200302160 (1) 玖、發明說明 【發明所屬之技術領域】 本發明係有關金屬材料基材的表面形成高分子膜的複 合金屬材料及其製造方法，以此複合金屬材料形成鈾刻槽 的被鈾刻金屬材料及其製造方法，及電解電容器。 又’本說明書有關使用到「鋁」一語的含意係指包含 銘及銘合金兩者。 【先前技術】 近年’電子機器的小型化，印刷基板的高密度實裝化 ，因實裝的效率化等而要求電子零件的晶片化，小型化顯 著的進展，隨著要求高容量化的電解電容器。 通常，電解電容器電極所使用的鋁箔，爲提高靜電容 量以蝕刻處理提高擴面率。由於鈾刻處理所形成的蝕刻槽 的數量愈多及愈長，擴面率愈高，爲改善蝕刻適性，鋁材 進行種種蝕刻處理的前步驟。例如對（100)結晶方位的 控制’絕材添加銅、銘等的微量元素調整組成，最後鈍燒 前的脫脂淸洗，最後鈍燒之結晶性氧化膜的形成處理等（ 日本特公昭58-34925號、日本特開平3-122260號等）。 但是，單以鋁箔的擴面率及長度提高容量已近極限。 爲提高鋁箱的擴面率，必要以局部蝕刻、未蝕刻、減少表 面溶解等、於蝕刻面均勻形成高密度的蝕刻槽。上述的種 種方法不能充分的產生高密度且均勻的蝕刻槽，不能因應 逐漸增大之靜電容量的要求。 -7- (2) (2)200302160 因此，現在的鋁箔，蝕刻過程中的孔蝕槽的分佈不能 控制，隧道狀槽的結合成爲損失應該擴大的表面積。所以 ，現狀的靜電容量停留於相對於理想容量的5 0〜6 5 %。 過去試著以附著異物質或以機械形成缺陷，但未能提高容 量。 【發明內容】 本發明有鑑於上述先行技術，提供產生高密度且均勻 的鈾刻槽，進行以此蝕刻槽作爲基點可深蝕且隧道內不易 結合狀態的蝕刻，確實提高擴面率，圖謀增大靜電容量的 複合金屬材料及其製造方法，及被蝕刻金屬材料及其製造 方法爲目的。 爲達成上述目的，本發明的第丨複合金屬材料具有以 下的構成。 金屬材料基材至少一面上，由自我組織化形成具有微 細模紋的高分子薄膜其特徵的複合金屬材料。 上述高分子膜係由高分子化合物的疏水性有機溶媒溶 液乾媒所形成的則項〗所記載的複合金屬材料。 上述細模紋爲多數的細孔排列之細孔構造之前項1或 2所記載的合金屬材料。 上述細孔的直徑芦；〇 ~ s Ω 今μ200302160 (1) (ii) Description of the invention [Technical field to which the invention belongs] The present invention relates to a composite metal material in which a polymer film is formed on the surface of a metal material substrate and a method for manufacturing the same. Carved metal material and its manufacturing method, and electrolytic capacitor. The meaning of the term "aluminum" used in this specification is to include both inscriptions and inscription alloys. [Prior art] In recent years, the miniaturization of electronic equipment, the high-density mounting of printed circuit boards, and the demand for wafering of electronic components due to the efficiency of mounting have significantly progressed in miniaturization. Capacitor. Generally, an aluminum foil used for an electrolytic capacitor electrode is etched to increase the electrostatic capacity to increase the surface area. As the number and length of the etching grooves formed by the uranium etching process are larger and longer, the expansion ratio is higher. In order to improve the etching suitability, the aluminum material is subjected to various pre-etching steps. For example, the control of the (100) crystal orientation 'addition of trace elements such as copper and Ming to adjust the composition, degreasing and washing before the final incineration, and the formation of a crystalline oxide film in the last incineration (Japanese Patent Publication No. 58- 34925, Japanese Patent Application No. 3-122260, etc.). However, the increase in capacity and length of aluminum foil alone is nearing its limit. In order to increase the enlargement ratio of the aluminum box, it is necessary to uniformly form a high-density etching groove on the etched surface by local etching, non-etching, and reduction of surface dissolution. The above-mentioned methods cannot sufficiently generate high-density and uniform etching grooves, and cannot meet the requirements of gradually increasing electrostatic capacity. -7- (2) (2) 200302160 Therefore, in the current aluminum foil, the distribution of pitting grooves during the etching process cannot be controlled, and the combination of tunnel-shaped grooves becomes a loss of surface area that should be enlarged. Therefore, the current electrostatic capacity stays at 50 ~ 65% relative to the ideal capacity. In the past, attempts were made to attach foreign matter or to form defects mechanically, but failed to increase the capacity. [Summary of the Invention] In view of the foregoing prior technology, the present invention provides a high-density and uniform uranium etched groove, which is etched with the etched groove as a base point and can be easily etched in a tunnel, thereby increasing the expansion rate and increasing A composite metal material having a large electrostatic capacity and a manufacturing method thereof, and an etched metal material and a manufacturing method thereof are aimed at. To achieve the above object, the first composite metal material of the present invention has the following constitution. A composite metal material with at least one side of a metal material substrate that is self-organized to form a polymer film with fine pattern. The polymer film is a composite metal material as described in the item [Formation] of a hydrophobic organic solvent solution dry polymer of a polymer compound. The fine pattern is a metal material as described in the preceding item 1 or 2 in a pore structure having a large number of pores. Diameter of the above pores; 〇 ~ s Ω this μ
Ltn爲0.01〜5〇// m之刖項3所記載的 複合金屬材料。 上述細孔爲1〜50 # m的間隔所形成之前項3或4所 記載的複合金屬材料。 -8 - (3) (3)200302160 上述細孔內塡充較上述金屬材料基材的氧化物具有更 局導電性物質之則項3〜5的任一項所記載的複合金屬材 上述金屬材料基材爲閥作用金屬所成之前項丨〜6之 任一項所記載的複合金屬材料。 上述閥作用金屬爲鋁之前項7所記載的複合金屬材料 〇 上述複合金屬材料係電解電容器電極用鋁材料之前項 8所記載的複合金屬材料。 又，本發明的第2複合金屬材料具有下列構成。 金屬材料基材至少有一面上，配列較多數的該金屬材 料基材的氧化物的具有更高導電性的物質所成的微細斑點 爲其特徵的複合金屬材料。 上述微細斑點爲直徑〇 · 〇〗〜5 〇 # m之前項丨〇所記載 的複合金屬材料。 上述微細斑點依1〜50// m的間隔所形成之前項n 或1 2所記載的複合金屬材料。 上述金屬材料基材爲閥作用金屬所成之前項〗〇〜i 2 之任一項所記載的複合金屬材料。 上述閥作用金屬爲鋁之前項ls所記載的複合金屬材 料。 上述複合金屬材料係電解電容器電極用鋁材料之前項 1 4所記載的複合金屬材料。 本發明的第1複合金屬材料的製造方法，係以適切的 -9 - (4) (4)200302160 方法製造以得到本發明第1金屬複合材料，具有以下的構 金屬材料基材至少一面上，由具有微細模紋的高分子 薄膜自我組織化而成之複合金屬材料的製造方法， 上述高分子薄膜以高分子化合物的疏水性有機溶媒溶 液的乾燥所形成爲其特徵之複合金屬材料的製造方法。 上述金屬材料基材之表面上，以高分子化合物的疏水 性有機溶媒溶液鑄塑，於蒸發該有機溶媒的同時使溶液表 面結露，又，因蒸發結露而產生之微小水滴，而形成多數 的細孔配列之高分子薄膜之前項1 6所記載之複合金屬材 料的製造方法。 於其他的表面’以高分子化合物的疏水性有機溶媒溶 液鑄塑，於蒸發該有機溶媒的同時使溶液表面結露，又蒸 發結露而產生之微小水滴，而形成多數的細孔配列之高分 子薄膜，將高分子薄膜由上述基材取出，與上述金屬材料 基材的表面接合而配置之前項1 6所記載的複合金屬材料 的製造方法。 上述細孔內塡充較上述金屬材料基材的氧化物具有更 高導電性物質之前項1 7〜1 8的任一項所記載的複合金屬 材料。 較上述金屬材料基材的氧化物具有更高導電性物質的 塡充方法，係以電鍍、蒸鍍、浸漬中任一方法進行的前項 19所記載之複合金屬材料的製造方法。 上述高分子化合物係兩親媒性高分子化合物之前項 -10- (5) (5)200302160 1 6〜2 0的任一項所記載之複合金屬的製造方法。 上述兩親媒性高分子化合物係聚苯乙烯磺酸與長鏈二 院基氨鹽的離子錯合物之前項2 1所記載之的複合金屬材 料的製造方法。 上述高分子化合物的疏水性溶媒溶液的濃度爲〇 〇 1〜 10質量％的前項16〜22的任一項所記載形成之複合金屬 材料的製造方法。 上述高分子薄膜的成膜’係於高溫高濕度的環境下進 行的前項16〜23的任一項所記載之複合金屬材料的製造 方法。 本發明的第2複合金屬材料的製造方法，係以適切的 方法製造得到本發明第2金屬複合材料，具有以下的構成 〇 金屬材料基材至少一面上，由具有微細模紋的高分子 薄膜自我組織化而成爲複合金屬材料的製造方法， 上述筒分子薄膜的基材表面配置配列多數細孔的高分 子薄膜’該細孔內塡充較上述的該金屬材料基材具更低電 位的金屬塡充後，再除去高分子薄膜爲其特徵複合金屬材 料的製造方法。 上述金屬材料基材以高分子化合物的疏水性有機溶媒 溶液禱塑，於蒸發該有機溶媒的同時使溶液表面結露，又 ’黑發結露所產生之微小水滴，以進行高分子薄膜之形成 ’及配置至上述金屬材料基材的前項25所記載的複合金 屬材料的製造方法。 -11 - (6) (6)200302160 於其他的表面上，以高分子化合物的疏水性有機溶媒 溶液鑄塑，於蒸發該有機溶媒的同時使溶液表面結露，.又 蒸發結露所產生之微小水滴，形成多數的細孔配列之高分 子薄膜，將高分子薄膜由上述基材取出，與上述金屬材料 基材的表面接合之則項2 5所記載的合金屬材料的製造方 法。 較上述金屬材料基材的氧化物具有更高導電性物質的 塡充方法，係以電鍍、蒸鍍、浸漬中任一方法進行的前項 2 5〜2 7所記載的合金屬材料的製造方法。 上述高分子化合物係兩親媒性高分子化合物之前項 2 5〜2 8的任一項所記載的複合金屬的製造方法。 上述兩親媒性高分子化合物係聚苯乙烯磺酸與長鏈二 院基氨鹽的離子錯合物之前項2 9所記載的複合金屬材料 的製造方法。 上述高分子化合物的疏水性溶媒溶液的濃度爲〇 〇 1〜 質量％的前項25〜30的任一項所記載的複合金屬材料 的製造方法。 上述高分子薄膜的成膜，係於高溫高濕度的環境下進 行的項25〜3 1的任一項所記載的複合金屬材料的製造 方法。 以丨谷解進行去除上述咼分子薄膜的前項2 5〜3 2的任 一項所記載的複合金屬材料的製造方法。 以前項1〜9所記載的複合金屬材料，以細微模紋爲 準形成鈾刻槽爲其特徵的被蝕刻之金屬材料。 -12- (7) 200302160 ±述被蝕刻之金屬材料係被鈾刻之電解電容器電極用 鋁材料之前項3 4所記載的被鈾刻之金屬材料。 本發明的第2被鈾刻金屬材料，係使用本發明第2 複合金屬材料餓刻者，具有以下構成。 以前項1 0〜1 5所記載的複合金屬材料，由微細斑點 爲準形成蝕刻槽所成者爲其特徵的被蝕刻金屬材料。 上述被蝕刻金屬材料，爲被鈾刻電解電容器電極用鋁 材料之前項3 6的被蝕刻金屬材料。 本發明的第1被蝕刻金屬材料的製造方法，係以適切 製造得到本發明第1被蝕刻之金屬材料的製造方法，具有 以下的構成。 以前項1〜9所記載之複合金屬材料，不除去高分子 薄膜施以蝕刻處理形成蝕刻槽爲其特徵的被蝕刻金屬材料 的製造方法。 前項1〜9所記載之複合金屬材料，初期不除去高分 子薄膜施以蝕刻處理生成蝕刻槽後，除去上述高分子薄膜 ’再施以蝕刻處理成長蝕刻槽爲其特徵的被餓刻金屬材料 的製造方法。 上述被蝕刻金屬材料係被蝕刻電解電容器電極用銘材 料之則項3 8或3 9所記載的被蝕刻金屬材料。 本發明第2被鈾刻金屬材料的製造方法，係以適切製 造得到本發明第2被鈾刻金屬材料的方法，具有以下的構 成。 以前項1 0 1 5所記載之複合金屬材料，施以蝕刻處 -13- (8) (8)200302160 理形成蝕刻槽爲其特徵的被蝕刻金屬材料的製造方法。 上述被蝕刻之金屬材料，係被蝕刻電解電容器電極用 鋁材料之前項4 1所記載的被蝕刻金屬材料的製造方法。 本發明的電解電容器，係使用本發明的第1或第2的 被蝕刻金屬材料所成者，具有以下構成。 使用前項3 4或3 5所記載的被蝕刻金屬材料爲電極 材料所成者爲其特徵之電解電容器。 使用前項3 6或3 7所記載的被蝕刻金屬材料爲電極 材料所成者爲其特徵之電解電容器。 依本發明的第1複合金屬材料，施以鈾刻處理以細微 模紋爲準形成高密度且均勻分佈的鈾刻槽，擴大表面積。 上述細微模紋爲大量的細孔所排列的細孔構造時，可 形成高密度均勻的鈾刻槽，上述細孔的直徑爲〇 . 〇 1〜5 0 Μ πι時，或上述細孔的間隔爲1〜5 0 // m時可達成高擴面 碎4 〇 又，上述細孔內使用較金屬材料基材的氧化物具有更 高導電物質塡充時，由於該高導電性物質成爲蝕刻槽引發 核，形成高密度且均勻的分佈的蝕刻槽。 上述金屬材基材由閥用金屬材料所成時，可作爲電解 電容器的電極材料使用。例如上述該閥作用金屬爲鋁時， 可作爲電解電容器用鋁材料使用。 依本發明的第2複合金屬材料，施以鈾刻處理，由於 較金屬材料基材的氧化物具有更高的導電物質的微細斑爲 蝕刻槽的引發核，所以形成高密度且均勻佈的蝕刻槽，擴 -14- 200302160 Ο) 大表面積。 上述微細斑點的直徑爲0.01〜50//m時，或上述微 細斑點的間隔爲1〜5 0 // m時可達成高擴面率。 上述金屬材料基材由閥作用金屬所成時，可作爲電解 電容器的電極材料使用。例如上述該閥作用金屬爲鋁時， 可作爲電解電容器用鋁材料使用。 依本發明的第1複合金屬材料的製造方法，可製造得 到合適的上述第1複合金屬材料。 相關於本製造方法，上述金屬材料基材的表面，直接 以高分子化合物的疏水性有機溶媒溶液鑄塑乾燥時，可形 成配列大量細孔的高分子膜與金屬材料基材密合的狀態， 高分子膜的成膜與金屬材料基材的層合可同時進行。又， 可於其他基材上以不同方式形成的高分子膜，與所要的金 屬箔基材表面接合而製造。 又，上述細孔內使用較比金屬材料基材的氧化物具有 更高導電物質塡充時，由於該高導電性物質成爲蝕刻槽引 發核，塡充此高導電性物質，可容易以電鍍、蒸鍍、浸漬 中任一方法進行。 又，上述高分子化合物，例如爲聚苯乙烯磺酸與長鏈 二烷基胺鹽的離子錯合物之兩親媒性高分子化合物時，可 形成細孔構造的高分子薄膜。 又，上述高分子化合物的疏水性溶媒溶液的濃度爲 〇 . 0 1〜1 0質量％時，可形成具有所要求強度且安定形狀的 微細模紋、細孔構造。 -15- (10) (10)200302160 又，上述高分子薄膜的成膜，由於高溫高濕度的環境 下進行，可確實形成微細模紋、細孔構造。 依本發明的第2複合金屬材料的製造方法，可製造得 到合適的上述第2複合金屬材料。 相關於本製造方法，上述金屬材料基材的表面上，直 接以高分子化合物的疏水性有機溶媒溶液鑄塑乾燥時，可 · 形成配列大量細孔的高分子膜與金屬材料基材密合的狀態 ，高分子膜的成膜與金屬材料基材的層合可同時進行。又 鲁 ’可於其他基材上以不同方式形成的高分子膜，與所要的 金屬箔基材表面接合而製造。 又，上述細孔內使用較金屬材料基材的氧化物具有更 高導電物質的塡充方法，可容易以電鍍、蒸鍍、浸漬中任 一方法進行。 又，上述高分子化合物，例如爲聚苯乙烯磺酸與長鏈 二院基胺鹽的離子錯合物之兩親媒性高分子化合物時，可 形成細孔構造的高分子薄膜。 · 又，上述高分子化合物的疏水性溶媒溶液的濃度爲 〇 . 〇 1〜1 〇質量％時，可形成具有所要求強度且安定形狀的 微細模紋、細孔構造。 % 又，上述高分子薄膜的成膜，由於高溫高濕度的環境 下進行，可確實形成微細模紋、細孔構造。 又，塡充高導電性物質後的高分子薄膜容易以溶解去 除，由微細模紋高導電性物質爲準可於金屬材料基材表面 形成微細斑點。 -16- (11) (11)200302160 本發明的第1被蝕刻金屬材料，係相對於第1複合金 S #料’以微細模紋爲準形成蝕刻槽而成者，如以上所述 ’形成高密度且均勻分佈的蝕刻槽，表面積充分的擴大。 如上述被蝕刻金屬材料，由於使用被蝕刻電解電容器 的電極用銘材料，可增大靜電容量。 本發明第1被蝕刻金屬材料的一種製造方法，係初期 不除去高分子薄膜，施以蝕刻處理生成蝕刻槽後，除去上 述高分子薄膜，再施以蝕刻處理成長蝕刻槽，得到高密度 蝕刻槽且均勻分佈的被鈾刻金屬材料。 有關本被蝕刻金屬材料的製造方法，使用電解電容器 的電極材料爲上述被蝕刻金屬材料時，由於擴大表面積可 得到高靜電容的電極材料。 本發明的第2被蝕刻金屬材料，係相對於第2複合金 屬材料，以微細斑點爲準形成蝕刻槽，得到高密度蝕刻槽 且均勻分佈的被蝕刻金屬材料。 有關此被餓刻金屬材料的製造方法，使用電解電容器 的電極材料爲上述被蝕刻金屬材料時，由於擴大表面積可 得到高靜電容的電極材料。 本發明的電解電容器，由於使用上述被蝕金屬材料作 爲電極材料，可得到高靜電容量，電解電容器的小形化及 尚性能，進而組裝此電解電容器之電子機器可小型化及高 性能化。 【實施方式】 -17- (12) (12)200302160 用以實施發明之最佳型態 [第1複合金屬材料] 以圖1 (A) (B)顯示本發明的第1複合金屬材料的一 種實施形態模式的斷面圖。有關上述第1複合金屬材料 (1)，金屬材料基材（1〇)的表面層合的高分子薄膜（11) ，係由高分子化合物自我組織化所形成的膜，具有成膜時 所形成的微細模紋。上述高分子薄膜（1 1)至少與金屬材 料基材（10)的一面層合即可，作爲電解電容器的電極用 銘材料使用時’爲盡可能擴大表面積以兩面層合爲理想。 上述高分子薄膜（1 1 )，係由高子化合物以疏水性有 機溶媒溶解之溶液（以下以聚合物溶液略稱之）經乾燥而 形成。例如，基材表面以聚合物溶液鑄塑乾燥時，高分子 化合物於基材上自我組織化形成具有微細模紋的薄膜。 上述微細模紋，可例示如圖1 (B)所示配列大量的細 孔（1 2)的細孔構造。本發明的第1複合金屬材料的一種 實施形態模式，係利用細孔（1 2)作爲金屬材料基材 (1 〇)的表面蝕刻液的導入路徑。 又，圖1 (A) (B)顯示本發明的第1複合金屬材料的 另一種實施形態模式的斷面圖。第1複合金屬材料， 上述細孔（12)內以導電性高於金屬材料基材 （1()) 化物之物質（以下以高導電性物質略稱之）塡充。上 導電性物質，作爲蝕刻核使用，詳如後述。 作爲上述微細模紋的具有細孔構造之高分子胃月莫 (1 1 )，係經由如下的過程所形成。 -18- (13) (13)200302160 於基材上所鑄塑之聚合物溶液，於有機溶媒蒸發時吸 取潛熱，空氣中的水分子以微粒子凝結於聚合物溶液表面 。一方面，由聚合物溶液的親水性部份的作用，水與疏水 性有機溶媒之間的表面張力減少，水微粒子凝集成爲微小 的水滴。由於水滴的大小絡略均一，隨著溶媒的蒸發，水 滴以細密塡充的狀態排列，成爲規則的配列狀態。更進一 . 步蒸發水滴時，有水滴的部份成爲空隙，沿膜厚的方向形 j 成細孔（1 2)。水滴成爲鑄膜作用，形成具有規則細孔構 φ 造，蜂巢構造的高分子薄膜 （1 1)。圖1 (Β)及圖2 (Β) 例示大量六角型的細孔（1 2)形成細密狀態的高分子薄膜 。細孔如圖示例的六角型以外，成爲接近六角型的圓型， 或圓形爲多。又，規則細孔構造不意味著嚴密的幾何學上 的規則造，意味著構造的規則性不是隨機的構造。因此， 細孔形狀、細孔的直徑、細孔的間隔等多少有一點混亂亦 含於規則的細孔構造。多少有一點混亂，對後述的高密度 且均勻的蝕刻槽無成形上的問題。 · 本發明的第1複合金屬材料 （1) (2)的製造時，上 述局分子薄膜 （11)係金屬材料基材 （10)的表面直接 以聚合物溶液鑄塑，可與金屬材料基材（1 〇)形成密合狀 · 態。即，高分子薄膜 （1 1)與金屬材料基材 （1 0)的層 j 合可同時進行。又，可取下於其他基材上另行形成高分子 薄膜（1 1)，與金屬材料基材（10)接合而製造。於其他 基材上形成時，基材可使用金屬以外的玻璃、矽晶圓等的 無機材料，聚丙烯、聚乙烯、聚醚酮等的耐有機溶劑性優 -19- (14) (14)200302160 的有機高分子材料等的固體、水、液臘、液狀聚酯等的液 體。此等其他基材之中，以高分子薄膜容易取出且細孔構 造的保持性優的觀點，以水爲合適。 形成上述高分子薄膜的高分子化合物無特別限定。合 適的高分子化合物可例示如疏水性基及親水性基的兩親媒 性高分子化合物，1種的兩親媒性分子的單獨聚合物’或 2種以上的兩親媒性分子共聚物亦可。又，兩親媒性以外 的分子的共聚物亦可，界面活性劑存在亦可。 上述兩親媒性高分子化合物以利用聚苯乙烯酸及長鏈 二烷基氨鹽離子錯合物、聚乙二醇/聚丙二醇嵌段共聚 物、丙烯酸胺聚合物作爲主鏈骨幹，倂持疏水性側鏈的十 二烷基及親水性側鏈的乳糖基或羧基的兩親媒性高分子化 合物，或肝素或葡聚糖硫酸，核酸 （DNA或RNA)等的 陰離子性高分子及長鏈烷基氨鹽的離子錯合物，明膠，柯 拉精，白蛋白等的水溶蛋白質爲親水性基的兩親媒性聚合 物等爲理想。 又，其他的高分子化合物可例示如聚苯乙烯磷酸、聚 苯乙烯磺酸、聚乳酸、聚碳酸等。 溶解高分子化合物的疏水性有機溶媒可使用氯仿等的 鹵系溶媒，醋酸乙酯等的酯系，非水性酮，二硫化碳等， 此等的混合溶媒亦可使用。 上述聚合物溶液其高分子化合物的濃度以0.01〜10 質量％爲理想。低於0.01重量％時高分子薄膜 （11)的強 度不足，超過1〇質量％時難於保持細孔（12)的成形及 -20- (15) (15)200302160 保護的安定形狀。理想的濃度爲〇 〇 5〜5重量％。 又’成膜環境’即作爲有機溶媒的蒸發，微小水滴的 結露及蒸發的進行環境，以高濕度環境爲理想。具體的以 相對濕度：5 0〜9 5 %，溫度：} 〇〜2 5 °C的大氣中爲理想 〇 上述細孔 （12)的尺寸以直徑 （D) 0.01〜50//m爲 理想’此一尺寸，係提供作爲電解電容器蝕刻處理的複合 金®材料（1)使用’適用於形成大量均勻蝕刻槽擴面率 擴大效率優良的情況。特別理想的細孔 （1 2)的直徑 (D)爲 〇ι 〜5〇# mo 又，上述細孔（12)的間隔（P)以1〜50 // m爲 理想。低於1 // m蝕刻時鄰近的槽有連結的憂慮，超過 5 〇 m時槽數增多有困難。細孔（丨2)特別理想的間隔爲 1 〜1 5 // m。 更進一步，上述高分子薄膜 （11)的厚度 （T)以 10 0 nm〜2 # m程度形成。使用電解電容器電極用鋁材料 時以〇.5〜爲理想。 構成上述複合金屬材料 （1) (2)的金屬材料基材 (1 0)不問金屬的種類、厚度等，因應用途作適宜的選擇 〇 金屬的種類，可例示如作爲電解電容器的電極材料@ 用的閥作用金屬。閥作用金屬可舉例如鋁、鉅、鎂、妖、 鈮、鉻、鋅、鉍、矽、紿的金屬單體，鈦與硼及錫、銘與 釩、釩與銨的合金，其中可推薦者爲銘。又，有關此等的 -21 - (16) (16)200302160 金屬材料基材，容許雜質存在，或因應必要添加適宜的微 量元素。例如鋁的情況，可添加矽、鐵、銅、鉛、鋅、鎵 、锆等。但是，電解電容器用電極材料的情況時，爲抑制 生成處理被膜發生缺陷，以使用純度99.9%以上高純度鋁 爲理想。 又，厚度無限定，爲確保被蝕刻金屬材料蝕刻後的強 度及可撓性，以0.05〜0.3 mm爲理想。以0.07〜0.2 mm 爲特別理想，更理想爲0.07〜0. 1 5 mm。 又，金屬材料基材（1〇)無限制熱處理或結晶構造。 例如鋁材料時，不施以熱處理的硬質材料，集合體呈軋壓 方向延伸的細長纖維狀結晶。相對於此硬質材料，以300 〜400°C鈍燒時，可成爲具有高（100)面成長結晶粒的軟 質材料。有關本發明，可使用上述之任一金屬材料基材。 又，金屬材料基材（10)爲螺旋狀捲裝的長尺寸亦好，裁 斷的材料亦可。 又，上述細孔（1 2)內塡充之高導電性物質（13)， 由於蝕刻時會優先溶解成爲槽的引發核，可依金屬材料基 材 （1〇)的導電性的關係而選擇。金屬材料基材 （10) 爲鋁的時候，可例示如導電性高於鋁的鉛、氧化鉛、銅、 氧化銅、氧化亞銅、碳，推薦使用鉛或氧化鉛。 上述高導電性物質 （13)的細孔 （12)的塡充方法 可例示如電鍍、潑射、蒸鍍、浸漬、CVD、溶射、離子鍍 等，依塡充速度快高分子膜損傷少，且可低成本處理的觀 點，以電鍍、蒸鍍、浸漬爲理想。 -22- (17) (17)200302160 上述第1的複合金屬材料（1) (2)提供蝕刻處理 ’製作本發明的第1被蝕刻金屬材料。 相關的蝕刻處理，如圖1 (A) (B)所示僅形成高分子 膜（1 1)的複合金屬材料（1)蝕刻液由微細模紋的上述 細孔（1 2)到達金屬材料基材（1 0)，形成蝕刻槽。上述 細孔（1 2)爲微細的配列狀，蝕刻槽亦倣微細模紋朝膜厚 方向以隧道狀成長，形成微細、高密度且均勻，而擴大表 面積。又，鄰接的細孔的間隔確保生成被膜以上，不易引 起細孔的結合。如此形成蝕刻槽的被鈾金屬材料，例如使 用鋁材料時，因表面積的擴大得到高靜電容量。 又’圖2 (A) (B)所示細孔（12)內塡充高導電性物 質材料 （13)的合金屬材料 （2)，高導電性物質材料 (1 3 )優先溶解露出細孔（1 2)，接著相對於金屬材料基材 (1 〇)的細孔（1 2)的位置形成蝕刻槽。由於高導電性物 質（1 3 )所在的位置即爲細孔（1 2)存在的位置，所以 與上述複合金屬材料基材（1)同樣，蝕刻槽亦倣微細模 紋朝膜厚方向以隧道狀成長，表面積擴大得到高靜電容量 〇 鈾刻的條件無限制，因應用途依常法即可。例如一般 的電解電容器電極用鋁材料時，含氯離子水溶液添加磷酸 、硫酸、硝酸等的處理液中電解蝕刻。又，一般低壓用材 料時爲交流蝕刻’中高壓用材料時爲直流蝕刻。蝕刻條件 ，1 〜1000Hz，電流密度 0.025 〜20A/cm2，電量 〇.〇2 〜1 〇 〇 c / c m2的交流或直流蝕刻。倂用直流電解蝕刻及 -23- (18) (18)200302160 交流電解蝕刻亦可，單1直流電解蝕刻亦可。又，多段蝕 刻亦可，以化學蝕刻進行亦可。 依本發明製作的電解電容器電極用鋁材料適用中高壓 用，不限定於中高壓用材料。 上述高分子薄膜，於蝕刻槽形成後除去亦可，不除去 依原樣殘留亦可。又，於蝕刻槽形成的初期除去高分子薄 膜，其後施以爲提高擴面率的鈾刻處理亦可。任一情況， 均可以丙酮、甲乙基酮、甲苯、甲基溶纖素、醋酸乙酯、 石油醚等的有機溶劑輕易除去高分子薄膜。又，以高分子 薄膜的溶解溫度以上的溫水浸漬’該高分子薄膜可容易除 去。 本發明的被蝕刻金屬材料係包含除去及殘留高分子薄 膜者兩方。 相關於本發明的被蝕刻金屬材料，蝕刻槽的適正槽係 與電解電容器的使用電壓而異。中壓（2 50〜35〇 V)用 材料時，槽徑以0.7〜2 // m爲理想，槽間隔以1〜2 · 5 /zm爲理想。局壓（5〇〇 V以上）時，槽徑以1.5〜3//m 爲理想，槽間隔以2〜4 // m爲理想。此處所謂槽徑爲平 均値，不必要全部槽均在此範圍內。 又’被餓刻電解電谷益電極用銘材料，需要生成處理 ，此生成處理無限制。處理的條件爲至少使用草酸、己二 酸、硼酸、磷酸、砂酸鈉等的一種，其電解液的濃度爲 0.0 5〜2 0質量％，電解液溫度爲〇〜9 〇艺，電流密度爲 0.1 mA/cm2〜lA/cm2，依所需要的生成電壓於6〇分鐘生 -24- (19) (19)200302160 成時間以內生成處理。特別理想的生成處理條件爲電解液 的濃度爲〇. 1〜15質量％，電解液溫度爲20〜70 °C，·電 流密度爲1 mA/cm2〜100 mA/cm2，生成電壓爲30分鐘生 成時間以內。生成處理後，更依必要，可進行爲提高耐水 性的磷酸浸泡處理，爲強化被膜的熱處理或沸騰水的浸漬 處理。 又’關於電解電容器，以上述的被鈾刻金屬材料作爲 其電極材料，即由使用擴大表面積的金屬材料，可得到高 靜電容量。 [第2複合金屬材料] 以圖3 (A) (B)顯示本發明的第2複合金屬材料的一 種實施形態模式的斷面圖。有關此第2複合金屬材料（3 ) ，金屬材料基材（1〇)至少一面上，以導電性高於金屬材 料基材（1〇)的氧化物的物質，即由上述第1複合金屬材 料（2)的細孔（1 2)內所塡充的高導電性物質的同等物 質所成配列大量的微細斑點（14)。 上述微細斑點（1 4)金屬材料基材（1 〇)的表面配 置配列大量細孔的高分子薄膜，該細孔以導電性高於金屬 材料基材（1 〇)的氧化物的物質塡充後，除去高分子薄膜 而形成。換言之’上述第1複合金屬材料 （2)的製造步 驟’尚分子薄膜（1 1 )的細孔（1 2 )內塡充高導電性物 質（1 3 )後’除去高分子薄膜（1 1)而形成。因此，第2 複合金屬材料 （3)之金屬材料基材 （10)的材質及厚度 -25- (20) (20)200302160 、高導電性物質的材質係以第1複合金屬材料爲準。又， 由局導電性物質所成的微細斑點（1 4)的直徑（D)及間 隔（P)以第1複合金屬材料（1) (2)料細孔（丨2)的直 徑（D)及間隔（P)作爲根據。 又’有關桌2複合金屬材料（3)的製造方法。於金 屬材料基材（10)的表面配置的高分子薄膜（11)的細 ， 孔內塡充高導電性物質的步驟止與第i複合金屬材料（2) 的製造步驟共通。因此，高分子薄膜（1 1)的形成方法及 · 高導電性物質的塡充方法以第1複合金屬材料（2)的製 造方法作爲基準。 除去高分子薄膜（1 1)的方法，可以例示之丙酮、甲 乙基酮、甲苯、甲基溶纖素、醋酸乙酯、石油醚等的有機 溶劑輕易除去。或以高分子薄膜的溶解溫度以上的溫水浸 漬，該高分子薄膜可容易除去。 上述第2的複合金屬材料（3)提供蝕刻處理，製作 本發明的第2被蝕刻金屬材料。 Φ 相關的蝕刻處理，由於高導電性物質以微細斑點 (1 4)配列，蝕刻槽亦倣微細斑點朝膜厚方向以隧道狀成 長，形成微細、高密度且均勻，而擴大表面積。又，鄰接 * 的細孔的間隔確保生成被膜以上，不易引起細孔的結合。 . 如此形成蝕刻槽的被蝕金屬材料，例如使用鋁材料時，因 表面積的擴大得到高靜電容量。 鈾刻條件依上述第1被蝕刻金屬材料的製造方法爲準 ，使用電解電容器電極用鋁材料時的適正槽或蝕刻後的生 -26- (21) (21)200302160 成處理條件亦以第1被蝕刻金屬材料作爲根據。 金屬材料基材的製造時，首先，以半連續鑄造，製作 鋁純度99.99過％高純度鋁鑄塊。 對此鑄塊，依常法經均質化處理、削面、熱間軋壓、 冷間軋壓、中間鈍燒等延壓成箔，製作成厚度1 1 0 // m的 鋁材料基材 （1 〇)。上述鋁材料基材 （1 〇)經脫脂淸洗後 ，於氬氣環境下的鈍燒爐，實體溫度由室溫以5 /h的 昇溫速度昇溫至540°C後，於54(TC保持24小時，於爐內 自然冷卻再出爐，以此作爲以下實施例的共同鋁材料基材 使用。 對上述同鋁材料基材（1 〇)，變更處理條件形成具有 不同細孔構想的高分薄膜（1 1 )，製作複數種複合鋁材料 I-A，I-B、I-C、Ι-D。此等的複合材料 ι-a，I-B、I-C、I- D，對應圖1 (A) (B)所示本發明的第1複合金屬材料 (1)。 (複合鋁材料 I-A) 高分子薄膜（η)的形成時，由聚苯乙烯磺酸及氯化 二甲基十八烷基銨所成的聚離子錯合物調製3 g / 1氯仿 溶液作爲聚合物溶液。於上述鋁材料基材（1 0)的一面以 5 ml / m2比例的上述聚合物溶液鑄塑，以流量 3L / min 之2 〇 °C，相對濕度7 〇 %的高濕空氣吹拂1分鐘。其結果 ，如圖1所示的複合金屬材料（1)，鋁材料基材（10)的 表面形成略正六角形隧道的細孔（1 2)規則配列的高分子 薄膜（1 1)。此高分子薄膜（1 1)的膜厚（T)爲 1 β m， (22) 200302160 細孔 （12)的平均直徑 （D)爲3 // m，平均孔 5//m。更且，上述鋁材料基材 （10)的另一 樣的操作形成具有規則細孔構造的高分子薄膜 (複合鋁材料 I-B) 上述I-A ’除聚離子錯合物濃度改爲1 g 液’商濕空氣吹拂量改爲2 L / m i η外，與I - A 合鋁材料。形成之高分子薄膜 （1 1)的膜厚 ，細孔 （12)的平均直徑 （D)爲2// m，平均 爲 3 // m。 (複合鋁材料 I - C ) 上述Ι-A，除聚合物的聚苯乙烯磺酸改爲 ，與Ι-A同樣得到複合鋁材料。形成之高分」 的膜厚（T)爲 10//m，細孔（12)的平均直 //m’平均孔間隔 （P)爲7//m。 (複合鋁材料 I-D) 上述Ι-C，除聚合物溶液的鑄塑量爲〇5 ，與Ι-C同樣到複合鋁材料。形成之高分子薄 膜厚（T )爲 1 // m ’細孔（1 2 )的平均直徑 ，平均孔間隔 （P)爲7 // m。 又，相對於此等的複合銘材料I - A，I - b、 高分子薄膜（1 1)的細孔（1 2)以高導電性 製作如圖2(A) (B)所示構造的複合金屬材 ，II-B、II-C、II-D。此等的複合鋁材料η·Α 、II-D ’對應本發明的第1複合金屬材料。Ltn is the composite metal material according to item 3 of 0.01 to 50 // m. The pores are a composite metal material according to the above item 3 or 4 formed at intervals of 1 to 50 # m. -8-(3) (3) 200302160 The above-mentioned pores are filled with the composite metal material according to any one of items 3 to 5 of the above-mentioned metal material, which has a more conductive substance than the oxide of the metal material substrate. The base material is the composite metal material according to any one of the preceding items 1 to 6 made of a valve action metal. The valve-acting metal is the composite metal material described in Item 7 above. The composite metal material is an aluminum material for electrolytic capacitor electrodes. The composite metal material described in Item 8 above. The second composite metal material of the present invention has the following configuration. A composite metal material characterized by at least one side of a metal material substrate having fine spots formed by a larger number of oxides of the metal material substrate having a higher conductivity. The fine spots are a composite metal material as described in the above item Ø, with a diameter of 0.. The fine spots are formed at intervals of 1 to 50 // m. The composite metal material according to the item n or 12 above. The metal material base material is a composite metal material according to any one of the foregoing items [0 to i 2] made of a valve action metal. The valve action metal is the composite metal material described in the foregoing item ls of aluminum. The composite metal material is an aluminum material for electrolytic capacitor electrodes. The first composite metal material manufacturing method of the present invention is manufactured by a suitable method of -9-(4) (4) 200302160 to obtain the first metal composite material of the present invention, which has at least one side of the following metal material base material, A method for manufacturing a composite metal material formed by self-organizing a polymer film having a fine pattern, the method for manufacturing a composite metal material characterized by drying a hydrophobic organic solvent solution of a polymer compound . The surface of the metal material substrate is cast with a hydrophobic organic solvent solution of a polymer compound, and the surface of the solution is condensed while the organic solvent is evaporated, and minute water droplets generated by the evaporation and condensation form a large number of fine particles. The method for producing a composite metal material according to the foregoing item 16 in the polymer thin film with pores aligned. On the other surface, it is cast with a hydrophobic organic solvent solution of a polymer compound, and the surface of the solution is condensed while evaporating the organic solvent, and the water droplets generated by the condensation are evaporated to form a large number of pore-aligned polymer films. The method for producing a composite metal material according to the foregoing item 16 is arranged by taking out a polymer film from the substrate and bonding the surface of the metal material substrate with the polymer film. The fine pores are filled with the composite metal material according to any one of the foregoing items 17 to 18, which is more conductive than the oxide of the metal material substrate. The method of charging a material having a higher conductivity than the oxide of the metal material substrate is a method for producing a composite metal material according to the above item 19 by any one of electroplating, vapor deposition, and dipping. The above-mentioned polymer compound is the method for producing a composite metal according to any one of the foregoing paragraphs (10) (5) and (5) 200302160 1 6 to 20. The method for producing a composite metal material as described in the foregoing item 21 in an ionic complex of the amphiphilic polymer compound based on polystyrenesulfonic acid and a long-chain diammonium ammonium salt. The method for producing a composite metal material as described in any one of 16 to 22 above, wherein the concentration of the hydrophobic solvent solution of the polymer compound is 0.01 to 10% by mass. The film formation of the polymer thin film is a method for producing a composite metal material according to any one of the foregoing paragraphs 16 to 23, which is performed in an environment of high temperature and high humidity. The manufacturing method of the second composite metal material of the present invention is to obtain the second metal composite material of the present invention by an appropriate method. The second metal composite material has the following structure. At least one side of the metal material substrate is composed of a polymer film with fine pattern. A method for fabricating a composite metal material by organizing it, a polymer film having a large number of pores arranged on the substrate surface of the tube molecular film, and the pores are filled with a metal having a lower potential than the metal material substrate. After filling, the manufacturing method of the composite metal material whose characteristic is the polymer film is removed. The above-mentioned metal material substrate is molded with a hydrophobic organic solvent solution of a polymer compound, and the surface of the solution is condensed while the organic solvent is evaporated, and 'the tiny water droplets generated by the black hair condensation are used to form the polymer film' and The manufacturing method of the composite metal material as described in the above paragraph 25 arrange | positioned to the said metal material base material. -11-(6) (6) 200302160 On other surfaces, cast with a hydrophobic organic solvent solution of a polymer compound, and evaporate the organic solvent while condensing the surface of the solution, and evaporate the tiny water droplets generated by the condensation A method for producing a metal composite material as described in Item 25, in which a plurality of polymer films with fine pores are formed, and the polymer thin film is taken out from the substrate and bonded to the surface of the metal material substrate. The method of charging a material having a higher conductivity than the oxide of the metal material substrate is a method for manufacturing a metal material according to the foregoing paragraphs 2 5 to 2 by any one of electroplating, vapor deposition, and dipping. The above-mentioned polymer compound is a method for producing a composite metal according to any one of the preceding items 25 to 28, which is an amphiphilic polymer compound. The method for producing a composite metal material according to the foregoing item 29, wherein the amphiphilic polymer compound is an ion complex of polystyrenesulfonic acid and a long-chain diammonium ammonium salt. The method for producing a composite metal material according to any one of the foregoing paragraphs 25 to 30 in which the concentration of the hydrophobic solvent solution of the polymer compound is 0.01 to 1% by mass. The formation of the polymer thin film is a method for producing a composite metal material according to any one of items 25 to 31, which is performed in an environment of high temperature and high humidity. The method for producing a composite metal material according to any one of the foregoing paragraphs 2 5 to 3 2 of the above-mentioned rhenium molecular thin film is carried out by using a solution. The composite metal material described in the preceding paragraphs 1 to 9 is an etched metal material characterized by the formation of uranium grooves based on the fine pattern. -12- (7) 200302160 ± The metal material to be etched refers to the metal material engraved with uranium as described in Item 3 4 of the foregoing aluminum material for electrolytic capacitor electrodes etched with uranium. The second uranium-engraved metal material according to the present invention is a person who has been engraved using the second composite metal material of the present invention, and has the following structure. The composite metal material described in the foregoing paragraphs 10 to 15 is an etched metal material characterized by forming an etching groove based on fine spots. The metal material to be etched is the metal material to be etched according to item 3 to 6 of the aluminum material for electrolytic capacitor electrodes etched by uranium. The first method for producing a metal material to be etched according to the present invention is a method for producing the first metal material to be etched according to the present invention by appropriate manufacturing, and has the following configuration. The manufacturing method of the composite metal material described in the foregoing paragraphs 1 to 9, which does not remove the polymer film and performs an etching process to form an etching groove having the characteristics of the etching method. For the composite metal material described in the preceding paragraphs 1 to 9, after the polymer film is not removed, an etching process is performed to generate an etching groove, and the polymer film is removed, and then the etching process is performed to grow the etching groove. Production method. The metal material to be etched is the metal material to be etched as described in Item 3 8 or 39 of the material for etching electrolytic capacitor electrodes. The manufacturing method of the second uranium-engraved metal material of the present invention is a method for appropriately manufacturing the second uranium-engraved metal material of the present invention, and has the following structure. The method for manufacturing an etched metal material characterized by forming an etched groove on the composite metal material described in the foregoing paragraph 10 1 5 (-13) (8) (8) 200302160. The above-mentioned etched metal material is a method for manufacturing an etched metal material as described in the foregoing item 4 1 of the aluminum material for electrolytic capacitor electrodes. The electrolytic capacitor of the present invention is formed by using the first or second etched metal material of the present invention, and has the following configuration. An electrolytic capacitor using the metal material to be etched as described in the preceding paragraph 3 4 or 3 5 as an electrode material is used. An electrolytic capacitor using the metal material to be etched as described in the above item 3 6 or 37 as an electrode material is used. According to the first composite metal material of the present invention, a uranium engraving process is performed to form a high-density and uniformly distributed uranium engraving groove based on the fine pattern to expand the surface area. When the fine pattern is a pore structure in which a large number of pores are arranged, a high-density and uniform uranium engraved groove can be formed. When the diameter of the pores is 0.001 to 50 m, or the interval between the pores. When it is 1 ~ 5 0 // m, a high expansion surface can be achieved. 4 〇 In addition, when the above pores are filled with a higher conductive substance than the oxide of a metal material substrate, the highly conductive substance becomes an etching groove. The nucleus is triggered to form a high-density and uniformly distributed etched trench. When the metal base material is made of a metal material for a valve, it can be used as an electrode material for an electrolytic capacitor. For example, when the valve action metal is aluminum, it can be used as an aluminum material for electrolytic capacitors. According to the second composite metal material of the present invention, a uranium etching process is performed, and since fine spots having a higher conductive substance than the oxide of the metal material substrate are the initiation nuclei of the etching groove, a high-density and uniform cloth etch is formed. Groove, enlarged -14-200302160 0) large surface area. When the diameter of the fine spots is 0.01 to 50 // m, or when the interval of the fine spots is 1 to 50 / m, a high expansion ratio can be achieved. When the above-mentioned metal material substrate is made of a valve-acting metal, it can be used as an electrode material for an electrolytic capacitor. For example, when the valve action metal is aluminum, it can be used as an aluminum material for electrolytic capacitors. According to the manufacturing method of the first composite metal material of the present invention, the above-mentioned first composite metal material can be obtained suitably. In relation to this manufacturing method, when the surface of the metal material substrate is directly cast and dried with a hydrophobic organic solvent solution of a polymer compound, a polymer film with a large number of fine pores can be formed in a state in which the metal material substrate is in close contact. The film formation of the polymer film and the lamination of the metal material substrate can be performed simultaneously. Moreover, a polymer film which can be formed in a different manner on other substrates can be produced by bonding to the surface of a desired metal foil substrate. In addition, when a higher conductive substance is used in the pores than the oxide having a higher conductivity than the base material of the metal material, the highly conductive substance becomes a nucleus due to the etching groove. Therefore, filling the highly conductive substance can be easily performed by plating, Either vapor deposition or dipping is performed. In addition, when the polymer compound is, for example, an amphiphilic polymer compound that is an ionic complex of polystyrenesulfonic acid and a long-chain dialkylamine salt, a polymer film having a pore structure can be formed. When the concentration of the hydrophobic solvent solution of the polymer compound is 0.01 to 10% by mass, a fine pattern and a pore structure having a stable shape with a required strength can be formed. -15- (10) (10) 200302160 In addition, the formation of the above-mentioned polymer thin film is performed under an environment of high temperature and high humidity, so that a fine mold pattern and a pore structure can be surely formed. According to the manufacturing method of the second composite metal material of the present invention, a suitable second composite metal material can be manufactured. Related to this manufacturing method, when the surface of the above-mentioned metal material substrate is directly cast and dried with a hydrophobic organic solvent solution of a polymer compound, a polymer film with a large number of fine pores and a metal material substrate can be formed. In the state, the film formation of the polymer film and the lamination of the metal material substrate can be performed simultaneously. Furthermore, a polymer film formed in a different manner on other substrates can be produced by bonding to the surface of a desired metal foil substrate. In addition, the charging method using a conductive material having a higher conductive substance than the oxide of a metal material substrate in the pores can be easily performed by any method such as plating, vapor deposition, and dipping. When the above-mentioned polymer compound is, for example, an amphiphilic polymer compound which is an ionic complex of polystyrenesulfonic acid and a long-chain diamylamine salt, a polymer film having a pore structure can be formed. · When the concentration of the hydrophobic solvent solution of the polymer compound is 0.001 to 10% by mass, a fine pattern and a pore structure having a stable shape with a required strength can be formed. % In addition, the formation of the above-mentioned polymer thin film is performed under an environment of high temperature and high humidity, so that a fine pattern and a pore structure can be surely formed. In addition, a polymer film filled with a highly conductive material can be easily removed by dissolution, and fine spots can be formed on the surface of a metal material base on the basis of the finely patterned highly conductive material. -16- (11) (11) 200302160 The first etched metal material of the present invention is formed by forming an etching groove based on a fine pattern with respect to the first composite gold S # material, and is formed as described above. High-density and uniformly distributed etching grooves with a sufficiently enlarged surface area. Since the metal material to be etched as described above uses an electrode material for an electrolytic capacitor to be etched, the capacitance can be increased. In the first manufacturing method of the metal material to be etched according to the present invention, the polymer film is not removed at the initial stage. After the etching process is performed to generate an etching tank, the polymer film is removed, and then the etching process is performed to grow the etching tank to obtain a high-density etching tank And uniformly distributed engraved metal material. In the manufacturing method of the etched metal material, when the electrode material of the electrolytic capacitor is the above-mentioned etched metal material, an electrode material with a high capacitance can be obtained by increasing the surface area. The second etched metal material of the present invention is an etched groove formed on the basis of fine spots with respect to the second composite metal material, to obtain a high-density etched groove and a uniformly distributed etched metal material. Regarding the manufacturing method of the metal material to be engraved, when the electrode material of the electrolytic capacitor is the metal material to be etched as described above, an electrode material with a high capacitance can be obtained by increasing the surface area. Since the electrolytic capacitor of the present invention uses the above-mentioned etched metal material as an electrode material, a high electrostatic capacity can be obtained, and the size and performance of the electrolytic capacitor can be reduced. Further, the electronic equipment for assembling the electrolytic capacitor can be miniaturized and highly functional. [Embodiment] -17- (12) (12) 200302160 The best form for implementing the invention [First composite metal material] Figure 1 (A) (B) shows one of the first composite metal materials of the present invention Sectional view of the implementation mode. The polymer film (11) laminated on the surface of the first composite metal material (1) and the metal material substrate (10) is a film formed by self-organizing a polymer compound, and is formed during film formation. Fine pattern. The polymer film (1 1) may be laminated on at least one surface of the metal material base material (10). When used as an electrode material for an electrode of an electrolytic capacitor, it is desirable to laminate both surfaces in order to maximize the surface area. The polymer film (1 1) is formed by drying a solution of a polymer compound (hereinafter referred to as a polymer solution) dissolved in a hydrophobic organic solvent. For example, when the surface of a substrate is cast-dried with a polymer solution, the polymer compound self-organizes on the substrate to form a thin film with fine patterns. The fine pattern can be exemplified by a pore structure in which a large number of pores (12) are arranged as shown in Fig. 1 (B). One embodiment mode of the first composite metal material according to the present invention uses the fine pores (12) as the introduction path of the surface etching solution of the metal material base material (10). Fig. 1 (A) (B) is a cross-sectional view showing another embodiment mode of the first composite metal material of the present invention. In the first composite metal material, the pores (12) are filled with a substance having a higher conductivity than the metal material base material (1 ()) (hereinafter referred to as a highly conductive substance). The conductive material is used as an etching core, as described later. The macromolecule (1 1) having a fine pore structure, which is the fine pattern, is formed through the following process. -18- (13) (13) 200302160 The polymer solution cast on the substrate absorbs latent heat when the organic solvent evaporates, and water molecules in the air condense as fine particles on the surface of the polymer solution. On the one hand, due to the action of the hydrophilic portion of the polymer solution, the surface tension between water and the hydrophobic organic solvent is reduced, and the water particles are aggregated into minute droplets. Because the size of the water droplets is slightly uniform, as the solvent evaporates, the water droplets are arranged in a dense and dense state, and become a regular arrangement. When the water droplets are further evaporated, the water droplets become voids, and pores are formed in the direction of film thickness (1 2). Water droplets act as a cast film, forming a polymer film with a regular pore structure φ and a honeycomb structure (1 1). Figures 1 (B) and 2 (B) illustrate a large number of hexagonal pores (12) forming a polymer film in a fine state. As for the pores, other than the hexagonal shape shown in the example, the pores are round or nearly hexagonal. Moreover, the regular pore structure does not mean strict geometric regular construction, it means that the regularity of the structure is not a random construction. Therefore, the shape of the pores, the diameter of the pores, and the interval between the pores are somewhat confounded and are also included in the regular pore structure. There is some confusion, and there is no problem in forming the high-density and uniform etching groove described later. · When manufacturing the first composite metal material (1) (2) of the present invention, the surface of the local molecular film (11) -based metal material substrate (10) is directly cast from a polymer solution, and can be used with the metal material substrate (10) A close-contact state is formed. That is, lamination of the polymer film (1 1) and the metal material substrate (1 0) can be performed simultaneously. Alternatively, it can be produced by removing a polymer film (1 1) separately from another base material and bonding it to a metal material base material (10). When forming on other substrates, inorganic materials such as glass and silicon wafers other than metals can be used for the substrate. Polypropylene, polyethylene, and polyetherketone have excellent resistance to organic solvents. 19- (14) (14) 200302160 organic polymer materials such as solids, water, liquid wax, liquid polyester and other liquids. Among these other substrates, water is suitable from the viewpoint that the polymer film can be easily taken out and the retention of the pore structure is excellent. The polymer compound forming the polymer film is not particularly limited. Examples of suitable polymer compounds include amphiphilic polymer compounds having a hydrophobic group and a hydrophilic group, single polymers of one type of amphiphilic molecule, or copolymers of two or more types of amphiphilic molecules. can. Copolymers of molecules other than amphiphilic molecules may be used, and a surfactant may be present. The amphiphilic polymer compound uses polystyrene acid and a long-chain dialkyl ammonium salt ion complex, a polyethylene glycol / polypropylene glycol block copolymer, and an acrylic amine polymer as the backbone backbone. Dodecyl group with hydrophobic side chain and amphiphilic polymer compound with lactose group or carboxyl group on hydrophilic side chain, or anionic polymer such as heparin or dextran sulfate, nucleic acid (DNA or RNA) and long An ionic complex of an alkanolammonium salt, an amphiphilic polymer having a hydrophilic group, and a water-soluble protein such as gelatin, colamide, albumin, etc. are preferable. Examples of other polymer compounds include polystyrene phosphoric acid, polystyrene sulfonic acid, polylactic acid, and polycarbonic acid. As the hydrophobic organic solvent that dissolves the polymer compound, a halogen-based solvent such as chloroform, an ester-based agent such as ethyl acetate, a non-aqueous ketone, carbon disulfide, or the like can be used. These mixed solvents can also be used. The polymer solution preferably has a polymer compound concentration of 0.01 to 10% by mass. When it is less than 0.01% by weight, the strength of the polymer film (11) is insufficient, and when it exceeds 10% by mass, it is difficult to maintain the shape of the pores (12) and the stable shape protected by -20- (15) (15) 200302160. The ideal concentration is from 0.05 to 5% by weight. The "film-forming environment" is an environment in which the evaporation of the organic solvent, the condensation of minute water droplets, and the progress of evaporation are performed, and a high-humidity environment is preferable. Specifically, the relative humidity: 50 ~ 95%, temperature:} 〇 ~ 2 5 ° C is ideal in the atmosphere 〇 The size of the pores (12) is preferably the diameter (D) 0.01 ~ 50 // m ' This size is provided as a composite gold material (1) used as an electrolytic capacitor for etching treatment. It is suitable for the case where a large number of uniform etching grooves are formed and the expansion rate is excellent. The diameter (D) of the particularly preferable pores (12) is 〇ι ~ 5〇 # mo, and the interval (P) of the pores (12) is preferably 1 to 50 // m. When the etching is less than 1 // m, there is anxiety about the adjacent grooves, and when it exceeds 50 m, it is difficult to increase the number of grooves. The fine holes (丨 2) have a particularly ideal interval of 1 to 1 5 // m. Furthermore, the thickness (T) of the polymer film (11) is formed in a range of about 100 nm to 2 #m. When an aluminum material for electrolytic capacitor electrodes is used, 0.5 to 5 is preferable. The metal material base material (1 0) constituting the above-mentioned composite metal material (1) (2) does not matter the type and thickness of the metal, and is appropriately selected according to the application. The type of metal can be exemplified as an electrode material of an electrolytic capacitor @ 用Valve action metal. Examples of the valve-acting metal include aluminum, giant, magnesium, demon, niobium, chromium, zinc, bismuth, silicon, and thallium. Monomers of titanium and boron and tin, and alloys of vanadium, vanadium, and ammonium. For the Ming. In addition, regarding these -21-(16) (16) 200302160 metal material substrates, impurities are allowed to exist, or appropriate microelements are added as necessary. For example, in the case of aluminum, silicon, iron, copper, lead, zinc, gallium, zirconium and the like can be added. However, in the case of electrode materials for electrolytic capacitors, it is desirable to use high-purity aluminum having a purity of 99.9% or more in order to suppress the occurrence of defects in the coating film. The thickness is not limited, and in order to ensure the strength and flexibility of the metal material to be etched, it is preferably 0.05 to 0.3 mm. 5 mm。 Particularly ideal is 0.07 ~ 0.2 mm, more preferably 0.07 ~ 0. 1 5 mm. In addition, the metal material base material (10) has no limited heat treatment or crystal structure. In the case of an aluminum material, for example, the hard material is not heat-treated, and the aggregates are elongated fibrous crystals extending in the rolling direction. In contrast to this hard material, when it is sintered at 300 to 400 ° C, it can become a soft material with high (100) plane growth crystal grains. In the present invention, any of the above-mentioned metal material substrates can be used. The metal material base material (10) may be a long package in a spiral package, and the material may be cut. In addition, the highly conductive substance (13) filled in the pores (12) can be preferentially dissolved as an initiating nucleus of a groove during etching, and can be selected according to the conductivity of the metal material substrate (10). . When the base material of the metal material (10) is aluminum, for example, lead, lead oxide, copper, copper oxide, cuprous oxide, carbon having higher conductivity than aluminum can be exemplified. Lead or lead oxide is recommended. The method for filling the pores (12) of the above-mentioned highly conductive substance (13) can be exemplified by electroplating, sputtering, vapor deposition, dipping, CVD, dissolution, ion plating, etc., and the polymer film has less damage due to fast charging speed. From the viewpoint of low-cost processing, plating, vapor deposition, and dipping are preferred. -22- (17) (17) 200302160 The first composite metal material (1) (2) is provided with an etching treatment 'to produce a first metal material to be etched according to the present invention. Related etching process, as shown in Fig. 1 (A) (B), the composite metal material (1) forming only the polymer film (1 1), the etching solution reaches the metal material base from the fine pores (1 2) of the fine pattern. Material (1 0) to form an etching groove. The above-mentioned pores (12) are finely aligned, and the etching groove also grows in a tunnel shape in the direction of film thickness, forming fine, high-density and uniformity, thereby expanding the surface area. In addition, the interval between adjacent pores ensures that a coating is formed or more, and it is difficult to cause the pores to join. In the case where the uranium metal material having the etching grooves formed in this way, for example, an aluminum material is used, a high electrostatic capacity is obtained due to an increase in surface area. Also, the pores (12) shown in Fig. 2 (A) are filled with a metal material (2) filled with a highly conductive material (13), and the highly conductive material (1 3) is preferentially dissolved to expose the pores. (1 2), and an etching groove is formed next to the position of the pores (12) of the metal material substrate (10). Since the position of the highly conductive substance (1 3) is the position where the pores (12) exist, the same as the above-mentioned composite metal material substrate (1), the etching groove also mimics the fine pattern and tunnels in the direction of the film thickness. As the surface grows, the surface area is enlarged to obtain a high electrostatic capacity. There are no restrictions on the conditions of uranium engraving. For example, in the case of a general aluminum material for electrolytic capacitor electrodes, a chloride ion-containing aqueous solution is added with a treatment solution such as phosphoric acid, sulfuric acid, or nitric acid to perform electrolytic etching. In addition, in the case of a low-voltage material, an AC etching method is used, and in a case of a high-voltage material, a DC etching method is used. Etching conditions, 1 to 1000 Hz, current density 0.025 to 20 A / cm2, electric power 0.02 to 1 〇c / c m2 AC or DC etching.直流 DC electrolytic etching and -23- (18) (18) 200302160 AC electrolytic etching are also available, and single 1 DC electrolytic etching is also available. It is also possible to perform multi-stage etching or chemical etching. The aluminum material for electrolytic capacitor electrodes manufactured according to the present invention is suitable for medium and high voltage, and is not limited to materials for medium and high voltage. The polymer film may be removed after the etching bath is formed, or it may be left as it is without being removed. Alternatively, the polymer film may be removed at the initial stage of the formation of the etching bath, and thereafter, a uranium etching process may be performed to increase the spreading ratio. In any case, the polymer film can be easily removed with an organic solvent such as acetone, methyl ethyl ketone, toluene, methyl lysin, ethyl acetate, and petroleum ether. The polymer film can be easily removed by being immersed in warm water at a temperature higher than the dissolution temperature of the polymer film. The metal material to be etched according to the present invention includes both a polymer film and a polymer film. Regarding the metal material to be etched according to the present invention, the proper tank system of the etching tank and the operating voltage of the electrolytic capacitor differ. In the case of medium-pressure (2 50 to 350,000 V) materials, the groove diameter is preferably 0.7 to 2 // m, and the groove interval is preferably 1 to 2 · 5 / zm. For partial pressure (500 V or more), the groove diameter is preferably 1.5 to 3 // m, and the groove interval is preferably 2 to 4 // m. Here, the so-called groove diameter is average, and it is not necessary that all grooves are within this range. In addition, the inscription material for electrolytic electrode Guyi electrode needs to be engraved, and there is no limitation on the generation process. The treatment conditions are at least one of oxalic acid, adipic acid, boric acid, phosphoric acid, and sodium oxalate. The concentration of the electrolytic solution is 0.0 5 to 20 mass%, the temperature of the electrolytic solution is 0 to 90, and the current density is 0.1 mA / cm2 ~ 1A / cm2, according to the required generation voltage within 60 minutes to generate -24- (19) (19) 200302160 generation time within processing time. Particularly ideal conditions for the generation and treatment are that the concentration of the electrolyte is 0.1 to 15% by mass, the temperature of the electrolyte is 20 to 70 ° C, and the current density is 1 mA / cm2 to 100 mA / cm2. The generation voltage is 30 minutes. Within time. After the formation treatment, if necessary, a phosphoric acid immersion treatment for improving water resistance, a heat treatment for strengthening the film, or a boiling water immersion treatment may be performed. Further, with regard to the electrolytic capacitor, the above-mentioned uranium-etched metal material is used as its electrode material, that is, by using a metal material with an enlarged surface area, a high capacitance can be obtained. [Second composite metal material] A sectional view showing one embodiment mode of the second composite metal material of the present invention is shown in Figs. 3 (A) and (B). With regard to the second composite metal material (3), at least one side of the metal material substrate (10) is made of a substance having higher conductivity than the oxide of the metal material substrate (10), that is, the first composite metal material described above. A large number of fine spots (14) are formed by the equivalent substance of the highly conductive substance filled in the pores (12) of (2). A polymer film with a large number of pores is arranged on the surface of the fine spots (14) of the metal material substrate (10), and the pores are filled with a substance having higher conductivity than the oxide of the metal material substrate (10). Then, the polymer film is removed and formed. In other words, 'the manufacturing process of the above-mentioned first composite metal material (2)', the polymer thin film (1 1) is filled with the highly conductive substance (1 3) in the pores (1 2) of the molecular film (1 1). And formed. Therefore, the material and thickness of the metal material base material (10) of the second composite metal material (3) -25- (20) (20) 200302160, and the material of the highly conductive material is based on the first composite metal material. In addition, the diameter (D) and the interval (P) of the fine spots (1 4) made of the locally conductive material are the diameter (D) of the first composite metal material (1) (2) and the pores (丨 2) of the material. And interval (P) as the basis. It also relates to a method for manufacturing the table 2 composite metal material (3). The thin polymer film (11) disposed on the surface of the metal material substrate (10), and the step of filling the hole with a highly conductive substance is the same as the manufacturing step of the i-th composite metal material (2). Therefore, the method of forming the polymer film (1) and the method of filling the highly conductive material are based on the method of manufacturing the first composite metal material (2). The method of removing the polymer film (11) can be easily removed by using organic solvents such as acetone, methyl ethyl ketone, toluene, methylcellulose, ethyl acetate, and petroleum ether. Alternatively, the polymer film can be easily removed by being immersed in warm water at a temperature higher than the melting temperature of the polymer film. The second composite metal material (3) is subjected to an etching treatment to produce a second metal material to be etched according to the present invention. For the Φ related etching process, the highly conductive material is arranged in fine spots (1 4), and the etching groove also grows like a fine spot in the direction of the film thickness in a tunnel shape, forming a fine, high density and uniform, and expanding the surface area. In addition, the interval between the pores adjacent to * ensures that a film is formed or more, and it is difficult to cause the pores to join. When an etched metal material is formed in this way, for example, when an aluminum material is used, the surface area is enlarged to obtain a high capacitance. The uranium engraving conditions are based on the above-mentioned first manufacturing method of the metal material to be etched. When using an aluminum material for electrolytic capacitor electrodes, the proper groove or the etched -26- (21) (21) 200302160 processing conditions are also the first The etched metal material is used as a basis. When manufacturing a metal material substrate, first, semi-continuous casting is performed to produce a high-purity aluminum ingot having an aluminum purity of 99.99% or more. For this ingot, it was homogenized, faced, hot-rolled, cold-rolled, middle-blown, etc. rolled into a foil in accordance with the usual method, and made into an aluminum material substrate with a thickness of 1 1 0 // m (1 〇). After the above aluminum material substrate (10) was degreased and washed, in a blaze furnace under an argon atmosphere, the solid temperature was raised from room temperature to a temperature of 5 / h to 540 ° C, and then maintained at 54 ° C (24 ° C). After being allowed to cool naturally in the furnace for another hour, the furnace was used as a common aluminum material substrate in the following examples. For the same aluminum material substrate (10), the processing conditions were changed to form high-resolution films with different pore concepts ( 1 1), to produce a plurality of composite aluminum materials IA, IB, IC, I-D. These composite materials ι-a, IB, IC, I-D correspond to the present invention shown in Fig. 1 (A) (B) The first composite metal material (1). (Composite aluminum material IA) During the formation of the polymer film (η), a polyion composed of polystyrene sulfonic acid and dimethyl octadecyl ammonium chloride was mismatched. A 3 g / 1 chloroform solution was prepared as a polymer solution. The above polymer solution was casted at a ratio of 5 ml / m2 on one side of the aluminum material substrate (10), and the flow rate was 3 L / min at 20 ° C. High humidity air with a relative humidity of 70% was blown for 1 minute. As a result, the composite metal material (1) and the aluminum material substrate (10) shown in FIG. The pores (1 2) with a regular hexagonal tunnel formed on the surface are regularly arranged polymer films (1 1). The film thickness (T) of this polymer film (1 1) is 1 β m, (22) 200302160 pores ( 12) The average diameter (D) is 3 // m, and the average pores are 5 // m. Furthermore, another operation of the above-mentioned aluminum material substrate (10) forms a polymer film (composite aluminum) with a regular pore structure. Material IB) The above IA is an aluminum material combined with I-A, except that the concentration of polyion complex is changed to 1 g of liquid, and the amount of wet air blow is changed to 2 L / mi η. The polymer film formed (1 1) Film thickness, the average diameter (D) of the pores (12) is 2 // m, and the average is 3 // m. (Composite aluminum material I-C) The above-mentioned I-A, except for the polymer polystyrene sulfonic acid Instead, a composite aluminum material was obtained in the same way as I-A. The film thickness (T) of the formed high score was 10 // m, and the average pores (12) of the fine pores (12) had an average pore interval (P) of 7 // m. (Composite aluminum material ID) The above I-C, except for the polymer solution, has a casting amount of 0,5, which is the same as I-C for composite aluminum materials. The thickness of the polymer film (T) is 1 // m 'fine holes (1 2) average straight , The average pore interval (P) is 7 // m. In addition, in contrast to these composite materials I-A, I-b, the pores (1 2) of the polymer film (1 1) are made with high conductivity. The composite metal materials, such as II-B, II-C, and II-D, as shown in Fig. 2 (A) and (B). These composite aluminum materials η · A and II-D 'correspond to the first composite of the present invention. metallic material.
間隔（Ρ)爲 面亦進行同 ⑴）。 / 1氯仿溶 同樣得到複 (Τ)爲 2 /a m 孔間隔（Ρ) 聚己內酯外 薄膜（11) 徑（D)爲5 ml/m2以外 膜（1 1)的 (D)爲 5 μ m I-C、I-D， 物質塡充， 料（2) II-A ，II-B、II-C -28 - (23) (23)200302160 (複合錦材料Π_Α) 1寸複合錦材料Ι-Α，以電鍍將鉛塡充至高分子薄膜的 細孔。電鑛的條件爲鉛板作爲陽極，以1 A/m2電流密度 通電3 0秒。 (複合鋁材料：Π-Β) -對複合銘材料I_B，以電鍍將銅塡充至高分子薄膜的 ， 細孔。電鑛的條件爲銅板爲陽極，以1 A/m2電流密度通 _ 電30秒。 φ (複合鋁材料X c ) ^複合_材料I-C，以常法將碳蒸鍍，高分子薄膜的 細孔以碳塡充。 (複合銘材料Π-D) ϊ寸複合錦材料I-D，以鉛離子濃度：〇.5莫耳/ 1的 水洛液，浸漬該複合鋁材料2分鐘，其後於8 0 °C的乾燥 機中乾燥’高分子薄膜的細孔內塡充鉛化合物（氧化鉛） 又’對此等的複合鋁材料n_A，n_B、n_c、n_D， 除去高分子薄膜（η)製作金屬材料基材（10)的表面 配列由局導電性質物質所成的微細斑點（丨4)的複合鋁材 · 料IH-A，m-B、m-c、In-D。此等複合鋁材料ha， III-B、III-C、In_D對應本發明的如圖3 (a) (B)所示 構造的第3複合金屬材料（3) (複合鋁材料III-A) 複合鋁材料Π-A於丙酮中浸漬丨分鐘而除去高分子 -29- (24) (24)200302160 _ Μ ’彳辱S1由鉛所成配列微細斑點的複合鋁材料ΙΠ-α。 (複合鋁材料111 - Β ) 複合銘材料ΙΙ-Β於甲酮中浸漬1分鐘而除去高分子 _ Μ ’得到由銅所成配列微細斑點的複合鋁材料ΙΙΙ-Β。 (複合鋁材料111 · C ) 複合銘材料II-C於9〇t溫水中浸漬3分鐘而除去高 # + ¾ g莫’得到由碳所成配列微細斑點的複合鋁材料 III-C 。 其次’各實施例，上述的各複合鋁材料以下述a，b 之任一條件施以蝕刻處理，製作成表1所示No. 1〜1 9的 被蝕刻電解電容器用電極用鋁材料。又，比較例No. 20 以無高分子薄膜 （1 1)的鋁材料 （10)施以蝕刻處理。 [蝕刻條件 A] 上述複合鋁材料，以8〇t的第1電解液 （1莫耳/ L 鹽酸 + 3.2莫耳/L1硫酸水溶液）浸漬，施以電流密度 0.2 A/cm2的直流通電100秒的電解鈾刻。更進一步，以 9 0°C的第1電解液 （1.5莫耳/ L鹽酸 + 0.05 6莫耳/L1 草酸水溶液）浸漬，施以1 0分鐘的化學鈾刻。 [鈾刻條件 B] 上述複合鋁材料，以5 0 °C的1 0%氯化亞鐵水溶液浸 漬1 〇分鐘後，取出水洗。由此僅高分子薄膜的細孔部份 或高導電性物質的微細斑點部份化學蝕刻。更進一步’以 -30- (25) (25)200302160 7 5 °C的第2電解液（5%鹽酸+ 10%硫酸水溶液）浸漬’ 施以電流密度0.2 A/cm2 的直流通電1 00秒的電解蝕刻。 接著以同液施以1 〇分鐘的化學鈾刻。 相關於上述實施例及比較例被蝕刻的電解電容器用電 極鋁材料，測定其蝕刻槽的槽徑及槽間隔。測定値如表1 所示。又，所示此等的測定値係槽的半數以上在此範圍內 〇 一方面，被蝕刻的電解電容器用電極鋁材料各自以硼 酸浴350V生成處理後，測定靜電容量，靜電容量以比較 例N 〇 . 2 0的靜電容量爲1 0 0 %的相對値，如表i所示。 -31 - (26)200302160 表1 實施例 比較 0. 複合鋁材料 _ 蝕刻 靜電容量 % 形態 膜厚 T μιη 細孔(斑點） 高導電 性物質 條件 槽徑 μιη 槽間隔 μιη D μιη Ρ μιη 1 I-A 2 3 5 A 1.0-6.0 2.Ο-6.0 130 2 I-A 2 3 5 - B 0.8 〜7.0 1.0-4.0 125 3 I-B 2 — 2 3 一 A 1.0-4.0 1.0-4.0 140 4 I-C 10 5 7 - A 1.0 〜8.0 4.0 〜10.0 120 5 I-D 1 5 7 - A 1.0 〜8.0 4.0 〜10.0 120 6 II-A 2 3 5 Pb A 1.0 〜5.0 3.0 〜5.0 145 7 II-A 2 3 5 Pb B 0.8^6.0 2.0 〜4.0 140 8 II-B 2 2 3 Cu A 1.0 〜3.5 1.0 〜4.0 135 9 II-B 2 2 3 Cu B 0.8 〜4.5 1.0 〜8.0 135 10 II-C 10 5 7 C A 1.0 〜7.0 4.0 〜10.0 125 11 II-C 10 5 7 C B 0.8 〜7.5 4.0 〜9.0 125 12 II-D 1 5 7 Pb氧化物 A 1.0 〜7.0 4.0 〜10.0 125 13 II-D 1 5 7 Pb氧化物 B 1.0 〜7.5 4.0 〜9.0 125 14 III-A 2(除去） 3 5 Pb A 1.0 〜5.5 2.5 〜5.5 130 15 III-A 2(除去） 3 5 Pb B 0.84.5 1.5 〜4.5 125 16 III-B 2(除去） 2 3 Cu A 1.0 〜4.0 1.5 〜4.5 130 17 III-B 2(除去） 2 3 Cu B 0.8 〜4.5 1.0 〜3.5 125 18 III-C 1〇(除去) 5 7 C A 1.04.5 3.5 〜10.5 130 19 III-C 1〇(除去） 5 7 C B 0.8 〜7.0 9.0 〜9.5 125 20 僅鋁基材 A 0.7-4.0 不均勻 100 由表1的結果，各實施例之被蝕刻電解電容器電用鋁 材料，蝕刻槽的孔徑與間隔較比較例均勻，由擴面率的增 大確認可得到高靜電容量。一方面，比較例發見蝕刻槽結 合，形成巨大的槽，槽間隔亦不均勻。 此處所使用的用語及表示，係爲說明而使用，非限定 解釋而使用者，此處所示且述說的特徵事項不排除均等物 -32- (27) 200302160 ，不得不認爲此發明的請求範圍的各種變形亦爲 〔商業上之利用領域〕 本發明的複合金屬材料’係以高分子薄膜的 微細模紋作爲根據，可產生高密度且均勻的蝕刻 ，以此槽作爲基點不易在隧道內結合可更深的蝕 確實的提高擴面率謀取增大電解電容器的靜電容 小型化及高性能化電解電容器，組裝此電解電容 機器的小型化及高性能生成爲可行。 【圖式簡單說明】 圖1 (A)本發明的第1金屬材的一'種貫施 式顯不的縱斷面圖，圖1 (B)爲圖1 (A)的1B -斷面圖。 圖2 (A)本發明的第丨金屬材的一種實施 式顯示的縱斷面圖，圖2 (B)爲圖2 (A)的2B -斷面圖。 圖3 (A)本發明的第2金屬材的一種實施 式顯示的縱斷面圖，圖3 (B)爲圖3 (A)的3B -斷面圖。 主要元件對照表 T :厚度 10·金屬材料基材 容許者。 規則列的 槽。因此 刻狀態， 量。進而 器的電子 形態以模 _ 1 B線之 形態以模 -2B線之 形態以模 -3 B線之 -33- (28) 200302160 1 1 :高分子薄膜 1 2 :細孔 P :間隔 D :直徑 1 2 ( 1 3 ):高導電性物質 1 4 :微細斑點 -34-The interval (P) is also the same for surfaces). / 1 chloroform solution also gives a complex (T) of 2 / am. Pore spacing (P) Polycaprolactone outer film (11) Diameter (D) is 5 ml / m2 Outer film (1 1) (D) is 5 μ m IC, ID, material charge, (2) II-A, II-B, II-C -28-(23) (23) 200302160 (composite brocade material Π_Α) 1-inch composite brocade material Ⅰ-Α, Electroplating fills the pores of the polymer film with lead. The condition of the power ore is that the lead plate is used as the anode, and the current is applied at a current density of 1 A / m2 for 30 seconds. (Composite aluminum material: Π-Β)-For the composite material I_B, copper is filled into the polymer film with electroplating, and the pores are fine. The condition of the power ore is that the copper plate is the anode, and the electricity is passed for 30 seconds at a current density of 1 A / m2. φ (composite aluminum material X c) ^ composite_material I-C, carbon is vapor-deposited by a conventional method, and the pores of the polymer film are filled with carbon. (Composite material Π-D) ϊ inch composite brocade material ID, impregnated the composite aluminum material with lead ion concentration: 0.5 mol / 1 of water solution for 2 minutes, and then in a dryer at 80 ° C Middle-drying 'lead compounds (lead oxide) are filled in the pores of the polymer film' and these composite aluminum materials n_A, n_B, n_c, n_D are removed, and the polymer film (η) is removed to produce a metallic material substrate (10) The composite aluminum material IH-A, mB, mc, and In-D with fine spots (丨 4) made of locally conductive substances are arranged on the surface. These composite aluminum materials ha, III-B, III-C, and In_D correspond to the third composite metal material (3) (composite aluminum material III-A) of the present invention having a structure as shown in FIG. 3 (a) (B). The aluminum material Π-A was immersed in acetone for one minute to remove the polymer -29- (24) (24) 200302160 _ M 'stigma S1 a composite aluminum material Π-α composed of fine spots arranged by lead. (Composite aluminum material 111-Β) The composite material ΙΙ-Β was immersed in ketone for 1 minute to remove the polymer _M 'to obtain a composite aluminum material ΙΙΙ-B composed of fine spots arranged by copper. (Composite aluminum material 111 · C) The composite material II-C was immersed in 90 t of warm water for 3 minutes to remove the high # + ¾ g ', and a composite aluminum material III-C composed of fine spots arranged by carbon was obtained. Next, in each of the embodiments, each of the above-mentioned composite aluminum materials was subjected to an etching treatment under any one of the following conditions a and b, to produce aluminum materials for electrodes for electrolytic capacitors No. 1 to 19 shown in Table 1. In Comparative Example No. 20, an aluminum material (10) without a polymer film (1 1) was subjected to an etching treatment. [Etching Condition A] The composite aluminum material was immersed in 80 t of a first electrolyte (1 mol / L hydrochloric acid + 3.2 mol / L1 sulfuric acid aqueous solution), and a DC current of 0.2 A / cm2 was applied for 100 seconds. Carved electrolytic uranium. Furthermore, the first electrolytic solution (1.5 mol / L hydrochloric acid + 0.05 6 mol / L1 oxalic acid aqueous solution) was immersed at 90 ° C, and chemical uranium etching was performed for 10 minutes. [Uranium engraving condition B] The above composite aluminum material was immersed in a 10% aqueous solution of ferrous chloride at 50 ° C for 10 minutes, and then taken out and washed. As a result, only the pore portion of the polymer film or the minute spot portion of the highly conductive substance is chemically etched. Furthermore, 'Immerse with -30- (25) (25) 200302160 7 5 ° C second electrolyte (5% hydrochloric acid + 10% sulfuric acid aqueous solution)' with a DC current of 0.2 A / cm2 for 100 seconds Electrolytic etching. Then, a chemical uranium engraving was applied in the same solution for 10 minutes. Regarding the electrode aluminum material for electrolytic capacitors etched in the above examples and comparative examples, the groove diameters and groove intervals of the etching grooves were measured. Measurements are shown in Table 1. It should be noted that more than half of these measurement sacral tanks are within this range. On the one hand, each of the etched electrolytic capacitor electrode aluminum materials was treated with a boric acid bath 350V, and the capacitance was measured. The electrostatic capacity of 0.20 is a relative value of 100%, as shown in Table i. -31-(26) 200302160 Table 1 Comparison of Examples 3 5 A 1.0-6.0 2.Ο-6.0 130 2 IA 2 3 5-B 0.8 ～ 7.0 1.0-4.0 125 3 IB 2 — 2 3 One A 1.0-4.0 1.0-4.0 140 4 IC 10 5 7-A 1.0 ～ 8.0 4.0 to 10.0 120 5 ID 1 5 7-A 1.0 to 8.0 4.0 to 10.0 120 6 II-A 2 3 5 Pb A 1.0 to 5.0 3.0 to 5.0 145 7 II-A 2 3 5 Pb B 0.8 ^ 6.0 2.0 to 4.0 140 8 II-B 2 2 3 Cu A 1.0 to 3.5 1.0 to 4.0 135 9 II-B 2 2 3 Cu B 0.8 to 4.5 1.0 to 8.0 135 10 II-C 10 5 7 CA 1.0 to 7.0 4.0 to 10.0 125 11 II -C 10 5 7 CB 0.8 to 7.5 4.0 to 9.0 125 12 II-D 1 5 7 Pb oxide A 1.0 to 7.0 4.0 to 10.0 125 13 II-D 1 5 7 Pb oxide B 1.0 to 7.5 4.0 to 9.0 125 14 III-A 2 (excluded) 3 5 Pb A 1.0 to 5.5 2.5 to 5.5 130 15 III-A 2 (excluded) 3 5 Pb B 0.84.5 1.5 to 4.5 125 16 III-B 2 (excluded) 2 3 Cu A 1.0 ～ 4.0 1.5 ～ 4.5 130 17 III-B 2 (excluding) 2 3 Cu B 0.8 ～ 4 .5 1.0 to 3.5 125 18 III-C 1〇 (excluded) 5 7 CA 1.04.5 3.5 to 10.5 130 19 III-C 1〇 (excluded) 5 7 CB 0.8 to 7.0 9.0 to 9.5 125 20 Aluminum substrate A only 0.7-4.0 Nonuniformity 100 From the results in Table 1, the etched grooves of the electrolytic capacitors used in each example have a uniform hole diameter and space as compared with the comparative example. It is confirmed from the increase in the expansion ratio that a high capacitance can be obtained. On the one hand, in the comparative example, it was found that the etching grooves were combined to form huge grooves, and the groove intervals were not uniform. The terms and expressions used here are for explanation and are not limited to interpretation. The features shown and described here do not exclude the equivalent -32- (27) 200302160, and I have to consider the request of this invention. Various deformations in the range are also [commercial use fields] The composite metal material of the present invention is based on the fine pattern of the polymer film, which can produce high-density and uniform etching, and it is difficult to use the groove as a base point in the tunnel. Combining the deepening of the etch to increase the surface area and increase the miniaturization of the electrostatic capacitor and the high performance of the electrolytic capacitor, it is feasible to assemble the miniaturization and high performance of this electrolytic capacitor machine. [Brief description of the drawings] Fig. 1 (A) A longitudinal sectional view showing one type of through-putting method of the first metal material of the present invention, and Fig. 1 (B) is a 1B-sectional view of Fig. 1 (A). Fig. 2 (A) is a longitudinal sectional view showing an embodiment of the first metal material of the present invention, and Fig. 2 (B) is a 2B-sectional view of Fig. 2 (A). Fig. 3 (A) is a longitudinal sectional view showing an embodiment of the second metal material of the present invention, and Fig. 3 (B) is a 3B-sectional view of Fig. 3 (A). Comparison table of main components T: Thickness 10 · Metal material substrate Allowable. Slots for regular columns. Hence the moment state, quantity. The electronic form of the further device is in the form of the mode _ 1 B line and the form of the mode-2 B line. The mode of the mode-3 B line is -33- (28) 200302160 1 1: polymer film 1 2: pores P: interval D: Diameter 1 2 (1 3): Highly conductive material 1 4: Fine spots -34-