1287589 玖、發明說明 (發明說明應敘明：發明所屬之技術領域、先前技術、内容、實施方式及圖式簡單說明） 【發明所屬之^技術領域】 本發明疋有關於電解再生處理裝置，更詳而古之，是 有關於使含有金屬離子之蝕刻處理液在設有電極之再生槽 5内再生之電解再生處理裝置。 r先前技術;j 用於半導體裝置等之多層電路基板，是使用所謂增層 基板。 該增層基板之製造，係例如在各自形成於核心基板之 10兩面側之預定厚度之樹脂層上，形成可使形成於核心基板 之導體圖案等露出底面之通孔穴後，於包含通孔穴内壁面 之樹脂層之全表面上形成鍍金屬層，接著，於該鍍金屬層 施行圖案化，形成導體圖案及通孔。又，重複相同的操作 ，即可得到核心基板兩面侧積層有多數導體圖案之多層電 15 路基板。 該增層基板之製造步驟中，於樹脂層之表面形成鍍金 屬層時’為了使樹脂層與鑛金屬層之密著性良好，故在樹 脂層表面施行形成細微凹凸之粗面化處理。 該粗面化處理中，係使用例如過錳酸鹽水溶液或含6 20價鉻液等之含有金屬離子之蝕刻液來作為蝕刻樹脂層之蝕 刻液。 這種含有金屬離子之蝕刻液，會因在樹脂層之表面施 行粗面化處理等，而使該蝕刻性能降低，不過藉由對該蝕 刻性能降低之蝕刻處理液施行電解處理，可使其蝕刻性能 1287589 玖、發明說明 再生。 在特開平10-245443號公報中，揭示了第5圖所示之 裝置來作為這種電解處理裝置。 第5圖所示之電解處理裝置100設有再生槽108，該 5 再生槽108藉配管106而與將欲施行粗面化處理之樹脂製 基板102浸潰於蝕刻液中之蝕刻處理槽104 —體化，且該 再生槽108中配置有電性連接於整流器之多數根電極 110，110···。 該再生槽108與蝕刻處理槽104間設有連結兩槽之循 10 環配管112，且藉由設於該循環配管112之途中之循環泵 114，從蝕刻處理槽104流入再生槽108之蝕刻處理液藉電 極110，110…之電解處理再生，並回到蝕刻處理槽104。 然而，再生槽108内之電解處理在進行之際，在使蝕 刻處理液再生之再生反應之同時，還會引起生成不溶性之 15 淤渣之副反應。例如，使用過錳酸鹽水溶液作為蝕刻液時 ，當Mn7+在蝕刻處理槽104内還原為Mn6+時，樹脂製基 板102之表面粗化即形成。在該蝕刻處理槽104生成之含 有Mn6+之蝕刻液進入再生槽108，藉電極110,110···之電解 處理，Mn6+氧化為Mn7+，並再度回到蝕刻處理槽104。藉 20 該電極110，110···進行電解處理時，係將Mn6+氧化為Mn7+ 而再生。然而，基於再生效率，一部份的Mn6+不會再生而 生成二氧化猛（Μη02)。 如此生成之二氧化猛（Μη02)會成為不溶性之於渣（ 以下簡稱淤渣）而循環於蝕刻處理槽104及再生槽108， 1287589 玖、發明說明 並逐漸蓄積，容易成為配管等堵塞之原因，且對樹脂製基 板102之表面粗化也會產生不良影響。 因此，第5圖所示之電解處理裝置10〇中，設有用以 將钱刻處理液中之淤渣沉澱除去之淤渣除去槽2〇〇。該游 5渣除去槽2〇〇與再生槽係藉由設置有循環泵202之循環配 管204,206連接，因此再生槽1〇8内之於渣可與餘刻處理 液一起流到淤渣除去槽200,而業已除去淤渣之處理液也 可回到再生槽108。 第5圖所示之電解處理裝置1〇〇中，藉於渣除去槽 10 200之設置而可除去蝕刻處理液中之淤渣，故可防止齡潰 在蝕刻處理槽104與再生槽1〇8内蓄積。 然而，在淤渣除去槽200中沉澱蓄積之淤渣必須定期 除去，而該除去作業非常繁雜，且，業已沉澱蓄積之淤渣 塊很硬’更增加該於渣之除去作業之困難。 15 又，併設淤渣除去槽200會導致電解處理裝置1〇〇大 型化。 因此，必須有一種儘可能減少淤渣產生、而可達到不 需設置游渣除去槽200之再生槽1〇8的方案。 【發明内容3 1〇 因此，本發明之課題，即在提供一種電解再生處理裝 置，係在將含有金屬離子之蝕刻處理液在設有電極之再生 槽内再生之際，可盡量減少所產生之不溶性淤渣，而不需 特別併設於渣除去槽等之淤渣除去機構者。 本發明人為了解決上述課題而不斷檢討，結果發現， 1287589 玖、發明說明 藉由使流入再生槽之蝕刻處理液交互向上或向下流動，並 設置電極使之與向上流動之蝕刻處理液接觸，更對蝕刻處 理液沉澱之部分施行攪拌，如此即可儘可能地減少再生槽 内所產生之淤渣量，而完成了本發明。 5 亦即，藉由本發明，可提供一種電解再生處理裝置， 係可再生含有金屬離子之蝕刻處理液者，包含有： 再生槽，其内部區分為多數個區域，使由供給側所供 給之前述蝕刻處理液一面交互向上或向下地變更流動方向 ，一面依序流至出口侧方向； 10 電極，設於在前述多數個區域當中之前述蝕刻液向上 流之區域内，及 攪拌機構，設於前述區域内之蝕刻液沉澱之部分且用 以攪拌前述蝕刻液。 本發明中，前述電極以使用陽極面積較陰極面積大者 15 為佳，尤其是使用由筒狀網體形成之陽極、及由插入該網 體内之棒體形成之陰極所構成之電極，該電極以前述網體 及棒體沿處理液之流動方向直立設置之狀態來使用為佳。 又，將前述攪拌機構設於蝕刻處理液之流動方向由向 下變更為向上之部位之附近，藉此可防止不溶性淤渣在變 20 更蝕刻處理液之流動方向之部分蓄積。且以具有將前述再 生槽内之蝕刻處理液喷出之喷嘴者作為該攪拌機構為佳。 本發明以設有循環路徑，可從前述再生槽取出蝕刻處 理液，並將該蝕刻處理液再度送回該再生槽，而該循環路 徑上設有前述喷嘴為佳。 1287589 玖、發明說明 藉由有關本發明之電解再生裝置，相較於習知之裝置 ’可大幅減少再生槽内產生之不溶性淤渣量。 且’將生成二氧化猛（Μη02)等不溶性淤渣之電極， 設置成與向上流動之蝕刻處理液接觸之狀態，同時在蝕刻 5處理液沉澱之部分設置攪拌機構，如此一來因電極生成之 不溶性於渣實質上不會蓄積在再生槽内，因此可藉由設於 循環配管中途之過濾器等簡易之淤渣除去機構而輕易地除 去。 · 結果’由於關於本發明之電解再生處理裝置中，不需 10特別併設於渣除去槽等淤渣除去機構，因此可謀求電解再 生裝置之小型化。 圖式簡單說明 第1圖是說明有關本發明之電解再生處理裝置之一例 之說明圖。 15 第2圖是第1圖所示之電解再生處理裝置之平面圖。 第3圖是第1圖所示之電解再生處理裝置中所使用之 · 電極之立體圖。 第4圖是說明第1圖所示之電解再生處理裝置中，用 來作為授拌機構之用以將再生槽内之蝕刻處理液喷出之喷 ’ 20 嘴孔。 · 第5圖是用以說明習知之電解處理裝置之說明圖。 第6圖是顯示相對於時間之過錳酸之增加率之圖形。 第7圖是顯示相對於電流密度之過猛酸之再生率之圖 形〇 10 1287589 玖、發明說明 【實施方式3 有關本發明之電解再生處理裝置之一例顯示於第1圖 。構成第1圖所示之電解再生處理裝置10之再生槽12, 係從供給含金屬離子之蝕刻處理液之供給側到出口侧方向 5 區分為多數個區域12a〜12h，而該蝕刻液係使用過錳酸鹽 水溶液等含有金屬離子之蝕刻液於樹脂製基板之表面施行 粗面化處理等後所形成者。1287589 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明More specifically, there is an electrolytic regeneration processing apparatus for regenerating an etching treatment liquid containing metal ions in a regeneration tank 5 provided with electrodes. r Prior art; j A multilayer circuit substrate for a semiconductor device or the like is a so-called build-up substrate. The build-up substrate is formed, for example, on a resin layer having a predetermined thickness formed on both sides of the core substrate, and a through hole formed in the bottom surface of the conductor pattern formed on the core substrate can be formed in the through hole. A metal plating layer is formed on the entire surface of the resin layer on the wall surface, and then the metal plating layer is patterned to form a conductor pattern and a via hole. Further, by repeating the same operation, a multilayer electric circuit substrate having a plurality of conductor patterns laminated on both sides of the core substrate can be obtained. In the step of producing the build-up substrate, when the metal plating layer is formed on the surface of the resin layer, in order to improve the adhesion between the resin layer and the mineral metal layer, the surface of the resin layer is subjected to a roughening treatment for forming fine unevenness. In the roughening treatment, for example, an etching solution containing a metal ion such as a permanganate aqueous solution or a hexavalent chromium-containing liquid is used as the etching solution for etching the resin layer. Such an etching liquid containing a metal ion may be subjected to a roughening treatment on the surface of the resin layer to lower the etching performance. However, the etching treatment liquid having a reduced etching performance may be subjected to electrolytic treatment to be etched. Performance 1287589 玖, invention description regeneration. In Japanese Laid-Open Patent Publication No. Hei 10-245443, the apparatus shown in Fig. 5 is disclosed as such an electrolytic treatment apparatus. The electrolytic treatment apparatus 100 shown in Fig. 5 is provided with a regeneration tank 108 which is immersed in the etching treatment tank 104 in which the resin substrate 102 to be subjected to the roughening treatment is immersed in the etching liquid by the piping 106. The plurality of electrodes 110, 110, . . . electrically connected to the rectifier are disposed in the regeneration tank 108. Between the regeneration tank 108 and the etching treatment tank 104, a 10-ring pipe 112 connecting the two grooves is provided, and the circulation pump 114 provided on the way of the circulation pipe 112 flows into the regeneration tank 108 from the etching treatment tank 104. The liquid is regenerated by electrolytic treatment of the electrodes 110, 110, and returned to the etching treatment tank 104. However, when the electrolytic treatment in the regeneration tank 108 is progressing, the regeneration reaction for regenerating the etching treatment liquid is caused, and a side reaction of insoluble 15 sludge is caused. For example, when a permanganate aqueous solution is used as the etching liquid, when Mn7+ is reduced to Mn6+ in the etching treatment bath 104, the surface of the resin substrate 102 is roughened. The etching liquid containing Mn6+ generated in the etching treatment tank 104 enters the regeneration tank 108, and is oxidized to Mn7+ by the electrolytic treatment of the electrodes 110, 110, and returns to the etching treatment tank 104 again. When the electrode 110, 110··· is subjected to electrolytic treatment, Mn6+ is oxidized to Mn7+ to be regenerated. However, based on the regeneration efficiency, a part of Mn6+ does not regenerate to form oxidized sputum (Μη02). The oxidized sensitized Μ 02 02 02 会 循环 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , Further, the surface of the resin substrate 102 is roughened and adversely affected. Therefore, in the electrolytic treatment apparatus 10A shown in Fig. 5, a sludge removing tank 2 for removing and removing sludge in the money processing liquid is provided. The slag removal tank 2 is connected to the regeneration tank by the circulation piping 204, 206 provided with the circulation pump 202, so that the slag in the regeneration tank 1 〇 8 can flow to the sludge removal tank 200 together with the residual treatment liquid. The treatment liquid from which the sludge has been removed may also be returned to the regeneration tank 108. In the electrolytic treatment apparatus 1 shown in Fig. 5, the sludge in the etching treatment liquid can be removed by the arrangement of the slag removing tank 10200, so that the etching treatment tank 104 and the regeneration tank 1〇8 can be prevented. Accumulated inside. However, the sludge accumulated in the sludge removal tank 200 must be periodically removed, and the removal operation is very complicated, and the sludge which has accumulated and accumulated is very hard, which further increases the difficulty in the removal operation of the slag. Further, the addition of the sludge removing tank 200 causes the electrolytic treatment apparatus 1 to be enlarged. Therefore, it is necessary to have a scheme of reducing the generation of sludge as much as possible, and achieving the regeneration tank 1〇8 in which the slag removing tank 200 is not required to be provided. SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide an electrolytic regeneration processing apparatus capable of minimizing generation of an etching treatment liquid containing metal ions in a regeneration tank provided with an electrode. The insoluble sludge does not need to be particularly provided in a sludge removing mechanism such as a slag removing tank. The present inventors have continuously reviewed in order to solve the above problems, and as a result, it has been found that 1287589 玖, the invention describes that the etching treatment liquid flowing into the regeneration tank is alternately flowed upward or downward, and an electrode is provided to be in contact with the upward flowing etching treatment liquid. Further, the portion where the etching treatment liquid is precipitated is agitated, so that the amount of sludge generated in the regeneration tank can be reduced as much as possible, and the present invention has been completed. In other words, according to the present invention, it is possible to provide an electrolytic regeneration processing apparatus which is capable of regenerating an etching treatment liquid containing metal ions, and includes a regeneration tank which is divided into a plurality of regions and supplied by the supply side. The etching treatment liquid alternately changes the flow direction upward or downward, and sequentially flows to the outlet side direction; 10 electrodes are disposed in an area in which the etching liquid flows upward in a plurality of the plurality of regions, and a stirring mechanism is provided in the foregoing A portion of the etchant in the region is precipitated and used to agitate the etchant. In the present invention, it is preferable that the electrode has a larger anode area than the cathode area, in particular, an anode formed of a cylindrical mesh body and an electrode formed of a cathode formed by a rod inserted into the mesh body. It is preferable that the electrode is used in a state where the mesh body and the rod body are erected in the flow direction of the treatment liquid. Further, the stirring mechanism is provided in the vicinity of the flow direction in which the etching treatment liquid is changed from the downward direction to the upward direction, whereby the insoluble sludge can be prevented from accumulating in the flow direction of the etching treatment liquid. It is preferable that the nozzle having the nozzle for ejecting the etching treatment liquid in the regeneration tank is used as the stirring mechanism. According to the present invention, the etching treatment liquid is taken out from the regeneration tank, and the etching treatment liquid is returned to the regeneration tank again, and the nozzle is preferably provided on the circulation path. 1287589 发明Inventive Description With the electrolytic regeneration apparatus according to the present invention, the amount of insoluble sludge generated in the regeneration tank can be greatly reduced as compared with the conventional apparatus. And 'the electrode which generates an insoluble sludge such as oxidized Μ (Μη02) is placed in contact with the upwardly flowing etching treatment liquid, and at the same time, a stirring mechanism is provided in the portion where the etching treatment liquid is precipitated, so that the electrode is generated Since the insoluble slag does not substantially accumulate in the regeneration tank, it can be easily removed by a simple sludge removing mechanism such as a filter provided in the middle of the circulation piping. In the electrolytic regeneration treatment apparatus of the present invention, it is not necessary to provide a sludge removal mechanism such as a slag removal tank, and therefore, the electrolytic regeneration apparatus can be downsized. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is an explanatory view for explaining an example of an electrolytic regeneration processing apparatus according to the present invention. 15 Fig. 2 is a plan view showing the electrolytic regeneration processing apparatus shown in Fig. 1. Fig. 3 is a perspective view of an electrode used in the electrolytic regeneration processing apparatus shown in Fig. 1. Fig. 4 is a view showing a spray nozzle 20 for ejecting an etching treatment liquid in a regeneration tank as a feeding mechanism in the electrolytic regeneration processing apparatus shown in Fig. 1. Fig. 5 is an explanatory view for explaining a conventional electrolytic treatment apparatus. Figure 6 is a graph showing the increase rate of permanganic acid with respect to time. Fig. 7 is a graph showing the regeneration rate of the super acid with respect to the current density. 1 10 1287589 玖 Description of the invention [Embodiment 3] An example of the electrolytic regeneration processing apparatus according to the present invention is shown in Fig. 1. The regeneration tank 12 constituting the electrolytic regeneration processing apparatus 10 shown in Fig. 1 is divided into a plurality of regions 12a to 12h from the supply side to the outlet side direction 5 for supplying the metal ion-containing etching treatment liquid, and the etching liquid system is used. An etching solution containing a metal ion such as a permanganate aqueous solution is formed after the surface of the resin substrate is subjected to roughening treatment or the like.
該區域12a〜12h係各自藉由2種類之隔板14a，14b區 隔開來，隔板14a其上端突出於蝕刻處理液之水面上，而 10 其下端與再生槽12之底面間形成有蝕刻處理液可通過之通 路。另一方面，隔板14b係設置成：其下端密著於再生槽 12之底面，而蝕刻液可越過其上端流出到下一區域。The regions 12a to 12h are each separated by two types of separators 14a and 14b. The upper end of the separator 14a protrudes from the water surface of the etching treatment liquid, and the lower end of the separator 14a is formed with an etching between the lower end and the bottom surface of the regeneration tank 12. The passage through which the treatment fluid can pass. On the other hand, the spacer 14b is disposed such that its lower end is adhered to the bottom surface of the regeneration tank 12, and the etching liquid can flow out over the upper end to the next region.
第1圖所示之再生槽12中，由於流入再生槽12之内 壁面與隔板14a所形成之區域12a之蝕刻處理液，會從隔 15 板14a之下端與再生槽12之底面間形成之間隙流入區域 12b，因此在區域12a中，蝕刻處理液之流動方向向下。 又，區域12b係藉隔板14a與隔板14b形成，故從隔 板14a下端側之間隙流入區域12b之蝕刻處理液會越過隔 板14b之上端，流入隔板14b與隔板14a所形成之區域 20 12c，因此#刻處理液在區域12b中之流動方向向上。 如此，區域12a〜12h係各自藉2種類之隔板14a，14b 隔開，使流入區域12a之蝕刻處理液一面交互地向上或向 下地變更流動方向，一面朝出口方向（區域12h之方向）； 亦即，以 12a—i2b—i2c->12d—12e—12f—12g—12h 之順 11 1287589 玖、發明說明 序依序流動。 · 第1圖所示之再生槽12中，蝕刻處理液之流動方向朝 上之£域12b，12d，12f之各區域中設置有電極16 〇該電極 16係如第3圖所示，係一由筒狀網體16a形成之陽極、與 5由插入網體16a内之棒體16b形成之陰極所構成之電極。 棒體16b係例如以聚四氟乙烯製之管覆蓋導體表面之一部 分者。又，筒狀網體16由金屬製板條或網狀物形成。因此 ，電極16中，由網體16a形成之陽極係形成為面積大於由 · 棒體16b形成之陰極。該第3圖所示之電極16係網體16扛 1〇及棒體16b在區域12b，12d，12f之各區域中沿著蝕刻處理液 之向上之流動方向直立設置。陽極與陰極之面積比或電流 值會因蝕刻處理液之處理量如何設定而不同，不過處理二 氧化錳（Mn〇2)時，如後所述地將陽極陰極面積比設定為 2 0 : 1較為適當。 15 又，設於區域12b，12d，12f之各區域之電極16係如第 2圖所示，亦可設置多數個電極ι6，16，16。 · 第1圖所示之再生槽12中，流入區域12a之蝕刻處理 液係一面交互地向上或向下變更流動方向，一面依序流過 各區域朝向出口方向（區域12h)。 1〇 該蝕刻處理液之流動方向在從向上變更為向下、或從 向下變更為向上時，餘刻處理液之流速會變得極為緩慢而 產生阻塞。#刻處理液中所含淤渣即容易在該阻塞部分沉 > 澱。 這-點，第1圖所示之再生槽12中，在蝕刻處理液之 12 1287589 玖、發明說明 ’ 流動方向從向上變更為向下或從向下變更為向上之附近， 設有攪拌蝕刻處理液之攪拌手段。該攪拌手段中，沿再生 槽12底面没置配管20，而位於蝕刻處理液之流動方向變 更之附近之配管20之部分，係如第4圖所示，從配管2〇 5之形成於再生槽12底面侧之喷嘴孔20a，20a將流入區域 Uh之業已再生之再生蝕刻液以泵18昇壓而喷出，攪拌再 生中之蝕刻處理液。 再生蝕刻液從該喷嘴孔20a，20a朝再生槽12底面側噴 · 出，如此亦可防止淤渣在再生槽12之底面沉澱蓄積。 該贺嘴孔20a，20a所形成之配管20係如第2圖所示， 沿著各區域與蝕刻處理液接著流入之區域間之隔板14a，14b 而略平行地、且設於再生槽12底面之附近。之所以將配管 2〇如此設置，是由於在該隔板14a，14b之附近且再生槽12 底面之附近位置，蝕刻處理液之流動方向從向下變更為向 15 上，淤渣容易在其附近沉澱積蓄的緣故。 又，從配管20之喷嘴孔20a，20a噴出之喷出液攪拌入 · 再生中之蝕刻處理液，防止了淤渣在再生槽12底面沉澱蓄 積，因此亦可如第1圖之虛線所示，將再生槽12之區域 12h以外之區域中所積存之蝕刻處理液從配管2()之喷嘴孔 - 20 20a，20a 喷出。 · 如第1圖所示之電解再生裝置10係併設在對樹脂製基 板之表面施行粗面化處理等蝕刻之處理裝置3()内。該處理 裝置30中，設置有處理槽32 ,用以貯留對樹脂製基板之 表面施行粗面化處理等蝕刻之過錳酸鹽水溶液等含有金屬 13 1287589 玖、發明說明 ‘ 離子之蝕刻液，該處理槽32之外周設置有溢流槽34，用 以接收從處理槽32溢流出之蝕刻液。業已再生之再生蝕刻 液從電解再生處理裝置1〇之區域12h經由配管36回到溢 流槽34中。 5 流入溢流槽34之蝕刻液及再生蝕刻液經由配管38、 泵40及過濾器42回到處理槽32。該過濾器42係用以將 流入溢流槽34之蝕刻液及再生蝕刻液中之樹脂粉分離者。 又，處理槽32中設置有配管44，用以將貯留之蝕刻 · 液之一部分作為姓刻處理液送到電解再生處理裝置1 〇之再 10生槽12，該配管44上設置有送液泵46及過濾器48。過濾 器48係用以將送到再生槽12之蝕刻處理液中之樹脂粉分 離者。藉過濾器48除去之淤渣主要是處理槽32中之對樹 脂製基板表面進行粗表面化處理等蝕刻所產生之樹脂粉。 藉第1圖所示之處理裝置30及電解再生處理裝置1〇 15 ，藉再生槽12内之電解使餘刻處理液再生之際，於潰之產 生極少，相較於第5圖所示之習知蝕刻處理槽1〇4所產生 · 之淤渣量，約可抑制為1/1〇。因此，第i圖所示之處理裝 置30及電解再生處理裝置1〇中，在將流入溢流槽34之蝕 刻液及再生蝕刻液送回處理槽32之配管38之途中設置過 - 20濾器42 ,即可充分作為除去業經再生之再生蝕刻液及蝕刻 · 液中之淤渣之機構，而不須在再生槽12併設如第5圖所示 之淤渣除去槽200等特別裝置。 ’ 從而，在第1圖所示之處理裝置3〇及電解再生裝置 10中，以過濾器42之交換程度即足以作為淤渣除去作業 14 1287589 玖、發明說明 ，因此，可省略將沉澱蓄積在淤渣除去槽200之淤渣塊除 去之作業，而亦可達到裝置之體積小型化。 接著，參照表1及表2、第6圖及第7圖說明本發明 之效果。這些圖表係顯示使用第1圖所示之電解再生處理 5 裝置，並使用含過錳酸鹽水溶液之蝕刻液作為金屬離子來 進行電解處理時之實驗結果。In the regeneration tank 12 shown in Fig. 1, the etching treatment liquid flowing into the inner wall surface of the regeneration tank 12 and the region 12a formed by the separator 14a is formed from the lower end of the separator 15a and the bottom surface of the regeneration tank 12. The gap flows into the region 12b, so in the region 12a, the flow direction of the etching treatment liquid is downward. Further, since the region 12b is formed by the separator 14a and the separator 14b, the etching treatment liquid flowing from the gap inflow region 12b on the lower end side of the separator 14a passes over the upper end of the separator 14b, and flows into the separator 14b and the separator 14a. The region 20 12c, therefore, the flow direction of the process liquid in the region 12b is upward. In this manner, the regions 12a to 12h are separated by the separators 14a and 14b of the two types, and the etching treatment liquid of the inflow region 12a alternately changes the flow direction upward or downward while facing the outlet direction (direction of the region 12h). That is, in the order of 12a-i2b-i2c->12d-12e-12f-12g-12h, 11 1287589 玖, the invention instructions flow sequentially. In the regeneration tank 12 shown in Fig. 1, the electrode 16 is provided in each of the regions 12b, 12d, and 12f in which the flow direction of the etching treatment liquid flows upward. The electrode 16 is as shown in Fig. 3 An anode formed of a cylindrical mesh body 16a and an electrode formed by a cathode formed by a rod 16b inserted into the mesh body 16a. The rod 16b is, for example, a part of the surface of the conductor covered with a tube made of polytetrafluoroethylene. Further, the cylindrical net body 16 is formed of a metal slat or a mesh. Therefore, in the electrode 16, the anode formed by the mesh body 16a is formed to have a larger area than the cathode formed by the rod body 16b. The electrode 16, which is shown in Fig. 3, is a mesh body 16扛1〇 and a rod body 16b which is erected in the upward flow direction of the etching treatment liquid in each of the regions 12b, 12d, and 12f. The area ratio of the anode to the cathode or the current value may vary depending on how the treatment amount of the etching treatment liquid is set. However, when manganese dioxide (Mn〇2) is treated, the anode cathode area ratio is set to 2 0 : 1 as will be described later. More appropriate. Further, as shown in Fig. 2, the electrodes 16 provided in the respective regions of the regions 12b, 12d, and 12f may be provided with a plurality of electrodes ι6, 16, and 16. In the regeneration tank 12 shown in Fig. 1, the etching treatment liquid in the inflow region 12a alternately changes the flow direction upward or downward, and sequentially flows through the respective regions toward the outlet direction (region 12h). 1〇 When the flow direction of the etching treatment liquid changes from upward to downward or from downward to upward, the flow rate of the remaining treatment liquid becomes extremely slow and clogging occurs. # The sludge contained in the treatment liquid is likely to sink in the clogging portion > In this point, in the regeneration tank 12 shown in Fig. 1, in the vicinity of the etching treatment liquid 12 1287589 玖, the invention describes that the flow direction changes from upward to downward or from downward to upward, and a stirring etching treatment is provided. The means of stirring the liquid. In the stirring means, the pipe 20 is not disposed along the bottom surface of the regeneration tank 12, and the portion of the pipe 20 located in the vicinity of the flow direction of the etching treatment liquid is formed in the regeneration tank from the pipe 2〇5 as shown in Fig. 4 The nozzle holes 20a and 20a on the bottom surface side pressurize the regenerated etching liquid which has been regenerated in the inflow region Uh by the pump 18, and agitate the etching treatment liquid during regeneration. The regenerated etching liquid is ejected from the nozzle holes 20a, 20a toward the bottom surface side of the regeneration tank 12, so that the sludge can be prevented from being deposited and accumulated on the bottom surface of the regeneration tank 12. The piping 20 formed by the nozzle holes 20a, 20a is provided in the regeneration tank 12 in a direction slightly parallel to the partitions 14a, 14b between the respective regions and the region in which the etching treatment liquid flows in, as shown in Fig. 2; Near the bottom. The reason why the piping 2 is disposed in this manner is that the flow direction of the etching treatment liquid is changed from downward to 15 in the vicinity of the separators 14a and 14b and in the vicinity of the bottom surface of the regeneration tank 12, and the sludge is easily in the vicinity thereof. The reason for the accumulation of sediment. Further, the ejecting liquid ejected from the nozzle holes 20a and 20a of the pipe 20 agitates the etching treatment liquid during the regeneration, thereby preventing the sludge from being deposited and accumulated on the bottom surface of the regeneration tank 12, and therefore, as shown by the broken line in Fig. 1, The etching treatment liquid accumulated in the region other than the region 12h of the regeneration tank 12 is ejected from the nozzle holes - 20 20a, 20a of the pipe 2 (). The electrolytic regenerating apparatus 10 shown in Fig. 1 is provided in a processing apparatus 3 () for performing etching such as roughening treatment on the surface of a resin substrate. The processing apparatus 30 is provided with a processing tank 32 for storing a metal containing a permanganate aqueous solution such as a surface for etching a surface of a resin substrate, such as a permanganate aqueous solution, and an ion etching solution. An overflow tank 34 is provided on the outer circumference of the treatment tank 32 for receiving the etching liquid overflowing from the treatment tank 32. The regenerated etching liquid which has been regenerated is returned from the region 12h of the electrolytic regeneration processing apparatus 1 to the overflow tank 34 via the piping 36. The etching liquid and the regenerating etching liquid which have flowed into the overflow tank 34 are returned to the processing tank 32 via the piping 38, the pump 40, and the filter 42. The filter 42 is for separating the etching liquid flowing into the overflow tank 34 and the resin powder in the regenerating etching liquid. Further, the processing tank 32 is provided with a pipe 44 for supplying a part of the stored etching liquid to the re-processing tank 1 of the electrolytic regeneration processing apparatus 1 , and the liquid feeding pump is provided on the piping 44 46 and filter 48. The filter 48 is for separating the resin powder in the etching treatment liquid sent to the regeneration tank 12. The sludge removed by the filter 48 is mainly a resin powder produced by etching the surface of the resin substrate in the treatment tank 32 by rough surface treatment or the like. When the processing apparatus 30 and the electrolytic regeneration processing apparatus 1〇15 shown in Fig. 1 are used to regenerate the residual processing liquid by electrolysis in the regeneration tank 12, there is little occurrence of collapse, as compared with that shown in Fig. 5. The amount of sludge generated by the conventional etching treatment tank 1〇4 can be suppressed to about 1/1 〇. Therefore, in the processing apparatus 30 and the electrolytic regeneration processing apparatus 1 shown in Fig. i, the -20 filter 42 is provided in the middle of returning the etching liquid flowing into the overflow tank 34 and the regenerated etching liquid to the piping 38 of the processing tank 32. Further, it is sufficient as a mechanism for removing the regenerated etching liquid and the sludge in the etching liquid, and it is not necessary to provide a special device such as the sludge removing tank 200 shown in Fig. 5 in the regeneration tank 12. Therefore, in the processing apparatus 3〇 and the electrolytic regeneration apparatus 10 shown in Fig. 1, the degree of exchange of the filter 42 is sufficient as the sludge removing operation 14 1287589 发明, and the invention is described. Therefore, the deposition of the precipitate can be omitted. The operation of removing the sludge block of the sludge removal tank 200 can also achieve miniaturization of the volume of the apparatus. Next, the effects of the present invention will be described with reference to Table 1 and Table 2, Figure 6, and Figure 7. These graphs show the results of experiments conducted using the electrolytic regeneration treatment 5 shown in Fig. 1 and electrolytic treatment using an etching solution containing a permanganate aqueous solution as a metal ion.
表1 :藉攪拌條件之再生效率 條件 攪拌 攪拌量（通過 速度） 電壓/電流 電解 時間 過錳酸率 (%) 過錳酸上昇 率 (%) 游渣量 (g) 5V/96A Oh 72.02 0.00 1 無噴嘴 67L/分 5V/96A 2h 75.18 3.16 1 縱隔板 (12mm/秒） 5V/96A 4h 77.53 5.51 4.59g 5V/96A 6h 6.88g 5V/96A Oh 71.03 0.00 無喷嘴 150L/分 5V/96A 2h 72.77 1.74 Z 縱隔板 (27mm/秒） 5V/96A 4h 74.27 3.24 5V/96A 6h 75.22 4.19 1.63g 5V/96A Oh 78.80 0.00 有喷嘴 67L/分 5V/96A 2h 80.27 1.47 J 縱隔板 (12mm/秒） 5V/96A 4h 80.70 1.90 5V/96A 6h 83.68 4.88 0.04g 5V/96A Oh 71.49 0.00 Λ 有喷嘴 150L/分 5V/96A 2h 74.38 2.89 Η 縱隔板 (27mm/秒） 5V/96A 4h 78.69 7.20 5V/96A 6h 84.70 13.21 0.002gTable 1: Regeneration efficiency conditions by stirring conditions Stirring amount (passing speed) Voltage/current electrolysis time Permanganic acid rate (%) Permanganic acid rising rate (%) Slag amount (g) 5V/96A Oh 72.02 0.00 1 No nozzle 67L/min 5V/96A 2h 75.18 3.16 1 Vertical partition (12mm/sec) 5V/96A 4h 77.53 5.51 4.59g 5V/96A 6h 6.88g 5V/96A Oh 71.03 0.00 No nozzle 150L/min 5V/96A 2h 72.77 1.74 Z vertical partition (27mm/sec) 5V/96A 4h 74.27 3.24 5V/96A 6h 75.22 4.19 1.63g 5V/96A Oh 78.80 0.00 Nozzle 67L/min 5V/96A 2h 80.27 1.47 J Vertical partition (12mm/sec) 5V/96A 4h 80.70 1.90 5V/96A 6h 83.68 4.88 0.04g 5V/96A Oh 71.49 0.00 Λ There are nozzles 150L/min 5V/96A 2h 74.38 2.89 纵 Vertical partition (27mm/sec) 5V/96A 4h 78.69 7.20 5V/96A 6h 84.70 13.21 0.002g
表1是顯示出當改變喷嘴20a，20b之有無、攪拌量（ 10 通過裝置之蝕刻液之流速）時，每個電解時間（初期狀態 、2小時、4小時、6小時經過後）之過錳酸之含有率之變 化（上昇率）以及淤渣量之變化者。每一個條件皆存在有 縱方向之隔板14a，14b，不過，條件1是無喷嘴20a，20b、 通過流速為67L/分時之情況，條件2同樣是無喷嘴 15 1287589 玖、發明說明 2〇a，2〇b、而通過流速提升為15〇L/分時之情況，條件3是 有噴嘴20a，20b、通過流速為67L/分時之情況，條件4同 樣是有喷嘴20a，20b、而通過流速提升為15〇L/分時之情況 。第ό圖是顯示表1之結果之圖形。 從該實驗結果可得知，再生率亦即過錳酸增加率會因 著再生電極之通過流速與停滯部分之攪拌而上昇，不過在 這種情況下，僅藉再生電極之通過流速產生之攪拌是無法 充分除去淤渣的。另一方面，藉喷嘴2〇a，2〇b攪拌，可使 淤渣量顯著減少。 表2 ·藉極比之再生效率與電流密度範圍 NO 陰極：陽極比 陽極電流密度 (A/dm2) 電流 (A) 電壓 (V) 電解前 (g/L) 電解後 (g/L) 過猛酸再生率 (g/AH) 1 1 10 2.3 1.75 3.01 18 17 1.23 2 1 10 5.5 4.18 4.19 18 13 2.57 3 1 10 10.5 7.98 6.76 18 11 1.89 4 1 20 2.3 1.75 3.22 18 17 1.23 5 1 20 5.5 4.18 4.25 18 13 2.57 6 1 20 10.5 7.98 6.9 18 8 2.70 7 1 20 20 15.2 11.8 18 8 1.42 8 1 40 2.3 1.75 4.02 18 17 1.23 9 1 40 5.5 4.18 5.7 18 15 1.54 10 1 40 10.5 7.98 9.03 18 14 1.08 表2係顯示藉改變極比（陰極16b與陽極16a之電極 面積比率）及陽極電流密度時之實驗結果產生之再生效率 ’第7圖係顯示該結果者，顯示相對於電流密度之過錳酸 15 再生率。再生率之高峰值在極比1 : 20時與1 : 1〇時並無 實質差異，不過由於在實用上應儘可能擴大可取得使用電 流之密度範圍，因此極比以1 : 20為佳。 16 1287589 玖、發明說明 產業上可利用性 如以上說明，藉由關於本發明之電解再生處理裝置， 在將含金屬離子之蝕刻處理液電解再生之際，可儘可能地 減少不溶性淤渣之發生，因此不僅可使淤渣之除去機構為 5 簡單化者、使淤渣之除去作業簡單化，同時可謀求裝置之 小型化。 【圖式簡單說明】 第1圖是說明有關本發明之電解再生處理裝置之一例 ^ 之說明圖。 10 第2圖是第1圖所示之電解再生處理裝置之平面圖。 第3圖是第1圖所示之電解再生處理裝置中所使用之 電極之立體圖。 第4圖是說明第1圖所示之電解再生處理裝置中，用 來作為攪拌機構之用以將再生槽内之蝕刻處理液喷出之喷 15 嘴孔。 第5圖是用以說明習知之電解處理裝置之說明圖。 · 苐6圖是顯不相對於時間之過猛酸之增加率之圖形。 第7圖是顯示相對於電流密度之過錳酸之再生率之圖 形〇 m 20 【圖式之主要元件代表符號表】 10…電解再生處理裝置 16· · ·電極 12···再生槽 16a···陽極（筒狀網體16a) 12a〜12h···區域 16b···陰極（棒體16b) 14aJ4b…隔板 18···泵 17 1287589Table 1 shows the permanganese per electrolysis time (initial state, 2 hours, 4 hours, 6 hours after passing) when the presence or absence of the nozzles 20a, 20b and the amount of agitation (10 flow rate of the etching liquid passing through the apparatus) are changed. The change in the acid content (rise rate) and the change in the amount of sludge. Each of the conditions has longitudinal partitions 14a, 14b. However, condition 1 is the case where no nozzles 20a, 20b, the flow rate is 67 L/min, and condition 2 is the same without nozzles 15 1287589 玖, invention description 2〇 a, 2〇b, and when the flow rate is increased to 15〇L/min, condition 3 is when there are nozzles 20a, 20b, the flow rate is 67L/min, and condition 4 is similar to nozzles 20a, 20b. Increase the flow rate to 15 〇L/min. The figure is a graph showing the results of Table 1. It can be seen from the experimental results that the rate of increase of the permanganic acid, that is, the rate of increase of permanganic acid, rises due to the flow rate of the regenerative electrode and the agitation of the stagnation portion, but in this case, only the agitation by the flow rate of the regenerative electrode is generated. It is impossible to remove the sludge sufficiently. On the other hand, by stirring the nozzles 2〇a, 2〇b, the amount of sludge can be significantly reduced. Table 2 · Regeneration efficiency and current density range by NO. Cathode: anode to anode current density (A/dm2) current (A) voltage (V) before electrolysis (g/L) after electrolysis (g/L) Acid regeneration rate (g/AH) 1 1 10 2.3 1.75 3.01 18 17 1.23 2 1 10 5.5 4.18 4.19 18 13 2.57 3 1 10 10.5 7.98 6.76 18 11 1.89 4 1 20 2.3 1.75 3.22 18 17 1.23 5 1 20 5.5 4.18 4.25 18 13 2.57 6 1 20 10.5 7.98 6.9 18 8 2.70 7 1 20 20 15.2 11.8 18 8 1.42 8 1 40 2.3 1.75 4.02 18 17 1.23 9 1 40 5.5 4.18 5.7 18 15 1.54 10 1 40 10.5 7.98 9.03 18 14 1.08 Table 2 The system shows the regenerative efficiency by the experimental results when the ratio of the electrode (the ratio of the electrode area of the cathode 16b to the anode 16a) and the anode current density are shown. [Fig. 7 shows the result, showing the permanganic acid 15 regeneration relative to the current density. rate. The peak value of the regeneration rate is not substantially different from that of 1:1 when the ratio is 1:20. However, since it is practically possible to maximize the density range in which the current can be used, the ratio is preferably 1:20. 16 1287589 发明Inventive Description Industrial Applicability As described above, with the electrolytic regeneration processing apparatus of the present invention, the insoluble sludge can be reduced as much as possible while electrolytically regenerating the etching solution containing metal ions. Therefore, not only the sludge removal mechanism can be simplified, but also the sludge removal operation can be simplified, and the size of the apparatus can be reduced. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is an explanatory view showing an example of an electrolytic regeneration processing apparatus according to the present invention. 10 Fig. 2 is a plan view showing the electrolytic regeneration processing apparatus shown in Fig. 1. Fig. 3 is a perspective view of an electrode used in the electrolytic regeneration processing apparatus shown in Fig. 1. Fig. 4 is a view showing a nozzle hole for ejecting an etching treatment liquid in a regeneration tank as an agitation mechanism in the electrolytic regeneration processing apparatus shown in Fig. 1. Fig. 5 is an explanatory view for explaining a conventional electrolytic treatment apparatus. · Figure 6 is a graph showing the rate of increase in acidity relative to time. Fig. 7 is a graph showing the reproduction rate of permanganic acid with respect to current density 〇m 20 [Main component representative symbol table of the drawing] 10: Electrolytic regeneration processing device 16 · · Electrode 12···Regeneration tank 16a· ·Anode (cylindrical mesh body 16a) 12a~12h···region 16b···cathode (rod 16b) 14aJ4b...separator 18···pump 17 1287589
玖、發明說明 20…配管 100…電解處理裝置 20a…喷嘴孔 102…樹脂製基板 30…處理裝置 104···触刻處理槽 32…處理槽 106…配管 34…溢流槽 108…再生槽 36…配管 110…多數根電極 38…配管 112···循環配管 40…栗 114…循環泵 42…過：?慮器 200…淤渣除去槽 44…配管 202…循環泵 46…送液泵 204,206…循環配管 48…過慮器 18发明, invention description 20: piping 100...electrolysis processing apparatus 20a...nozzle hole 102...resin substrate 30...processing apparatus 104··touch processing tank 32...processing tank 106... piping 34...overflow tank 108...regeneration tank 36 ...pipe 110...most electrode 38...pipe 112···recycling pipe 40...chest 114...circulating pump 42...over: treater 200...sludge removal tank 44...pipe 202...circulation pump 46...feed pump 204,206... Circulating piping 48... filter 18