512373 A7 B7五、發明説明（1 ) 【發明詳細說明】 【技術領域】 本發明係相關在閥作用金屬多孔體基板表面上，形成 作爲固體電解質之導電性聚合物之固體電解電容器及其製 造方法。 更詳言之，乃相關基板裁斷面及罩幕邊界之固體電解 質層厚度，較其他部分厚的高性能固體電容器，及特別是 使用單體液與氧化劑液，製造此類固體電解電容器‘的方法 經濟部智慧財產局員工消費合作社印製 【技術背景】 按，固體電解電容器之基本元件，如第1圖所示，一 '般乃在由經蝕刻處理過之比表面積較大金屬箔所構成的陽 極基體1上，形成介電質氧化皮膜層2，並於外側上形成 .相對向電極的固體半導體層（以下稱「固體電解質」）， 然後最好形成導電塗料等導電層5而製得。其次，此類元 件便單獨或疊層接合導線6，7，且整體以環氧樹脂8等 完全封裝，而形成電容器元件，並被廣泛的使用於電子產 品。 近年，.隨電子機械的數位化、個人電腦高速發展，便 需求小型且大容量的電容器，及在高頻區域中屬低阻抗的 電容器。 小型且大容量的電容器，有如鋁電解電容器或鉅電解 電容器等電解電容器。 -；-4- 本纸張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） (請先閲讀背面之注意事項再填寫本頁)512373 A7 B7 V. Description of the invention (1) [Detailed description of the invention] [Technical field] The present invention relates to a solid electrolytic capacitor that forms a conductive polymer as a solid electrolyte on the surface of a valve-acting metal porous body substrate and a method for manufacturing the same . In more detail, it is the thickness of the solid electrolyte layer of the relevant substrate cutting surface and the border of the curtain. It is a high-performance solid capacitor thicker than other parts, and especially the method of manufacturing such solid electrolytic capacitors using monomer liquid and oxidant liquid. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs [Technical background] According to Figure 1, the basic components of solid electrolytic capacitors are generally made of metal foil with a large specific surface area after etching. A dielectric oxide film layer 2 is formed on the anode substrate 1 and is formed on the outside. A solid semiconductor layer (hereinafter referred to as a "solid electrolyte") of an opposing electrode is preferably formed by forming a conductive layer 5 such as a conductive paint. Secondly, such components are individually or laminated with bonding wires 6, 7 and are completely packaged with epoxy resin 8 or the like to form capacitor components, which are widely used in electronic products. In recent years, with the digitization of electronic machinery and the rapid development of personal computers, small and large-capacity capacitors and capacitors with low impedance in the high-frequency region are required. Small and large-capacity capacitors include electrolytic capacitors such as aluminum electrolytic capacitors and giant electrolytic capacitors. -;-4- This paper size applies to Chinese National Standard (CNS) A4 specification (210X 297 mm) (Please read the precautions on the back before filling this page)
512373 A7 B7 ___ 五、發明説明（2 ) 鋁電解電容器雖具有低成本且可大容量的優點，但是 當電解質係使用離子導電性之液狀電解質時，在高頻區域 下的阻抗便較高，且電解質將隨時間而蒸發，造成容量降 低，且溫度特性亦不佳的問題點。 此外，在鉅電解電容器中，一般雖採用錳氧化物爲電 解質，但卻存在於主要利用硝酸錳之熱分解而所形成的錳 氧化物中，無法避免熱分解時的介電質皮膜損傷之可能性 ，且因爲比阻抗偏高，所以在高頻區域之阻抗較高‘的問題 〇 爲解決該等問題，遂有採用具電子導電性的導電性聚 合物爲固體電解質之.提案。 譬如眾所週知之採用導電率在1 〇 — 3〜1 0. 3 S / c m範圍內之真性導電性聚合物（日本特開平 1 一 1 6 9 9 1 4號公報（美國專利第 4，8 0 3，5 9 6號））或聚苯胺（特開昭 6 1 - 2 3 9 6 1 7號公報）、聚吡咯（特開昭 61 - 240625號公報）、聚噻吩衍生物（特開平 2 — 15611號公報（美國專利第4，91〇，645 號）公報）、聚異苯並噻吩（特開昭62 — 118511 號公報）等聚合物。大多數由該等7Γ共轭系構造所構成的 導電性聚合物，係使用含摻質的組成物。 再者之前亦有不僅添加摻質，且合倂如二氧化锰（特 公平6 — 1 0 1 4 1 8號公報（美國專利第 4，9 5 9，7 5 3號））或塡料（特開平 本紙張尺度適用中國國家標準（CNS ) A4規格（210X29*7公釐） ^ ' 一 (請先閲讀背面之注意事項再填寫本頁) 裝· 訂 經濟部智慧財產局員工消費合作社印製 512373 A7 B7 五、發明説明（3 ) 9 — 3 2 0 9〇1號公報）。 相關固體電解質的形狀，有提案將依電解氧化聚合的 導電性聚合物沉積起點，當作熔接於鋁箔上的金屬，而形 成於整體鋁箔表面上（特開平4 一 3 0 7 9 1 7號公報） 〇 此外，亦有提案分別交叉1〜2 0次浸漬於單體溶液 與氧化劑溶液中，且更浸漬於氧化劑溶液中5分鐘〜5小 時，而提昇聚合效率（特開平1 1 一 2 3 8 6 4 8號公報 【發明欲解決之課題】 在如上述採用導電性聚合物作爲固體電解質的習知固 體電解電容器之製造方法中，便將存在如下述問題點。 (1 )在形成固體電解質之際，當使用單體之情況時 ，因爲採用單體與氧化劑的混合溶液，所以混合溶液中的 單體，亦將隨混合溶液中之氧化劑的氧化作用，而聚合成 聚合物。此聚合物必需廢棄，而無法有效的使用混合溶液 中的單體，材料效率極差劣。 f \ \ ;因爲單體與氧化劑之混合溶液將變性，所以將削弱氧 化劑的氧化作用、降低混合溶液的壽命等，因此固體電解 質的形成程序便呈不穩定。 (3 )再者，即便在交叉浸漬於以氧化劑與單體的各 溶液（二液）之情況時，在將含浸於單體液的金屬箔基板 ，於氧化劑溶液中浸漬特定時間時，單體將由氧化劑溶液 -:-g- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） (請先閲讀背面之注意事項再填寫本頁) •裝 經濟部智慧財產局員工消費合作社印製 512373 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（4 ) 中溶出，而在氧化劑溶液中單體將聚合，而造成氧化劑溶 液壽命極端惡化。同樣的，在將浸漬於氧化劑溶後的單體 液的金屬箔基板，浸漬於單體溶.液中特定時間之情況下’ 將降低單體溶液的壽命。 (4 )在調配單體與氧化劑之混合溶液時’因爲二者 濃度、混合比率等存在一定的限制，所以無法任意設定單 體濃度，在爲形成所期待厚度之固體電解質層上，：便必需 增加聚合次數。 ^ .(5 )在重複交叉浸漬於氧化劑與單體液的聚合方法 中，通常雖在各次的聚合程序後，均設有洗淨程序，但各 次洗淨程序的作業與所需時間，不僅造成固體電解電容器 元件製造效率的降低，同時亦因爲高分子固體電解質層之 層間重疊較少，所以將降低高分子固體電解質層部分的強 度，而使在固體電解電容器性能的改善上尙有待改善的空 間。 — (6 )當將閥作用金屬多孔體裁斷成特定形狀時，相 關裁斷面（裁切口），因爲僅在後續程序的轉化處理中形 成介電質層，所以此部分便較除裁斷面以外的部分爲弱， 並具有固體電解質附著量較少的傾向。 (7 )·將固體電解電容器之陽極部，與陰極部設成絕 緣，而在爲防止固體電解質爬上等現象的罩幕部分，便產 生較不易充分附著於固體電解質的傾向，而造成容量較低 的問題點發生。另，罩幕部分係相當於疊層固體電解電容 器元件時的陽極接合，因爲較容易賦加應力，所以遺漏電 (請先閲讀背面之注意事項再填寫本頁) 裝. 訂 本纸張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） 512373 A7 _____ B7 五、發明説明（5 ) 流將變大，而較容易產生短路。 (請先閲讀背面之注意事項再填寫本頁) (8 )在將導電性聚合物之固體電解質，浸漬於有機 高分子單體溶液與氧化劑溶液中的方法，如前述在基板（ 鋁箔）中心’將附著頗多的固體電解質，而發現存在有在 裁斷面切口與罩幕部分上的附著將較少的傾向，更將破壞 氧化劑與單體附著狀態的平衡，而無法獲得一定性能的聚 合物的傾向。 . 【發明開示】 * 本發明有鑑於上述諸項課題，經深入鑽硏，結果隨確 認在爲求使切口部與罩幕邊界區域中的固體電解質之形成 增大上，利用在基板上使氧化劑溶液之溶劑徐緩蒸發，而 在殘存的氧化劑上使單體進行聚合係屬極有效的，同時所 獲得的固·_電解電容器係提昇與形成在介電質皮膜上之固 .體電解質與介電質層間的密接性，且具優越容量、介電損 失（t a n ¢5 )、遺漏電流、短路不良率等基本諸特性， 甚至回流耐熱性或耐濕負荷特性等安定性的電容器。 經濟部智慧財產局員工消費合作社印製 再者，亦發現在將具上述優越特性的固體電解電容器 ，浸漬於有機高分子單體溶液或分散液（以下簡稱「含單 體液」）、-及氧化劑溶液或分散液（以下簡稱「含氧化劑 液」）中而形成的方法中，在爲求將單體對含氧化劑的溶 出、或含氧化劑液對含單體液的溶出予以減少上，利用控 制浸漬於含氧化劑液或含單體液中的時間，以及在浸漬於 含單體液後，再追加特定溫度與時間的乾燥程序，並控制 __!____Q _____ 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） 512373 A7 B7 五、發明説明（6 ) (請先閱讀背面之注意事項再填寫本頁) 聚合時間，乃屬極有效的方法，甚至在重複特定次數的交 叉浸漬於含單體液與含氧化劑液並聚合後，最後再經由洗 淨便可形成確保層間重疊之優越性能的固體電解質。 換句話說，本發明乃提供以下固體電解電容器與其製 造方法。 1 .在閥作用金屬多孔體基板表面的介電質皮膜上， 設置將有機高分子單體作爲固體電解質，並利用氧化劑進 行氧化聚合而所獲得之導電性聚合物的固體電解電容器中 ，基板周圍之固體電解質層厚度，大於基板中央部位之固 體電解質的厚度爲特徵的固體電解電容器。 2 .在閥作用金屬多孔體基板表面的介電質皮膜上， 設置將有機高分子單體作爲固體電解質，並利用氧化劑進 行氧化聚合而所獲得之導電性聚合物的固體電解電容器中 ，基板之裁斷面周圍的固體電解質層厚度，大於基板中央 部位之固體電解質的厚度爲特徵的固體電解電容器。 經濟部智慧財產局員工涓費合作社印製 3 .在閥作用金屬多孔體基板表面的介電質皮膜上， 設置將有機高分子單體作爲固體電解質，並利用氧化劑進 行氧化聚合而所獲得之導電性聚合物的固體電解電容器中 ，基板之裁斷面周圍及罩幕邊界的固體電解質層厚度，大 於基板中央·部位之固體電解質的厚度爲特徵的固體電解電 容器。 4 .如前項1至3所記載之固體電解電容器，其中該 固體電解質的厚度偏置，係利用在具該介電質皮膜之閥作 用金屬基板上的有機高分子單體之溶液化學氧化聚合或氣 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 512373 A7 ______B7 五、發明説明（7 ) 相化學氧化聚合而形成。 (請先閲讀背面之注意事項再填寫本頁) 5 ·如前項4所記載之固體電解電容器，其中該固體 電解質的厚度偏置，係利用重複操作將具該介電質皮膜之 閥作用金屬基板，交叉浸漬於有機高分子之含單體液與含 氧化劑液中而形成。 6 ·如前項1至5所記載之固體電解電容器，其中該 閥作用金屬多孔基板係平板狀或箔狀。 ’ 7 ·如前項6所記載之固體電解電容器，其中該閥作 用金屬多孔基板中央部位的長度方向與寬度方向的截面係 形成葫蘆狀或絲瓜狀。 8 .如前項7所記載之固體電解電容器，其中形成固 體電解質層的基板中央部位截面的最大厚度與最小厚度之 差，在0以上且200//m以下。 9 ·如前項1至8所記載之固體電解電容器，其中該 閥作用金屬多孔板係選擇自鋁、鉅、鈮及鈦中的單體金屬 、或該等合金。 經濟部智慧財產局員工消費合作社印製 1〇·如前項1至9所記載之固體電解電容器，其中 形成導電性聚合物之有機高分子單體，係含複數五元環之 化合物、或具苯胺骨架之化合物。 1 1 ··如前項1 0所記載之固體電解電容器，其中該 含複數五元環的化合物係具噻吩骨架或多環狀硫醚骨架之 化合物。 1 2 ·如前項1 1所記載之固體電解電容器，其中該 具噻吩骨架之單體化合物，係3 -乙基噻吩、3 —己基噻 -----丨丨--- 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ 297公釐） 512373 A7 ____ B7 _ 五、發明説明（8 ) 吩、3 ，4 一二甲基噻吩、3，4 一甲撐二氧基噻吩、3 ’ 4 一乙撐二氧基噻吩。 1 3 ·將前項1至1 2所記載之固體電解電容器，複 數片疊層而成的疊層型固體電解電容器。 1 4 .在具閥作用金屬多孔體基板表面的介電質皮膜 上’利用有機高分子單體的單體氧化劑之氧化聚合，設置 導電性聚合物之固體電解質的固體電解電容器之製造方法 中’使形成基板周圍之固體電解質層厚度，大於基板中央 部位之固體電解質的厚度挺特徵的固體電解電容器之製造 方法。 1 5 .如前項1 4所記載之固體電解電容器之製造方 法，其中該固體電解質的厚度偏置，係利用在具該介電質 皮膜之閥作用金屬基板上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而形成。 1 6 .如前項1 5所記載之固體電解電容器，其中該 固體電解質的厚度偏置，係利用重複操作將具該介電質皮 膜之閥作用金屬基板，交叉浸漬於有機高分子之含單體液 與含氧化劑液中而形成。 1 7 ·如前項1 6所記載之固體電解電容器之製造方 法，其中交叉浸漬於各含液的時間爲低於5分鐘。 1 8 .如前項1 6所記載之固體電解電容器之製造方 法，其中交叉浸漬的程序爲重複1 5〜3 0次數。 1 9 .如前項1 6所記載之固體電解電容器之製造方 法，其中將閥作用金屬基板浸漬於含單體液後’放置於空 ______U---- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁) 裝· 訂 經濟部智慧財產局員工消費合作社印製 512373 A7 B7 五、發明説明（9 ) 氣中5秒〜1 5分鐘。 2〇.如前項1 6所記載之固體電解電容器之製造方 法，其中將閥作用金屬基板浸漬於含氧化劑液後，放置於 空氣中1 0秒〜1 5分鐘。 2 1 .如前項1 9或2 0所記載之固體電解電容器之 製造方法，係在空氣中於溫度0〜6 0 °C下放置。 2 2 .如前項1 6所記載之固體電解電容器之製造方 法，其中在重複進行將閥作用金屬基板分別交叉浸漬於含 單體液與含氧化劑液並進行聚合後，再施行洗淨。 2 3 .採用利用氧化劑作用而形成之導電性聚合物的 含單體液與含氧化劑液，在具介電質皮膜之多孔體的閥作 用金屬基板表面上，形成導電聚合物之固體電解質層的固 體電解電容器之製造方法中，將該閥作用金屬基板分別交 叉浸漬於含單體液與含氧化劑液中的時間爲低於5分鐘進 行聚合。 2 4 .採用利用氧化劑作用而形成之導電性聚合物的 含單體液與含氧化劑液，在具介電質皮膜之多孔體的閥作 用金屬基板表面上，形成導電聚合物之固體電解質層的固 體電解電容器之製造方法中，將該閥作用金屬基板重複操 作1 5〜3· 0次之分別交叉浸漬於含單體液與含氧化劑液 中的時間爲低於5分鐘，並進行聚合。 2 5 .如前項2 3或2 4所記載之固體電解電容器之 製造方法，其中將閥作用金屬基板浸漬於含單體液後，放 置於空氣中5秒〜15分鐘。 -νλ- 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） (請先閲讀背面之注意事項再填寫本頁) 裝· 訂 經濟部智慧財產局員工消費合作社印製 512373 A7 ___B7 五、發明説明（10) (請先閱讀背面之注意事項再填寫本頁) 2 6 ·如前項2 3至2 5所記載之固體電解電容器之 製造方法，其中將閥作用金屬基板浸漬於含氧化劑液後， 放置於空氣中1 0秒〜1 5分鐘。 2 7 .如前項2 5或2 6所記載之固體電解電容器之 製造方法，係在空氣中於溫度0〜6 0 °C下放置。 2 8 ·在前項2 3至2 7中任一項所記載之固體電解 電容器之製造方法中，在重複進行聚合程序後，苒進行洗 淨程序爲特徵的固體電解電容器之製造方法。 2 9 .如前項2 3或2 8中任一項所記載之固體電解 電容器之製造方法，其中該導電性聚合物之固體電解質的 其中部分，係具薄片構造或絲狀構造。 3 0 .如前項2 3至2 9中任一項所記載之固體電解 電容器之製造方法，其中形成導電性聚合物之單體，係含 複數五元環之化合物。 3 1 ·如前項2 3至3 0中任一項所記載之固體電解 電容器之製造方法，其中形成導電性聚合物之單體’係含 苯胺骨架之化合物。 經濟部智慧財產局員工消費合作社印製 3 2 ·如前項3 0所記載之固體電解電容器之製造方 法，其中該含複數五元環的化合物係具噻吩骨架之化合物 0 - 3 3 ·如前項3 0所記載之固體電解電容器之製造方 法，其中該具噻吩骨架之單體化合物，係3 -乙基噻吩、 3 —己基噻吩、3 ，4 —二甲基噻吩、3 ，4 —甲撐二氧 基噻吩、3，4 一乙撐二氧基噻吩。 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） -：____- A7 ------ B7 五、發明説明（H) ——~ 一 (請先閲讀背面之注意事項再填寫本頁) 3 4 .如前項2 3至3 3所記載之固體電解電容器之 製造方法’其中該閥作用金屬係選擇自鋁、鉅、鈮及鈦中 的單體金屬、或該等合金。 3 5 .利用前項2 3所記載之製造方法所獲得的固體 電解電容器。 ~ 3 6 ·利用前項2 4所記載之製造方法所獲得的固體 電解電容器丨 丨 3 7 ·利用前項2 5至3 4中任一項所記載之製造方 法所獲得的固體電解電容嘉。 【圖式簡單說明】 第1圖係電容器元件之剖面示意圖。 第2圖係實施例1之電容器元件材料的縱剖面示意圖 第3圖係疊層實施例1之電容器元件而所獲得之固體 電解電容器的剖面示意圖。 第4圖係比較例1之電容器元件材料的縱剖面示意圖 經濟部智慧財產局員工消費合作社印製 0 【圖示符號說明】 1 :陽極基體 2 :氧化皮膜層 5 :導電層 8 :環氧樹脂 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 512373 A7 ___ B7 _ 五、發明説明（12) 【發明詳細說明】 本發明中所使用之基板表面.的介電質皮膜，通常係將 具閥作用之金屬的多孔質形成體利用轉化處理等方法而形 成。 . 轉化上所採用的轉化液、轉化電壓等轉化條件，配合 所製得之固體電解電容器所需的容量、耐電壓性等，預先 經由實驗確認並設定適當値。另，在轉化處理之際，爲確 實防止轉化液滲出於形成_體電解電容器陽極的部分，及 與後續程序中所形成之固體電解質（陰極部分）的絕緣， 一般均設置罩幕。 罩幕的材料，一般可採用耐熱性樹脂，最好採用可溶 解或可膨潤的耐熱性樹脂或其先質、由無機質微粉與纖維 素系樹脂所構成之組成物（日本特開平1 1 — 8 0 5 9 6 .號公報）等，惟在材料上並無限制。具體而言，可舉例如 聚苯基砸（P P S )、聚醚碩（P E S )、氰酸酯樹脂、 氟樹脂（四氟乙烯、四氟乙烯•全氟烷基乙烯醚共聚物等） 、低分子量聚醯亞胺、以及該等衍生物及其先質等。其中 ，特別以低分子量聚醯亞胺、聚醚碾、氟樹脂及該等之先 質爲佳。· 一般在介電質氧化皮膜上形成導電性聚合物的方法’ 雖可使用依氣相聚合法形成導電性高分子層與依《解聚€ 法形成導電性高分子層的方法（特開平3 — 6 2 1 7號公 報等）；將有機高分子單體附著於介電質氧化皮膜上之後 ----- 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ 297公釐） (請先閲讀背面之注意事項再填寫本頁) •裝· 訂 經濟部智慧財產局員工消費合作社印製 512373 A7 , B7 五、發明説明（13) (請先閱讀背面之注意事項再填寫本頁) ，再於氧化劑溶液中進行聚合的溶液化學聚合法（特開平 1 1 一 2 5 1 1 9 1號公報等）；利用切換裝置相隔特定 時間改變對陽極的供電點，而將.導電性高分子層厚度平均 化的電解聚合方法（特開平1 1 一 2 8 3 8 7 8號公報等 ):但在本發明中最好採用包含有將閥作用金屬多孔體基 板浸漬於氧化劑溶液後並乾燥，而將氧化劑溶液濃度，在 基板上徐緩提昇之程序的有機高分子單體的溶液论學氧化 聚合、或氣相化學氧化聚合。特別以溶液化學氧化聚合爲 佳。. 在本發明中，利甩氣相化學氧化聚合而製造固體電解 質之際的單體分壓（當混合氣體引進於介電質皮膜上之情 況）及氣壓（當加壓調整引進於介電質皮膜上之情況）， 雖隨其化合物之取代基種類或溶劑等種類而有所不同，但 一般最好在1 0 — 3〜1 0氣壓範圍內，尤以在1 0 — 2〜5 氣壓範圍內者爲佳。 經濟部智慧財產局員工消費合作社印製 此外，氣相化學氧化聚合時的反應溫度，因爲隨各自 所具有聚合起始能的化合物的種類及濃度、聚合性單體分 壓（壓力）等而決定，其餘並無特別限制，一般選擇 一 7 0 °C〜2 5〇°C溫度範圍。最好在〇°C〜1 5〇t：， 再者1 5 °C〜1 0 0 °C溫度範圍。 依本發明的話，如後述實施例所示，將含介電質氧化 皮膜之鋁箔，含浸於3，4 一乙撐二氧基噻吩E D T ) 之異丙醇（I P A )溶液，經風乾，將I P A幾乎全部去 除後，再含浸於約2 0質量％氧化劑（過硫酸銨）水溶液 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） --±g- 512373 A7 B7 五、發明説明（14) (請先閲讀背面之注意事項再填寫本頁) 中之後，在4 0°C左右下進行1 〇分鐘加熱，並重複實施 本程序，便可獲得使聚（3，4 一乙撐二氧基噻吩）聚合 物，形成在基板周圍的固體電解質層厚度大於中央部位厚 度的狀態。 產生此種固體電解質層厚度偏置的詳細理由，雖未必 明確’但可認爲在4 0 °C左右的加熱條件下，乃屬表面積 較大之介電質氧化皮膜上的水分較容易揮發的環境，於是 因爲對基板裁斷面（切口部）及罩幕的氧化劑溶液，將利 用毛細管現象進行移動，而水將由氧化劑溶液中徐緩蒸發 而形成高濃度，並接觸於單體而進行聚合，所以在切口及 罩幕邊界區域附近，便附著頗多的聚合物，而使基板周圍 的固體電解質層厚度，大於基板中央部位處的固體電解質 層厚度。 換句話說，形成本發明之固體電解電容器特有的閥作 用金屬多孔體基板，在其中央部位的長度方向與寬度方向 上之截面呈葫蘆狀或絲瓜狀固體電解質的主要原因，可認 爲利用經轉化多孔質體的表面張力與滲透壓關係，將裁斷 經濟部智慧財產局員工消費合作社印製 面（切口部）與罩幕處的氧化劑溶液予以濃縮，而呈高濃 度化，並在此析出聚合物，如此便將端部之聚合物的產生 樣式，引導於可獲得降低固體電解電容器的短路不良率， 且縮小遺漏電流之優越特性的方向。 固體電解質層厚度的偏置，雖隨在閥作用金屬基板上 ’浸漬於有機高分子之含單體液與含氧化劑液中的操作次 數等固體電解質形成條件而有不同，但可獲得較佳固體電 ------±j.__ 本紙張尺度適用中國國家標準（CNS ) A4規格（21〇χ297公釐） 512373 A7 B7 五、發明説明（15) (請先閲讀背面之注意事項再填寫本頁) 解電容器特性的範圍，則形成固體電解質層之基板中央部 位的長度方向與寬度方向截面的對大厚度與最小厚度間的 差値在〇〜2 0 0 //m範圍內，最好在〇〜1 8〇//m範 圍內，尤以在0〜150#m範圍內者爲佳。 再者，依照本發明方法所形成的導電性聚合物之固體 電解質層，係可認爲因呈絲狀構造或薄片狀（薄層狀）構 造，而此類構造存在有橫跨廣範圍之聚合物鏈間的重疊， 所以便可容易形成電子跳動而提昇電導度，並提昇低阻抗 等特性。 · 經濟部智慧財產局員工消費合作社印製 在溶液化學聚合法中，使單體附著於陽極基體之具細 微孔的介電質氧化皮膜上，並在可形成導電性高分子雜摻 的化合物存在下，利用氧化劑與空氣中水分的作用.，而產 生氧化聚合，將所產生的聚合物組成物作爲該固體電解質 ，而形成於介電質表面上。此時在爲求形成良好聚合物組 成物上，便必需調整含浸（浸漬）於含單體液與含氧化劑 液之時間，俾控制單體與氧化劑的附著量。譬如，若浸漬 時間過久的話，聚合反應便無法結束，而使所獲得聚合物 組成物較容易形成低分子量。此外，當浸漬於未飽和濃度 之含氧化劑液中的時間過久的話，因爲經包含乾燥程序在 內的前置程·序，而附著於金屬箔基板上的氧化劑便將再溶 解，同時所附著的單體或所產生的聚合物亦將溶出或流出 ，因此便將使聚合物的生成變遲緩，同時將產生流出物污 染含液的情形。同樣的情形，在浸漬於含單體液之情況時 亦將發生。 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） - 512373 Α7 Β7 五、發明説明（16) (請先閲讀背面之注意事項再填寫本頁) 顯影係依譬如低分子量的含氧化劑液、含單體液著色 、聚合物浮游、形成附著之固體電解質的重量減少傾向、 含單體液黏度、比重變化等而顯現。 所以，在本發明的方法中，將浸漬於含單體液與含氧 化劑液中的時間，設定成含液中之單體成分與氧化劑成分 附著於金屬箔基板之介電質表面上所需充分時間以上，且 低於5分鐘的時間範圍內，最好爲0 · 1秒〜2分鐘，尤 以1秒〜1分鐘爲佳。 再者，在爲使單體均％附著於介電質表面上與聚合物 組成物上，而在含浸於含單體液後，必需於空氣中放置一 定時間，俾使溶劑汽化。此條件雖依溶劑種類而異，但大 約在由0 /C以上至溶劑沸點爲止的溫度下進行。敗置時間 雖依溶劑種類而異，但大約在5秒〜1 5分鐘，譬如乙醇 系溶劑中，僅要在5分鐘以內便可。隨此放置時間的設計 ，便可使單體均勻附著於介電質表面上，甚至可減少下一 程序之含氧化劑液浸漬時的污染。 經濟部智慧財產局員工消費合作社印製 在含單體液與含氧化劑液的浸漬處理後，便於一定溫 度範圍下，於特定時間內，保持於空氣中，而使單體進行 氧化聚合。 聚合溫·度雖隨單體種類而異，譬如在吡咯中僅需5 t 以下便可，但在噻吩中則需約3 0〜6 0 °C。 聚合時間，隨浸漬時的單體附著量而決定。附著量因 爲隨含單體液與含氧化劑液之濃度與黏度等因素而變化， 所以雖並未槪括性的限制，但一般上單次附著量較少的話 本紙張尺度適用中國國家標準（CNS ) A4規格（210Χ297公釐） 512373 A7 ___B7 五、發明説明（17) ，便可縮短聚合時間，且單次附著量若增加的話，便需增 長聚合時間。 (請先閲讀背面之注意事項再填寫本頁) 在本發明之方法中，單次聚合時間在1 〇秒〜1 5分 鐘，最好在3〜10分鐘範圍內。 利用本發明之方法而形成於介電質皮膜上的導電性聚 合物層，利用電子顯微照相，便可確認屬薄層結構或絲狀 結構的形狀。 ： 導電性聚合物之薄層結構或絲狀結構，係對提昇導電 度主要原因的聚合物鏈一維性之提昇與聚合鏈間廣範圍重 疊產生影響，可判定對聚合物固體電解質之導電度的提昇 與低阻抗化等電容器特性的提昇上，產生正面影響。 在本發明之方法中，在爲求將所形成之導電性聚合物 組成物，設定成具備有對溼度、熱、應力等耐性的厚度上 ，必需控制含浸次數。將該製造程序，對單一陽極基體重 複操作1 5次以上，最好重複2 0〜3 0次，俾能輕易形 成所需固體電解質層。 經濟部智慧財產局員工消費合作社印製 形成固體電解電容器中所使用之固體電解質的程序， 係在含閥作用之金屬上有形成介電質皮膜的陽極體上，交 叉浸漬於含單體液與含氧化劑液，並乾燥，而使單體與氧 化劑交叉重複附著，然後再於空氣中化學氧化聚合的過程 〇 此時，將環境中的溼度設定在1 0 %以上且低於8〇 %以下，最好在1 5 %以上且低於6 0 %，更以2 0 %以 上且低於5 0 %範圍的條件下，進行化學氧化聚合，而形 本紙張尺度適用中國國家標準（CNS ) A4規格（210X29*7公釐） 512373 經濟部智慧財產局員工消費合作社印製 A7 _ B7五、發明説明（18) 成含有以單體或其衍生物爲重複單位的導電性聚合物層。 環境中的溫度與壓力，因爲隨聚合物組成物的種類、 聚合方法等而改變，雖未槪括的限定，但一般最好在溫度 一 7 0 t：〜2 5 0 °C範圍，壓力則在常壓以下爲佳。 含單體液濃度係在3〜5 0質量％範圍內，最好在5 〜3 5質量％範圍內，尤以在1 0〜2 5質量％範圍內者 爲更佳。而含氧化劑液濃度係在5〜7 0質量％ _圍內， 最好在1 5〜5 0質量％範圍內。另，含單體液與含氧化 劑液之黏度係在1 0 0厘泊（c P )以下，最好在3 0 c P以下，尤以在0.6〜10〇?者。 依照本發明的話，利用交叉浸漬含單體液與含氧化劑 液，便可形成具有層狀構造（薄層結構或絲狀結構）之導 電性聚合物的固體電解質，甚至在此層中，爲求產生提昇 聚合物鏈之一維性與聚合物鏈間重疊，得知最好不要每次 進行洗淨，可在最後才進行。藉此便可將聚合程序中未反 應而殘存的過剩（未反應）單體，亦可在下一次程序中進 行聚合，結果便可形成由具廣範圍重疊之層狀構造導電性 聚合物所組成的固體電解質。 在依本發明之方法所獲得之被覆腸極體外表面的薄層 結構或絲狀·結構固體電解質，產生相對連續或獨立的空間 ，而此類空間則將發揮緩和在封裝程序等電容器製造處理 程序中所接受到熱應力或機械應力等的影響。此外，不僅 製造程序，亦可謂屬於可對應於由實際使用電容器時之環 境中所接收到各種應力的有效構造。 ---：——；--- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） (請先閲讀背面之注意事 4 -項再填- 裝— 寫本頁) 訂 512373 A7 B7512373 A7 B7 ___ V. Description of the invention (2) Although aluminum electrolytic capacitors have the advantages of low cost and large capacity, when the electrolyte is an ionic conductive liquid electrolyte, the impedance is higher in the high frequency region. In addition, the electrolyte will evaporate over time, causing problems such as a decrease in capacity and poor temperature characteristics. In addition, in giant electrolytic capacitors, although manganese oxide is generally used as the electrolyte, it exists in the manganese oxide formed mainly by the thermal decomposition of manganese nitrate, and the possibility of damage to the dielectric film during thermal decomposition cannot be avoided. In order to solve these problems, there is a proposal to use a conductive polymer with electronic conductivity as a solid electrolyte. For example, it is well known to use a true conductive polymer having a conductivity in the range of 10 to 3 S / cm (Japanese Patent Application Laid-Open No. 1-6 1 9 9 1 4 (US Patent No. 4, 8 0 3 , 5 9 6)) or polyaniline (Japanese Patent Laid-Open No. 6 1-2 3 9 6 17), polypyrrole (Japanese Patent Laid-open No. 61-240625), polythiophene derivatives (Japanese Patent Laid-Open No. 2-15611 (US Patent No. 4,9110,645), polyisobenzothiophene (Japanese Patent Application Laid-Open No. 62-118511), and other polymers. Most of the conductive polymers composed of such 7Γ conjugated systems use a dopant-containing composition. In addition, there have been previously added not only dopants, but also compounds such as manganese dioxide (Special Publication No. 6-1 0 1 4 1 8 (U.S. Patent No. 4, 9 5 9, 7 5 3)) or materials ( The size of this paper is applicable to China National Standard (CNS) A4 (210X29 * 7mm) ^ 'I (Please read the precautions on the back before filling this page) 512373 A7 B7 V. Description of the invention (3) 9 — 3 2 0 9001). As for the shape of the solid electrolyte, it is proposed that the starting point of the conductive polymer polymerized by electrolytic oxidation polymerization be used as a metal fused to the aluminum foil and formed on the entire aluminum foil surface (Japanese Patent Laid-Open No. 4-3 0 7 9 1 7 ) 〇 In addition, there are also proposals to cross 1 to 20 times of immersion in the monomer solution and the oxidant solution, and more immersion in the oxidant solution for 5 minutes to 5 hours to improve the polymerization efficiency (Japanese Patent Laid-Open No. 1 1 2 3 8 6 4 8 [Problems to be Solved by the Invention] The conventional solid electrolytic capacitor manufacturing method using a conductive polymer as a solid electrolyte as described above has the following problems. (1) In forming a solid electrolyte In the case of monomers, because a mixed solution of monomers and oxidants is used, the monomers in the mixed solution will also polymerize into polymers with the oxidation of the oxidants in the mixed solution. This polymer must be Discarded, and the monomer in the mixed solution cannot be effectively used, the material efficiency is extremely poor. F \ \; Because the mixed solution of monomer and oxidant will be denatured, so The weak oxidant oxidizes, reduces the life of the mixed solution, etc., so the formation procedure of the solid electrolyte becomes unstable. (3) Furthermore, even when cross-immersed in each solution (two-liquid) of oxidant and monomer When the metal foil substrate impregnated with the monomer solution is immersed in the oxidant solution for a specific period of time, the monomer will be oxidized by the oxidant solution-:-g- This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) (Please read the precautions on the back before filling out this page) • Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, printed 512373 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, 5. Disclosed in (4) Invention Invention, and The monomer in the oxidant solution will polymerize, which will cause the life of the oxidant solution to be extremely deteriorated. Similarly, when the metal foil substrate immersed in the monomer solution after the oxidant solution is immersed in the monomer solution. Reduce the life of the monomer solution. (4) When preparing a mixed solution of monomer and oxidant, 'there are certain restrictions on the concentration and mixing ratio of the two, so Since the monomer concentration cannot be arbitrarily set, in order to form a solid electrolyte layer of a desired thickness, it is necessary to increase the number of polymerizations. ^. (5) In the polymerization method of repeated cross-immersion in an oxidant and a monomer solution, it is usually After each polymerization process, a washing process is provided. However, the operation and time required for each washing process not only causes a reduction in the manufacturing efficiency of the solid electrolytic capacitor element, but also because of the overlap between the layers of the polymer solid electrolyte layer. Less, so the strength of the polymer solid electrolyte layer will be reduced, and there is room for improvement in the performance of solid electrolytic capacitors. (6) When the valve-acting metal porous body is cut into a specific shape, the relevant cutting surface (Cutting) Because the dielectric layer is formed only in the conversion process of the subsequent procedure, this portion is weaker than the portion other than the cut surface and tends to have a smaller amount of solid electrolyte adhesion. (7) · The anode part of the solid electrolytic capacitor is insulated from the cathode part, and in the part of the screen to prevent the solid electrolyte from climbing up, there is a tendency that it is not easy to fully adhere to the solid electrolyte, resulting in a relatively large capacity. Low problem points occur. In addition, the cover part is equivalent to the anodic bonding when laminated solid electrolytic capacitor elements. Because it is easier to apply stress, leakage of electricity (please read the precautions on the back before filling this page). China National Standard (CNS) A4 specification (210 X 297 mm) 512373 A7 _____ B7 V. Description of the invention (5) The current will become larger, and short circuit is more likely to occur. (Please read the precautions on the back before filling this page) (8) The method of immersing the solid electrolyte of conductive polymer in organic polymer monomer solution and oxidant solution, as described above in the center of the substrate (aluminum foil) A large amount of solid electrolyte will be attached, and it is found that there is a tendency that the adhesion on the cut surface and the mask portion will be less, and the balance between the oxidant and the monomer adhesion state will be broken, and a polymer of a certain performance cannot be obtained. tendency. [Invention] * In view of the above-mentioned problems, the present invention has been thoroughly drilled, and the results have been confirmed to increase the formation of solid electrolyte in the boundary area between the cutout portion and the mask. The solvent of the solution slowly evaporates, and it is extremely effective to polymerize the monomer on the remaining oxidant. At the same time, the obtained solid electrolytic capacitor is promoted and formed on the dielectric film. Body electrolyte and dielectric The tightness between the quality layers and the basic capacitors with excellent capacity, dielectric loss (tan ¢ 5), leakage current, short-circuit failure rate, and even stability such as reflow heat resistance or humidity load resistance. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, we also found that the solid electrolytic capacitors with the above-mentioned superior characteristics were immersed in an organic polymer monomer solution or dispersion (hereinafter referred to as "containing monomer solution"),-and In a method formed by an oxidant solution or a dispersion liquid (hereinafter referred to as "oxidant-containing liquid"), in order to reduce the dissolution of monomers from the oxidant-containing solution or the dissolution of the oxidant-containing liquid from the monomer-containing solution, the use of control The time of immersion in oxidant-containing or monomer-containing liquid, and after immersing in monomer-containing liquid, adding a specific temperature and time drying program, and control __! ____ Q _____ This paper size applies Chinese national standards (CNS ) Α4 specification (210X297 mm) 512373 A7 B7 V. Description of the invention (6) (Please read the notes on the back before filling this page) Polymerization time is a very effective method, even after repeated dipping in a specific number of times After the monomer-containing liquid and the oxidant-containing liquid are polymerized, and finally washed, a solid electrolyte with excellent performance to ensure interlayer overlap can be formed. In other words, the present invention provides the following solid electrolytic capacitors and a method for manufacturing the same. 1. A solid electrolytic capacitor having a conductive polymer obtained by oxidizing and polymerizing an organic polymer monomer as a solid electrolyte on a dielectric film on a surface of a valve-acting porous metal substrate, and surrounding the substrate, is provided. The solid electrolytic capacitor is characterized by a thickness of the solid electrolyte layer larger than that of the solid electrolyte in the center of the substrate. 2. A solid electrolytic capacitor having a conductive polymer obtained by using an organic polymer monomer as a solid electrolyte and oxidative polymerization with an oxidant is provided on a dielectric film on the surface of a valve-acting porous metal substrate. Solid electrolytic capacitors characterized by a thickness of the solid electrolyte layer around the cutting surface that is greater than the thickness of the solid electrolyte in the center of the substrate. Printed by the staff of the Intellectual Property Bureau of the Ministry of Economic Affairs on the cooperative 3. On the dielectric film on the surface of the porous metal substrate of the valve, an organic polymer monomer is used as a solid electrolyte, and the conductivity obtained by oxidative polymerization using an oxidant is provided. In solid electrolytic capacitors made of polymer, the thickness of the solid electrolyte layer around the cut surface of the substrate and the boundary of the screen is larger than the thickness of the solid electrolyte in the center and part of the substrate. 4. The solid electrolytic capacitor according to the foregoing paragraphs 1 to 3, wherein the thickness of the solid electrolyte is offset by using a solution of organic polymer monomers on a valve substrate of the dielectric film to chemically oxidize or polymerize The size of the paper is applicable to the Chinese National Standard (CNS) A4 (210X297 mm) 512373 A7 ______B7 V. Description of the invention (7) Formed by chemical oxidation polymerization of the phase. (Please read the precautions on the back before filling out this page) 5 · The solid electrolytic capacitor as described in item 4 above, where the thickness of the solid electrolyte is offset, and the valve action metal substrate with the dielectric film is used by repeated operations , Formed by cross immersion in a monomer-containing liquid and an oxidant-containing liquid of an organic polymer. 6 · The solid electrolytic capacitor according to the foregoing paragraphs 1 to 5, wherein the valve-acting metal porous substrate is a flat plate or a foil. '7. The solid electrolytic capacitor according to the above item 6, wherein the valve serves as a metal porous substrate and the cross section of the longitudinal direction and the width direction of the central portion of the valve is formed into a gourd shape or a gourd shape. 8. The solid electrolytic capacitor according to the item 7, wherein the difference between the maximum thickness and the minimum thickness of the cross section of the central portion of the substrate on which the solid electrolyte layer is formed is 0 or more and 200 // m or less. 9 · The solid electrolytic capacitor according to the preceding paragraphs 1 to 8, wherein the valve-acting metal porous plate is selected from a single metal of aluminum, giant, niobium, and titanium, or these alloys. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 10. The solid electrolytic capacitors described in the preceding paragraphs 1 to 9, in which the organic polymer monomers forming the conductive polymer are compounds containing multiple five-membered rings or Compound of aniline skeleton. 1 1. The solid electrolytic capacitor according to the item 10 above, wherein the compound containing a plurality of five-membered rings is a compound having a thiophene skeleton or a polycyclic sulfide skeleton. 1 2 · The solid electrolytic capacitor according to the above item 1 1, wherein the monomer compound having a thiophene skeleton is 3-ethylthiophene, 3-hexylthio ----- 丨 丨 --- This paper standard applies to China National Standard (CNS) A4 specification (210 × 297 mm) 512373 A7 ____ B7 _ 5. Description of the invention (8) phen, 3,4 dimethylthiophene, 3,4 monomethyldioxythiophene, 3 '4 One ethylene dioxythiophene. 1 3 · A multilayer solid electrolytic capacitor in which a plurality of solid electrolytic capacitors according to the preceding paragraphs 1 to 12 are laminated. 1 4. In the method for manufacturing a solid electrolytic capacitor using a solid electrolyte of a conductive polymer by the oxidative polymerization of a monomeric oxidant of an organic polymer monomer on a dielectric film on the surface of a porous metal substrate having a valve function A method for manufacturing a solid electrolytic capacitor, which has a characteristic that the thickness of the solid electrolyte layer around the substrate is larger than the thickness of the solid electrolyte at the center of the substrate. 15. The method for manufacturing a solid electrolytic capacitor as described in the preceding paragraph 14, wherein the thickness of the solid electrolyte is offset by using a solution chemistry of an organic polymer monomer on a metal substrate with a valve function of the dielectric film. Formed by oxidative polymerization or gas phase chemical oxidation polymerization. 16. The solid electrolytic capacitor according to the preceding paragraph 15, wherein the thickness of the solid electrolyte is offset, and the valve-acting metal substrate with the dielectric film is cross-impregnated with a monomer containing an organic polymer through repeated operations. And the oxidant-containing liquid. 17 · The method for manufacturing a solid electrolytic capacitor according to the above item 16, wherein the time of cross-immersion in each liquid-containing capacitor is less than 5 minutes. 18. The method for manufacturing a solid electrolytic capacitor as described in the foregoing paragraph 16, wherein the cross-impregnation procedure is repeated 15 to 30 times. 19. The method for manufacturing a solid electrolytic capacitor as described in the preceding paragraph 16, wherein the valve-acting metal substrate is immersed in a monomer-containing liquid and 'placed in a space ______ U ---- This paper size applies to Chinese National Standards (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling out this page) Binding and printing Printed by the Intellectual Property Bureau Staff Consumer Cooperatives of the Ministry of Economic Affairs 512373 A7 B7 V. Description of the invention (9) 5 seconds to 1 5 in the air minute. 20. The method for manufacturing a solid electrolytic capacitor according to the above item 16, wherein the valve-acting metal substrate is immersed in an oxidant-containing liquid, and then placed in the air for 10 seconds to 15 minutes. 2 1. The manufacturing method of solid electrolytic capacitors as described in item 19 or 20 above, is placed in air at a temperature of 0 ~ 60 ° C. 2 2. The method for manufacturing a solid electrolytic capacitor according to the above item 16, wherein the valve-acting metal substrate is repeatedly cross-immersed in a monomer-containing liquid and an oxidant-containing liquid and polymerized, and then washed. 2 3. The monomer-containing liquid and the oxidant-containing liquid of a conductive polymer formed by the action of an oxidant are used to form a solid electrolyte layer of a conductive polymer on the surface of a valve-acting metal substrate of a porous body having a dielectric film. In the method for manufacturing a solid electrolytic capacitor, the valve-acting metal substrate is cross-immersed in a monomer-containing solution and an oxidant-containing solution for polymerization for less than 5 minutes, respectively. 24. The monomer-containing liquid and the oxidant-containing liquid of a conductive polymer formed by the action of an oxidant are used to form a solid electrolyte layer of a conductive polymer on the surface of a valve-acting metal substrate of a porous body having a dielectric film. In the method for manufacturing a solid electrolytic capacitor, the valve-acting metal substrate is repeatedly operated for 15 to 3 · 0 times, and then cross-immersed in a monomer-containing liquid and an oxidant-containing liquid for less than 5 minutes, and polymerization is performed. 25. The method for manufacturing a solid electrolytic capacitor according to the foregoing paragraph 2 3 or 24, wherein the valve-acting metal substrate is immersed in a monomer-containing liquid, and then placed in air for 5 seconds to 15 minutes. -νλ- This paper size applies Chinese National Standard (CNS) A4 specification (210 × 297 mm) (Please read the precautions on the back before filling out this page) Binding · Order Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs Consumer Cooperative 512373 A7 ___B7 5 2. Description of the invention (10) (Please read the precautions on the back before filling out this page) 2 6 · The manufacturing method of solid electrolytic capacitors as described in the preceding paragraphs 2 3 to 25, in which the valve-acting metal substrate is immersed in an oxidant-containing liquid After that, leave it in the air for 10 seconds to 15 minutes. 27. The method for manufacturing a solid electrolytic capacitor as described in the preceding paragraph 25 or 26, is placed in the air at a temperature of 0 to 60 ° C. 2 8 · In the method for manufacturing a solid electrolytic capacitor according to any one of the preceding paragraphs 23 to 27, after repeating the polymerization procedure, the method for manufacturing a solid electrolytic capacitor characterized by performing a cleaning procedure is performed. 29. The method for manufacturing a solid electrolytic capacitor according to any one of the foregoing paragraphs 2 3 or 28, wherein a part of the solid electrolyte of the conductive polymer has a sheet structure or a filament structure. 30. The method for manufacturing a solid electrolytic capacitor according to any one of the foregoing paragraphs 23 to 29, wherein the monomer forming the conductive polymer is a compound containing a plurality of five-membered rings. 31. The method for producing a solid electrolytic capacitor according to any one of the foregoing paragraphs 23 to 30, wherein the monomer forming the conductive polymer is a compound containing an aniline skeleton. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 3 2 · The manufacturing method of solid electrolytic capacitors as described in the preceding paragraph 30, wherein the compound containing a plurality of five-membered rings is a compound having a thiophene skeleton 0-3 3 The method for manufacturing a solid electrolytic capacitor according to 30, wherein the monomer compound having a thiophene skeleton is 3-ethylthiophene, 3-hexylthiophene, 3,4-dimethylthiophene, 3,4-methylidene Oxythiophene, 3,4-ethylenedioxythiophene. This paper size applies to Chinese National Standard (CNS) A4 specification (210 X 297 mm)-: ____- A7 ------ B7 V. Description of the invention (H) ---- ~ (Please read the notes on the back first (Fill in this page again) 3 4. The method for manufacturing solid electrolytic capacitors as described in the preceding paragraphs 2 3 to 3 3, where the valve-acting metal is selected from the single metals of aluminum, giant, niobium, and titanium, or these alloys . 3 5. The solid electrolytic capacitor obtained by the manufacturing method according to the item 23 above. ~ 3 6 · The solid electrolytic capacitor obtained by the manufacturing method described in the foregoing paragraph 2 4 丨 3 7 · The solid electrolytic capacitor obtained by the manufacturing method described in any of the foregoing paragraphs 25 through 34. [Schematic description] Figure 1 is a schematic cross-sectional view of a capacitor element. Fig. 2 is a schematic longitudinal sectional view of the material of a capacitor element of Example 1 Fig. 3 is a schematic sectional view of a solid electrolytic capacitor obtained by laminating the capacitor elements of Example 1; Fig. 4 is a schematic longitudinal sectional view of the capacitor element material of Comparative Example 1. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 0 [Illustration of Symbols] 1: Anode substrate 2: Oxide film layer 5: Conductive layer 8: Epoxy resin This paper size applies the Chinese National Standard (CNS) A4 specification (210X297mm) 512373 A7 ___ B7 _ V. Description of the invention (12) [Detailed description of the invention] The dielectric film on the surface of the substrate used in the present invention, usually It is formed by forming a porous body of a metal having a valve function by a method such as conversion treatment. The conversion conditions such as the conversion solution and voltage used in the conversion, and the required capacity and voltage withstand capacity of the solid electrolytic capacitors obtained, are confirmed in advance through experiments and set appropriately. In addition, in the conversion process, a cover is generally provided to ensure that the conversion solution does not leak out of the portion forming the anode of the bulk electrolytic capacitor and the insulation from the solid electrolyte (cathode portion) formed in the subsequent procedures. The material of the curtain can generally be a heat-resistant resin, preferably a soluble or swellable heat-resistant resin or a precursor thereof, and a composition composed of inorganic fine powder and a cellulose resin (Japanese Patent Laid-Open No. 1 1-8 0 5 9 6.), Etc., but there are no restrictions on materials. Specifically, for example, polyphenylene terephthalate (PPS), polyether master (PES), cyanate resin, fluororesin (tetrafluoroethylene, tetrafluoroethylene • perfluoroalkyl vinyl ether copolymer, etc.), low Molecular weight polyfluorene imine, and these derivatives and their precursors. Among them, low molecular weight polyimide, polyether mill, fluororesin, and the precursors thereof are particularly preferred. · Generally a method for forming a conductive polymer on a dielectric oxide film 'Although a method for forming a conductive polymer layer by a gas phase polymerization method and a method for forming a conductive polymer layer by a depolymerization method (Japanese Patent Application Laid-Open No. 3 — 6 2 1 7 etc.); After attaching the organic polymer monomer to the dielectric oxide film ----- This paper size applies the Chinese National Standard (CNS) A4 specification (210 × 297 mm) (please first Read the precautions on the back and fill in this page) • Binding · Order printed by the Consumers' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 512373 A7, B7 V. Invention Description (13) (Please read the precautions on the back before filling out this page), then Solution chemical polymerization method for polymerization in an oxidant solution (Japanese Unexamined Patent Publication Nos. 1 1 to 2 5 1 1 9 1 etc.); using a switching device to change the power supply point to the anode at specific time intervals, and the thickness of the conductive polymer layer An averaged electrolytic polymerization method (Japanese Patent Application Laid-Open No. 1 1-2 8 3 8 7 8 etc.): However, in the present invention, it is preferable to use a method comprising immersing a porous metal substrate of a valve action in an oxidant solution and drying the substrate. oxygen The solution concentration of the chemical agent solution is a solution theoretical oxidation polymerization, or a gas phase chemical oxidation polymerization of an organic polymer monomer that is slowly raised on the substrate. Particularly preferred is solution chemical oxidation polymerization. In the present invention, the monomer partial pressure (when a mixed gas is introduced into the dielectric film) and the air pressure (when pressure is adjusted and introduced into the dielectric material) when manufacturing solid electrolytes by gas phase chemical oxidation polymerization The situation on the film), although it varies depending on the type of the substituents of the compound or the type of the solvent, etc., it is generally preferably in the range of 10 to 3 to 10 pressure, especially in the range of 10 to 2 to 5 pressure. The insider is better. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs In addition, the reaction temperature during gas-phase chemical oxidation polymerization is determined by the type and concentration of the compounds each having a polymerization initiation energy, and the partial pressure (pressure) of the polymerizable monomer. There are no special restrictions on the rest. Generally, a temperature range of 70 ° C to 250 ° C is selected. It is preferably in a temperature range of 0 ° C to 150 ° C, and furthermore, a temperature range of 15 ° C to 100 ° C. According to the present invention, as shown in the examples described below, an aluminum foil containing a dielectric oxide film is impregnated with an isopropyl alcohol (IPA) solution of 3,4-ethylenedioxythiophene EDT), and the IPA is dried by air-drying. After almost all of it is removed, it is then impregnated with about 20% by mass of oxidant (ammonium persulfate) aqueous solution. The paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm)-± g- 512373 A7 B7 V. Description of the invention ( 14) (Please read the precautions on the back before filling in this page), then heat at about 40 ° C for 10 minutes, and repeat this procedure to obtain poly (3,4-ethylene 2 An oxythiophene) polymer is formed in a state where the thickness of the solid electrolyte layer around the substrate is greater than the thickness of the central portion. The detailed reason for such a thickness deviation of the solid electrolyte layer is not necessarily clear, but it can be considered that the water on the dielectric oxide film with a large surface area is more volatile under heating conditions of about 40 ° C. Environment, because the oxidant solution of the substrate cutting surface (notch portion) and the mask will move using the capillary phenomenon, and water will slowly evaporate from the oxidant solution to form a high concentration, and contact with the monomer to polymerize, so In the vicinity of the cutout and the mask boundary area, a large amount of polymer is attached, so that the thickness of the solid electrolyte layer around the substrate is greater than the thickness of the solid electrolyte layer at the center of the substrate. In other words, the main reason for forming the valve-acting porous metal substrate unique to the solid electrolytic capacitor of the present invention is a gourd-shaped or loofah-shaped solid electrolyte in the cross section of the central portion in the length and width directions. The relationship between the surface tension and osmotic pressure of the porous body was converted, and the oxidant solution at the printed surface (notch section) of the consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs of the Ministry of Economic Affairs was concentrated, and the oxidant solution at the screen was concentrated to a high concentration. In this way, the generation pattern of the polymer at the end is guided in a direction that can obtain the superior characteristics of reducing the short-circuit failure rate of the solid electrolytic capacitor and reducing the leakage current. The offset of the thickness of the solid electrolyte layer varies depending on the solid electrolyte formation conditions such as the number of operations of the monomer-containing liquid and the oxidant-containing liquid immersed in the organic polymer on the valve-acting metal substrate, but a better solid can be obtained. Electricity ------ ± j .__ This paper size is applicable to Chinese National Standard (CNS) A4 specification (21 × 297 mm) 512373 A7 B7 V. Description of invention (15) (Please read the notes on the back before filling (On this page) If the range of capacitor characteristics is decomposed, the difference between the maximum thickness and the minimum thickness of the cross section of the central portion of the substrate where the solid electrolyte layer is formed is within the range of 0 ~ 2 0 0 // m. In the range of 0 to 1 800 // m, especially in the range of 0 to 150 # m is preferable. Furthermore, the solid electrolyte layer of the conductive polymer formed according to the method of the present invention can be considered to have a filament-like structure or a sheet-like (thin-layer) structure, and such structures have a wide range of polymerization. The overlap between the material chains makes it easy to form electronic beats to improve electrical conductivity and low impedance. · The Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed the solution chemical polymerization method to make the monomers adhere to the microporous dielectric oxide film on the anode substrate, and to form a compound doped with conductive polymers In the presence, oxidative polymerization is caused by the action of oxidant and moisture in the air, and the polymer composition produced is used as the solid electrolyte to form on the surface of the dielectric. At this time, in order to form a good polymer composition, it is necessary to adjust the time of impregnation (impregnation) in the monomer-containing liquid and the oxidant-containing liquid, and to control the adhesion amount of the monomer and the oxidant. For example, if the immersion time is too long, the polymerization reaction cannot be completed, and the obtained polymer composition is more likely to have a low molecular weight. In addition, if the immersion time in the oxidant-containing liquid having an unsaturated concentration is too long, the oxidant adhered to the metal foil substrate will be re-dissolved by the pre-procedure and procedure including the drying process, and the attached The monomer or polymer produced will also dissolve or flow out, so the polymer formation will be delayed, and the effluent will contaminate the liquid. The same situation occurs when immersed in a monomer-containing liquid. The size of this paper applies Chinese National Standard (CNS) A4 (210 × 297 mm)-512373 Α7 Β7 V. Description of the invention (16) (Please read the precautions on the back before filling this page) The development system is based on low molecular weight oxidants Liquid, monomer-containing liquid coloring, polymer floating, the weight reduction tendency of the solid electrolyte forming adhesion, monomer-containing liquid viscosity, specific gravity change, and so on. Therefore, in the method of the present invention, the time required for immersion in the monomer-containing liquid and the oxidant-containing liquid is set to be sufficient for the monomer component and the oxidant component in the liquid to adhere to the dielectric surface of the metal foil substrate. In the time range of more than time and less than 5 minutes, it is preferably from 0.1 seconds to 2 minutes, and more preferably from 1 second to 1 minute. Furthermore, in order to uniformly adhere the monomers to the surface of the dielectric and the polymer composition, after impregnating the monomer-containing liquid, it is necessary to leave it in the air for a certain period of time to evaporate the solvent. Although this condition varies depending on the type of the solvent, it is performed at a temperature from about 0 / C or more to the boiling point of the solvent. The incubation time varies depending on the type of solvent, but it is about 5 seconds to 15 minutes. For example, in an ethanol-based solvent, it only takes less than 5 minutes. With the design of this storage time, the monomer can be uniformly adhered to the surface of the dielectric, and even the pollution during immersion of the oxidant-containing liquid in the next procedure can be reduced. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs After the impregnation of the monomer-containing liquid and the oxidant-containing liquid, it is convenient to keep the monomer in the air at a certain temperature range for a specific period of time to oxidize and polymerize the monomer. Although the polymerization temperature and degree vary depending on the type of monomer, for example, it only needs 5 t or less in pyrrole, but it needs about 30 to 60 ° C in thiophene. The polymerization time is determined by the amount of monomers attached during the immersion. The amount of adhesion varies with the concentration and viscosity of the monomer-containing solution and the oxidant-containing solution, so although there is no comprehensive limitation, in general, if the amount of single adhesion is small, the paper size applies the Chinese national standard (CNS ) A4 specification (210 × 297 mm) 512373 A7 ___B7 5. Description of the invention (17), the polymerization time can be shortened, and if the single adhesion amount is increased, the polymerization time needs to be increased. (Please read the notes on the back before filling this page) In the method of the present invention, the single polymerization time is in the range of 10 seconds to 15 minutes, preferably in the range of 3 to 10 minutes. The conductive polymer layer formed on the dielectric film by the method of the present invention can be confirmed to have a thin layer structure or a filament-like structure using an electron micrograph. : The thin layer structure or filament structure of conductive polymers has an effect on the increase of the one-dimensionality of the polymer chain that is the main reason for increasing the conductivity and the wide overlap between the polymer chains, which can determine the conductivity of the polymer solid electrolyte. The improvement of capacitor characteristics such as the improvement of capacitors and the reduction of impedance has a positive impact. In the method of the present invention, it is necessary to control the number of impregnations in order to set the formed conductive polymer composition to a thickness having resistance to humidity, heat, and stress. This manufacturing procedure is repeated 15 or more times for a single anode base, preferably 20 to 30 times, so that the desired solid electrolyte layer can be easily formed. The procedure for printing the solid electrolyte used in solid electrolytic capacitors by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is based on the anode body with a dielectric film formed on the valve-containing metal and cross-immersed in the monomer-containing liquid and An oxidant-containing liquid is dried, so that the monomer and the oxidant are cross-repeatedly attached, and then chemically oxidized and polymerized in the air. At this time, the humidity in the environment is set to be above 10% and below 80%. It is best to perform chemical oxidation polymerization under the conditions of more than 15% and less than 60%, and more than 20% and less than 50%. The size of the paper is applicable to the Chinese National Standard (CNS) A4. (210X29 * 7 mm) 512373 Printed by A7 _ B7 of the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (18) A conductive polymer layer containing monomers or derivatives as repeating units. The temperature and pressure in the environment vary with the type of polymer composition, polymerization method, etc., although not specifically limited, but it is generally best to be in the temperature range of 7 0 t: ~ 2 50 ° C, and the pressure is It is preferably below normal pressure. The concentration of the monomer-containing solution is in the range of 3 to 50 mass%, preferably in the range of 5 to 35 mass%, and more preferably in the range of 10 to 25 mass%. The concentration of the oxidant-containing liquid is in the range of 5 to 70% by mass, and preferably in the range of 15 to 50% by mass. In addition, the viscosity of the monomer-containing liquid and the oxidant-containing liquid is below 100 centipoise (c P), preferably below 30 c P, especially between 0.6 and 100%. According to the present invention, a solid electrolyte having a layered structure (thin layer structure or filamentous structure) of a conductive polymer can be formed by cross-impregnating a monomer-containing liquid and an oxidant-containing liquid, and even in this layer, it is The one-dimensionality of the raised polymer chain and the overlap between the polymer chains are generated, and it is learned that it is best not to perform washing each time, and it can be performed at the end. In this way, the excess (unreacted) monomers left unreacted in the polymerization process can be polymerized in the next process, and as a result, a conductive polymer having a layered structure with a wide range of overlap can be formed. Solid electrolyte. The thin-layered structure or filamentary-structured solid electrolyte covering the outer surface of the intestinal pole obtained by the method of the present invention produces a relatively continuous or independent space, and such space will play a role in relaxing capacitor manufacturing processing procedures such as packaging procedures The thermal stress or mechanical stress received. In addition, it is not only a manufacturing process, but also an effective structure that can respond to various stresses received in the environment when the capacitor is actually used. ---: —— ;; --- This paper size applies to China National Standard (CNS) A4 (210X 297 mm) (Please read the note on the back 4-item before filling-packaging-write this page) Order 512373 A7 B7
五、發明説明（19) J (請先閲讀背面之注意事項再填寫本頁) 本發明固體電解質之其中一種最佳形成程序，係將：$ 成有該介電質氧化皮膜層的閥作用金屬陽極箔，浸漬於含 氧化劑之含液（含液1 )中的程.序，與浸漬於含單體與雜 摻之含液（含液2 )中的程序。此順序係可爲先浸潰於該 含液1後，再浸漬於含液2中的程序（正順序），另，# 可爲相反順序，將該閥作用金屬陽極箔先浸漬於該含、液2 後，再浸漬於含液1中的程序。 ’ 或者其他實施態樣，亦可爲將該陽極箔浸漬於含氧t 劑與雜摻之溶液（含液3 )中的程序，與浸漬於含單n & 溶液（含液4 )中的程序。即便此情況下，雖在浸漬於^該 含液3後，再浸漬於該含液4的程序（正順序），但# q 採用相反順序，即採用將該陽極箔浸漬於該含液4後，胃 浸漬於該含液3中之程序的製造方法。該含液1至含、液4 亦可分別採用懸浮狀態。再者，亦可利用塗布作業取# M 浸漬程序。 經濟部智慧財產局員工消費合作社印製 含液1至含液4之溶劑，配合需要可爲相同者，或# 可爲相異的溶劑系。另，配合溶劑的種類，在含液1與含 液2之間，或含液3與含液4之間的程序，亦可另外*** 該乾燥程序。此外，在形成固體電解質後，亦可利用溶劑 進行洗淨。· 可使用於本發明之具閥作用的金屬，有如鋁、钽、鈮 、鈦、锆、鎂、矽等單體金屬、或該等合金。另，相關型 態，則僅需爲軋延箔之蝕刻物、微粉燒結體等多孔質成形 體型態的話便可。 -：-------22___ 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 512373 A7 B7 五、發明説明（20) 其次，陽極基板雖可採用該等金屬之多孔質燒結體、 經蝕刻等表面處理的板（包括帶、箔等）、線等，但最好 爲平板狀、箔狀。再者，在此金屬多孔體表面形成介電質 氧化皮膜的方法，可採用習知方法。譬如當使用钽粉末燒 結體之情況時，可在磷酸水溶液中進行陽極氧化，並施行 燒結體而形成氧化皮膜。 · 譬如閥作用金屬箔的厚度，雖依使用目的而各有不同 ，但一般則使用厚度約4 0〜1 5 0 v m的箔。此外，閥 作用金屬箔的大小與形狀\亦依用途而有所不同，最好平 板狀元件單位爲寬約1.〜5 0 m m，長度約1〜5 0 m m 矩形者，尤以寬約2〜1 5 m m，長度約2〜2 5 m m矩 形者爲更佳。 本發明中，可使用於固體電解質形成之水溶液系氧化 劑，可舉例如過氧化二硫酸及其N a鹽、K鹽、N Η 4鹽、 硝酸硒（IV )、硝酸硒（IV )銨、硫酸鐵（瓜）、氯化鐵 (瓜）等。另，有機溶劑系氧化劑則如有機磺酸之亞鐵鹽 ，譬如十二烷基苯磺酸鐵（ffl )等。此處所使用的有機溶 劑，可舉例如Τ -丁內脂、及丁醇、異丙醇等一元醇。另 ，氧化劑溶液的濃度最好爲5〜5 0質量％，而氧化劑溶 液的溫度則最好爲一 1 5〜6 0 °C。 本發明中所使用形成固體電解質之導電性聚合物，係 含7Γ電子共軛構造的有機高分子單體之聚合物，聚合度2 以上、2 0 0 0以下，尤以5以上、1 0 0 0以下爲佳。 具體例有如含有以如具噻吩骨架的化合物、具多環狀硫醚 —-----23---- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） IJ--：-----I (請先閲讀背面之注意事項再填寫本頁) 訂 經濟部智慧財產局員工消費合作社印製 512373 A7 _ B7 五、發明説明（21) (請先閲讀背面之注意事項再填寫本頁j 骨架的化合物、具吡咯骨架的化合物、具呋喃骨架的化合 物、具苯胺骨架的化合物等所示構造爲重複單位的導電性 聚合物。但，導電性聚合物並不僅限於此。 具噻吩骨架的化合物，係可舉例如3 -甲基噻吩、3 一乙基噻吩、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 -氟化噻吩、3 —氯化噻吩 、3 -溴化噻吩、3 -氰化噻吩、3，4 —二甲基噻吩、 3，4 —二乙基噻吩、3 _，4 — 丁烯噻吩、3，4 一甲撐 二氧基噻吩、3，4 -乙撐二氧基噻吩等衍生物。該等化 合物，可採用一般市售化合物，或利用習知方法（譬如V. Description of the invention (19) J (Please read the precautions on the back before filling this page) One of the best forming procedures of the solid electrolyte of the present invention is to: $ form the valve-acting metal with the dielectric oxide film layer The anode foil is immersed in a oxidant-containing liquid (liquid 1), and a procedure of immersion in a monomer-containing and doped liquid (liquid 2). This sequence can be a procedure of immersing in the containing liquid 1 and then immersing in the containing liquid 2 (positive sequence). In addition, # can be the reverse sequence, and the valve-acting metal anode foil is first immersed in the containing, Procedure of immersing in liquid 1 after liquid 2. 'Or other embodiments, it can also be a procedure of immersing the anode foil in an oxygen-containing agent and a doped solution (containing liquid 3), and a procedure of immersing the anode foil in a single n & solution (containing liquid 4). program. Even in this case, although the process of immersing in the liquid-containing 3 and then immersing in the liquid-containing 4 (positive order), # q uses the reverse order, that is, the anode foil is immersed in the liquid-containing 4 , A method for manufacturing a procedure in which the stomach is immersed in the liquid 3. The liquid-containing liquids 1 to 4 and liquid 4 can also be suspended respectively. Furthermore, the # M dipping procedure can also be taken by a coating operation. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Solvents containing liquid 1 to liquid 4, can be the same as required, or # can be different solvent systems. In addition, the type of the solvent to be mixed may be a program between liquid 1 and liquid 2 or between liquid 3 and liquid 4, and the drying program may be inserted separately. After the solid electrolyte is formed, it may be washed with a solvent. · Metals that can be used for the valve of the present invention include single metals such as aluminum, tantalum, niobium, titanium, zirconium, magnesium, and silicon, or these alloys. In addition, the relevant type is only required to be a porous shaped body such as an etched material of rolled foil or a fine powder sintered body. -: ------- 22___ This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) 512373 A7 B7 V. Description of the invention (20) Secondly, although the anode substrate can be made of porous metal A sintered body, a surface-treated plate (including a tape, a foil, etc.), a wire, or the like is preferred, but it is preferably a flat plate or a foil. In addition, as a method for forming a dielectric oxide film on the surface of the porous metal body, a conventional method can be adopted. For example, when a tantalum powder is used to sinter the body, anodization may be performed in an aqueous phosphoric acid solution, and the sintered body may be formed to form an oxide film. · For example, the thickness of the valve-acting metal foil varies depending on the purpose of use, but generally a foil with a thickness of about 40 to 150 v m is used. In addition, the size and shape of the valve-acting metal foil also varies depending on the application. It is best that the flat-shaped element unit is a rectangle with a width of about 1. to 50 mm and a length of about 1 to 50 mm, especially a width of about 2 ~ 15 mm, rectangular with a length of about 2 ~ 25 mm is more preferred. In the present invention, an aqueous solution-based oxidant that can be used for the formation of a solid electrolyte may be, for example, peroxodisulfuric acid and its Na salt, K salt, N Η 4 salt, selenium (IV) nitrate, selenium (IV) ammonium nitrate, sulfuric acid Iron (melon), iron chloride (melon), etc. In addition, organic solvent-based oxidants are ferrous salts of organic sulfonic acids, such as iron dodecylbenzenesulfonate (ffl). Examples of the organic solvent used herein include T-butyrolactone, and monohydric alcohols such as butanol and isopropanol. In addition, 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. The conductive polymer used in the present invention to form a solid electrolyte is a polymer containing an organic polymer monomer having a 7Γ electron conjugate structure, and has a degree of polymerization of 2 or more and 2000 or less, especially 5 or more and 100 0 or less is preferred. Specific examples include compounds with a thiophene skeleton and polycyclic sulfide ------- 23 ---- This paper is sized to the Chinese National Standard (CNS) A4 (210X297 mm) IJ--: ----- I (Please read the notes on the back before filling out this page) Order printed by the Intellectual Property Bureau of the Ministry of Economic Affairs's Consumer Cooperatives 512373 A7 _ B7 V. Description of the invention (21) (Please read the notes on the back before Fill in the j-frame compound, compound with pyrrole skeleton, compound with furan skeleton, compound with aniline skeleton, and other conductive polymers with repeating units shown in this page. However, conductive polymers are not limited to this. Examples of compounds having a thiophene skeleton include 3-methylthiophene, 3-ethylthiophene, 3-propylthiophene, 3-butylthiophene, 3-pentylthiophene, 3-hexylthiophene, 3-heptylthiophene, 3-octylthiophene, 3-nonylthiophene, 3-decylthiophene, 3-fluorinated thiophene, 3-chlorothiophene, 3-bromothiophene, 3-cyanothiophene, 3,4-dimethylthiophene , 3,4-diethylthiophene, 3 _, 4-butenethiophene, 3,4 dimethylene Thiophene, 3,4 - ethylene dioxythiophene other derivatives of such compounds, generally commercially available compounds may be used, or the use of conventional methods (for example,
Synthetic Metals 誌、1986 年、15 卷、第 169 頁） 準備，但並不僅限定於此。 再者，具多環狀硫醚骨架的單體化合物具體例，則可 使用如具1，3 —二氫多環狀硫醚（偏名·· 1，3 —二 經濟部智慧財產局員工消費合作社印製 氫多苯並〔c〕噻吩）骨架的化合物、具1，3 -二氫萘 〔2，3 — c〕噻吩骨架的化合物。甚至於可舉例如具1 ，3 -二氫蒽〔2，3 - c〕噻吩骨架的化合物、具1， 3 -二氫萘並〔2，3 - c〕噻吩骨架的化合物。該等可 利用習知方法，譬如特開平8 — 3 1 5 6號公報中所記載 的方法進行準備。 此外，亦可使用如具1 ，3 -二氫萘〔1，2 — c〕 噻吩骨架的化合物、1，3 —二氫菲〔2，3 - c〕噻吩 衍生物、或具1，3 -二氫苯〔2，3 — c〕噻吩骨架的Synthetic Metals, 1986, Vol. 15, p. 169), but it is not limited to this. In addition, for specific examples of monomer compounds having a polycyclic sulfide skeleton, for example, 1,3-dihydropolycyclic sulfide (partial name ·· 1,3—II Intellectual Property Bureau, Ministry of Economic Affairs, employee consumption) Cooperatives print compounds with a hydrogen polybenzo [c] thiophene) skeleton, and compounds with a 1,3-dihydronaphthalene [2,3-c] thiophene skeleton. Even a compound having a 1,3-dihydroanthracene [2,3-c] thiophene skeleton and a compound having a 1,3-dihydronaphtho [2,3-c] thiophene skeleton can be mentioned. These can be prepared by a conventional method, for example, the method described in Japanese Unexamined Patent Publication No. 8-3156. In addition, a compound having a 1,3-dihydronaphthalene [1,2-c] thiophene skeleton, a 1,3-dihydrophenanthrene [2,3-c] thiophene derivative, or a 1,3- Dihydrobenzene [2,3- —c] thiophene skeleton
QA 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 512373 Μ Β7 五、發明説明（22) 化合物、具1，3 —二氫蒽並〔7，8 - c〕噻吩引生物 等。 可使用縮合環上任意含氮或N -氧化的化合物，譬如 1，3 —二氫噻吩〔3，4 一 b〕D奎噁啉、1，3 —二氫 噻吩〔3，4 — b〕喹噁啉一 4 —氧化物、1，3 —二氫 噻吩〔3，4 一 b〕喹噁啉一 4，9 —氧化物等。惟並不 僅限制於此。 ： 具吡咯骨架的化合物則可舉例如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 —氟化吡咯、3 —氯化吡咯、 3 —溴化吡咯、3 -氰化吡咯、3，4 —二甲基吡咯、3 ，4 一二乙基吡咯、3，4 一丁烯吡咯、3，4 —甲撐二 氧基吡咯、3，4 -乙撐二氧基吡咯等衍生物。該等化合 物，可採用一般市售化合物，或利用習知方法準備，但並 不僅限定於此。 具呋喃骨架的化合物則可舉例如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 基咲喃、3'-癸基咲喃、3 —氧化咲喃、3 -氯化咲喃、 3 -溴化呋喃、3 -氰化呋喃、3，4 一二甲基呋喃、3 ，4 —二乙基呋喃、3，4 — 丁烯呋喃、3，4 —甲撐二 氧基咲喃、3 .，4 -乙撐二氧基咲喃等衍生物。該等化合 物，可採用一般市售化合物，或利用習知方法準備，但並 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） |丨.——I —— — (請先閱讀背面之注意事項再填寫本頁) 裝. 訂 經濟部智慧財產局員工消費合作社印製 512373 A7 B7 五、發明説明（23) 不僅限定於此。 具苯胺骨架的化合物則可舉例如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 -氟 2 -溴化苯胺、2 -氰化苯胺 2，3 -丁烯苯胺、2，3」甲撐二 經濟部智慧財產局員工消費合作社印製 ，5 —二 氧基苯胺 物，可採 本發明並 該等 合物，尤 一二氫苯 此外 甲醇、乙 丁醇等） 任意濃度 在由 上並無特 俾較容易 此外 化合物， 組成比等 ，可利用 苯胺、2 乙基苯胺 、2，3 用一般市 不僅限定 之中，最 以3，4 並噻吩爲 ，該有機 化苯胺、2 —氯化苯胺 ，5 —二甲基苯胺、 -乙撐二氧基苯胺等衍生物。該等化合 售化合物，或利用習知方法準備，但在 於此。 好爲具噻吩骨架或多環狀硫醚骨架知化 一乙撐二氧基噻吩（EDT) 、.1，3 佳 溶劑，最好採用一元醇（ 、η —丁醇 '異丁醇、四 高分子單體的 醇、η -丙醇、異丙醇 。單體溶劑中的單體濃度並無特別限制，可使用 上述化合物組群中選擇化合物的聚合條件等方面 別限制，可利用簡單實驗，預先確認較佳條件’ 實'施。 ，亦可合倂使用選擇自上述單體化合物組群中的 而形成共聚物的固體電解質。此時的聚合性單體 ，係依存於聚合條件等，較佳組成比、聚合條件 簡單的測試進行確認。 _26----- 本纸張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁) 512373 A7 _ B7 五、發明説#( 24) 譬如可利用在E D T單體與氧化劑之較佳的溶液型態 中，前後各別或一齊塗布於金屬箔之氧化皮膜層而形成的 (請先閲讀背面之注意事項再填寫本頁) 方法（特開平2 — 1 5 6 1 1號公報、特開平 1〇一3 2 1 4 5號公報）等。 在本發明中，較佳使用的3，4 一乙撐二氧基噻吩（ E D T )，係充分溶解於上述一兀醇中，或因與水相容性 不佳，而接觸於高濃度氧化劑水溶液時，E D T便在其界 面上，進行良好的聚合，而形成絲狀結構或薄層（薄層狀 )結構的導電性高分子固體電解質層。 在本發明的製造方法中所採用的溶液、或形成固體電 解質後的洗淨用溶劑，可舉例如四氫呋喃（T H F )或二 噁烷、二***等醚類；丙酮、甲乙酮等酮類；二甲基甲醯 胺、乙腈、苯甲腈、Ν —甲基吡咯啉酮（ΝΜΡ)、二甲 基亞砸（D M S〇）等非質子性極性溶劑；醋酸乙酯、醋 酸丁酯等酯類；氯仿、氯化甲撐等非芳香族性氯系溶劑； 硝化甲烷、硝化乙烷、硝化苯等硝基化合物；甲醇、乙醇 、丙醇等醇類；蟻酸、醋酸、丙酸等有機酸；該有機酸的 經濟部智慧財產局員工消費合作社印製 酸無水物（如無水醋酸等）、或水、或該等混合溶劑。最 好爲水、醇類或酮類、或該等混合系。 在本發·明之導電性聚合物中，係採用芳基磺酸系摻質 。譬如摻質的原料，可採用苯磺酸、甲苯磺酸、萘磺酸、 蒽磺酸、蒽醌磺酸等之鹽類。 依此方式所製得之固體電解質的導電度約〇·1〜 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 2 0 0 S/cm範圍，最好爲約1〜1 5〇S/cm範圍 --------27--- 512373 經濟部智慧財產局員工消費合作社印製 A7 ___._ B7五、發明説明（25) 內，尤以在約1 0〜1 0 0 s/cm範圍內者爲佳。 再者，在所形成的導電性聚合物層上，爲與陰極導線 端子有良好的電性接觸，最好設置導電層。譬如施行形成 導電塗料之固體、或電鍍或金屬蒸鍍、導電樹脂薄膜等。 而且，所獲得之固體電解電容器元件，通常依形成所 需電容器容量方式疊層複數片，並連接於導線端子，在利 用如樹脂模具、樹脂盒、金屬製外裝盒、樹脂浸漬等方式 ，施行外包裝，便形成各種用途的電容器產品。 【實施發明較佳態樣】 以下，雖舉實施例針對本發明進行詳細說明，惟本發 明並不僅限於下述實施例。 實施例1 : 將經融刻過的銘范切成短軸方向3 in m X長軸方向 1 0 m m，並將長軸方向刻劃出4 m m與5 m m部分，並 於雙面上於周圍塗布寬度1 m m的聚醯亞胺溶液，並乾燥 而製成罩幕。將經蝕刻過鋁轉化箔的3 m m X 4 m m部分 ，利用1 0質量％之己二酸銨水溶液並賦加1 3 V電壓而 轉化，而於切口部分形成介電質氧化皮膜。其次，將此金呂 箔的3 m m X 4 m m部分，浸漬於溶解有5 g之3 ’ 4 一 乙撐二氧基噻吩（Bayer AG製）的1 2 m ο 1 / L異丙醇 (I P A )溶液中5秒鐘，再將其於室溫下進行5分鐘乾 燥，然後在浸漬於調配成0 · 0 0 7質量％懸浮狀2 一蒽 ------ (請先閱讀背面之注意事項再填寫本頁) ’裝- 訂 本紙張尺度適用中國國家標準（CNS ) A4規格（210X：297公釐） 512373 A7 B7 五、發明説明（26) 醌磺酸鈉的2 m ο 1 / L過硫酸銨水溶液中5秒鐘。接著 (請先閱讀背面之注意事項再填寫本頁) ，將此鋁箔在4 0 °C大氣中放置1 0分鐘，俾進行氧化聚 合。然後在將浸漬程序與聚合程序整體進行2 5次’而在 經鈾刻過鋁箔的外表面上形成聚合物組成物的固體電解質 層。將最後所生成的聚（3，4一乙撐二氧基噻吩）’在 5 0 °C溫水中進行洗淨，然後於1 0 〇 °C下施行3 0分鐘 的乾燥，而形成固體電解質層。 . 採用膜厚度計（Peacock公司產製：浐夕少〆 < 十 y' — 9 D G - 2 0 5 (精度3 // m ))，從容的將鋁箔夾 製於膜厚度計的測量部中，進行測量。 結果如第2圖示意圖所示的周圍部位的突出部分厚度 (h i )爲2 6 0 # m，而中央部位的掐腰部分厚度（h 2 )則爲 2 1 ’ 膜厚差（hi — 1ΐ2)爲 5 。 其次，如第3圖所示，將上述鋁箔形成有導電性聚合 物的部分，沾上碳塗料或銀塗料，並疊層4層上述鋁箔， 在連接於陰極導線端子。再者，未形成聚合物組成物的部 分，則連接於陽極導線端子。然後，在將此元件利用環氧. 經濟部智慧財產局員工消費合作社印製 樹脂封裝後，於1 2 5 °C下賦加額定電壓，並進行2小時 的老化，總計完成3 0個電容器。 針對此3 0個電容器元件，測量初期特性的1 2〇QA The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) 512373 Μ B7 V. Description of the invention (22) Compounds with 1,3-dihydroantholo [7,8-c] thiophene-induced biological Wait. Any nitrogen- or N-oxidized compound on the condensation ring can be used, such as 1,3-dihydrothiophene [3,4-b] D quinoxaline, 1,3-dihydrothiophene [3,4-b] quine Oxaline-4-oxide, 1,3-dihydrothiophene [3,4-b] quinoxaline-4,9-oxide, etc. But it is not limited to this. : For compounds with a pyrrole skeleton, for example, 3-methylpyrrole, 3-ethylpyrrole, 3-propylpyrrole: 3-butylpyrrole, 3-pentylpyrrole, 3-hexylpyrrole, 3-heptylpyrrole , 3-octylpyrrole, 3-nonylpyrrole, 3-decylpyrrole, 3-fluorinated pyrrole, 3-chloropyrrole, 3-bromopyrrole, 3-cyanopyrrole, 3,4-dimethyl Derivatives such as pyrrole, 3,4-diethylpyrrole, 3,4-butenepyrrole, 3,4-methylenedioxypyrrole, and 3,4-ethylenedioxypyrrole. These compounds can be prepared using common commercially available compounds or using conventional methods, but are not limited thereto. Examples of the compound having a furan skeleton include 3-methylfuran, 3-ethylfuran, 3-propylfuran, 3-butylfuran, 3-pentylfuran, 3-hexylfuran, 3-heptylfuran, 3 -octylfuran, 3 -nonylsulfan, 3'-decylsulfan, 3-oxalan, 3-chlorosulfan, 3-bromofuran, 3-cyanofuran, 3,4- Derivatives such as dimethylfuran, 3,4-diethylfuran, 3,4-butenefuran, 3,4-methyldioxypyran, 3,4-ethylenedioxypyran. These compounds can be prepared using common commercially available compounds, or prepared by conventional methods, but this paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) | 丨 .—— I —— — (Please read first Note on the back, please fill out this page again) Packing. Order printed by the Intellectual Property Bureau of the Ministry of Economic Affairs's Consumer Cooperatives 512373 A7 B7 V. Invention Description (23) is not limited to this. Examples of compounds 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-fluoro2-bromoaniline, 2-cyanoaniline 2,3-buteneaniline, 2,3 "methylene diene Printed by the Consumer Cooperative of the Property Bureau. 5-Dioxoaniline can be used in the present invention, especially dihydrobenzene. In addition, methanol, ethyl butanol, etc.) It is not easy to arbitrarily have any special concentration. In addition, compounds, composition ratios, and the like can be used aniline, 2 ethylaniline, 2, 3 not only limited by the general market, the most common is 3,4 thiothiophene, the organic aniline, 2-chloroaniline, 5-di Derivatives such as methylaniline and ethylenedioxyaniline. These compounds are sold commercially or prepared using conventional methods, but here they are. It is a good solvent with a thiophene skeleton or a polycyclic sulfide skeleton. Ethylenedioxythiophene (EDT), .1, 3, preferably a monohydric alcohol (, η-butanol 'isobutanol, tetra-high Alcohol, η-propanol, and isopropanol of the molecular monomer. There is no particular limitation on the monomer concentration in the monomer solvent, and the polymerization conditions of the selected compound in the above-mentioned compound group can be used. The simple experiment can be used. It is confirmed in advance that the best conditions are to be applied. A solid electrolyte selected from the above-mentioned monomer compound groups to form a copolymer may also be used in combination. The polymerizable monomer at this time depends on the polymerization conditions and the like. Good composition ratio and simple polymerization conditions to confirm. _26 ----- This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page) 512373 A7 _ B7 五 、 发明 说 # (24) For example, it can be formed in the preferred solution type of EDT monomer and oxidant, and it can be formed by coating on the oxide film layer of metal foil before or after (please read the back first) Please fill in the matters needing attention Page) Method (Japanese Patent Application Laid-Open No. 2-1 5 6 1 1 and Japanese Patent Application Laid-open No. 103-2 1 4 5), etc. In the present invention, 3,4-ethylenedioxythiophene is preferably used. (EDT), which is fully dissolved in the above monoalcohol, or because of poor compatibility with water, when it comes into contact with a high-concentration oxidant aqueous solution, EDT undergoes good polymerization at its interface to form a filamentous structure Or a conductive polymer solid electrolyte layer with a thin layer (thin layer structure). The solution used in the production method of the present invention or the cleaning solvent after forming the solid electrolyte may be, for example, tetrahydrofuran (THF) or dihydrofuran (THF). Ethers such as oxane and diethyl ether; ketones such as acetone and methyl ethyl ketone; dimethylformamide, acetonitrile, benzonitrile, N-methylpyrrolidone (NMP), dimethylimide (DMS) Aprotic polar solvents; esters such as ethyl acetate and butyl acetate; non-aromatic chlorine solvents such as chloroform and methyl chloride; nitro compounds such as nitrated methane, nitroethane, and nitrobenzene; methanol, ethanol, Alcohols such as propanol; organic acids such as formic acid, acetic acid, and propionic acid ; The organic acid of the Ministry of Economic Affairs, the Intellectual Property Bureau, the employees' cooperatives printed acid anhydrides (such as anhydrous acetic acid, etc.), or water, or these mixed solvents. Preferably water, alcohols or ketones, or these mixed systems In the conductive polymer of the present invention, arylsulfonic acid is used as the dopant. For example, benzenesulfonic acid, toluenesulfonic acid, naphthalenesulfonic acid, anthracenesulfonic acid, and anthraquinonesulfonic acid can be used as the dopant material. The conductivity of the solid electrolyte prepared in this way is about 0.1 · ~ This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) 2 0 0 S / cm, preferably The range of about 1 ~ 15.0S / cm -------- 27 --- 512373 Printed by A7 ___._ B7 in the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, especially in the description of the invention (25) It is preferably within a range of about 10 to 100 s / cm. Furthermore, it is preferable to provide a conductive layer on the formed conductive polymer layer in order to have good electrical contact with the cathode lead terminal. Examples include solids that form conductive paint, electroplating or metal deposition, and conductive resin films. In addition, the obtained solid electrolytic capacitor element is generally laminated in a manner to form a required capacitor capacity and connected to a lead terminal, and is implemented by means such as a resin mold, a resin box, a metal outer box, and a resin impregnation. The outer packaging forms capacitor products for various uses. [Preferred Aspects of Implementing the Invention] Although the present invention will be described in detail in the following embodiments, the present invention is not limited to the following embodiments. Example 1: Cut the engraved inscription fan into the short-axis direction 3 in m X long-axis direction 10 mm, and cut the long-axis direction into 4 mm and 5 mm parts, and surround it on both sides A polyimide solution with a width of 1 mm was applied and dried to form a mask. A 3 m m × 4 m m portion of the etched aluminum conversion foil was converted with a 10 mass% ammonium adipate aqueous solution and a voltage of 13 V was applied to form a dielectric oxide film on the cut portion. Next, a 3 mm X 4 mm portion of this gold foil was immersed in 1 2 m ο 1 / L isopropyl alcohol (IPA) in which 5 g of 3 '4 ethylenedioxythiophene (manufactured by Bayer AG) was dissolved. ) In the solution for 5 seconds, and then dried at room temperature for 5 minutes, and then immersed in a mixture of 0 · 0 0 7 mass% suspended 2 anthracene ------ (Please read the note on the back first Please fill in this page again for the matter) 'Binding-The size of the paper is applicable to the Chinese National Standard (CNS) A4 (210X: 297 mm) 512373 A7 B7 V. Description of the invention (26) 2 m of sodium quinone sulfonate 1 / L In ammonium persulfate solution for 5 seconds. Then (please read the precautions on the back before filling this page), and place this aluminum foil in the air at 40 ° C for 10 minutes to carry out the oxidation polymerization. Then, a solid electrolyte layer of a polymer composition was formed on the outer surface of the aluminum foil etched with uranium by performing the entire impregnation procedure and the polymerization procedure 25 times'. The resulting poly (3,4-ethylenedioxythiophene) 'was washed in warm water at 50 ° C, and then dried at 100 ° C for 30 minutes to form a solid electrolyte layer. . . Using a film thickness meter (manufactured by Peacock: 浐 夕 少 〆 < ten y '— 9 DG-2 0 5 (accuracy 3 // m)), the aluminum foil is easily clamped in the measurement section of the film thickness meter To make a measurement. As a result, as shown in the schematic diagram in FIG. 2, the thickness (hi) of the protruding part of the surrounding part is 2 6 0 # m, and the thickness of the hip region (h 2) at the central part is 2 1 'film thickness difference (hi — 1ΐ2). For 5. Next, as shown in Fig. 3, a portion of the aluminum foil formed with a conductive polymer was coated with a carbon paint or a silver paint, and the aluminum foil was laminated in four layers to be connected to a cathode lead terminal. The portion where the polymer composition is not formed is connected to the anode lead terminal. Then, this component was printed with resin using epoxy resin printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, and then the rated voltage was applied at 125 ° C and aged for 2 hours. A total of 30 capacitors were completed. For these 30 capacitor elements, 1 2 of the initial characteristics was measured.
Hz中之容量與損耗係數（tan0xl〇〇 (%))、 共振頻率之阻抗、^漏電流。另，遺漏電流係在賦加額定 電壓後1分鐘進行測量。表1所示係該等測量質之平均値 、當將〇 · 5 9 # A ( 〇 · 〇 〇 2 C V )以上遺漏電流視 本紙張尺度適用中國國家標準（CNS ) A4規格（21〇><297公釐） 29___ 512373 A7 _____ B7五、發明説明（27) 爲不良品時的不良率、及短路產品數量。此處，遺漏電流 平均値係除以不良品的計算値。另，表2所示係回流試驗 與接著所進行的耐濕試驗之結果。但，在耐濕試驗中的胃 漏電流値，係將1 1 · 8 M a ( 〇 . 〇 4 C V )以上者視 爲不良品。此處，回流試驗係依在2 3 0 °C溫度區域下s 過3 0秒鐘方式而進行。此外，耐濕試驗係在8 5 °C、8 5 % R Η高溫高濕下，放置2 4 0小時而進行。| 實施例2 : ' 除在實施例1中，將過硫酸銨，取代爲硫酸亞鐵，且 將3，4 -乙撐二氧基噻吩，取代爲二氫異苯並噻吩之外 ，其餘均如同實施例1，完成30個電容器。 如同實施例1，測量固體電解質層突出部分厚度爲 2 5 0 Am，而中央部位的掐腰部分厚度則爲2 0 0 Am (請先閱讀背面之注意事項再填寫本頁) -裝- ,π 膜厚差（h h 經濟部智慧財產局員工消費合作社印製 針對所製得電容器元件，進行如同實施例1的特性言平 估，結果顯示於表1及表2。 貫施例3 · 除在實施例1中，將3，4 一乙撐二氧基噻吩，取代 爲吡咯，且此時吡咯溶液係浸漬後，在於3 °C下進行5分 鐘乾燥，並在浸漬於氧化劑溶液後，於5 °C下進行1 0分 鐘聚合之外，其餘均如同實施例1 ，完成3 0個電容器。 如同實施例1，測量固體電解質層突出部分厚度爲 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 512373The capacity and loss coefficient (tan0x100 (%)) in Hz, the impedance of the resonance frequency, and the leakage current. The leakage current is measured 1 minute after the rated voltage is applied. Table 1 shows the average of these measurement qualities. When the leakage current above 0.59 # A (〇 〇〇〇2 CV) is considered as the standard of this paper, the Chinese National Standard (CNS) A4 specification (21〇 > < 297 mm) 29___ 512373 A7 _____ B7 V. Description of the invention (27) The defective rate when the product is defective, and the number of short-circuit products. Here, the average missing current is calculated by dividing the defective product. Table 2 shows the results of the reflow test and the subsequent moisture resistance test. However, the gastric leakage current in the moisture resistance test is considered to be a defective product of 1 1 8 M a (0.04 C V) or more. Here, the reflow test was performed in a manner that s passed 30 seconds in a temperature range of 230 ° C. In addition, the humidity resistance test was performed at 85 ° C, 85% R Η high temperature and high humidity, and left for 240 hours. Example 2: 'Except in Example 1, ammonium persulfate was replaced with ferrous sulfate, and 3,4-ethylenedioxythiophene was replaced with dihydroisobenzothiophene. As in Example 1, 30 capacitors were completed. As in Example 1, the thickness of the protruding portion of the solid electrolyte layer was measured at 250 Am, and the thickness of the waist region at the central part was 200 Am (please read the precautions on the back before filling this page) -pack-, π Film thickness difference (hh Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs of the People's Republic of China. The characteristics of the capacitor elements obtained were evaluated in the same way as in Example 1. The results are shown in Tables 1 and 2. Implementation Example 3 • Except during implementation In Example 1, 3,4-ethylenedioxythiophene was replaced with pyrrole. At this time, the pyrrole solution was impregnated, dried at 3 ° C for 5 minutes, and immersed in an oxidant solution at 5 °. Except for 10 minutes of polymerization under C, the rest are the same as in Example 1 and 30 capacitors are completed. As in Example 1, the thickness of the protruding portion of the solid electrolyte layer is measured based on the paper size and the Chinese National Standard (CNS) A4 specification (210X297) is applied. Mm) 512373
2 8 0 ’而中央部位的掐腰部分厚度則爲2 1 q “见 ，膜厚差（hi — h2)爲 7 0//m。 針對所製得電容器元件，進行如同實施例1的特性評 估，結果顯示於表1及表2。 實施例4 : 除在實施例1中，將3，4 一乙撐二氧基噻吩，取代 爲呋喃之外’其餘均如同實施例1，完成3 〇個電容器。 .如同實施例1，測量固體電解質層突出部分厚度爲 2 6 Ο β m ’而中央部位的掐腰部分厚度則爲2 〇 〇 μ m ，膜厚差（hi — h2)爲 60#m。 針對所製得電容器元件，進行如同實施例1的特性評 估，結果顯示於表1及表2。 實施例5 : 除在實施例1中，將3，4 一乙撐二氧基噻吩，取代 爲苯胺之外，其餘均如同實施例1，完成3 0個電容器。 如同實施例1，測量固體電解質層突出部分厚度爲 2 7 Ο V m，而中央部位的掐腰部分厚度則爲2 1 Ο V m 膜厚差C h 針對所製得電容器元件，進行如同實施例1的特性評 估，結果顯示於表1及表2。 比較例 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁} 裝· 訂 經濟部智慧財產局員工消費合作社印製 Ά3 A? __ 五、發明説明（29) 將3，4 一乙撐二氧基噻吩（Bayer AG製）依等莫耳 溶解於十二烷基苯磺酸鐵7 5 % I P A溶液中，再將此溶 '液點滴或浸漬於實施例1所製得鋁箔上。接著，將此鋁箔 在4 〇 t的大氣中，放置約6 0分鐘，俾進行氧化聚合。 採用膜厚度計（Peacock公司產製：r ^夕少夕'' 4个少 y — v D G — 2 0 5 (精度3 // m ))，從容的將鋁箔夾 製於膜厚度計的測量部中，進行測量。 ' 結果如第4圖示意圖所示的周圍部位的突出部分厚度 (h. 3 )爲2 3 〇 #①，而中央部位的掐腰部分厚度（h 4 )則爲 240//m，膜厚差（h3 — li4)爲一 1 〇vm。 除改變聚合方法之外，其餘均如同實施例1，完成 3 〇個電容器。如同實施例1進行該等電容器元件的特性 評估，結果如表1與表2所示。 —iilr (請先閲讀背面之注意事項再填寫本頁) 裝· 訂 經濟部智慧財產局員工消費合作社印製 |用 適 尺 |張 紙 準 標 家 釐 公 7 9 2 512373 A7 _ B7 五、發明説明（30) 表1 初期 特性 容量 β F 損耗係數 % 阻抗 m Ω 遺漏電流 β A 不良率 短路 數量 實施例1 51.9 0.603 0.008 0.03 0/30 0 實施例2 50.3 0.635 0.013 0.05 0/30 0 實施例3 5 0.9 0.624 0.012 0.06 0/30 0 實施例4 49.8 0.653 0.017 0.07 0/30 0 實施例5 49.6 0.678 0.019 0.09 0/30 0 比較例1 40.1 1.658 0.045 0.95 4/30 4 (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 表2 回流試驗 耐濕試驗 不良率 短路數 遺漏電流 不良率 短路數 實施例1 0/30 0 0.49 0/30 0 實施例2 0/30 0 0.54 0/30 0 實施例3 0/30 0 0.59 0/30 • 0 實施例4 0/30 0 0.57 0/30 0 實施例5 0/30 〇 0.61 0/30 0 比較例1 3/26 3 2.10 3/23 1 -；_ 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 512373 A7 B7 五、發明説明（ 31) 由實施例1〜5及比較例1之結果，得知閥作用金屬 多孔基板、基板周圍之固體電解質厚度，大於基板中央部 位處之固體電解質厚度的固體電解電容器，不論在容量、 介電損耗（t a n5)、遺漏電流、短路不良率等基本特 性、回流耐熱性或耐濕負載特性等方面，均具優越的安定 性。 實施例6 : ‘ 除浸漬於氧化劑溶液中設定成3分鐘，而製成固體電 解質之外，其餘均如同實施例1，完成3 0個電容器。進 行如同實施例1的該等電容器元件特性評估。結果如表3 與表4所示。 實施例7 : 除浸漬於氧化劑溶液中設定成4分鐘，而製成固體電 解質之外，其餘均如同實施例1，完成3 0個電容器。進 行如同實施例1的該等電容器元件特性評估。結果如表3 與表4所示。 實施例8「 除浸漬於單體溶液中設定成4分鐘，而製成固體電解 質之外，其餘均如同實施例1 ，完成3 0個電容器。進行 如同實施例1的該等電容器元件特性評估。結果如表3與 表4所示。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） I 丨一--^----jjjf 裝！ (請先閲讀背面之注意事項再填寫本頁) 訂 缝濟部智慧財產局員工消費合作社印製 ^4 犯373 A7 B7 五、發明説明（32) 1 實施例9 : 除浸漬程序與聚合程序設定成2 〇次，而製成固體電 解質之外，其餘均如同實施例1 ，完成3〇個電容器。進 行如同實施例1的該等電容器元件特性評估。結果如表3 與表4所示。 實施例10: ‘ 除浸漬程序與聚合程序設定成2 8次，而製成固體電 解質之外，其餘均如同實施例1，完成3 〇個電容器。進 行如同實施例1的該等電容器元件特性評估。結果如表3 與表4所示。 實施例1 1 : 如同實施例1，將形成介電質氧化皮膜的經蝕刻過鋁 轉化箔的3 m m X 4 m m部分，浸漬於調配成2 -蒽醌磺 酸鈉0，0 5質量％的1 · 5 m ο 1 / L過硫酸銨懸浮水 溶液中5秒鐘，然後靜置於經加熱至6 0 °C的聚合槽中。 將依加熱至約8 0 °C而所產生之3，4 一乙撐二氧基噻吩 的氣體，與氮氣一倂引進聚合槽中，俾進行氣相化學氧化 聚合。接著，將此經蝕刻過鋁轉化箔在4 0 t大氣中放置 1〇分鐘，乾燥之。然後在將氧化劑浸漬程序與聚合程序 整體進行1 5次，而在經鈾刻過銘箱的外表面上形成聚合 物組成物的固體電解質層。將最後所生成的聚合物，在 本纸張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁) -裝· 訂 經濟部智慧財產局員工消費合作社印製 M2373 A7 B72 8 0 ', and the thickness of the lumbo-sacral part in the central part is 2 1 q "See, the film thickness difference (hi — h2) is 7 0 // m. For the capacitor element obtained, characteristics evaluation as in Example 1 was performed. The results are shown in Tables 1 and 2. Example 4: Except that in Example 1, 3,4-ethylenedioxythiophene was replaced with furan, the rest were the same as in Example 1, and 30 were completed. Capacitor: As in Example 1, the thickness of the protruding portion of the solid electrolyte layer was measured as 2 6 Ο β m ', and the thickness of the hip region at the central portion was 2000 μm, and the film thickness difference (hi — h2) was 60 # m. For the obtained capacitor element, characteristics evaluation was performed as in Example 1, and the results are shown in Tables 1 and 2. Example 5: Except in Example 1, 3,4-ethylenedioxythiophene was substituted Except for aniline, the rest are the same as in Example 1, and 30 capacitors are completed. As in Example 1, the thickness of the protruding portion of the solid electrolyte layer is measured at 2 7 〇 V m, and the thickness of the waist portion of the central portion is 2 1 Ο V m Film thickness difference C h For the obtained capacitor element, characteristics evaluation as in Example 1 was performed. The results are shown in Tables 1 and 2. Comparative Example The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page.) Printed by employees' cooperatives Ά 3 A? __ V. Description of the invention (29) 3,4-Ethylenedioxythiophene (manufactured by Bayer AG) was dissolved in ferrous dodecylbenzenesulfonate 75% IPA In the solution, the solution was dripped or immersed on the aluminum foil prepared in Example 1. Then, the aluminum foil was left in a 40 t atmosphere for about 60 minutes, and then subjected to oxidative polymerization. Using a film thickness meter (Manufactured by Peacock: r ^ 夕 少 夕 '' 4 small y — v DG — 2 0 5 (accuracy 3 // m)), sandwich the aluminum foil in the measuring section of the film thickness meter, and measure The result is that the thickness (h. 3) of the protruding part of the surrounding part shown in the schematic diagram of FIG. 4 is 2 3 〇 # ①, and the thickness of the hip region (h 4) at the central part is 240 // m, and the film thickness is The difference (h3 — li4) is -10 vm. Except for changing the polymerization method, the rest are the same as in Example 1, and 30 watts are completed. The characteristics of these capacitor elements were evaluated as in Example 1. The results are shown in Tables 1 and 2. —iilr (Please read the precautions on the back before filling this page) Printed by cooperatives | Appropriate ruler | Sheets of paper standard standard 7 9 2 512373 A7 _ B7 V. Description of invention (30) Table 1 Initial characteristic capacity β F Loss coefficient% Impedance m Ω Missing current β A Defective rate Short circuit number Example 1 51.9 0.603 0.008 0.03 0/30 0 Example 2 50.3 0.635 0.013 0.05 0/30 0 Example 3 5 0.9 0.624 0.012 0.06 0/30 0 Example 4 49.8 0.653 0.017 0.07 0/30 0 Example 5 49.6 0.678 0.019 0.09 0/30 0 Comparative Example 1 40.1 1.658 0.045 0.95 4/30 4 (Please read the precautions on the back before filling out this page) Printed by Employee Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Number of missing current defect rate Short circuit number Example 1 0/30 0 0.49 0/30 0 Example 2 0/30 0 0.54 0/30 0 Example 3 0/30 0 0.59 0/30 • 0 Example 4 0/30 0 0.57 0/30 0 Example 5 0/30 〇0.61 0 / 30 0 Comparative Example 1 3/26 3 2.10 3/23 1-; _ This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 512373 A7 B7 V. Description of the invention (31) From Example 1 ~ The results of 5 and Comparative Example 1 show that the thickness of the solid electrolyte of the valve-acting metal porous substrate and the substrate is larger than the thickness of the solid electrolyte at the center of the substrate, regardless of the capacity, dielectric loss (ta n5), or omission. The basic characteristics such as current and short-circuit failure rate, reflow heat resistance, and wet load resistance characteristics have excellent stability. Example 6: ′ Except that it was immersed in an oxidant solution for 3 minutes to make a solid electrolyte, the rest were the same as in Example 1, and 30 capacitors were completed. The capacitor element characteristics were evaluated in the same manner as in Example 1. The results are shown in Tables 3 and 4. Example 7: Except that it was immersed in an oxidant solution for 4 minutes to make a solid electrolyte, the rest were the same as in Example 1, and 30 capacitors were completed. The capacitor element characteristics were evaluated in the same manner as in Example 1. The results are shown in Tables 3 and 4. Example 8 "Except that it was immersed in a monomer solution for 4 minutes to make a solid electrolyte, the rest were the same as in Example 1 and 30 capacitors were completed. The characteristics of these capacitor elements were evaluated as in Example 1. The results are shown in Table 3 and Table 4. This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) I 丨 A-^ ---- jjjf Pack! (Please read the notes on the back before filling (This page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs ^ 4 Criminal 373 A7 B7 V. Description of the Invention (32) 1 Example 9: The impregnation procedure and the polymerization procedure were set to 200 times to make a solid electrolyte. Except for the rest, 30 capacitors were completed as in Example 1. The characteristics of the capacitor elements were evaluated as in Example 1. The results are shown in Tables 3 and 4. Example 10: 'Except the impregnation process and the polymerization process It was set to 28 times. Except for the solid electrolyte, the rest were the same as in Example 1, and 30 capacitors were completed. The characteristics of these capacitor elements were evaluated as in Example 1. The results are shown in Tables 3 and 4. Example 11: As in Example 1, a 3 mm X 4 mm portion of the etched aluminum conversion foil forming a dielectric oxide film was immersed in a compound prepared as sodium 2-anthraquinone sulfonate at 0.5% by mass and 1.5 m. 1 / L ammonium persulfate suspension in an aqueous solution for 5 seconds, and then placed in a polymerization tank heated to 60 ° C. The 3,4 ethylenedioxide produced by heating to about 80 ° C The gas of thiothiophene was introduced into the polymerization tank together with nitrogen gas, and the gas phase was chemically oxidized and polymerized. Then, the etched aluminum conversion foil was left in a 40 t atmosphere for 10 minutes, and dried. Then, the oxidant was dried. The impregnation process and the polymerization process were performed 15 times as a whole, and a solid electrolyte layer of a polymer composition was formed on the outer surface of the engraved box with uranium. The final polymer was applied to the Chinese standard at this paper scale (CNS) A4 size (210X297 mm) (Please read the precautions on the back before filling out this page)-Binding and ordering Printed by the Intellectual Property Bureau Employee Consumer Cooperative of the Ministry of Economic Affairs M2373 A7 B7
五、發明説明（ 33) J 7 〇 t：溫水中進行洗淨，然後於1 〇 〇 °c下施行3 0分鐘 白勺乾燥，而形成固體電解質層。 如同實施例1，所測得固體電解質層突出部分厚度（ hi)爲1 80//m，而中央部位的掐腰部分厚度（h2) 則爲1 3 0从in，膜厚差（hi—h2)爲5 Ο //πι。 其次，如同實施例1，製作3 0個電容器。進行如同 實施例1的該等電容器元件特性評估。結果顯示於表3 & 表4。 比較例2 ·♦ 除浸漬程序與聚合程序設定成1 0次，而製成固體電 解質之外，其餘均如同實施例1 ，製成30個電容器。進 行如同實施例1的該等電容器元件特性評估。結果如袠3 與表4所示。 比較例3 : 除浸漬於氧化劑溶液中設定成1 〇分鐘，而製成固體 電解質之外，其餘均如同實施例1 ’完成3 0個電容器。 進行如同實施例1的該等電容器元件特性評估。結果如表 3與表4所示。 比較例4 : 除在每次實施程序與聚合程序後便進行洗淨而製成固 體電解質之外’其餘均如同實施例1 ’製成3 0個電容器 本紙張尺度適用中國國家標準（CNS ) A4規格（X 297公釐） (請先閲讀背面之注意事項再填寫本頁} -裝- 、11 經濟部智慧財產局員工消費合作社印製 512373 A7 B7 五、發明説明（34) 。進行如同實施例1的該等電容器元件特性評估。結果如 表3與表4所示。 ’ (請先閲讀背面之注意事項再填寫本頁) 比較例5 : 除將聚合溫度設定成7 0 °C而製作固體電解質之外， 其餘均如同實施例1 ，完成3 0個電容器。進行如同實施 例1的該等電容器元件特性評估。結果如表3與表4所示 比較例6 : 除浸漬於單體溶液中設定成1 0分鐘，而製成固體電 解質之外，其餘均如同實施例1，完成3 0個電容器。進 行如同實施例1的該等電容器元件特性評估。結果如表3 與表4所示。 比較例7 : 經濟部智慧財產局員工消費合作社印製 除浸漬於氧化劑溶液中設定成7分鐘，而製成固體電 解質之外，其餘均如同實施例1，完成30個電容器。進 行如同實施例1的該等電容器元件特性評估。結果如表3 與表4所示。 比較例8 : 除浸漬於單體溶液中設定成7分鐘，而製成固體電解 質之外，其餘均如同實施例1 ，完成3 0個電容器。進行 本紙張尺度適用中國國家標準（CNS ) A4規格（21〇Χ29*7公釐） 512373 A7 B7 五、發明説明（35) 如同實施例1的該等電容器元件特性評估。結果如表3與 表4所示。 比較例9 :. 除浸漬程序與聚合程序設定成4 0次，而製成固體電 解質之外，其餘均如同實施例1，完成3 0個電容器。進 行如同實施例1的該等電容器元件特性評估。結果如表3 與表4所示。 — Jin Id- (請先閲讀背面之注意事項再填寫本頁) •裝· 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 512373 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明説明（36 ) 表3 初期特性 容量 β F 損耗係數* % 阻抗 m Ω 遺漏電流 β A 不良率 短路 數量 實施例6 51.7 0.62 0.009 0.03 0/30 0 實施例7 50.3 0.63 0.013 0.04 0/30 0 實施例8 51.6 0.61 0.009 0.03 0/30 0 實施例9 50.2 0.62 0.010 0.03 0/30 0 實施例1 0 51.9 0.65 0.008 0.08 0/30 0 貫施例11 49.3 0.84 0.19 0.31 0/30 0 比較例2 42.1 0.76 0.035 0.80 3/30 3 比較例3 40.8 0.77 0.027 0.69 4/30 4 比較例4 30.7 0.79 0.030 0.89 3/30 3 比較例5 36.9 0.74 0.035 0.95 5/30 5 比較例6 45.2 0.69 0.024 0.1 1 2/30 1 比較例7 49.7 0.72 0.032 0.73 2/30 1 比較例8 48.0 0.69 0.022 0.10 1/30 1 比較例9 51.7 0.78 0.010 0.85 4/30 2 *損耗係數（％ ) = t a η δ X 1 0 0 ( % ) II丨丨i-lr (請先閱讀背面之注意事項再填寫本頁) -裝·V. Description of the invention (33) J 7 〇t: Wash in warm water, and then dry at 1000 ° C for 30 minutes to form a solid electrolyte layer. As in Example 1, the measured thickness (hi) of the protruding portion of the solid electrolyte layer was 1 80 // m, and the thickness of the waist portion (h2) at the central portion was 1 3 0 from in, and the film thickness difference (hi-h2 ) Is 5 Ο // πι. Next, as in Example 1, 30 capacitors were fabricated. The capacitor element characteristics were evaluated as in the first embodiment. The results are shown in Table 3 & Comparative Example 2 ♦ 30 capacitors were made in the same manner as in Example 1 except that the impregnation procedure and the polymerization procedure were set to 10 times to make a solid electrolyte. The capacitor element characteristics were evaluated in the same manner as in Example 1. The results are shown in 袠 3 and Table 4. Comparative Example 3: 30 capacitors were completed in the same manner as in Example 1 except that a solid electrolyte was prepared by immersing in an oxidant solution for 10 minutes to make a solid electrolyte. The capacitor element characteristics were evaluated as in Example 1. The results are shown in Tables 3 and 4. Comparative Example 4: Except that after each implementation of the procedure and the polymerization procedure, it was washed to make a solid electrolyte, and the rest were the same as in Example 1. 30 capacitors were made. The paper size is applicable to the Chinese National Standard (CNS) A4 Specifications (X 297 mm) (Please read the precautions on the back before filling out this page} -Installation-, 11 Printed by the Intellectual Property Bureau Employees Consumer Cooperatives of the Ministry of Economic Affairs 512373 A7 B7 5. Invention Description (34) The characteristics of these capacitor elements were evaluated in Table 1. The results are shown in Tables 3 and 4. '(Please read the precautions on the back before filling out this page) Comparative Example 5: A solid was produced except that the polymerization temperature was set to 70 ° C Except for the electrolyte, the rest were the same as in Example 1, and 30 capacitors were completed. The characteristics of these capacitor elements were evaluated as in Example 1. The results are shown in Tables 3 and 4 Comparative Example 6: Except immersion in the monomer solution It was set to 10 minutes, except for the solid electrolyte, the rest were the same as in Example 1, and 30 capacitors were completed. The characteristics of these capacitor elements were evaluated as in Example 1. The results are shown in Tables 3 and 4. ratio Example 7: Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, except that the solid electrolyte was made by immersing it in an oxidant solution for 7 minutes, and the rest were made as in Example 1, and 30 capacitors were completed. The characteristics of these capacitor elements were evaluated. The results are shown in Tables 3 and 4. Comparative Example 8: Except that the solid electrolyte was made by immersing in a monomer solution for 7 minutes, the rest were the same as in Example 1, and completed 3 0 capacitors. The Chinese standard (CNS) A4 size (21 × 29 * 7 mm) applicable to this paper size is 512373 A7 B7. 5. Description of the invention (35) The characteristics of these capacitor elements are evaluated as in Example 1. The results are as follows: Table 3 and Table 4. Comparative Example 9: Except that the impregnation procedure and the polymerization procedure were set to 40 times to make a solid electrolyte, the rest were the same as in Example 1, and 30 capacitors were completed. Characteristic evaluation of these capacitor components in 1. The results are shown in Tables 3 and 4. — Jin Id- (Please read the notes on the back before filling out this page) The printed paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 512373 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (36) Table 3 Initial characteristic capacity β F Loss coefficient *% Impedance m Ω Leakage current β A Defect rate Short circuit number Example 6 51.7 0.62 0.009 0.03 0/30 0 Example 7 50.3 0.63 0.013 0.04 0/30 0 Example 8 51.6 0.61 0.009 0.03 0/30 0 Example 9 50.2 0.62 0.010 0.03 0/30 0 Example 1 0 51.9 0.65 0.008 0.08 0/30 0 Example 11 49.3 0.84 0.19 0.31 0/30 0 Comparative Example 2 42.1 0.76 0.035 0.80 3/30 3 Comparative Example 3 40.8 0.77 0.027 0.69 4/30 4 Comparative Example 4 30.7 0.79 0.030 0.89 3/30 3 Comparative Example 5 36.9 0.74 0.035 0.95 5/30 5 Comparative Example 6 45.2 0.69 0.024 0.1 1 2/30 1 Comparative Example 7 49.7 0.72 0.032 0.73 2/30 1 Comparative Example 8 48.0 0.69 0.022 0.10 1/30 1 Comparative Example 9 51.7 0.78 0.010 0.85 4/30 2 * Loss factor (%) = ta η δ X 1 0 0 (%) II 丨 丨 i-lr (Please read the precautions on the back before (Fill in this page)
、1T --S& 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ 297公釐） 512373 A7 B7 五、發明説明（37) 表4 回流試驗 耐濕試驗 不良率 短路數 遺漏電流// A 不良率 短路數 實施例6 0/30 0 0.5 3 0/30 0 實施例7 0/30 0 0.60 0/30 0 實施例8 0/30 0 0.46 0/30 〇 實施例9 0/30 0 0.71 0/30 0 實施例1 0 0/30 0 0.85 0/30 0 實施例11 0/30 0 0.87 0/30 0 比較例2 1/28 1 2.10 1/27 1 比較例3 1/29 0 1.75 2/28 1 比較例4 2/27 1 3.57 4/25 2 比較例5 2/28 1 3.45 3/26 2 比較例6 1/28 0 1.12 2/27 1 比較例7 3/29 1 1.02 3/28 2 比較例8 1/28 0 1.52 2/28 1 比較例9 .2/28 1 2.12 3/27 2 (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 由顯示實施例6〜1 0與比較例2〜9結果的表3〜 4，及由顯示之前實施例1〜5與比較例1結果的表1〜 2中得知，採用各種單體溶液，在浸漬時間少於5分鐘之 情況（實施例1 : 3，4 一乙撐二氧基噻吩、實施例2 ·· ---4Θ- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 512373 A7 B7 五、發明説明（邓） 〜氫異苯並噻吩、實施例3 ··吡咯、實施例4 :呋喃、實 施例5 :苯胺，各浸漬時間5秒，實施例8 : 3，4 —乙 撐=氧基噻吩，浸漬時間4分鐘.），浸漬於氧化劑溶液的 0寺間少於5分鐘之情況（實施例6〜7 )、重複交叉浸漬 於單體溶液與酸溶液中1 5〜3 0次之情況（實施例9〜 1 〇 )時，可獲得不論容量、介電損耗（t a η 5 )、阻 @ '遺漏電流等初期基本特性，在回流耐熱試驗或耐濕負 載試驗上，均具優越安定性的電容器。但是，當浸漬於單 體溶液的浸漬時間超過5分鐘之情況（比較例6，8 )、 浸漬於氧化劑溶液的浸漬時間超過5分鐘之情況（比較例 3 ’ 7 )、交叉浸漬於單體溶液與酸溶液的次數偏少之情 況（比較例2 )以及過多之情況（比較例9 )、每次交叉 浸漬聚合後施行洗淨之情況（比較例4 )、聚合溫度超過 6 0 t之情況（比較例5 )，得知不管初期基本特性或回 流耐熱性與耐濕負載特性均未安定。 【產業可利用性】 依本發明之形成於切口部與罩幕部的固體電解質厚度 較其他部分爲大的固體電解電容器’可提昇形成於介電質 皮膜上之固·體電解質與介電質層間的密接性，不論容量、 介電損耗（t a ηδ)、遺漏電流、短路不良率等各基本 特性，甚至回流耐熱試驗或耐濕負載試驗等，均具優越安 定性。 此類固體電解電容器’特別係依照本發明方法，將閥 ______44-___ 本紙張尺度適用中國國家標準（CNS ) A4規格（2i〇x 297公着） 丨—nr (請先閱讀背面之注意事項再填寫本頁) 裝— 訂 經濟部智慧財產局員工消費合作社印製 512373 A7 B7 五、發明説明（39) 作用金屬多孔體表面浸漬於含單體液與含氧化劑液中的浸 漬時間、含單體液之溶劑的汽化時間、與浸漬於含單體液 後的聚合條件，限制於特定範圍.，便可在介電質皮膜上形 成導電性聚合物。此時，利用分別在含單體液與含氧化劑 液中交叉浸漬特定次數，並在最後進行洗淨處理，便可獲 得具層狀構造（薄層結構或絲狀結構）且具優越特性的導 電性聚合物。 (請先閲讀背面之注意事項务填寫本頁) 經濟部智慧財產局員工消費合作社印製 4Qr 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）、 1T --S & This paper size applies to Chinese National Standard (CNS) A4 specification (210 × 297 mm) 512373 A7 B7 V. Description of invention (37) Table 4 Reflow test Moisture resistance test failure rate Short circuit number Missing current // A Defective rate short circuit Example 6 0/30 0 0.5 3 0/30 0 Example 7 0/30 0 0.60 0/30 0 Example 8 0/30 0 0.46 0/30 〇 Example 9 0/30 0 0.71 0 / 30 0 Example 1 0 0/30 0 0.85 0/30 0 Example 11 0/30 0 0.87 0/30 0 Comparative Example 2 1/28 1 2.10 1/27 1 Comparative Example 3 1/29 0 1.75 2 / 28 1 Comparative Example 4 2/27 1 3.57 4/25 2 Comparative Example 5 2/28 1 3.45 3/26 2 Comparative Example 6 1/28 0 1.12 2/27 1 Comparative Example 7 3/29 1 1.02 3/28 2 Comparative Example 8 1/28 0 1.52 2/28 1 Comparative Example 9. 2/28 1 2.12 3/27 2 (Please read the precautions on the back before filling out this page) Printed by the Intellectual Property Bureau Staff Consumer Cooperatives of the Ministry of Economic Affairs Tables 3 to 4 of the results of Examples 6 to 10 and Comparative Examples 2 to 9 and Tables 1 to 2 showing the results of previous Examples 1 to 5 and Comparative Example 1 show that various monomer solutions were used to impregnate When the time is less than 5 minutes (Example 1: 3, 4 ethylene Oxythiophene, Example 2 ·· --4Θ- This paper size is applicable to Chinese National Standard (CNS) A4 (210X297 mm) 512373 A7 B7 V. Description of the Invention (Deng) ~ Hydroisobenzothiophene, Examples 3. Pyrrole, Example 4: Furan, Example 5: Aniline, each immersed for 5 seconds, Example 8: 3,4-Ethylene = oxythiophene, immersed for 4 minutes.), Immersed in the oxidant solution In the case of less than 5 minutes between temples (Examples 6 to 7), and repeated cross immersion in the monomer solution and acid solution 15 to 30 times (Examples 9 to 10), regardless of capacity , Initial basic characteristics such as dielectric loss (ta η 5), resistance @ 'leakage current, etc., capacitors with superior stability in the reflow heat resistance test or humidity load test. However, when the immersion time in the monomer solution exceeds 5 minutes (Comparative Examples 6, 8), when the immersion time in the oxidant solution exceeds 5 minutes (Comparative Example 3'7), the cross-immersion in the monomer solution When the number of times with the acid solution is too small (Comparative Example 2) and when it is too much (Comparative Example 9), when washing is performed after each cross-immersion polymerization (Comparative Example 4), when the polymerization temperature exceeds 60 t Comparative Example 5) It was found that the initial basic characteristics, reflow heat resistance, and moisture load resistance characteristics were not stable. [Industrial Applicability] The solid electrolytic capacitor having a thicker thickness of the solid electrolyte formed in the cutout portion and the cover portion according to the present invention than the other portions can increase the solid electrolyte and the dielectric material formed on the dielectric film. The interlayer adhesion is superior in stability regardless of the basic characteristics such as capacity, dielectric loss (ta ηδ), leakage current, and short-circuit failure rate, and even the reflow heat resistance test or the wet load test. This type of solid electrolytic capacitor 'is specifically in accordance with the method of the present invention, the valve ______ 44 -___ This paper size applies Chinese National Standard (CNS) A4 specifications (2i0x 297) 丨 -nr (Please read the precautions on the back first (Fill in this page again) Packing — Ordered by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 512373 A7 B7 V. Description of the invention (39) Immersion time of the surface of the porous metal body immersed in the monomer-containing and oxidant-containing solutions The vaporization time of the solvent of the body fluid and the polymerization conditions after immersion in the monomer-containing liquid are limited to a specific range. A conductive polymer can be formed on the dielectric film. At this time, by cross-immersing the monomer-containing liquid and the oxidizing agent-containing liquid for a specific number of times, and finally performing a washing treatment, a layered structure (thin layer structure or filamentous structure) with excellent characteristics can be obtained. Sexual polymer. (Please read the precautions on the back and fill out this page first) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 4Qr This paper size applies to China National Standard (CNS) A4 (210X297 mm)