200825212 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種電解用電極之再活化方法，气杂π 電極之電解活性已經降低，原因在於含錯化合物 物及氧化銻之電極表面沉積物於工業電解例如銅°制: 電解或鍍銅電解中沉積於電解用電極之I ^ ^ 別為其中金屬或金屬合金製成之一薄膜藉真空；=寺 於藉真空濺鍍而由閥金屬或閥金屬合金所製成之二二風 基板表面上，以及一電極催化劑層經形成 ：極 表面之-電解用電極。 m寻膜之 【先前技術】 =工業電解例如銅箔製造電解或鍍銅電解之電解中， 目前為止係使用一種氧生成用電極，其中含有氧化銥之恭 極催化劑層係直接形成來塗覆㈣金屬諸如鈦及知或= 金屬合金所製成之電極基板之表面。 〜 ，但於此種氧生成用電極中，t使用—段時間或更久护， 閥金屬（諸如鈦及组）或閥金屬合金所製成之電極守 電極催化劑層諸如氧化銀間之界面腐姓，鈍化態層形成ς 該基板之表面上。如此難以達成再活化處理，須_ 表面直到形成新表面或須新製備電極基板。 另一方面，於其中金屬（諸如鈕及鈮）製成之具有厚声由 U微米至3微米之薄膜，藉真空賤鍍（諸如離子鍍覆^ :成於由閥金屬(諸如鈦及鈕)或閥金屬合金所製成之一 电極基板表面上’及含氧化銥之電極催化劑層形成以塗覆 312ΧΡ/發明說明書(補件)/96·12/9614296ι 6 200825212 於薄膜表面之-電解用電極用作為氧生成用電極之 :利=)板與催化劑層間之界面不會被腐糊如:考 、土但=於前述氧生成用電極中，當該電極係用於銅箱製 以之电解或n銅之電解時，於銅_製造之情 解液所含㈣物之硫酸錯或含硫酸錯及氧化錄之:： 物沉積於該電解用電極表面上；而於電解鍍銅之情況下口， 作為電解液所含錯化合物之氧化錯或含氧化錯及氧化録 之化合物：積於該電解用電極表面上。電解時，電解液所 含之錯係呈氧化錯沉積，氧化錯為良好導體；而銻 化銻沉積，氧化銻為不良導栌。 ^ 〇个良V體。此外，於電解結束時， 於良好導體之氧化錯轉成屬於又肖道 将风屬於不良導體之硫酸鉛。此外， 作為錯化合物之硫㈣或氧Μ及氧輯（各自為電極表 =沉積物）’於電解開始時或電解結束時或於電解過程 中，由電解用電極表面落下。結果’前述氧生成用電極具 有電流分布變不均句之缺Λ . ^ ^ j之缺，結果導致銅箔之缺陷厚度起 因；且無法長時間連續用作為電解用電極。 於此專情況下，於v 、+、各丄 於則述乳生成用電極中，藉 sC〇TCH-BRITE (註冊商標）（Sumit〇m。3M Umited 製造 之拋先機）刮除用於電解之電解用電極表面，含錯化合物 或含錯化合物及氧化銻之電極表面沉積物被移除，藉此再 活化電解用電極。 士但於别心生成用電極中’於該電極連續使用3個月 時，使用丽述拋光機難以再活化電解用電極。 312XP/發明說明書(補件)/96-12/96142961 n 200825212 曰本專利案2761751 專利文件1 【發明内容】 本發明之一目的係解決前述相關技 ，可有效且容易地移除沉積於電解用電去極之表缺:上： 方法，兮♦妒田兩 巧及虱化銻之屯極表面沉積物之 用•解：：柄电極之電解活性於工業電解例如銅箔製造 解中已經降低’原因在於含錯化合物或 :仏物及氧化銻之電極表面沉積物 屬合金所製成之薄膜係藉真心 上，及Λ 閥金屬合金所製成之電極基板表面 及一电極催化劑層經形成來塗覆該薄膜之一表 種电解用電極上’藉此方法達成電解用電極之再活化。 =，為了達成前述目的，本發明之第一態樣係提供一 ^解用電極之再活化方法’包含連續進行—酸處理步 打’^由於含錯化合物之電極表面沉積物沉積於電解用電 極之表面上而其電解活性已經降低之—電解用電極， 於含5%質量比至3_量比石肖酸及&㈣質量比至2⑽質量 ^過氧化氫之水溶液中；以及進行一高壓水洗務步驟，'於 =〇 MPa至⑽MPa之壓力下’進行高壓水洗條以去除 呑含金口之弘極表面沉積物，藉此經由酸處理步驟及高壓 :滌步驟等二步驟而再度活化其活性已經降低之電解7用 電極。 &此外，本發明之第二態樣係提供包含前述酸處理步驟及 馬壓水洗務步驟等二步驟之再活化方法，其中該電極表面 312XP/發明說明書(補件)/96-12/96142961 8 200825212 沉積物為含有鉛化合物及氧化銻之電極表面沉積物。 此外’本發明之第三態樣係提供包含前述酸處理步驟及 高壓水洗滌步驟等二步驟之再活化方法，其中該鉛化合物 為氧化鉛。 此外’本發明之第四態樣係提供包含前述酸處理步驟及 高壓水洗滌步驟等二步驟之再活化方法，其中該電解為鍍 銅之電解。 此外，本發明之第五態樣係提供包含前述酸處理步驟及 咼壓水洗滌步驟等二步驟之再活化方法，其中該電解用電 極為經由藉真空濺鍍將金屬或金屬合金製成之一薄膜形 成於由閥金屬或閥金屬合金所製成之一電極基板之表面 上，以及以電極催化劑層塗覆該薄膜之一表面所製備之一 電解用電極。 此外，本發明之第六態樣係提供包含前述酸處理步驟及 高壓水洗滌步驟等二步驟之再活化方法，纟中該薄膜為由200825212 IX. INSTRUCTIONS OF THE INVENTION: TECHNICAL FIELD The present invention relates to a method for reactivation of an electrode for electrolysis, in which the electrolysis activity of a gas-paste π electrode has been lowered due to electrode surface deposits containing a wrong compound and cerium oxide. In the industrial electrolysis, such as copper: electrolysis or copper electrolysis, deposited in the electrode for electrolysis, I ^ ^ is a film made of metal or metal alloy by vacuum; = temple by vacuum sputtering by valve metal or On the surface of the second air substrate made of the valve metal alloy, and an electrode catalyst layer are formed: the electrode for the surface of the electrode. [Previous technique] = Industrial electrolysis, for example, copper foil manufacturing electrolysis or copper electrolysis electrolysis. Currently, an oxygen generating electrode is used, in which a cerium oxide-containing chevron catalyst layer is directly formed for coating (4) The surface of an electrode substrate made of a metal such as titanium and a metal alloy. ~ , but in such an oxygen generating electrode, t is used for a period of time or longer, a valve metal (such as titanium and group) or a valve metal alloy electrode electrode layer such as silver oxide interface rot The surname, the passivated layer is formed on the surface of the substrate. It is so difficult to achieve reactivation treatment, the surface must be formed until a new surface is formed or an electrode substrate must be newly prepared. On the other hand, a film made of a metal (such as a button and a crucible) having a thick sound from U micron to 3 micron is coated by vacuum crucible (such as ion plating): formed by a valve metal (such as titanium and a button). Or on the surface of one of the electrode substrates made of the valve metal alloy and the electrode catalyst layer containing ruthenium oxide is formed by coating 312 ΧΡ / invention specification (supplement) / 96·12/9614296ι 6 200825212 on the surface of the film - for electrolysis The electrode is used as an electrode for oxygen generation: the interface between the plate and the catalyst layer is not smeared. For example, in the electrode for oxygen generation, the electrode is used for electrolysis in a copper box. Or in the electrolysis of copper, the sulfuric acid mis- or sulfuric acid-containing error and oxidation recorded in the copper-containing electrolyte solution are: deposited on the surface of the electrode for electrolysis; and in the case of electrolytic copper plating The oxidative error or the compound containing the oxidative error and the oxidation recorded as the wrong compound contained in the electrolyte is accumulated on the surface of the electrode for electrolysis. During electrolysis, the error contained in the electrolyte is oxidized and deposited, and the oxidation is a good conductor; while yttrium oxide is deposited, yttrium oxide is a poor guide. ^ A good V body. In addition, at the end of the electrolysis, the oxidation of the good conductor is converted into lead sulfate which belongs to the poor conductor and which belongs to the poor conductor. Further, sulfur (tetra) or oxygen oxime (each electrode table = deposit) as a wrong compound is dropped from the surface of the electrode for electrolysis at the start of electrolysis or at the end of electrolysis or during electrolysis. As a result, the electrode for oxygen generation has a defect that the current distribution becomes uneven. The absence of ^ ^ j results in a defect in the thickness of the copper foil, and cannot be used continuously as an electrode for electrolysis for a long period of time. In this special case, in the electrode for the generation of v, +, and 丄, the sC〇TCH-BRITE (registered trademark) (Sumit〇m. 3M Umited manufacturing machine) scraping for electrolysis The surface of the electrode for electrolysis, the surface deposit of the electrode containing the wrong compound or the compound containing the wrong compound and cerium oxide is removed, thereby re-activating the electrode for electrolysis. When the electrode is used continuously for 3 months, it is difficult to reactivate the electrode for electrolysis using the Lisho polishing machine. 312XP/Invention Manual (Supplement)/96-12/96142961 n 200825212 Patent No. 2761751 Patent Document 1 SUMMARY OF THE INVENTION One object of the present invention is to solve the aforementioned related art, and to effectively and easily remove deposition for electrolysis. Electrode depolarization: On: Method, 兮 ♦ 妒 两 两 虱 and 虱 锑 锑 • • • • • • Solution: The electrolysis activity of the stalk electrode has been reduced in industrial electrolytic, such as copper foil manufacturing solutions 'The reason is that the film containing the wrong compound or the electrode surface deposit of the cerium and cerium oxide is made of an alloy, and the surface of the electrode substrate and the electrode catalyst layer formed by the valve metal alloy are formed. To apply an electrolysis electrode to one of the films of the film 'by this method, reactivation of the electrode for electrolysis is achieved. In order to achieve the above object, the first aspect of the present invention provides a method for re-activation of an electrode for use, including continuous-acid treatment stepping, and deposition of an electrode surface deposit containing a wrong compound on an electrode for electrolysis On the surface of which the electrolysis activity has been reduced - the electrode for electrolysis is contained in an aqueous solution containing 5% by mass to 3 liters of tartaric acid and <(4) mass ratio to 2 (10) by mass of hydrogen peroxide; and performing a high pressure In the water washing step, 'at a pressure of 〇 MPa to (10) MPa', a high-pressure water-washing strip is removed to remove the ruthenium-containing ruthenium surface deposit, thereby re-activating it through two steps of an acid treatment step and a high pressure: polyester step. An electrode for electrolysis 7 whose activity has been lowered. In addition, the second aspect of the present invention provides a two-step reactivation method comprising the foregoing acid treatment step and a horse water washing step, wherein the electrode surface 312XP/invention specification (supplement)/96-12/96142961 8 200825212 Sediment is an electrode surface deposit containing lead compounds and antimony oxide. Further, the third aspect of the present invention provides a reactivation method comprising two steps of the foregoing acid treatment step and high pressure water washing step, wherein the lead compound is lead oxide. Further, the fourth aspect of the present invention provides a reactivation method comprising two steps of the foregoing acid treatment step and high pressure water washing step, wherein the electrolysis is electrolysis of copper plating. In addition, the fifth aspect of the present invention provides a reactivation method comprising the foregoing two steps of an acid treatment step and a pressure water washing step, wherein the electrode for electrolysis is one of a metal or a metal alloy by vacuum sputtering. The film is formed on a surface of an electrode substrate made of a valve metal or a valve metal alloy, and an electrode for electrolysis is prepared by coating one surface of the film with an electrode catalyst layer. Further, the sixth aspect of the present invention provides a reactivation method comprising the foregoing two steps of an acid treatment step and a high pressure water washing step, wherein the film is
選自於由鈦、鈕、鈮、锆及铪所組成之組群中之至少一成 員之金屬或其合金所製成之一薄膜。 此外，本發明之第七態樣係提供包含前述酸處理步驟及 高壓水絲步料二步驟之再活化方法，其中該電極催化 劑層為含氧化銥之電極催化劑層。 此外，本發明之第八態樣係提供包含前述酸處理步驟及 高壓水洗滌步驟等二步驟之再活化方法，進一步包含於去 除電極表面沉積物後形成一電極催化劑層。 種電解用電極之再活 此外，本發明之第九態樣為提供一 312XP/發明說明書(補件)/96-12/96142961 9 200825212 化方法，&含連續進行一驗處理步驟 之電極表面沉積物沉積於電解用之、3錯化合物 活性已經降低之一電解用電極，浸潰二表面上而其電解 貝里比之驗金屬虱乳化物水溶液；—酸處理 、、主A film selected from the group consisting of a metal of at least one member of the group consisting of titanium, knob, yttrium, zirconium and hafnium or an alloy thereof. Further, the seventh aspect of the present invention provides a reactivation method comprising the foregoing acid treatment step and two steps of a high pressure water filament step, wherein the electrode catalyst layer is an iridium oxide-containing electrode catalyst layer. Further, the eighth aspect of the present invention provides a reactivation method comprising the two steps of the acid treatment step and the high pressure water washing step, and further comprising forming an electrode catalyst layer after removing the electrode surface deposit. Further, the ninth aspect of the present invention provides a 312XP/invention specification (supplement)/96-12/96142961 9 200825212, and an electrode surface containing a continuous processing step. Sediment deposited in electrolysis, the activity of the 3 wrong compound has been reduced by one of the electrodes for electrolysis, impregnated on the two surfaces and the electrolysis of the Berri ratio of the metal emulsifier aqueous solution; - acid treatment, the main
於含有由5%質量比至30%質量比硝 ' …又/R 質詈p 貝里比峭酸及5%質量比至20% 二Γο: 液;以及進行一高壓水洗務步驟， 除兮人鈕《力、，^ 進仃鬲壓水洗滌以去 除^氣及鍊之笔極表面沉積物，藉此再活化其 降低之該電解用電極。 、 ^ =外’本發明之第十態樣係提供包含驗處理步驟、酸處 .理乂驟及高壓水洗滌步驟等前述三步驟之再活化方法，盆 中5亥電極表面沉積物為含有鉛化合物及氧化銻之電極表 面沉積物。 书《衣 發明之第十一態樣係提供包含鹼處理步驟、酸 處理步驟&高壓水洗蘇步驟等前述三步驟之再活化方 馨法’其中該錯化合物為硫酸錯。 此外，本發明之第十二態樣係提供包含驗處理步驟、酸 處理步驟&高壓水洗務步料前豸三步驟之再活化方 法’其中該電解為用於銅箔製造之電解。 此外本發明之第十三態樣係提供包含鹼處理步驟、酸 處理y驟及鬲壓水洗滌步驟等前述三步驟之再活化方 法制其中该電解用電極為經由藉真空濺鍍將金屬或金屬合 金製成之一薄膜形成於由閥金屬或閥金屬合金所製成之 一電極基板之表面上，以及以電極催化劑層塗覆該薄膜之 312XP/發明說明書(補件)/96-12/9614296:1 10 200825212 一表面所製備之一電解用電極。 此外本务明之第十四態樣係提供包含驗處理步驟、酸 處理步驟及高壓水洗滌步驟等前述三步驟之再活化方 法，其中該薄膜為由選自於由鈦、组、銳、錯及給所组成 -之組群中之至少一成員之金屬或其合金所製成之一薄膜。 此外，本發明之第十五態樣係提供包含驗處理步驟、酸 處理步驟及高壓水洗膝步驟等前述三步驟之再活化方 _法其中°亥电極催化劑層為含氧化銥之電極催化劑層。 此外，本發明之第十六態樣係提供包含驗處理步驟、酸 處理步驟及高壓水洗滌步驟等前述三步驟之再活化方 法進一步包含於去除電極表面沉積物後形成一電極催化 劑層。 根據本發明，藉由酸處理步驟，係以含确酸及過氧化氮 之水溶液浸泡含氧化錯作為錯化合物或氧化鉛及氧化銻 之電極表面沉積物，可溶解及去除氫氧化錯及氧化錄；以 _及藉將剩餘氧化鉛及氧化銻接受高壓水洗之高壓水洗滌 步驟’可以物理方式去除氧化錯及氧化録。此外，於錯化 合物為硫酸鉛之情況下，藉由使用氫氧化鈉水溶液之鹼處 理步驟，含硫酸鉛或硫酸鉛及氧化銻之電極表面沉積物被 轉成氫氧化鉛；接著，經由使用含硝酸及過氧化氫之水溶 •夜之敲處理步驟，氫氧化鉛及氧化銻可被溶解及去除；以 ，及經由將剩餘鉛和銻接受高壓水洗之一高壓水洗滌步 =可以物理方式去除鉛及銻。如此可有效且容易地去除 3釔化合物或含鉛化合物及氧化銻之電極表面沉積物，藉 3ΐ2χΡ/發明說明書(補件)/96-12/96142961 η 200825212 此讓電解用電極之再活化變容易。 【實施方式】 將進一步詳細說明本發明如後。 '於電解為例如鍍銅之電解之情況下，含有氧化錯作為錯 化口物或含有氧化鉛及銻之電極表面沉積物係沉積於電 解用電極表面上，因此電解用電極活性降低。於此種情況 下’於本發明中，首先，如一酸處理步驟，其活性已 低之電解用電極浸潰於含有5%f量比至3_量比确酸 及5%貝篁士比至2〇%質量比過氧化氮之水溶液中經歷$小時 至15小時’藉此氫氧化錯及氧化娣溶解於含确酸及過氧 化=之水溶液中且被移除。接著，如一高壓水洗務步驟， =侍電解用電極於由5〇 MPa至1〇〇 Μρ&之壓力下接受言 壓水洗滌，以物理方式去除剩餘之錯化合物及銻化合t 藉此再活化其活性已經降低之電解用電極。 另一方面，於電解為例如用於銅箔製造之電解之情況 • I，含硫酸錯作為錯化合物或含硫酸鉛及銻之電極表面沉 知物，儿考貝於电解用電極之表面上，因而電解用電極之活性 降低。於此種情況下，於本發明中，如一驗處理步驟，盆 :性已經降低之電解用電極浸潰於由5%質量比至質 里比之驗金屬氫氧化物水溶液中經歷i小時至3小時，藉 :匕含鉛及銻之電極表面沉積物中之硫酸鉛藉氫氧化鈉： 液而被轉成氫氧化鉛。接著，如一酸處理步驟，電解用 ^極浸潰於含有5%f量比至3_量比確酸及5%質量比 20%質量比過氧化氫之水溶液中經歷5小時至15小時， 312XP/發明說明書(補件)/96·12/96ΐ4296ι 200825212 藉此氫氧化鉛及氧化銻溶解於含硝酸及過氧化鉛之水溶 液中且被移除。此外，如一高壓水洗滌步驟，所得電解用 電極於由50 MPa至100 MPa之壓力下接受高壓水洗滌， —以物理方式去除剩餘之鉛化合物及銻化合物，藉此再活化 ♦ 其活性已經降低之電解用電極。 於酸處理步驟中，當於含硝酸及過氧化氫之水溶液中之 硝酸濃度超過30%質量比時或當於含硝酸及過氧化氫水溶 液中之過氧化氫濃度超過2〇%質量比時，不僅電解用電極 之基板例如鈦開始腐蝕，同時電解用電極之電極催化劑層 也可能剝離。另一方面，當硝酸濃度低於5%質量比或當 過氧化氫濃度低於5%質量比時，溶解氫氧化鉛及氧化銻 之反應不充分。因此理由故，要求含硝酸及過氧化氫之水 洛液中之硝酸濃度係由5%質量比至3〇%質量比；以及含硝 酸及過氧化氫之水溶液中之過氧化氫濃度係由5%質量比 至20%質量比。此外，電解用電極浸潰於含硝酸及過氧化 ❿氫之水溶液中之浸潰時間要求為5小時或以上，且較佳為 15小時或以上。 尸於驗處理步驟中，鹼金屬氫氧化物較佳為氳氧化鈉或氫 氧1鉀。當水溶液中之鹼金屬氫氧化物濃度超過2〇%質量 比日寸，毛解用電極之基板例如鈦開始腐蝕，因此要求水溶 液中之鹼金屬氫氧化物濃度不超過20°/◦質量比。另一方 面，當水溶液中之鹼金屬氳氧化物濃度低於5%質量比時， 轉化3 I及銻之電極表面沉積物巾之硫酸錯成為氯氧化 氣之反應不充分。如此，要求水溶液中之驗金屬氫氧化物 312XP/發明說明書(補件)/96·12/96142961 200825212 ▲度係由^量比至2_量比。此外，當電解用電極浸 潰於驗金屬氫氧化物水溶液之時3小時之 時，電解用電極之基板例如鈦開始腐韻，因此要求電^用 電極浸潰於驗金屬氫氧化物水溶液之浸潰時間不超過3 小時。 於冋[水洗滌步騾中，為了以物理 之鉛化合物及銻化合物，要电古两> * ㈣ 求问廢水洗務係於由50 MPa 之麼力下進行。當高麼水洗滌之壓力低於50 M=，移除效率低；而當超過刚_時，電解用電極 之基板例如鈦可能被鏜孔。 ^卜，如前文說明，財發明中，於電極沉積物移除後， 笔極催化劑層被耗用時，藉如後文說明之方法新形成一電 極催化劑層。 對電解用電極之電極基板，可使用金屬材料，金屬材料 之品質及形狀並無特殊限制，只要具有傳導性以及有適當 •挺度（…㈣⑽）即可。例如，具有良好防姓性之闕金^ :如Ti Ta、Nb及Zr或其合金為宜。當電極基板表面藉 3防姓塗覆之非晶形層❼變成充分防钱性時纟可使用具 有良好傳$性之金屬，諸如銅及銘。視情況需要，電極基 板可，先藉退火、噴砂等接受表面粗化處理，或事先接^ •例如猎酸洗條等表面清潔之物理性前處理或化學性前處 、，著，將金屬製成之薄膜形成於該基板表面上。用來形 成薄膜之五屬並無特殊限制’只要該金屬具有良好傳導性 312XP/發明說明書(補件)/%·12/96142961 200825212 及防㈣，或縣板或電極催化劑層有&好㈣ 。 基板之典型實例包括鈦、|£ U及給及其合金，上述 全部皆具有良好防錄。此等材料對閥金屬例如鈇所制^ 之電極基板具有特佳黏著性。 衣 至於於電極基板上形成此種薄膜之方法，採用藉真 :而形成薄膜之方法。根據真空濺鍍法’容易以無晶：邊 界之非晶形形式獲得薄膜。用於真空濺鍍，可施用多種方 法，諸如直流濺It、高頻誠、電弧離子鑛覆、離 覆及叙狀離子束法。經由適纽定條件可獲得具有所 之物理性質之薄膜，該等條件諸如真空度、基板溫度、^ 靶板之組成或純度、及沉積速率（欲施加之電功率）。因薄 膜形成所得表面改性層之厚度通常係於01微米至1〇微 米之範圍’而可由防蝕性、生產力等有用的觀點中選擇： 如此其表面已經藉形成無晶粒邊界之非晶形層之薄膜而 改性f電極基板可獲得對抗表面熱氧化之絕佳特性，換言 之氧化物膜成長表現之特性顯著。藉脫脂及酸洗條讓市 售純鈦板（TP2B)接受表面清潔所製備之鈦板、及經由藉真 空錢鍍同時使用純鈦板作為標把而於其表©上形成純鈦 薄膜㈣㈣成之—鈦板，各自於電爐中接受加熱處理， 於一大氣壓下均勻溫度分布於由45(rc至6〇〇它經歷〇小 時至5小時且置於可於鈦上形成微小氧化物膜之條件。結 果，比較先前採用之原則鈦板(principle出如簡 pla^e)，後者表面經改性之鈦板顯示顯著差異，諸如色調 為單-色調；未觀察到色彩不均勻度，諸如斑點；氧化物 312XP/發明說明書(補件 y96_12/96142961 200825212 之成長極為均勻’·及氧化物膜之成長速率為緩慢。當非晶 5層之材料組成係由合金組成物所製成而非單一金屬所 衣成犄，此種抑制氧化物膜成長之效果顯著。認為均勻化 以及表面改性層#抗熱氧化之抑制效I，不僅於電極催化 劑層形成步驟（容後詳述）中獲得熱影響之鬆弛，同時也獲 得對抗電解時之電化學氧化之鬆他效應，藉此大為促成電 極耐用性的提升。 然後，其上已經形成薄膜之電極基板係以電極催化劑層 塗^以提供—電解用電極。至於電極催化制，依據用途 而疋’可施用多種已知材料，電極催化劑層並無特殊限 制1於要求耐用性之氧生成反應，適合使用含有紐族金 屬氧化物諸如氧化銥之材料。至於以電極催化劑層塗覆之 方法，多種方法為已知且可適當施用該等方法。以熱分解 ，為典型方法。電極塗覆層之成分金屬之原料鹽類，例如 氯化物、硝酸鹽、烷氧化物及共振化物溶解於溶劑（諸如 鹽酸、硝酸、醇類及有機溶劑）中以形成塗覆液，塗覆液 施用於表面改性基板表面上，於乾職，於氧化氛圍例如 於空氣中，於烤爐中接受加熱處理。 此外，也可制厚財法，其中預先準備金屬氧化物， 將適當有機黏結劑及有機溶劑添加至其中而形成糊料，缺 後將糊料塗覆於電極基板上及烤乾；或應用cvd方法。2 外，金屬氧化物層也可提供作為中間層，採用之方法為其 中於以電極催化劑層塗覆前，前述經表面改性之基板接^ 加熱處理，於其表面上形成極薄之高溫氧化膜層^為中^ 312ΧΡ/發明說明書(補件)/96-12/96142961 16 200825212 層’或接受加熱分解、Cvd方、、表楚 ^ L . n μ , 万法荨。耩此中間層，預期雷 極催化劑層之黏著強度 、/月包 之保罐义里π 獲得基板對熱氧化及電氧化 之保遵效果，因此藉由萁4 # ,,m 精由基板上之溥膜不僅可達成前述主要 效果，同時也可進_牛担 ^ 了也』進步棱升電解用電極之耐用性。 [實施例] =著’㈣參照下列實例說明本發明，但不可解 發明囿限於此。 | [實施例1] + JIS第-類鈦板表面接受使用鐵格網（12G號尺寸） 貝◊處理’及接X於2G%硫酸水溶液（於1()5〇之酸洗條 處理歷¥ 1 〇分# ’藉此進行電極基板之洗條處理。洗條 後之電極基板架設於電弧離切覆裝置内，且接受以純^ 材料之濺鍍塗覆。塗覆條件說明如下。 標靶：JIS第一類鈦圓盤（背面係以水冷卻） 真空度：1.0 X ΙΟ—2托耳（Torr)(導入氬氣滌氣） 施加之電功率：500瓦（3· 〇千伏特） 基板溫度·· 150°C(於濺鍍時） 時間：35分鐘 塗層厚度· 2微米（隨著重量之增加計算） 於濺鍍塗覆後進行X光繞射分析結果，觀察到指定予基 板本體之銳結晶峰以及指定予濺鍍塗層之寬圖樣，以及發 現該塗層為非晶形。 接著，將四氯化銥及五氯化鈕溶解於35g/g鹽酸以形成塗 覆液，然後刷塗於前述已完成濺鍍塗覆處理之基板上。於 312XP/發明說明書(補件)/96-12/96142961 17 200825212 草=v後 >所得基板於空氣循環電爐（於經歷分鐘 日接又熱分解，以形成由氧化銀及氧化紐之固體溶液 所i成之電極催化劑層。至於刷塗一次之塗層厚度，前述 塗覆液之量係設定為相對於銀金屬實質上為U克/平方 ' 米。 重，12次由塗覆至烤乾之操作以製備電解用電極。如 此所4備之電解用電極係於下列條件下接受電解。Included from 5% by mass to 30% by mass of nitric acid, ... / R, 詈p, and 5% by mass to 20% of dioxo: and a high pressure water washing step The button "force," is pressed into the water to remove the electrode surface deposit of the gas and the chain, thereby re-activating the electrode for the reduction. The first tenth aspect of the present invention provides a reactivation method comprising the above three steps, such as a treatment step, an acid treatment step, and a high pressure water washing step. The surface sediment of the 5 hai electrode in the pot is lead-containing. Electrode surface deposits of compounds and cerium oxide. The eleventh aspect of the invention provides a reactivation method comprising the alkali treatment step, the acid treatment step & the high pressure water washing step, and the like, wherein the wrong compound is sulfuric acid. Further, the twelfth aspect of the present invention provides a reactivation method comprising a treatment step, an acid treatment step & a high pressure water washing step before the third step, wherein the electrolysis is electrolysis for copper foil production. In addition, the thirteenth aspect of the present invention provides a reactivation method comprising the alkali treatment step, the acid treatment step, and the pressure water washing step, wherein the electrolysis electrode is made of metal or metal by vacuum sputtering. A film made of an alloy is formed on the surface of an electrode substrate made of a valve metal or a valve metal alloy, and the film is coated with an electrode catalyst layer 312XP/invention specification (supplement)/96-12/9614296 :1 10 200825212 An electrode for electrolysis prepared on a surface. In addition, the fourteenth aspect of the present invention provides a reactivation method comprising the above three steps, such as a treatment step, an acid treatment step and a high pressure water washing step, wherein the film is selected from the group consisting of titanium, group, sharp, and A film made of a metal or alloy thereof of at least one member of the group of constituents. In addition, the fifteenth aspect of the present invention provides a reactivation method comprising the above three steps, such as a treatment step, an acid treatment step, and a high pressure water washing step, wherein the nanoelectrode catalyst layer is an iridium oxide-containing electrode catalyst layer. . Further, the sixteenth aspect of the present invention provides a reactivation method comprising the above three steps, such as a treatment step, an acid treatment step and a high pressure water washing step, which further comprises forming an electrode catalyst layer after removing the electrode surface deposit. According to the present invention, by the acid treatment step, the surface of the electrode containing the oxidized error as the wrong compound or the lead oxide and the cerium oxide is immersed in the aqueous solution containing the acid and the nitrogen peroxide to dissolve and remove the oxidized and oxidized The oxidative and oxidation records can be physically removed by the _ and the high pressure water washing step of the high-pressure water washing of the remaining lead oxide and cerium oxide. Further, in the case where the wrong compound is lead sulfate, the electrode surface deposit containing lead sulfate or lead sulfate and ruthenium oxide is converted into lead hydroxide by an alkali treatment step using an aqueous sodium hydroxide solution; Water-soluble and night-time treatment steps of nitric acid and hydrogen peroxide, lead hydroxide and antimony oxide can be dissolved and removed; and, by washing the remaining lead and antimony with high-pressure water, a high-pressure water washing step = physical removal of lead And 锑. Thus, the electrode surface deposit of the 3 钇 compound or the lead compound and the cerium oxide can be effectively and easily removed, and the reactivation of the electrode for electrolysis is facilitated by the 3 ΐ 2 χΡ / invention specification (supplement) / 96-12/96142961 η 200825212 . [Embodiment] The present invention will be described in further detail as follows. In the case where the electrolysis is electrolysis such as copper plating, an electrode surface deposit containing oxidized oxidization as a staggered or a lead oxide and ruthenium is deposited on the surface of the electrode for electrolysis, so that the electrode activity for electrolysis is lowered. In this case, in the present invention, first, as an acid treatment step, the electrode for electrolysis having a low activity is impregnated to a ratio of 5% f to 3 Å to 0.02 and a ratio of 5% to 2% by mass of the aqueous solution of nitrogen peroxide is subjected to an hour to 15 hours, whereby the hydrolytic and cerium oxide are dissolved in an aqueous solution containing acid and peroxide = and removed. Then, as a high-pressure water washing step, the electrode for electrolysis is subjected to pressure water washing under a pressure of 5 MPa to 1 〇〇Μ ρ & and physically removing the remaining erroneous compound and hydrazine compound t to reactivate it. An electrode for electrolysis having reduced activity. On the other hand, in the case where electrolysis is, for example, electrolysis for the production of copper foil, I, sulfuric acid is used as a fault compound or an electrode surface containing lead sulfate and antimony, and on the surface of the electrode for electrolysis, Therefore, the activity of the electrode for electrolysis is lowered. In this case, in the present invention, as in the case of a treatment step, the electrode for electrolysis having a reduced potency is immersed in an aqueous solution of a metal hydroxide at a ratio of 5% by mass to a mass ratio of 1 hour to 3 hours. Hours, borrowed: lead sulfate in the electrode surface deposits containing lead and antimony was converted to lead hydroxide by sodium hydroxide: liquid. Then, as an acid treatment step, the electrolysis is immersed in an aqueous solution containing 5% by weight to 3% by volume of acid and 5% by mass of 20% by mass of hydrogen peroxide for 5 hours to 15 hours, 312XP /Inventive Manual (Supplement)/96·12/96ΐ4296ι 200825212 The lead hydroxide and cerium oxide are dissolved in an aqueous solution containing nitric acid and lead peroxide and are removed. Further, as a high-pressure water washing step, the obtained electrolysis electrode is subjected to high-pressure water washing under a pressure of 50 MPa to 100 MPa, physically removing the remaining lead compound and antimony compound, thereby re-activation ♦ its activity has been lowered Electrode for electrolysis. In the acid treatment step, when the concentration of nitric acid in the aqueous solution containing nitric acid and hydrogen peroxide exceeds 30% by mass or when the concentration of hydrogen peroxide in the aqueous solution containing nitric acid and hydrogen peroxide exceeds 2% by mass, Not only the substrate of the electrode for electrolysis such as titanium starts to corrode, but also the electrode catalyst layer of the electrode for electrolysis may be peeled off. On the other hand, when the nitric acid concentration is less than 5% by mass or when the hydrogen peroxide concentration is less than 5% by mass, the reaction for dissolving lead hydroxide and cerium oxide is insufficient. Therefore, it is required that the concentration of nitric acid in the aqueous solution containing nitric acid and hydrogen peroxide is from 5% by mass to 3% by mass; and the concentration of hydrogen peroxide in the aqueous solution containing nitric acid and hydrogen peroxide is from 5 % mass ratio to 20% by mass. Further, the impregnation time of the electrode for electrolysis impregnated in the aqueous solution containing nitric acid and hydrogen peroxide is 5 hours or more, and preferably 15 hours or more. In the test treatment step, the alkali metal hydroxide is preferably sodium bismuth oxide or potassium oxyhydroxide. When the concentration of the alkali metal hydroxide in the aqueous solution exceeds 2% by mass, the substrate of the electrode for decapitation such as titanium starts to corrode, and therefore the alkali metal hydroxide concentration in the aqueous solution is required to not exceed 20 ° / ◦ mass ratio. On the other hand, when the concentration of the alkali metal cerium oxide in the aqueous solution is less than 5% by mass, the reaction of converting the sulfuric acid of the surface of the electrode surface of the electrode and the surface of the ruthenium into the chlorinated gas is insufficient. Thus, the metal hydroxide in the aqueous solution is required to be 312XP/invention specification (supplement)/96·12/96142961 200825212 ▲ degree is from the ratio to the ratio of 2 to the amount. In addition, when the electrode for electrolysis is immersed in the aqueous solution of the metal hydroxide for 3 hours, the substrate of the electrode for electrolysis, such as titanium, starts to rot, and therefore the electrode is required to be immersed in the metal hydroxide aqueous solution. The collapse time is no more than 3 hours. In Yu [water washing step, in order to use physical lead compounds and antimony compounds, it is necessary to use electricity and electricity.] (4) The wastewater washing system is carried out under the force of 50 MPa. When the pressure of the high water washing is lower than 50 M =, the removal efficiency is low; and when it exceeds the temperature, the substrate of the electrode for electrolysis such as titanium may be bored. ^b, as explained above, in the invention, when the electrode catalyst layer is consumed after the electrode deposit is removed, an electrode catalyst layer is newly formed by the method described later. A metal material can be used for the electrode substrate of the electrode for electrolysis. The quality and shape of the metal material are not particularly limited as long as they have conductivity and appropriate stiffness (...(4)(10)). For example, a sheet metal having a good anti-surname property: such as Ti Ta, Nb, and Zr or an alloy thereof is preferable. When the surface of the electrode substrate is changed to a sufficient anti-money property by the anti-surname coated amorphous layer, the device can have a good metal, such as copper and Ming. Depending on the situation, the electrode substrate may be subjected to surface roughening treatment by annealing, sand blasting, etc., or in advance, such as physical pretreatment or chemical front treatment such as hunting pickling strips, etc. A film is formed on the surface of the substrate. There are no special restrictions on the five genus used to form the film 'as long as the metal has good conductivity 312XP / invention specification (supplement) /%·12/96142961 200825212 and prevention (four), or county plate or electrode catalyst layer & good (four) . Typical examples of the substrate include titanium, ?U, and alloys thereof, all of which have good anti-recording. These materials have excellent adhesion to electrode substrates made of valve metals such as tantalum. Clothing As a method of forming such a film on an electrode substrate, a method of forming a film by using the film is employed. According to the vacuum sputtering method, it is easy to obtain a film in the form of an amorphous: boundary amorphous form. For vacuum sputtering, a variety of methods can be applied, such as DC Sputter It, High Frequency, Arc Ion Cover, Ion, and Shaped Ion Beam. Films having physical properties such as vacuum, substrate temperature, composition or purity of the target, and deposition rate (electric power to be applied) can be obtained via suitable conditions. The thickness of the surface-modified layer obtained by film formation is usually in the range of 01 μm to 1 μm, and can be selected from the viewpoints of corrosion resistance, productivity, and the like: Thus, the surface thereof has been formed by forming an amorphous layer having no grain boundaries. The film-modified f-electrode substrate can obtain excellent characteristics against surface thermal oxidation, in other words, the oxide film has a remarkable characteristic of growth performance. A titanium plate prepared by surface cleaning of a commercially available pure titanium plate (TP2B) by a degreasing and pickling strip, and a pure titanium film formed on the surface thereof by using a vacuum plate and a pure titanium plate as a standard (4) Titanium plates, each of which is subjected to heat treatment in an electric furnace, and uniformly distributed at a temperature of 45 rc to 6 Torr for a period of from 〇 to 5 hours and placed on a titanium oxide film to form a fine oxide film on titanium. As a result, comparing the previously adopted principle titanium plate (principal is as simple as pla^e), the latter surface of the modified titanium plate shows significant differences, such as the hue is single-tone; no color unevenness, such as spots; Oxide 312XP/Invention Manual (Supplement y96_12/96142961 200825212 is extremely uniform growth'· and the growth rate of the oxide film is slow. When the material composition of the amorphous 5 layer is made of the alloy composition instead of the single metal The effect of suppressing the growth of the oxide film is remarkable. It is considered that the homogenization and the suppression effect of the surface modification layer # against thermal oxidation are not only obtained in the electrode catalyst layer forming step (described later in detail). The relaxation of the sound, as well as the anti-slip effect of electrochemical oxidation against electrolysis, thereby greatly contributing to the improvement of the durability of the electrode. Then, the electrode substrate on which the thin film has been formed is coated with an electrode catalyst layer to provide - Electrode electrode. As for electrode catalysis, various known materials can be applied depending on the application, and the electrode catalyst layer is not particularly limited to an oxygen generating reaction requiring durability, and is preferably used with a metal oxide containing a lanthanum oxide such as cerium oxide. As for the method of coating with the electrode catalyst layer, various methods are known and can be suitably applied. Thermal decomposition is a typical method. Raw material salts of constituent metals of the electrode coating layer, such as chloride, nitric acid The salt, the alkoxide and the resonance compound are dissolved in a solvent such as hydrochloric acid, nitric acid, an alcohol, and an organic solvent to form a coating liquid, and the coating liquid is applied to the surface of the surface-modified substrate, for example, in an oxidizing atmosphere, for example, In the air, it is heated in the oven. In addition, it can also be used to make thick money, in which metal oxides are prepared in advance, A binder and an organic solvent are added thereto to form a paste, and the paste is applied to the electrode substrate and baked after the absence; or the cvd method is applied. 2, the metal oxide layer can also be provided as an intermediate layer by using the method. In order to coat the surface of the electrode catalyst layer, the surface-modified substrate is subjected to heat treatment to form a very thin high-temperature oxide film layer on the surface thereof, which is a medium 312 ΧΡ / invention specification (supplement) / 96- 12/96142961 16 200825212 Layer 'or accept heat decomposition, Cvd square, and table ^ L. n μ , Wanfa 荨. 中间 中间 中间 中间 中间 中间 中间 中间 中间 中间 中间 中间 中间 中间 中间 中间 中间 中间 中间 中间 中间 中间 中间 中间 中间 中间 中间 中间 中间 中间 中间 中间 中间 中间 中间 中间 中间 中间 中间 中间 中间π obtains the effect of the substrate on thermal oxidation and electro-oxidation. Therefore, the ruthenium film on the substrate can not only achieve the above-mentioned main effects by 萁4 # , m, but also can be improved. The durability of the electrode for electrolysis. [Embodiment] = [4] The present invention will be described with reference to the following examples, but the invention is not limited thereto. [Example 1] + JIS type - Titanium plate surface accepted using iron mesh (12G size) Bessie treatment 'and X in 2G% sulfuric acid aqueous solution (in 1 () 5 〇 pickling strip treatment calendar ¥ 1 〇分# 'The strip substrate is processed by the electrode substrate. The electrode substrate after the stripping is mounted in the arc-discharging device and is coated with a pure material. The coating conditions are as follows. JIS first type titanium disc (water cooling on the back side) Vacuum degree: 1.0 X ΙΟ 2 Torr (introduced argon gas scrubbing) Applied electric power: 500 watts (3·〇 kV) Substrate temperature· · 150 ° C (during sputtering) Time: 35 minutes Coating thickness · 2 microns (calculated as the weight increases) X-ray diffraction analysis results after sputter coating, observed sharpness specified to the substrate body The crystallization peak and the wide pattern designated for the sputter coating, and the coating was found to be amorphous. Next, the antimony tetrachloride and the pentachloride button were dissolved in 35 g/g hydrochloric acid to form a coating liquid, which was then applied to the coating liquid. The above-mentioned substrate on which the sputter coating treatment has been completed. 312XP/Invention Manual (supplement)/96-12/96142961 17 200825212 Grass = v after > The obtained substrate is placed in an air circulating electric furnace (which is thermally decomposed after a minute to form an electrode catalyst layer formed of a solid solution of silver oxide and oxidized neon. As for the coating thickness once applied by brushing) The amount of the coating liquid is set to be substantially U g / square 'm with respect to the silver metal. Heavy, 12 times from the operation of coating to baking to prepare an electrode for electrolysis. Electrolysis was carried out under the following conditions.
電流密度·· 125安培/平方分米 0電解溫度：6〇°C 接著 %解液· g氣化錯之鑛銅用模擬液 所使用之電解用電極經6個月後變成無法摔作 此電解用電極訂_件下接受再活化處理。 〃含氧化鉛之電極表面沉積物形成於電極表面上人 =錯之電極表面沉積物之電解用電極浸潰於 : ，及_量比過氧化氫之水溶液中經歷15小時二 為酸處理步驟，·隨後，於50 MPa Μ力下接受高 南壓水洗滌步驟。結果，沉積於電解用電極：上： έ氧化鉛之電極表面沉積物可完全被去除。 之 隨後’測定本電解用電極之電極 量。當⑽低於5克/平方米時，添加; :=克/平方米或以上時’該電“極可:： 電解係於料電靠件下騎。縣1 如同新品般使用超過6個月。 解用电極可 312Χρ/發明說明書(補件)/96-12/96142961 18 200825212 [實施例2] 於前述實_ 1巾’含氯㈣及氧化狀賴賴擬液 係用作為電解液，於實施例i之相同條件下進行相同操 作。結果獲得如實施例1之相同結果。 •[實施例3]Current density · · 125 amps / square metre 0 Electrolysis temperature: 6 〇 ° C Next, the solution of the electrolytic solution used for the copper solution of the copper solution is changed to 6 Reactivation treatment is carried out with an electrode. The electrode surface deposit containing bismuth oxide is formed on the surface of the electrode. The electrolysis electrode of the surface electrode of the electrode is immersed in: , and the amount of the solution is 15 hours in the aqueous solution of hydrogen peroxide. • Subsequently, the high-pressure water washing step was accepted at 50 MPa. As a result, it is deposited on the electrode for electrolysis: on the electrode surface deposit of lead antimony oxide can be completely removed. Then, the electrode amount of the electrode for electrolysis was measured. When (10) is less than 5 g/m2, add; := g/m2 or more, the 'electricity' can be:: The electrolysis is carried under the electric power supply. The county 1 is used as a new product for more than 6 months. The electrode for dissolving can be used as an electrolyte, and the invention is directed to the invention (removal)/96-12/96142961 18 200825212. [Example 2] The chlorine-containing (tetra) and oxidized-like liquid used in the above-mentioned 1st towel is used as an electrolyte. The same operation was carried out under the same conditions as in Example i. As a result, the same results as in Example 1 were obtained. [Example 3]
Jis第一類鈦板表面接受使用鐵格網（12〇號尺寸）之乾 噴砂處理’及接受於2G%硫酸水料（於丨阶）之酸洗務 •處理歷時10分鐘，藉此進行電極基板之洗務處理。洗務 後之電極基板架設於電弧離子鍍覆裝置内，且接受以純鈦 材料之濺鍍塗覆。塗覆條件說明如下。 標靶：JIS第一類鈦圓盤（背面係以水冷卻） 真空度：1.0 X 1〇-2托耳（Torr)(導入氬氣滌氣） 施加之電功率：500瓦（3· 0千伏特） 基板溫度：15 〇 °C (於濺鍍時） 時間·· 3 5分鐘 春 塗層厚度：2微米（隨著重量之增加計算） 於濺鍍塗覆後進行X光繞射分析結果觀察到指定予基 板本體之銳結晶峰以及指定予濺鍍塗層之寬圖樣，以及ς 現該塗層為非晶形。 χ 接著，將四氣化銥及五氯化钽溶解於35%鹽酸以形成塗 ^覆液，然後刷塗於前述已完成濺鍍塗覆處理之基板上。2 乾燥後，所得基板於空氣循環電爐（於55(rc經歷20分鐘 '時間）接受熱分解，以形成由氧化銥及氧化鈕之固體二= 所製成之電極催化劑層。至於刷塗一次之塗層厚户，1、求 312XP/發明說明書(補件)/96· 12/96142961 19 200825212 塗覆液之量係設定為相對於銥金屬實質上為1 米。 ·兄/平方 重複12次由塗覆至烤乾之操作以製備電解用電極 此所製備之電解用電極係於下列條件下接受電解电…如 電流密度：125安培/平方分米 電解溫度：6〇。匚 電解液：含硫酸鉛之銅箔製造用模擬液 所使用之電解用電極經6個月後變成無法操作。 此電解用電極於下列條件下接受再活化處理。 耆， 如一鹼處理步驟，將具有含硫酸鉛及氧化銻之恭 沉積物於其表面上之電解用電極浸潰☆ 5%質量：氫、： 鈉水溶液經歷3小時；如-酸處理步驟，將該電解用: 浸潰於_量比械及5%質量比過氧化氫之水溶液^經 歷15小時；以及隨後，如一高壓水洗條步驟，接受於^ MPa壓力下之高壓水洗滌。結果’沉積於電解用電極表面 上之含硫酸鉛之電極表面沉積物可完全被去除。 —隨後，敎本電解用電極之電極催化劑層之氧化銀含 罝。當田㈣含量低於5克/平方米時，添加塗層；而當氧 化銀含量為5克/平方米或以上時，該電解用電極可如前 而再度使用。電解係於前述電解條件下進行。結果，該電 解用電極可如同新品般使用超過6個月。 [實施例4] 實施例3所製備之電極於8()安培/平方分米電流密度於 55C電解溫度使用。結果，經過1()個⑽，無法再製造 312XP/發明說明書(補件)/96-12/96142961 ?0 200825212 箔。 該電極浸潰於10%質量比氫氧化鈉水溶液經歷i小時， 然後浸潰於10%質量比硝酸及10%質量比過氧化氫水溶液 中15小時，以及隨後，接受於7〇MPa壓力下之高壓水洗 滌。結果，沉積於電解用電極表面上之含錯及銻之電極表 面沉積物可完全被去除，該電解用電極可再額外使用】〇 個月。 [實施例5] 瞻實施例3所製備之電極於50安培/平方分米電流密度於 45 C電解溫度使用。結果，經過12個月後，無法再製造 箔。 ’ 該電極浸潰於20%質量比氫氧化鈉水溶液經歷2小時， 然後次潰於30%質1比硝酸及20%質量比過氧化氫水溶液 中15小時，以及隨後，接受於1〇〇 Mpa壓力下之高壓水 洗滌。結果，沉積於電解用電極表面上之含鉛及銻之電極 φ表面沉積物可完全被去除，該電解用電極可再額外使用 12個月。 [實施例6 ] 於前述實_ 3巾’含硫酸缺氧化銻之㈣製造用模 擬液用作為電解液，於實施例3之相同條件下進行相同操 作。結果’獲得與實施例3之相同結果。 ^ [比較例1] '另一方面’於只使用破酸或只使用過氧化氫來替代含硝 酸及過氧化氫之水溶液之情況下，沉積物之轉及移除反 312ΧΡ/發明說明書(補件)/96-12/96142961 21 200825212 f效f不佳。此外，於使用硫酸來替代硝酸之情、兄下，及 應效〒也同樣極差，所得f ' 反 m ± ^ L 电％用电極热法供使用。此外， 於使用鹽酸來替代靖酸# Γ 點。 Ά兄下’有工作環境不良的缺 本發明不僅可應用於電解銅粉或Jis's first type of titanium plate surface was subjected to dry blasting using iron mesh (12 〇 size) and subjected to pickling treatment of 2G% sulphuric acid water (in 丨 order). The treatment was carried out for 10 minutes. Substrate processing. The electrode substrate after the cleaning is mounted in an arc ion plating apparatus and subjected to sputtering coating of a pure titanium material. The coating conditions are explained below. Target: JIS Class I titanium disc (backed with water cooling) Vacuum: 1.0 X 1 〇 - 2 Torr (introduced argon purge) Applied electric power: 500 watts (3.0 kV) Substrate temperature: 15 〇 ° C (during sputtering) Time · · 3 5 minutes Spring coating thickness: 2 μm (calculated as the weight increases) X-ray diffraction analysis after sputter coating is observed A sharp crystallization peak assigned to the substrate body and a wide pattern designated for the sputter coating, and the coating is rendered amorphous. Next, four vaporized bismuth and antimony pentachloride were dissolved in 35% hydrochloric acid to form a coating liquid, which was then applied to the above-mentioned substrate on which the sputter coating treatment was completed. 2 After drying, the obtained substrate was subjected to thermal decomposition in an air circulating electric furnace (at 55 (rc for 20 minutes 'time) to form an electrode catalyst layer made of solid oxide = yttrium oxide and oxidized button. Coating thick household, 1, seeking 312XP / invention manual (supplement) / 96 · 12/96142961 19 200825212 The amount of coating liquid is set to be substantially 1 meter relative to the base metal. · Brother / square repeat 12 times by The operation of coating to dryness to prepare an electrode for electrolysis is prepared by subjecting an electrolysis electrode to electrolysis under the following conditions: for example, current density: 125 amps/cm 2 electrolysis temperature: 6 Torr. 匚 electrolyte: sulfuric acid The electrode for electrolysis used in the simulation liquid for the production of lead copper foil becomes inoperable after 6 months. The electrode for electrolysis is subjected to reactivation treatment under the following conditions. 耆, such as a base treatment step, will have lead sulfate and oxidation.锑之恭 sediment is electrolyzed on the surface of the electrode by electrode ☆ 5% mass: hydrogen, sodium solution for 3 hours; such as - acid treatment step, the electrolysis: immersed in _ amount of machinery and 5% Mass than hydrogen peroxide The solution ^ is subjected to 15 hours; and then, as a high-pressure water washing step, it is subjected to high-pressure water washing under a pressure of MPa. As a result, the surface deposit of the lead sulfate-containing electrode deposited on the surface of the electrode for electrolysis can be completely removed. Subsequently, the silver oxide electrode of the electrode catalyst layer of the electrode for electrolysis contains ruthenium. When the content of the field (four) is less than 5 g/m 2 , a coating layer is added; and when the content of silver oxide is 5 g/m 2 or more, the The electrode for electrolysis can be reused as before. The electrolysis is carried out under the aforementioned electrolysis conditions. As a result, the electrode for electrolysis can be used as a new product for more than 6 months. [Example 4] The electrode prepared in Example 3 was 8 ( The current density of ampere/square decimeter is used at 55C electrolysis temperature. As a result, after 1 () (10), it is impossible to manufacture 312XP/invention specification (supplement)/96-12/96142961?0 200825212 foil. 10% by mass of aqueous sodium hydroxide solution was subjected to i hours, and then impregnated in 10% by mass of nitric acid and 10% by mass aqueous hydrogen peroxide solution for 15 hours, and then, subjected to high-pressure water washing under a pressure of 7 MPa. , The electrode surface deposit containing the wrong electrode and the ruthenium deposited on the surface of the electrode for electrolysis can be completely removed, and the electrode for electrolysis can be additionally used for 〇 months. [Example 5] The electrode prepared in Example 3 was 50. The amperage/square decimeter current density is used at 45 C electrolysis temperature. As a result, after 12 months, the foil can no longer be produced. 'The electrode was immersed in a 20% by mass aqueous solution of sodium hydroxide for 2 hours and then collapsed at 30. % of the material 1 was compared with nitric acid and 20% by mass of aqueous hydrogen peroxide solution for 15 hours, and then, it was subjected to high-pressure water washing under a pressure of 1 〇〇Mpa. As a result, an electrode containing lead and antimony deposited on the surface of the electrode for electrolysis was used. The surface deposit of φ can be completely removed, and the electrode for electrolysis can be used for an additional 12 months. [Example 6] The same operation as in Example 3 was carried out under the same conditions as in Example 3, except that (4) a molding liquid for producing sulfuric acid-deficient ruthenium was used as the electrolytic solution. Results 'The same results as in Example 3 were obtained. ^ [Comparative Example 1] 'On the other hand' in the case of using only acid-breaking or hydrogen peroxide alone to replace the aqueous solution containing nitric acid and hydrogen peroxide, the transfer and removal of the sediment 312 ΧΡ / invention instructions (complement Pieces) /96-12/96142961 21 200825212 f effect f is not good. In addition, the use of sulfuric acid instead of nitric acid, brother, and the effect of the same is also very poor, the obtained f 're-m ± ^ L electricity % is used by electrode thermal method. In addition, use hydrochloric acid instead of yoghurt #Γ. Under the brothers, there is a lack of working environment. The invention can be applied not only to electrolytic copper powder or
::電極或鑛銅用電解用電極之多種電解用電：：：、: 化方法’同時也可應用於其它電解用電極之再活化方法 雖然已經就細節且參照其特定具體例說明本發 =藝人士顯然易知可未㈣其精髓及範圍而於其中^ 出多項變化及修改。 本案係基於日本專利申請案第2〇〇6 —313252號（ 2006年11月20日）及第2007-230379號（申請日2〇〇7年 9月5日），二案内容以引用方式併入此處。:: Electrode for electrolysis electrodes for electrodes or copper ore:::,: Method of re-activation of other electrodes for electrolysis. Although the details have been described with reference to specific examples thereof. Artists are clearly aware of the essence and scope of the artist (4) and have made many changes and modifications. This case is based on Japanese Patent Application No. 2-6-313252 (November 20, 2006) and 2007-230379 (Application Date: September 5, 2007). Enter here.
312ΧΡ/發明說明書(補件)/96·12/96142961 22312ΧΡ/Invention Manual (supplement)/96·12/96142961 22