3CC544 A6 B6 哩濟部中夬標準局員工消Φ合泎社印製 五、發明説明（1 ) 發明之領域 、 本發明偽鬭於一種金屬箔之連鑛霄解製法，待別是關於 銅箔之電解製法。 發明之背景 依照金羼之品質及金颶箔之用途，有各種金羼箔之製法 ,但以棍壓製法及鬣解製法最普遍。 在金羼箔之輥歷製法中，金屬像藉通過罹壓篛，同時用 棍壓榨金羼而被辊製成。在辊壓之情況，為了製造較薄金 靥箔，轎歷技術極為複雜，並在施加拉力、控制韫之距離 等方面會産生問題。又，一般認為欲形成之金羼箔寬度方 向厚度之均勻性，由於棍形式所造成之限制，而不會永逮 一定。 又，電解製法近來己被廣泛地用來製迪鏑箔，待別是欲 用於印刷霄路板之鋦層合板之鋦箔。此製法如下。卽，如 附圈所示之電解鋦箔製造裝置1之例之剖面圈，一霜流被 通過在一大型陰極輥4 (其下部被浸漬於包含於電解槽2内 之鋦霉解液3中作為陰極）與一不溶性陽極5作為相對《極 之間，同時藉由隈極之電解液供應缝陳6供應電解液，以 連續鎪鎘在钃4之表面上，且沈稹之金羼鋦7自辊4之表面 被連鑛廢棄。 此法具有之待徽為，所得鋦箔8之平均厚度可薙控制供 應電流之量而被容易地控制，亦可容易地獾得薄鋦箔。 對於用於印刷霣路板之鋦箔，因需要具有極离純度之鋦 ，在輥壓製造鋦箔之情況，必須輥製具有高純度之銅作為 {請先閲讀背面之注意事項再填，薄本頁) 裝 訂 炎'"* 本纸張尺度適用中國國家橒準丨CNS)甲4規格（210X297公董1 3 ㈣ 544 A6 B6 經濟部中夬標準局員工消費合作杜印製 五、發明説明（2 ) 原料，但電解鏑箔之製法具有待擻為，具有可能含雜質之 廢鋦等可被用作原料。 即，《解鋦箔之製造的前述待微在於，在製迪霣解銅箔 時，通常使用硫酸鋦浴，且由於鐮於硫酸鋦浴中之沈積電 位較其他金靥之沈積電位更贵重，邸使在其他金屬成份被 包含於硫酸鋦浴中，此等其他金靥成份並未自硫酸銅浴沈 稹，因此霣解箔製造裝置可完成純化之角色。 然而，銅通常包含徽量鉛而來自廢銅之許多鉛被潺合 於硫酸鋦浴中。結果，鉛於硫酸鋦浴中之含量隨著電解之 進展逐漸增加，最後鉛成為硫酸鉛沈稹於硫酸鋦浴中。如 此沈積之硫酸鉛里粒子狀態分散於硫酸鋦浴中，有時發生 的是，分散的碕酸鋦粒子被沈積於鋦箔内，與鐧一起沈積 在陰極上。 在具有厚度較厚的鋦箔之慵況.可使用鋦箔，邸使硫酸 鉛之粒子存在於鑼箔内亦然，但含有硫酸鉛粒子之鋦箔無 法被用來形成一具有厚度約10tf η或更薄之印刷霣路作為 近來微細的印刷霣路板，因此，在錮箔之電解製造中，具 有問題是，無法實際製成具有厚度不厚於20 mb之薄鋦箔 。因此，開於具有厚度為20« b或以下之較薄銅箔.經常 使用蠼歷銪箔。 又，在霣解製迪鏑箔中，由於傅統上鉛合金被用作陽槿 ，所得鋦箔中硫酸鉛及金羼鉛之沈積具有大問鼸，且實際 上，》加入硝酸锶等共沈澱鉛合成並藉邋濾移除之。 近來，在鋦箔之«解製造中，使用一其上形成有含鉑基 裝......................訂 {請先閲讀背面之注*'事項再填窝本頁) 本紙張尺度適用中圉國家標準（CNS)甲4規格<210X297公釐>4 30S544 經濟部中夬標準局員工消费合作社印製 A6 B6 五、發明説明（3 ) 金羼之翥化物塗膜之薄膜形成金颶基齷稱'為DSE(因次安定 性霄極）所組成之不溶性金屬電極，如美國專利43187 94號 ,因此可防止硫酸鋦浴被自傅統陽極溶解之鉛之混合所污 染，但如上所述，鋦原料所含之鉛被堆積於電解液内以沈 澱硫酸鉛，雖然其量很小，其會在銅箔上産生不良彩響， 卽使頻率低於上述情況亦然。 另外，由於鉛量與使用鉛合金電極之慵況比較時很小， 所欲目的仍無法充分達成，邸使藉在使用鉛電極情況實施 之共沈澱法亦然，又.由於僅硫酸鉛之極細絮狀沈澱物被 形成，很難藉使用一手段如過濾等充分除去絮狀沈澱物。 發明之槪述 為解決前述傳統技術之間題，得以完成本發明，本發明 之目的為提供一種金屬箔之製法，其中，其可防止混合於 硫酸邇浴所溶解之金屬原料的鉛成份沈積於金羼箔因而劣 化金羼箔之特性。 本發明之另一目的為提供一種金屬箔之電解製法，其實 質上可省略自霣解浴除去鉛之作業。 特別是，本發明之又一目的為提供一種具有優異品質之 金屬箔之連鏞製法。 上述目的可藉下述本發明予以遽成。 即，依照本發明之一態樣，提供一種金靥箔之《解製法 ,其包含使用一不溶性電極作為陽栅，其具有一由形成在 薄膜成形金羼基黼上之不透氧塗膜上，銥與鉅之禊合《化 物所組成之霣極活性塗膜，並在陽極霄位高於在《解質浴 --------------------------- ------------..................... 裝...........................訂 {請先閱讀背面之注意事項再填寫本頁) 本纸張尺度適用中國國家搮準（CNS)f 4规格（210x297公釐）$3CC544 A6 B6 Printed by the staff of the Central Standards Bureau of the Ministry of Economy and Economy, printed by Helusha V. Description of the invention (1) The field of the invention, the method of the invention is to solve the method of continuous mining of a metal foil, not to mention copper foil The electrolytic method. Background of the invention According to the quality of Jin Yi and the use of gold hurricane foil, there are various methods of making Jin Yong foil, but the most popular is the method of stick pressing and the method of decomposing. In the roll calendaring method of Jinyin foil, the metal image is made by rolling by pressing the grate while pressing Jinyong with a stick. In the case of rolling, in order to manufacture thinner gold foil, the car calendar technology is extremely complicated, and it will cause problems in applying tension and controlling the distance of the yoke. In addition, it is generally believed that the uniformity of the width and thickness of the gold foil to be formed is not always constant due to the limitation caused by the form of the stick. In addition, the electrolytic manufacturing method has recently been widely used to make dysprosium foil, but not to be used for printing the laminated foil of the laminated sheet of the road board. This method is as follows. By the way, the profile circle of the example of the electrolyzed foil manufacturing device 1 shown in the attached circle, a frost stream is passed through a large cathode roller 4 (the lower part of which is immersed in the solution 3 of the lycium mold contained in the electrolytic cell 2 As a cathode) and an insoluble anode 5 as the opposite electrode, and the electrolyte is supplied through the electrolyte supply slit 6 of the Kuma electrode, with continuous cadmium cadmium on the surface of the strontium 4, and Shen Zhen ’s Jin Yugan 7 self-roller The surface of 4 was abandoned by continuous mine. This method has the following features: the average thickness of the obtained foil 8 can be easily controlled by controlling the amount of supply current, and the thin foil can be easily obtained. For the foil used to print the road board, because of the need for extremely pure lithium, in the case of rolling to manufacture the foil, the copper with high purity must be rolled as {please read the precautions on the back before filling. This page) Binding Binder '" * This paper size is applicable to the Chinese National Standards (CNS) A 4 specifications (210X297 Gong Dong 1 3 ㈣ 544 A6 B6 Ministry of Economic Affairs China Consumer Standards Bureau employee consumption cooperation du printing five, invention description (2) Raw materials, but the production method of electrolytic dysprosium foil has a waiting process, and waste ramie, etc., which may contain impurities can be used as raw materials. That is, the aforementioned waiting for the manufacture of liquefaction foil lies in the production of copper When using foil, the sulphate bath is usually used, and because the deposition potential of the sickle in the sulphate bath is more expensive than the deposition potential of other gold talc, the other metal components are included in the sulphate bath. It is not precipitated from the copper sulfate bath, so the foil-making equipment can complete the role of purification. However, copper usually contains trace amounts of lead and much of the lead from waste copper is combined in the sulfate sulfate bath. As a result, lead is in sulfuric acid With the content of The progress gradually increased, and finally the lead became lead sulfate precipitated in the sulfate sulfate bath. The particles of lead sulfate deposited in this way were dispersed in the sulfate sulfate bath, and sometimes it happened that the dispersed aluminate particles were deposited on the foil It is deposited on the cathode together with the flash. In the case of thick foil, the foil can be used, so that the particles of lead sulfate exist in the gong foil, but the foil containing lead sulfate particles cannot It is used to form a printed circuit board with a thickness of about 10tf η or thinner as a recently fine printed circuit board. Therefore, in the electrolytic manufacturing of foil, there is a problem that it cannot be actually produced with a thickness not less than 20 Thin thin foil of mb. Therefore, it is made of thin copper foil with a thickness of 20 «b or less. Lili europium foil is often used. In addition, in the production of didysprosium foil, the lead alloy is used. As a sun hibiscus, the deposition of lead sulfate and gold lead in the resulting foil has a big problem, and in fact, it is synthesized by adding coprecipitated lead such as strontium nitrate and removed by sloppy filtration. Recently, the solution In manufacturing, a platinum-containing Installed ................... Order (please read the note on the back * 'before filling the nest page) This paper standard is applicable to China National Standard (CNS ) A4 specifications < 210X297mm > 4 30S544 A6 B6 printed by the Employee Consumer Cooperative of the Central Bureau of Standards and Economics of the Ministry of Economic Affairs V. Description of the invention (3) The film formation of the film of Jinyi ’s suicide compound is called DSE (DSE ( Because of the instability of the insoluble metal electrode, such as U.S. Patent No. 43187 94, it can prevent the sulfate bath from being contaminated by the mixture of lead dissolved from the anode, but as mentioned above, the raw material contains Lead is deposited in the electrolyte to precipitate lead sulfate. Although its amount is small, it will cause bad color sound on the copper foil, even if the frequency is lower than the above. In addition, because the amount of lead is very small when compared with the use of lead alloy electrodes, the desired purpose cannot be fully achieved. The co-precipitation method implemented by the use of lead electrodes is also the same, and because only lead sulfate is extremely fine The flocculent precipitate is formed, and it is difficult to sufficiently remove the flocculent precipitate by using a means such as filtration. The purpose of the invention is to solve the aforementioned problems between the conventional technologies and to complete the present invention. The object of the present invention is to provide a method for manufacturing a metal foil, in which it can prevent the lead component mixed in the metal raw material dissolved in the sulfuric acid bath from being deposited in Jinyin foil thus deteriorates the characteristics of Jinyin foil. Another object of the present invention is to provide an electrolytic production method of metal foil, which can substantially omit the operation of removing lead from the enzymatic bath. In particular, another object of the present invention is to provide a method for producing continuous yokes of metal foil with excellent quality. The above objects can be achieved by the following invention. That is, according to one aspect of the present invention, there is provided a "decomposition method" of gold-tallow foil, which includes using an insoluble electrode as an anode grid, which has an Combined with Juzhi's "The extremely active coating film composed of chemical compounds, which is higher in the anode position than in the" Resolution Bath ---------------------- " ----- ------------........................ Installed ... ................ order {please read the precautions on the back before filling in this page) This paper size is applicable to China National Standard (CNS) f 4 specifications (210x297 mm) $
If.. 經濟部中央標準局貝工消费合作社印製 -4- —il .：j * - f * i 五、 發明説明（4 ) Iff } )\ji ,....-... 1 内 之 m 霣 在 隔 極 上 形 成 不 溶 性 氣 化 物 時 之 霣 位 下 將 m 霣 1 1 I 沈 積 在 鵰 槿 上 〇 1 1 又 9 依 照 本 創 作 之 另 態 樣 提 供 一 種 金 鼷 箔 之 爾 解 製 先 1 1 法 9 其 為 鋦 箔 之 爾 解 製 法 9 其 包 含 η 保 持 跚 禳 電 位 离 於 禰 背 1 I 準氳電極霣位16伏特或Κ上 $ 將 氣 化 鉛 沈 積 在 隔 極 上 使 之 注 1 I 碲 酸 酸 性 疎 酸 钃 電 解 浴 内 之 鉛 可 被 沈 積 作 為 二 氣 化 鉛 因 1 項 1 1 而 金 颺 萡 被 沈 積 在 除 槿 上 〇 再 % % 另 外 依 照 本 m 作 之 另 一 戆 樣 f 提 供 一 種 使 用 不 溶 性 金 本 頁 丨 鼷 霣 極 之 金 鼷 萡 之 霣 解 製 法 其 包 含 用 具 有 莫 耳 比 為 1 1 1 1 3 7之銥與艇 之 禊 合 氣 化 物 作 為 霪 極 活 性 塗 m 塗 佈 矚 槿。 1 1 _ 式 之 簡 犟 說 明 1 訂 _ 1為* -剖面鼸 •顧示瞒箔之霣解製缠装置之例 3 1 1 發 明 之 细 節 說 明 1 | 以 下 詳 述 發 明 作 0 1 1 在 金 钃 箔 » 通 常 為 鑭 箔 之 9 解 製 缠 中 9 主 要 是 除 去 包 含 1 政 於 所 製 成 之 金 臑 箱 内 之 雜 霣 〇 在 金 麵 成 份 為 雑 霣 中 包 含 1 1 於 碲 酸 酸 性 霣 解 浴 内 具 有 低 溶 解 度 之 鉛 成 份 之 去 除 為 一 最 丨 1 重 要 課 颶 9 已 提 出 各 種 m 程 惟 有 效 製 程 尚 未 發 展 出 〇 1 1 在 本發嘀中 » 已 發 現 鞴 保 持 疏 酸 酸 性 鬣 解 浴 内 之 鵰 檷 電 1 1 位 高 於 禰 準 氫 霣 檯 電 位 1 . 6伏特或Μ上 ，霣解浴中之鉛成 ί i 份 沈 稹 在 隈 極 之 表 面 上 成 為 二 氣 化 鉛 〇 -j* I 又 發 規 電 解 浴 内 m 蠹 堆 積 之 鉛 沈 積 在 隔 檷 之 表 面 上 * 成 1 ! I 為 疏 酸 鉛 > 但 當 m 極 之 電 位 高 於 樣 準 氫 霣 位 1 . 6伏特成K 1 ] 上 時 9 碘 酸 鉛 在 陽 檯 之 表 面 上 被 氣 化 成 二 氣 化 鉛 * 而 二 氧 1 1 本紙張尺度適用中阐國家標準（cnsM4規格πιοχ 297公嫠）6修正貫 309544 A6 B6 經濟部♦夬標準局員工消费合作社印製 五、發明説明（5 ) 化鉛以相當強沈積物沈積在陽極之表面上'，沈稹物随箸電 解之進展而生長。 另方面，若陽極之電位對樣準氫電極低於1.6伏待時，Pb2+ 變成較Pb4+M安定，溶解會發生或鉛以硫酸鉛覆蓋陽極之 表面，其對電解而言是不希望的。 另發現如此沈稹之二氣化鉛具有導霉性，並可被用作霉 極之一部份，在二氣化鉛沈積在《化物隈極之表面上之情 況，沈積的二氣化鉛在製造霄解金羼箔時，不會顯示特別 對二氣化鉛之高霣位，陽極之霣位幾乎未變，且電解«歷 幾乎未增加。 本發明人等基於上述發現己成功地完成本發明。 在本發明中，為了沈積並除去包含於電解浴内之鉛，重 要的是，將電解浴内之鉛沈積在陽極上成為二氣化鉛，並 以二氯化鉛安定地配置在暘極上，如上所述.且為此目的 ，需要藉保持陽極之霄位在离於樣摩氫霄極之電位至少 1 . 6伏特實施鬣解。 然而，在傅统金靨箔之霄解製迪中，須注意降低電解電 壓。闋於陽極，在使用塗佈有由氣化銥輿氧化鉅所組成之 二元複合氧化物之隱極之情況，為了降低《解電壓.實際 上可增加銨/鉅之莫耳比或在陽極表面上提供氣化銥。 另方面，在用於本發明金匾箔之電解製造的罎極中，複 合氣化物中鉋之量被增加以安定電極，同時電極（》槿）之 «位被提离至高於標華《電極電位1.6伏特或以上.其為 鉛以二氧化鉛沈積時之電位並以二氣化鉛安定地存在於陽 表紙張又度適用中國國家標準ICNSI甲4规格（210x297公釐ΐγ ^ 裝......................訂 (請先閱讀背面之注意事項再填窝本頁) 竣濟部"夬標準局員工消Φ合作杜印製 A6 B6五、發明説明（6 ) 極上，為此目的，銥與鉋之金颶奠耳比為各Ta。又，若 鉋之量被增至超過Ir: Tatb = 3: 7時，陽極之壽命迅速被 縮短，因此，不希望钽之*被增至超遇該比率。 又，當陽極之霄位被增加時，鈍氣化物容易被形成在活 性塗膜與薄禊形成金羼基臞間之界面，以實質上縮短作為 鬣極之壽命，因此，較好是在電極活性塗膜與基《間形成 一不透氣塗層。 不透氣塗靥可與習用者相同，但由於《位較高，随著二 氧化鉛靥之形成，雖然其為微不足道，但電位仍被逐漸升 高，塗層較佳為具有离度不透氣功能。 關於不透氧層，可使用各種材料，但以具有鈦與鉋之半 導電性複合氣化物較佳。鈦與鉅之複合氣化物為四價鈦與 五價鉅之複合氣化物。普通半導鬣性氣化鈦使用有的氧之 缺陷結構，即，非化學計量性.惟藉加入鉅，由鈦與鉅之 半導體複合氧化物所组成之不透缜層具有之特性為.邸使 氱化鈦藉氧之移動被改變成不具缺陷结構之氣化物.由於 五價鉅之共存並進入相同氧晶格内，導電性被_持。另外 ,有效手段是，藉加入鉑，因鉑之導霣性而使鈍化不易發 生〇 鈦與鉅之複合*化物，或其翥量被有意地控制以安定氣 化物之鈦與鉅之《化物，亦被用作不透氣層，在此情況， 其並非由塗佈一含鈦或钽之塗佈液齷在由薄膜成形金靨所 組成之基讎表面上，接著如傅統般燒结所製成者，而是由 諝整如形成陶瓷氛醑予以堍结所製成者。對於該燒结材料 各紙張尺度逋用中國國家標準（CMS)甲4規格ι_210χ297公釐1 〇〇 {請先閱讀背面之注意事項再填寫本頁) 30S544 A6 B6 毯濟部中夬櫟準局員工消f合作钍印製 五、發明説明（7 ) 之塗佈，可使用一調整氛圍至一弱邇原氛獮之方法，例如 ，霣漿火焰塗佈法、火焰塗佈法、反應性PVD(物理蒸氣沈 積）法等。 電極活性材料在皤極上之塗佈可鞲塗佈一含有銥及鉅之 溶液，然後在氣化氛圈中燒结塗膜而被形成。 例如，塗佈液體偽在加熱下於其内溶解有5〜20重量％ 氣化組之水性鹽酸溶液内溶解一特定量之氣化銥而被製成 ,或塗佈液驩愾藉溶解有機鉅化合物如鉅酸5-丁酯於溶_ 如丁酵等内，將約10重量％稀釋鹽酸作為安定劑加入其中 ，然後在加熱下以一定*之氰化銥溶解於其内而被製成。 將如此製備之塗佈液龌塗佈在其上形成有不透氣層並薙 普通熱分解法爍結之基嫌表面上。塗佈僳11_塗佈法、钃 塗佈法或噴霧塗佈法實施之。對燒結溫度並無待殊限制， 但為了改良耐蝕性並保持高電位，燒結溫度較佳為450〜 550t：。氛園較佳為氯化氛画如空氣等。另外，塗佈及燫 結之步骤被重複資施以形成所欲塗佈*之塗佈。 電極活性塗膜内之銥輿鎔（Ir: Ta)之莫耳比較佳為1: 1 〜3: 7。若銥之比例太大，使Ir: Ta莫耳比不落在上述範 園内時，有降低電位之傾向，罨解霣浴内之沈稹鉛之機能 會降低，同時，塗膜之摩度會加摩，而發生電極強度之問 題。又，若鉅之比例較大，使Ir: Ta之其耳比不會落在上 述範園内時，有縮短霣極壽命之傾向。 在本發明方法中，在形成在薄膜成形金羼基體上之不透 氣塗膜上具有由銥與鉋之複合氧化物所組成之電極活性塗 {請先閱讀背面之注^-事項再赛寫本頁) 裝If .. Printed by the Beigong Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs -4- —il.: J *-f * i 5. Description of the invention (4) Iff}) \ ji, ....-... 1難 霣 deposits m 霣 1 1 I on the hibiscus under the position of the insoluble gasification on the septum. 1 1 and 9 According to another aspect of this creation, a gold foil is provided for the first solution 1 1 Method 9 It is the solution of the aluminum foil. Method 9 It contains η Keeping the electric potential away from the back 1 I quasi-knob electrode at 16 volts or K $ Deposit the vaporized lead on the separator to make it note 1 I Telluric acid The lead in the acidic strontium electrolysis bath can be deposited as lead dioxide, due to 1 item 1 1 and Jin Yangyu is deposited on the hibiscus.%% In addition, another sample f according to this m is provided for use Insoluble gold page 丨 The method of solution of the gold eyebrows of 銹 霣 极, which contains a molar ratio of 1 1 1 1 3 7 Together with the gas purification boats compound as electrode active coating downpour m hibiscus coating visions. 1 1 _ Brief description of the formula 1 Set _ 1 to be *-profile 頸 • Gu Shi concealing the example of the foil unwinding device 3 1 1 Detailed description of the invention 1 | The following detailed description of the invention is 0 1 1 in gold Metal foil »Usually 9 of lanthanum foil. Unwinding 9 is mainly to remove the impurities contained in the gold box made by the government. The gold surface is composed of 難 霣. Contains 1 1 in the acidic solution of telluric acid. The removal of lead components with low solubility in the bath is one of the most important. 1 Important course Hurricane 9 Various processes have been proposed but effective processes have not yet been developed. 1 1 In this issue »It has been found that the serotonin has been kept in the acidic and acidic bath The power of the sacred kibble 11 is higher than the potential of the quasi-hydrogen platform at 1.6 volts or Μ, and the lead in the bath decomposes into ί i parts of Shen Zhen on the surface of the Kuji electrode. I also issued regulations for lead deposition in the electrolytic bath * 1 on the surface of the sills! I is lead succinate > but when the potential of the m pole is higher than the sample quasi-hydrogen level of 1.6 volts to K 1] 9 lead iodate on the surface of the balcony It is gasified to lead digasification * and dioxygen 1 1 This paper scale is applicable to the national standard (cnsM4 specification πιοχ 297 gong) 6 revised through 309544 A6 B6 Ministry of Economic Affairs Printed by the Employee Consumer Cooperative of the Bureau of Standards and Technology V. Description of invention (5) The lead compound is deposited on the surface of the anode with fairly strong deposits, and the sinker deposits grow with the progress of the galvanic electrolysis. On the other hand, if the potential of the anode is lower than 1.6 volts to the sample quasi-hydrogen electrode, Pb2 + becomes more stable than Pb4 + M, dissolution will occur or lead will cover the surface of the anode with lead sulfate, which is undesirable for electrolysis. It is also found that such Shen Zhen's second vaporized lead is mold-inducing and can be used as a part of the mildew pole. In the case where the second vaporized lead is deposited on the surface of the compound Kuma pole, the deposited lead dioxide is in manufacturing When resolving the Jinyi foil, it will not show the high position of the special two-gas lead, the position of the anode is almost unchanged, and the electrolytic history has hardly increased. The present inventors have successfully completed the present invention based on the above findings. In the present invention, in order to deposit and remove the lead contained in the electrolytic bath, it is important that the lead in the electrolytic bath is deposited on the anode to become lead dioxide, and it is stably arranged on the sink electrode with lead dichloride. As mentioned above, and for this purpose, it is necessary to carry out the hydrolysis by keeping the anode electrode at a potential of at least 1.6 volts away from the sample electrode. However, in the solution of Fu Tongjin's foil, we must pay attention to reducing the electrolytic voltage. For the anode, in the case of using the hidden pole coated with a binary composite oxide composed of vaporized iridium and oxidized giant, in order to reduce the "decompression voltage. In fact, it is possible to increase the ammonium / gigantic molar ratio or at the anode Vaporized iridium is provided on the surface. On the other hand, in the altar pole used for the electrolytic manufacturing of the gold plaque foil of the present invention, the amount of planing in the composite gasification is increased to stabilize the electrode, and at the same time, the position of the electrode ("hibiscus") is lifted away from the standard "electrode" The potential is 1.6 volts or more. It is the potential when lead is deposited with lead dioxide and is stably present on the surface of the paper with lead dioxide. It is also applicable to the Chinese National Standard ICNSI A 4 specifications (210x297 mm lγ ^ Pack ... ............. Order (please read the precautions on the back before filling the nest page) Junji Ministry of "Quality and Standards Bureau staff consumption Φ cooperation du printed A6 B6 V. Description of invention (6) Extremely, for this purpose, the gold hurdle ratio of iridium to planer is each Ta. Furthermore, if the amount of planer is increased to exceed Ir: Tatb = 3: 7, the life of the anode is quickly shortened Therefore, it is undesirable that the tantalum * is increased to exceed this ratio. Also, when the anode level is increased, passive vapors are easily formed at the interface between the active coating film and the thin layer forming the gold base, to substantially To shorten the life span of the electrode, it is preferable to form an air-impermeable coating between the electrode active coating film and the substrate. The tungsten can be the same as the conventional one, but due to the higher position, with the formation of lead dioxide tungsten, although it is negligible, the potential is still gradually increased, and the coating preferably has the function of air tightness. Various materials can be used for the oxygen-permeable layer, but the semi-conductive composite gasification compound with titanium and planer is preferred. The composite gasification compound of titanium and giant is a composite gasification compound of tetravalent titanium and pentavalent giant. Vaporized titanium uses the oxygen defect structure, that is, non-stoichiometric. However, by adding giant, the impermeable layer composed of titanium and giant semiconductor composite oxide has the characteristics of. The movement of oxygen is changed to a gaseous substance with no defect structure. Due to the coexistence of the five-valent giant and into the same oxygen lattice, the conductivity is maintained. In addition, an effective means is that by adding platinum, due to the conductivity of platinum Passivation is not likely to occur. The compound of titanium and giant, or its amount is intentionally controlled to stabilize the vaporized titanium and giant compound, also used as a gas-impermeable layer, in this case, it is not by coating A coating liquid containing titanium or tantalum On the surface of the base metal composed of shaped gold, it is then sintered like a traditional system, but it is made by sintering and forming a ceramic atmosphere. The paper size of the sintered material is different. Use Chinese National Standard (CMS) A4 specifications ι_210χ297mm 1 〇 (please read the precautions on the back and then fill out this page) 30S544 A6 B6 Blanket Ministry of Economic Affairs, the Central Bureau of Quarantine Liquor staff cooperation and thorium printing V. Invention For the coating of (7), a method of adjusting the atmosphere to a weak atmosphere can be used, for example, the bead flame coating method, flame coating method, reactive PVD (physical vapor deposition) method, etc. The coating of the electrode active material on the electrode can be formed by coating a solution containing iridium and giant, and then sintering the coating film in a gas atmosphere. For example, the coating liquid is prepared by dissolving a specific amount of vaporized iridium in the aqueous hydrochloric acid solution of 5 to 20% by weight of the vaporization group in the solution under heating, or the coating liquid may dissolve the organic giant Compounds such as 5-butyric acid giant acid are dissolved in butyrate, etc., about 10% by weight diluted hydrochloric acid is added as a stabilizer, and then dissolved under heating with a certain amount of iridium cyanide. The coating liquid prepared in this way is coated on the base surface on which the air-impermeable layer is formed and is formed by ordinary thermal decomposition. The coating method 11_ coating method, metal coating method or spray coating method is implemented. There is no special limitation on the sintering temperature, but in order to improve the corrosion resistance and maintain a high potential, the sintering temperature is preferably 450 ~ 550t :. The atmosphere garden is preferably a chlorinated atmosphere painting such as air. In addition, the steps of coating and sintering are repeated to form the desired coating *. The molar ratio of iridium and iridium (Ir: Ta) in the electrode active coating is preferably 1: 1 to 3: 7. If the ratio of iridium is too large, so that Ir: Ta molar ratio does not fall in the above-mentioned fan garden, there is a tendency to lower the potential, the function of decondensing Shen Zhen lead in the bath will be reduced, and the friction of the coating film will be reduced. Gamo, and the problem of electrode strength occurs. In addition, if the ratio is large, the ear ratio of Ir: Ta will not fall within the above-mentioned fan garden, and there is a tendency to shorten the life of the ear pole. In the method of the present invention, an electrode active coating composed of a compound oxide of iridium and a planer is formed on the air-impermeable coating film formed on the thin-film formed gold-substrate substrate {please read the note on the back ^-Matters before writing Page)
-1T 本纸張尺度適用中國國家標準iCXSl甲4規格1210x297公*1 9 A6 B6 五、發明説明（8 ) 膜之一不溶性電極被用作陽極，罨解偽在電解霣浴内之鉛 沈積在陽極表面上成為不溶性二氣化鋁之陽極電位下被實 施，且金屬箔僳以電解方式沈積在陰極上。在本發明中， 所得金羼箔並未含有包含於電解質浴内之鉛，不需要使用 特定手段以除去電解質浴内之鉛成份，而可以電解方式製 成具有優異品質之金饜箔。 以下以下列實施例詳述本發明。 實施例1 經濟部中夬標準局員工消費合作社印製 鈦板被用作基龌以製備一陽極。首先，在藉喷砂法粗化 鈦之表面後，在85¾下將鈦基醱浸泡於20重量％硫酸之水 溶液内3小時，以實施其表面之活化。 關於不透氣層，將一藉溶解四氛化鈦於10重置％氯化钽 之水溶液中，使鈦對鉅之比率變成9: 1莫耳比所製成之塗 佈液髏藉刷子塗佈在基體上，然後在550t：下於流動空氣 中燒結10分鐘。藉重複前述步驟4次，形成由0.02莫耳/ #金屬所組成之氣化物塗膜。 可證實所形成之氣化物塗禊具有充分導電性。 举後，藉熱分解，將一藉溶解三氰化銥於10重量％氰化 鉅之鹽酸水溶液内，使銥對鉅之比率變成40: 60莫耳所製 成之塗佈液醱塗佈在前述氧化物塗膜上。即，藉一刷子将 塗佈液«塗佈在塗有導電性氣化物之基體上，如上所述， 並在60 =乾燥後，在5401下於流動空氣中燒结10分鐘。 薙重複前述步驟20分鐘，可得一含有15g/nf銥之塗膜之霄 極。 裝..................、tT (請先閱讀背面之注悉事項再璘寫本頁) 衣纸張尺度適用中國國家標準丨CNS)甲4規格1 210x297公釐 10 A6 B6 經濟部中央標準局員工消Φ合作社印製 五、發明説明ί 9 ) 當如此所得之鬣極在20安培/ d#下作為陽極於60υ下 1 5 0 g /升之硫酸内之單一電極電位被測定時，電位對標準 氫電極為1 . 6 5伏待。 然後，在電解液溫度為60C及霜流密度為6 0安培/dnf 下，使用前述電搔作為陽極及鈦作為陰極，於由150g /升 含Ippbi鉛之硫酸鋦及100g/升硫酸所組成之電解液内實施 電解，同時除去沈積在陰極上之銅時，可看到在陽極表面 上棕色二氣化鉛之沈稹。又，隨著電解時間之進展，二氣 化鉛之形成量會增加。另外，在硫酸酸性電解浴内之電解 中，電解可在電流密度為300安培/ dm2下實施2300小時， 因而可證實其使用赛命充分長，而電極之電位略高。 另方面.除了銥對鉋之莫耳比被改變成70: 30以外，以 如上述相同條件製成之電極情況下，電極之單一電位為 1 . 58伏待，而當霜解愾在如上述相同條件下實施時，未曾 看到在電極表面上二氣化鉛之形成。 實施例2 除了進一步將實施例1之不透氣的氣化物與鉑混合，使 鈦與鉅之總和對鉑之莫耳比變成75: 25而電極活性塗層之 銥對鉅之莫耳比被改變成30: 70以外，依照實施例1相同 程序，製備一電極（陽極）。如實施例1所潮之電極之單一 電極霉位對標準氫竜極為1.68伏特，其較實施例1之電極更 高。 當電極被用作實施例1電解之陽極時，形成二氣化鉛在 電極表面上之機能與實施例1者相同.由實施電解之結果 裝.....................訂 (請先¾讀背面之注意事項再蜴寫本頁)-1T This paper scale is applicable to the Chinese national standard iCXSl A4 specification 1210x297 g * 1 9 A6 B6 V. Description of the invention (8) One of the insoluble electrodes of the membrane is used as an anode, and the lead deposited in the electrolytic bath is solved The anode surface which becomes insoluble aluminum dioxide on the anode surface is implemented at the anode potential, and the metal foil is deposited on the cathode electrolytically. In the present invention, the obtained gold foil does not contain the lead contained in the electrolyte bath, and no special means is required to remove the lead component in the electrolyte bath, and a gold tumbler foil with excellent quality can be produced electrolytically. The present invention will be described in detail in the following examples. Example 1 Titanium plates were used as substrates to prepare an anode by printing at the Consumer Cooperative of the Ministry of Economic Affairs, China National Standards Bureau. First, after roughening the surface of the titanium by sand blasting, the titanium-based compound was immersed in a 20% by weight sulfuric acid aqueous solution at 85 ° C for 3 hours to activate the surface. Regarding the air-impermeable layer, a coating solution made by dissolving titanium tetrachloride in 10% aqueous solution of tantalum chloride to make the ratio of titanium to giant into 9: 1 molar ratio is applied by brush On the substrate, it was then sintered in flowing air for 10 minutes at 550t :. By repeating the foregoing steps 4 times, a vaporized coating film composed of 0.02 mol / # metal is formed. It can be confirmed that the formed vapor coating has sufficient conductivity. After lifting, by thermal decomposition, a coating solution prepared by dissolving iridium tricyanide in 10% by weight of giant cyanide hydrochloride aqueous solution so that the ratio of iridium to giant becomes 40: 60 moles is coated on On the aforementioned oxide coating film. That is, apply the coating liquid «to the substrate coated with the conductive vapor by a brush, as described above, and after 60 = drying, sinter in flowing air at 5401 for 10 minutes. After repeating the above steps for 20 minutes, a coating film containing 15g / nf iridium can be obtained. Install .................., tT (please read the notes on the back before writing this page) The size of the clothing paper is applicable to the Chinese national standard 丨 CNS) A4 specifications 1 210x297 mm 10 A6 B6 Printed by the staff of the Central Standards Bureau of the Ministry of Economic Affairs Φ Cooperative Society V. Description of invention ί 9) When the so-obtained electrode is used as an anode at 20 amperes / d # at 60 υ 1 50 g / litre of sulfuric acid When the potential of the single electrode inside is measured, the potential is 1.65 volts to the standard hydrogen electrode. Then, at an electrolyte temperature of 60C and a frost flow density of 60 amps / dnf, using the aforementioned electroclamp as the anode and titanium as the cathode, composed of 150g / liter of Ippbi lead-containing sulfuric acid and 100g / liter of sulfuric acid When electrolysis is carried out in the electrolyte and the copper deposited on the cathode is removed at the same time, it is possible to see the sedimentation of brown digasified lead on the surface of the anode. Also, as the electrolysis time progresses, the amount of lead dioxide formed will increase. In addition, in electrolysis in a sulfuric acid electrolysis bath, electrolysis can be carried out at a current density of 300 amperes / dm2 for 2300 hours, so it can be confirmed that the use life is sufficiently long, and the electrode potential is slightly higher. On the other hand, except that the molar ratio of iridium to planer is changed to 70: 30, in the case of electrodes made under the same conditions as above, the single potential of the electrode is 1.58 volts, and when the cream solution is as above When implemented under the same conditions, the formation of lead dioxide on the electrode surface has never been seen. Example 2 In addition to further mixing the gas impermeable gaseous compound of Example 1 with platinum, the total molar ratio of titanium and giant to platinum becomes 75: 25 and the iridium of the electrode active coating is changed to giant molar ratio An electrode (anode) was prepared according to the same procedure as Example 1 except for 30:70. The single electrode mildew position of the electrode wetted in Example 1 is 1.68 volts to the standard hydrogen, which is higher than the electrode of Example 1. When the electrode is used as the anode of the electrolysis of Example 1, the function of forming lead dioxide on the surface of the electrode is the same as that of Example 1. The result of the electrolysis is ... ........ Order (please read the notes on the back before writing this page)
表纸張尺度適用中圉國家標準iCNSi® 4规格（210x 297公釐H A6 B6 經濟部中央標準局員工消费合作社印製 五、發明説明（10 ) ，電解可在300安培/ duf下連绩實施254 0小時，其顯示充 分的電極赛命。 實施例3 如實施例1般處理一鈦基體並藉電漿嘖塗法將在1350=C 下於氬氛圍中燒结氣化鈦與海綿狀鈦之10: 1混合物3小時 所得之10〜50iiB粉末噴在基體上，以在其上形成具有厚 度為50Wm之不透氣的氣化物之塗膜。由X射線繞射分析之 結果，可證實塗膜形成Magnel〖相氣化鈦。 其表面上形成有一由銥與鉅之複合氣化物所組成之電極 活性塗膜，如實施例1般。關於其組成物，電極活性塗膜 内銥對鉅之莫耳比為32: 68。 在60Ϊ：下於150g/升硫酸内單一霄極電位（在20安培/d# /)對檫準氫電極為1.69伏特，在含鉛溶液中，二氣化鉛之 棕色塗膜被形成在陽極之表面上，而二氣化鉛之形成随電 解之進展而增加。 另方面，在其中電極活性塗膜内銥輿鉋之比為29: 72之 電極之情況，在如上述相同條件下，單一電極電位對標準 氫電極為1.73伏待，因此可充分證實二氣化鉛沈積在陽極 表面上之充分機能，但當電解傜在電流密度為300安培/ dm2下，如實施例1於硫酸浴中實施時，陽極之壽命為1 , 300 小時，其被降低很多。 如上所述，在本發明中，由於使用一不溶性霄極作為陽 極，該不溶性電極具有：由銥與鉅之複合氣化物所組成之 電極活性塗膜，在形成在薄膜成形金屬基髓上之不透氣塗 本纸張尺度適用中國國家標準ICNS丨甲4規格ί210χ 297公釐！12 3544 於·9.25修正丨 年月曰補充; A7 B7 五、發明说明（U ) 膜 活 中 霣 t 鉛 霣 人 各 _ 經濟部中央橾準局負工消費合作社印製 上，如此之金靨箔之霣解製法中，Μ檷爾位鶼控鋪霣概 性塗臢之組成物而被控制成一 «位，Μ賻包含於電解浴 之鉛沈積在«極上成為不溶性二氣化鉛*而金屬箔係Μ 解方式沈稹在除極上 > 不會發生有»雉鷗槿壽命之間題 包含於II解浴中之鉛成份沈積在Μ檯之表面成為二氣化 而無沈積在金颸箔內•因而具有優興品霣之金颺箔可Μ 解方式製成而不必使用頫外除鉛之手段。 雖然本削作參照特定具驩例詳述之，任何热悉此技鷗之 士當可明白，在不脫鐮本創作之精神及外可對其作 種改變及修正。 式之主要部份代表符號之銳明 霱解鋦箔製造裝置 霣解播 鋦霣解液 除極輥 不溶性曝禳 霣解液供應鼸隙 沈積之金屬鋦 銅箔 Ί — ΤΓ------^------訂-------政 I (請先閲讀背面之炷$項再填寫本頁) 本紙張尺度逋用中國國家梂牟（CNS)A4规格（210Χ297公釐）13修正賓The table paper scale is applicable to the Chinese national standard iCNSi® 4 specifications (210x 297 mm H A6 B6 Printed by the Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs V. Invention description (10), and the electrolysis can be implemented continuously at 300 amps / duf 254 0 hours, it shows sufficient electrode life. Example 3 Treat a titanium substrate as in Example 1 and sinter vaporized titanium and spongy titanium in an argon atmosphere at 1350 = C by plasma coating method No. 10: 10 ~ 50iiB powder obtained from the mixture for 3 hours is sprayed on the substrate to form a coating film with a gas-impermeable vaporized material with a thickness of 50 Wm on it. The result of X-ray diffraction analysis can confirm the coating film Magnel 〖phase vaporized titanium is formed. On its surface is formed an electrode active coating film composed of a composite vapor of iridium and giant, as in Example 1. Regarding its composition, the electrode active coating film contains iridium to giant. The ear ratio is 32: 68. At 60Ϊ: under 150g / L sulfuric acid, the single potential (at 20 amps / d # /) is 1.69 volts for the sassafras hydrogen electrode. In the lead-containing solution, the color of lead dioxide is brown. The coating film is formed on the surface of the anode, and the formation of lead dioxide is The progress of the solution increases. On the other hand, in the case where the electrode in the electrode active coating film has an iridium-to-plane ratio of 29: 72, under the same conditions as above, the single electrode potential is 1.73 volts to the standard hydrogen electrode, so It can fully confirm the sufficient function of the deposition of lead dioxide on the surface of the anode, but when the electrolysis is carried out at a current density of 300 amperes / dm2, as in Example 1 in a sulfuric acid bath, the life of the anode is 1,300 hours, It is reduced a lot. As mentioned above, in the present invention, since an insoluble electrode is used as the anode, the insoluble electrode has an electrode active coating film composed of iridium and giant composite vaporized material, which is formed on the film-forming metal The size of the air-impermeable coated paper on the base is applicable to the Chinese national standard ICNS 丨 A 4 specifications ί210χ 297 mm! 12 3544 Amended on 9.25 丨 Supplement of the date of the month; A7 B7 Fifth, the description of the invention (U) The film is lively t 雜 霣 人 each_ Printed on the Consumer Labor Cooperative of the Central Department of Economics of the Ministry of Economic Affairs. In such a method of manufacturing gold foil, the M.P.R.«Bit, the lead contained in the electrolytic bath deposited on the« pole becomes insoluble digasified lead ** and the metal foil is the M solution method Shen Zhen on the depolarization > does not happen there »The life between the pheasant and hibiscus is included in II. The lead component in the solution bath is deposited on the surface of the M table to become two gasification without being deposited in the gold foil. Therefore, the gold foil with excellent products can be made by the M solution without removing the lead. Means. Although this work is described in detail with reference to specific examples, any person who knows the skill of the gull can understand that it can make various changes and corrections without departing from the spirit of Kamamoto's creation. A representative symbol of the sharp and clear solution for the manufacture of aluminum foil. The device for dissolving the liquid for dissolving the depolarizing roller. The insoluble exposure solution for the depolarizing roller. The metal foil for the deposition of manganese. Τ — ΤΓ ------ ^ --- --- Subscribe --- Politics I (please read the 炷 $ item on the back and then fill in this page) The size of this paper is based on China National Amu (CNS) A4 specification (210Χ297mm)