JPH0925417A - Heat-sensitive and electroconductive polymer, its production and solid electrolytic capacitor using the same electroconductive polymer - Google Patents
Heat-sensitive and electroconductive polymer, its production and solid electrolytic capacitor using the same electroconductive polymerInfo
- Publication number
- JPH0925417A JPH0925417A JP17472995A JP17472995A JPH0925417A JP H0925417 A JPH0925417 A JP H0925417A JP 17472995 A JP17472995 A JP 17472995A JP 17472995 A JP17472995 A JP 17472995A JP H0925417 A JPH0925417 A JP H0925417A
- Authority
- JP
- Japan
- Prior art keywords
- heat
- conductive polymer
- resistant conductive
- organic compound
- electrolytic capacitor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- Compositions Of Macromolecular Compounds (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Description
【発明の詳細な説明】Detailed Description of the Invention
【０００１】[0001]
【発明の属する技術分野】本発明は、電池、コンデン
サ、ダイオード、表示素子、センサーなどの電子デバイ
スに利用される耐熱性導電性高分子およびその製造方法
に関し、とくにこの導電性高分子を用いた固体電解コン
デンサに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-resistant conductive polymer for use in electronic devices such as batteries, capacitors, diodes, display elements, and sensors, and a method for producing the same. The present invention relates to a solid electrolytic capacitor.
【０００２】[0002]
【従来の技術】導電性高分子は、従来π電子を有する芳
香族化合物の化学的、または電気化学的酸化により製造
されている。しかし、アニオンがドーピングされた高酸
化状態であるため、熱、酸素、光、水等の協同的な外部
刺激による性能の劣化が著しく、長期で安定に性能保持
することが困難とされてきた。特に熱に対しては劣化が
著しく、デバイスの開発に対して限界となっていた。2. Description of the Related Art Conventionally, conductive polymers have been produced by chemical or electrochemical oxidation of aromatic compounds having π electrons. However, since it is in a highly oxidized state doped with anions, its performance is significantly degraded by cooperative external stimuli such as heat, oxygen, light, and water, and it has been difficult to maintain stable performance for a long period of time. In particular, the deterioration with respect to heat was remarkable, which was a limit to the development of the device.
【０００３】通常導電性高分子の重合には、例えば電解
重合をする場合、重合性モノマーと支持電解質の混合溶
液を電解液として用いることが知られている。In the polymerization of conductive polymers, for example, in the case of electrolytic polymerization, it is known that a mixed solution of a polymerizable monomer and a supporting electrolyte is used as an electrolytic solution.
【０００４】ところで耐熱性向上のため、特開平５−２
１２８１、特開平５−２１２８３では重合性モノマー、
支持電解質に加えて、ＮＯ2 基、ＣＮ基、ＳＯ2 ＮＯ2
基、ＣＸ3 基、ＣＯＲ基、ＳＯＲ基、ＣＯＯＨ基、ＣＯ
ＯＲ基、ＳＣＯＲ基、ＣＯＮＨ2 基（但しＲはアルキル
基、Ｘはハロゲン）の少なくとも一つから選ばれる置換
基を有する芳香族誘導体もしくはフェノール誘導体また
はフェノキシド誘導体を混合させた電解液を用いて電解
重合法により導電性高分子を得ることを提案している。Incidentally, in order to improve heat resistance, Japanese Patent Application Laid-Open No.
1281, JP-A-5-21283 discloses a polymerizable monomer,
In addition to the supporting electrolyte, NO 2 groups, CN groups, SO 2 NO 2
Group, CX 3 group, COR group, SOR group, COOH group, CO
Electrolysis using an electrolyte mixed with an aromatic derivative, a phenol derivative or a phenoxide derivative having a substituent selected from at least one of an OR group, a SCOR group, and a CONH 2 group (where R is an alkyl group and X is a halogen) It is proposed to obtain a conductive polymer by a polymerization method.
【０００５】また、特開平３−１１４２１３では導電性
高分子のドーパントとして、Ｉ2 ，Ｂｒ2 ，ＳＯ3 ，Ａ
ｓＦ6 ，ＳｂＦ6 等の電子受容体あるいはＢＦ4 - ，Ｃ
ｌＯ4 - ，ＰＦ6 - ，ＡＳＦ6 - 等のアニオンを用いる
ことを提案している。In Japanese Patent Application Laid-Open No. 3-114213, I 2 , Br 2 , SO 3 , A
electron acceptors such as sF 6 and SbF 6 or BF 4 − , C
It has been proposed to use anions such as 10 4 − , PF 6 − and ASF 6 − .
【０００６】さらに、特開平１−１７００１０では導電
性高分子のドーパント中にＣＯＯＨ基やＯＨ基にあわせ
て必ずフッ素（Ｆ）を含有することにより、著しい誘電
体酸化皮膜の補修能力を付与することができることを提
案している。[0006] Further, Japanese Patent Application Laid-Open No. 1-170010 discloses that a conductive polymer dopant always contains fluorine (F) in accordance with a COOH group or an OH group, thereby providing a remarkable ability to repair a dielectric oxide film. Suggest that you can.
【０００７】[0007]
【発明が解決しようとする課題】しかしながら、特開平
５−２１２８１、特開平５−２１２８３では３成分混合
系を用いているが、一般に３成分混合系ではその適正条
件範囲は非常に狭く、また、適正濃度での制御が困難で
ある。However, in JP-A-5-21281 and JP-A-5-21283, a three-component mixed system is used. In general, a three-component mixed system has a very narrow range of appropriate conditions. It is difficult to control at an appropriate concentration.
【０００８】また、特開平３−１１４２１３では分子量
の小さいドーパントを用いており、この場合導電性高分
子主鎖からの脱ドープ（ドーパントの脱離）が起こりや
すいことが知られている。この脱ドープ現象は高温下ほ
ど顕著になり、従って高温下での安定性が低下する。In Japanese Patent Application Laid-Open No. 3-114213, a dopant having a small molecular weight is used. In this case, it is known that undoping (dopant removal) from the conductive polymer main chain is likely to occur. This undoping phenomenon becomes more pronounced at higher temperatures, so that the stability at high temperatures is reduced.
【０００９】さらに、特開平１−１１４２１３ではフッ
素を含む化合物をドーパントとして用いているが、フッ
素を含む化合物は合成が困難であり、従って高価になり
工業的には不向きである。また、フッ素を含むドーパン
トは酸性度が高く、樹脂外装した場合に外装樹脂を腐食
するおそれがある。また、特開平１−１７００１０にお
いての効果は誘電体酸化皮膜の補修能力に限定されてい
るのに対し、本発明の効果は耐熱性の向上である。Furthermore, in JP-A-1-114213, a compound containing fluorine is used as a dopant, but a compound containing fluorine is difficult to synthesize, and therefore is expensive and industrially unsuitable. Further, the fluorine-containing dopant has a high acidity and may corrode the exterior resin when it is packaged with the resin. The effect of JP-A-1-170010 is limited to the ability to repair a dielectric oxide film, whereas the effect of the present invention is to improve heat resistance.
【００１０】[0010]
【課題を解決するための手段】本発明者らは、前記課題
を解決するため耐熱性導電性高分子およびその製造方
法、並びにこの導電性高分子を用いた固体電解コンデン
サについて鋭意研究を行った。その結果、特定の化学構
造式を有する耐熱性導電性高分子およびその製造方法、
並びにこの導電性高分子を用いた固体電解コンデンサの
発明に至った。Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have conducted intensive studies on a heat-resistant conductive polymer, a method for producing the same, and a solid electrolytic capacitor using the conductive polymer. . As a result, a heat-resistant conductive polymer having a specific chemical structural formula and a method for producing the same,
Further, the invention of a solid electrolytic capacitor using the conductive polymer has been reached.
【００１１】すなわち、 （１）図１の化学構造式１で表される有機化合物を成分
として含有させたことを特徴とする耐熱性導電性高分
子。 （２）化学構造式１のうち、有機化合物Ｍが芳香族化合
物、強アニオン性解離基Ｙがスルホン酸基であることを
特徴とした、図２の化学構造式２で表される（１）項記
載の耐熱性導電性高分子。 （３）導電性高分子がポリピロールポリチオフェン、ポ
リアニリンであることを特徴とする耐熱性導電性高分
子。 （４）上記耐熱性導電性高分子を化学構造式１で表され
る有機化合物を含む溶液中で化学酸化重合したことを特
徴とする上記耐熱性導電性高分子の製造方法。 （５）上記耐熱性導電性高分子を化学構造式２で表され
る有機化合物を含む溶液中で化学酸化重合したことを特
徴とする上記耐熱性導電性高分子の製造方法。 （６）上記耐熱性導電性高分子を化学構造式１で表され
る有機化合物を含む溶液中で電解酸化重合したことを特
徴とする上記耐熱性導電性高分子の製造方法。 （７）上記耐熱性導電性高分子を化学構造式２で表され
る有機化合物を含む溶液中で電解酸化重合したことを特
徴とする上記耐熱性導電性高分子の製造方法。 （８）導電性高分子がポリピロールであることを特徴と
した耐熱性導電性高分子の製造方法。 （９）皮膜形成性金属上に、誘電体酸化皮膜、固体電解
質、導電層を順次形成した後に陽・陰極端子を取り出
し、樹脂外装した固体電解コンデンサにおいて、上記固
体電解質が化学構造式１で表される耐熱性導電性高分子
であることを特徴とする固体電解コンデンサ。 （１０）皮膜形成性金属上に、誘電体酸化皮膜、固体電
解質、導電層を順次形成した後に陽・陰極端子を取り出
し、樹脂外装した固体電解コンデンサにおいて、上記固
体電解質が化学構造式２耐熱性導電性高分子であること
を特徴とする固体電解コンデンサ。 （１１）皮膜形成性金属上に、誘電体酸化皮膜、固体電
解質、導電層を順次形成した後に陽・陰極端子を取り出
し、樹脂外装した固体電解コンデンサにおいて、上記固
体電解質が耐熱性導電性ポリピロールであることを特徴
とする固体電解コンデンサ。である。(1) A heat-resistant conductive polymer comprising an organic compound represented by the chemical structural formula 1 in FIG. 1 as a component. (2) In chemical structural formula 1, organic compound M is an aromatic compound, and strong anionic dissociating group Y is a sulfonic acid group, and is represented by chemical structural formula 2 in FIG. Item 8. The heat-resistant conductive polymer according to item 1. (3) A heat-resistant conductive polymer, wherein the conductive polymer is polypyrrole polythiophene or polyaniline. (4) The method for producing a heat-resistant conductive polymer, wherein the heat-resistant conductive polymer is chemically oxidized and polymerized in a solution containing an organic compound represented by Chemical Formula 1. (5) The method for producing a heat-resistant conductive polymer, wherein the heat-resistant conductive polymer is chemically oxidized and polymerized in a solution containing an organic compound represented by Chemical Formula 2. (6) The method for producing a heat-resistant conductive polymer, wherein the heat-resistant conductive polymer is electrolytically oxidized and polymerized in a solution containing an organic compound represented by Chemical Formula 1. (7) The method for producing a heat-resistant conductive polymer, wherein the heat-resistant conductive polymer is electrolytically oxidatively polymerized in a solution containing an organic compound represented by the chemical structural formula 2. (8) A method for producing a heat-resistant conductive polymer, wherein the conductive polymer is polypyrrole. (9) A dielectric oxide film, a solid electrolyte, and a conductive layer are sequentially formed on a film-forming metal, and then the positive and negative terminals are taken out. In a solid electrolytic capacitor with a resin exterior, the solid electrolyte is represented by the chemical structural formula 1. A solid electrolytic capacitor characterized by being a heat-resistant conductive polymer to be used. (10) A dielectric oxide film, a solid electrolyte, and a conductive layer are sequentially formed on a film-forming metal, and then the positive / negative terminals are taken out. A solid electrolytic capacitor characterized by being a conductive polymer. (11) A dielectric oxide film, a solid electrolyte, and a conductive layer are sequentially formed on a film-forming metal, and then the positive and negative electrodes are taken out. In a solid electrolytic capacitor provided with a resin, the solid electrolyte is made of heat-resistant conductive polypyrrole. A solid electrolytic capacitor characterized by the following. It is.
【００１２】導電性高分子のドーパントとしてＯＨ基ま
たはＣＯＯＨ基の少なくとも一方を含む化合物を用いる
ことにより、３成分系での比較的困難な重合から２成分
系の比較的容易な重合が可能になり、さらに従来、高温
／空気雰囲気下で用いることの出来なかった化学的に不
安定な導電性高分子が、本来の性能を長期にわたり安定
に保持することが可能となった。By using a compound containing at least one of an OH group and a COOH group as a dopant for the conductive polymer, it is possible to carry out relatively difficult polymerization of a three-component system to relatively easy polymerization of a two-component system. Furthermore, a chemically unstable conductive polymer which could not be used in a high-temperature / air atmosphere can maintain its original performance stably for a long period of time.
【００１３】本発明により、信頼性の高い導電性高分子
を用いた光、電子、電磁デバイスが可能となる。According to the present invention, an optical, electronic, or electromagnetic device using a highly reliable conductive polymer can be obtained.
【００１４】[0014]
〔実施例１〕重合溶液として０．１Ｍ ピロール／０．
１Ｍ ｐ−フェノールスルホン酸ナトリウム／Britton-
Robinson緩衝溶液（ｐＨ＝１．８）を使用し、作用極お
よび対極にステンレス電極板（６ｃｍ×６ｃｍ）を用
い、定電流（２．５ｍＡ）で２０分間電解を行った。参
照極は飽和カロメル電極とした。電解後、電極上に生成
したポリピロール膜（０．０２ｍｍ厚）を水およびアセ
トンにより洗浄、電極上から剥離して真空中にて１２時
間乾燥を行った後、１０ｍｍφの円形に切り取った。こ
れを空気中で加熱（１５０℃、１００時間）し、標準４
端子法により測定した抵抗値より加熱中の電導度を算出
した。その結果、加熱中の電導度の変化は小さく、熱劣
化による電導度の低下は測定中に示した最も高い導電度
の８０％程度で、高い熱安定度が認められた。[Example 1] 0.1 M pyrrole / 0.
1M sodium p-phenolsulfonate / Britton-
Using a Robinson buffer solution (pH = 1.8), a stainless steel electrode plate (6 cm × 6 cm) was used for the working electrode and the counter electrode, and electrolysis was performed at a constant current (2.5 mA) for 20 minutes. The reference electrode was a saturated calomel electrode. After the electrolysis, the polypyrrole film (0.02 mm thick) formed on the electrode was washed with water and acetone, peeled off from the electrode, dried in a vacuum for 12 hours, and then cut into a 10 mmφ circle. This is heated in air (150 ° C, 100 hours), and standard 4
The electrical conductivity during heating was calculated from the resistance value measured by the terminal method. As a result, the change in conductivity during heating was small, and the decrease in conductivity due to thermal deterioration was about 80% of the highest conductivity shown during measurement, and high thermal stability was recognized.
【００１５】〔比較例１〕重合溶液として０．１Ｍ ピ
ロール／０．１Ｍ ｐ−トルエンスルホン酸ナトリウム
／Britton-Robinson緩衝溶液（ｐＨ＝１．８）を使用し
た以外は実施例１と同様の条件で生成したポリピロール
を空気中で加熱（１５０℃）し電導度を測定した。その
結果、ポリピロールの電導度は加熱後２０時間で測定中
に示した最も高い値の５％にまで低下し、加熱によるポ
リピロールの電導度の劣化が確認された。Comparative Example 1 The same conditions as in Example 1 were used except that a 0.1 M pyrrole / 0.1 M sodium p-toluenesulfonate / Britton-Robinson buffer solution (pH = 1.8) was used as a polymerization solution. Was heated (150 ° C.) in air to measure the electric conductivity. As a result, the electric conductivity of the polypyrrole decreased to 5% of the highest value shown during the measurement 20 hours after the heating, and deterioration of the electric conductivity of the polypyrrole due to the heating was confirmed.
【００１６】〔実施例２〕重合溶液として０．１Ｍ ピ
ロール／０．１Ｍ スルホサリチル酸／水溶液を使用し
た以外は実施例１と同様の条件で生成したポリピロール
を空気中で１５０℃、１００時間加熱し、標準４端子法
により測定した抵抗値より加熱中の電導度を算出した。
その結果、加熱中電導度に変化は見られず、熱劣化によ
る電導度の低下は測定中に示した最も高い値の９０％程
度で、高い熱安定度が認められた。Example 2 Polypyrrole produced under the same conditions as in Example 1 except that 0.1 M pyrrole / 0.1 M sulfosalicylic acid / water solution was used as a polymerization solution was heated in air at 150 ° C. for 100 hours. The electric conductivity during heating was calculated from the resistance value measured by the standard 4-terminal method.
As a result, no change was observed in the conductivity during heating, and the decrease in conductivity due to thermal degradation was about 90% of the highest value shown during the measurement, indicating high thermal stability.
【００１７】〔比較例２〕重合溶液として０．１Ｍ ピ
ロール／０．１Ｍ ２−ナフタレンスルホン酸／ナトリ
ウム／水溶液を使用した以外は、実施例１と同様の条件
で生成したポリピロールを空気中で加熱（１５０℃）し
電導度を測定した。その結果、ポリピロールの電導度は
加熱後３０時間で測定中に示した最も高い値の１５％に
まで低下し、加熱によるポリピロールの電導度の劣化が
確認された。Comparative Example 2 Polypyrrole produced under the same conditions as in Example 1 except that a 0.1 M pyrrole / 0.1 M 2-naphthalenesulfonic acid / sodium / water solution was used as a polymerization solution was heated in air. (150 ° C.) and the conductivity was measured. As a result, the conductivity of polypyrrole was reduced to 15% of the highest value shown during the measurement 30 hours after heating, and deterioration of the conductivity of polypyrrole due to heating was confirmed.
【００１８】〔実施例３〕重合溶液として０．１Ｍ チ
オフェン／０．１Ｍ スルホ安息香酸／アセトニトリル
を使用し、作用極および対極にステンレス電極板（６ｃ
ｍ×６ｃｍ）を用い、定電流（２．５ｍＡ）で２０分間
電解を行った。参照極は飽和カロメル電極とした。電解
後、電極上に生成したポリチオフェン膜（０．０２ｍｍ
厚）を水およびアセトンにより洗浄、電極上から剥離
し、真空中にて１２時間乾燥を行った後、１０ｍｍφの
円形に切り取った。これを空気中で１５０℃、１００時
間加熱し、標準４端子法により測定した抵抗値より加熱
中の電導度を算出した。その結果、加熱中電導度に変化
は見られず、熱劣化による電導度の低下は測定中に示し
た最も高い値の８５％程度で、高い熱安定度が認められ
た。Example 3 A 0.1 M thiophene / 0.1 M sulfobenzoic acid / acetonitrile solution was used as a polymerization solution, and a stainless steel electrode plate (6c
(m × 6 cm), and electrolysis was performed at a constant current (2.5 mA) for 20 minutes. The reference electrode was a saturated calomel electrode. After electrolysis, polythiophene film (0.02mm) formed on the electrode
Was washed with water and acetone, peeled off from the electrode, dried in a vacuum for 12 hours, and then cut into a 10 mmφ circle. This was heated in air at 150 ° C. for 100 hours, and the conductivity during heating was calculated from the resistance value measured by the standard four-terminal method. As a result, there was no change in the conductivity during heating, and the decrease in conductivity due to thermal degradation was about 85% of the highest value shown during the measurement, indicating high thermal stability.
【００１９】〔実施例４〕重合溶液として０．２ｍｏｌ
アニリン／０．１ｍｏｌ スルホサリチル酸／塩酸１
５０ｍｌを使用し、酸化剤として過硫酸アンモニウムを
使用して、２５時間かけて化学酸化重合を行った。沈殿
したポリマーをろ別し、蒸留水で洗浄液のｐＨが６以上
になるまで洗浄し、続いてメタノールで溶液が透明にな
るまで繰り返し洗浄した後、真空中にて１２時間乾燥を
行い、乾燥後約７ｍｇを秤量、０．１ｍｍ厚、１０ｍｍ
φのペレット状に加圧成形した。これを空気中で１５０
℃、１００時間加熱し、標準４端子法により測定した抵
抗値より加熱中の電導度を算出した。その結果、加熱中
電導度に変化は見られず、熱劣化による電導度の低下は
測定中に示した最も高い値の９０％で、高い熱安定度が
認められた。Example 4 0.2 mol as a polymerization solution
Aniline / 0.1 mol sulfosalicylic acid / hydrochloric acid 1
Using 50 ml, ammonium persulfate was used as an oxidizing agent, and chemical oxidative polymerization was carried out for 25 hours. The precipitated polymer is separated by filtration, washed with distilled water until the pH of the washing solution becomes 6 or more, then repeatedly washed with methanol until the solution becomes transparent, and then dried under vacuum for 12 hours. Weigh about 7mg, 0.1mm thickness, 10mm
It was pressed into a pellet of φ. 150 in air
After heating at 0 ° C for 100 hours, the electric conductivity during heating was calculated from the resistance value measured by the standard 4-terminal method. As a result, no change was observed in the electrical conductivity during heating, and the decrease in electrical conductivity due to thermal degradation was 90% of the highest value shown during the measurement, indicating high thermal stability.
【００２０】〔実施例５〕あらかじめ陽極リード線３を
引き出したタンタル焼結体４（２ｍｍ×３ｍｍ×１ｍ
ｍ）をリン酸水溶液中において１１．５Ｖで陽極酸化し
て誘電体酸化皮膜５を形成した後、０．１Ｍ ピロー
ル、０．２Ｍ フェリシアン化カリウム、０．１Ｍ ｍ
−スルホ安息香酸を含むエーテル溶液を浸透、乾燥、純
水洗浄を５回繰り返し、最後に再度乾燥し誘電体酸化皮
膜５上にポリピロール膜６を形成した。その上に順次グ
ラファイトペースト層７、銀ペースト層８を形成した。
陽極リード線３に陽極端子９を溶接、陰極側には導電性
接着剤１０を介して陰極端子１１を接続した後、モール
ド樹脂１２を用いて樹脂外装を行い固体電解コンデンサ
を得た。Example 5 A tantalum sintered body 4 (2 mm × 3 mm × 1 m
m) was anodized in a phosphoric acid aqueous solution at 11.5 V to form a dielectric oxide film 5, and then 0.1 M pyrrole, 0.2 M potassium ferricyanide, 0.1 M m
-Penetration of ether solution containing sulfobenzoic acid, drying and washing with pure water were repeated 5 times, and finally drying was performed again to form polypyrrole film 6 on dielectric oxide film 5. A graphite paste layer 7 and a silver paste layer 8 were sequentially formed thereon.
The anode terminal 9 was welded to the anode lead wire 3, the cathode terminal 11 was connected to the cathode side via a conductive adhesive 10, and then resin-encased using a mold resin 12 to obtain a solid electrolytic capacitor.
【００２１】得られたコンデンサを１５０℃空気中で１
０００時間の高温無負荷試験を実施し、その前後での１
ｋＨｚでの静電容量・１００ｋＨｚでの等価直列抵抗
（ＥＳＲ）を測定した。The obtained capacitor was placed in air at 150 ° C. for 1 hour.
000 hours high-temperature no-load test, and before and after
The capacitance at kHz and the equivalent series resistance (ESR) at 100 kHz were measured.
【００２２】その結果、試験前後での静電容量、ＥＳＲ
の比はそれぞれ０．８８，１．１５で有り高温雰囲気下
で安定したコンデンサが得られた。As a result, the capacitance before and after the test, the ESR
Are 0.88 and 1.15, respectively, and a stable capacitor was obtained in a high temperature atmosphere.
【００２３】〔比較例２〕実施例５の０．１Ｍ ｍ−ス
ルホ安息香酸を０．１Ｍ ｐ−トルエンスルホン酸に変
更した以外は実施例５と同様にコンデンサを作成した。Comparative Example 2 A capacitor was produced in the same manner as in Example 5 except that the 0.1 M m-sulfobenzoic acid in Example 5 was changed to 0.1 M p-toluenesulfonic acid.
【００２４】得られたコンデンサを実施例５と同様に、
１５０℃空気中で１０００時間の高温無負荷試験を実施
し、その前後での１ｋＨｚでの静電容量・１００ｋＨｚ
での等価直列抵抗（ＥＳＲ）を測定した。The obtained capacitor was used in the same manner as in Example 5,
A 1000-hour high-temperature no-load test was performed in air at 150 ° C., and before and after that, the capacitance at 1 kHz and 100 kHz
Was measured for equivalent series resistance (ESR).
【００２５】その結果、試験前後での静電容量、ＥＳＲ
の比はそれぞれ０．２１，５２．９となり高温雰囲気下
でコンデンサ特性が大きく劣化した。As a result, the capacitance before and after the test, the ESR
Were 0.21 and 52.9, respectively, and the capacitor characteristics were significantly deteriorated in a high-temperature atmosphere.
【００２６】以上の結果を表１、表２にまとめた。The above results are summarized in Tables 1 and 2.
【００２７】[0027]
【表１】 [Table 1]
【００２８】[0028]
【表２】 [Table 2]
【００２９】[0029]
【発明の効果】このように本発明を用いれば、高温空気
中で信頼性の高い導電性高分子膜が得られ、さらに前記
導電性高分子を固体電解コンデンサに用いることで高温
空気中において安定固体電解コンデンサが得られる。As described above, according to the present invention, a highly reliable conductive polymer film can be obtained in high-temperature air, and the conductive polymer can be stabilized in high-temperature air by using the conductive polymer in a solid electrolytic capacitor. A solid electrolytic capacitor is obtained.
【図１】化学構造式１FIG. 1 Chemical structural formula 1
【図２】化学構造式２FIG. 2 Chemical structural formula 2
【図３】固体電解コンデンサの断面図FIG. 3 is a sectional view of a solid electrolytic capacitor.
１ 化学構造式１ ２ 化学構造式２ ３ 陽極リード線 ４ タンタル焼結体 ５ 誘電体酸化皮膜 ６ ポリピロール膜 ７ グラファイトペースト層 ８ 銀ペースト層 ９ 陽極端子 １０ 導電性接着剤 １１ 陰極端子 １２ モールド樹脂 Reference Signs List 1 Chemical structural formula 1 2 Chemical structural formula 2 3 Anode lead wire 4 Tantalum sintered body 5 Dielectric oxide film 6 Polypyrrole film 7 Graphite paste layer 8 Silver paste layer 9 Anode terminal 10 Conductive adhesive 11 Cathode terminal 12 Mold resin
───────────────────────────────────────────────────── フロントページの続き (72)発明者 原 富太郎 東京都中野区中野４−20−７ (72)発明者 武岡 真司 東京都世田谷区玉川３−40−16 フォレス ト玉川404 (72)発明者 山本 公寿 東京都大田区田園調布南９−２−304 (72)発明者 土田 英俊 東京都練馬区関町南２−10−10 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tomitaro Hara 4-20-7 Nakano, Nakano-ku, Tokyo (72) Inventor Shinji Takeoka 3-40-16 Tamagawa, Setagaya-ku, Tokyo Forest Tamagawa 404 (72) Inventor Koju Yamamoto 9-2-304 Denenchofu Minami, Ota-ku, Tokyo (72) Inventor Hidetoshi Tsuchida 2-10-10 Seki-cho Minami, Nerima-ku, Tokyo
Claims (11)
物を成分として含有させたことを特徴とする耐熱性導電
性高分子。 （Ｘ）1 −（Ｍ）m −（Ｙ- ）n ・・・１ 但し、Ｘ：−ＣＯＯＨ基または−ＯＨ基の少なくとも一
方、Ｍ：有機化合物 Ｙ：強アニオン性解離基、ｌ，ｍ，ｎは１以上の整数1. A heat-resistant conductive polymer comprising an organic compound represented by the following chemical structural formula 1 as a component. (X) 1- (M) m- (Y − ) n ... 1 wherein X: at least one of —COOH group or —OH group, M: organic compound Y: strong anionic dissociating group, 1, m, n is an integer of 1 or more
が芳香族化合物、強アニオン性解離基Ｙがスルホン酸基
であることを特徴とした、化学構造式２で表される請求
項１記載の耐熱性導電性高分子。 （Ｘ）1 −（Ａｒ）m −（ＳＯ3 - ）n ・・・２ 但し、Ｘ：−ＣＯＯＨ基または−ＯＨ基の少なくとも一
方、Ａｒ：芳香族化合物 ｌ，ｍ，ｎは１以上の整数2. The organic compound M of the above chemical structural formula 1.
Is a aromatic compound, and the strong anionic dissociating group Y is a sulfonic acid group. (X) 1- (Ar) m- (SO 3 − ) n ... 2 where X: at least one of —COOH group or —OH group, Ar: aromatic compound 1, m, and n are integers of 1 or more
チオフェン、ポリアニリンであることを特徴とする請求
項１記載の耐熱性導電性高分子。3. The heat-resistant conductive polymer according to claim 1, wherein the conductive polymer is polypyrrole, polythiophene, or polyaniline.
で表される有機化合物を含む溶液中で化学酸化重合した
ことを特徴とする請求項１記載の耐熱性導電性高分子の
製造方法。4. The heat-resistant conductive polymer is represented by the following chemical structural formula 1.
The method for producing a heat-resistant conductive polymer according to claim 1, wherein the polymer is chemically oxidized and polymerized in a solution containing an organic compound represented by the formula:
で表される有機化合物を含む溶液中で化学酸化重合した
ことを特徴とする請求項２記載の耐熱性導電性高分子の
製造方法。5. The heat-resistant conductive polymer according to chemical formula 2
3. The method for producing a heat-resistant conductive polymer according to claim 2, wherein the polymer is chemically oxidized and polymerized in a solution containing an organic compound represented by the formula:
で表される有機化合物を含む溶液中で電解酸化重合した
ことを特徴とする請求項１記載の耐熱性導電性高分子の
製造方法。6. The heat-resistant conductive polymer according to chemical formula 1
The method for producing a heat-resistant conductive polymer according to claim 1, wherein the electrolytic polymerization is carried out in a solution containing an organic compound represented by the formula:
で表される有機化合物を含む溶液中で電解酸化重合した
ことを特徴とする請求項２記載の耐熱性導電性高分子の
製造方法。7. The heat-resistant conductive polymer is represented by the following chemical structural formula 2.
3. The method for producing a heat-resistant conductive polymer according to claim 2, wherein the electrolytic oxidation polymerization is carried out in a solution containing an organic compound represented by the formula:
を特徴とする請求項４記載の耐熱性導電性高分子の製造
方法。8. The method for producing a heat-resistant conductive polymer according to claim 4, wherein the conductive polymer is polypyrrole.
固体電解質、導電層を順次形成した後に陽・陰極端子を
取り出し、樹脂外装した固体電解コンデンサにおいて、 前記固体電解質が請求項１記載の耐熱性導電性高分子で
あることを特徴とする固体電解コンデンサ。9. A dielectric oxide film on a film-forming metal,
A solid electrolytic capacitor comprising a solid electrolyte and a conductive layer, in which the positive / negative terminals are taken out and then covered with a resin, wherein the solid electrolyte is the heat-resistant conductive polymer according to claim 1. .
膜、固体電解質、導電層を順次形成した後に陽・陰極端
子を取り出し、樹脂外装した固体電解コンデンサにおい
て、 前記固体電解質が請求項２記載の耐熱性導電性高分子で
あることを特徴とする固体電解コンデンサ。10. A solid electrolytic capacitor in which a dielectric oxide film, a solid electrolyte, and a conductive layer are sequentially formed on a film-forming metal, and then a positive electrode terminal and a negative electrode terminal are taken out, and the resin-coated solid electrolytic capacitor is used. A solid electrolytic capacitor characterized in that it is a heat-resistant conductive polymer.
膜、固体電解質、導電層を順次形成した後に陽・陰極端
子を取り出し、樹脂外装した固体電解コンデンサにおい
て、 前記固体電解質が請求項３記載の耐熱性導電性高分子で
あることを特徴とする固体電解コンデンサ。11. A solid electrolytic capacitor in which a dielectric oxide film, a solid electrolyte, and a conductive layer are sequentially formed on a film-forming metal, and then a positive / negative terminal is taken out and covered with a resin. A solid electrolytic capacitor characterized in that it is a heat-resistant conductive polymer.
Priority Applications (1)
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|---|---|---|---|
| JP17472995A JP2701798B2 (en) | 1995-07-11 | 1995-07-11 | Heat-resistant conductive polymer, method for producing the same, and solid electrolytic capacitor using the conductive polymer |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17472995A JP2701798B2 (en) | 1995-07-11 | 1995-07-11 | Heat-resistant conductive polymer, method for producing the same, and solid electrolytic capacitor using the conductive polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0925417A true JPH0925417A (en) | 1997-01-28 |
| JP2701798B2 JP2701798B2 (en) | 1998-01-21 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5986046A (en) * | 1997-03-07 | 1999-11-16 | Nec Corporation | Oxzidant solution for synthesizing heat-resistant electroconductive polymer and method for preparing electroconductive polymer |
| WO2001036382A1 (en) * | 1999-11-16 | 2001-05-25 | Mitsui Chemicals, Inc. | Process for producing benzenesulfonic acid derivative compound, dopant, conductive polymeric material, and solid electrolytic capacitor |
| EP1138669A4 (en) * | 1998-11-13 | 2002-01-23 | Mitsui Chemicals Inc | Benzenesulfonic acid derivative compounds, process for producing the same, and use thereof |
| WO2004075220A1 (en) * | 2003-02-19 | 2004-09-02 | Matsushita Electric Industrial Co., Ltd. | Solid electrolytic capacitor and method for manufacturing same |
-
1995
- 1995-07-11 JP JP17472995A patent/JP2701798B2/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5986046A (en) * | 1997-03-07 | 1999-11-16 | Nec Corporation | Oxzidant solution for synthesizing heat-resistant electroconductive polymer and method for preparing electroconductive polymer |
| EP1138669A4 (en) * | 1998-11-13 | 2002-01-23 | Mitsui Chemicals Inc | Benzenesulfonic acid derivative compounds, process for producing the same, and use thereof |
| WO2001036382A1 (en) * | 1999-11-16 | 2001-05-25 | Mitsui Chemicals, Inc. | Process for producing benzenesulfonic acid derivative compound, dopant, conductive polymeric material, and solid electrolytic capacitor |
| WO2004075220A1 (en) * | 2003-02-19 | 2004-09-02 | Matsushita Electric Industrial Co., Ltd. | Solid electrolytic capacitor and method for manufacturing same |
| US7289313B2 (en) | 2003-02-19 | 2007-10-30 | Matsushita Electric Industrial Co., Ltd. | Solid electrolytic capacitor and method for manufacturing same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2701798B2 (en) | 1998-01-21 |
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