JP4978827B2 - Solid electrolytic capacitor and manufacturing method thereof - Google Patents

Description

  The present invention relates to a solid electrolytic capacitor including a conductive polymer layer on a dielectric film and a method for manufacturing the same.

  For example, as shown in FIG. 1, a basic element of a solid electrolytic capacitor is formed by forming a dielectric oxide film layer (2) on an anode substrate (1) generally made of a metal foil having a large specific surface area that has been etched. A solid semiconductor layer (hereinafter referred to as a solid electrolyte) (4) is formed as an electrode facing the outside, and a conductor layer (5) such as a conductive paste is preferably formed. Usually, in order to ensure the insulation between the solid electrolyte (4) (cathode portion) and the anode substrate (1), a masking layer (3) made of an insulating material is further provided. Then, such elements are singly or laminated to join the lead wires (6, 7), and the whole is completely sealed with an epoxy resin (8) or the like to be widely used as a capacitor (9) component in a wide range of electrical products. in use.

  In recent years, with the digitization of electrical equipment and the speeding up of personal computers, small and large-capacitance capacitors and low-impedance capacitors in the high-frequency region are required. Recently, it has been proposed to use a conductive polymer having electronic conductivity as a solid electrolyte.

  In general, an electrolytic oxidation polymerization method and a chemical oxidation polymerization method are known as methods for forming a conductive polymer on a dielectric oxide film. The chemical oxidative polymerization method is difficult to control the reaction or the form of the polymer film, but various methods have been proposed because it is easy to form a solid electrolyte and enables mass production in a short time. For example, there is disclosed a method of forming a solid electrolyte having a layered structure by alternately repeating a step of immersing an anode substrate in a solution containing a monomer and a step of immersing in a solution containing an oxidizing agent (Patent Document 1: Patent) No. 3187380). According to this method, it is possible to produce a solid electrolytic capacitor having a high capacity, low impedance, and excellent heat resistance by forming a solid electrolyte layer having a layered structure with a film thickness of 0.01 to 5 μm. There is a problem that the space between layers of the layered structure portion forming the layer is large, and as a multilayer capacitor element in which a plurality of capacitor elements are stacked, it is required to further reduce the thickness of the entire solid electrolyte layer.

  As a method for forming a solid electrolyte in the pores and the outer surface of the capacitor element without forming a solid electrolyte layer having a layered structure, the anode substrate is immersed in a solution containing a monomer compound and then polymerized in an oxidizer solution. Although a method of repeating a drying cycle after washing an oxidizing agent is disclosed (Patent Document 2: Japanese Patent Laid-Open No. 9-306788), the solid electrolyte layer formed by this method has a space between the layers. Therefore, the resistance to external stress was insufficient.

  As a method for forming a solid electrolyte, there is disclosed a method in which two kinds of conductive polymers are arranged between an anode and a cathode, in addition to a method in which a single conductive polymer is coated on pores and outer peripheral portions. That is, after immersing in a water-soluble sulfonated polyaniline solution, the first conductive polymer layer is formed by repeating the drying process, and then the second conductive polymer layer is formed by electrolytic polymerization. Has been proposed (Patent Document 3: Japanese Patent Laid-Open No. 10-321474). Furthermore, in order to prevent the conductive polymer from dissolving when forming the second conductive polymer, a method is proposed in which the first conductive polymer layer is insolubilized by heat treatment at a higher temperature. (Patent Document 4: JP 2002-313684 A).

On the other hand, in the anode substrate, in order to form a solid electrolytic capacitor, insulation separation between the anode portion and the cathode portion is essential. That is, in Patent Document 5 (Japanese Patent Publication No. 2000-67267), a low molecular weight polyimide having good insulation and heat resistance after solidification or a precursor thereof is applied to the surface of the anode substrate on which the porous layer is formed. By doing so, it is disclosed that insulation can be separated.
However, the insulation separation of the anode part and the cathode part by the application of the insulating material is still insufficient because there is variation in the penetration of the insulating material into the porous layer formed on the anode substrate. The inventors have found out. That is, in the process of forming the cathode part by alternately repeating the step of immersing the anode substrate in the solution containing the monomer and the step of immersing in the solution containing the oxidant, the monomer solution and the oxidant solution are fed from the cathode side to the anode substrate. Insulation of the insulating material into the porous layer formed in the electrode penetrates through the defective part, and the leakage current increases or reaches the anode due to the formation of the solid electrolyte reaching the vicinity of the anode. Caused a short circuit. The present inventors have found that the insulation can be improved by widening the coating width of the insulating material used for insulation separation, but there is a dielectric area where a solid electrolytic capacitor of a predetermined size can be effectively used. Since it relatively decreased, the capacity expression rate decreased, which was not preferable.

Japanese Patent No. 3187380 Japanese Patent Laid-Open No. 9-306788 JP 10-32174 A JP 2002-313684 A Special Table 2000-67267

  It is known that sulfonated polyaniline, which is a kind of self-doped conductive polymer, has lower conductivity than polypyrrole or polyethylenedioxythiophene using an exogenous dopant. For this reason, when the dielectric layer is coated with sulfonated polyaniline, chemical oxidation polymerization or electrochemical polymerization is carried out independently, and compared with the case where a single conductive polymer film such as polypyrrole derivative or polyethylenedioxythiophene is used as the coating film. As a result, the equivalent series resistance increases. Furthermore, since the high temperature treatment for insolubilizing the sulfonated polyaniline is accompanied by detachment of the sulfonic acid group, the equivalent series resistance increases with the dedoping of the conductive polymer. In addition, neither Patent Document 3 nor Patent Document 4 using sulfonated polyaniline describes the equivalent series resistance.

  On the other hand, in order to obtain a solid electrolytic capacitor having a predetermined capacity, usually a plurality of capacitor elements are laminated, an anode lead wire is connected to the anode terminal, and a cathode lead wire is connected to the conductor layer containing the conductive polymer. Further, the whole is sealed with an insulating resin such as an epoxy resin, but in a solid electrolytic capacitor, the polymerization condition of the conductive polymer is controlled at the cathode portion of the capacitor element to increase the thickness of the conductive polymer. There is a need. Unless the polymerization conditions of the conductive polymer on the cathode part of the capacitor element are carefully controlled, the thickness of the conductive polymer becomes non-uniform so that a thin part of the conductive polymer is formed. This is because direct contact with the layer is facilitated, leading to an increase in leakage current. Further, since the number of capacitor elements that can be stacked on a solid electrolytic capacitor chip of a predetermined size is limited by the thickness of the element, the capacity of the solid electrolytic capacitor chip cannot be increased. Furthermore, when the adhesion thickness of the conductive polymer is not uniform, the contact area between the laminated capacitor element and the capacitor element is reduced, and there is a problem that the equivalent series resistance (ESR) is increased.

  Therefore, the problem of the present invention is to solve the above-mentioned problems without increasing the equivalent series resistance, to reduce the variation in element shape without increasing short-circuit failure, and to stably produce a thin capacitor element, It is formed to increase the number of capacitor elements in the solid electrolytic capacitor chip to increase the capacity, further reduce the variation in equivalent series resistance, and insulate and separate the anode and cathode without decreasing the capacity. Another object of the present invention is to provide a multilayer solid electrolytic capacitor element and a method for manufacturing the same, which eliminates a defective portion of the insulating material.

As a result of intensive studies in view of the above problems, the present inventors have
(1) Self-doped conductive polymer, which is a precursor of self-doped conductive polymer having cross-links between polymer chains, is a soluble conductive polymer and a low-viscosity solution. The capacity appearance rate is improved because it can be easily penetrated into the fine holes formed by the surface enlargement treatment and uniformly coated with the dielectric film,
(2) Covering the surface of the valve metal with the self-doped conductive polymer having a bridge between the polymer chains is particularly effective because the equivalent series resistance does not increase,
(3) Furthermore, the coating film made of this polymer has high hardness, water resistance, and chemical resistance, so that it can relieve external stress on the dielectric film,
(4) In particular, after the formation of the solid electrolyte, it is possible to prevent the paste formed for current collection from coming into direct contact with the dielectric oxide film layer at the thin portion of the conductive polymer, thereby increasing the leakage current. In addition to being able to prevent, it is possible to provide a useful solid electrolytic capacitor that can withstand the reflow temperature at a high temperature corresponding to lead-free because of its high heat resistance,
(5) Also, by having the coating structure of the present invention, the liquid absorbency of the monomer solution or the oxidant solution in the process of forming the second solid electrolyte layer and the valve metal surface having no micropores and / Or can increase liquid retention and promote uniform polymer film formation,
(6) and at least a part of the dielectric film on the cathode side adjacent to the insulating material formed to insulate and separate the anode and the cathode in the valve metal having fine holes, between the polymer chains By forming a self-doped conductive polymer having a crosslink, it is possible to eliminate the defective portion of the insulating material formed to insulate and separate the anode and the cathode without lowering the capacity and reduce the leakage current. I found.

  The present inventors have found that the solid electrolytic capacitor thus obtained has improved adhesion of the solid electrolyte formed on the dielectric film, high capacity, low dielectric loss (tan δ), leakage current, and defective rate. It was confirmed. Furthermore, the present invention was completed by confirming that the capacitor can be reduced in size and increased in capacity by stacking a plurality of the above-mentioned excellent solid electrolytic capacitor elements.

（式中、Ｒ¹〜Ｒ³は、それぞれ独立して、水素原子、炭素数１〜２０の直鎖状もしくは分岐状のアルキル基、炭素数１〜２０の直鎖状もしくは分岐状のアルコキシ基、炭素数２〜２０の直鎖状もしくは分岐状のアルケニル基、炭素数２〜２０の直鎖状もしくは分岐状のアルケニルオキシ基、水酸基、ハロゲン原子、ニトロ基、シアノ基、トリハロメチル基、フェニル基、置換フェニル基、または−Ｂ¹−ＳＯ₃ ^-Ｍ⁺基を表わす。Ｂ¹およびＢ²は、それぞれ独立して−（ＣＨ₂）_p−（Ｏ）_q−（ＣＨ₂）_r−を表わし、ｐおよびｒは、それぞれ独立して、０または１〜３の整数を表わし、ｑは０または１を表わす。Ｍ⁺は、水素イオン、アルカリ金属イオン、または第４級アンモニウムイオンを表わす。Ａｒは、高分子鎖を有していてもよい、一価の芳香族基、置換された一価の芳香族基、一価の複素環基もしくは置換された一価の複素環基を表わす。）で示される化学構造である自己ドープ型導電性高分子を含むことを特徴とする前記５に記載の固体電解コンデンサ。
７．スルホン結合の架橋構造が、一般式（２）

（式中、Ｒ¹〜Ｒ⁶は、それぞれ独立して、水素原子、炭素数１〜２０の直鎖状もしくは分岐状のアルキル基、炭素数１〜２０の直鎖状もしくは分岐状のアルコキシ基、炭素数２〜２０の直鎖状もしくは分岐状のアルケニル基、炭素数２〜２０の直鎖状もしくは分岐状のアルケニルオキシ基、水酸基、ハロゲン原子、ニトロ基、シアノ基、トリハロメチル基、フェニル基、置換フェニル基、または−Ｂ¹−ＳＯ₃ ^-Ｍ⁺基を表わす。Ｂ¹は、−（ＣＨ₂）_p−（Ｏ）_q−（ＣＨ₂）_r−を表わし、ｐおよびｒは、それぞれ独立して、０または１〜３の整数を表わし、ｑは０または１を表わす。Ｍ⁺は、水素イオン、アルカリ金属イオン、または第４級アンモニウムイオンを表わす。）で示される化学構造である自己ドープ型導電性高分子を含むことを特徴とする前記６に記載の固体電解コンデンサ。
８．スルホン結合の架橋構造が、一般式（３）

（式中、Ｂ¹は、−（ＣＨ₂）_p−（Ｏ）_q−（ＣＨ₂）_r−を表わし、ｐおよびｒは、それぞれ独立して、０または１〜３の整数を表わし、ｑは０または１を表わす。Ｍ⁺は、水素イオン、アルカリ金属イオン、または第４級アンモニウムイオンを表わす。）で示される化学構造である自己ドープ型導電性高分子を含むことを特徴とする前記７に記載の固体電解コンデンサ。
９．自己ドープ型導電性高分子が、スルホン酸基を有する複素五員環骨格を含む自己ドープ型導電性高分子を含むことを特徴とする前記２〜４のいずれかに記載の固体電解コンデンサ。
１０．スルホン結合の架橋構造が、一般式（４）

（式中、Ｘは−Ｓ−、−Ｏ−、または−Ｎ（−Ｒ¹⁵）−を表わし、Ｒ¹⁵は、水素原子、炭素数１〜２０の直鎖状もしくは分岐状のアルキル基、炭素数２〜２０の直鎖状もしくは分岐状のアルケニル基を表わし、Ｂ¹およびＢ²は、それぞれ独立して−（ＣＨ₂）_p−（Ｏ）_q−（ＣＨ₂）_r−を表わし、ｐおよびｒは、それぞれ独立して、０または１〜３の整数を表わし、ｑは０または１を表わす。Ｍ⁺は、水素イオン、アルカリ金属イオン、または第４級アンモニウムイオンを表わす。Ａｒは、高分子鎖を有していてもよい、一価の芳香族基、置換された一価の芳香族基、一価の複素環基もしくは置換された一価の複素環基を表わす。）で示される化学構造を含む自己ドープ型導電性高分子を含むことを特徴とする前記９に記載の固体電解コンデンサ。
１１．スルホン結合の架橋構造が、一般式（５）

（式中、Ｘは−Ｓ−、−Ｏ−、または−Ｎ（−Ｒ¹⁵）−を表わし、Ｒ¹⁵は、水素原子、炭素数１〜２０の直鎖状もしくは分岐状のアルキル基、炭素数２〜２０の直鎖状もしくは分岐状のアルケニル基を表わし、Ｂ¹は、−（ＣＨ₂）_p−（Ｏ）_q−（ＣＨ₂）_r−を表わし、ｐおよびｒは、それぞれ独立して、０または１〜３の整数を表わし、ｑは０または１を表わす。Ｍ⁺は、水素イオン、アルカリ金属イオン、または第４級アンモニウムイオンを表わす。）で示される化学構造を含む自己ドープ型導電性高分子を含むことを特徴とする前記１０に記載の固体電解コンデンサ。
１２．スルホン結合の架橋構造が、一般式（６）

（式中、Ｂ¹は、−（ＣＨ₂）_p−（Ｏ）_q−（ＣＨ₂）_r−を表わし、ｐおよびｒは、それぞれ独立して、０または１〜３の整数を表わし、ｑは０または１を表わす。Ｍ⁺は、水素イオン、アルカリ金属イオン、または第４級アンモニウムイオンを表わす。）で示される化学構造である自己ドープ型導電性高分子を含むことを特徴とする前記１０または前記１１のいずれかに記載の固体電解コンデンサ。
１３．金属表面に形成された誘電体皮膜上に、高分子鎖間架橋を有する自己ドープ型導電性高分子を含む第一の固体電解質層を有し、その上に第二の固体電解質層を有する前記１〜１２のいずれかに記載の固体電解コンデンサ。
１４．第一の固体電解質層が水不溶性である前記１３に記載の固体電解コンデンサ。
１５．金属が微細孔を有する弁作用金属である前記１〜１４のいずれかに記載の固体電解コンデンサ。
１６.微細孔を有する弁作用金属における陽極と陰極とを絶縁分離する絶縁材料を有し、これに隣接する陰極側の誘電体皮膜の少なくとも一部に、高分子鎖間架橋を有する自己ドープ型導電性高分子を含む第一の固体電解質層を有し、その上に第二の固体電解質層を有する前記１５に記載の固体電解コンデンサ。
１７.高分子鎖間が架橋している自己ドープ型導電性高分子を含む固体電解質層の膜厚が１ｎｍ〜１０００ｎｍの範囲である前記１〜１６のいずれかに記載の固体電解コンデンサ。
１８.高分子鎖間が架橋している自己ドープ型導電性高分子を含む固体電解質層の導電率が０．００１〜１００Ｓ／ｃｍの範囲にある前記１〜１７のいずれかに記載の固体電解コンデンサ。
１９.高分子鎖間が架橋している自己ドープ型導電性高分子を含む固体電解質層の鉛筆硬度がＨＢ〜４Ｈの硬度を有する前記１〜１８のいずれかに記載の固体電解コンデンサ。
２０.一般式（７）

（式中、Ｒ¹〜Ｒ³は、それぞれ独立して、水素原子、炭素数１〜２０の直鎖状もしくは分岐状のアルキル基、炭素数１〜２０の直鎖状もしくは分岐状のアルコキシ基、炭素数２〜２０の直鎖状もしくは分岐状のアルケニル基、炭素数２〜２０の直鎖状もしくは分岐状のアルケニルオキシ基、水酸基、ハロゲン原子、ニトロ基、シアノ基、トリハロメチル基、フェニル基、置換フェニル基、または−Ｂ¹−ＳＯ₃ ^-Ｍ⁺基を表わすが、Ｒ¹〜Ｒ³のいずれか一つは水素原子である。Ｂ¹は、−（ＣＨ₂）_p−（Ｏ）_q−（ＣＨ₂）_r−を表わし、ｐおよびｒは、それぞれ独立して、０または１〜３の整数を表わし、ｑは０または１を表わす。Ｍ⁺は、水素イオン、アルカリ金属イオン、または第４級アンモニウムイオンを表わす。）で示される化学構造を含む自己ドープ型導電性高分子同士を誘電体皮膜に被覆した後、脱水縮合することによって請求項６に記載の一般式（１）で示される高分子鎖間が架橋した自己ドープ型導電性高分子で誘電体皮膜を被覆することを特徴とする前記１〜１９のいずれかに記載の固体電解コンデンサの製造方法。
２１.一般式（７）および／または一般式（８）

（式（７）中、Ｒ¹〜Ｒ³、Ｂ¹、およびＭ⁺は請求項２０に記載の一般式（７）中と同じ意味を表す。式（８）中、Ｒ⁷〜Ｒ¹⁰は、それぞれ独立して、水素原子、炭素数１〜２０の直鎖状もしくは分岐状のアルキル基、炭素数１〜２０の直鎖状もしくは分岐状のアルコキシ基、炭素数２〜２０の直鎖状もしくは分岐状のアルケニル基、炭素数２〜２０の直鎖状もしくは分岐状のアルケニルオキシ基、水酸基、ハロゲン原子、ニトロ基、シアノ基、トリハロメチル基、フェニル基、置換フェニル基、または−Ｂ¹−ＳＯ₃ ^-Ｍ⁺基を表わすが、式（７）および式（８）で示される化学構造を含む自己ドープ型導電性高分子を脱水縮合するときはＲ⁷〜Ｒ¹⁰のいずれか一つは水素原子であり、このとき式（７）中のＲ¹〜Ｒ³のいずれも水素原子でなくてもよい。式（８）で示される化学構造を含む自己ドープ型導電性高分子を脱水縮合するときはＲ⁷〜Ｒ¹⁰のうち少なくとも一つは−Ｂ¹−ＳＯ₃ ^-Ｍ⁺基を表わし、かつ少なくとも一つは水素原子である。Ｂ¹は、−（ＣＨ₂）_p−（Ｏ）_q−（ＣＨ₂）_r−を表わし、ｐおよびｒは、それぞれ独立して、０または１〜３の整数を表わし、ｑは０または１を表わす。Ｍ⁺は、水素イオン、アルカリ金属イオン、または第４級アンモニウムイオンを表わす。）で示される化学構造を含む自己ドープ型導電性高分子同士を誘電体皮膜に被覆した後、脱水縮合することによって請求項６に記載の一般式（１）で示される高分子鎖間が架橋した自己ドープ型導電性高分子で誘電体皮膜を被覆することを特徴とする前記１〜１９のいずれかに記載の固体電解コンデンサの製造方法。
２２.一般式（９）

（式中、Ｂ¹は、−（ＣＨ₂）_p−（Ｏ）_q−（ＣＨ₂）_r−を表わし、ｐおよびｒは、それぞれ独立して、０または１〜３の整数を表わし、ｑは０または１を表わす。Ｍ⁺は、水素イオン、アルカリ金属イオン、または第４級アンモニウムイオンを表わす。）で示されるモノマーを（共）重合させた自己ドープ型導電性高分子を誘電体皮膜に被覆した後、脱水縮合することによって請求項８に記載の一般式（３）で示される高分子鎖間が架橋した自己ドープ型導電性高分子で誘電体皮膜を被覆することを特徴とする前記１〜１９のいずれかに記載の固体電解コンデンサの製造方法。
２３.一般式（１０）

（式中、Ｂ¹は、−（ＣＨ₂）_p−（Ｏ）_q−（ＣＨ₂）_r−を表わし、ｐおよびｒは、それぞれ独立して、０または１〜３の整数を表わし、ｑは０または１を表わす。Ｍ⁺は、水素イオン、アルカリ金属イオン、または第４級アンモニウムイオンを表わす。）で示される化学構造を含む自己ドープ型導電性高分子同士を誘電体皮膜に被覆した後、脱水縮合することによって請求項１２に記載の一般式（６）で示される高分子鎖間が架橋した自己ドープ型導電性高分子で誘電体皮膜を被覆することを特徴とする前記１〜１９のいずれかに記載の固体電解コンデンサの製造方法。
２４.一般式（１１）

（式中、Ｂ¹は、−（ＣＨ₂）_p−（Ｏ）_q−（ＣＨ₂）_r−を表わし、ｐおよびｒは、それぞれ独立して、０または１〜３の整数を表わし、ｑは０または１を表わす。Ｍ⁺は、水素イオン、アルカリ金属イオン、または第４級アンモニウムイオンを表わす。）で示されるモノマーを（共）重合させた自己ドープ型導電性高分子を誘電体皮膜に被覆した後、脱水縮合することによって請求項１２に記載の一般式（６）で示される高分子鎖間が架橋した自己ドープ型導電性高分子で誘電体皮膜を被覆すること特徴とする前記１〜１９のいずれかに記載の固体電解コンデンサの製造方法。
２５.微細孔を有する弁作用金属を一般式（７）および／または一般式（８）

（式（７）および（８）中、Ｒ¹〜Ｒ³、Ｒ⁷〜Ｒ¹⁰、Ｂ¹、およびＭ⁺は、請求項２１に記載の一般式（７）および（８）中と同じ意味を表わす。）で示される自己ドープ型導電性高分子を含む溶液に浸漬した後、加熱することにより脱水縮合することを特徴とする前記１〜１９のいずれかに記載の固体電解コンデンサの製造方法。
２６.一般式（７）および／または一般式（８）

（式（７）および（８）中、Ｒ¹〜Ｒ³、Ｒ⁷〜Ｒ¹⁰、Ｂ¹、およびＭ⁺は、請求項２１に記載の一般式（７）および（８）中と同じ意味を表わす。）で示される自己ドープ型導電性高分子を含む溶液を微細孔を有する弁作用金属に塗布した後、加熱することにより脱水縮合することを特徴とする前記１〜１９のいずれかに記載の固体電解コンデンサの製造方法。
２７.一般式（７）および／または一般式（８）

（式（７）および（８）中、Ｒ¹〜Ｒ³、Ｒ⁷〜Ｒ¹⁰、Ｂ¹、およびＭ⁺は、請求項２１に記載の一般式（７）および（８）中と同じ意味を表わす。）で示される自己ドープ型導電性高分子を含む溶液を、微細孔を有する弁作用金属における陽極と陰極とを絶縁分離する絶縁性材料を有するコンデンサの絶縁性材料に隣接する陰極側の誘電体被膜の少なくとも一部に塗布した後、加熱することにより脱水縮合することを特徴とする前記１〜１９のいずれかに記載の固体電解コンデンサの製造方法。
２８.一般式（９）

（式中、Ｂ¹、およびＭ⁺は、請求項２２に記載の一般式（９）中と同じ意味を表わす。）で示されるモノマーを（共）重合させた自己ドープ型導電性高分子を含む溶液を微細孔を有する弁作用金属に塗布した後、加熱することにより脱水縮合することを特徴とする前記１〜１９のいずれかに記載の固体電解コンデンサの製造方法。
２９.微細孔を有する弁作用金属を一般式（９）

（式中、Ｂ¹、およびＭ⁺は、請求項２２に記載の一般式（９）中と同じ意味を表わす。）で示されるモノマーを（共）重合させた自己ドープ型導電性高分子を含む溶液に浸漬した後、加熱することにより脱水縮合することを特徴とする前記１〜１９のいずれかに記載の固体電解コンデンサの製造方法。
３０.微細孔を有する弁作用金属を一般式（９）

（式中、Ｂ¹、およびＭ⁺は、請求項２２に記載の一般式（９）中と同じ意味を表わす。）で示されるモノマーを（共）重合させた自己ドープ型導電性高分子を含む溶液を、微細孔を有する弁作用金属における陽極と陰極とを絶縁分離する絶縁性材料を有するコンデンサの絶縁性材料に隣接する陰極側の誘電体被膜の少なくとも一部に塗布した後、加熱することにより脱水縮合することを特徴とする前記１〜１９のいずれかに記載の固体電解コンデンサの製造方法。
３１.脱水縮合反応が、２１０℃以上３５０℃以下の範囲内の温度で加熱処理して行われる前記２０〜２２および前記２５〜３０のいずれかに記載の固体電解コンデンサの製造方法。
３２.脱水縮合反応が、１２０〜２５０℃の温度で、１０秒〜６０分加熱処理することによって行われる前記２３または前記２４に記載の固体電解コンデンサの製造方法。
３３.誘電体皮膜層を有する弁作用金属を、高分子鎖間での架橋が可能な自己ドープ型導電性高分子を含む水溶液に浸漬したのち脱水縮合反応により硬化させ誘電体皮膜層を水不溶性の第一の固体電解質層で被覆する工程（工程１）、第二の固体電解質層を形成させるモノマーを含む溶液に浸漬後乾燥する工程（工程２）、酸化剤を含む溶液に浸漬後乾燥する工程（工程３）を含む方法により、第二の固体電解質層を設けることを特徴とする前記１〜１９のいずれかに記載の固体電解コンデンサの製造方法。
３４.誘電体皮膜層を有する弁作用金属を、高分子鎖間での架橋が可能な自己ドープ型導電性高分子を含む水溶液に浸漬したのち脱水縮合反応により硬化させ誘電体皮膜層を水不溶性の第一の固体電解質層で被覆する工程（工程１）、第二の固体電解質層を形成させるモノマーを含む溶液に浸漬後乾燥する工程（工程２）、酸化剤を含む溶液に浸漬後乾燥する工程（工程３）を複数回繰り返す方法により、第二の固体電解質層を設けることを特徴とする前記３３に記載の固体電解コンデンサの製造方法。
３５.誘電体皮膜層を有する弁作用金属に高分子鎖間での架橋が可能な自己ドープ型導電性高分子を含む水溶液を塗布したのち脱水縮合反応により硬化させ誘電体皮膜層を水不溶性の第一の固体電解質層で被覆する工程（工程１）、第二の固体電解質層を形成させるモノマーを含む溶液に浸漬後乾燥する工程（工程２）、酸化剤を含む溶液に浸漬後乾燥する工程（工程３）を複数回繰り返す方法により、第二の固体電解質層を設けることを特徴とする前記３３に記載の固体電解コンデンサの製造方法。
３６.酸化剤が過硫酸塩である前記３３〜３５のいずれかに記載の固体電解コンデンサの製造方法。
３７.酸化剤を含む溶液が有機微粒子を含む懸濁液である前記３３〜３６のいずれかに記載の固体電解コンデンサの製造方法。
３８.有機微粒子の平均粒子径（Ｄ₅₀）が、１〜２０μｍの範囲である前記３７に記載の固体電解コンデンサの製造方法。
３９.有機微粒子が脂肪族スルホン酸化合物、芳香族スルホン酸化合物、脂肪族カルボン酸化合物、芳香族カルボン酸化合物、それらの塩、及びペプチド化合物からなる群から選ばれる少なくとも１種である前記３８に記載の固体電解コンデンサの製造方法。
４０.前記２０〜３９のいずれかに記載の製造方法で製造された固体電解コンデンサ。 1. A solid electrolytic capacitor comprising a self-doped conductive polymer layer having a polymer chain bridge on a dielectric film formed on a valve action metal surface.
2. 2. The solid electrolytic capacitor as described in 1 above, wherein the self-doped conductive polymer contains a sulfonic acid group.
3. 3. The solid electrolytic capacitor as described in 2 above, comprising a self-doped conductive polymer in which crosslinking is carried out via a sulfone bond, and the sulfone bond is contained in an amount of 0.01 to 90 mol% of the repeating unit of the polymer.
4). Self-doped conductive polymer having a sulfonic acid group, in which the polymer chains are cross-linked through a bond having a bond energy 0.5 to 2 eV lower than the bond energy of the sulfonate group by X-ray photoelectron spectroscopy 4. The solid electrolytic capacitor as described in any one of 1 to 3 including a doped conductive polymer.
5. 5. The solid electrolytic capacitor as described in any one of 1 to 4 above, comprising a self-doped conductive polymer containing an isothianaphthene skeleton having a sulfonic acid group.
6). The crosslinked structure of the sulfone bond is represented by the general formula (1)

(In the formula, R ^{1 to} R ³ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, or a linear or branched alkoxy group having 1 to 20 carbon atoms. , A linear or branched alkenyl group having 2 to 20 carbon atoms, a linear or branched alkenyloxy group having 2 to 20 carbon atoms, a hydroxyl group, a halogen atom, a nitro group, a cyano group, a trihalomethyl group, phenyl A group, a substituted phenyl group, or a —B ¹ —SO ₃ ⁻ M ⁺ group, wherein B ¹ and B ² each independently represent — (CH ₂ ) _p — (O) _q — (CH ₂ ) _r —; And p and r each independently represents an integer of 0 or 1 to 3, and q represents 0 or 1. M ⁺ represents a hydrogen ion, an alkali metal ion, or a quaternary ammonium ion. Ar may have a polymer chain Represents a monovalent aromatic group, a substituted monovalent aromatic group, a monovalent heterocyclic group or a substituted monovalent heterocyclic group). 6. The solid electrolytic capacitor as described in 5 above, comprising a polymer.
7). The crosslinked structure of the sulfone bond is represented by the general formula (2)

(Wherein R ^{1 to} R ⁶ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, or a linear or branched alkoxy group having 1 to 20 carbon atoms. , A linear or branched alkenyl group having 2 to 20 carbon atoms, a linear or branched alkenyloxy group having 2 to 20 carbon atoms, a hydroxyl group, a halogen atom, a nitro group, a cyano group, a trihalomethyl group, phenyl A group, a substituted phenyl group, or a —B ¹ —SO ₃ ⁻ M ⁺ group, B ¹ represents — (CH ₂ ) _p — (O) _q — (CH ₂ ) _r —, and p and r are Each independently represents an integer of 0 or 1 to 3, q represents 0 or 1. M ⁺ represents a hydrogen ion, an alkali metal ion, or a quaternary ammonium ion. Including a self-doped conductive polymer 7. The solid electrolytic capacitor as described in 6 above.
8). The crosslinked structure of the sulfone bond is represented by the general formula (3)

(In the formula, B ¹ represents — (CH ₂ ) _p — (O) _q — (CH ₂ ) _r —, p and r each independently represents an integer of 0 or 1 to 3, Represents 0 or 1. M ⁺ represents a hydrogen ion, an alkali metal ion, or a quaternary ammonium ion. 7. The solid electrolytic capacitor according to 7.
9. 5. The solid electrolytic capacitor as described in any one of 2 to 4 above, wherein the self-doped conductive polymer includes a self-doped conductive polymer including a hetero five-membered ring skeleton having a sulfonic acid group.
10. The crosslinked structure of the sulfone bond is represented by the general formula (4)

(Wherein X represents —S—, —O—, or —N (—R ¹⁵ ) —, and R ¹⁵ represents a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, carbon, Represents a linear or branched alkenyl group of 2 to 20, B ¹ and B ² each independently represent — (CH ₂ ) _p — (O) _q — (CH ₂ ) _r —, p And r each independently represents an integer of 0 or 1 to 3, and q represents 0 or 1. M ⁺ represents a hydrogen ion, an alkali metal ion, or a quaternary ammonium ion. A monovalent aromatic group, a substituted monovalent aromatic group, a monovalent heterocyclic group or a substituted monovalent heterocyclic group which may have a polymer chain. 10. The solid electrolytic core as described in 9 above, which comprises a self-doped conductive polymer having a chemical structure. Ndensesa.
11. The crosslinked structure of the sulfone bond has the general formula (5)

(Wherein X represents —S—, —O—, or —N (—R ¹⁵ ) —, and R ¹⁵ represents a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, carbon, Represents a linear or branched alkenyl group of 2 to 20, B ¹ represents — (CH ₂ ) _p — (O) _q — (CH ₂ ) _r —, and p and r are each independently And q represents an integer of 0 to 1 and q represents 0 or 1. M ⁺ represents a hydrogen ion, an alkali metal ion, or a quaternary ammonium ion.) 11. The solid electrolytic capacitor as described in 10 above, comprising a type conductive polymer.
12 The crosslinked structure of the sulfone bond is represented by the general formula (6)

(In the formula, B ¹ represents — (CH ₂ ) _p — (O) _q — (CH ₂ ) _r —, p and r each independently represents an integer of 0 or 1 to 3, Represents 0 or 1. M ⁺ represents a hydrogen ion, an alkali metal ion, or a quaternary ammonium ion. 10. The solid electrolytic capacitor as described in 10 or 11 above.
13. On the dielectric film formed on the metal surface, the first solid electrolyte layer containing a self-doped conductive polymer having a cross-link between polymer chains is provided, and the second solid electrolyte layer is provided thereon. The solid electrolytic capacitor in any one of 1-12.
14 14. The solid electrolytic capacitor as described in 13 above, wherein the first solid electrolyte layer is insoluble in water.
15. 15. The solid electrolytic capacitor as described in any one of 1 to 14 above, wherein the metal is a valve metal having fine holes.
16. Self-doping type having an insulating material for insulating and separating the anode and the cathode of the valve action metal having fine holes, and having a polymer inter-chain bridge on at least a part of the dielectric film on the cathode side adjacent thereto 16. The solid electrolytic capacitor as described in 15 above, which has a first solid electrolyte layer containing a conductive polymer and has a second solid electrolyte layer thereon.
17. The solid electrolytic capacitor as described in any one of 1 to 16 above, wherein the thickness of the solid electrolyte layer containing the self-doped conductive polymer in which the polymer chains are crosslinked is in the range of 1 nm to 1000 nm.
18. The solid electrolysis according to any one of 1 to 17 above, wherein the conductivity of the solid electrolyte layer containing the self-doped conductive polymer in which the polymer chains are crosslinked is in the range of 0.001 to 100 S / cm. Capacitor.
19. The solid electrolytic capacitor as described in any one of 1 to 18 above, wherein the pencil hardness of the solid electrolyte layer containing the self-doped conductive polymer in which the polymer chains are crosslinked has a hardness of HB to 4H.
20. General formula (7)

(In the formula, R ^{1 to} R ³ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, or a linear or branched alkoxy group having 1 to 20 carbon atoms. , A linear or branched alkenyl group having 2 to 20 carbon atoms, a linear or branched alkenyloxy group having 2 to 20 carbon atoms, a hydroxyl group, a halogen atom, a nitro group, a cyano group, a trihalomethyl group, phenyl group, a substituted phenyl group, or a -B ¹ -SO ₃ ^- represents the M ⁺ group, .B ¹ one of R ¹ to R ³ is a hydrogen _{atom, - (CH 2) p -} (O ) _Q — (CH ₂ ) _r —, p and r each independently represent an integer of 0 or 1 to 3 and q represents 0 or 1. M ⁺ represents a hydrogen ion or an alkali metal ion. Or a quaternary ammonium ion.) The self-doped conductive polymer in which the polymer chains represented by the general formula (1) according to claim 6 are cross-linked by dehydration condensation after coating the self-doped conductive polymers including the structure with each other on the dielectric film. The method for producing a solid electrolytic capacitor as described in any one of 1 to 19 above, wherein the dielectric film is coated with a conductive polymer.
21. General formula (7) and / or general formula (8)

(In the formula ^{(7), R 1 ~R 3} , B 1, and M ⁺ is in. The formula represents the same meaning as in the general formula (7) as claimed in claim ^{20 (8), R 7 ~R} 10 is , Independently of each other, a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkoxy group having 1 to 20 carbon atoms, or a straight chain having 2 to 20 carbon atoms Or a branched alkenyl group, a linear or branched alkenyloxy group having 2 to 20 carbon atoms, a hydroxyl group, a halogen atom, a nitro group, a cyano group, a trihalomethyl group, a phenyl group, a substituted phenyl group, or -B ¹ When dehydrating and condensing a self-doped conductive polymer which represents a —SO ₃ ⁻ M ⁺ group and includes a chemical structure represented by the formulas (7) and (8), any one of R ^{7 to} R ¹⁰ a hydrogen atom, each is hydrogen atom R ¹ to R ³ in this case formula (7) Without at least one of R ⁷ to R ¹⁰ when dehydration condensation of self-doping type electrically conducting polymer containing a chemical structure represented by or formula also (8) is -B ¹ -SO ₃ ^-. M ⁺ group And at least one is a hydrogen atom, B ¹ represents — (CH ₂ ) _p — (O) _q — (CH ₂ ) _r —, and p and r are each independently 0 or 1 represents an integer of 1 to 3, q represents 0 or 1. M ⁺ represents a hydrogen ion, an alkali metal ion, or a quaternary ammonium ion.) The molecules are coated with a dielectric film, and then dehydrated and condensed to coat the dielectric film with a self-doped conductive polymer in which the polymer chains represented by the general formula (1) according to claim 6 are crosslinked. Any one of said 1-19 characterized by the above-mentioned Method of manufacturing a body electrolytic capacitor.
22. General formula (9)

(In the formula, B ¹ represents — (CH ₂ ) _p — (O) _q — (CH ₂ ) _r —, p and r each independently represents an integer of 0 or 1 to 3, Represents 0 or 1. M ⁺ represents a hydrogen ion, an alkali metal ion, or a quaternary ammonium ion.) A dielectric film is formed from a self-doped conductive polymer obtained by (co) polymerizing a monomer represented by The dielectric film is coated with a self-doped conductive polymer in which the polymer chains represented by the general formula (3) according to claim 8 are cross-linked by dehydration condensation after coating. The manufacturing method of the solid electrolytic capacitor in any one of said 1-19.
23. General formula (10)

(In the formula, B ¹ represents — (CH ₂ ) _p — (O) _q — (CH ₂ ) _r —, p and r each independently represents an integer of 0 or 1 to 3, Represents 0 or 1. M ⁺ represents a hydrogen ion, an alkali metal ion, or a quaternary ammonium ion.) Self-doped conductive polymers having a chemical structure represented by: The dielectric film is then coated with a self-doped conductive polymer in which the polymer chains represented by the general formula (6) according to claim 12 are crosslinked by dehydration condensation. 20. A method for producing a solid electrolytic capacitor as described in any one of 19 above.
24. General formula (11)

(In the formula, B ¹ represents — (CH ₂ ) _p — (O) _q — (CH ₂ ) _r —, p and r each independently represents an integer of 0 or 1 to 3, Represents 0 or 1. M ⁺ represents a hydrogen ion, an alkali metal ion, or a quaternary ammonium ion.) A dielectric film is formed from a self-doped conductive polymer obtained by (co) polymerizing a monomer represented by The dielectric film is coated with a self-doped conductive polymer in which the polymer chains represented by the general formula (6) according to claim 12 are cross-linked by dehydration condensation after the coating. The manufacturing method of the solid electrolytic capacitor in any one of 1-19.
25. The valve action metal having fine pores is represented by the general formula (7) and / or the general formula (8).

(In the formulas (7) and (8), R ^{1 to} R ³ , R ^{7 to} R ¹⁰ , B ¹ , and M ⁺ have the same meanings as in the general formulas (7) and (8) according to claim 21. The method for producing a solid electrolytic capacitor as described in any one of 1 to 19 above, wherein the solid electrolytic capacitor is dehydrated and condensed by heating after being immersed in a solution containing the self-doped conductive polymer represented by .
26. General formula (7) and / or general formula (8)

(In the formulas (7) and (8), R ^{1 to} R ³ , R ^{7 to} R ¹⁰ , B ¹ , and M ⁺ have the same meanings as in the general formulas (7) and (8) according to claim 21. Any one of 1 to 19 above, wherein a solution containing a self-doped conductive polymer represented by the formula (1) is applied to a valve metal having fine pores and then dehydrated and condensed by heating. The manufacturing method of the solid electrolytic capacitor of description.
27. General formula (7) and / or general formula (8)

(In the formulas (7) and (8), R ^{1 to} R ³ , R ^{7 to} R ¹⁰ , B ¹ , and M ⁺ have the same meanings as in the general formulas (7) and (8) according to claim 21. The cathode side adjacent to the insulating material of the capacitor having the insulating material that insulates and separates the anode and the cathode in the valve action metal having a fine hole from the solution containing the self-doped conductive polymer represented by 20. The method for producing a solid electrolytic capacitor as described in any one of 1 to 19 above, wherein after applying to at least a part of the dielectric coating, dehydration condensation is performed by heating.
28. General formula (9)

(Wherein B ¹ and M ⁺ represent the same meaning as in general formula (9) according to claim 22). A self-doped conductive polymer obtained by (co) polymerizing a monomer represented by (22) 20. The method for producing a solid electrolytic capacitor as described in any one of 1 to 19 above, wherein the solution is applied to a valve metal having fine pores and then dehydrated and condensed by heating.
29. A valve action metal having fine pores is represented by the general formula (9)

(Wherein B ¹ and M ⁺ represent the same meaning as in general formula (9) according to claim 22). A self-doped conductive polymer obtained by (co) polymerizing a monomer represented by (22) The method for producing a solid electrolytic capacitor as described in any one of 1 to 19 above, wherein the solid electrolytic capacitor is dehydrated and condensed by heating after being immersed in the solution.
30. The valve action metal having fine pores is represented by the general formula (9)

(Wherein B ¹ and M ⁺ represent the same meaning as in general formula (9) according to claim 22). A self-doped conductive polymer obtained by (co) polymerizing a monomer represented by (22) The solution containing is applied to at least a part of the dielectric film on the cathode side adjacent to the insulating material of the capacitor having an insulating material that insulates and separates the anode and the cathode of the valve metal having fine holes, and then heated. The method for producing a solid electrolytic capacitor as described in any one of 1 to 19 above, wherein dehydration condensation is performed.
31. The method for producing a solid electrolytic capacitor as described in any one of 20 to 22 and 25 to 30, wherein the dehydration condensation reaction is performed by heat treatment at a temperature in the range of 210 ° C. to 350 ° C.
32. The method for producing a solid electrolytic capacitor as described in 23 or 24 above, wherein the dehydration condensation reaction is performed by heat treatment at a temperature of 120 to 250 ° C. for 10 seconds to 60 minutes.
33. A valve metal having a dielectric film layer is immersed in an aqueous solution containing a self-doped conductive polymer capable of crosslinking between polymer chains, and then cured by a dehydration condensation reaction to make the dielectric film layer insoluble in water. The step of coating with the first solid electrolyte layer (step 1), the step of drying after immersing in the solution containing the monomer for forming the second solid electrolyte layer (step 2), and the step of drying after immersing in the solution containing the oxidizing agent 20. The method for producing a solid electrolytic capacitor as described in any one of 1 to 19 above, wherein the second solid electrolyte layer is provided by a method including a step (step 3).
34. A valve metal having a dielectric film layer is immersed in an aqueous solution containing a self-doped conductive polymer capable of crosslinking between polymer chains, and then cured by a dehydration condensation reaction to make the dielectric film layer insoluble in water. The step of coating with the first solid electrolyte layer (step 1), the step of drying after immersing in the solution containing the monomer for forming the second solid electrolyte layer (step 2), and the step of drying after immersing in the solution containing the oxidizing agent The method for producing a solid electrolytic capacitor as described in 33 above, wherein the second solid electrolyte layer is provided by a method of repeating the step (step 3) a plurality of times.
35. Applying an aqueous solution containing a self-doped conductive polymer capable of cross-linking between polymer chains to a valve metal having a dielectric film layer, and then curing it by dehydration condensation reaction to make the dielectric film layer insoluble in water The step of covering with the first solid electrolyte layer (step 1), the step of drying after immersing in the solution containing the monomer for forming the second solid electrolyte layer (step 2), and the step of drying after immersing in the solution containing the oxidizing agent The method for producing a solid electrolytic capacitor as described in 33 above, wherein the second solid electrolyte layer is provided by a method of repeating (Step 3) a plurality of times.
36. The method for producing a solid electrolytic capacitor as described in any one of 33 to 35, wherein the oxidizing agent is persulfate.
37. The method for producing a solid electrolytic capacitor as described in any one of 33 to 36 above, wherein the solution containing the oxidizing agent is a suspension containing organic fine particles.
38. The method for producing a solid electrolytic capacitor as described in 37 above, wherein the average particle diameter (D ₅₀ ) of the organic fine particles is in the range of 1 to 20 μm.
39. In the above 38, wherein the organic fine particles are at least one selected from the group consisting of an aliphatic sulfonic acid compound, an aromatic sulfonic acid compound, an aliphatic carboxylic acid compound, an aromatic carboxylic acid compound, a salt thereof, and a peptide compound. The manufacturing method of the solid electrolytic capacitor of description.
40. A solid electrolytic capacitor produced by the production method according to any one of 20 to 39.

  According to the present invention, there is less short circuit failure, less variation in element shape, stable production of a thin capacitor element, an increase in the number of capacitor elements in a solid electrolytic capacitor chip, a higher capacity, and an equivalent series resistance. It is possible to provide a solid electrolytic capacitor element suitable for a multilayer solid electrolytic capacitor having a small variation.

Hereinafter, the present invention will be described with reference to the accompanying drawings.
The solid electrolytic capacitor used in the present invention has a dielectric film on the surface of a metal anode base (hereinafter also referred to as a substrate). The dielectric film (2) on the surface of the substrate (1) is usually formed by subjecting a metal porous formed body having a valve action to chemical conversion treatment or the like.
The metal having a valve action that can be used in the present invention is a simple metal such as aluminum, tantalum, niobium, titanium, zirconium, magnesium, silicon, or an alloy thereof. Further, the porous form may be any form as long as it is a form of a porous molded body such as an etching product of a rolled foil or a fine powder sintered body.

  Specific examples of the anode substrate include porous sintered bodies of these metals, plates (including ribbons, foils, and the like) surface-treated by etching and the like, and preferably have a flat plate shape or a foil shape. Is. Furthermore, a known method can be used as a method of forming a dielectric oxide film on the surface of the porous metal body. For example, when an aluminum foil is used, an oxide film can be formed by anodizing in an aqueous solution containing boric acid, phosphoric acid, adipic acid, or a sodium salt or an ammonium salt thereof. Moreover, when using the sintered compact of a tantalum powder, it can anodize in phosphoric acid aqueous solution and can form an oxide film in a sintered compact.

  For example, the thickness of the valve action metal foil varies depending on the purpose of use, but a foil having a thickness of about 40 to 300 μm is used. In order to obtain a thin solid electrolytic capacitor, for example, an aluminum foil having a thickness of 80 to 250 μm is preferably used, and the maximum height of the element provided with the solid electrolytic capacitor is preferably 250 μm or less. Although the size and shape of the metal foil vary depending on the application, a rectangular element having a width of about 1 to 50 mm and a length of about 1 to 50 mm is preferable as a flat element unit, more preferably about 2 to 15 mm in width and about 2 in length. ~ 25 mm.

  Chemical conversion conditions such as chemical conversion liquid and chemical conversion voltage used for chemical conversion are confirmed in advance by experiments and set to appropriate values according to the capacity, withstand voltage, etc. required for the solid electrolytic capacitor to be produced. In addition, in the chemical conversion treatment, the chemical conversion solution is prevented from spreading to the portion that becomes the anode of the solid electrolytic capacitor, and the insulation from the solid electrolyte (4) (cathode portion) formed in the subsequent process is ensured. Generally, masking (3) is provided.

  As the masking material, an insulating material that insulates and separates the anode and the cathode is used. A general heat-resistant resin, preferably a heat-resistant resin that can be dissolved or swelled in a solvent or a precursor thereof, an inorganic fine powder, and a cellulose resin. However, the material is not limited. Specific examples include polyphenylsulfone (PPS), polyethersulfone (PES), cyanate ester resin, fluororesin (tetrafluoroethylene, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer, etc.), low molecular weight polyimides and their Examples thereof include derivatives and precursors thereof, and low molecular weight polyimides, polyethersulfones, fluororesins and their precursors are particularly preferable.

  Hereinafter, the method for forming a solid electrolytic capacitor having a self-doped conductive polymer layer having a polymer chain bridge on a dielectric film formed on the surface of a valve action metal having fine holes in the present invention will be described in order. explain. The solid electrolytic capacitor of the present invention is a solid electrolytic capacitor characterized by having a self-doped conductive polymer layer having a polymer chain bridge on a dielectric film formed on a metal surface, preferably A second solid electrolyte layer is provided on the first solid electrolyte layer containing the self-doped conductive polymer. The self-doped conductive polymer in which the polymer chains that are the first solid electrolyte layer are cross-linked is preferably insoluble in water.

Hereinafter, the self-doped conductive polymer in which the polymer chains that are the first solid electrolyte layer are crosslinked will be described.
The self-doped conductive polymer having a polymer chain bridge used in the present invention contains a sulfonic acid group, the bridge is formed through a sulfone bond, and the sulfone bond is 0.01 of the repeating unit of the polymer. It is more preferable to include a self-doping type conductive polymer contained in an amount of ˜90 mol%, preferably 1 to 90 mol%.

Until now, as a method for imparting solvent resistance, particularly water resistance, to a self-doped conductive polymer, a water-soluble polyaniline-type self-doped conductive polymer is heated at about 200 ° C. for about 15 minutes. The carboxylic acid group, sulfonic acid group and the like of the conductive polymer are partly eliminated to increase the water resistance.
However, it has also been known that the surface resistance, which is an inherently necessary property, significantly increases due to the decomposition of the substance itself by heat treatment at a high temperature.

The present inventors have found that the solvent resistance can be improved without a significant decrease in conductivity by partially crosslinking such a water-soluble self-doped conductive polymer.
Any method may be used as the crosslinking method. However, when the polymerization is performed using a crosslinking monomer, the solubility in a solvent such as water, which is originally necessary, is lowered. preferable.
In a self-doped conductive polymer containing a water-soluble isothianaphthene skeleton, some sulfonic acid groups are condensed with the benzene ring of another isothianaphthene by heating at 300 ° C. for a short time (within 5 minutes). As a result, a crosslinked structure is formed, and the water resistance is increased without deteriorating the electrical characteristics.
By cross-linking the polymer chain of the self-doped conductive polymer containing the isothianaphthene skeleton as described above, not only the water resistance but also the solvent resistance is excellent. The crosslinking method may be basically any method, but the polyisothianaphthene type self-doped conductive polymer containing a chemical structure crosslinked by a sulfone bond is not only heat resistant and water resistant. Excellent solvent resistance.

で示されるスルホン結合を介して架橋を形成した化学構造を含有するものであってもよい。 More specifically, in a preferred embodiment of the present invention, the self-doped conductive polymer crosslinked between polymer chains has a Bronsted acid group in at least one structural unit of the repeating unit of the π-electron conjugated polymer. More specifically, the chemical structure is not limited,
Preferably, general formula (1)

It may contain the chemical structure which formed the bridge | crosslinking through the sulfone bond shown by these.

In general formula (1), R ^{1 to} R ³ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, or a linear or branched structure having 1 to 20 carbon atoms. Alkoxy group, linear or branched alkenyl group having 2 to 20 carbon atoms, linear or branched alkenyloxy group having 2 to 20 carbon atoms, hydroxyl group, halogen atom, nitro group, cyano group, trihalomethyl It represents an M ⁺ group ^- group, a phenyl group, a substituted phenyl group or -B ¹ -SO _3,. B ¹ and B ² each independently represent — (CH ₂ ) _p — (O) _q — (CH ₂ ) _r —, and p and r each independently represent an integer of 0 or 1 to 3. Q represents 0 or 1. M ⁺ represents a hydrogen ion, an alkali metal ion, or a quaternary ammonium ion.

  Further, the self-doped conductive polymer having a cross-link between polymer chains in the present invention may have a polymer chain, a monovalent aromatic group, a substituted monovalent aromatic group, A self-doped conductive polymer having a polymer chain bridge that is bridged between a monovalent heterocyclic group or a substituted monovalent heterocyclic group is included. That is, Ar in the general formula (1) may have a polymer chain, a monovalent aromatic group, a substituted monovalent aromatic group, a monovalent heterocyclic group or a substituted group. Represents a monovalent heterocyclic group. As such monovalent aromatic group and monovalent heterocyclic group which may have a polymer chain, more specifically, phenyl group, substituted phenyl group, naphthyl group, substituted naphthyl group , Anthranyl group, substituted anthranyl group, quinolyl group, substituted quinolyl group, quinoxalyl group, substituted quinoxalyl group, thienyl group, substituted thienyl group, pyrrolyl group, substituted pyrrolyl group, furanyl group, substituted furanyl group, isothianaphthenylene group, substituted An isothianaphthenylene group, a carbazolyl group, and a substituted carbazolyl group are preferred, and a phenyl group, a substituted phenyl group, a naphthyl group, a substituted naphthyl group, a quinoxalyl group, a substituted quinoxalyl group, a thienyl group, a substituted thienyl group, a pyrrolyl group, a substituted pyrrolyl group, An isothianaphthenylene group and a substituted isothianaphthenylene group are particularly preferred.

で示されるスルホン結合で架橋された化学構造を含有するものであってもよい。 Furthermore, the self-doped conductive polymer having a polymer inter-chain bridge including a chemical structure in which a bridge is formed via a sulfone bond represented by the general formula (1) is preferably the general formula (2).

It may contain the chemical structure bridge | crosslinked by the sulfone bond shown by these.

In general formula (2), R ^{1 to} R ⁶ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, or a linear or branched alkyl group having 1 to 20 carbon atoms. Alkoxy group, linear or branched alkenyl group having 2 to 20 carbon atoms, linear or branched alkenyloxy group having 2 to 20 carbon atoms, hydroxyl group, halogen atom, nitro group, cyano group, trihalomethyl group , phenyl group, substituted phenyl group, -B ¹ -SO ₃ ^- represents an M ⁺ group. B ¹ represents — (CH ₂ ) _p — (O) _q — (CH ₂ ) _r —, p and r independently represent an integer of 0 or 1 to 3, and q represents 0 or 1. M ⁺ represents a hydrogen ion, an alkali metal ion, or a quaternary ammonium ion.

で示される化学構造を有する自己ドープ型導電性高分子同士（但し、Ｒ⁷〜Ｒ¹⁰のいずれも−Ｂ¹−ＳＯ₃ ^-Ｍ⁺基ではないときは少なくとも一方は一般式（７）の−Ｂ¹−ＳＯ₃ ^-Ｍ⁺基を有する化学構造を有し、これと脱水縮合するもう一方のベンゼン環には少なくとも一つの水素原子が置換している）を分子間で脱水縮合することにより製造することができる。 The crosslinked structure represented by the general formula (2) has the general formula (7) and / or the general formula (8).

In self-doping type electrically conducting polymer between (but having a chemical structure represented, none of _{^{R 7 ~R 10 -B 1 -SO 3}} - is at least one of when it is not M ⁺ group of general formula (7) - B ¹ -SO ₃ ^- has a chemical structure having a M ⁺ group, prepared by dehydrating condensation between molecules at least one hydrogen atom is substituted) on the other benzene ring dehydration condensation therewith can do.

In general formulas (7) and (8), R ^{1 to} R ³ and R ^{7 to} R ¹⁰ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, 20 linear or branched alkoxy groups, linear or branched alkenyl groups having 2 to 20 carbon atoms, linear or branched alkenyloxy groups having 2 to 20 carbon atoms, hydroxyl groups, halogen atoms, nitro group, a cyano group, a trihalomethyl group, a phenyl group, a substituted phenyl group or -B ¹ -SO _3, ^- represents the M ⁺ group, the self-doping, including the chemical structure represented by the formula (7) and (8) When the type conductive polymer is dehydrated and condensed between molecules, any one of R ^{7 to} R ¹⁰ is a hydrogen atom, and at this time, any of R ^{1 to} R ³ in formula (7) is not a hydrogen atom. May be. When the self-doped conductive polymer having the chemical structure represented by the formula (8) is subjected to dehydration condensation between molecules, at least one of R ^{7 to} R ¹⁰ represents a —B ¹ —SO ₃ ⁻ M ⁺ group. , And at least one is a hydrogen atom. B ¹ represents — (CH ₂ ) _p — (O) _q — (CH ₂ ) _r —, p and r independently represent an integer of 0 or 1 to 3, and q represents 0 or 1. M ⁺ represents a hydrogen ion, an alkali metal ion, or a quaternary ammonium ion.

Here, particularly preferable examples of R ^{1 to} R ¹⁰ include a hydrogen atom, an alkyl group, an alkoxy group, an alkenyl group, an alkenyloxy group, a phenyl and substituted phenyl group, and a sulfonic acid group. Specific examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, hexadecyl, ethoxyethyl, methoxyethyl, methoxyethoxyethyl, acetonyl, Specific examples of alkenyl groups include allyl, 1-butenyl, and alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, butoxy, pentyloxy, hexyloxy, octyloxy, dodecyloxy, and the like. Specific examples of the alkenyloxy group include allyloxy and 1-butenyloxy. Specific examples of the substituted phenyl group include a fluorophenyl group, a chlorophenyl group, a bromophenyl group, a methylphenyl group, Kishifeniru group, and the like.
In the chain of the above alkyl group, alkoxy group, alkenyl group or alkenyloxy group, carbonyl bond, ether bond, ester bond, sulfonate bond, amide bond, sulfonamide bond, sulfide bond, sulfinyl bond, sulfonyl bond, It may have an imino bond. Among these, for example, specific examples of the alkyl ester group include alkoxycarbonyl groups such as methoxycarbonyl, ethoxycarbonyl, and butoxycarbonyl, acyloxy groups such as acetoxy, butyroyloxy, methoxyethoxy, methoxyethoxyethoxy, and the like.

M ⁺ represents a hydrogen ion, an alkali metal ion such as Na ⁺ , Li ⁺ or K ^+, or a quaternary ammonium cation represented by N (R ¹¹ ) (R ¹² ) (R ¹³ ) (R ¹⁴ ) ^+. , M ⁺ may be a mixture containing one or more of the cations.
R ^{11 to} R ¹⁴ each independently represents a hydrogen atom, a linear or branched substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, or a substituted or unsubstituted aryl group, an alkoxy group, a hydroxyl group It may be an alkyl or aryl group containing a group containing an element other than carbon and hydrogen, such as a group, an oxyalkylene group, a thioalkylene group, an azo group, an azobenzene group, and a p-diphenyleneoxy group.

Examples of quaternary ammonium cations include NH ₄ ⁺ , NH (CH ₃ ) ₃ ⁺ , NH (C ₆ H ₅ ) ₃ ⁺ , N (CH ₃ ) ₂ (CH ₂ OH) (CH ₂ —Z) ^+. (Wherein Z represents an arbitrary substituent having a chemical formula weight of 600 or less. For example, phenoxy group, p-diphenyleneoxy group, p-alkoxydiphenyleneoxy group, p-alkoxyphenylazophenoxy group, etc.) Is a substituent of In order to convert to a specific cation, a normal ion exchange resin may be used.

B ¹ or B ² in the general formula (1) to the general formula (11) represents — (CH ₂ ) _p — (O) _q — (CH ₂ ) _r —, and p and r are each independently 0. or represents an integer of 1 to 3, q is 0 or 1, in the case of p = q = r = 0, B represents a single bond, -B ¹ -SO ₃ ^- M ⁺ is, -SO ₃ ^- A sulfur atom directly binds to the target binding site as M ⁺ .
Desirable examples of B ¹ or B ² include a single bond, methylene, ethylene, propylene, butylene, pentylene, hexylene, arylene, butadienylene, oxymethylene, oxyethylene, oxypropylene, methyleneoxyethylene, ethyleneoxyethylene, and the like. .

（式中、Ｒ¹〜Ｒ³、Ｂ¹及びＭ⁺は前記の通りである。）で示される化学構造が部分的に含まれる自己ドープ型導電性高分子であることが好ましい。この場合スルホン酸基と脱水縮合させてスルホン結合で架橋させるためには前記Ｒ¹〜Ｒ³の内、少なくとも一つは水素原子である必要がある。 Examples of such particularly desirable B in — (CH ₂ ) _p — (O) _q — (CH ₂ ) _r — representing B ¹ or B ² include a single bond, ethylene, propylene, oxyethylene, ethyleneoxy Ethylene is mentioned.
Of the self-doped conductive polymer constituent components in a preferred embodiment of the present invention, the crosslinked structure portion represented by the general formula (1) is preferably contained in an amount of 1 to 90 mol% of the polymer repeating unit, 20 to 80 mol% is particularly preferable. If it is less than 1 mol%, the water resistance tends to decrease, and if it exceeds 90 mol%, the conductivity tends to decrease.
The self-doped conductive polymer according to the present invention may have a polyaniline structure, a polypyrrole structure, a polythiophene structure, a polycarbazole structure, or the like.
In the preferred embodiment of the present invention, among the self-doped conductive polymer constituent components, the portion other than the crosslinked structure portion represented by the general formula (1) is not particularly limited as long as the conductivity is not impaired. It preferably has a naphthene skeleton. That is, a (co) polymer having a chemical structure represented by the general formula (7) and / or a chemical structure represented by the general formula (8) is preferable. Furthermore, the general formula (7)

(Wherein R ^{1 to} R ³ , B ^1, and M ⁺ are as described above) are preferably self-doped conductive polymers partially including the chemical structure shown. In this case, at least one of R ^{1 to} R ³ must be a hydrogen atom in order to undergo dehydration condensation with a sulfonic acid group and crosslink with a sulfone bond.

（式中、Ｂ¹は、−（ＣＨ₂）_p−（Ｏ）_q−（ＣＨ₂）_r−を表わし、ｐおよびｒは、それぞれ独立して、０または１〜３の整数を表わし、ｑは０または１を表わす。Ｍ⁺は、水素イオン、アルカリ金属イオン、または第４級アンモニウムイオンを表わす。）で示されるモノマーを（共）重合させたものであり、これを分子間で脱水縮合させて架橋したものが一般式（３）

（式中、Ｂ¹は、−（ＣＨ₂）_p−（Ｏ）_q−（ＣＨ₂）_r−を表わし、ｐおよびｒは、それぞれ独立して、０または１〜３の整数を表わし、ｑは０または１を表わす。Ｍ⁺は、水素イオン、アルカリ金属イオン、または第４級アンモニウムイオンを表わす。）で示されるスルホン結合の架橋構造で架橋したものである。更に、前記Ｂ¹の構造は存在しないで、硫黄原子が直接ベンゼン環に結合した構造が好ましい。 Furthermore, a preferable chemical structure as a self-doped conductive polymer that serves as a precursor of the self-doped conductive polymer having a bridge between the polymer chains of the present invention is represented by the general formula (9).

(In the formula, B ¹ represents — (CH ₂ ) _p — (O) _q — (CH ₂ ) _r —, p and r each independently represents an integer of 0 or 1 to 3, Represents 0 or 1. M ⁺ represents a hydrogen ion, an alkali metal ion, or a quaternary ammonium ion). Cross-linked by general formula (3)

(In the formula, B ¹ represents — (CH ₂ ) _p — (O) _q — (CH ₂ ) _r —, p and r each independently represents an integer of 0 or 1 to 3, Represents 0 or 1. M ⁺ represents a hydrogen ion, an alkali metal ion, or a quaternary ammonium ion. Furthermore, the structure in which the structure of B ¹ does not exist and a sulfur atom is directly bonded to the benzene ring is preferable.

The self-doped conductive polymer having an isothianaphthene skeleton of the general formula (7) and / or the general formula (8) in the present invention is water-soluble with a sulfonic acid group covalently bonded directly or through a side chain of the molecule. It is a conductive polymer.
Specific polymers containing an isothianaphthene structure include poly (isothianaphthenesulfonic acid) or various salt structures and substituted derivatives thereof, and repeating units such as poly (isothianaphthenesulfonic acid-co-isothianaphthene). (Co) polymers containing these, or various salt structures and substituted derivatives thereof.

で示されるスルホン結合で架橋された化学構造を含有することが好ましい。
一般式（４）中、Ｘは−Ｓ−、−Ｏ−、または−Ｎ（−Ｒ¹⁵）−を表わし、Ｒ¹⁵は、水素原子、炭素数１〜２０の直鎖状もしくは分岐状のアルキル基、炭素数２〜２０の直鎖状もしくは分岐状のアルケニル基を表わし、Ｂ¹およびＢ²は、それぞれ独立して−（ＣＨ₂）_p−（Ｏ）_q−（ＣＨ₂）_r−を表わし、ｐおよびｒは、それぞれ独立して、０または１〜３の整数を表わし、ｑは０または１を表わす。Ｍ⁺は、水素イオン、アルカリ金属イオン、または第４級アンモニウムイオンを表わす。 More specifically, the self-doped conductive polymer crosslinked between polymer chains of the present invention is represented by the general formula (4)

It is preferable to contain the chemical structure bridge | crosslinked by the sulfone bond shown by these.
In the general formula (4), X represents —S—, —O—, or —N (—R ¹⁵ ) —, and R ¹⁵ represents a hydrogen atom, a linear or branched alkyl having 1 to 20 carbon atoms. A straight chain or branched alkenyl group having 2 to 20 carbon atoms, and B ¹ and B ² each independently represent — (CH ₂ ) _p — (O) _q — (CH ₂ ) _r —. P and r each independently represents an integer of 0 or 1 to 3, and q represents 0 or 1. M ⁺ represents a hydrogen ion, an alkali metal ion, or a quaternary ammonium ion.

  Further, the self-doped conductive polymer having a cross-link between polymer chains in the present invention may have a polymer chain, a monovalent aromatic group, a substituted monovalent aromatic group, A self-doped conductive polymer having a polymer chain bridge that is bridged between a monovalent heterocyclic group or a substituted monovalent heterocyclic group is included. That is, Ar in the general formula (4) may have a polymer chain, a monovalent aromatic group, a substituted monovalent aromatic group, a monovalent heterocyclic group or a substituted group. Represents a monovalent heterocyclic group. As such monovalent aromatic group and monovalent heterocyclic group which may have a polymer chain, more specifically, phenyl group, substituted phenyl group, naphthyl group, substituted naphthyl group , Anthranyl group, substituted anthranyl group, quinolyl group, substituted quinolyl group, quinoxalyl group, substituted quinoxalyl group, thienyl group, substituted thienyl group, pyrrolyl group, substituted pyrrolyl group, furanyl group, substituted furanyl group, isothianaphthenylene group, substituted An isothianaphthenylene group, a carbazolyl group, and a substituted carbazolyl group are preferred, and a phenyl group, a substituted phenyl group, a naphthyl group, a substituted naphthyl group, a quinoxalyl group, a substituted quinoxalyl group, a thienyl group, a substituted thienyl group, a pyrrolyl group, a substituted pyrrolyl group, An isothianaphthenylene group and a substituted isothianaphthenylene group are particularly preferred.

で示されるスルホン結合で架橋された化学構造を含有することが好ましい。 Further, the self-doped conductive polymer having a polymer inter-chain bridge containing a chemical structure in which a bridge is formed through a sulfone bond represented by the general formula (4) is preferably the general formula (5).

It is preferable to contain the chemical structure bridge | crosslinked by the sulfone bond shown by these.

In General Formula (5), X represents any of —S—, —O—, and —N (—R ¹⁵ ) —. R ¹⁵ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, or a linear or branched alkenyl group having 2 to 20 carbon atoms. B ¹ represents — (CH ₂ ) _p — (O) _q — (CH ₂ ) _r —, p and r independently represent an integer of 0 or 1 to 3, and q represents 0 or 1. M ⁺ represents a hydrogen ion, an alkali metal ion or a quaternary ammonium ion.
Here, specific examples of the particularly preferred alkyl group represented by R ¹⁵ include methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, hexadecyl, ethoxyethyl. , Methoxyethyl, methoxyethoxyethyl, acetonyl, phenacyl and the like, and specific examples of the alkenyl group include allyl, 1-butenyl and the like.

（式中、Ｂ¹は、−（ＣＨ₂）_p−（Ｏ）_q−（ＣＨ₂）_r−を表わし、ｐおよびｒは、それぞれ独立して、０または１〜３の整数を表わし、ｑは０または１を表わす。Ｍ⁺は、水素イオン、アルカリ金属イオン、または第４級アンモニウムイオンを表わす。）で示される架橋構造は、一般式（１０）

（式中、Ｂ¹は、−（ＣＨ₂）_p−（Ｏ）_q−（ＣＨ₂）_r−を表わし、ｐおよびｒは、それぞれ独立して、０または１〜３の整数を表わし、ｑは０または１を表わす。Ｍ⁺は、水素イオン、アルカリ金属イオン、または第４級アンモニウムイオンを表わす。）で示される化学構造を有する自己ドープ型導電性高分子を分子間で脱水縮合することにより製造することができる。 General formula (6)

(In the formula, B ¹ represents — (CH ₂ ) _p — (O) _q — (CH ₂ ) _r —, p and r each independently represents an integer of 0 or 1 to 3, Represents 0 or 1. M ⁺ represents a hydrogen ion, an alkali metal ion, or a quaternary ammonium ion.) The crosslinked structure represented by the general formula (10)

(In the formula, B ¹ represents — (CH ₂ ) _p — (O) _q — (CH ₂ ) _r —, p and r each independently represents an integer of 0 or 1 to 3, Represents 0 or 1. M ⁺ represents a hydrogen ion, an alkali metal ion, or a quaternary ammonium ion.) Dehydration condensation between molecules of a self-doped conductive polymer having a chemical structure represented by Can be manufactured.

（式中、Ｂ¹は、−（ＣＨ₂）_p−（Ｏ）_q−（ＣＨ₂）_r−を表わし、ｐおよびｒは、それぞれ独立して、０または１〜３の整数を表わし、ｑは０または１を表わす。Ｍ⁺は、水素イオン、アルカリ金属イオン、または第４級アンモニウムイオンを表わす。）で示されるモノマーを（共）重合させた自己ドープ型導電性高分子を分子間で脱水縮合することにより製造することができる。 Furthermore, the crosslinked structure represented by the general formula (6) is represented by the general formula (11).

(In the formula, B ¹ represents — (CH ₂ ) _p — (O) _q — (CH ₂ ) _r —, p and r each independently represents an integer of 0 or 1 to 3, Represents 0 or 1. M ⁺ represents a hydrogen ion, an alkali metal ion, or a quaternary ammonium ion.) A self-doped conductive polymer obtained by (co) polymerizing a monomer represented by It can be produced by dehydration condensation.

The repeating unit of the chemical structure containing a sulfonic acid group in the (co) polymer is usually in the range of 100 mol% to 50 mol%, preferably 100 mol% to 80 mol% of all repeating units of the (co) polymer. And may be a (co) polymer containing repeating units composed of other π-conjugated chemical structures, or a (co) polymer composition consisting of 2 to 5 repeating units.
In the present invention, the “(co) polymer containing repeating units” is not necessarily limited to the (co) polymer containing the units continuously, and has a desired conductivity based on the π-conjugated main chain. As long as it is expressed, it also includes (co) polymers containing random and discontinuous repeating units in the π-conjugated main chain as in random copolymers.

  Preferable specific examples of the chemical structure represented by the general formula (7) include 5-sulfoisothianaphthene-1,3-diyl, 4-sulfoisothianaphthene-1,3-diyl, 4-methyl-5-sulfo Isothianaphthene-1,3-diyl, 6-methyl-5-sulfoisothianaphthene-1,3-diyl, 6-methyl-4-sulfoisothianaphthene-1,3-diyl, 5-methyl-4- Sulfoisothianaphthene-1,3-diyl, 6-ethyl-5-sulfoisothianaphthene-1,3-diyl, 6-propyl-5-sulfoisothianaphthene-1,3-diyl, 6-butyl-5 -Sulfoisothianaphthene-1,3-diyl, 6-hexyl-5-sulfoisothianaphthene-1,3-diyl, 6-decyl-5-sulfoisothianaphthene-1,3-diyl, 6-methoxy- -Sulfoisothianaphthene-1,3-diyl, 6-ethoxy-5-sulfoisothianaphthene-1,3-diyl, 6-chloro-5-sulfoisothianaphthene-1,3-diyl, 6-bromo- 5-sulfoisothianaphthene-1,3-diyl, 6-trifluoromethyl-5-sulfoisothianaphthene-1,3-diyl, 5- (sulfomethane) isothianaphthene-1,3-diyl, 5- ( 2′-sulfoethane) isothianaphthene-1,3-diyl, 5- (2′-sulfoethoxy) isothianaphthene-1,3-diyl, 5- (2 ′-(2 ″ -sulfoethoxy) methane) -Isothianaphthene-1,3-diyl, 5- (2 '-(2 "-sulfoethoxy) ethane) -isothianaphthene-1,3-diyl or the like or lithium salt, sodium salt, a Moniumu salts, methyl ammonium salts, ethyl ammonium salts, dimethyl ammonium salts, diethyl ammonium salts, trimethylammonium salts, triethylammonium salts, tetramethylammonium salts, tetraethylammonium salts and the like.

  Specific preferred examples of the chemical structure represented by the general formula (8) include 5-sulfoisothianaphthene-1,3-diyl, 4-sulfoisothianaphthene-1,3-diyl, 4-methyl-5-sulfo. Isothianaphthene-1,3-diyl, 6-methyl-5-sulfoisothianaphthene-1,3-diyl, 6-methyl-4-sulfoisothianaphthene-1,3-diyl, 5-methyl-4- Sulfoisothianaphthene-1,3-diyl, 6-ethyl-5-sulfoisothianaphthene-1,3-diyl, 6-propyl-5-sulfoisothianaphthene-1,3-diyl, 6-butyl-5 -Sulfoisothianaphthene-1,3-diyl, 6-hexyl-5-sulfoisothianaphthene-1,3-diyl, 6-decyl-5-sulfoisothianaphthene-1,3-diyl, 6-methoxy- -Sulfoisothianaphthene-1,3-diyl, 6-ethoxy-5-sulfoisothianaphthene-1,3-diyl, 6-chloro-5-sulfoisothianaphthene-1,3-diyl, 6-bromo- 5-sulfoisothianaphthene-1,3-diyl, 6-trifluoromethyl-5-sulfoisothianaphthene-1,3-diyl, 5- (sulfomethane) isothianaphthene-1,3-diyl, 5- ( 2′-sulfoethane) isothianaphthene-1,3-diyl, 5- (2′-sulfoethoxy) isothianaphthene-1,3-diyl, 5- (2 ′-(2 ″ -sulfoethoxy) methane) -Isothianaphthene-1,3-diyl, 5- (2 '-(2 "-sulfoethoxy) ethane) -isothianaphthene-1,3-diyl or the like, or lithium salts, sodium salts, ammonia Salt, methylammonium salt, ethylammonium salt, dimethylammonium salt, diethylammonium salt, trimethylammonium salt, triethylammonium salt, tetramethylammonium salt, tetraethylammonium salt, etc., or isothianaphthene-1,3-diyl, 4- Methyl-isothianaphthene-1,3-diyl, 5-methyl-isothianaphthene-1,3-diyl, 4,5-dimethyl-isothianaphthene-1,3-diyl, 5,6-dimethyl-isothia Naphthene-1,3-diyl, 4,5-dimethoxy-isothianaphthene-1,3-diyl, 5,6-dimethoxy-isothianaphthene-1,3-diyl, 4-ethyl-isothianaphthene-1, 3-diyl, 5-ethyl-isothianaphthene-1,3-diyl, 4,5-diethyl-i Thianaphthene-1,3-diyl, 5,6-diethyl-isothianaphthene-1,3-diyl, 4,5-diethoxy-isothianaphthene-1,3-diyl, 5,6-diethoxy-isothianaphthene- 1,3-diyl, 4-propyl-isothianaphthene-1,3-diyl, 5-propyl-isothianaphthene-1,3-diyl, 4,5-diethyl-isothianaphthene-1,3-diyl, 5,6-dipropyl-isothianaphthene-1,3-diyl, 4-butyl-isothianaphthene-1,3-diyl, 5-butyl-isothianaphthene-1,3-diyl, 5-hexyl-isothia Naphthene-1,3-diyl, 5-decyl-isothianaphthene-1,3-diyl, 5-methoxy-isothianaphthene-1,3-diyl, 5-ethoxy-isothianaphthene-1,3- And diyl, 5-chloro-isothianaphthene-1,3-diyl, 5-bromo-isothianaphthene-1,3-diyl, 5-trifluoromethyl-isothianaphthene-1,3-diyl, and the like. it can.

  Preferable specific examples of the chemical structure represented by the general formula (9) include 1,3-dihydroisothianaphthene-5-sulfonic acid, 1,3-dihydroisothianaphthene-4-sulfonic acid, 4-methyl-1 , 3-Dihydroisothianaphthene-5-sulfonic acid, 4-methyl-1,3-dihydroisothianaphthene-5-sulfonic acid, 6-methyl-1,3-dihydroisothianaphthene-5-sulfonic acid, 5 -Methyl-1,3-dihydroisothianaphthene-4-sulfonic acid, 6-methyl-1,3-dihydroisothianaphthene-4-sulfonic acid, 6-ethyl-1,3-dihydroisothianaphthene-5 Sulfonic acid, 6-propyl-1,3-dihydroisothianaphthene-5-sulfonic acid, 6-butyl-1,3-dihydroisothianaphthene-5-sulfonic acid, 6-hexyl 1,3-dihydroisothianaphthene-5-sulfonic acid, 6-decyl-1,3-dihydroisothianaphthene-5-sulfonic acid, 6-methoxy-1,3-dihydroisothianaphthene-5-sulfonic acid, 6-ethoxy-1,3-dihydroisothianaphthene-5-sulfonic acid, 6-chloro-1,3-dihydroisothianaphthene-5-sulfonic acid, 6-bromo-1,3-dihydroisothianaphthene-5 -Sulfonic acid, 6-trifluoromethyl-1,3-dihydroisothianaphthene-5-sulfonic acid, 1,3-dihydroisothianaphthene-5-methanesulfonic acid, (1 ', 3'-dihydro-5' -Isothianaphthenyl) methanesulfonic acid, 2- (1 ', 3'-dihydro-5'-isothianaphthenyl) ethanesulfonic acid, (2- (1', 3'-dihydro-) '-Isothianaphthenyl) ethyloxy) methanesulfonic acid or the like or lithium salt, sodium salt, ammonium salt, methylammonium salt, ethylammonium salt, dimethylammonium salt, diethylammonium salt, trimethylammonium salt, triethylammonium salt, tetramethyl Examples thereof include ammonium salts and tetraethylammonium salts.

  Preferred specific examples of the chemical structure represented by the general formula (10) include 3-sulfothiophene-2,5-diyl, 3-sulfomethylthiophene-2,5-diyl, 3- (2′-sulfoethyl) thiophene— 2,5-diyl, 3- (3′-sulfopropyl) thiophene-2,5-diyl, 3- (4′-sulfobutyl) thiophene-2,5-diyl, 3- (5′-sulfopentyl) thiophene— 2,5-diyl, 3- (6′-sulfohexyl) thiophene-2,5-diyl, 3- (7′-sulfoheptyl) thiophene-2,5-diyl, 3- (8′-sulfooctyl) thiophene -2,5-diyl, 3- (9'-sulfononyl) thiophene-2,5-diyl, 3- (10'-sulfodecyl) thiophene-2,5-diyl, 3- (2'-sulfoethyloxy) ) Thiophene-2,5-diyl, 3- (3′-sulfopropoxy) thiophen-2,5-diyl, 3- (4′-sulfobutoxy) thiophene-2,5-diyl, 3- (5′-sulfo) Pentyloxy) thiophene-2,5-diyl, 3- (6′-sulfohexyloxy) thiophene-2,5-diyl, 3- (7′-sulfoheptyloxy) thiophene-2,5-diyl, 3- ( 8'-sulfooctyloxy) thiophene-2,5-diyl, 3- (9'-sulfononyloxy) thiophene-2,5-diyl, 3- (10'-sulfodecyloxy) thiophene-2,5-diyl 3-sulfopyrrole-2,5-diyl, 3-sulfomethylpyrrole-2,5-diyl, 3- (2′-sulfoethyl) pyrrole-2,5-diyl, 3- (3′-sulfopropyl) Pyll) pyrrole-2,5-diyl, 3- (4′-sulfobutyl) pyrrole-2,5-diyl, 3- (5′-sulfopentyl) pyrrole-2,5-diyl, 3- (6′-sulfo) (Hexyl) pyrrole-2,5-diyl, 3- (7′-sulfoheptyl) pyrrole-2,5-diyl, 3- (8′-sulfooctyl) pyrrole-2,5-diyl, 3- (9′- Sulfononyl) pyrrole-2,5-diyl, 3- (10′-sulfodecyl) pyrrole-2,5-diyl or the like, or a lithium salt, sodium salt, ammonium salt, methylammonium salt, ethylammonium salt, dimethylammonium salt, Examples include diethylammonium salt, trimethylammonium salt, triethylammonium salt, tetramethylammonium salt, and tetraethylammonium salt. I can make it.

Preferable specific examples of the chemical structure represented by the general formula (10) include 3-thienylsulfonic acid, 3-thienylmethanesulfonic acid, 2- (3′-thienyl) ethanesulfonic acid, and 3- (3′-thienyl). ) Propanesulfonic acid, 4- (3′-thienyl) butanesulfonic acid, 5- (3′-thienyl) pentanesulfonic acid, 6- (3′-thienyl) hexanesulfonic acid, 7- (3′-thienyl) heptane Sulfonic acid, 8- (3′-thienyl) octanesulfonic acid, 9- (3′-thienyl) nonanesulfonic acid, 10- (3′-thienyl) decanesulfonic acid, 2- (3′-thienyl) oxyethanesulfone Acid, 3- (3′-thienyl) oxypropanesulfonic acid, 4- (3′-thienyl) oxybutanesulfonic acid, 5- (3′-thienyl) oxypentanesulfonic acid, 6- (3′- Enyl) oxyhexanesulfonic acid, 7- (3′-thienyl) oxyheptanesulfonic acid, 8- (3′-thienyl) oxyoctanesulfonic acid, 9- (3′-thienyl) oxynonanesulfonic acid, 10- (3 '-Thienyl) oxydecanesulfonic acid or the like, or lithium salt, sodium salt, ammonium salt, methylammonium salt, ethylammonium salt, dimethylammonium salt, diethylammonium salt, trimethylammonium salt, triethylammonium salt, tetramethylammonium salt, Examples thereof include tetraethylammonium salt.
Specific examples other than the formulas (1) to (6) include poly (carbazole-N-alkanesulfonic acid), poly (phenylene-oxyalkanesulfonic acid), poly (phenylene vinylene-alkanesulfonic acid), poly ( Phenylenevinylene-oxyalkanesulfonic acid), poly (anilinealkanesulfonic acid), poly (anilinethioalkanesulfonic acid), poly (aniline-N-alkanesulfonic acid), or substituted derivatives thereof, 6-sulfonaphtho [2,3 -C] A structure crosslinked with a sulfone bond of a self-doped conductive polymer represented by thiophene-1,3-diyl can be given.

  The molecular weight of a self-doped conductive polymer having an isothianaphthene skeleton or thiophene skeleton used for the production of a self-doped conductive polymer crosslinked between polymer chains in a preferred embodiment of the present invention is a constituent repeat Since it differs depending on the chemical structure of the unit, it cannot be defined unconditionally, but it is not particularly limited as long as it meets the object of the present invention. When expressed by the number of repeating units (polymerization degree) constituting the main chain, those having a polymerization degree in the range of 5 to 2000, preferably 10 to 1000 are usually mentioned.

The chemical structure represented by the general formula (7) and / or the general formula (8) used for the production of the self-doped conductive polymer represented by the general formula (2) or the general formula (3) of the present invention. As a particularly preferred specific example of a self-doped conductive polymer containing a thianaphthene skeleton,
i) a polymer of 5-sulfoisothianaphthene-1,3-diyl which is an example of a chemical structure represented by the general formula (7), and / or a lithium salt, a sodium salt, an ammonium salt, a triethylammonium salt,
ii) A random copolymer containing at least 80 mol% of 5-sulfoisothianaphthene-1,3-diyl, which is an example of the chemical structure represented by the general formula (7), poly (5-sulfoisothianaphthene-1,3) -Diyl-co-isothianaphthene-1,3-diyl) and / or its lithium salt, sodium salt, ammonium salt, triethylammonium salt,
Etc.

Self-doped conductivity including a thiophene skeleton having a chemical structure represented by the general formula (10) used for the production of the self-doped conductive polymer represented by the general formula (5) or the general formula (6) of the present invention As particularly preferred specific examples of the conducting polymer,
i) A polymer of 3- (2′-sulfoethyl) thiophene-2,5-diyl which is an example of a chemical structure represented by the general formula (10), and / or its lithium salt, sodium salt, ammonium salt, triethylammonium salt,
ii) A polymer of 3- (3′-sulfopropyl) thiophene-2,5-diyl which is an example of a chemical structure represented by the general formula (10), and / or its lithium salt, sodium salt, ammonium salt, triethyl Ammonium salt,
Etc.

The crosslinked self-doped conductive polymer having an isothianaphthene skeleton represented by general formula (2) or general formula (3) in the present invention is represented by general formula (7) and / or general formula (8). The self-doped conductive polymer sulfonic acid is produced by a dehydration condensation reaction between molecules or molecular chains.
The crosslinked self-doped conductive polymer having a thiophene skeleton represented by the general formula (5) or the general formula (6) in the present invention is a self-doped conductive polymer represented by the general formula (10). Is produced by a dehydration condensation reaction between molecules or between molecular chains.

  The conductive polymer obtained by heat-treating the self-doped conductive polymer represented by the general formula (7) and / or the general formula (8) or the general formula (10) of the present invention includes a sulfone bond. And an isothianaphthene skeleton crosslinked with a sulfone bond represented by the general formula (2) or the general formula (3), or a thiophene skeleton represented by the general formula (5) or the general formula (6). This is because when the coating film formed on the substrate is analyzed by X-ray photoelectron spectroscopy (hereinafter abbreviated as XPS), the peak based on the S2p of the sulfur atom constituting the thiophene ring and the spin 3/2 binding energy, sulfonic acid This is confirmed by the fact that a peak derived from a sulfone bond is newly generated in addition to the peak based on the binding energy of S2p and spin 3/2 of the sulfur atom constituting the group.

The bond energy of the sulfur atom derived from the sulfone bond has an intermediate bond energy between the sulfur atom constituting the thiophene ring and the sulfur atom constituting the sulfonic acid group. More specifically, it has a peak at a position 0.5 eV to 2 eV lower than the S2p and spin 3/2 binding energy of the sulfur atom constituting the sulfonic acid group. When the difference between the bond energy of the sulfur atom derived from the sulfone bond and the bond energy of the sulfur atom constituting the sulfonic acid group is 0.5 eV to 1 eV, the individual bond energy peaks are integrated into a broad half-width peak. Each peak can be separated by peak fitting.
The self-doped conductive polymer crosslinked between polymer chains in the present invention is preferably a conductor or a conductive composition in which a peak derived from a sulfone bond is detected by XPS analysis, more preferably strength. A conductor or conductive composition having an intensity ratio in the range of ratio = peak intensity based on the presence of a sulfone bond / peak intensity based on the presence of a sulfur atom constituting the sulfonic acid in the range of 0.1 to 10. The intensity ratio is particularly preferably in the range of 0.5-10.
The molar content of the crosslinked structure in the present invention can be calculated from the peak intensity ratio based on the S2p and spin 3/2 binding energy of the sulfur atom obtained by analysis by XPS. That is,
[(Peak intensity based on the presence of a sulfone bond) / {(peak intensity based on the presence of a sulfone bond) + (peak intensity based on the presence of a sulfur atom constituting the sulfonic acid)}] × 100
Given by.

  The self-doped conductive polymer having a crosslinked structure represented by the general formula (2) in the present invention is a self-doped conductive polymer having a chemical structure represented by the general formula (7) and / or the general formula (8). It is preferably obtained by heating the molecule. In particular, after a conductive composition containing a self-doped conductive polymer having a chemical structure represented by the general formula (7) and / or the general formula (8) is applied to the surface of the substrate to form a film, It is preferable to manufacture by performing a heat treatment for 1 second to 120 minutes within a temperature range of 210 ° C to 350 ° C. The temperature range is preferably 250 to 300 ° C., and the heating time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes. When the heating temperature is less than 210 ° C, solvent resistance, particularly water resistance is difficult to obtain, and when it exceeds 350 ° C, the conductivity tends to decrease. If the heating time is too short, the solvent resistance tends to decrease, and if it is too long, the conductivity decreases.

  The self-doped conductive polymer having a crosslinked structure represented by the general formula (6) in the present invention is obtained by heating the self-doped conductive polymer having a chemical structure represented by the general formula (10). Is preferred. In particular, after a conductive composition containing a self-doped conductive polymer having a chemical structure represented by the general formula (10) is applied to the surface of the substrate to form a film, the substrate is within a temperature range of 120 to 250 ° C. In this case, it is preferable to carry out the heat treatment for 1 second to 60 minutes, preferably 10 seconds to 60 minutes. A more preferable temperature range is 150 to 200 ° C. When the heating temperature is less than 120 ° C, the solvent resistance or the like tends to be lowered, and when it exceeds 250 ° C, the conductivity tends to be lowered. If the heating time is too short, the solvent resistance tends to be lowered, and if it is too long, the conductivity tends to be lowered.

  In addition, when forming a crosslinked structure by heat processing, the drying process of a solvent and a crosslinking reaction can be distinguished and implemented. That is, once the solvent is volatilized at a temperature lower than the temperature at which the crosslinking reaction proceeds and higher than the temperature at which the solvent used volatilizes, the mixture is heated at a temperature higher than the temperature at which the crosslinking reaction proceeds. It may be manufactured. This method is more preferable because the adhesiveness to the dielectric coating is improved by passing through a solvent drying process. More specifically, it cannot be defined unconditionally because it differs depending on the structure of the self-doped conductive polymer that serves as a precursor, but it has a chemical structure represented by the general formula (7) and / or the general formula (8). When heating a dope-type conductive polymer, it is preferable to implement a heat-drying process at 40 to 210 degreeC. In addition, heat drying can be implemented within the range of 1 minute-120 minutes. In the case where the self-doped conductive polymer having the chemical structure represented by the general formula (10) is heated, the heat drying process is preferably performed at 40 ° C. to less than 120 ° C. In addition, heat drying can be implemented within the range of 1 minute-120 minutes.

According to the preferable method of the present invention, the influence of deterioration due to oxygen oxidation is not recognized even in the heat treatment in the air, and the heat treatment in the air can be carried out without any problem. The formation of the sulfone bond by heating is basically not affected by the atmosphere because of the dehydration condensation reaction, and can be carried out in an inert gas atmosphere.
A heating method for obtaining a self-doped conductive polymer having a crosslinked structure is as follows: a self-doped conductive polymer having a chemical structure of the general formula (7), (8) or (10) that is not crosslinked is formed on a substrate. After coating, there are a method of heating with a hot plate and a method of heating the entire substrate in an oven, but a method using a hot plate that has good thermal conductivity and can be heated efficiently is preferred.
On the other hand, since the self-doped conductive polymer having a thiophene skeleton represented by the general formula (5) becomes a sulfone crosslinked body at a relatively low temperature, a polymer film, polymer fiber, polymer substrate, polymer resin molded body An antistatic film can be easily formed by heat treatment after coating the surface.

The self-doped conductive polymer cross-linked between the polymer chains of the present invention is most efficiently produced on the substrate surface, but after being applied to the surface of the molded body, it is heated by hot plate heating or oven heating. It is also possible to produce useful conductive coated articles such as sensors and electrodes.
The self-doped conductive polymer having an isothianaphthene skeleton represented by the general formula (2) has very high heat resistance even if it is a thin film. That is, the film thickness of the self-doped conductive polymer having an isothianaphthene skeleton represented by the general formula (2) is preferably in the range of 1 nm to 1000 nm, and particularly preferably 1 nm to 100 nm. In general, when a thin film is heat-treated in air at a high temperature, deterioration due to oxygen oxidation is very easy to proceed. Even if it is a thin film which has a film thickness of -100 nm, the remarkable electroconductive fall is not recognized by the heat processing of the manufacturing method of this invention.

The surface resistance value of the self-doped conductive polymer having an isothianaphthene skeleton represented by the general formula (2) varies depending on the type of composition, film thickness, heating method, heating temperature, heating time, type of substrate, etc. For this reason, it cannot be specified unconditionally, but it is preferably in the range of 1 × 10 ³ Ω / □ to 5 × 10 ⁹ Ω / □, and more preferably in the range of 1 × 10 ⁴ Ω / □ to 5 × 10 ⁸ Ω / □. A range of 1 × 10 ⁴ Ω / □ to 5 × 10 ⁷ Ω / □ is particularly preferable. The surface resistance value after the heat treatment of the substrate coated with the conductive polymer having the chemical structure represented by the general formula (5) and / or the general formula (6) is the type, film thickness, and heating of the composition. Since it varies depending on the method, heating temperature, heating time, type of substrate, etc., it cannot be specified unconditionally, but the surface resistance value is in the range of 1/10 to 1000 times the initial (before heating) surface resistance value. The surface resistance value is particularly preferably in the range of 1/10 to 100 times.

  Since the self-doped conductive polymer having a thiophene skeleton represented by the general formula (5) is easily formed even by low-temperature heating, it is particularly effective for an organic device in which the presence of water in the thin film causes deterioration. . The film thickness of the self-doped conductive polymer having a thiophene skeleton represented by the general formula (5) is preferably in the range of 1 nm to 1000 nm, particularly preferably 1 nm to 100 nm.

The surface resistance value of the self-doped conductive polymer having a thiophene skeleton represented by the general formula (5) varies depending on the type of composition, film thickness, heating method, heating temperature, heating time, type of substrate, etc. However, it is preferably in the range of 1 × 10 ³ Ω / □ to 5 × 10 ⁹ Ω / □, and preferably in the range of 1 × 10 ⁴ Ω / □ to 5 × 10 ⁸ Ω / □. Particularly preferred. The surface resistance value after the heat treatment of the substrate coated with the conductive polymer having the chemical structure represented by the general formula (5) is the kind of the composition, the film thickness, the heating method, the heating temperature, the heating time, Since it differs depending on the type of the substrate, etc., it cannot be specified unconditionally, but it is preferable that the surface resistance value is in the range of 1/10 to 1000 times the initial (before heating) surface resistance value. A surface resistance value in the range of 100 times is particularly preferable.

  The self-doped conductive polymer having an isothianaphthene skeleton represented by the general formula (2) and the self-doped conductive polymer having a thiophene skeleton represented by the general formula (5) are usually used alone. However, high electrical conductivity is required, or it has a non-crosslinked chemical structure of general formula (7), (8) or (10) in order to obtain a solvent resistance by sulfone crosslinking at a heating temperature of 200 ° C. or less. By mixing and heating the self-doped conductive polymer, the self-doped conductive polymer in which the general formula (7) or / and (8) or the general formula (10) is mutually sulfone-crosslinked can be obtained. . A preferable heating temperature in producing the two or more kinds of crosslinked self-doped conductive polymers cannot be generally defined by the chemical structure and composition ratio of each self-doped conductive polymer. C. to 300.degree. C. is preferred, and 200.degree. C. to 250.degree. C. is particularly preferred.

  The self-doped conductive polymer, which is a precursor of the self-doped conductive polymer having a cross-link between polymer chains, can be applied to the entire dielectric film or any part of the cathode part. it can. An example of impregnating the entire cathode forming portion is shown in FIG. In FIG. 7, the cathode formation of the aluminum conversion foil separated by the insulating material (masking) (11) for insulating and separating the anode formation portion (10) of the aluminum conversion foil and the cathode formation portion (13) of the aluminum conversion foil. The whole part (13) is a conductive polymer coating area (12) crosslinked between polymer chains. Furthermore, after applying to at least a part of the dielectric film on the cathode side adjacent to the insulating material that insulates and separates the anode part and the cathode part in the valve action metal having fine holes, It can also be used by crosslinking between polymer chains. An example of partial coating of the cathode forming portion is shown in FIG. In FIG. 6, at least a portion of the dielectric film on the cathode side adjacent to the insulating material (11) that insulates and separates the anode forming portion (10) and the cathode forming portion (13) is provided between polymer chains. It has the application area | region (12) of the conductive polymer bridge | crosslinked by. The present inventors have found that the insulating material penetrates into the porous layer, but the self-doped conductive polymer having a bridge between the polymer chains selectively penetrates and fills in the remaining defective portion. Or by preventing water from passing through an aqueous solution containing an oxidant caused by a defective portion of the insulating material due to water repellency and water resistance of the self-doped conductive polymer having a bridge between the penetrating polymer chains. It has been found that by preventing penetration into the portion, the conductive polymer can be prevented from forming the second solid electrolyte layer in the vicinity of the anode or in the anode portion. In this case, since a conductive path between the anode part and the cathode part through the defective part of the insulating material is not formed, short circuit failure is eliminated and leakage current is reduced.

  The self-doped conductive polymer used as a precursor of the self-doped conductive polymer having a bridge between polymer chains used in the present invention is applied in a state where the surface of the insulating material is overlapped. It is preferable. Thus, the porous layer penetrates along the insulating material, reaches the defective portion of the insulating material, and is applied. When there is a sufficient amount of solid content with respect to the defective portion, hole filling is performed. Even if it is insufficient, the penetration of an aqueous solution containing an oxidizing agent can be prevented by the water repellent effect of the self-doped conductive polymer having a cross-link between polymer chains.

The width of applying the self-doped conductive polymer that is a precursor of the self-doped conductive polymer having a cross-link between the polymer chains is within the range of the anode substrate (1) where the porous layer exists. A dielectric film (2) is usually formed on the surface of the substrate (1). A solid semiconductor layer (4) is formed on the outside by applying a self-doped conductive polymer serving as a precursor of a self-doped conductive polymer having a bridge between polymer chains as an opposing electrode. Usually, in order to ensure insulation between the solid electrolyte (4) (cathode portion) and the anode substrate (1), a masking layer (3) made of an insulating material is provided, and the solid electrolytic capacitor of the present invention is provided. (Element) is produced. Cathode-side dielectric adjacent to insulating material of capacitor (element) having masking layer (3) made of insulating material formed to insulate and separate anode and cathode in valve metal having fine holes It is preferable to form a self-doped conductive polymer having a bridge between polymer chains on at least a part of the film. That is, for example, a self-doped conductive polymer that can be a precursor of a self-doped conductive polymer having an arbitrary width and a bridge between polymer chains over any part or all of the circumference of the dielectric film. It is preferred that the molecules be applied circumferentially. In this case, for example, referring to the embodiment corresponding to FIG. 6, in the case of a rectangular thin plate capacitor element, as shown in FIG. 5A, a self-doped type is formed on the cathode side along the masking layer (3). A first solid electrolyte layer (4a) made of a conductive polymer can be provided, and a second solid electrolyte layer (4b) can be further provided thereon by a method described later. As shown in FIG. 5B (a cross-sectional view taken along the longitudinal direction of the rectangular member in FIG. 5A), typically, the first solid electrolyte layer (4a) is formed with a masking layer (4a). 3) is provided so as to partially overlap. The second solid electrolyte layer (4b) is also typically provided so as to partially overlap the first solid electrolyte layer (4a). Note that these overlapping widths may generally be not less than 0 and not more than the coating width of the lower layer. Here, the method of applying the first solid electrolyte layer (4a) is not particularly limited. The material may be transferred to a transfer means (for example, a thin blade) having an appropriate width and pressed against the corresponding part, or a printing method such as brushing or ink jet may be used. These methods can be arbitrarily changed according to the purpose. For example, in the case of transfer printing, it may be transferred to the periphery of the disk-shaped member instead of the blade, and further transferred again to the vicinity of the masking layer (3). In the embodiment corresponding to FIG. 7, the first solid electrolyte layer (4a) may be formed by dipping in the same manner as the second solid electrolyte layer (4b) described later.
The width for applying the self-doped conductive polymer that is a precursor of the self-doped conductive polymer having a bridge between the polymer chains is usually within a range of 0.1 to 10 times the width of the insulating material. In addition, 0.1 to 3 times is more preferable, and 0.5 to 2 times is particularly preferable. The width does not necessarily have to be constant as long as it does not reach the anode side adjacent to the opposite side of the insulating material. In addition, the coating method is not limited to the circumferential shape, when the amount of the self-doped conductive polymer to be a precursor of the self-doped conductive polymer having a bridge between polymer chains is large, Even when the coating is applied from both sides, the same effect as the circumferential shape can be obtained.

The amount of the self-doped conductive polymer to be applied as a precursor of the self-doped conductive polymer having a cross-link between the polymer chains varies depending on the surface area of the dielectric of the porous layer, but cannot be specified unconditionally. preferably it is applied in the range of 0.01 to 50 mg / cm ^2, and more preferably applied in the range of 0.1 to 10 mg / cm ^2.

  The concentration of the solution containing the self-doped conductive polymer that is a precursor of the self-doped conductive polymer having a cross-link between polymer chains depends on the chemical structure of the self-doped conductive polymer that is the precursor, the solvent However, 0.01 to 10% by mass is preferable, and 0.1 to 5% by mass is more preferable. In general, the masking layer (3) penetrates into the dielectric film (2) as schematically shown in FIG. 5B, but the first solid electrolyte layer (4a) also exceeds this penetration portion. It is preferable that it penetrates within a range. The concentration of the solution containing the self-doped conductive polymer serving as the precursor is preferably 0.01% by mass or more in order to sufficiently exhibit the water-repellent effect and prevent the penetration of the aqueous solution containing the oxidizing agent. . On the other hand, when the amount exceeds 10% by mass, the solution viscosity may increase, and thus there is a possibility that the solution cannot enter a minute defect portion in the porous layer.

Hereinafter, a method for forming the second solid electrolyte layer will be described.
The second method for forming a solid electrolyte in the present invention includes a step of immersing a valve metal porous substrate in an oxidant solution and then drying to gradually increase the oxidant solution concentration on the substrate. Based on chemical oxidative polymerization. In the chemical oxidative polymerization method of the present invention, a monomer is deposited on the dielectric film having fine pores of the anode substrate, and oxidative polymerization is caused in the presence of a compound that can be a dopant of the conductive polymer. A composition is formed on the dielectric surface as the solid electrolyte.

  The solid electrolyte layer of the conductive polymer formed by the method of the present invention has a fibril structure or a lamellar (thin layered) structure, and in such a structure, there is a wide overlap between polymer chains. In the present invention, the total thickness of the solid electrolyte layer is in the range of about 10 to about 100 μm, the space of the layer structure of the polymer is 0.01 to 5 μm, preferably 0.05 to 3 μm, more preferably 0.1 to 2 μm, By setting the space occupancy ratio between the layers of the solid electrolyte in the entire polymer film within the range of 0.1 to 20%, the electron hopping between polymer chains is facilitated, the electrical conductivity is improved, and the characteristics such as low impedance are improved. I found out.

The step 2 of drying after being immersed in the solution containing the monomer in the present invention is carried out in order to supply the monomer on the dielectric surface and on the polymer composition. Further, in order to uniformly deposit the monomer on the dielectric surface and the polymer composition, after impregnating the monomer-containing liquid, the solvent is allowed to evaporate by being left in the air for a certain period of time. This condition varies depending on the type of solvent, but is generally performed at a temperature from 0 ° C. or higher to the boiling point of the solvent. The standing time varies depending on the type of the solvent, but it is generally about 5 seconds to 15 minutes, for example, within 5 minutes for alcohol solvents. By providing this standing time, the monomer can uniformly adhere to the surface of the dielectric, and contamination during immersion in the oxidizing agent-containing liquid in the next step can be reduced.
The monomer supply can be controlled by the type of solvent used in the solution containing the monomer, the concentration of the monomer-containing liquid, the solution temperature, the immersion time, and the like.

The immersion time applied in step 2 may be a time sufficient for the monomer component in the contained liquid to adhere to the dielectric surface of the metal foil substrate, and is usually less than 15 minutes, preferably 0.1 Second to 10 minutes, more preferably 1 second to 7 minutes.
Moreover, -10-60 degreeC is preferable and, as for immersion temperature, 0-40 degreeC is especially preferable. If it is less than -10 degreeC, it may take time for a solvent to volatilize and reaction time may become long. If it exceeds 60 ° C., volatilization of the solvent and monomer cannot be ignored, and concentration control is difficult.
The concentration of the monomer-containing liquid is not particularly limited, and an arbitrary concentration can be used, but it is preferably 3 to 70% by mass, and more preferably 25 to 25%, which is excellent in impregnation into the fine pores of the valve action metal. Used at 45% by weight.

  Examples of the solvent of the solution used in Step 2 include ethers such as tetrahydrofuran (THF), dioxane, and diethyl ether; ketones such as acetone and methyl ethyl ketone; dimethylformamide, acetonitrile, benzonitrile, and N-methylpyrrolidinone (NMP). Aprotic polar solvents such as dimethyl sulfoxide (DMSO); esters such as ethyl acetate and butyl acetate; non-aromatic chlorinated solvents such as chloroform and methylene chloride; nitro compounds such as nitromethane, nitroethane, and nitrobenzene; methanol Further, alcohols such as ethanol and propanol, water, or a mixed solvent thereof can be used. Preferably, alcohols or ketones or a mixed system thereof is desirable.

In the present invention, the monomer is oxidatively polymerized by immersing in an oxidant-containing solution and maintaining in air in a predetermined temperature range for a predetermined time in step 3. A method mainly comprising oxidative polymerization held in The temperature maintained in air varies depending on the type of monomer, but may be, for example, 5 ° C. or lower for pyrrole and about 30 to 60 ° C. for thiophene.
The polymerization time depends on the amount of monomer attached during immersion. The amount of adhesion varies depending on the concentration and viscosity of the monomer and oxidant-containing liquid, and thus cannot be specified in general. Longer polymerization times are required. In the method of the present invention, one polymerization time is 10 seconds to 30 minutes, preferably 3 to 15 minutes.

The immersion time applied as step 3 may be a time sufficient for the oxidant component to adhere to the dielectric surface of the metal foil substrate, and is usually a time of less than 15 minutes, preferably 0.1 seconds to 10 seconds. Minute, more preferably 1 second to 7 minutes.
Examples of the oxidizing agent used in Step 3 include an aqueous oxidizing agent and an organic solvent oxidizing agent. Examples of the aqueous oxidizing agent preferably used in the present invention include peroxodisulfuric acid and its Na salt, K salt, NH ₄ salt, cerium (IV) nitrate, cerium (IV) ammonium nitrate, iron (III) sulfate, nitric acid Examples thereof include iron (III) and iron (III) chloride. Examples of the organic solvent-based oxidizing agent include ferric salts of organic sulfonic acids such as iron (III) dodecylbenzenesulfonate and iron (III) p-toluenesulfonate.
Examples of the solvent of the solution used in Step 3 of the present invention include ethers such as tetrahydrofuran (THF), dioxane, and diethyl ether; ketones such as acetone and methyl ethyl ketone; dimethylformamide, acetonitrile, benzonitrile, N-methylpyrrolidinone ( NMP), aprotic polar solvents such as dimethyl sulfoxide (DMSO); alcohols such as methanol, ethanol, propanol, water, or a mixed solvent thereof can be used. Preferably, water, alcohols or ketones or a mixed system thereof is desirable.
The concentration of the oxidant solution is preferably 5 to 50% by mass, and the temperature of the oxidant solution is preferably −15 to 60 ° C.

In step 3, a suspension containing organic fine particles is more preferably used. The organic fine particles remain on the dielectric surface or the polymer composition, and thus are effective for assisting the supply of the oxidant and the monomer to the smooth polymer film surface filled with the polymer film in the pores. In particular, after forming the solid electrolyte layer by using soluble organic fine particles, the soluble organic fine particles can be dissolved and removed, and the reliability of the capacitor element can be improved.
Solvents used in the process of dissolving and removing the organic fine particles include water; alcohols such as methanol, ethanol and propanol; ketones such as acetone and methyl ethyl ketone; and non- solvents such as dimethylformamide, N-methyl-2-pyrrolidinone and dimethyl sulfoxide. A protic polar solvent is used, but water, alcohols, or a mixed solvent thereof is preferable, and a solvent that also dissolves the oxidizing agent is more preferable because it can be performed simultaneously with removal of the oxidizing agent.

Soluble inorganic fine particles that can be removed by using a strong acid are not preferable because they cause damage such as dissolution or corrosion of the dielectric film on the surface of the valve metal.
The soluble organic fine particles preferably have an average particle diameter (D ₅₀ ) in the range of 0.1 to 20 μm, and more preferably 0.5 to 15 μm. If the average particle diameter (D ₅₀ ) of the soluble organic fine particles exceeds 20 μm, the gap formed in the polymerized film becomes large, which is not preferable.
Specific examples of the soluble organic fine particles include an aliphatic sulfonic acid compound, an aromatic sulfonic acid compound, an aliphatic carboxylic acid compound, an aromatic carboxylic acid compound, a peptide compound, and / or a salt thereof. Acid compounds, aromatic carboxylic acid compounds, and peptide compounds are preferably used.

  More specifically, aromatic sulfonic acid compounds include benzene sulfonic acid, toluene sulfonic acid, naphthalene sulfonic acid, anthracene sulfonic acid, anthraquinone sulfonic acid and / or salt thereof, and more specifically, aromatic carboxylic acid compounds include benzoic acid. More specific examples of the acid, toluene carboxylic acid, naphthalene carboxylic acid, anthracene carboxylic acid, anthraquinone carboxylic acid or / and salts thereof, and peptide compounds include surfactin, iturin, prepastatin, and serauchen.

In the method of the present invention, it is necessary to control the number of impregnations so that the conductive polymer composition to be formed has a thickness resistant to humidity, heat, stress, and the like.
One of the preferable formation steps of the second solid electrolyte according to the present invention is a method in which the steps 2 and 3 are repeated as one cycle. A desired solid electrolyte layer can be formed by repeating the cycle three times or more, preferably 8 to 30 times, for one anode substrate. Step 2 and step 3 may be performed in reverse order.

  According to the present invention, an aluminum foil having a dielectric oxide film is impregnated, for example, in an isopropyl alcohol (IPA) solution of 3,4-ethylenedioxythiophene (EDT), as shown in the following examples. After substantially drying IPA to remove IPA, impregnation with about 20% by mass of an oxidizing agent (ammonium persulfate) aqueous solution, followed by heating at about 40 ° C. for 10 minutes, and by repeating this step, poly (3 , 4-ethylenedioxythiophene) polymer can be obtained.

  The conductive polymer forming the solid electrolyte used in the present invention is a polymer of an organic polymer monomer having a π-electron conjugated structure, preferably a degree of polymerization of 2 or more and 2000 or less, more preferably 3 or more and 1000 or less, and still more preferably. Is 5 or more and 200 or less. As specific examples, a conductive polymer containing a structure represented by a compound having a thiophene skeleton, a compound having a polycyclic sulfide skeleton, a compound having a pyrrole skeleton, a compound having a furan skeleton, a compound having an aniline skeleton, or the like as a repeating unit. Is mentioned.

  Examples of the monomer having a thiophene skeleton include 3-methylthiophene, 3-ethyloffene, 3-propylthiophene, 3-butylthiophene, 3-pentylthiophene, 3-hexylthiophene, 3-heptylthiophene, 3-octylthiophene, 3-nonylthiophene, 3-decylthiophene, 3-fluorothiophene, 3-chlorothiophene, 3-bromothiophene, 3-cyanothiophene, 3,4-dimethylthiophene, 3,4-diethylthiophene, 3,4-butylenethiophene , Derivatives of 3,4-methylenedioxythiophene, 3,4-ethylenedioxythiophene, and the like. These compounds can be prepared by commercially available compounds or by known methods (for example, Synthetic Metals, 1986, Vol. 15, p. 169).

  Specific examples of the monomer having a polycyclic sulfide skeleton include compounds having a 1,3-dihydropolycyclic sulfide (also known as 1,3-dihydrobenzo [c] thiophene) skeleton, 1,3-dihydronaphtho [2,3 -C] A compound having a thiophene skeleton can be used. Furthermore, a compound having a 1,3-dihydroanthra [2,3-c] thiophene skeleton and a compound having a 1,3-dihydronaphthaseno [2,3-c] thiophene skeleton can be given. These can be prepared by a known method, for example, the method described in JP-A-8-3156.

A compound having a 1,3-dihydronaphtho [1,2-c] thiophene skeleton is a 1,3-dihydrophenanthra [2,3-c] thiophene derivative or 1,3-dihydrotriphenylo [2]. , 3-c] thiophene skeleton, 1,3-dihydrobenzo [a] anthraceno [7,8-c] thiophene derivatives and the like can also be used.
A compound optionally containing nitrogen or N-oxide in the condensed ring can also be used, such as 1,3-dihydrothieno [3,4-b] quinoxaline, 1,3-dihydrothieno [3,4-b] quinoxaline- 4-oxide, 1,3-dihydrothieno [3,4-b] quinoxaline-4,9-dioxide and the like can be mentioned.

  Examples of the monomer having a pyrrole skeleton include 3-methylpyrrole, 3-ethylpyrrole, 3-propylpyrrole, 3-butylpyrrole, 3-pentylpyrrole, 3-hexylpyrrole, 3-heptylpyrrole, 3-octylpyrrole, 3-nonylpyrrole, 3-decylpyrrole, 3-fluoropyrrole, 3-chloropyrrole, 3-bromopyrrole, 3-cyanopyrrole, 3,4-dimethylpyrrole, 3,4-diethylpyrrole, 3,4-butylenepyrrole , Derivatives of 3,4-methylenedioxypyrrole, 3,4-ethylenedioxypyrrole, and the like. These compounds can be prepared commercially or by known methods.

Examples of the monomer having a furan skeleton include 3-methylfuran, 3-ethylfuran, 3-propylfuran, 3-butylfuran, 3-pentylfuran, 3-hexylfuran, 3-heptylfuran, 3-octylfuran, 3-nonylfuran, 3-decylfuran, 3-fluorofuran, 3-chlorofuran, 3-bromofuran, 3-cyanofuran, 3,4-dimethylfuran, 3,4-diethylfuran, 3,4-butylenefuran, 3,4 -Derivatives such as methylenedioxyfuran and 3,4-ethylenedioxyfuran can be mentioned. These compounds can be prepared commercially or by known methods.
Examples of the monomer having an aniline skeleton include 2-methylaniline, 2-ethylaniline, 2-propylaniline, 2-butylaniline, 2-pentylaniline, 2-hexylaniline, 2-heptylaniline, 2-octylaniline, 2-nonylaniline, 2-decylaniline, 2-fluoroaniline, 2-chloroaniline, 2-bromoaniline, 2-cyanoaniline, 2,5-dimethylaniline, 2,5-diethylaniline, 2,3-butyleneaniline , Derivatives of 2,3-methylenedioxyaniline, 2,3-ethylenedioxyaniline, and the like. These compounds can be prepared commercially or by known methods.

Among these, compounds having a thiophene skeleton or a polycyclic sulfide skeleton are preferable, and 3,4-ethylenedioxythiophene (EDT) and 1,3-dihydroisothianaphthene are particularly preferable.
There is no restriction | limiting in particular in the polymerization conditions etc. of the compound selected from the said compound group, It can implement easily, after confirming preferable conditions beforehand by simple experiment.
In addition, a compound selected from the above monomer group may be used in combination to form a solid electrolyte as a copolymer. The composition ratio of the polymerizable monomer at that time depends on the polymerization conditions and the like, and the preferred composition ratio and polymerization conditions can be confirmed by a simple test.
For example, a method in which the EDT monomer and the oxidizing agent are preferably applied in the form of a solution and applied separately or together to the oxide film layer of the metal foil can be used (Patent No. 3040113, US Pat. 6229689).

3,4-ethylenedioxythiophene (EDT) preferably used in the present invention dissolves well in the above monohydric alcohol, but is not well-suited with water, so when brought into contact with a high concentration aqueous oxidant solution, In the EDT, polymerization proceeds satisfactorily at the interface, and a conductive polymer solid electrolyte layer having a fibril structure or a lamellar (thin layered) structure is formed.
In the production method of the present invention, as a solvent for washing after formation of the solid electrolyte, for example, ethers such as tetrahydrofuran (THF), dioxane and diethyl ether; ketones such as acetone and methyl ethyl ketone; dimethylformamide, acetonitrile, benzonitrile, N -Aprotic polar solvents such as methylpyrrolidinone (NMP) and dimethyl sulfoxide (DMSO); esters such as ethyl acetate and butyl acetate; non-aromatic chlorinated solvents such as chloroform and methylene chloride; nitromethane, nitroethane, and nitrobenzene Nitro compounds such as: alcohols such as methanol, ethanol, propanol, etc .; organic acids such as formic acid, acetic acid, propionic acid; acid anhydrides of the organic acids (eg, acetic anhydride, etc.) or water or mixed solvents thereof Can do. Preferably, water, alcohols or ketones or a mixed system thereof is desirable.

The electrical conductivity of the solid electrolyte thus produced is in the range of about 0.1 to about 200 S / cm, preferably about 1 to about 150 S / cm, more preferably about 10 to about 100 S / cm. It is.
On the conductive polymer composition layer thus formed, it is preferable to provide a conductor layer in order to improve electrical contact with the cathode lead terminal. The conductor layer is formed by, for example, a conductive paste, plating, vapor deposition, or a conductive resin film.

In the present invention, the conductive layer can be compressed after being formed. For example, in the case of a conductor layer including an elastic body, it can be plastically deformed by compression to make it thinner, and also has an effect of smoothing the surface of the conductor layer.
The solid electrolytic capacitor element thus obtained is usually made into a capacitor product for various applications by connecting lead terminals and applying an exterior such as a resin mold, a resin case, a metal outer case, or a resin dipping.
Further, in the present invention, after the conductor layers are formed, they are laminated, and a lead terminal is connected to the obtained laminated body and sealed to form a laminated solid electrolytic capacitor. In this case, as shown in FIG. 2, one capacitor element may be laminated on each side of the lead portion (lead frame in the embodiment shown in this figure) 7, or a plurality of elements may be bonded with a conductive paste or the like. You may laminate | stack on the single side | surface or both surfaces of a lead part.

The present invention will be described in more detail below with typical examples. Note that these are merely illustrative examples, and the present invention is not limited thereto.
1) Synthesis of self-doped conductive polymer compound:
In the general formula (7), R ^{1 to} R ³ and M are hydrogen atoms, B ¹ is not present, and a sulfonic acid group is directly bonded, a self-doped conductive polymer compound, poly (5-sulfoisothia Naphthene-1,3-diyl) was synthesized with reference to a method disclosed in JP-A-7-48436.
A self-doped conductive polymer compound, poly (3- (3′-sulfopropyl) thiophene-2,5-diyl), in which B ¹ in general formula (10) is propylene and M is a hydrogen atom, is disclosed in The synthesis was carried out with reference to the method described in JP-A-189333.

2) Preparation of conductive composition Conductive composition 1:
7.0 g of 1N ammonia water was added to 100 mL of a 2 mass% aqueous solution of poly (5-sulfoisothianaphthene-1,3-diyl) to adjust the pH to 4.4.
Conductive composition 2:
10.5 g of 1N aqueous ammonia was added to 100 mL of a 3% by mass aqueous solution of poly (5-sulfoisothianaphthene-1,3-diyl) to adjust the pH to 4.3.
Conductive composition 3:
17.5 g of 1N ammonia water was added to 100 mL of a 5 mass% aqueous solution of poly (5-sulfoisothianaphthene-1,3-diyl) to adjust the pH to 4.4.
Conductive composition 4:
To 100 mL of a 1% by mass aqueous solution of poly (3- (3′-sulfopropyl) thiophene-2,5-diyl), 3.1 g of 1N aqueous ammonia was added to adjust the pH to 4.3.
Conductive composition 5:
To 100 mL of a 3 mass% aqueous solution of poly (3- (3′-sulfopropyl) thiophene-2,5-diyl), 9.3 g of 1N aqueous ammonia was added to adjust the pH to 4.0.
Conductive composition 6: prepared by mixing 75 ml of conductive composition 3 and 25 ml of conductive composition 4.
3) pH measurement:
The pH of the self-doped conductive polymer aqueous solution was measured with a glass electrode type hydrogen ion concentration meter pH METER F-13 (manufactured by Horiba, Ltd.).

4) Heat treatment method:
The aluminum chemical conversion foil dipped or coated with the conductive composition was subjected to heat treatment by putting it in an oven type: ACS-A made by ISUZU SEISAKUSHO.
5) X-ray photoelectron spectroscopy (XPS):
XPS was measured using AXIS-Ultra manufactured by KRATOS.
In order to identify the peak positions of various sulfur atoms, a thiophene trimer (terthiophene) is used as a standard sample of sulfur atoms derived from a thiophene ring, and p-toluene is used as a standard sample of sulfur atoms derived from sulfonic acid. Sodium sulfonate was used, and phenylsulfone was used as a standard sample of sulfur atoms derived from sulfone bonds (FIG. 3).
6) Evaluation of water resistance and solvent resistance:
Evaluation of water resistance and solvent resistance was performed as follows.
The aluminum formed foil after heating was put into ultrapure water, acetone, N-methylpyrrolidinone, polyethylene glycol monomethyl ether, and the presence or absence of elution was confirmed after 1 hour.

Example 1:
Cut the aluminum conversion foil in the short axis direction 3.5mm x long axis direction 11mm, and apply the polyimide solution with a width of 1mm on both sides to make the long axis direction into 5mm and 5mm parts, and dry to create masking did. One side (cathode forming part) of this conversion foil of 3.5 mm × 5 mm was formed into a cut part by applying a voltage of 3.8 V with a 10 mass% ammonium adipate aqueous solution to form a dielectric oxide film. Next, the part was impregnated with the conductive composition 1 for 5 seconds and dried at room temperature for 5 minutes. The spectrum of the S2p binding energy obtained by measuring the surface of the dielectric film of the layer having fine pores of the aluminum conversion foil after drying by XPS is shown by a broken line in FIG. Subsequently, a dehydration condensation reaction was performed at 300 ° C. for 15 minutes to advance the crosslinking reaction, thereby forming a self-doped conductive polymer in which the polymer chains were crosslinked on the surface of the dielectric film (Step 1). The molar content of the crosslinked structure determined from FIG. 4 was 30%. The coated part of the aluminum foil was immersed in pure water for 1 hour, but no elution of the self-doped conductive polymer was observed. The spectrum of the binding energy of S2p obtained by measuring the surface of the dielectric film of the layer having fine pores of the aluminum conversion foil after the heat treatment by XPS is shown by a solid line in FIG. Subsequently, a 2.0 mol / L isopropyl alcohol (IPA) solution in which 3,4-ethylenedioxythiophene was dissolved was impregnated for 5 seconds, and this was dried at room temperature for 5 minutes (step 2). Sodium 2-anthraquinonesulfonate (D ₅₀ = 11 μm; measured using a master sizer manufactured by Sysmex Corporation) was immersed in an aqueous 1.5 mol / L ammonium persulfate solution adjusted to 0.07% by mass for 5 seconds. Subsequently, the aluminum foil was left in the atmosphere at 40 ° C. for 10 minutes to carry out oxidative polymerization (step 3). Subsequently, this foil was impregnated with distilled water for 5 seconds, the aluminum foil was taken out, and left in the atmosphere at 40 ° C. for 10 minutes to carry out oxidative polymerization. Furthermore, the solid electrolyte layer of the conductive polymer was formed on the outer surface of the aluminum foil so that the dipping process and the polymerization process were performed 22 times in total. The finally produced poly (3,4-ethylenedioxythiophene) was washed in 50 ° C. warm water, and then dried at 100 ° C. for 30 minutes to form a solid electrolyte layer.

Next, a 3.5 mm × 5 mm portion on which the solid electrolyte layer is formed is immersed in a 15% by mass ammonium adipate solution, and an anode contact is provided on the portion of the valve-acting metal foil where the solid electrolyte layer is not formed. Then, a voltage of 3.8 V was applied to perform re-chemical conversion.
Next, a carbon paste and a silver paste were adhered to the portion where the conductive polymer composition layer of the aluminum foil was formed, two aluminum foils were laminated, and a cathode lead terminal was connected. Moreover, the anode lead terminal was connected to the part in which the conductive polymer composition layer was not formed by welding. Furthermore, after sealing this element with an epoxy resin, a rated voltage (2 V) was applied at 125 ° C. and aging was performed for 2 hours to complete a total of 30 capacitors.
For these 30 capacitor elements, the capacity and loss factor (tan δ × 100 (%)) at 120 Hz, equivalent series resistance (ESR), and leakage current were measured as initial characteristics. The leakage current was measured 1 minute after applying the rated voltage. Table 1 shows the average value of these measured values and the defective rate when a leakage current of 0.002 CV or more is regarded as a defective product. Here, the average value of the leakage current is a value calculated excluding defective products.
Subsequently, 20 non-defective products were soldered by printing a solder paste on a substrate on which copper wiring was applied, mounting the non-defective capacitors thereon, and passing them through a reflow furnace (peak temperature: 250 ° C.). For the capacitor soldered on this substrate, the capacity and loss factor at 120 Hz (tan δ × 100 (%)), equivalent series resistance (ESR), and leakage current were measured. The leakage current was measured 1 minute after applying the rated voltage. Table 2 shows the average value of these measured values and the defective rate when a leakage current of 0.002 CV or more is regarded as a defective product. Here, the average value of the leakage current is a value calculated excluding defective products.

Example 2:
One of the 3.5 mm × 5 mm aluminum conversion foils formed with masking in the same manner as in Example 1 (cathode forming portion) was formed into a cut portion in the same manner as in Example 1 to form a dielectric oxide film. Next, the portion is impregnated with the conductive composition 1 for 5 seconds, dried at room temperature for 5 minutes, and then subjected to a dehydration condensation reaction at 300 ° C. for 15 minutes to cause a crosslinking reaction to proceed on the surface of the dielectric film. A self-doped conductive polymer having cross-linked chains was formed (Step 1). Further, a solid electrolyte was formed in the same manner as in Example 1 except that this operation was repeated once more.
Next, re-chemical conversion, application of carbon paste and silver paste, lamination, connection of cathode lead terminals, sealing with an epoxy resin, and aging operation were carried out in the same manner as in Example 1 to complete a total of 30 capacitors. Tables 1 and 2 show the results of characteristic evaluation performed on the obtained capacitor element in the same manner as in Example 1.

Example 3:
One of the 3.5 mm × 5 mm aluminum conversion foils formed with masking in the same manner as in Example 1 (cathode forming portion) was formed into a cut portion in the same manner as in Example 1 to form a dielectric oxide film. Next, the portion is impregnated with the conductive composition 2 for 5 seconds, dried at room temperature for 5 minutes, and then subjected to a dehydration condensation reaction at 250 ° C. for 30 minutes to advance a crosslinking reaction, thereby causing a polymer film on the surface of the dielectric film. A total of 30 capacitors were completed in the same manner as in Example 1 except that a self-doped conductive polymer having cross-linked chains was formed. Tables 1 and 2 show the results of characteristic evaluation performed on the obtained capacitor element in the same manner as in Example 1.

Example 4:
One of the 3.5 mm × 5 mm aluminum conversion foils formed with masking in the same manner as in Example 1 (cathode forming portion) was formed into a cut portion in the same manner as in Example 1 to form a dielectric oxide film. Next, the conductive composition 3 is impregnated with the conductive composition 3 for 5 seconds, dried at room temperature for 5 minutes, and then subjected to a dehydration condensation reaction at 250 ° C. for 30 minutes to advance the crosslinking reaction, thereby polymerizing the surface of the dielectric film. A total of 30 capacitors were completed in the same manner as in Example 1 except that a self-doped conductive polymer having cross-linked chains was formed. Tables 1 and 2 show the results of characteristic evaluation performed on the obtained capacitor element in the same manner as in Example 1.

Example 5:
One of the 3.5 mm × 5 mm aluminum conversion foils formed with masking in the same manner as in Example 1 (cathode forming portion) was formed into a cut portion in the same manner as in Example 1 to form a dielectric oxide film. Next, the conductive composition 4 is impregnated with the conductive composition 4 for 5 seconds, dried at room temperature for 5 minutes, and then subjected to a dehydration condensation reaction at 200 ° C. for 30 minutes to promote a crosslinking reaction, and the surface of the dielectric film is polymerized. A self-doped conductive polymer having cross-linked chains was formed (Step 1). Further, a total of 30 capacitors were completed in the same manner as in Example 1 except that this operation was repeated once more. Tables 1 and 2 show the results of characteristic evaluation performed on the obtained capacitor element in the same manner as in Example 1.

Example 6:
One of the 3.5 mm × 5 mm aluminum conversion foils formed with masking in the same manner as in Example 1 (cathode forming portion) was formed into a cut portion in the same manner as in Example 1 to form a dielectric oxide film. Next, the conductive composition 5 is impregnated with the conductive composition 5 for 5 seconds, dried at room temperature for 5 minutes, and then subjected to a dehydration condensation reaction at 200 ° C. for 30 minutes to advance the crosslinking reaction, thereby polymer chains on the surface of the dielectric film. A total of 30 capacitors were completed in the same manner as in Example 1 except that a self-doped conductive polymer having a crosslinked structure was formed. Tables 1 and 2 show the results of characteristic evaluation performed on the obtained capacitor element in the same manner as in Example 1.

Example 7:
One of the 3.5 mm × 5 mm aluminum conversion foils formed with masking in the same manner as in Example 1 (cathode forming portion) was formed into a cut portion in the same manner as in Example 1 to form a dielectric oxide film. Next, the conductive composition 6 is impregnated with the conductive composition 6 for 5 seconds, dried at room temperature for 5 minutes, and then subjected to a dehydration condensation reaction at 250 ° C. for 30 minutes so that a crosslinking reaction proceeds, and the surface of the dielectric film is polymerized. A total of 30 capacitors were completed in the same manner as in Example 1 except that a self-doped conductive polymer having cross-linked chains was formed. Tables 1 and 2 show the results of characteristic evaluation performed on the obtained capacitor element in the same manner as in Example 1.

Comparative Example 1
Example 3 Except not applying Step 1 in which a conductive composition 1 is applied and a dehydration condensation reaction is performed on a 3 mm × 4 mm portion of an aluminum foil formed with a dielectric oxide film prepared in the same manner as in Example 1. A total of 30 capacitors were completed in the same manner as in 1. Tables 1 and 2 show the results of characteristic evaluation performed on the obtained capacitor element in the same manner as in Example 1.

Comparative Example 2
Conductivity is obtained by adding 95.0 g of ultrapure water to 5.0 g of poly (2-methoxy-5-sulfo-1,4-iminophenylene) synthesized with reference to the method described in JP-A-7-196791. A composition was obtained.

A 3 mm × 4 mm portion of an aluminum foil formed with a dielectric oxide film prepared in the same manner as in Example 1 was impregnated with the conductive composition for 5 seconds, dried at room temperature for 5 minutes, and then at 300 ° C. for 15 minutes. Heat treatment was performed to remove sulfonic acid groups, and a self-doped conductive polymer insoluble in water was formed on the surface of the dielectric film (step 1). The coated part of the aluminum foil was immersed in pure water for 1 hour, but no elution of the self-doped conductive polymer was observed. Subsequently, steps 2 and 3 were repeated in the same manner as in Example 1 to form a solid electrolyte layer.
Next, re-chemical conversion, application of carbon paste and silver paste, lamination, connection of cathode lead terminals, sealing with an epoxy resin, and aging operation were carried out in the same manner as in Example 1 to complete a total of 30 capacitors. Tables 1 and 2 show the results of characteristic evaluation performed on the obtained capacitor element in the same manner as in Example 1.

Example 8
In Step 1 of Example 1, the conductive composition 1 is 1 mm wide by syringe discharge on one 3.5 mm × 5 mm part (cathode forming part) side adjacent to the masking part of the cut aluminum sheet. 30 mg was applied and dried at room temperature for 5 minutes. After drying at 150 ° C. for 30 minutes, a dehydration condensation reaction is subsequently carried out at 300 ° C. for 30 minutes to advance the crosslinking reaction, and the self-doped conductive polymer having a polymer chain crosslinked on the surface of the dielectric film Formed. Thereafter, a total of 30 capacitors were completed in the same manner as in Example 1. Tables 3 and 4 show the initial characteristics and reflow characteristics of these 30 capacitor elements measured in the same manner as in Example 1.

Example 9
In step 1 of Example 1, the conductive composition 2 is 1 mm wide by syringe discharge on one 3.5 mm × 5 mm portion (cathode forming portion) side adjacent to the masking portion of the cut aluminum sheet. 30 mg was applied and dried at room temperature for 5 minutes. After drying at 150 ° C. for 30 minutes, a dehydration condensation reaction is subsequently carried out at 300 ° C. for 30 minutes to advance the crosslinking reaction, and the self-doped conductive polymer having a polymer chain crosslinked on the surface of the dielectric film Formed. Thereafter, a total of 30 capacitors were completed in the same manner as in Example 1. Tables 3 and 4 show the initial characteristics and reflow characteristics of these 30 capacitor elements measured in the same manner as in Example 1.

Example 10
In Step 1 of Example 1, the conductive composition 5 is 1 mm wide by syringe discharge on one 3.5 mm × 5 mm part (cathode forming part) side adjacent to the masking part of the cut aluminum sheet. 30 mg was applied and dried at room temperature for 5 minutes. After drying at 90 ° C. for 30 minutes, a dehydration condensation reaction is subsequently carried out at 160 ° C. for 30 minutes, so that a crosslinking reaction proceeds to form a self-doped conductive polymer whose polymer chains are crosslinked on the surface of the dielectric film. Formed. Thereafter, a total of 30 capacitors were completed in the same manner as in Example 1. Tables 3 and 4 show the initial characteristics and reflow characteristics of these 30 capacitor elements measured in the same manner as in Example 1.

Comparative Example 3
Cut the aluminum conversion foil into 3.5mm minor axis direction x 11mm major axis direction and apply a 1.5mm wide polyimide solution on both sides in a circular shape to divide the major axis direction into 5mm and 4.5mm parts, and dry, masking It was created. A 3.5 mm × 4.5 mm portion (cathode forming portion) of this conversion foil was formed into a cut portion by igniting a voltage of 3.8 V with a 10 mass% ammonium adipate aqueous solution to form a dielectric oxide film. Thereafter, a total of 30 capacitors were completed in the same manner as in Example 1. Tables 3 and 4 show the initial characteristics and reflow characteristics of these 30 capacitor elements measured in the same manner as in Example 1.

Sectional drawing which shows an example of the solid electrolytic capacitor manufactured using a capacitor | condenser element. Sectional drawing which shows an example of the solid electrolytic capacitor manufactured by laminating | stacking a capacitor | condenser element. Spectral diagram of S2p binding energy obtained by XPS (solid line indicates phenylsulfone, dashed line indicates 2,2 ′, 5 ′, 2 ″ -terthiophene, dotted line indicates sodium p-toluenesulfonate) . By applying the self-doped conductive polymer of the present invention on the dielectric layer on the surface of the aluminum conversion foil and drying only (dashed line in the figure) and when performing the crosslinking treatment according to the present invention (solid line) by XPS The spectrum figure which shows the binding energy of obtained S2p. (A) includes a first solid electrolyte layer (4a) made of a self-doped conductive polymer on the cathode side along the masking layer (3) provided on the dielectric coating (2), and further The perspective view which shows the rectangular thin plate-shaped capacitor | condenser element which provided the 2nd solid electrolyte layer (4b) on it. (B) is sectional drawing which cut | disconnected the rectangular member of said (A) along the longitudinal direction. Conductive polymer cross-linked between polymer chains partially coated with aluminum forming foil cathode forming portion (13) insulated from aluminum forming foil anode forming portion (10) by insulating material (masking) (11) The schematic diagram which shows an example of the application area | region (12). Conductive polymer crosslinked between polymer chains impregnating the entire cathode forming part (13) of the aluminum conversion foil insulated and separated from the anode forming part (10) of the aluminum conversion foil by the insulating material (masking) (11) The schematic diagram which shows an example of the application area | region (12).

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Anode base | substrate 2 Dielectric (oxide film) layer 3 Masking 4 Semiconductor (solid electrolyte) layer 5 Conductor layers 6 and 7 Lead wire 8 Sealing resin 9 Solid electrolytic capacitor 10 Anode formation part 11 Insulating material 12 Application area | region 13 Cathode Forming part

Claims (31)

A dielectric film formed on the valve action metal surface includes a self-doped conductive polymer layer having a polymer chain bridge, and the conductive polymer of the conductive polymer layer has a sulfonic acid group. the solid electrolytic capacitor viewing including the self-doping type electrically conducting polymer, between the polymer chain bridge is characterized in that it is formed through a sulfone bond containing naphthenic backbone.   2. The solid electrolytic capacitor according to claim 1, wherein the solid electrolytic capacitor includes a self-doped conductive polymer in which crosslinking is performed via a sulfone bond, and the sulfone bond is included in 0.01 to 90 mol% of the repeating unit of the polymer.   Self-doped conductive polymer having a sulfonic acid group, in which the polymer chains are cross-linked through a bond having a bond energy 0.5 to 2 eV lower than the bond energy of the sulfonate group by X-ray photoelectron spectroscopy The solid electrolytic capacitor according to claim 1, comprising a doped conductive polymer. The crosslinked structure of the sulfone bond is represented by the general formula (1)

(In the formula, R ^{1 to} R ³ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, or a linear or branched alkoxy group having 1 to 20 carbon atoms. , A linear or branched alkenyl group having 2 to 20 carbon atoms, a linear or branched alkenyloxy group having 2 to 20 carbon atoms, a hydroxyl group, a halogen atom, a nitro group, a cyano group, a trihalomethyl group, phenyl A group, a substituted phenyl group, or a —B ¹ —SO ₃ ⁻ M ⁺ group, wherein B ¹ and B ² each independently represent — (CH ₂ ) _p — (O) _q — (CH ₂ ) _r —; And p and r each independently represents an integer of 0 or 1 to 3, and q represents 0 or 1. M ⁺ represents a hydrogen ion, an alkali metal ion, or a quaternary ammonium ion. Ar may have a polymer chain Represents a monovalent aromatic group, a substituted monovalent aromatic group, a monovalent heterocyclic group or a substituted monovalent heterocyclic group). The solid electrolytic capacitor according to claim 1, comprising a polymer. The crosslinked structure of the sulfone bond is represented by the general formula (2)

(Wherein R ^{1 to} R ⁶ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, or a linear or branched alkoxy group having 1 to 20 carbon atoms. , A linear or branched alkenyl group having 2 to 20 carbon atoms, a linear or branched alkenyloxy group having 2 to 20 carbon atoms, a hydroxyl group, a halogen atom, a nitro group, a cyano group, a trihalomethyl group, phenyl A group, a substituted phenyl group, or a —B ¹ —SO ₃ ⁻ M ⁺ group, B ¹ represents — (CH ₂ ) _p — (O) _q — (CH ₂ ) _r —, and p and r are Each independently represents an integer of 0 or 1 to 3, q represents 0 or 1. M ⁺ represents a hydrogen ion, an alkali metal ion, or a quaternary ammonium ion. Including a self-doped conductive polymer The solid electrolytic capacitor according to claim 1, wherein: The crosslinked structure of the sulfone bond is represented by the general formula (3)

(In the formula, B ¹ represents — (CH ₂ ) _p — (O) _q — (CH ₂ ) _r —, p and r each independently represents an integer of 0 or 1 to 3, Represents 0 or 1. M ⁺ represents a hydrogen ion, an alkali metal ion, or a quaternary ammonium ion. Item 6. The solid electrolytic capacitor according to Item 5.   Claim: Having a first solid electrolyte layer containing a self-doped conductive polymer having a polymer inter-chain bridge on a dielectric film formed on a metal surface, and having a second solid electrolyte layer thereon Item 7. The solid electrolytic capacitor according to any one of Items 1 to 6.   The solid electrolytic capacitor according to claim 7, wherein the first solid electrolyte layer is insoluble in water.   The solid electrolytic capacitor according to claim 1, wherein the metal is a valve metal having fine holes.   Self-doped conductivity with an insulating material that isolates and separates the anode and cathode of the valve action metal having fine pores, and at least part of the dielectric film on the cathode side adjacent to this has polymer chain cross-linking The solid electrolytic capacitor according to claim 9, further comprising a first solid electrolyte layer containing a polymer and a second solid electrolyte layer thereon.   The solid electrolytic capacitor according to any one of claims 1 to 10, wherein the thickness of the solid electrolyte layer containing the self-doped conductive polymer in which the polymer chains are cross-linked is in the range of 1 nm to 1000 nm.   The solid electrolytic capacitor according to any one of claims 1 to 11, wherein the electric conductivity of the solid electrolyte layer containing a self-doped conductive polymer in which polymer chains are cross-linked is in the range of 0.001 to 100 S / cm. .   The solid electrolytic capacitor according to any one of claims 1 to 12, wherein a pencil hardness of the solid electrolyte layer containing a self-doped conductive polymer in which polymer chains are crosslinked has a hardness of HB to 4H. General formula (7)

(In the formula, R ^{1 to} R ³ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, or a linear or branched alkoxy group having 1 to 20 carbon atoms. , A linear or branched alkenyl group having 2 to 20 carbon atoms, a linear or branched alkenyloxy group having 2 to 20 carbon atoms, a hydroxyl group, a halogen atom, a nitro group, a cyano group, a trihalomethyl group, phenyl group, a substituted phenyl group, or a -B ¹ -SO ₃ ^- represents the M ⁺ group, .B ¹ one of R ¹ to R ³ is a hydrogen _{atom, - (CH 2) p -} (O ) _Q — (CH ₂ ) _r —, p and r each independently represent an integer of 0 or 1 to 3 and q represents 0 or 1. M ⁺ represents a hydrogen ion or an alkali metal ion. Or a quaternary ammonium ion.) The self-doped conductive polymer in which the polymer chains represented by the general formula (1) according to claim 4 are cross-linked by dehydration condensation after coating the self-doped conductive polymers including the structure with each other on the dielectric film. The method for producing a solid electrolytic capacitor according to claim 1, wherein the dielectric film is coated with a conductive polymer. General formula (7) and / or general formula (8)

(In the formula ^{(7), R 1 ~R 3} , B 1, and M ⁺ is in. The formula represents the same meaning as in the general formula (7) as claimed in claim ^{14 (8), R 7 ~R} 10 is , Independently of each other, a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkoxy group having 1 to 20 carbon atoms, or a straight chain having 2 to 20 carbon atoms Or a branched alkenyl group, a linear or branched alkenyloxy group having 2 to 20 carbon atoms, a hydroxyl group, a halogen atom, a nitro group, a cyano group, a trihalomethyl group, a phenyl group, a substituted phenyl group, or -B ¹ When dehydrating and condensing a self-doped conductive polymer which represents a —SO ₃ ⁻ M ⁺ group and includes a chemical structure represented by the formulas (7) and (8), any one of R ^{7 to} R ¹⁰ a hydrogen atom, each is hydrogen atom R ¹ to R ³ in this case formula (7) Without at least one of R ⁷ to R ¹⁰ when dehydration condensation of self-doping type electrically conducting polymer containing a chemical structure represented by or formula also (8) is -B ¹ -SO ₃ ^-. M ⁺ group And at least one is a hydrogen atom, B ¹ represents — (CH ₂ ) _p — (O) _q — (CH ₂ ) _r —, and p and r are each independently 0 or 1 represents an integer of 1 to 3, q represents 0 or 1. M ⁺ represents a hydrogen ion, an alkali metal ion, or a quaternary ammonium ion.) The molecules are covered with a dielectric film, and then dehydrated and condensed to coat the dielectric film with a self-doped conductive polymer having a cross-linked polymer chain represented by the general formula (1) according to claim 4 14. The method according to claim 1, wherein The method for producing a solid electrolytic capacitor. General formula (9)

(In the formula, B ¹ represents — (CH ₂ ) _p — (O) _q — (CH ₂ ) _r —, p and r each independently represents an integer of 0 or 1 to 3, Represents 0 or 1. M ⁺ represents a hydrogen ion, an alkali metal ion, or a quaternary ammonium ion.) A dielectric film is formed from a self-doped conductive polymer obtained by (co) polymerizing a monomer represented by The dielectric film is coated with a self-doped conductive polymer in which the polymer chains represented by the general formula (3) according to claim 6 are cross-linked by dehydration condensation after coating. The manufacturing method of the solid electrolytic capacitor in any one of Claims 1-13. The valve metal having fine holes is represented by the general formula (7) and / or the general formula (8).

(In the formulas (7) and (8), R ^{1 to} R ³ , R ^{7 to} R ¹⁰ , B ¹ , and M ⁺ have the same meaning as in the general formulas (7) and (8) according to claim 15. The solid electrolytic capacitor according to any one of claims 1 to 13, wherein the solid electrolytic capacitor is dehydrated and condensed by heating after being immersed in a solution containing a self-doped conductive polymer represented by: Method. General formula (7) and / or general formula (8)

(In the formulas (7) and (8), R ^{1 to} R ³ , R ^{7 to} R ¹⁰ , B ¹ , and M ⁺ have the same meaning as in the general formulas (7) and (8) according to claim 15. 14. A solution containing a self-doping type conductive polymer represented by the formula (1) is applied to a valve metal having fine pores and then dehydrated and condensed by heating. The manufacturing method of the solid electrolytic capacitor of description. General formula (7) and / or general formula (8)

(In the formulas (7) and (8), R ^{1 to} R ³ , R ^{7 to} R ¹⁰ , B ¹ , and M ⁺ have the same meaning as in the general formulas (7) and (8) according to claim 15. The cathode side adjacent to the insulating material of the capacitor having an insulating material that insulates and separates the anode and the cathode in the valve metal having a fine hole from the solution containing the self-doped conductive polymer represented by The method for producing a solid electrolytic capacitor according to claim 1, wherein after applying to at least a part of the dielectric coating, dehydration condensation is performed by heating. General formula (9)

(Wherein B ¹ and M ⁺ represent the same meaning as in formula (9) according to claim 16). A self-doped conductive polymer obtained by (co) polymerizing the monomer represented by (16) The method for producing a solid electrolytic capacitor according to claim 1, wherein the solution is applied to a valve action metal having fine pores and then dehydrated and condensed by heating. The valve action metal having fine holes is represented by the general formula (9)

(Wherein B ¹ and M ⁺ represent the same meaning as in formula (9) according to claim 16). A self-doped conductive polymer obtained by (co) polymerizing the monomer represented by (16) The method for producing a solid electrolytic capacitor according to claim 1, wherein the solid electrolytic capacitor is dehydrated and condensed by heating after being immersed in the solution. The valve action metal having fine holes is represented by the general formula (9)

(Wherein B ¹ and M ⁺ represent the same meaning as in formula (9) according to claim 16). A self-doped conductive polymer obtained by (co) polymerizing the monomer represented by (16) The solution containing is applied to at least a part of the dielectric film on the cathode side adjacent to the insulating material of the capacitor having an insulating material that insulates and separates the anode and the cathode of the valve metal having fine holes, and then heated. The method for producing a solid electrolytic capacitor according to claim 1, wherein dehydration condensation is performed.   The method for producing a solid electrolytic capacitor according to any one of claims 14 to 22, wherein the dehydration condensation reaction is performed by heat treatment at a temperature within a range of 250 ° C or higher and 300 ° C or lower.   A valve action metal having a dielectric film layer is immersed in an aqueous solution containing a self-doped conductive polymer capable of crosslinking between polymer chains, and then cured by a dehydration condensation reaction to make the dielectric film layer insoluble in water. A step of covering with one solid electrolyte layer (step 1), a step of drying after immersion in a solution containing a monomer for forming the second solid electrolyte layer (step 2), and a step of drying after immersion in a solution containing an oxidizing agent (step 2). The method for producing a solid electrolytic capacitor according to claim 1, wherein the second solid electrolyte layer is provided by a method including step 3).   A valve action metal having a dielectric film layer is immersed in an aqueous solution containing a self-doped conductive polymer capable of crosslinking between polymer chains, and then cured by a dehydration condensation reaction to make the dielectric film layer insoluble in water. A step of covering with one solid electrolyte layer (step 1), a step of drying after immersion in a solution containing a monomer for forming the second solid electrolyte layer (step 2), and a step of drying after immersion in a solution containing an oxidizing agent (step 2). The method for producing a solid electrolytic capacitor according to claim 24, wherein the second solid electrolyte layer is provided by a method of repeating step 3) a plurality of times.   After applying an aqueous solution containing a self-doped conductive polymer capable of cross-linking between polymer chains to a valve action metal having a dielectric coating layer, the dielectric coating layer is cured by a dehydration condensation reaction to make the dielectric coating layer insoluble in water. The step of covering with a solid electrolyte layer (step 1), the step of drying after immersion in a solution containing a monomer for forming the second solid electrolyte layer (step 2), the step of drying after immersion in a solution containing an oxidizing agent (step) The method for producing a solid electrolytic capacitor according to claim 24, wherein the second solid electrolyte layer is provided by a method of repeating 3) a plurality of times.   27. The method for producing a solid electrolytic capacitor according to claim 24, wherein the oxidizing agent is a persulfate.   The method for producing a solid electrolytic capacitor according to any one of claims 24 to 27, wherein the solution containing the oxidizing agent is a suspension containing organic fine particles. The method for producing a solid electrolytic capacitor according to claim 28, wherein an average particle diameter (D ₅₀ ) of the organic fine particles is in a range of 1 to 20 µm.   30. The organic fine particle is at least one selected from the group consisting of an aliphatic sulfonic acid compound, an aromatic sulfonic acid compound, an aliphatic carboxylic acid compound, an aromatic carboxylic acid compound, a salt thereof, and a peptide compound. Manufacturing method for solid electrolytic capacitor.   The solid electrolytic capacitor manufactured with the manufacturing method in any one of Claims 14-30.

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