200414244 (1) 玖、發明說明 【發明所屬之技術領域】 本發明係有關，以導電性聚合物做爲固體電解質 固體電解質電容器，及其製造方法者。 【先前技術】 固體電解質電容器之基本元件，如圖1所示，一 在經蝕刻處理，比表面積大之金屬箔所成的陽極基 上形成電介質之氧化皮膜層（2)，其外側形成對向電 固體半導體層（以下稱爲固體電解質）（4)，然後依所期 更形成導電糊狀物等之導電體層（5)，即製作完成； ，如此之元件，單獨或層合，以導線（6，7)連接，全 用環氧樹脂（8)等完全密封，成爲電容器（9)之構件， 使用於電氣製品。 近年來，隨著電氣機器之數位化、個人電腦之高 ，更要求小型而大容量之電容器、於高週波領域具低 之電容器；最近，甚且有使用具電子傳導性之導電性 物做爲固定電解質之提案。 對於固體電解質之形狀，有以電解氧化聚合使導 聚合物之生長起點，在鋁箔上銲接形成鋁箔表面整體 的提案（例如，參照特開平4-3 079 1 7號公報）。 又，謀求提高靜電容量或小型化，而將陽極箔之 表面積擴大的技術開發，亦熱烈的在進行；有以鋁范 刻處理後，將蝕刻層壓下之技術的提案（例如，參照 層之 般以 體（1) 極之 望， 其次 體再 廣泛 速化 阻抗 聚合 電性 金屬 有效 經蝕 專利 -5- (2) (2)200414244 第3 0 8 4 3 3 0號公報，及特開2002-2 6096 8公報）。 更有，要求半導體標準件之小型化、高密度化、暗藏 於基板內的薄型、基板密著型之固體電解質電容器的提案 (例如，參照特開2 0 0 2 - 2 6 0 9 6 7號公報）。· 【發明內容】 [發明之揭示] 固體電解質電容器，爲使成爲所定容量之電容器，在 由複數個電容器元件層合而成之陽極接頭，以陽極導線連 接；在含有導電性聚合物之導電體層，以陰極導線連接； 更將整體以環氧樹脂等絕緣性樹脂密封，製作成固體電解 質電容器；但是，在固體電解質電容器之陰極部份的導電 性聚合物黏著步驟中，聚合條件如不加以嚴密的控制，導 電性聚合物之厚度會發生不均勻的情況，以致導電性聚合 物出現較薄部份，容易使糊狀物等與電介質氧化皮膜層直 接接觸’致使漏泄電流上升，因而導電性聚合物必須加厚 ;在所定晶片中，可層合之電容器元件的片數，受到元件 厚度之限制’不能使固體電解質電容器晶片的容量增大； 又’導電性聚合物之黏著厚度不均勻時，會使層合之電容 器元件與電容器元件的接觸面積減少，有使等效串聯電阻 (ESR)增大之問題存在。 爲使導電性聚合物之厚度的離散情況減少，必須長時 間的嚴密控制聚合條件，有使生產性顯著下降之問題存在 -6 - (3) (3)200414244 因此’本發明爲解決上述各項問題，以提供能縮短形 成精緻聚合體之必要時間、無短路不良之增加情況，元件 形狀之離散情形極少，而且可以安定的製作較薄之電容器 兀件；藉此，可使固體電解質電容器晶片內之電容器元件 的層合片數增加，而得以高容量化，更能使等效串聯電阻 之離散減小，的層合型固體電解質電容器，及其製造方法 爲目的。 本發明之工作同仁，有鑑於上述各項問題，經深入探 討’不斷硏究之結果發現，將固體電解質之形狀整理，形 成導電性聚合物後再壓縮之方法有效；如此所得之固體電 解質電容器，確認可提高在電介質皮膜上形成之固體電解 質的密著性，高容量，而且介質損耗（tan (5 )、漏泄電流、 不良率均很小。 更確認以複數片上述之特性優越的固體電解質電容器 元件，層合而成之電容器，可以小型化、高容量化。 即是說，本發明爲提供下述之固體電解質電容器，及 其製造方法者。 (1) 以具有在活門作用金屬多孔體基板表面之電介質 皮膜上，設置有含導電性聚合物之固體電解質’且依基板 之厚度方向壓縮的電容器元件爲特徵之固體電解質電容器 〇 (2) 如上述（1)記載之固體電解質電容器’其中具備有 在活門作用金屬多孔體基板表面之電介質皮膜上’設置有 含導電性聚合物之固體電解質’且在依基板之厚度方向壓 (4) 200414244 縮的固體電解質層上設置陰極層之電容器元件。 (3) 如上述（1)或（2)記載之固體電解質電容器，其中# 活門作用金屬多孔體之電介質皮膜上的含導電性聚合物之 固體電解質，爲以化學聚合或電化學聚合而設置者。 (4) 如上述（1)〜（3)任一項記載之固體電解質電容器， 其中設置有固體電解質之元件的壓縮後厚度爲，最大高度 (Rmax)在 2 5 0μιη以下者。 (5) 如上述（2)記載之固體電解質電容器，其中具備有 在活門作用金屬多孔體基板表面之電介質皮膜上，設置有 含導電性聚合物之固體電解質層，使在依基板之厚度方向 壓縮的導電性聚合物層之厚度均勻化後，於固體電解質層 上設置陰極層的電容器元件。 (6) 如（1)〜（5)任一項記載之固體電解質電容器，其中 包含壓縮前基板之導電性聚合物層的最大厚度爲Hamax、 最小厚度爲Hamin，包含壓縮後基板之導電性聚合物層的 最大厚度爲Hbm ax、最小厚度爲Hbm in時，如下式所示之 厚度差的減少率△ Η，爲在5〜95 %之範圍者。 (Hbmax-Hbmin) ΔΗ (%)= 1 - - X 10 0 (Hamax —Hamin) (7)如上述（1)〜（6)任一項記載之固體電解質電容器， 其中設置有固體電解質層之基板，整體的壓縮率，爲在 5〜9 0 %者° (5) (5)200414244 (8) 如上述（1)〜（7)任一項記載之固體電解質電容器， 其中固體電解質之導電性聚合物爲，在具有電介質皮膜之 活門作用金屬基板上’以有機高分子單體之溶液化學氧化 聚合、或氣相化學氧化聚合而形成者。 (9) 如上述（1)〜（7)任一項記載之固體電解質電容器， 其中固體電解質之導電性聚合物爲，使具有電介質皮膜之 活門作用金屬基板，藉由在有機高分子單體之含有液，及 氧化劑含有液的交互浸漬作業之重覆操作而形成者。 (10) 如上述（1)〜（9)任一項記載之固體電解質電容器， 其中活門作用金屬多孔體基板爲，平板狀或箔狀者。 (11) 如上述（1)〜（10)任一項記載之固體電解質電容器 ，其中活門作用金屬多孔體爲，選自鋁、鉅、鈮、鈦、锆 、鎂、及矽之單體金屬、或此等之合金者。 (12) 如上述（1)〜（11)任一項記載之固體電解質電容器 ，其中形成導電性聚合物之有機高分子單體爲，含有雜五 節環之化合物、或具有苯胺骨架之化合物者。 (13) 如上述（12)記載之固體電解質電容器，其中含有 雜五節環之化合物爲，具有噻吩骨架、或具有多環狀硫化 物骨架之化合物者。 (14) 如上述（13)記載之固體電解質電容器，其中具有 噻吩骨架之單體化合物爲，3 -乙基噻吩、己基噻吩、3 ，4 -二甲基噻吩、3，4 -甲二氧基噻吩、或3，4 -乙二氧基 噻吩。 (15) 如上述（1)〜（14)任一項記載之固體電解質電容器 (6) (6)200414244 ，其中導電性聚合物之固體電解質層的一部份爲，具有板 層結構或原纖維結構者。 (16) —種層合型固體電解質電容器，其特徵爲，以複 數片的上述（1 )〜（1 5 )任一項記載之電容器元件層合而成者 〇 (17) —種層合型固體電解質電容器，其特徵爲，含有 在活門作用金屬多孔體基板表面之電介質皮膜上，設置以 氧化劑使有機高分子單體行氧化聚合而得導電性聚合物所 成固體電解質層之基板，複數片層合且在厚度方向壓縮， 於固體電解質層之外表表面上設置有陰極層的電容器元件 〇 (18) 如上述（17)記載之層合型電解質電容器，其中設 置有固體電解質層之層合基板的整體壓縮率，爲在5〜9 0 % 者。 (19) 一種固體電解質電容器之製造方法，其特徵爲， 在具有電介質皮膜之多孔體的活門作用金屬基板表面上， 藉由氧化劑之作用，以形成導電性聚合物之單體含有液及 氧化劑含有液，形成導電性聚合物之固體電解質層後，將 設置有導電性聚合物之基板依厚度方向壓縮，接著在固體 電解質層上設置陰極層。 (2 0)—種固體電解質電容器之製造方法，其特徵爲， 在具有電介質皮膜之多孔體的活門作用金屬基板表面上， 藉由氧化劑之作用，以形成導電性聚合物之單體含有液及 氧化劑含有液，形成導電性聚合物之固體電解層，將設置 -10- (7) 200414244 有導電性聚合物之基板，複數片層合後，依厚度方向壓縮 接著在固體電解質層之外表表面上設置陰極層。 (2 1)—種固體電解質電容器之製造方法，其特徵爲， 在具有電介質皮膜之多孔體的活門作用金屬基板表面上， 藉由氧化劑之作用，以形成導電性聚合物之單體含有液及 氧化劑含有液，形成導電性聚合物之固體電解質層，接著 使設置有固體電解質層之基板依厚度方向壓縮後，在固體 電解質層上設置陰極層，接著依陰極層之厚度方向壓縮。 (22) 如上述（19)〜（21)任一項記載之固體電解質電容器 的製造方法，其中設置有固體電解質層之基板整體，以 5〜9 0 %之壓縮率壓縮。 (23) 如上述（19)〜（21)任一項記載之固體電解質電容器 的製造方法，其中包含壓縮前基板之導電性聚合物層的最 大厚度爲Ha max、最小厚度Ha min，包含壓縮後基板之導 電性聚合物層的最大厚度爲Hbmax、最小厚度爲Hbmin時 ，壓縮至如下式所示之厚度差的減少率△ Η，爲在5〜9 5 % 之範圍。 (Hbmax-Hbmin) ΔΗ (%)= X 10 0 1 一 *- (Hamax-Hamin) (24)如上述（19)〜（23)任一項記載之固體電解質電容器 的製造方法，其中在將設置有固體電解質層之基板，依厚 度方向壓縮之步驟後，還有再形成之步驟。 -11 - (8) (8)200414244 (25) 如上述（19)〜（23)任一項記載之固體電解質電容器 的製造方法，其中在設置有固體電解質層之基板，依厚度 方向壓縮之步驟後，還有加濕熟化之步驟。 (26) 如上述（25)記載之固體電解質電容器的製造方法 ，其中加濕熟化步驟爲，在跳火電壓以下之形成電壓下， 20〜95°C、40〜95%相對濕度之條件下進行者。 參照附上之圖面，就本發明之方法說明如下。 本發明使用之基板（1)表面的電介質皮膜（2)通常是以 具有活門作用之金屬多孔質成形體，經形成處理等而形成 〇 形成中使用之形成液、形成電壓等之形成條件係，因 應製造固體電解質電容器必要之容量、耐電壓等，藉由預 備實驗確認之適當値予以設定者；還有，形成處理之際， 爲防止形成液滲入固體電解質電容器之陽極形成部份，更 爲與在後步驟形成之固體電解質（4)(陰極部份）確實的絕緣 ，設置一般之掩蔽罩（3)。 掩蔽罩材料，可以使用一般的耐熱性樹脂，以可溶於 溶劑或膨脹之耐熱性樹脂或其前驅體、無機質微粉與纖維 素系樹脂所成組成物等爲適合，材料沒有任何限制；具例 的有，聚苯基碼（PPS)、聚醚碼（PES)、氰酸酯樹脂、氟樹 脂（四氟乙烯，及四氟乙烯·全氟烷基乙烯基醚共聚物等） 、低分子量聚醯亞胺、及此等之衍生物、及其前驅體等等 •，以低分子量聚醯亞胺、聚醚碼、氟樹脂、及此等之前驅 體，較爲適合。 -12 - (9) (9)200414244 一般而言，在電介質氧化皮膜上形成導電性聚合物之 技術，可使用以氣相聚合法形成導電性高分子層，與以電 解聚合法形成導電性高分子層之方法（特開平3-621 7號公 報等）、以有機高分子單體黏著於電介質氧化皮膜上後， 在氧化劑溶液中聚合之溶液化學聚合法（特開平1卜251 191 號公報等）、藉由轉換裝置，在每隔所定時間改變陽極之 供電點，使導電性高分子層之厚度均勻化的電化學聚合法 (美國專利第6 1 6 8 63 9號，及第63 1 3 97 9號公報等）；本發明 中’較適合的是，將活門作用金屬多孔體基板，浸漬於氧 化劑溶液中，取出乾燥之，使用包含有使氧化劑溶液濃度 在基板Jl徐徐升高之步驟的有機高分子單體之溶液化學氧 化聚合’或氣相化學氧化聚合；以溶液化學氧化聚合，最 爲適用。 使用本發明，如後述之實施例所示，將具有電介質氧 化皮膜之鋁箔，例如，浸漬於3，4 -乙二氧基噻吩（E D T)之 異丙醇（IP A)溶液，使此等風乾以完全除去異丙醇；浸漬 於約20重量％之氧化劑（過硫酸銨）水溶液，於4(rc左右加 熱10分鐘，或重覆施行本步驟，可得聚（3，4 -乙二氧基噻 吩）之聚合物。 以本發明之方法，使形成的導電性聚合物固體電解質 層’成爲原纖維結構、或板層（較薄之層狀）結構，此等結 構廣範圍的持續聚合物鏈間之重覆，容易造成電子跳躍， 而使電導度上升，想必爲有助於提高低阻抗等之特性者。 在彳谷液化學聚合法中，單體黏著於陽極基板之具有微 -13- (10) (10)200414244 細孔的電介質皮膜上，於成爲導電性高分子之摻雜劑的所 得化合物存在下，由於氧化劑與空氣中水份之作用發生氧 化聚合，生成之聚合物組成物，在電介質表面上形成固體 電解質；此時，爲形成良好之聚合物組成物，必須調整單 體含有液及氧化劑含有液之浸漬時間，以控制單體及氧化 劑之黏著量；例如，浸漬時間過長時，聚合反應不能完結 ，所得聚合物組成物，容易成爲低分子量者；又，在未飽 和濃度之氧化劑含有液中，其浸漬時間過長時，經由含乾 燥步驟之前步驟，黏著於金屬箔基板之氧化劑會再溶解， 同時，黏著之單體、生成之聚合物亦將溶出或流出；造成 聚合物之生成緩慢，同時，流出物使氧化劑含有液產生污 染；同時的事情，也會在單體含有液之浸漬時發生。 顯像時，例如，使用低分子量成份之氧化劑含有液， 會出現單體含有液之著色、聚合物之浮遊、黏著形成之固 體電解質重量有減少之傾向、單體含有液之粘度、比重之 變化等情形。 因此，在本發明之方法中，浸漬於單體含有液及氧化 劑含有液之時間’以含有液中之單體成份及氧化劑成份， 黏著於金屬箔基板之電介質表面所需之充分時間的低於1 5 分鐘以上，爲適合；以0.1秒〜10分鐘較佳，以1秒〜7分鐘 更適合。 進而，爲求單體均勻黏著於電介質表面上及聚合物組 成物上，在以單體含有液浸漬後，必須於空氣中放置一定 時間，使溶媒氣化；此條件隨溶媒之種類而改變，大體上 -14- (11)200414244 在 隨200414244 (1) 发明 Description of the invention [Technical field to which the invention belongs] The present invention relates to a solid electrolyte capacitor using a conductive polymer as a solid electrolyte, and a method for manufacturing the same. [Prior technology] As shown in Figure 1, the basic components of solid electrolytic capacitors are formed by forming a dielectric oxide film layer (2) on the anode base made of metal foil with a large specific surface area after etching treatment, and the opposite side forms an opposite An electric solid semiconductor layer (hereinafter referred to as a solid electrolyte) (4), and then a conductor layer (5), such as a conductive paste, is formed as expected, and the production is completed; such components, alone or laminated, are formed by wires ( 6, 7) Connection, completely sealed with epoxy resin (8), etc., become the component of capacitor (9), used in electrical products. In recent years, with the digitization of electrical equipment and the increase in personal computers, small and large-capacity capacitors and capacitors with low frequency in the high-frequency field have been required. Recently, even conductive materials with electronic conductivity have been used. Proposed electrolyte fixation. Regarding the shape of the solid electrolyte, there has been a proposal of starting the growth of a conductive polymer by electrolytic oxidation polymerization, and welding the aluminum foil to form the entire surface of the aluminum foil (for example, refer to Japanese Patent Application Laid-Open No. 4-3 079 17). In addition, the development of technology to increase the electrostatic capacity or miniaturization and increase the surface area of the anode foil is also actively carried out; there are proposals for a technology (such as a reference layer In general, the body (1) is extremely hopeful, and the body is then widely used to accelerate the effective polymerization of the resistive polymerized electric metal. Patent -5- (2) (2) 200414244 No. 3 0 8 4 3 3 0, and JP 2002 -2 6096 8 bulletin). Furthermore, proposals for miniaturized, high-density semiconductor substrates, thin, and substrate-adhered solid electrolyte capacitors hidden in substrates have been proposed (for example, refer to JP 2 0 2-2 6 0 9 6 7 Bulletin). · [Summary of the Invention] [Disclosure of the Invention] In order to make a capacitor of a predetermined capacity, a solid electrolyte capacitor is connected to an anode lead by laminating a plurality of capacitor elements, and connected by an anode wire; on a conductor layer containing a conductive polymer The cathode is connected by a cathode wire; the whole is sealed with an insulating resin such as epoxy resin to make a solid electrolyte capacitor; however, in the conductive polymer adhesion step of the cathode portion of the solid electrolyte capacitor, the polymerization conditions are not strict. Control, the thickness of the conductive polymer will be uneven, so that the conductive polymer appears thinner, and it is easy for the paste and the like to directly contact the dielectric oxide film layer, which causes the leakage current to rise, so the conductive polymerization The material must be thickened; in a given chip, the number of capacitor elements that can be laminated is limited by the thickness of the element 'cannot increase the capacity of the solid electrolyte capacitor chip; and' when the adhesive thickness of the conductive polymer is uneven, It will reduce the contact area between the laminated capacitor element and the capacitor element. Equivalent series resistance (ESR) increases the problem exists. In order to reduce the dispersion of the thickness of the conductive polymer, it is necessary to strictly control the polymerization conditions for a long time, and there is a problem that the productivity is significantly reduced. -6-(3) (3) 200414244 Therefore, the present invention is to solve the above problems The problem is to provide shortening the time required to form a delicate polymer, no increase in short-circuit defects, few discrete component shapes, and stable fabrication of thinner capacitors. Laminated solid electrolyte capacitors for capacitor elements with a higher number of laminated chips, higher capacity, and reduced dispersion in equivalent series resistance, and a method for manufacturing the same, are intended. In view of the above problems, working colleagues of the present invention, after in-depth discussion, 'continuous research has found that the method of arranging the shape of the solid electrolyte to form a conductive polymer and then compressing it is effective; the solid electrolyte capacitor thus obtained, It is confirmed that the solid electrolyte formed on the dielectric film can improve the adhesion, high capacity, and small dielectric loss (tan (5), leakage current, and defective rate). It is also confirmed that a plurality of solid electrolyte capacitors with superior characteristics as described above Components and laminated capacitors can be miniaturized and increased in capacity. That is, the present invention is to provide the following solid electrolyte capacitors and methods for manufacturing the same. (1) A porous metal substrate having a valve function A solid electrolyte capacitor characterized by a capacitor element that is compressed in the thickness direction of the substrate is provided with a solid electrolyte containing a conductive polymer on the surface dielectric film. (2) The solid electrolyte capacitor described in (1) above. It is provided on the dielectric film on the surface of the porous metal substrate of the valve. A solid electrolyte containing a conductive polymer 'and a capacitor element having a cathode layer provided on the solid electrolyte layer (4) 200414244 which is compressed in the thickness direction of the substrate. (3) The solid electrolyte as described in (1) or (2) above Capacitors, in which the solid electrolyte containing a conductive polymer on the dielectric film of the #valve metal porous body is provided by chemical polymerization or electrochemical polymerization. (4) As described in any of (1) to (3) above The solid electrolyte capacitor according to the description, wherein the thickness of the element provided with the solid electrolyte after compression is such that the maximum height (Rmax) is below 250 μm. (5) The solid electrolyte capacitor according to the above (2), which includes a valve A solid electrolyte layer containing a conductive polymer is provided on the dielectric film on the surface of the porous metal substrate. After the thickness of the conductive polymer layer compressed in the thickness direction of the substrate is uniformized, a cathode is provided on the solid electrolyte layer. (6) The solid electrolyte capacitor according to any one of (1) to (5), which includes the conductive polymer When the maximum thickness of the physical layer is Hamax, the minimum thickness is Hamin, and the maximum thickness of the conductive polymer layer including the compressed substrate is Hbm ax and the minimum thickness is Hbmin, the reduction rate of the thickness difference Δ Η as shown in the following formula, (Hbmax-Hbmin) ΔΗ (%) = 1--X 10 0 (Hamax —Hamin) (7) The solid electrolyte according to any one of (1) to (6) above Capacitor, in which a substrate provided with a solid electrolyte layer, has an overall compression ratio of 5 to 90% (5) (5) 200414244 (8) The solid as described in any one of (1) to (7) above An electrolytic capacitor, in which a conductive polymer of a solid electrolyte is formed by a chemical oxidation polymerization of a solution of an organic polymer monomer or a gas phase chemical oxidation polymerization on a metal substrate having a gate function of a dielectric film. (9) The solid electrolyte capacitor according to any one of the above (1) to (7), wherein the conductive polymer of the solid electrolyte is a metal substrate having a gate function having a dielectric film, and Contained liquid and oxidant containing liquid are formed by repeated operations of the dipping operation. (10) The solid electrolyte capacitor according to any one of the above (1) to (9), wherein the porous metal substrate of the valve action is a flat plate or a foil. (11) The solid electrolytic capacitor according to any one of the above (1) to (10), wherein the porous metal having a valve action is a single metal selected from the group consisting of aluminum, giant, niobium, titanium, zirconium, magnesium, and silicon; Or these alloys. (12) The solid electrolyte capacitor according to any one of (1) to (11) above, wherein the organic polymer monomer forming the conductive polymer is a compound containing a hetero five-membered ring or a compound having an aniline skeleton . (13) The solid electrolytic capacitor according to the above (12), wherein the compound containing a hetero five-membered ring is a compound having a thiophene skeleton or a polycyclic sulfide skeleton. (14) The solid electrolytic capacitor according to the above (13), wherein the monomer compound having a thiophene skeleton is 3-ethylthiophene, hexylthiophene, 3,4-dimethylthiophene, 3,4-methyldioxy Thiophene, or 3,4-ethylenedioxythiophene. (15) The solid electrolyte capacitor according to any one of (1) to (14) above (6) (6) 200414244, wherein a part of the solid electrolyte layer of the conductive polymer has a layer structure or fibrils Structurer. (16) A laminated solid electrolyte capacitor, characterized by being formed by laminating a plurality of capacitor elements described in any one of the above (1) to (1 5). (17)-A laminated type A solid electrolyte capacitor is characterized in that a plurality of sheets are provided on a dielectric film on the surface of a valve-operated porous metal substrate, and a solid electrolyte layer made of a conductive polymer is obtained by oxidizing and polymerizing an organic polymer monomer with an oxidizing agent. The capacitor element is laminated and compressed in the thickness direction, and a cathode layer is provided on the outer surface of the solid electrolyte layer. (18) The laminated electrolyte capacitor according to the above (17), wherein the laminated substrate of the solid electrolyte layer is provided. The overall compression ratio is between 5 and 90%. (19) A method for manufacturing a solid electrolyte capacitor, characterized in that, on the surface of a valve-acting metal substrate of a porous body having a dielectric film, an oxidant acts to form a conductive polymer-containing monomer-containing liquid and an oxidant-containing After forming a solid electrolyte layer of a conductive polymer, the substrate provided with the conductive polymer is compressed in the thickness direction, and then a cathode layer is provided on the solid electrolyte layer. (20) A method for manufacturing a solid electrolyte capacitor, characterized in that, on the surface of a valve-acting metal substrate of a porous body having a dielectric film, an oxidizing agent is used to form a conductive polymer-containing monomer-containing liquid and The oxidant contains a liquid to form a solid electrolytic layer of a conductive polymer. A substrate with a conductive polymer is set to -10- (7) 200414244. After laminating a plurality of sheets, they are compressed in the thickness direction and then placed on the outer surface of the solid electrolyte layer. A cathode layer is provided. (2 1) A method for manufacturing a solid electrolyte capacitor, characterized in that, on the surface of a valve-acting metal substrate of a porous body having a dielectric film, a conductive polymer-containing monomer-containing liquid and The oxidant contains a liquid to form a solid electrolyte layer of a conductive polymer. After the substrate provided with the solid electrolyte layer is compressed in the thickness direction, a cathode layer is provided on the solid electrolyte layer and then compressed in the thickness direction of the cathode layer. (22) The method for manufacturing a solid electrolyte capacitor according to any one of (19) to (21) above, wherein the entire substrate provided with the solid electrolyte layer is compressed at a compression ratio of 5 to 90%. (23) The method for manufacturing a solid electrolyte capacitor according to any one of (19) to (21) above, wherein the maximum thickness of the conductive polymer layer including the substrate before compression is Ha max and the minimum thickness Ha min, including after compression When the maximum thickness of the conductive polymer layer of the substrate is Hbmax and the minimum thickness is Hbmin, it is compressed to a reduction rate ΔΗ of the thickness difference shown by the following formula, which is in the range of 5 to 95%. (Hbmax-Hbmin) ΔΗ (%) = X 10 0 1 1 *-(Hamax-Hamin) (24) The method for manufacturing a solid electrolyte capacitor according to any one of (19) to (23) above, wherein After the substrate having the solid electrolyte layer is compressed in the thickness direction, it is further formed. -11-(8) (8) 200414244 (25) The method for manufacturing a solid electrolyte capacitor according to any one of (19) to (23) above, wherein the substrate provided with the solid electrolyte layer is compressed in the thickness direction Later, there is a step of humidifying and ripening. (26) The method for manufacturing a solid electrolyte capacitor according to the above (25), wherein the humidification and maturation step is performed at a formation voltage lower than the flashover voltage at a temperature of 20 to 95 ° C and a relative humidity of 40 to 95% By. The method of the present invention will be described with reference to the attached drawings. The dielectric film (2) on the surface of the substrate (1) used in the present invention is usually formed by a metal porous formed body having a shutter function, and is formed by a forming process, etc. The forming conditions, forming voltage, and the like used in forming are formed. The capacity and withstand voltage necessary for the manufacture of solid electrolytic capacitors are set by appropriate tests confirmed by preliminary experiments; in addition, during the formation process, in order to prevent the formation liquid from penetrating into the anode forming part of the solid electrolytic capacitor, The solid electrolyte (4) (cathode part) formed in the subsequent step is reliably insulated, and a general mask (3) is provided. As the masking material, a general heat-resistant resin can be used, and a solvent-soluble or swellable heat-resistant resin or a precursor thereof, a composition of inorganic fine powder and a cellulose resin are suitable, and the material is not limited in any way; Yes, polyphenyl code (PPS), polyether code (PES), cyanate resin, fluororesin (tetrafluoroethylene, and tetrafluoroethylene · perfluoroalkyl vinyl ether copolymer, etc.), low molecular weight poly Perylene imine, its derivatives, and its precursors, etc. • Low molecular weight polyimide, polyether code, fluororesin, and these precursors are more suitable. -12-(9) (9) 200414244 Generally speaking, the technology for forming a conductive polymer on a dielectric oxide film can be formed using a gas phase polymerization method to form a conductive polymer layer and an electrolytic polymerization method to form a conductive polymer. Layer method (Japanese Unexamined Patent Publication No. 3-621 7, etc.), a solution chemical polymerization method in which an organic polymer monomer is adhered to a dielectric oxide film, and then polymerized in an oxidant solution (Japanese Unexamined Patent Publication No. 251-191, etc.) Electrochemical polymerization method in which the power supply point of the anode is changed at a predetermined time by the conversion device to uniformize the thickness of the conductive polymer layer (US Patent Nos. 6 1 6 8 63 9 and 63 1 3 97 In the present invention, etc.); In the present invention, it is more appropriate to immerse a valve-acting porous metal substrate in an oxidant solution, take it out and dry it, and use an organic material that includes a step of gradually increasing the concentration of the oxidant solution on the substrate J1. Solution chemical oxidation polymerization of polymer monomers or gas phase chemical oxidation polymerization; solution chemical oxidation polymerization is most suitable. Using the present invention, as shown in the examples described later, an aluminum foil having a dielectric oxide film, for example, is dipped in an isopropyl alcohol (IP A) solution of 3,4-ethylenedioxythiophene (EDT), and these are air-dried. Isopropyl alcohol is completely removed; immersed in about 20% by weight of an oxidant (ammonium persulfate) aqueous solution, and heated at about 4 (rc for 10 minutes, or repeat this step to obtain poly (3,4-ethylenedioxy Thiophene) polymer. According to the method of the present invention, the formed conductive polymer solid electrolyte layer is made into a fibril structure or a lamellar (thinner layered) structure, and these structures have a wide range of continuous polymer chains. Repeatedly, it is easy to cause electrons to jump and increase the conductivity. It is presumably the one that contributes to the improvement of low impedance. In the Kariya liquid chemical polymerization method, monomers adhered to the anode substrate have micro-13- (10) (10) 200414244 On the fine-pored dielectric film, in the presence of a compound obtained as a dopant of a conductive polymer, the polymer composition is oxidized and polymerized due to the action of an oxidant and water in the air, In dielectric A solid electrolyte is formed on the surface; at this time, in order to form a good polymer composition, the immersion time of the monomer-containing liquid and the oxidant-containing liquid must be adjusted to control the adhesion amount of the monomer and the oxidant; for example, when the immersion time is too long, The polymerization reaction cannot be completed, and the obtained polymer composition is likely to become a low-molecular-weight one. In addition, when the immersion time in the oxidant-containing liquid having an unsaturated concentration is too long, the oxidant adhered to the metal foil substrate through the step before the drying step is included. Will re-dissolve, at the same time, the adhesive monomers and the resulting polymer will also dissolve or flow out; causing the polymer to be produced slowly, and at the same time, the effluent will contaminate the oxidant-containing liquid; at the same time, the monomer-containing liquid will also Occurs during the immersion. During development, for example, when an oxidant-containing liquid with a low molecular weight component is used, the color of the monomer-containing liquid, the polymer floating, and the weight of the solid electrolyte formed by adhesion tend to decrease. Changes in viscosity, specific gravity, etc. Therefore, in the method of the present invention, the And the time when the oxidant contains the liquid, the sufficient time required for the monomer component and the oxidant component in the containing liquid to adhere to the dielectric surface of the metal foil substrate is less than 15 minutes, which is suitable; 0.1 seconds to 10 minutes is more suitable It is more suitable that it is 1 second to 7 minutes. Furthermore, in order to uniformly adhere the monomer on the surface of the dielectric and the polymer composition, after impregnating with the monomer-containing liquid, it must be left in the air for a certain period of time to make the solvent gas This condition varies with the type of solvent. Generally, -14- (11) 200414244 varies with
之 下進行；放置時間， 至1 5分鐘爲宜，例如 此放置時間之設立， 〇 °c以上至溶媒之沸點爲止之溫度 溶媒之種類而改變，大體上以5秒 爲醇系溶媒，以5分鐘以內爲佳； 使單體均勻的黏著於電介暂寿面ί μ 」‘有iK祖）丨貞衣囱上，更可以減少下步驟 浸漬於氧化劑含有液時的污染。 浸漬於單體含有液，及氧化劑含有液後，在一定之溫 度範圍，依所定時間保持於空氣中，單體進行氧化聚合。 聚合溫度’隨單體之種類而異，例如，吡咯以5艺以 下爲佳，噻吩系必須爲30〜60°C。 聚合時間’依浸漬時之單體的黏著量而定；黏著量隨 單體及氧化劑含有液之濃度，粘度等而改變，不能一槪的 規定；一般而言，減少一次之黏著量，可以縮短聚合時間 ;又，增加一次之黏著量，則必須加長聚合時間。 在本發明之方法中，一次之聚合時間爲1 〇秒〜3 0分鐘 ，以3〜1 5分鐘更爲適合。 以本發明之方法，在電介質皮膜上形成之導電性聚合 物層，藉由電子顯微鏡照相，確認成爲板層結構，或原纖 維結構之形狀。 導電性聚合物之板層結構及原纖維結構，由於聚合物 鏈之單向性的提高、及聚合物鏈間之廣泛的重覆，有助於 成爲提高電導度之要因；對聚合體固體電解質之電導度的 提升及低阻抗化等電容器之特性的提高’料必授與相當之 影響。 在本發明之方法中，爲使形成之導電性聚合物組成物 - 15- (12) (12)200414244 ，在厚度上具有對濕度、熱、應力等之耐性，必須控制浸 漬之次數；上述製造步驟，以對一個陽極基體而言，浸漬 次數爲5次以上，較適合的爲8〜3 〇次重覆操作，可以輕易 地形成所期望之固體電解質層。 形成使用於固體電解質電容器之固體電解質的步驟爲 ’將在具有活門作用之金屬上形成電介質皮膜的陽極體， 交互浸漬於單體含有液、及氧化劑含有液、乾燥後，重覆 操作，使之黏著，於空氣中進行化學氧化聚合之過程。 大氣中之溫度’隨聚合物組成物之種類、聚合方法等 而改變，不能總括規定，一般而言，以_ 7 〇艺〜2 5 〇它之範 圍較爲適宜。 單體含有液之濃度，爲3〜50重量％，以5〜〜35重量％ 較佳，以10〜25重量％最爲適合；氧化劑含有液之濃度， 爲5.〜70質量％，以15〜50重量％較爲適合；又，單體含有 液及氧化劑含有液之粘度’爲1 〇 〇 c p以下，以3 0 c p以下較 佳，以0.6〜10cp最爲適合。 使用本發明，以單體含有液及氧化劑含有液交互浸漬 ，可以形成具有層狀結構（板層結構或原纖維結構）之導電 性聚合物的固體電解質；更於此層中，由於聚合物鏈之單 向性的提高，及產生聚合物鏈間之重覆，確定不必進行各 次之洗淨，以最後進行較爲適合；如此，在聚合步驟中沒 有反應，而餘留之過剩的（未反應的）單體，也可在下次之 步驟聚合’其結果’可以形成廣泛而重覆的具有層狀結構 之導電性聚合物所成之固體電解質。 -16 - (13) (13)200414244 本發明固體電解質之適合的形成步驟之一爲’包含將 形成上述電介質皮膜層的活門作用金屬陽極箔，浸瀆於含 氧化劑之含有液（含有液1)的步驟，及浸漬於含單體及摻 雜劑之含有液（含有液2)的步驟者；依此順序，浸漬於上 述含有液1之後，再浸漬於含有液2之步驟（正順序）進行亦 可；又，依逆順序，將上述活門作用金屬陽極箔，浸漬於 上述含有液2之後，再浸漬於含有液1之步驟進行亦可。 或者另外之實施型態，包含將上述陽極箔，浸漬於含 氧化劑及摻雜劑之溶液（含有液3)的步驟，與浸漬於含單 體之溶液（含有液4)的步驟者，亦可，此情形，亦包含依 正順序浸漬於上述含有液3之後，再浸漬於上述含有液4之 步驟進行，或依逆順序，將上述陽極箔浸漬於上述含有液 4之後，再浸漬於上述含有液3之步驟的製造方法亦可；上 述含有液1至含有液4，分別以懸濁狀態使用亦佳；而且， 上述之浸漬步驟以塗佈作業代替亦可。 含有液1至含有液4之溶媒，因應需求使用相同者亦可 ，或者使用相異之溶媒系亦可；又’因應溶媒之種類，含 有液1與含有液2之間，或含有液3與含有液4之間的步驟， 置入另外之乾燥步驟亦可；而且形成固體電解質後，進行 洗淨亦佳。 本發明中可以使用之具有活門作用的金屬，有鋁、鉅 、隹尼、駄、錶、錶、砂寺之早體金屬、或此寺之合金；又 ，對型態而言，壓延箔之蝕刻物、微粉熔結體等之多孔質 成形體之型態均可。 (14) (14)200414244 其次，陽極基板雖可使用此等金屬之多孔質熔結體' 蝕刻等表面處理板（彩帶、范等包含在內）、線等’但以平 板狀、箔狀者較爲適合；而且，在此金屬多孔體之表面， 形成電介質氧皮膜之方法，可以使用眾所周知的方法；例 如，使用鉅粉末之熔結體時，可以在磷酸水溶液中進行陽 極氧化，於熔結體形成氧化皮膜。 例如，活門作用金屬箔之厚度，隨使用目的之不同而 異，一般使用厚度在4〇〜300 μηι之箔；爲製造薄型之固體 電解質電容器，例如鋁箔，使用80〜2 50 Mm者，設置固體 電解質電容器之元件的壓縮後最大高度（Rmax)，以可達 2 5 0 μιη以下爲適合；金屬箔之大小及形狀，亦隨用途而異 ，平板狀元件單位，以寬約1〜50公厘、長約1〜50公厘之矩 形者爲適合，以寬約2〜15公厘、長約2〜25公厘更加適當。 本發明中，形成固體電解質可以使用之水溶液系氧化 劑有，過氧二硫酸及其鈉鹽、鉀鹽、銨鹽、硝酸鈽（IV)， 硝酸鈽（IV)銨，硫酸鐵（III)，硝酸鐵（III)，氯化鐵（III)等 等；又，有機溶劑系之氧化劑有，有機磺酸鐵，例如，十 二烷基苯磺酸鐵（III)，對-甲苯磺酸鐵（ΠΙ)等等；此處所 用之有機溶劑有，r - 丁內酯、及丁醇、異丙醇等一價之 醇類等等；還有，氧化劑溶液之濃度，以5〜5 0質量％爲宜 ，又，氧化劑溶液之溫度，以-1 5〜6 0 °C爲適合。 本發明中，用以形成固體電解質之導電性聚合物，爲 具有7Γ電子共軛結構之有機高分子單體的聚合物，其聚合 度爲2以上2000以下，以3〜1 000較適合，以5〜200更爲適當 -18- (15) (15)200414244 •，具體例有，具有噻吩骨架之化合物，具有多環狀硫化物 骨架之化合物，具有吡咯骨架之化合物，具有呋喃骨架之 化合物、具有苯胺骨架之化合物等含有顯示結構重覆單位 之導電性聚合物等等，導電性聚合物不限定於此等化合物 〇 具有噻吩骨架之單體化合物有，3_甲基噻吩、3 -乙基 噻吩、3 -丙基噻吩、3 -丁基噻吩、3 -戊基噻吩、3 -己基噻 吩、3 -庚基噻吩、3 -辛基噻吩、3 -壬基噻吩、3 -癸基噻吩 、3-氟噻吩、3-氯噻吩、3-溴噻吩、3·氰基噻吩、3，4-二 甲基噻吩、3，4 -二乙基噻吩、3，4 -丁嫌基噻吩、3，4 -甲 二氧基噻吩、3，4-乙二氧基噻吩等之衍生物；此等化合 物，可以一般市售之化合物，或以眾所周知之方法（例如 ，合成金屬誌，1 9 8 6年，1 5卷，1 6 9頁）準備，對此沒有任 何限制。 又，具有多環狀硫化物骨架之單體化合物，具體例有 ，具有1，3-二氫多環狀硫化物（別名爲，1，3_二氫苯并 喧吩）骨架之化合物、具有丨，3_二氫萘并[2，3_c]噻吩 骨架之化合物可以使用；更有，具有1，二氫蒽[2，夂C] 噻吩骨架之化合物、具有丨，3-二氫并四苯[2, 3_c]噻吩骨 架之化合物等等；此等可以眾所周知的方法，例如，特開 平8 - 3 1 5 6號公報上記載之方法準備。 又，具有1，3-一氫奈并[1，2-c]噻吩骨架之化合物， 可以使用1，3-二氫菲并[2，3-c]噻吩衍生物；具有丨，3_ 二氫三苯并[2，3-c]噻吩骨架之化合物，可以使用丨，3•二 ‘ 19 - (16) (16)200414244 氫苯并[a]蒽[7，8-c]噻吩衍生物等等。 縮合環上任意含有氮或N -氧化物之化合物，可以使用 1，3-二氫噻吩并[3，4-b]喹喔啉、1，3-二氫噻吩并[3，扣 b ] D奎喔啉_ 4 -氧化物、1，3 -二氫噻吩并[3，4 - b ]喹喔啉4， 9 -二氧化物等等；對此等沒有特別之限制。 具有吡咯骨架之化合物有，3 -甲基吡咯、3 -乙基吡咯 、3 -丙基吡咯、3 - 丁基吡咯、3 -戊基吡咯、3 -己基吡咯、 3 ·庚基吡咯、3 -辛基吡咯、3 -壬基吡咯、3 -癸基吡咯、3 -氟吡咯、3 -氯吡咯、3 -溴吡咯、3 -氰基吡咯、3，4 -二甲基 吡咯、3，4-二乙基吡咯、3，4-丁烯基吡咯、3，4-甲二 氧基吡咯、3，4 -乙二氧基吡咯等之衍生物等等；此等化 合物可以巾售品或眾所周知的方法準備，本發明對此沒有 特別之限制。 具有呋喃骨架之化合物有，3 -甲基呋喃' 3 -乙基呋喃 、3 -丙基呋喃、3 - 丁基呋喃、3 -戊基呋喃、3 -己基呋喃、 3 -庚基呋喃、3 -辛基呋喃、3 -壬基呋喃、3 -癸基D夫喃、3 -氟D夫喃、3 -氯呋喃、3 -溴咲喃、3 -氰基D夫喃、3，4 -二甲基 呋喃、3，4 -二乙基呋喃、3，4 - 丁烯基呋喃、3，4 ·甲二 氧基D夫喃、3，4 -乙二氧基咲喃等之衍生物等等；此等化 合物可以市售品或眾所周知的方法準備，本發明對此沒有 特別之限制。 具有本fl女骨架之化合物有，2 -甲基苯胺、2 -乙基苯胺 、2-丙基苯胺、2-丁基苯胺、2-戊基苯胺、2-己基苯胺、 2-庚基苯胺、2-辛基苯胺、2-壬基苯胺、2-癸基苯胺、 2- -20- (17) (17)200414244 氟苯胺、2-氯苯胺、2-溴苯胺、氰基苯胺、2 , 5_二甲基 苯胺、2，二乙基苯胺、2，3-丁烯基苯胺、2 , %甲二氧 基苯胺、2，3-乙二氧基苯胺等之衍生物等等；此等化合 物可以市售σπ或眾所周知的方法準備，本發明對此沒有特 別之限制° 此％之中，以具有噻吩骨架或具有多環狀硫化物骨架 之化合物，較爲適合；以3，4-乙二氧基噻吩（EDT)、1， 3 -二氫異硫茚特別適用。 又’上述有機局分子單體之溶媒，以一價醇類（甲醇 、乙醇、正丙醇、異丙醇、正丁醇、異丁醇、第三級丁醇 等）較適合使用；單體溶液中之單體濃度，沒有特別之限 制，可以任意濃度使用。 上述選自化合物群之化合物的聚合條件等，沒有特別 的限制’以簡單的實驗預先確認適合之條件，可以容易的 施行。 又’倂用選自上述單體化合物群之化合物，形成共聚 物之固體電解質亦佳，此時聚合性單量體之組成比等，爲 依賴聚合條件者，適合之組成比、聚合條件，可用簡單的 貫驗確認。 例如，EDT單體及氧化劑在適合之溶液型態，前後分 別或一起塗佈於金屬箔之氧化皮膜層，而形成之方法等可 以利用（專利第3040 1 1 3號公報、美國專利第62296 89號公報 )° 本發明中適合使用之3，乙二氧基噻吩（EDT)，溶解 -21 - (18) (18)200414244 於上述之一價醇，與水的相容性不佳之故，與高濃度之氧 化劑水溶液接觸時，EDT在其接觸面，良好的進行聚合， 开夕成原纖維結構或板層結構（薄層狀）之導電性高分子固體 電解質層。 本發明之製造方法中使用的溶液，或固體電解質形成 後之洗淨用溶媒有，例如，四氫呋喃（THF)、二噁烷、二 乙醚等之醚類；丙酮、甲乙酮等之酮類；二甲基甲醯胺、 乙腈、苯甲腈、N -甲基吡咯烷酮（NMP)、二甲基亞碼 (D M S Ο )等之非質子性極性溶媒；醋酸乙酯、醋酸丁酯等 之酯類；氯仿、氯化甲烯基等之非芳香族性的氯系溶媒； 硝基甲烷、硝基乙烷、硝基苯等之硝基化合物；甲醇、乙 醇、丙醇等之醇類；甲酸、醋酸、丙酸等之有機酸；該有 機酸之酸無水物（例如，無水醋酸等），又水或此等之混合 溶媒，可以使用；較適合的，爲水、醇類、酮類、或此等 之混合系。 本發明之導電性聚合物，使用芳基磺酸系摻雜劑；例 如，摻雜劑之原料可以使用苯磺酸、甲苯磺酸、萘磺酸、 蒽磺酸、蒽醌磺酸等之鹽類。 如此製造而得之固體電解質的電導度，約在0.1〜2 〇〇 S/公分之範圍，以約1〜150 S/公分較佳，以約1〇〜1〇〇 s/公 分之範圍更爲適合。 本發明中，將以氧化聚合在縱（厚度）方向成長而形成 之導電性聚合物組成物層的基板壓縮使用；藉由此壓縮， 如圖2之模式圖所示，使固體電解質層之最大厚度（hQ與 -22 - (19) 200414244 最小厚度（h 2 )之差Π11 - h 2 ]的値變少，同時，基板及導電性 聚合物亦壓縮變薄’形成元件形狀及容量之離散情形極少 ，而且安定之電容器元件。 壓縮，在形成導電性聚合物組成物層之單一電容器元 件基板施行亦可，也可以在電容器元件基板層合之層合型 電容器製造過程，將複數片重疊之最外層施行壓縮。 壓縮，可以將形成導電性聚合物組成物層之基板，以 平板按壓施行；壓縮條件，在不影響電容器特性之範圍內 ，基板本身之壓縮變形也不要緊。 具體的說，壓縮前包含基板之導電性聚合物層的最大 厚度爲Hamax，最小厚度爲Hamiii，壓縮後包含基板之導 電性聚合物層的最大厚度爲Hbmax，最小厚度Hbm in時， 如下式所示之厚度差的減少率△ Η，以可達5〜9 5 %之範圍 施行。 (Hbmax - Hbmin) ΔΗ (%)= X 10 0 1 —--- (Hamax — Hami η) 又，設置有固體電解質層之基板整體（包含單板及層 合板元件之任何一種）的壓縮率，爲5〜9 0 %，以1 0〜8 5 %較 佳，以15〜80%更爲適合。 電導度爲，在約0.1〜200 S/公分之範圍者，以約1〜150 s/公分較佳，以約]〇〜1〇〇 S/公分更爲適合。 壓縮之際所使用之成形用平板的材質，沒有特別的規 -23- (20) 200414244 定，金屬板或具有彈性之材料，例如使用塑膠 縮；使用具有彈性之平板，在壓縮之際，自然 或塑性變形，使該基板成爲包裹彈性體之形態 而言，形成之導電性聚合物組成物層之基板， ;預先將形成導電性聚合物組成物層之基板， ，再經壓縮亦可，重覆壓縮亦佳。 壓縮所需之壓力爲0.05〜20 公斤/平） 0.1〜10 公斤/平方公厘爲較佳，以0.1〜2 公f 更爲適合；又，壓縮後之元件厚度的最小値有 以設定壓縮時之平板的間隔加以限制亦佳。 壓縮時之保持時間爲0.01秒〜5分鐘，以0. 佳，以0.1秒〜10秒更爲適合。 元件在即將壓縮之前，加熱至不滿200 °C 板加熱至2 3 0 °C亦佳，又，雙方均加熱亦佳。 壓縮之際，因應需求，爲防止元件黏著於 脫膜劑，例如，水亦佳；或爲防止含導電性聚 層發生溶解或分解等狀態變化，更使用沸點3 有機溶劑亦佳；或在後步驟，使用可去除之界 佳。 又，在平板上施行電鍍、類金剛石塗佈、 等表面處理，亦可防止元件黏著於平板。 由壓縮產生之電介質皮膜上的缺陷，可在 驟施行再形成、熟化而修復。 藉由如此之步驟，能使電容器元件之厚度 板，亦可壓 而然之彈性 時，就結果 經壓縮亦可 複數片層合 「公厘，以 -/平方公厘 所限制時， 1秒〜3 0秒較 亦佳，或平 平板，使用 合物之陰極 :滿1 〇 0 °c之 面活性劑亦 特氟隆塗佈 壓縮後之步 的離散情形 -24- (21) (21)200414244 不再發生，而且可使厚度減薄之故，可提局在所定之電容 器箱櫃容積空間中的基板密度，因而得以突破先前之容量 上限。 更且，電容器元件之薄膜化，單板亦能利用爲電路基 板密著型之電容器。 以本發明之方法，所得覆盖於陽極體外表面之板層結 構或原纖維結構的固體電解質，相對的產生連續或單獨之 空間；以本發明之方法，所得覆蓋於陽極體外表面之板層 結構或原纖維結構的固體電解質，產生連續或單獨之空間 ;在上述之壓縮步驟中，僅僅使空間之體積變小，而提高 固體電解質之密度，固體電解質之板層結構或原纖維結構 ，依然原封不動的保持著；因此之故，以壓縮使固體電解 質之厚度變薄，對密封步驟等電容器製造之製程中，所承 受之熱應力、機械應力等影響的緩和作用，與壓縮之前沒 有改變；又，不僅是製程，亦包含實際使用電容器之際， 承受來自環境之種種應力，也能對應，可稱爲有效之結構 〇 必須再形成時，可以使用與包含形成電壓等之形成條 件的形成所使用之形成液相同種類的形成液；較適合的， 爲己二酸銨等中性之鹽類，磷酸鹽等亦可使用。 再形成，以在電容器晶片處理前之步驟施行爲佳，在 電容器元件受到損傷時，或受到損傷後，一次施行亦佳。 又，電容器元件或電容器晶片，在大氣中施加電壓， 以加濕熟化亦能修復；預先使電容器元件或電容器晶片在 -25- (22) (22)200414244 20°C〜95°C、40%〜95%相對濕度之條件下放置5分鐘〜100小 時後，於常溫〜23 0 °C之大氣中，，施加額定電壓之0.5倍 至不破壞電容器之程度爲止的電壓、或在20t〜95 °C、 40%〜95%相對濕度之條件下，施加額定電壓之0.5倍至不破 壞電容器之程度爲止的電壓，亦可修復損傷。 還有，除非壓縮時受到損傷，此等再形成之技巧實際 上沒有必要。 在如此形成的導電性聚合物組成物層之上，爲使與陰 極導線接頭之電接觸良好，以設置導電體層較爲適合，例 如，施行形成導電糊狀物之固體，或電鍍、金屬蒸著之導 電樹脂膜等。 本發明中，亦可以在形成導電體層之後，施行壓縮； 例如，對含有彈性體之導電體層特別有效的，可以藉由壓 縮而塑性變形，更能使其變薄，亦有使導電體層表面平滑 化之效果。 如此所得之固體電解質電容器元件，通常，連接至導 線接頭，例如，將樹脂模具，樹脂提箱、金屬製之外裝提 箱、樹脂浸漬等，施行外裝，可做爲各種用途之電容器製 品0 [用以實施發明之最佳型態] 就本發明之代表例，更具體的說明如下，還有，此等 係’爲說明之單一例示，本發明對此沒有任何之限制。 -26- (23) (23)200414244 【實施方式】 [實施例1] 將鋁之化成箔（厚度爲100 μιη)切取短軸方向3公厘 ><長 軸方向10公厘，於長軸方向之4公厘與5公厘處劃分隔開， 雙面之週邊塗佈寬1公厘之聚醯亞胺溶液，乾燥後製成掩 蔽罩；此化成箔之3公厘χ4公厘的部份，以1〇重量％之己 二酸銨水溶液，施加4伏特之電壓，在切口部份進行化成 ，形成電介質氧化皮膜；其次，將此鋁箔之3公厘X 4公厘 之部份，以3，心乙二氧基噻吩溶解，浸漬於1.2莫耳/公升 之異丙醇（ΙΡΑ)溶液5秒鐘，將此置於室溫下乾燥5分鐘， 浸漬於含有八蒽醌磺酸鈉0.07重量％之2莫耳/公升的過硫 酸銨水溶液5秒鐘；接著，將此鋁箔放置於40 °C之大氣中 ，進行氧化聚合；進而，使此浸漬步驟及聚合步驟，整體 重覆操作25次，在鋁箔之外表面上形成導電性聚合物之固 體電解質層；將最後生成之聚（3，4-乙二氧基噻吩），在50 °C之溫水中洗淨，其後於1〇〇 °C下進行30分鐘之乾燥，即 形成固體電解質層。 使用膜厚計[皮口克公司製，數位度盤式指示器，DG_ 205 (精確度3μιη)]，將鋁箔緩慢的夾住於膜厚計之測定部 ，測定其厚度；其結果’如圖2之模示圖所示’週邊之鼓 起部份的厚度（h!)爲260μιη，中央之蜂腰部份的厚度（h2)爲 210μιη，膜厚之差（hi-h2)爲 50μιη。 其次，將厚度測定後之形成鋁箔的導電性聚合物組成 物層之部份，置於間隙之最小値爲I40 ^爪的金屬模具上’ -27- (24) (24)200414244 以約1 . 5公斤/平方公厘之壓力壓縮成形；接著，以同樣 的方法測定膜厚；其結果，如圖2之模式圖所示，最大厚 度（h】）爲180μιη，最小厚度（h2)爲170μιη’膜厚之差（h!-h2)爲 10 μηι ;壓縮後之固體電解質層的厚度差之減少率（△ H)爲 80%，壓縮率爲約30%。 其次，將形成電解質層之3公厘X 4公厘的部份，浸漬 於1 5重量％之己二酸銨溶液中，在未形成固體電解質層部 份之活門作用金屬箔上設置陽極之接點，施加3 · 8伏特之 電壓，進行再形成。 再其次，如圖3所不’在上述形成銘箱之導電性聚合 物組成物層的部份，以碳糊狀物及銀糊化物黏著，將上述 鋁箔4片層合，連接於陽極導線接頭；又，在未形成導電 性聚合物組成物層的部份，以焊接連接於陽極導線接頭； 更以氧樹脂將此兀件密封後，在1 2 5 °C下以額定電(2 伏特）施加，進行2小時之熟化，即完成合計3〇個之電容器 〇 對於30個之電容器元件，測定其初期特性之12〇以下 的各星與損耗係數[t a η δ X 1 〇 〇 ( % )]，等效串聯電阻（e s r ) ，及漏泄電流；還有，漏泄電流是在施加額定電壓丨分鐘 後測定；表1爲此等之測定値的平均値、與以〇〇〇2cv以上 之漏泄電流爲不良品之不良率；此處，漏泄電流之平均値 爲不良品除外之計算値。 [實施例2(1)〜2(3)] - 28 - (25) 200414244 以與實施例1中相同之製造條件，形成固體電解質後 ，經壓縮與層合，施行各種組合。 [實施例2(1)]It is better to leave it for 15 minutes. For example, the setting of this leaving time, the temperature of the solvent above 0 ° c to the boiling point of the solvent changes, the alcohol solvent is 5 seconds, and the time is 5 seconds. It is better to be within minutes; to make the monomers adhere to the dielectric temporary life surface uniformly (there are iK ancestors) and the chrysanthemum, which can further reduce the pollution when immersed in the oxidant-containing liquid in the next step. After being immersed in the monomer-containing liquid and the oxidizing agent-containing liquid, the monomer is oxidized and polymerized by being kept in the air for a predetermined time in a certain temperature range. The polymerization temperature 'varies depending on the type of monomer. For example, pyrrole is preferably 5 or less, and the thiophene system must be 30 to 60 ° C. Polymerization time 'depends on the amount of monomer adhesion during immersion; the amount of adhesion varies with the concentration and viscosity of the monomer and oxidant-containing liquid, and cannot be specified at one go; generally, reducing the amount of adhesion once can shorten Polymerization time; again, to increase the amount of adhesion once, you must increase the polymerization time. In the method of the present invention, the polymerization time of one time is 10 seconds to 30 minutes, and 3 to 15 minutes is more suitable. According to the method of the present invention, the conductive polymer layer formed on the dielectric film is photographed by an electron microscope to confirm the shape of a layer structure or a fibril structure. The lamellar structure and fibril structure of conductive polymers, due to the improvement of the unidirectionality of polymer chains and the extensive overlap between polymer chains, help to become a factor for improving electrical conductivity; for polymer solid electrolytes The improvement of the conductivity of capacitors and the improvement of the characteristics of capacitors such as the reduction of impedance will surely have a considerable impact. In the method of the present invention, in order to make the formed conductive polymer composition -15- (12) (12) 200414244 have resistance to humidity, heat, stress and the like in thickness, the number of impregnations must be controlled; the above manufacturing In the step, for an anode substrate, the number of dipping times is more than 5 times, and it is more suitable to repeat the operation from 8 to 30 times, and the desired solid electrolyte layer can be easily formed. The step of forming a solid electrolyte for a solid electrolyte capacitor is to 'dilute the anode body on the metal having a valve function, and alternately immerse it in the monomer-containing liquid and the oxidant-containing liquid, and repeat the operation after drying. Adhesion, the process of chemical oxidation polymerization in the air. The temperature in the atmosphere varies with the type of polymer composition, the polymerization method, etc., and cannot be specified in general. Generally speaking, it is more suitable to range from _70 ° to 2500 °. The concentration of the monomer-containing liquid is 3 to 50% by weight, preferably 5 to 35% by weight, and most preferably 10 to 25% by weight; the concentration of the oxidant-containing liquid is 5. to 70% by mass, to 15 A viscosity of ~ 50% by weight is more suitable; and the viscosity 'of the monomer-containing liquid and the oxidant-containing liquid is 100 cp or less, preferably 30 cp or less, and most preferably 0.6 to 10 cp. By using the present invention, a monomer-containing liquid and an oxidizing agent-containing liquid are alternately impregnated to form a solid electrolyte having a layered structure (plate structure or fibril structure) of a conductive polymer; moreover, in this layer, due to the polymer chain The unidirectionality is improved, and overlap between polymer chains is generated. It is determined that it is not necessary to perform each washing, and it is more suitable to be carried out in the end. In this way, there is no reaction in the polymerization step, and the excess (unused (Reactive) monomers can also be polymerized in the next step 'results' can form a broad and repeated solid electrolyte made of a conductive polymer with a layered structure. -16-(13) (13) 200414244 One of the suitable formation steps of the solid electrolyte of the present invention is' comprising a valve-acting metal anode foil that will form the above-mentioned dielectric film layer, immersed in an oxidant-containing liquid (containing liquid 1) And the step of immersing in the containing liquid containing the monomer and the dopant (containing liquid 2); in this order, the step of immersing in the containing liquid 1 and then immersing in the containing liquid 2 (positive order) are performed Alternatively, in the reverse order, the step of immersing the valve-acting metal anode foil in the containing liquid 2 and then dipping in the containing liquid 1 may be performed. Or another embodiment includes a step of dipping the anode foil in a solution containing oxidant and dopant (containing liquid 3) and a step of dipping in a monomer-containing solution (containing liquid 4). In this case, the step of immersing in the above-mentioned containing liquid 3 in the positive order and then immersing in the containing liquid 4 is performed, or in the reverse order, the anode foil is immersed in the containing liquid 4 and then immersed in the containing The manufacturing method of the liquid 3 step is also possible; the above-mentioned containing liquid 1 to containing liquid 4 may be used in a suspended state, respectively; and the above-mentioned dipping step may be replaced by a coating operation. Solvents containing Liquid 1 to Liquid 4 may be the same as required, or different solvent systems may be used; and 'depending on the type of solvent, between Liquid 1 and Liquid 2 or Liquid 3 and The step between the liquids 4 may be placed in another drying step; and after the solid electrolyte is formed, it may be washed. The metal having a shutter function that can be used in the present invention includes aluminum, giant, satin, osmium, watch, table, early temple metal of sand temple, or alloy of this temple; and, for the type, rolled foil The porous shaped body such as an etched material and a fine powder sintered body may be of any type. (14) (14) 200414244 Secondly, the anode substrate can be made of porous fused bodies of these metals, such as surface treatment boards (including ribbons and fans), wires, etc., but in flat or foil form. It is more suitable; moreover, the method for forming a dielectric oxygen film on the surface of the porous metal body can use a well-known method; for example, when using a sintered body of a giant powder, anodization can be performed in an aqueous phosphoric acid solution, and sintered The body forms an oxide film. For example, the thickness of the valve-acting metal foil varies with the purpose of use. Generally, a foil with a thickness of 40 to 300 μm is used. To manufacture a thin solid electrolytic capacitor, such as aluminum foil, use 80 to 2 50 Mm. The maximum height (Rmax) after compression of electrolytic capacitor components is suitable to be less than 250 μm; the size and shape of metal foils also vary with applications. Flat-shaped component units are about 1 to 50 mm wide A rectangular shape with a length of about 1 to 50 mm is suitable. A width of about 2 to 15 mm and a length of about 2 to 25 mm are more appropriate. In the present invention, the aqueous oxidant that can be used to form a solid electrolyte includes peroxodisulfuric acid and its sodium, potassium, ammonium, osmium (IV) nitrate, osmium (IV) ammonium nitrate, iron (III) sulfate, and nitric acid. Iron (III), iron (III) chloride, and the like; and organic solvent-based oxidants include iron sulfonates such as iron (III) dodecylbenzenesulfonate and iron (p-toluenesulfonate). ) Etc .; the organic solvents used here are r-butyrolactone, and monovalent alcohols such as butanol, isopropanol, etc .; and the concentration of the oxidant solution is 5 to 50% by mass as The temperature of the oxidant solution is preferably -15 to 60 ° C. In the present invention, the conductive polymer used to form the solid electrolyte is a polymer of an organic polymer monomer having a 7Γ electron conjugated structure, and the degree of polymerization is 2 or more and 2000 or less, and 3 to 1,000 is more suitable. 5 to 200 is more suitable. -18- (15) (15) 200414244 • Specific examples include compounds having a thiophene skeleton, compounds having a polycyclic sulfide skeleton, compounds having a pyrrole skeleton, compounds having a furan skeleton, Conductive polymers containing aniline skeletons, such as conductive polymers containing structural repeating units, are not limited to these compounds. Monomer compounds having a thiophene skeleton include 3-methylthiophene, 3-ethyl Thiophene, 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-butanylthiophene, 3,4 -Derivatives of methyldioxythiophene, 3,4-ethylenedioxythiophene, etc .; these compounds It can be prepared by a commercially available compound or by a well-known method (for example, Synthetic Metallurgy, 1986, vol. 15, pp. 169), without any restriction. Specific examples of the monomer compound having a polycyclic sulfide skeleton include a compound having a 1,3-dihydropolycyclic sulfide (alias, 1,3-dihydrobenzophene) skeleton,丨, 3_dihydronaphtho [2,3_c] thiophene skeletons can be used; moreover, compounds having a 1, dihydroanthracene [2, 夂 C] thiophene skeleton and 丨, 3-dihydrotetrabenzene [2, 3_c] Compounds of thiophene skeleton and the like; these can be prepared by a well-known method, for example, the method described in Japanese Patent Application Laid-Open No. 8-3161. In addition, for a compound having a 1,3-monohydronaphtho [1,2-c] thiophene skeleton, a 1,3-dihydrophenanthro [2,3-c] thiophene derivative can be used; For compounds with a tribenzo [2,3-c] thiophene skeleton, 丨, 3 • di '19-(16) (16) 200414244 hydrobenzo [a] anthracene [7,8-c] thiophene derivatives, etc. can be used. Wait. Any compound containing nitrogen or N-oxide on the condensed ring can use 1,3-dihydrothieno [3,4-b] quinoxaline, 1,3-dihydrothieno [3, b] Quinoxaline_4-oxide, 1,3-dihydrothieno [3,4-b] quinoxaline 4,9-dioxide, etc .; there is no particular limitation on this. Compounds 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- Derivatives of diethylpyrrole, 3,4-butenylpyrrole, 3,4-methyldioxypyrrole, 3,4-ethylenedioxypyrrole, etc .; these compounds can be sold as towels or well-known Method preparation, the present invention is not particularly limited by this. Examples of compounds having a furan skeleton include 3-methylfuran '3-ethylfuran, 3-propylfuran, 3-butylfuran, 3-pentylfuran, 3-hexylfuran, 3-heptylfuran, 3- Octylfuran, 3-nonylfuran, 3-decyl Dfuran, 3-fluoro Dfuran, 3-chlorofuran, 3-bromosulfan, 3-cyano Dfuran, 3,4-dimethyl Derivatives such as trimethylfuran, 3,4-diethylfuran, 3,4-butenylfuran, 3,4-methyldioxy Dfuran, 3,4-ethylenedioxypyran, etc .; These compounds can be prepared by commercial products or well-known methods, and the present invention is not particularly limited thereto. The compounds having this female skeleton include 2-methylaniline, 2-ethylaniline, 2-propylaniline, 2-butylaniline, 2-pentylaniline, 2-hexylaniline, 2-heptylaniline, 2-octylaniline, 2-nonylaniline, 2-decylaniline, 2--20- (17) (17) 200414244 fluoroaniline, 2-chloroaniline, 2-bromoaniline, cyanoaniline, 2, 5 _ Derivatives of dimethylaniline, 2, diethylaniline, 2,3-butenylaniline, 2,% methyldioxyaniline, 2,3-ethylenedioxyaniline, etc .; these compounds It can be prepared by commercially available σπ or a well-known method, and the present invention has no particular limitation on this. Among these%, a compound having a thiophene skeleton or a polycyclic sulfide skeleton is more suitable; Oxythiophene (EDT), 1,3-dihydroisothioindane are particularly suitable. Also, the solvent of the above-mentioned organic molecular monomers is preferably a monovalent alcohol (methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tertiary butanol, etc.); monomers The concentration of the monomer in the solution is not particularly limited and can be used at any concentration. There are no particular restrictions on the polymerization conditions and the like of the compounds selected from the group of compounds described above. 'Suitable conditions can be easily confirmed by simple experiments in advance, and can be easily implemented. It is also preferable to use a compound selected from the above-mentioned monomer compound group, and a solid electrolyte for forming a copolymer is also preferable. At this time, the composition ratio of the polymerizable monomer is dependent on the polymerization conditions. Suitable composition ratios and polymerization conditions can be used. Simple confirmation by inspection. For example, an EDT monomer and an oxidizing agent can be applied to the oxide film layer of the metal foil separately or together in a suitable solution type, and the formation method can be used (Patent No. 3040 1 13, US Patent No. 62296 89 (Publication No.) ° 3, ethylenedioxythiophene (EDT), which is suitable for use in the present invention, is soluble in -21-(18) (18) 200414244 in the above monovalent alcohol, and its compatibility with water is not good, and When a high-concentration oxidant aqueous solution is contacted, EDT polymerizes well on its contact surface, and becomes a conductive polymer solid electrolyte layer of fibril structure or plate structure (thin layer). The solution used in the manufacturing method of the present invention, or the cleaning solvent after the solid electrolyte is formed, for example, ethers such as tetrahydrofuran (THF), dioxane, and diethyl ether; ketones such as acetone and methyl ethyl ketone; Non-protonic polar solvents such as methylformamide, acetonitrile, benzonitrile, N-methylpyrrolidone (NMP), dimethylene code (DMS 0), etc .; esters such as ethyl acetate, butyl acetate, etc .; chloroform Non-aromatic chlorine-based solvents such as methylenyl chloride; nitro compounds such as nitromethane, nitroethane, and nitrobenzene; alcohols such as methanol, ethanol, and propanol; formic acid, acetic acid, Organic acids such as propionic acid; Anhydrous of the organic acid (for example, anhydrous acetic acid, etc.), or water or a mixed solvent of these, can be used; more suitable are water, alcohols, ketones, or the like Of the hybrid system. The conductive polymer of the present invention uses an arylsulfonic acid-based dopant; for example, as a raw material of the dopant, salts of benzenesulfonic acid, toluenesulfonic acid, naphthalenesulfonic acid, anthracenesulfonic acid, and anthraquinonesulfonic acid can be used. class. The electrical conductivity of the solid electrolyte obtained in this way is in the range of about 0.1 to 2000 S / cm, preferably about 1 to 150 S / cm, and more preferably in the range of about 10 to 100 s / cm. Suitable for. In the present invention, the substrate of the conductive polymer composition layer formed by oxidative polymerization growing in the longitudinal (thickness) direction is compressed and used; by this compression, as shown in the schematic diagram of FIG. 2, the maximum of the solid electrolyte layer is maximized. Thickness (hQ and -22-(19) 200414244 The difference between the minimum thickness (h 2) Π11-h 2] becomes smaller, at the same time, the substrate and the conductive polymer are also compressed and thinner, forming a discrete situation of element shape and capacity Very few and stable capacitor elements. Compression can be performed on a single capacitor element substrate forming a conductive polymer composition layer. It can also be laminated in the capacitor element substrate in the manufacturing process of laminated capacitors. The outer layer is compressed. Compression can be performed by pressing the substrate forming the conductive polymer composition layer with a flat plate; the compression conditions do not matter the compression deformation of the substrate itself within the range that does not affect the characteristics of the capacitor. Specifically, before compression The maximum thickness of the conductive polymer layer including the substrate is Hamax, and the minimum thickness is Hamiii. The conductive polymer including the substrate after compression When the maximum thickness is Hbmax and the minimum thickness Hbmin is, the reduction rate ΔΗ of the thickness difference shown in the following formula is implemented in the range of 5-95%. (Hbmax-Hbmin) ΔΗ (%) = X 10 0 1 —--- (Hamax — Hami η) In addition, the compression ratio of the entire substrate (including any one of the veneer and the laminated plate element) provided with the solid electrolyte layer is 5 to 9 0%, and 10 to 8 5 % Is more preferable, and 15 to 80% is more suitable. Conductivity is in a range of about 0.1 to 200 S / cm, preferably about 1 to 150 s / cm, and about] 〇 ~ 100〇 / The centimeter is more suitable. There is no special rule for the material of the flat plate used in the compression. 23- (20) 200414244, metal plates or materials with elasticity, such as plastic shrinkage, are used. During compression, natural or plastic deformation will make the substrate into the form of an elastic body. In terms of the substrate of the conductive polymer composition layer, the substrate of the conductive polymer composition layer will be formed in advance. Compression is also possible, and repeated compression is also good. The pressure required for compression is 0.05 ~ 20 kg / flat) 0 .1 ~ 10 kg / mm² is more suitable, and 0.1 ~ 2 mm f is more suitable; and the minimum thickness of the compressed component should be limited by setting the interval of the flat plate during compression. The holding time during compression is 0.01 second to 5 minutes, preferably from 0.1 to 0.1 second to 10 seconds. Immediately before the component is compressed, it is better to heat it to less than 200 ° C. The board is preferably heated to 230 ° C. It is also good to heat both sides. During compression, in order to prevent the components from sticking to the release agent, such as water; or to prevent the state of the conductive polymer-containing layer from dissolving or decomposing, it is better to use a boiling point 3 organic solvent; or later Steps to use the removable world. In addition, surface treatments such as plating, diamond-like coating, and the like on the flat plate can also prevent the components from sticking to the flat plate. Defects on the dielectric film caused by compression can be reformed and cured in a short time to repair. With such a step, when the thickness of the capacitor element can be made elastic, it can be laminated with multiple pieces as a result of compression. When limited by-/ mm2, 1 second ~ 30 seconds is better, or flat plate, using the cathode of the compound: the dispersion of the surfactant after Teflon coating compression at full 100 ° C-24- (21) (21) 200414244 It no longer occurs, and the thickness can be reduced, so that the density of the substrate in the volume space of the capacitor cabinet can be raised, so that the previous capacity limit can be exceeded. Moreover, the thinning of the capacitor element, the single board can also A capacitor with a circuit substrate adhesion type is used. According to the method of the present invention, a solid electrolyte covering a layer structure or a fibril structure on the outer surface of the anode is obtained, and a continuous or separate space is relatively generated; The solid electrolyte covering the laminar structure or fibril structure on the outer surface of the anode creates a continuous or separate space; in the above compression step, only the volume of the space is reduced, and solid electrolysis is improved. The density, the layer structure of the solid electrolyte or the fibril structure remain intact; therefore, the thickness of the solid electrolyte is reduced by compression, and the thermal stress experienced during the capacitor manufacturing process such as the sealing step The easing effect of mechanical and mechanical stress has not changed from that before compression. It is not only the manufacturing process, but also the actual use of capacitors. It can also respond to various stresses from the environment. It can also be called an effective structure. It must be re-formed In this case, it is possible to use the same kind of forming liquid as the forming liquid used for formation including formation conditions such as formation voltage; more suitable, neutral salts such as ammonium adipate, phosphates, etc. may also be used. It is best to perform the steps before the capacitor chip is processed, and it is also best to perform it once when the capacitor element is damaged, or after the damage. Also, the capacitor element or capacitor wafer can be humidified and matured by applying a voltage in the atmosphere. Repair; make capacitor element or capacitor wafer in advance at -25- (22) (22) 200414244 20 ° C ~ 95 ° C, 40% ~ 95% phase After standing for 5 minutes to 100 hours under humidity, apply a voltage of 0.5 times the rated voltage to the extent that the capacitor is not damaged in an atmosphere at normal temperature to 23 0 ° C, or at 20 t to 95 ° C, 40 Under the condition of relative humidity of% to 95%, the damage can be repaired by applying a voltage of 0.5 times the rated voltage to the extent that the capacitor is not damaged. Also, unless the damage is caused during compression, these re-formation techniques are actually unnecessary. On the conductive polymer composition layer thus formed, in order to make the electrical contact with the cathode lead connection good, it is more appropriate to provide a conductive layer, for example, a solid that forms a conductive paste, or plating, metal evaporation The conductive resin film, etc. In the present invention, compression can also be performed after the conductor layer is formed; for example, it is particularly effective for a conductor layer containing an elastomer, which can be plastically deformed by compression and can be made thinner. It also has the effect of smoothing the surface of the conductor layer. The solid electrolyte capacitor element thus obtained is usually connected to a lead connector, for example, a resin mold, a resin carrying case, a metal outer carrying case, a resin impregnation, etc. are applied to the exterior, and can be used as a capacitor product for various purposes. Taking the best form of implementing the invention] As for the representative examples of the present invention, a more specific description is as follows. Moreover, these are only a single example for illustration, and the present invention does not have any limitation on this. -26- (23) (23) 200414244 [Embodiment] [Example 1] A thin aluminum foil (thickness: 100 μm) was cut into a short axis direction of 3 mm > < long axis direction of 10 mm, and The 4mm and 5mm points in the axial direction are divided and separated. The periphery of both sides is coated with a polyimide solution with a width of 1mm and dried to make a mask; this is converted into a foil of 3mm x 4mm. Partly, a 10% by weight aqueous solution of ammonium adipate was applied at a voltage of 4 volts to form a dielectric oxide film on the incision portion. Next, a 3 mm x 4 mm portion of this aluminum foil was formed. Dissolved in 3, ethylene glycol dioxythiophene, immersed in a 1.2 mol / liter isopropyl alcohol (IPA) solution for 5 seconds, dried at room temperature for 5 minutes, and immersed in sodium octaanthraquinone sulfonate 0.07% by weight of a 2 mol / L ammonium persulfate aqueous solution for 5 seconds; then, the aluminum foil is placed in an atmosphere of 40 ° C for oxidative polymerization; further, the immersion step and the polymerization step are repeated as a whole 25 times, forming a solid electrolyte layer of conductive polymer on the outer surface of the aluminum foil; 4- ethylenedioxy thiophene), heated at 50 ° C in the wash, and dried 30 minutes at 1〇〇 ° C, i.e., a solid electrolyte layer. Using a film thickness meter [Pickock, a digital dial indicator, DG_205 (accuracy: 3 μιη)], the aluminum foil was slowly sandwiched between the measurement section of the film thickness meter and the thickness was measured; The thickness of the bulging part (h!) In the periphery is 260 μm, the thickness of the central bee waist part (h2) is 210 μm, and the difference in film thickness (hi-h2) is 50 μm. Next, the part of the conductive polymer composition layer forming the aluminum foil after the thickness measurement is placed on a metal mold having a minimum gap of I40 ^ claws' -27- (24) (24) 200414244 to about 1. Compression molding at a pressure of 5 kg / mm2; then, the film thickness was measured by the same method; as a result, as shown in the schematic diagram of FIG. 2, the maximum thickness (h) was 180 μιη, and the minimum thickness (h2) was 170 μιη ' The difference in film thickness (h! -H2) was 10 μηι; the reduction rate (ΔH) of the thickness difference of the solid electrolyte layer after compression was 80%, and the compression rate was about 30%. Next, the 3 mm by 4 mm portion forming the electrolyte layer was immersed in a 15% by weight ammonium adipate solution, and an anode connection was provided on the valve-acting metal foil where the solid electrolyte layer portion was not formed. Point, a voltage of 3.8 volts was applied to reform it. Secondly, as shown in FIG. 3, the conductive polymer composition layer forming the name box is adhered with carbon paste and silver paste, and the four aluminum foils are laminated and connected to the anode lead joint. ; And, in the portion where the conductive polymer composition layer is not formed, it is connected to the anode lead joint by welding; the element is sealed with an oxygen resin, and the rated electricity (2 volts) is at 1 2 5 ° C. After applying and curing for 2 hours, a total of 30 capacitors were completed. For 30 capacitor elements, each star and loss coefficient [ta η δ X 1 〇〇 (%)] of 120 or less of its initial characteristics were measured. , Equivalent series resistance (esr), and leakage current; In addition, the leakage current is measured after the rated voltage is applied for one minute; Table 1 shows the average value of these measurements, and the leakage current above 2000cv. Is the defective rate of defective products; here, the average leakage current 値 is calculated excluding defective products 値. [Examples 2 (1) to 2 (3)]-28-(25) 200414244 After the solid electrolyte was formed under the same manufacturing conditions as in Example 1, it was compressed and laminated to perform various combinations. [Example 2 (1)]
除在設置有固體電解質之基板表面，塗佈碳糊狀物與 銀糊狀物後，於依厚度之方向壓縮，所得鋁箔4片層合， 連接於陰極導線接頭以外，其他都和實施例1同樣的裝配 構成。 [實施例2(2)] 除將設置有固體電解質之基板，依厚度方向壓縮，壓 縮之電容器元件4片層合後，依層合之厚度方向再壓縮， 以碳糊狀物與銀糊狀物黏著，連接於陰極導線接頭以外， 其他都和實施例1同樣的裝配構成。Except for coating a carbon paste and a silver paste on the surface of a substrate provided with a solid electrolyte, the obtained aluminum foil was compressed in the direction of thickness, and four sheets of aluminum foil were laminated and connected to a cathode lead joint. The same assembly structure. [Example 2 (2)] Except that a substrate provided with a solid electrolyte was compressed in the thickness direction, after compressing four capacitor elements, they were further compressed in the thickness direction of the laminate to form a carbon paste and a silver paste. An object was adhered and connected to the cathode lead connector, and the other components were assembled in the same manner as in Example 1.
[實施例2 (3 )] 除將设置有固體電質之基板5 4片層合後，依層合 之厚度方向壓縮，以碳糊狀物與銀糊狀物黏著，連接於陰 極導線接頭以外，其他都和實施例1同樣的裝配構成。 由此等所得之電容器，進行與實施例丨同樣的特性評 估，其結果如表1所示。 [實施例3] 實施例1中，除以吡咯替代3，4 -乙二氧基噻吩，此時 -29 - (26) (26)200414244 ，於浸漬吡咯溶液後，在3 °C下乾燥5分鐘，更於浸漬氧化 劑溶液後，在5 °C下聚合 1 〇分鐘以外，其他都和實施例1 同樣的完成合計3 0個之電容器。 與實施例1同樣的，測得固體電解質層之最大厚度（hl) 爲2 90μιτι，最小厚度（h2)爲230μπι，膜厚之差（hu-112)爲60μΐΏ ;接著，壓縮後之最大厚度（hi)爲200μηι，最小厚度爲 180μπι，膜厚之差（h^h2)爲20μιη ;壓縮後，固體電解質層 之厚度差的減少率（ΔΗ)爲66.7 %。 所得電容器元件，進行與實施例1同樣的特性評估， 其結果如表1所示。 [比較例1 ] 實施例1中，除使用不經壓縮成形之製作成的電容器 元件以外，其他都和實施例1同樣的完成3 〇個之電容器。 與實施例1同樣的，測得固體電解質層之最大厚度（h;) 爲260μπι’最小厚度爲210μηι，膜厚之差（h】-h2)爲50μιη。 所得電容器元件，進行與實施例1同樣的特性評估， 其結果如表1所示。 [比較例2] 實施例1中，除使用不經壓縮之聚合次數丨5次製作成 的電容器元件以外，其他都和實施例1同樣的完成3〇個之 電容器。 與實施例1同樣的’測得固體電解質層之最大厚度（h 3 ) -30- (27) 200414244 爲180μιη，最小厚度（h2)爲120μπι，膜厚之差（hi-h2)爲60μιη 〇 所得電容器元件，進行與實施例1同樣的特性評估， 其結果如表1所示。 表1 實施例 初期特性 容量pF 損耗係數 ESR 漏泄電流 不良率 % (等效串聯電阻） μΑ 1 109 0.7 0.007 0.03 0/30 2(1) 108 0.9 0.008 0.06 0/30 2(2) 109 1.6 0.017 0.03 0/30 2(3) 110 1.8 0.018 0.04 0/30 3 105 1.7 0.014 0.09 1/30 比較例1 108* 3.6 0.025 0.05 1/30 比較例2 107 1.9 0.020 0.1 5 7/30 *未密封（密封時，一部份之元件露出，不能進行正常之密封）[Example 2 (3)] Except for laminating 5 or 4 substrates provided with a solid capacitor, they were compressed in the thickness direction of the laminate, adhered with a carbon paste and a silver paste, and connected to a cathode lead joint. The other components are the same as the first embodiment. The capacitors thus obtained were evaluated for the same characteristics as in Example 丨. The results are shown in Table 1. [Example 3] In Example 1, the pyrrole was used instead of 3,4-ethylenedioxythiophene. At this time, -29-(26) (26) 200414244 was impregnated with the pyrrole solution and dried at 3 ° C. 5 After immersing the oxidant solution for 10 minutes, polymerization was carried out at 5 ° C for 10 minutes, and a total of 30 capacitors were completed in the same manner as in Example 1. As in Example 1, the maximum thickness (hl) of the solid electrolyte layer was measured to be 2 90 μm, the minimum thickness (h2) was 230 μm, and the difference in film thickness (hu-112) was 60 μΐΏ; then, the maximum thickness after compression ( hi) is 200 μm, the minimum thickness is 180 μm, and the difference in film thickness (h ^ h2) is 20 μm; after compression, the reduction rate (ΔΗ) of the thickness difference of the solid electrolyte layer is 66.7%. The obtained capacitor element was evaluated for characteristics similar to those of Example 1. The results are shown in Table 1. [Comparative Example 1] In Example 1, 30 capacitors were completed in the same manner as in Example 1 except that a capacitor element produced without compression molding was used. As in Example 1, the maximum thickness (h;) of the solid electrolyte layer was measured to be 260 µm ', the minimum thickness was 210 µm, and the difference in film thickness (h)-h2) was 50 µm. The obtained capacitor element was evaluated for characteristics similar to those of Example 1. The results are shown in Table 1. [Comparative Example 2] In Example 1, 30 capacitors were completed in the same manner as in Example 1 except that the capacitor element was fabricated using the uncompressed number of polymerization cycles of 5 times. The maximum thickness (h 3) of -30- (27) 200414244 measured in the same manner as in Example 1 was 180 μm, the minimum thickness (h2) was 120 μm, and the difference in film thickness (hi-h2) was 60 μm η. The capacitor element was evaluated in the same manner as in Example 1. The results are shown in Table 1. Table 1 Example initial characteristic capacity pF loss coefficient ESR Leakage current defect rate% (equivalent series resistance) μA 1 109 0.7 0.007 0.03 0/30 2 (1) 108 0.9 0.008 0.06 0/30 2 (2) 109 1.6 0.017 0.03 0/30 2 (3) 110 1.8 0.018 0.04 0/30 3 105 1.7 0.014 0.09 1/30 Comparative Example 1 108 * 3.6 0.025 0.05 1/30 Comparative Example 2 107 1.9 0.020 0.1 5 7/30 * Unsealed (when sealed (A part of the components are exposed, and normal sealing cannot be performed)
由實施例1〜3及比較例1〜2之結果可知，使壓縮成形之 固體電解質平坦，厚度差（△ Η)儘力減少之固體電解質電 容器，確認具有高容量，低等效串聯電阻（ESR)，而且漏 泄電流，不良率甚小，極爲優越。 [實施例4 ] -31 - (28) 200414244 將形成鋁箔之導電性聚合物組成物層的基板，2片重 疊後’使形成導電性聚合物組成物層之部份壓縮成形，與 實施例1同樣的測定單板2片層合之元件的固體電解質層之 最大厚度（h!)爲430μπι，最小厚度（h2)爲4〇0μηι，膜厚之差 (hi，h2)爲 30μιη。 [實施例5 ]From the results of Examples 1 to 3 and Comparative Examples 1 to 2, it can be seen that the solid electrolyte capacitor that flattened the compression-molded solid electrolyte and reduced the thickness difference (△ Η) as much as possible, confirmed that it has high capacity and low equivalent series resistance (ESR). And, the leakage current, the defect rate is very small, which is extremely superior. [Example 4] -31-(28) 200414244 Two substrates on which the conductive polymer composition layer of the aluminum foil is formed are overlapped, and the portion forming the conductive polymer composition layer is compression-molded, as in Example 1. Similarly, the maximum thickness (h!) Of the solid electrolyte layer of the two laminated elements of the single board was 430 μm, the minimum thickness (h2) was 400 μm, and the difference in film thickness (hi, h2) was 30 μm. [Example 5]
除將形成鋁箔之導電性聚合物組成物層的基板，2片 重疊後，使形成導電性聚合物組成物層之部份壓縮成形， 壓縮成形之基板再2片重疊，再壓縮成形以外，其他都和 實施例1同樣的測定單板4片層合之元件的固體電解質層之 最大厚度（h!)爲7 80μηι，最小厚度（h2)爲760μπι，膜厚之差 (h ]，h 2)爲 2 0 μ m。 [產業上利用性] 本發明之固體電解質電容器爲，使用在活門作用金屬 多孔體基板表面之電介質皮膜上，設置有由有機高分子之 導電性聚合物所成固體電解質的基板，依基板之厚度方向 壓縮的電容器元件者；其具有，可以安定的製作形狀之離 散情形極少，而且甚薄的電容器元件，可以建造高度甚低 、小型而高容量之層合型固體電解質電容器，固體電解質 電容器具有無短不良而且安定之性能等的特長。 【圖式簡單說明】 -32- (29) 200414244 圖1爲，使用電容器元件之固體電解質電容器的剖面 圖。 圖2爲，實施例1之電容器元件部份的模式縱向剖面圖 圖3爲，電容器元件層合所得固體電解質電容器之剖 面圖。 [圖號說明] 1 :陽極基體 2 :電介質之氧化皮膜層 3 :掩蔽罩 4 :固體電解質 5 :導電體層 6 :導線 7 :導線Except that two substrates forming the conductive polymer composition layer of the aluminum foil are superimposed, the portion forming the conductive polymer composition layer is compression-molded, and the compression-molded substrate is further superimposed by two and then compression-molded. The maximum thickness (h!) Of the solid electrolyte layer of the four-layer laminated element of the veneer was measured in the same manner as in Example 1 to be 80 μm, the minimum thickness (h2) was 760 μm, and the difference in film thickness (h), h 2 It is 20 μm. [Industrial Applicability] The solid electrolyte capacitor of the present invention is a substrate provided with a solid electrolyte made of a conductive polymer of an organic polymer on a dielectric film on the surface of a porous metal substrate of a valve-acting substrate, depending on the thickness of the substrate. Capacitor elements that are compressed in the direction; they have few discrete cases that can be made in a stable shape, and have very thin capacitor elements. They can build laminated solid electrolyte capacitors with very low height, small size and high capacity. Features such as short short and stable performance. [Brief description of the drawings] -32- (29) 200414244 Figure 1 is a sectional view of a solid electrolyte capacitor using a capacitor element. Fig. 2 is a schematic longitudinal sectional view of a capacitor element portion of Example 1 Fig. 3 is a sectional view of a solid electrolyte capacitor obtained by laminating capacitor elements. [Illustration of drawing number] 1: anode substrate 2: dielectric oxide film layer 3: masking cover 4: solid electrolyte 5: conductor layer 6: lead wire 7: lead wire
8 :環氧樹脂 9 :電容器 -33-8: Epoxy resin 9: Capacitor -33-