive polymer layer, a suitable additive may be added to the electrolytic solution.
【００２５】なお本発明は、上記例示の化合物や処理工
程に限定されるものではないし、例示以外の代替可能な
化合物や処理工程を用いてもよいことはいうまでもな
い。The present invention is not limited to the above-exemplified compounds and treatment steps, and it goes without saying that alternative compounds and treatment steps other than those exemplified may be used.
【００２６】[0026]
【作用】上記構成によれば、アルキル燐酸エステルと芳
香族スルフォン酸塩、あるいはポリエチレンオキサイド
と芳香族スルフォン酸塩、あるいはアルキル燐酸エステ
ルとフェノ−ル誘導体と芳香族スルフォン酸塩、あるい
は架橋型ポリアクリル酸ソ−ダと芳香族スルフォン酸
塩、のいずれかと重合性モノマ−とを少なくとも含有す
る電解液を用いる電解重合により導電性高分子を得、こ
の導電性高分子を誘電体皮膜上に形成し電極として使用
する。According to the above construction, an alkyl phosphate and an aromatic sulfonate, a polyethylene oxide and an aromatic sulfonate, an alkyl phosphate, a phenol derivative and an aromatic sulfonate, or a cross-linked polyacrylic acid. A conductive polymer is obtained by electrolytic polymerization using an electrolytic solution containing at least one of acid soda and aromatic sulfonate and a polymerizable monomer, and the conductive polymer is formed on a dielectric film. Used as an electrode.
【００２７】このようにして作製したコンデンサは、誘
電体皮膜の修復能力に優れ従来の固体電解コンデンサに
はない使用電圧の高いコンデンサとなる。The capacitor thus manufactured has a high ability to repair the dielectric film and is a capacitor having a high operating voltage which is not available in conventional solid electrolytic capacitors.
【００２８】[0028]
【実施例】以下、本発明の実施例について、図面を用い
ながら詳細に説明する。Embodiments of the present invention will be described in detail below with reference to the drawings.
【００２９】（実施例１）本発明の第１の実施例とし
て、アルミ電解コンデンサへ適用した構成について詳細
に説明する。(Embodiment 1) As a first embodiment of the present invention, a configuration applied to an aluminum electrolytic capacitor will be described in detail.
【００３０】図１は、コンデンサ素子の断面図を示し、
図２は、その平面図を示す。又、図３は、導電性高分子
膜の形成の工程を示す。FIG. 1 shows a sectional view of a capacitor element,
FIG. 2 shows a plan view thereof. Further, FIG. 3 shows a process of forming a conductive polymer film.
【００３１】弁作用金属２の表面に耐熱絶縁テ−プ８を
貼着し、面積の小さい方を陽極リ−ド１の取り付け面に
し、面積の大きい方（３ｍｍ×４ｍｍ）を、誘電体皮膜
３の形成面として使用した。A heat-resistant insulating tape 8 is attached to the surface of the valve metal 2, the smaller area is used as the mounting surface of the anode lead 1, and the larger area (3 mm × 4 mm) is used as the dielectric film. 3 was used as the forming surface.
【００３２】次に、弁作用金属箔２（アルミニウムエッ
チド箔）を７％アジピン酸アンモニウム水溶液を用い、
約７０℃、４０分間、印加電圧１０６Ｖの条件で陽極酸
化し、誘電体皮膜３を形成した。Next, the valve action metal foil 2 (aluminum etched foil) was treated with a 7% ammonium adipate aqueous solution,
Anodization was performed under the condition of an applied voltage of 106 V at about 70 ° C. for 40 minutes to form the dielectric film 3.
【００３３】次に、硝酸マンガン水溶液を塗布し３００
℃、３０分の条件で熱分解し、マンガン酸化物膜４から
なる導電層を形成した。Next, an aqueous solution of manganese nitrate is applied to form 300
Thermal decomposition was carried out under conditions of 30 ° C. for 30 minutes to form a conductive layer composed of the manganese oxide film 4.
【００３４】そして、図３に示すごとくピロ−ル（０．
２５ｍｏｌ／ｌ）、トリイソプロピルナフタレンスルフ
ォン酸ナトリウム（０．１ｍｏｌ／ｌ）、ヘキシル燐酸
エステル（０．０１Ｎ）、および水からなる電解重合溶
液９に、マンガン酸化膜４まで形成した弁金属箔を浸
し、重合開始用電極７をマンガン酸化物膜４に近接さ
せ、２．５Ｖの定電圧を３０分印加し、マンガン酸化物
４上に対極用の導電性高分子膜５（ポリピロ−ル膜）を
形成した後で、カ−ボンペイント層１０、銀ペイント層
１１を積層し、図２に示すごとく陽極リ−ド１と陰極リ
−ド６を設けてコンデンサを得た。Then, as shown in FIG.
25 mol / l), sodium triisopropylnaphthalene sulfonate (0.1 mol / l), hexyl phosphate (0.01 N), and the electropolymerization solution 9 consisting of water, the valve metal foil formed up to the manganese oxide film 4 was dipped. Then, the polymerization initiating electrode 7 was brought close to the manganese oxide film 4, a constant voltage of 2.5 V was applied for 30 minutes, and a conductive polymer film 5 (polypyrrole film) for counter electrode was formed on the manganese oxide 4. After the formation, a carbon paint layer 10 and a silver paint layer 11 were laminated, and an anode lead 1 and a cathode lead 6 were provided as shown in FIG. 2 to obtain a capacitor.
【００３５】試料数は１０個として、得られたコンデン
サの１２０Ｈｚでの容量と損失係数を測定した。その
後、５０Ｖ／分の速度で電圧掃引し誘電体皮膜が絶縁破
壊する電圧を測定した。これらの測定値の平均を下記の
（表１）に示す。The number of samples was 10, and the capacitance and loss coefficient of the obtained capacitors at 120 Hz were measured. Then, the voltage was swept at a rate of 50 V / min to measure the voltage at which the dielectric film had a dielectric breakdown. The average of these measured values is shown in (Table 1) below.
【００３６】[0036]
【表１】 [Table 1]
【００３７】また、エポキシ樹脂により外装を施し、１
０５℃の高温槽に定電圧３５Ｖを印加した状態で１，０
００時間放置した後の特性を（表２）に示す。Also, the exterior is made of epoxy resin, and 1
1,0 with a constant voltage of 35 V applied to a high temperature tank at 05 ° C
The characteristics after standing for 00 hours are shown in (Table 2).
【００３８】[0038]
【表２】 [Table 2]
【００３９】また、比較例１として、ヘキシル燐酸エス
テルを添加しないこと以外は上記と同条件でコンデンサ
を１０個作製し同様の測定を行った。これらの測定値の
平均も上記（表１）、（表２）に示している。As Comparative Example 1, ten capacitors were prepared under the same conditions as above except that hexyl phosphate was not added, and the same measurement was carried out. The average of these measured values is also shown in (Table 1) and (Table 2) above.
【００４０】この（表１）から明らかなように、本実施
例によるコンデンサは、誘電体皮膜の絶縁破壊電圧が比
較例１に比べ著しく高く、優れた修復能力が得られた。As is clear from (Table 1), the dielectric breakdown voltage of the dielectric film of the capacitor according to this example was significantly higher than that of Comparative Example 1, and excellent repair ability was obtained.
【００４１】また（表２）から明らかなように、本実施
例によるコンデンサの熱安定性は比較例１に比べ著しく
高く、優れた信頼性が得られた。Further, as is clear from (Table 2), the thermal stability of the capacitor according to the present embodiment was significantly higher than that of Comparative Example 1, and excellent reliability was obtained.
【００４２】以上のように、本実施例によれば、電極に
用いる電解重合導電性高分子膜が、誘電体皮膜の修復性
に優れ、また熱安定性も優れているので、高耐圧、高信
頼性のコンデンサを実現することができた。As described above, according to this embodiment, the electrolytically polymerized conductive polymer film used for the electrode is excellent in the repairability of the dielectric film and also in the thermal stability. We were able to realize a reliable capacitor.
【００４３】（実施例２）ヘキシル燐酸エステルの濃度
を０．００５Ｎにしたこと以外は（実施例１）と同様に
してコンデンサを作製した。Example 2 A capacitor was manufactured in the same manner as in Example 1 except that the concentration of hexyl phosphate was 0.005N.
【００４４】試料数は１０個として、得られたコンデン
サの１２０Ｈｚでの容量と損失係数を測定した。その
後、５０Ｖ／分の速度で電圧掃引し誘電体皮膜が絶縁破
壊する電圧を測定した。これらの測定値の平均を前記
（表１）に示している。The number of samples was 10, and the capacitance and loss coefficient of the obtained capacitor at 120 Hz were measured. Then, the voltage was swept at a rate of 50 V / min to measure the voltage at which the dielectric film had a dielectric breakdown. The average of these measured values is shown in the above (Table 1).
【００４５】また、比較例２として、ヘキシル燐酸エス
テルの濃度を０．００１Ｎにしたこと以外は上記と同条
件でコンデンサを１０個作製し同様の測定を行った。As Comparative Example 2, ten capacitors were prepared under the same conditions as above except that the concentration of hexyl phosphate was set to 0.001 N, and the same measurement was carried out.
【００４６】この（表１）から明らかなように、本実施
例によるコンデンサにおいては、誘電体皮膜の絶縁破壊
電圧が比較例２に比べ著しく高く、優れた修復能力が得
られた。As is clear from (Table 1), in the capacitor according to this example, the dielectric breakdown voltage of the dielectric film was remarkably higher than that of Comparative Example 2, and excellent repair ability was obtained.
【００４７】以上のように、本実施例によれば、ヘキシ
ル燐酸エステルの濃度が少なくとも０．００５Ｎ以上で
あれば、誘電体皮膜の修復性に優れている電解重合導電
性高分子膜が得られ、更に（実施例１）で示すようにヘ
キシル燐酸エステルの濃度が０．０１Ｎ以上であればそ
の効果は高まり、高耐圧のコンデンサを実現することが
できた。As described above, according to this example, when the concentration of the hexyl phosphate ester is at least 0.005 N or more, an electrolytically polymerized conductive polymer film having excellent repairability of the dielectric film can be obtained. Further, as shown in (Example 1), when the concentration of the hexyl phosphate was 0.01 N or more, the effect was enhanced, and a high withstand voltage capacitor could be realized.
【００４８】（実施例３）ヘキシル燐酸エステルの濃度
を０．５Ｎにしたこと以外は（実施例１）と同様にして
コンデンサを作製した。Example 3 A capacitor was prepared in the same manner as in Example 1 except that the concentration of hexyl phosphate was 0.5N.
【００４９】試料数は１０個として、得られたコンデン
サの１２０Ｈｚでの容量と損失係数を測定し、その後、
５０Ｖ／分の速度で電圧掃引し誘電体皮膜が絶縁破壊す
る電圧を測定した。The number of samples was set to 10, and the capacitance and loss coefficient of the obtained capacitor at 120 Hz were measured.
The voltage was swept at a rate of 50 V / min to measure the voltage at which the dielectric film had a dielectric breakdown.
【００５０】これらの測定値の平均を前記（表１）に示
している。また、比較例３として、ヘキシル燐酸エステ
ルの濃度を１．０Ｎにしたこと以外は上記と同条件でコ
ンデンサを１０個作製し同様の測定を行った。The average of these measured values is shown in the above (Table 1). Further, as Comparative Example 3, ten capacitors were prepared under the same conditions as above except that the concentration of hexyl phosphate was set to 1.0 N, and the same measurement was performed.
【００５１】この（表１）から明らかなように、本実施
例によるコンデンサは、誘電体皮膜の絶縁破壊電圧が比
較例１に比べ著しく高く優れた修復能力が得られ、ま
た、比較例３に比べ絶縁破壊電圧は同等であるが、容
量、損失特性が良好で優れたコンデンサ特性が得られ
た。As is clear from this (Table 1), the capacitor according to this example has a significantly higher dielectric breakdown voltage of the dielectric film than that of Comparative Example 1, and an excellent repairing ability is obtained. In comparison, the breakdown voltage was the same, but the capacitance and loss characteristics were good and excellent capacitor characteristics were obtained.
【００５２】以上のように、本実施例によれば、電極に
用いる電解重合導電性高分子膜が、誘電体皮膜の修復性
に優れているので、高耐圧のコンデンサを実現すること
ができた。As described above, according to this example, since the electrolytically polymerized conductive polymer film used for the electrode is excellent in the repairability of the dielectric film, a high withstand voltage capacitor could be realized. .
【００５３】（実施例４）ヘキシル燐酸エステルの濃度
を０．１Ｎにしたこと以外は（実施例１）と同様にして
コンデンサを作製した。Example 4 A capacitor was prepared in the same manner as in Example 1 except that the concentration of hexyl phosphate was set to 0.1N.
【００５４】試料数は１０個として、得られたコンデン
サの１２０Ｈｚでの容量と損失係数を測定し、その後、
５０Ｖ／分の速度で電圧掃引し誘電体皮膜が絶縁破壊す
る電圧を測定した。The number of samples was set to 10, and the capacitance and loss coefficient of the obtained capacitor at 120 Hz were measured.
The voltage was swept at a rate of 50 V / min to measure the voltage at which the dielectric film had a dielectric breakdown.
【００５５】それらの測定値の平均を前記（表１）に示
している。この（表１）から明らかなように、本実施例
によるコンデンサにおいては、誘電体皮膜の容量、損失
などの特性が（実施例３）に比べより良好になる。The average of those measured values is shown in the above (Table 1). As is clear from (Table 1), in the capacitor according to the present embodiment, the characteristics such as capacitance and loss of the dielectric film are better than those in (Example 3).
【００５６】以上のように、本実施例によれば、電極に
用いる電解重合導電性高分子膜が、誘電体皮膜の修復性
に優れているので、高耐圧のコンデンサを実現すること
ができた。As described above, according to this example, since the electrolytically polymerized conductive polymer film used for the electrode is excellent in the repairability of the dielectric film, a high withstand voltage capacitor could be realized. .
【００５７】（実施例５）トリイソプロピルナフタレン
スルフォン酸ナトリウムの濃度を０．５ｍｏｌ／ｌにし
たこと以外は（実施例１）と同様にしてコンデンサを作
製した。Example 5 A capacitor was produced in the same manner as in Example 1 except that the concentration of sodium triisopropylnaphthalene sulfonate was 0.5 mol / l.
【００５８】試料数は１０個として、得られたコンデン
サの１２０Ｈｚでの容量と損失係数を測定し、その後、
５０Ｖ／分の速度で電圧掃引し誘電体皮膜が絶縁破壊す
る電圧を測定した。The number of samples was set to 10, and the capacitance and loss coefficient of the obtained capacitor at 120 Hz were measured.
The voltage was swept at a rate of 50 V / min to measure the voltage at which the dielectric film had a dielectric breakdown.
【００５９】これらの測定値の平均を前記（表１）に示
している。また、比較例４として、トリイソプロピルナ
フタレンスルフォン酸ナトリウムの濃度を１．０ｍｏｌ
／ｌにしたこと以外は上記と同条件でコンデンサを１０
個作製し同様の測定を行った。The average of these measured values is shown in the above (Table 1). Further, as Comparative Example 4, the concentration of sodium triisopropylnaphthalene sulfonate was 1.0 mol.
/ L is used under the same conditions as above, except that
Individual pieces were prepared and the same measurement was performed.
【００６０】この（表１）から明らかなように、本実施
例によるコンデンサは、誘電体皮膜の絶縁破壊電圧が比
較例１に比べ著しく高く、優れた修復能力が得られた。As is clear from this (Table 1), the capacitor according to this example had a significantly higher dielectric breakdown voltage of the dielectric film than that of Comparative Example 1, and an excellent repairing ability was obtained.
【００６１】また，比較例４に比べ絶縁破壊電圧は同等
であるが、容量、損失特性が良好で優れたコンデンサ特
性が得られた。Further, although the dielectric breakdown voltage was equivalent to that of Comparative Example 4, excellent capacitance and loss characteristics and excellent capacitor characteristics were obtained.
【００６２】以上のように、本実施例によれば、電極に
用いる電解重合導電性高分子膜が、誘電体皮膜の修復性
に優れているので、高耐圧のコンデンサを実現すること
ができた。As described above, according to this example, since the electrolytically polymerized conductive polymer film used for the electrode is excellent in the repairability of the dielectric film, it was possible to realize a high withstand voltage capacitor. .
【００６３】（実施例６）トリイソプロピルナフタレン
スルフォン酸ナトリウムの濃度を０．００５ｍｏｌ／ｌ
にしたこと以外は（実施例１）と同様にしてコンデンサ
を作製した。Example 6 The concentration of sodium triisopropylnaphthalene sulfonate was adjusted to 0.005 mol / l.
A capacitor was produced in the same manner as in (Example 1) except that the above was adopted.
【００６４】試料数は１０個として、得られたコンデン
サの１２０Ｈｚでの容量と損失係数を測定し、その後、
５０Ｖ／分の速度で電圧掃引し誘電体皮膜が絶縁破壊す
る電圧を測定した。The number of samples was 10, and the capacitance and loss coefficient at 120 Hz of the obtained capacitor were measured.
The voltage was swept at a rate of 50 V / min to measure the voltage at which the dielectric film had a dielectric breakdown.
【００６５】これらの測定値の平均を前記（表１）に示
している。また、比較例５として、トリイソプロピルナ
フタレンスルフォン酸ナトリウムの濃度を０．００１ｍ
ｏｌ／ｌにしたこと以外は上記と同条件でコンデンサを
１０個作製し同様の測定を行った。The average of these measured values is shown in the above (Table 1). Further, as Comparative Example 5, the concentration of sodium triisopropylnaphthalene sulfonate was 0.001 m.
Ten capacitors were prepared under the same conditions as described above except that ol / l was used, and the same measurement was performed.
【００６６】この（表１）から明らかなように、本実施
例によるコンデンサは、誘電体皮膜の絶縁破壊電圧が比
較例５に比べ高く優れた修復能力が得られ、さらに、容
量、損失についても優れている。As is clear from this (Table 1), the capacitor according to the present embodiment has a higher dielectric breakdown voltage of the dielectric film than that of Comparative Example 5, and an excellent repair ability is obtained. Are better.
【００６７】以上のように、本実施例によれば、電極に
用いる電解重合導電性高分子膜が、誘電体皮膜の修復性
に優れているので、高耐圧のコンデンサを実現すること
ができた。As described above, according to this example, since the electrolytically polymerized conductive polymer film used for the electrode is excellent in the repairability of the dielectric film, a high withstand voltage capacitor could be realized. .
【００６８】（実施例７）トリイソプロピルナフタレン
スルフォン酸ナトリウムの濃度を０．０１ｍｏｌ／ｌに
したこと以外は（実施例１）と同様にしてコンデンサを
作製した。Example 7 A capacitor was produced in the same manner as in Example 1 except that the concentration of sodium triisopropylnaphthalene sulfonate was 0.01 mol / l.
【００６９】試料数は１０個として、得られたコンデン
サの１２０Ｈｚでの容量と損失係数を測定し、その後、
５０Ｖ／分の速度で電圧掃引し誘電体皮膜が絶縁破壊す
る電圧を測定した。The number of samples was 10, and the capacitance and loss coefficient at 120 Hz of the obtained capacitor were measured.
The voltage was swept at a rate of 50 V / min to measure the voltage at which the dielectric film had a dielectric breakdown.
【００７０】これらの測定値の平均を前記（表１）に示
している。この（表１）から明らかなように、本実施例
によるコンデンサにおいては、誘電体皮膜の絶縁破壊電
圧および容量、損失などの特性が（実施例６）に比べよ
り良好になる。The average of these measured values is shown in the above (Table 1). As is clear from (Table 1), in the capacitor according to the present embodiment, the dielectric film has better characteristics such as dielectric breakdown voltage and capacity and loss than those in (Example 6).
【００７１】以上のように、本実施例によれば、電極に
用いる電解重合導電性高分子膜が、誘電体皮膜の修復性
に優れているので、高耐圧のコンデンサを実現すること
ができた。As described above, according to this example, since the electrolytically polymerized conductive polymer film used for the electrode is excellent in the repairability of the dielectric film, it was possible to realize a high withstand voltage capacitor. .
【００７２】（実施例８）ヘキシル燐酸エステルをブチ
ル燐酸エステルに変更したこと以外は（実施例１）と同
様にしてコンデンサを作製した。Example 8 A capacitor was manufactured in the same manner as in Example 1 except that hexyl phosphate was changed to butyl phosphate.
【００７３】試料数は１０個である。得られたコンデン
サの１２０Ｈｚでの容量と損失係数を測定し、その後、
５０Ｖ／分の速度で電圧掃引し誘電体皮膜が絶縁破壊す
る電圧を測定した。The number of samples is 10. Measure the capacitance and loss factor of the obtained capacitor at 120 Hz, and then
The voltage was swept at a rate of 50 V / min to measure the voltage at which the dielectric film had a dielectric breakdown.
【００７４】それらの測定値の平均値を前記（表１）に
示している。この（表１）から明らかなように、本実施
例によるコンデンサにおいては、誘電体皮膜の絶縁破壊
電圧が、比較例１に比べ著しく高く、（実施例１）と同
様に優れた修復能力が得られた。また容量、損失などの
特性も極めて良好であった。The average value of those measured values is shown in the above (Table 1). As is clear from this (Table 1), in the capacitor according to this example, the dielectric breakdown voltage of the dielectric film was significantly higher than that in Comparative Example 1, and the same excellent repairing ability as in (Example 1) was obtained. Was given. The characteristics such as capacity and loss were also very good.
【００７５】（実施例９）ヘキシル燐酸エステルをオク
チル燐酸エステルに変更したこと以外は（実施例１）と
同様にしてコンデンサを作製した。試料数は１０個であ
る。得られたコンデンサの１２０Ｈｚでの容量と損失係
数を測定した。その後、５０Ｖ／分の速度で電圧掃引し
誘電体皮膜が絶縁破壊する電圧を測定した。それらの測
定値の平均値を前記（表１）に示している。Example 9 A capacitor was produced in the same manner as in Example 1 except that hexyl phosphate was changed to octyl phosphate. The number of samples is 10. The capacity and loss coefficient of the obtained capacitor at 120 Hz were measured. Then, the voltage was swept at a rate of 50 V / min to measure the voltage at which the dielectric film had a dielectric breakdown. The average value of those measured values is shown in the above (Table 1).
【００７６】この（表１）から明らかなように、本実施
例によるコンデンサにおいては、誘電体皮膜の絶縁破壊
電圧が比較例１に比べ著しく高く、（実施例１）と同様
に優れた修復能力が得られた。また容量、損失などの特
性も極めて良好であった。As is clear from (Table 1), in the capacitor according to this example, the dielectric breakdown voltage of the dielectric film was remarkably higher than that of Comparative Example 1, and the same excellent repairability as that of (Example 1) was obtained. was gotten. The characteristics such as capacity and loss were also very good.
【００７７】（実施例１０）ヘキシル燐酸エステルをポ
リエチレンオキサイド（０．５重量％）に変更したこと
以外は（実施例１）と同様にしてコンデンサを作製し
た。Example 10 A capacitor was produced in the same manner as in Example 1 except that the hexyl phosphate was changed to polyethylene oxide (0.5% by weight).
【００７８】試料数は１０個である。得られたコンデン
サの１２０Ｈｚでの容量と損失係数を測定した。その
後、５０Ｖ／分の速度で電圧掃引し誘電体皮膜が絶縁破
壊する電圧を測定した。それらの測定値の平均値を前記
（表１）に示している。The number of samples is 10. The capacity and loss coefficient of the obtained capacitor at 120 Hz were measured. Then, the voltage was swept at a rate of 50 V / min to measure the voltage at which the dielectric film had a dielectric breakdown. The average value of those measured values is shown in the above (Table 1).
【００７９】この（表１）から明らかなように、本実施
例によるコンデンサにおいては、誘電体皮膜の絶縁破壊
電圧が比較例１に比べ著しく高く、（実施例１）と同様
に優れた修復能力が得られた。また容量、損失などの特
性も極めて良好であった。As is clear from (Table 1), in the capacitor according to this example, the dielectric breakdown voltage of the dielectric film was remarkably higher than that of Comparative Example 1, and the same excellent repairability as that of (Example 1) was obtained. was gotten. The characteristics such as capacity and loss were also very good.
【００８０】（実施例１１）ポリエチレンオキサイドの
濃度を０．１重量％にしたこと以外は（実施例１０）と
同様にしてコンデンサを作製した。Example 11 A capacitor was manufactured in the same manner as in Example 10 except that the concentration of polyethylene oxide was 0.1% by weight.
【００８１】試料数は１０個である。得られたコンデン
サは（実施例１０）と同様の測定を行った。それらの測
定値の平均値を前記（表１）に示している。The number of samples is 10. The obtained capacitor was measured in the same manner as in (Example 10). The average value of those measured values is shown in the above (Table 1).
【００８２】この（表１）から明らかなように、本実施
例によるコンデンサにおいては、誘電体皮膜の絶縁破壊
電圧が比較例１に比べ著しく高く、（実施例１０）と同
様に優れた修復能力が得られた。また容量、損失などの
特性も極めて良好であった。As is clear from (Table 1), in the capacitor according to this example, the dielectric breakdown voltage of the dielectric film was remarkably higher than that of Comparative Example 1, and the excellent repairing ability as in (Example 10) was obtained. was gotten. The characteristics such as capacity and loss were also very good.
【００８３】（実施例１２）ポリエチレンオキサイドの
濃度を０．０１重量％にしたこと以外は（実施例１０）
と同様にしてコンデンサを作製した。(Example 12) (Example 10) except that the concentration of polyethylene oxide was 0.01% by weight.
A capacitor was manufactured in the same manner as in.
【００８４】試料数は１０個である。得られたコンデン
サは（実施例１０）と同様の測定を行った。それらの測
定値の平均値を前記（表１）に示している。The number of samples is 10. The obtained capacitor was measured in the same manner as in (Example 10). The average value of those measured values is shown in the above (Table 1).
【００８５】また、比較例６として、ポリエチレンオキ
サイドの濃度を０．００５重量％にしたこと以外は上記
と同条件でコンデンサを１０個作製し同様の測定を行っ
た。As Comparative Example 6, ten capacitors were prepared under the same conditions as above except that the concentration of polyethylene oxide was 0.005% by weight, and the same measurement was carried out.
【００８６】この（表１）から明らかなように、本実施
例によるコンデンサにおいては、誘電体皮膜の絶縁破壊
電圧が比較例６に比べ著しく高く、（実施例１０）と同
様に優れた修復能力が得られた。また容量、損失などの
特性も極めて良好であった。As is clear from this (Table 1), in the capacitor according to this example, the dielectric breakdown voltage of the dielectric film was remarkably higher than that of Comparative example 6, and as in (Example 10), the excellent restoration ability was obtained. was gotten. The characteristics such as capacity and loss were also very good.
【００８７】以上のように、本実施例によれば、ポリエ
チレンオキサイドの濃度が少なくとも０．０１重量％以
上であれば、誘電体皮膜の修復性に優れている電解重合
導電性高分子膜が得られ、更に（実施例１１）で示すよ
うにポリエチレンオキサイドの濃度が０．１重量％以上
であれば、その効果は高まり、高耐圧のコンデンサを実
現することができた。As described above, according to the present embodiment, when the concentration of polyethylene oxide is at least 0.01% by weight or more, an electrolytically polymerized conductive polymer film having excellent repairability of the dielectric film is obtained. In addition, as shown in (Example 11), when the concentration of polyethylene oxide was 0.1% by weight or more, the effect was enhanced, and a high withstand voltage capacitor could be realized.
【００８８】（実施例１３）ポリエチレンオキサイドの
濃度を１．０重量％にしたこと以外は（実施例１０）と
同様にしてコンデンサを作製した。Example 13 A capacitor was produced in the same manner as in Example 10 except that the concentration of polyethylene oxide was 1.0% by weight.
【００８９】試料数は１０個である。得られたコンデン
サは（実施例１０）と同様の測定を行った。それらの測
定値の平均値を前記（表１）に示している。The number of samples is 10. The obtained capacitor was measured in the same manner as in (Example 10). The average value of those measured values is shown in the above (Table 1).
【００９０】また、比較例７として、ポリエチレンオキ
サイドの濃度を２．０重量％にしたこと以外は上記と同
条件でコンデンサを１０個作製し同様の測定を行った。As Comparative Example 7, ten capacitors were prepared under the same conditions as above except that the concentration of polyethylene oxide was 2.0% by weight, and the same measurement was carried out.
【００９１】この（表１）から明らかなように、本実施
例によるコンデンサにおいては、誘電体皮膜の絶縁破壊
電圧が比較例１に比べ著しく高く、（実施例１０）と同
様に優れた修復能力が得られた。As is clear from (Table 1), in the capacitor according to this example, the dielectric breakdown voltage of the dielectric film was remarkably higher than that of Comparative Example 1, and the excellent repairing ability as in (Example 10) was obtained. was gotten.
【００９２】また、比較例７に比べ絶縁破壊電圧は同等
であるが、容量、損失特性が良好で優れたコンデンサ特
性が得られた。Further, although the dielectric breakdown voltage was equivalent to that of Comparative Example 7, excellent capacitance and loss characteristics were obtained and excellent capacitor characteristics were obtained.
【００９３】（実施例１４）ヘキシル燐酸エステルを架
橋型ポリアクリル酸ソ−ダ（１．０重量％）に変更した
こと以外は（実施例１）と同様にしてコンデンサを作製
した。Example 14 A capacitor was manufactured in the same manner as in Example 1 except that the hexyl phosphate was changed to a cross-linked polyacrylic acid soda (1.0% by weight).
【００９４】試料数は１０個である。得られたコンデン
サの１２０Ｈｚでの容量と損失係数を測定した。その
後、５０Ｖ／分の速度で電圧掃引し誘電体皮膜が絶縁破
壊する電圧を測定した。それらの測定値の平均値を前記
（表１）に示している。The number of samples is 10. The capacity and loss coefficient of the obtained capacitor at 120 Hz were measured. Then, the voltage was swept at a rate of 50 V / min to measure the voltage at which the dielectric film had a dielectric breakdown. The average value of those measured values is shown in the above (Table 1).
【００９５】この（表１）から明らかなように、本実施
例によるコンデンサにおいては、誘電体皮膜の絶縁破壊
電圧が比較例１に比べ著しく高く、（実施例１）と同様
に優れた修復能力が得られた。また容量、損失などの特
性も極めて良好であった。As is clear from (Table 1), in the capacitor according to this example, the dielectric breakdown voltage of the dielectric film was remarkably higher than that of Comparative Example 1, and the same excellent repairability as that of (Example 1) was obtained. was gotten. The characteristics such as capacity and loss were also very good.
【００９６】（実施例１５）架橋型ポリアクリル酸ソ−
ダの濃度を０．１重量％にしたこと以外は（実施例１
４）と同様にしてコンデンサを作製した。(Example 15) Cross-linked poly (sodium acrylate)
(Example 1 except that the concentration of da was 0.1% by weight.
A capacitor was produced in the same manner as 4).
【００９７】試料数は１０個である。得られたコンデン
サは（実施例１４）と同様の測定を行った。それらの測
定値の平均値を前記（表１）に示している。The number of samples is 10. The obtained capacitor was measured in the same manner as in (Example 14). The average value of those measured values is shown in the above (Table 1).
【００９８】この（表１）から明らかなように、本実施
例によるコンデンサにおいては、誘電体皮膜の絶縁破壊
電圧が比較例１に比べ著しく高く、（実施例１４）と同
様に優れた修復能力が得られた。また容量、損失などの
特性も極めて良好であった。As is clear from this (Table 1), in the capacitor according to this example, the dielectric breakdown voltage of the dielectric film was remarkably higher than that of Comparative Example 1, and the same excellent repairability as that of (Example 14) was obtained. was gotten. The characteristics such as capacity and loss were also very good.
【００９９】（実施例１６）架橋型ポリアクリル酸ソ−
ダの濃度を０．０１重量％にしたこと以外は（実施例１
４）と同様にしてコンデンサを作製した。(Example 16) Cross-linked polyacrylic acid soap
(Example 1 except that the concentration of da was 0.01% by weight.
A capacitor was produced in the same manner as 4).
【０１００】試料数は１０個である。得られたコンデン
サは（実施例１４）と同様の測定を行った。それらの測
定値の平均値を前記（表１）に示している。The number of samples is 10. The obtained capacitor was measured in the same manner as in (Example 14). The average value of those measured values is shown in the above (Table 1).
【０１０１】また、比較例８として、架橋型ポリアクリ
ル酸ソ−ダの濃度を０．００５重量％にしたこと以外は
上記と同条件でコンデンサを１０個作製し同様の測定を
行った。As Comparative Example 8, ten capacitors were prepared under the same conditions as above except that the concentration of the cross-linked polyacrylic acid soda was set to 0.005% by weight, and the same measurement was carried out.
【０１０２】この（表１）から明らかなように、本実施
例によるコンデンサにおいては、誘電体皮膜の絶縁破壊
電圧が比較例８に比べ著しく高く、（実施例１４）と同
様に優れた修復能力が得られた。また容量、損失などの
特性も極めて良好であった。As is clear from (Table 1), in the capacitor according to this example, the dielectric breakdown voltage of the dielectric film was remarkably higher than that of Comparative Example 8, and the excellent repairing ability as in (Example 14) was obtained. was gotten. The characteristics such as capacity and loss were also very good.
【０１０３】以上のように、本実施例によれば、架橋型
ポリアクリル酸ソ−ダの濃度が少なくとも０．０１重量
％以上であれば、誘電体皮膜の修復性に優れている電解
重合導電性高分子膜が得られ、更に（実施例１５）で示
すように架橋型ポリアクリル酸ソ−ダの濃度が０．１重
量％以上であればその効果は高まり、高耐圧のコンデン
サを実現することができた。As described above, according to the present embodiment, when the concentration of the cross-linked polyacrylic acid soda is at least 0.01% by weight or more, the electrolytically-polymerized conductive material excellent in the repairability of the dielectric film is obtained. Of a high-performance polymer film, and as shown in (Example 15), if the concentration of the cross-linked polyacrylic acid soda is 0.1% by weight or more, the effect is enhanced, and a high voltage capacitor is realized. I was able to.
【０１０４】（実施例１７）架橋型ポリアクリル酸ソ−
ダの濃度を５．０重量％にしたこと以外は（実施例１
４）と同様にしてコンデンサを作製した。(Example 17) Cross-linked polyacrylic acid soap
(Example 1 except that the concentration of da was set to 5.0% by weight.
A capacitor was produced in the same manner as 4).
【０１０５】試料数は１０個である。得られたコンデン
サは（実施例１４）と同様の測定を行った。それらの測
定値の平均値を前記（表１）に示している。The number of samples is 10. The obtained capacitor was measured in the same manner as in (Example 14). The average value of those measured values is shown in the above (Table 1).
【０１０６】また、比較例９として、架橋型ポリアクリ
ル酸ソ−ダの濃度を１０．０重量％にしたこと以外は上
記と同条件でコンデンサを１０個作製し同様の測定を行
った。As Comparative Example 9, ten capacitors were prepared under the same conditions as above except that the concentration of the crosslinked polyacrylic acid soda was 10.0% by weight, and the same measurement was carried out.
【０１０７】この（表１）から明らかなように、本実施
例によるコンデンサにおいては、誘電体皮膜の絶縁破壊
電圧が比較例１に比べ著しく高く、（実施例１４）と同
様に優れた修復能力が得られた。また比較例９に比べ絶
縁破壊電圧は同等であるが、容量、損失特性が良好で優
れたコンデンサ特性が得られた。（実施例１８）ニトロ
フェノ−ル（０．０１ｍｏｌ／ｌ）を、更に加えたこと
以外は（実施例１）と同様にしてコンデンサを作製し
た。As is clear from (Table 1), in the capacitor according to this example, the dielectric breakdown voltage of the dielectric film was significantly higher than that of Comparative Example 1, and the repairing ability was excellent as in (Example 14). was gotten. Although the dielectric breakdown voltage was equivalent to that of Comparative Example 9, excellent capacitance and loss characteristics were obtained and excellent capacitor characteristics were obtained. (Example 18) A capacitor was produced in the same manner as in (Example 1) except that nitrophenol (0.01 mol / l) was further added.
【０１０８】試料数は１０個である。得られたコンデン
サは（実施例１）と同様の測定を行った。それらの測定
値の平均値を前記（表１）、（表２）に示している。The number of samples is 10. The obtained capacitor was measured in the same manner as in (Example 1). The average value of those measured values is shown in the above (Table 1) and (Table 2).
【０１０９】この（表１）から明らかなように、本実施
例によるコンデンサにおいては、誘電体皮膜の絶縁破壊
電圧が比較例１に比べ著しく高く、（実施例１）と同様
に優れた修復能力が得られた。さらに、容量、損失など
の特性も極めて良好であった。As is clear from (Table 1), in the capacitor according to this example, the dielectric breakdown voltage of the dielectric film was remarkably higher than that of Comparative Example 1, and the same excellent repairability as that of (Example 1) was obtained. was gotten. Further, the characteristics such as capacity and loss were also very good.
【０１１０】また（表２）から明らかなように、本実施
例によるコンデンサにおいては、長時間の高温放置を行
っても特性の劣化が小さく、優れた熱安定性が得られ
た。Further, as is clear from (Table 2), in the capacitor according to the present embodiment, the deterioration of the characteristics was small even when left at high temperature for a long time, and the excellent thermal stability was obtained.
【０１１１】以上のように、本実施例によれば、電極に
用いる電解重合導電性高分子膜が、誘電体皮膜の修復性
に優れ、また熱安定性も優れているので、高耐圧、高信
頼性のコンデンサを実現することができた。As described above, according to this example, the electrolytically polymerized conductive polymer film used for the electrode is excellent in the repairability of the dielectric film and also in the thermal stability. We were able to realize a reliable capacitor.
【０１１２】（実施例１９）ニトロフェノ−ルの濃度を
０．１５ｍｏｌ／ｌにしたこと以外は（実施例１８）と
同様にしてコンデンサを作製した。Example 19 A capacitor was produced in the same manner as in Example 18 except that the concentration of nitrophenol was 0.15 mol / l.
【０１１３】試料数は１０個である。得られたコンデン
サは（実施例１８）と同様の測定を行った。それらの測
定値の平均値を前記（表１）、（表２）に示している。The number of samples is 10. The same measurement as in (Example 18) was performed on the obtained capacitor. The average value of those measured values is shown in the above (Table 1) and (Table 2).
【０１１４】この（表１）から明らかなように、本実施
例によるコンデンサにおいては、誘電体皮膜の絶縁破壊
電圧が比較例１に比べ著しく高く、（実施例１８）と同
様に優れた修復能力が得られた。そして、容量、損失な
どの特性も極めて良好であった。As is clear from this (Table 1), in the capacitor according to this example, the dielectric breakdown voltage of the dielectric film was remarkably higher than that of Comparative Example 1, and as in (Example 18), the excellent repair ability was obtained. was gotten. The characteristics such as capacity and loss were also very good.
【０１１５】また（表２）から明らかなように、本実施
例によるコンデンサにおいては、長時間の高温放置を行
っても特性の劣化が小さく、優れた熱安定性が得られ
た。Further, as is clear from (Table 2), in the capacitor according to the present embodiment, deterioration of the characteristics was small even when left at high temperature for a long time, and excellent thermal stability was obtained.
【０１１６】以上のように、本実施例によれば、電極に
用いる電解重合導電性高分子膜が、誘電体皮膜の修復性
に優れ、また熱安定性も優れているので、高耐圧、高信
頼性のコンデンサを実現することができた。As described above, according to this example, the electrolytically polymerized conductive polymer film used for the electrode is excellent in the repairability of the dielectric film and also in the thermal stability. We were able to realize a reliable capacitor.
【０１１７】（実施例２０）ニトロフェノ−ルの濃度を
０．００５ｍｏｌ／ｌにしたこと以外は（実施例１８）
と同様にしてコンデンサを作製した。(Example 20) Except that the concentration of nitrophenol was 0.005 mol / l (Example 18)
A capacitor was manufactured in the same manner as in.
【０１１８】試料数は１０個である。得られたコンデン
サは（実施例１８）と同様の測定を行った。それらの測
定値の平均値を前記（表１）、（表２）に示している。The number of samples is 10. The same measurement as in (Example 18) was performed on the obtained capacitor. The average value of those measured values is shown in the above (Table 1) and (Table 2).
【０１１９】また、比較例１０として、ニトロフェノ−
ルの濃度を０．００１ｍｏｌ／ｌにしたこと以外は上記
と同条件でコンデンサを１０個作製し同様の測定を行っ
た。As Comparative Example 10, nitropheno-
10 capacitors were prepared under the same conditions as above except that the concentration of the catalyst was 0.001 mol / l, and the same measurement was performed.
【０１２０】この（表１）から明らかなように、本実施
例によるコンデンサにおいては、誘電体皮膜の絶縁破壊
電圧が比較例１に比べ著しく高く、（実施例１８）と同
様に優れた修復能力が得られた。そして、容量、損失な
どの特性も極めて良好であった。As is clear from this (Table 1), in the capacitor according to this example, the dielectric breakdown voltage of the dielectric film was remarkably higher than that of Comparative Example 1, and as in (Example 18), the excellent repair ability was obtained. was gotten. The characteristics such as capacity and loss were also very good.
【０１２１】また（表２）から明らかなように、本実施
例によるコンデンサにおいては、比較例１０のコンデン
サに比べ長時間の高温放置を行っても特性の劣化が小さ
く、優れた熱安定性が得られた。Further, as is clear from (Table 2), the capacitors according to the present example show less deterioration in characteristics than the capacitors of Comparative Example 10 even after being left at high temperature for a long time, and have excellent thermal stability. Was obtained.
【０１２２】以上のように、本実施例によれば、ニトロ
フェノ−ルの濃度が少なくとも０．００５ｍｏｌ／ｌ以
上であれば、熱安定性に優れている電解重合導電性高分
子膜が得られ、更に（実施例１８）で示すようにニトロ
フェノ−ルの濃度が０．０１ｍｏｌ／ｌ以上であればそ
の効果は高まり、高耐圧のコンデンサを実現することが
できた。As described above, according to this example, when the concentration of nitrophenol was at least 0.005 mol / l, an electropolymerized conductive polymer film having excellent thermal stability was obtained. Further, as shown in (Example 18), when the concentration of nitrophenol was 0.01 mol / l or more, the effect was enhanced, and a high withstand voltage capacitor could be realized.
【０１２３】（実施例２１）ニトロフェノ−ルの濃度を
１．０ｍｏｌ／ｌにしたこと以外は（実施例１８）と同
様にしてコンデンサを作製した。Example 21 A capacitor was manufactured in the same manner as in Example 18 except that the concentration of nitrophenol was 1.0 mol / l.
【０１２４】試料数は１０個である。得られたコンデン
サは（実施例１８）と同様の測定を行った。それらの測
定値の平均値を前記（表１）、（表２）に示している。The number of samples is 10. The same measurement as in (Example 18) was performed on the obtained capacitor. The average value of those measured values is shown in the above (Table 1) and (Table 2).
【０１２５】また、比較例１１として、ニトロフェノ−
ルの濃度を５．０ｍｏｌ／ｌにしたこと以外は上記と同
条件でコンデンサを１０個作製し同様の測定を行った。As Comparative Example 11, nitrophenol
10 capacitors were prepared under the same conditions as above except that the concentration of the catalyst was 5.0 mol / l, and the same measurement was performed.
【０１２６】この（表１）から明らかなように、本実施
例によるコンデンサにおいては、誘電体皮膜の絶縁破壊
電圧が比較例１に比べ著しく高く、（実施例１８）と同
様に優れた修復能力が得られた。また比較例１１に比べ
絶縁破壊電圧は同等であるが、容量、損失特性が良好で
優れたコンデンサ特性が得られた。As is clear from (Table 1), in the capacitor according to this example, the dielectric breakdown voltage of the dielectric film was remarkably higher than that of Comparative Example 1, and the same excellent repairability as that of (Example 18) was obtained. was gotten. Although the dielectric breakdown voltage was the same as that of Comparative Example 11, excellent capacitance and loss characteristics were obtained and excellent capacitor characteristics were obtained.
【０１２７】また（表２）から明らかなように、本実施
例によるコンデンサにおいては、長時間の高温放置を行
っても特性の劣化が小さく、優れた熱安定性が得られ
た。As is clear from (Table 2), in the capacitor according to this example, the characteristics were less deteriorated even when left at high temperature for a long time, and excellent thermal stability was obtained.
【０１２８】（実施例２２）ピロ−ルおよび水に代え
て、チオフェンおよびアセトニトリルを用いた以外は
（実施例１）と同様にしてコンデンサを作製した。Example 22 A capacitor was produced in the same manner as in Example 1 except that thiophene and acetonitrile were used instead of pyrrole and water.
【０１２９】試料数は１０個である。得られたコンデン
サの１２０Ｈｚでの容量と損失係数を測定した。その
後、５０Ｖ／分の速度で電圧掃引し誘電体皮膜が絶縁破
壊する電圧を測定した。それらの測定値の平均値を前記
（表１）に示している。The number of samples is 10. The capacity and loss coefficient of the obtained capacitor at 120 Hz were measured. Then, the voltage was swept at a rate of 50 V / min to measure the voltage at which the dielectric film had a dielectric breakdown. The average value of those measured values is shown in the above (Table 1).
【０１３０】また比較例１２として、ヘキシル燐酸エス
テルを添加しないこと以外は上記と同条件でコンデンサ
を１０個作製し同様の測定を行った。As Comparative Example 12, ten capacitors were prepared under the same conditions as above except that hexyl phosphate was not added, and the same measurement was carried out.
【０１３１】この（表１）から明らかなように、本実施
例によるコンデンサは、誘電体皮膜の絶縁破壊電圧が比
較例１２に比べ著しく高く、（実施例１）と同様に優れ
た修復能力が得られた。また容量、損失などの特性も極
めて良好であった。As is clear from (Table 1), the capacitor according to this example has a significantly higher dielectric breakdown voltage of the dielectric film than that of Comparative Example 12, and has the same excellent repair ability as (Example 1). Was obtained. The characteristics such as capacity and loss were also very good.
【０１３２】（実施例２３）トリイソプロピルナフタレ
ンスルフォン酸ナトリウムに代えて、ジブチルナフタレ
ンスルフォン酸ナトリウムを電解重合液に添加する以外
は（実施例１）と同様にしてコンデンサを作製した。Example 23 A capacitor was prepared in the same manner as in Example 1 except that sodium dibutylnaphthalene sulfonate was added to the electrolytic polymerization solution instead of sodium triisopropylnaphthalene sulfonate.
【０１３３】試料数は１０個である。得られたコンデン
サの１２０Ｈｚでの容量と損失係数を測定した。その
後、５０Ｖ／分の速度で電圧掃引し誘電体皮膜が絶縁破
壊する電圧を測定した。それらの測定値の平均値を前記
（表１）に示している。The number of samples is 10. The capacity and loss coefficient of the obtained capacitor at 120 Hz were measured. Then, the voltage was swept at a rate of 50 V / min to measure the voltage at which the dielectric film had a dielectric breakdown. The average value of those measured values is shown in the above (Table 1).
【０１３４】また、比較例１３として、ヘキシル燐酸エ
ステルを添加しないこと以外は上記と同条件でコンデン
サを１０個作製し同様の測定を行った。As Comparative Example 13, ten capacitors were prepared under the same conditions as above except that hexyl phosphate was not added, and the same measurement was carried out.
【０１３５】この（表１）から明らかなように、本実施
例によるコンデンサは、誘電体皮膜の絶縁破壊電圧が比
較例１３に比べ著しく高く、（実施例１）と同様に優れ
た修復能力が得られた。また容量、損失などの特性も極
めて良好であった。As is clear from (Table 1), the capacitor according to this example has a significantly higher dielectric breakdown voltage of the dielectric film than that of Comparative Example 13, and has the same excellent repair ability as (Example 1). Was obtained. The characteristics such as capacity and loss were also very good.
【０１３６】なお、上記実施例では芳香族スルフォン酸
塩として、トリイソプロピルナフタレンスルフォン酸
塩、ジブチルナフタレンスルフォン酸塩を使用した場合
についてのみ述べたが、他のアルキル置換基を有するモ
ノメチルナフタレンスルフォン酸塩、モノイソプロピル
ナフタレンスルフォン酸塩、ジブチルナフタレンスルフ
ォン酸塩等の芳香族スルフォン酸塩や、他の置換基を有
するものでも使用可能である。In the above examples, the case where triisopropylnaphthalene sulfonate or dibutylnaphthalene sulfonate is used as the aromatic sulfonate is described, but monomethylnaphthalene sulfonate having another alkyl substituent is used. Also, aromatic sulfonates such as monoisopropyl naphthalene sulfonate, dibutyl naphthalene sulfonate, and those having other substituents can be used.
【０１３７】なお、上記実施例ではアルキル燐酸エステ
ルのアルキル基としてブチル基、ヘキシル基、オクチル
基を使用した場合についてのみ述べたが、その他のプロ
ピル基からドデシル基を有するアルキル燐酸エステルで
も使用可能である。In the above-mentioned examples, only the case where a butyl group, a hexyl group or an octyl group is used as the alkyl group of the alkyl phosphate ester is described, but an alkyl phosphate ester having a dodecyl group from other propyl groups can also be used. is there.
【０１３８】なお、上記実施例ではフェノ−ル誘導体と
してパラニトロフェノ−ルを使用した場合についてのみ
述べたが、フェノ−ルまたは置換基を有する芳香族ヒド
ロキシ化合物であれば他のフェノ−ル誘導体でも使用可
能である。In the above examples, only the case where para-nitrophenol was used as the phenol derivative was described, but other phenol derivative may be used as long as it is a phenol or an aromatic hydroxy compound having a substituent. But it can be used.
【０１３９】この置換基としては、電子吸引性が大きい
ものであれば使用可能で、シアノフェノ−ル、ヒドロキ
シアセトフェノン、ヒドロキシベンズアルデヒド、ヒド
ロキシベンズアミド、ヒドロキシ安息香酸等でもよい。As the substituent, any one having a large electron-withdrawing property can be used, and cyanophenol, hydroxyacetophenone, hydroxybenzaldehyde, hydroxybenzamide, hydroxybenzoic acid and the like may be used.
【０１４０】なお、上記実施例では重合性モノマ−とし
てピロ−ルのほかにチオフェンを使用した場合について
のみ述べたが、それらの誘導体（Ｎ−メチルピロ−ル
等）やフラン等の他の重合性モノマ−、またはそれらの
複数種の併用したものをも使用することができる。In the above Examples, only the case where thiophene was used in addition to pyrrole as the polymerizable monomer was described, but other polymerizable compounds such as derivatives thereof (N-methylpyrrole, etc.) and furan, etc. A monomer or a combination of two or more kinds of them can be used.
【０１４１】さらに、導電性高分子を複合化する際に電
解液に適当な添加剤を混ぜてもよい。Further, a suitable additive may be mixed with the electrolytic solution when the conductive polymer is compounded.
【０１４２】なお、上記実施例では硝酸マンガンを用い
てマンガン酸化物を形成した場合についてのみ述べた
が、硝酸マンガンに限らずマンガン酸化物を形成できる
ものであれば他の物質でも使用可能である。In the above embodiments, only the case where manganese oxide is used to form manganese oxide has been described, but not only manganese nitrate but also other substances can be used as long as they can form manganese oxide. .
【０１４３】なお、上記実施例では陽極として弁金属の
アルミニウムを使用した固体電解コンデンサについての
み述べたが、本発明の主旨から明らかなように、電極と
して使用できる電気伝導度を有すれば他の物質も使用可
能である。In the above embodiments, only the solid electrolytic capacitor using the valve metal aluminum as the anode has been described, but as is clear from the gist of the present invention, other solid electrolytic capacitors having an electric conductivity that can be used as an electrode are used. Materials can also be used.
【０１４４】なお、上記実施例では誘電体としてアルミ
ニウム酸化物を使用した場合についてのみ述べたが、従
来の技術でふれた電着ポリイミドなどコンデンサの誘電
体として使用できる他の物質を使用しても本発明の効果
は何等妨げられるものではない。In the above embodiments, the case where aluminum oxide is used as the dielectric has been described, but other materials that can be used as the dielectric of the capacitor such as electrodeposited polyimide mentioned in the prior art may be used. The effect of the present invention is not hindered at all.
【０１４５】なお、上記実施例では極性を持ったコンデ
ンサについてのみ述べたが、本発明の主旨から明らかな
ように、無極性のコンデンサでも同様の効果がある。Although only the capacitor having the polarity is described in the above embodiment, the same effect can be obtained with the non-polar capacitor as is clear from the gist of the present invention.
【０１４６】なお、上記実施例では一つの電極に導電性
高分子を用いた場合についてのみ述べたが、さらに別の
電極に導電性高分子を用いることも可能であり、本発明
は導電性高分子を用いる電極の数によって何等制限を受
けるものではない。In the above embodiments, only the case where the conductive polymer is used for one electrode has been described, but it is also possible to use the conductive polymer for another electrode. No limitation is imposed by the number of electrodes using the molecule.
【０１４７】[0147]
【発明の効果】以上のように本発明は、アルキル燐酸エ
ステルと芳香族スルフォン酸塩、あるいはポリエチレン
オキサイドと芳香族スルフォン酸塩、あるいはアルキル
燐酸エステルとフェノ−ル誘導体と芳香族スルフォン酸
塩、あるいは架橋型ポリアクリル酸ソ−ダと芳香族スル
フォン酸塩、のいずれかと重合性モノマ−とを少なくと
も含有する電解液を用いる電解重合により得られる導電
性高分子を、誘電体皮膜、マンガン酸化物層を順次形成
させた電極上に積層し対極とするので、誘電体皮膜の修
復能力が優れた高耐圧コンデンサを効率よく作製できる
ものである。As described above, according to the present invention, an alkyl phosphate and an aromatic sulfonate, a polyethylene oxide and an aromatic sulfonate, an alkyl phosphate, a phenol derivative and an aromatic sulfonate, or A conductive polymer obtained by electrolytic polymerization using an electrolytic solution containing at least one of crosslinked polyacrylic acid soda and aromatic sulfonate and a polymerizable monomer, a dielectric film, a manganese oxide layer. Since it is laminated on an electrode formed sequentially to form a counter electrode, it is possible to efficiently manufacture a high breakdown voltage capacitor having an excellent ability to repair the dielectric film.
【図１】本発明のコンデンサの断面図FIG. 1 is a sectional view of a capacitor of the present invention.
【図２】本発明のコンデンサの平面図FIG. 2 is a plan view of the capacitor of the present invention.
【図３】本発明の電解重合導電性高分子膜を形成する図FIG. 3 is a diagram for forming an electropolymerized conductive polymer film of the present invention.
１ 陽極リード ２ 弁作用金属 ３ 誘電体皮膜 ４ マンガン酸化物膜 ５ 電解重合導電性高分子膜 ６ 陰極リード ７ 重合開始用電極 ８ 耐熱絶縁テープ ９ 電解重合溶液 １０ カーボンペイント膜 １１ 銀ペイント膜 1 Anode Lead 2 Valve Metal 3 Dielectric Film 4 Manganese Oxide Film 5 Electropolymerization Conductive Polymer Film 6 Cathode Lead 7 Polymerization Initiating Electrode 8 Heat Resistant Insulation Tape 9 Electropolymerization Solution 10 Carbon Paint Film 11 Silver Paint Film
───────────────────────────────────────────────────── フロントページの続き (72)発明者 吉田 浩一 神奈川県川崎市多摩区東三田３丁目10番１ 号 松下技研株式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Koichi Yoshida 3-10-1 Higashisanda, Tama-ku, Kawasaki City, Kanagawa Prefecture Matsushita Giken Co., Ltd.
Claims (15)
ン酸塩と重合性モノマ−とを少なくとも含有する電解液
を用いる電解重合により得られる導電性高分子を、誘電
体皮膜上に形成し電極として使用することを特徴とする
コンデンサの製造方法。1. A conductive polymer obtained by electrolytic polymerization using an electrolytic solution containing at least an alkyl phosphate, an aromatic sulfonate and a polymerizable monomer is formed on a dielectric film and used as an electrode. A method of manufacturing a capacitor characterized by the above.
ォン酸塩と重合性モノマ−とを少なくとも含有する電解
液を用いる電解重合により得られる導電性高分子を、誘
電体皮膜上に形成し電極として使用することを特徴とす
るコンデンサの製造方法。2. A conductive polymer obtained by electrolytic polymerization using an electrolytic solution containing at least polyethylene oxide, an aromatic sulfonate and a polymerizable monomer is formed on a dielectric film and used as an electrode. And a method for manufacturing a capacitor.
体と芳香族スルフォン酸塩と重合性モノマ−とを少なく
とも含有する電解液を用いる電解重合により得られる導
電性高分子を、誘電体皮膜上に形成し電極として使用す
ることを特徴とするコンデンサの製造方法。3. A conductive polymer obtained by electrolytic polymerization using an electrolytic solution containing at least an alkyl phosphate ester, a phenol derivative, an aromatic sulfonate and a polymerizable monomer is formed on a dielectric film. A method of manufacturing a capacitor, which is used as an electrode.
ルフォン酸塩と重合性モノマ−とを少なくとも含有する
電解液を用いる電解重合により得られる導電性高分子
を、誘電体皮膜上に形成し電極として使用することを特
徴とするコンデンサの製造方法。4. A conductive polymer obtained by electrolytic polymerization using an electrolytic solution containing at least a cross-linked polyacrylic acid soda, an aromatic sulfonate and a polymerizable monomer is formed on a dielectric film. A method of manufacturing a capacitor, which is used as an electrode.
を有するナフタレンスルフォン酸塩であり、電解液中の
添加濃度は０．００５ｍｏｌ／ｌ以上０．５ｍｏｌ／ｌ
以下であることを特徴とする請求項１から４記載のコン
デンサの製造方法。5. The aromatic sulfonate is a naphthalene sulfonate having an alkyl substituent, and the concentration added in the electrolytic solution is 0.005 mol / l or more and 0.5 mol / l.
The method of manufacturing a capacitor according to claim 1, wherein:
添加濃度が０．０１ｍｏｌ／ｌ以上０．１ｍｏｌ／ｌ以
下であることを特徴とする請求項１から４記載のコンデ
ンサの製造方法。6. The method for producing a capacitor according to claim 1, wherein the optimum addition concentration of the aromatic sulfonate in the electrolytic solution is 0.01 mol / l or more and 0.1 mol / l or less.
ステルであり、電解液中の添加濃度は０．００５規定以
上０．５規定以下であることを特徴とする請求項１、３
記載のコンデンサの製造方法。7. The alkyl phosphoric acid ester is a hexyl phosphoric acid ester, and the concentration added in the electrolytic solution is 0.005 N or more and 0.5 N or less.
A method for manufacturing the described capacitor.
添加濃度が０．０１規定以上０．１規定以下であること
を特徴とする請求項１、３記載のコンデンサの製造方
法。8. The method for producing a capacitor according to claim 1, wherein the optimum addition concentration of the alkyl phosphate ester in the electrolytic solution is 0.01 normal or more and 0.1 normal or less.
加濃度は０．０１重量％以上１．０重量％以下であるこ
とを特徴とする請求項２記載のコンデンサの製造方法。9. The method for producing a capacitor according to claim 2, wherein the concentration of polyethylene oxide added in the electrolytic solution is 0.01% by weight or more and 1.0% by weight or less.
最適添加濃度が０．１重量％以上０．５重量％以下であ
ることを特徴とする請求項２記載のコンデンサの製造方
法。10. The method for producing a capacitor according to claim 2, wherein the optimum addition concentration of polyethylene oxide in the electrolytic solution is 0.1% by weight or more and 0.5% by weight or less.
中の添加濃度は０．０１重量％以上５．０重量％以下で
あることを特徴とする請求項４記載のコンデンサの製造
方法11. The method for producing a capacitor according to claim 4, wherein the concentration of the crosslinked polyacrylic acid soda added to the electrolytic solution is 0.01% by weight or more and 5.0% by weight or less.
中の最適添加濃度が０．１重量％以上１．０重量％以下
であることを特徴とする請求項４記載のコンデンサの製
造方法12. The method for producing a capacitor according to claim 4, wherein the optimum addition concentration of the crosslinked polyacrylic acid soda in the electrolytic solution is 0.1% by weight or more and 1.0% by weight or less.
であり、電解液中の添加濃度は０．００５ｍｏｌ／ｌ以
上１．０ｍｏｌ／ｌ以下であることを特徴とする請求項
３記載のコンデンサの製造方法。13. The capacitor according to claim 3, wherein the phenol derivative is nitrophenol, and the concentration added in the electrolytic solution is 0.005 mol / l or more and 1.0 mol / l or less. Method.
加濃度が０．０１ｍｏｌ／ｌ以上０．１５ｍｏｌ／ｌ以
下であることを特徴とする請求項３記載のコンデンサの
製造方法。14. The method for producing a capacitor according to claim 3, wherein the optimum addition concentration of the phenol derivative in the electrolytic solution is 0.01 mol / l or more and 0.15 mol / l or less.
ンあるいはそれらの誘導体の少なくとも一つから選ばれ
るものである請求項１から４記載のコンデンサの製造方
法。15. The method for producing a capacitor according to claim 1, wherein the polymerizable monomer is selected from at least one of pyrrole, thiophene and their derivatives.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5051899A JP2982543B2 (en) | 1993-03-12 | 1993-03-12 | Manufacturing method of capacitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5051899A JP2982543B2 (en) | 1993-03-12 | 1993-03-12 | Manufacturing method of capacitor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06267798A true JPH06267798A (en) | 1994-09-22 |
| JP2982543B2 JP2982543B2 (en) | 1999-11-22 |
Family
ID=12899730
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5051899A Expired - Fee Related JP2982543B2 (en) | 1993-03-12 | 1993-03-12 | Manufacturing method of capacitor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2982543B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002025863A (en) * | 2000-07-07 | 2002-01-25 | Showa Denko Kk | Solid electrolytic capacitor device and its manufacturing method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04315412A (en) * | 1991-04-15 | 1992-11-06 | Matsushita Electric Ind Co Ltd | Solid electrolytic capacitor |
| JPH0521281A (en) * | 1991-07-10 | 1993-01-29 | Matsushita Electric Ind Co Ltd | Capacitor and its manufacture |
| JPH0521284A (en) * | 1991-07-10 | 1993-01-29 | Matsushita Electric Ind Co Ltd | Capacitor and its manufacture |
-
1993
- 1993-03-12 JP JP5051899A patent/JP2982543B2/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04315412A (en) * | 1991-04-15 | 1992-11-06 | Matsushita Electric Ind Co Ltd | Solid electrolytic capacitor |
| JPH0521281A (en) * | 1991-07-10 | 1993-01-29 | Matsushita Electric Ind Co Ltd | Capacitor and its manufacture |
| JPH0521284A (en) * | 1991-07-10 | 1993-01-29 | Matsushita Electric Ind Co Ltd | Capacitor and its manufacture |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002025863A (en) * | 2000-07-07 | 2002-01-25 | Showa Denko Kk | Solid electrolytic capacitor device and its manufacturing method |
| JP4655339B2 (en) * | 2000-07-07 | 2011-03-23 | 株式会社村田製作所 | Solid electrolytic capacitor element and manufacturing method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2982543B2 (en) | 1999-11-22 |
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