200302881 玖、發明說明 (發月說月應欽明·發明所属之技術領域、先前技術、内容、實施方式及囷式簡單說明） 【發明所屬之技術領域】200302881 发明 Description of invention (A brief description of the technical field, prior art, contents, embodiments, and formulas to which the invention belongs should be made clear by the invention) [Technical field to which the invention belongs]
本發明是有關於電解再生處理裝置，更詳而言之，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。 t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側積層有多數導體圖案之多層電 15 路基板。 5亥增層基板之製造步驟中，於樹脂層之表面形成錢金 屬層時，為了使樹脂層與鍍金屬層之密著性良好，故在樹 月曰層表面加彳于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 2〇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 200302881 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圖所不之電解處理裝置1〇〇設有再生槽1〇8，該 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1〇4 一體化，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··· 〇 10 15 該再生槽108餘刻處理槽1〇4 設有連結兩槽之循 環配管112,且藉由設於該循環配管112之途中之循環果 114，從蝕刻處理槽104流入再生槽1〇8之蝕刻處理液藉電 極110，110···之電解處理再生，並回到餘刻處理槽⑽。 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 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Μηό+時，樹脂製基 板102之表面粗化即形成。在該㈣處理槽1()4生成之含 有Mn6+之蝕刻液進入再生槽1〇8，藉電極ιι〇，ιι〇〜之電解 處理’ Μη6氧化為Mn7+，並再度回到飯刻處理槽。藉 該電極110，110·.·進行電解處理時，係將斷6+氧化為施7+ 而再生。然而，基於再生效率，_部份的Mn6+不會再生而 生成二氧化錳（Μη02)。 7久巧个浴· ΐ生之於渣（ 以下簡稱於潰）而循環於餘刻處理槽1〇4及再生槽1〇8, 20 200302881 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1〇〇中，設有用以 將姓刻處理液中之於渣沉殿除去之於渣除去槽2〇〇。該於 5渣除去槽200與再生槽係藉由設置有循環果2〇2之循環配 s 204,206㈣，因此再生槽⑽内之㈣可與敍刻處理 液-起流到於逢除去槽200,而業已除去於逢之處理液也 可回到再生槽108。 第5圖所示之電解處理裝置⑽中，藉於渣除去槽 1〇 200之設置而可除去蝕刻處理液令之淤渣，故可防止淤渣 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a亥除去作業非常繁雜，且，業已沉殿蓄積之於潰 塊很硬，更增加該淤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於逢產±、而可達到不 需設置淤渣除去槽200之再生槽1〇8的方案。 【潑^明内容】 -〇 口此本發明之課題，即在提供一種電解再生處理裝 置’係在將含有金屬離子之钱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於渣，而不需 特別併設淤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， 200302881 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= 内所產生之淤渣量，而完成了本發明。 5 ，亦即，藉由本發曰月，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 給之前述餘刻處理液-面交互向上或向下地變更流動方向 ，一面依序流至出口側方向； 10 冑極，設於在前述多數個區域當中之前述#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 以撥拌前述姓刻液。 本發明中’ ^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，藉此可防止不溶性於逢在變 2〇更㈣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㈣處理液噴出之噴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飾刻處 理液，並將該餘刻處理液再度送回該再生槽，而該循環路 徑上設有前述噴嘴為佳。 200302881 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，將生成二氧化链（Mn〇2)等不溶性於渣之電極， 設置成與向上流動之蚀刻處理液接觸之狀態，同時在姓刻 5處理液沉殿之部分設置㈣機構，如此一來因電極生成之 不岭f生游邊實質上不會蓄積在再生槽内，因此可藉由設於The present invention relates to an electrolytic regeneration treatment device, and more specifically, to an electrolytic regeneration treatment device for regenerating an etching treatment liquid containing metal ions in a regeneration tank 5 provided with electrodes. t Prior art; J Multilayer circuit boards used in semiconductor devices, etc., use so-called build-up substrates. The manufacturing of the build-up substrate is, for example, forming through-holes on the resin layers each having a predetermined thickness formed on both sides of the core substrate to expose the bottom surface of the conductor patterns and the like formed in the core substrate, and then including the through-holes. A metal plating layer is formed on the entire surface of the resin layer on the wall surface, and then a pattern is formed on the metal plating layer to form a conductor pattern and a through hole. In addition, by repeating the same operation, a multilayer circuit board having a plurality of conductor patterns laminated on both sides of the core substrate can be obtained. In the manufacturing process of the 5th layer substrate, in order to form a fine metal layer on the surface of the resin layer, in order to make the resin layer and the metal plating layer have good adhesion, the surface of the tree layer is added with a rough surface to form fine unevenness. Surface treatment. In this roughening treatment, an etching solution containing a metal ion, such as an aqueous solution of permanganate or a chromium solution containing 620 valence, is used as an etching solution for etching the resin layer. Such an etching solution containing metal ions may reduce the etching performance by performing a roughening treatment on the surface of the resin layer. However, the electrolytic treatment may be performed on the etching treatment solution whose etching performance is reduced, so that the etching solution may be etched. Performance 200302881 玖, invention description regeneration. Japanese Patent Application Laid-Open No. 10-245443 discloses a device shown in Fig. 5 as such an electrolytic treatment device. The electrolytic processing apparatus 100 shown in FIG. 5 is provided with a regeneration tank 108. The regeneration tank 108 is immersed in an etching solution by immersing a pipe 106 with a resin substrate 102 to be roughened. The tank 104 is integrated, and the regeneration tank 108 is provided with a plurality of electrodes 110, 110 which are electrically connected to the rectifier. 1015 The regeneration tank 108 is provided with a processing tank 104 for connecting the two tanks. The circulation piping 112 and the circulation fruit 114 provided on the way of the circulation piping 112 flow from the etching treatment tank 104 into the regeneration tank 108 and the etching treatment liquid is regenerated by the electrolytic treatment of the electrodes 110, 110 ... Until the remainder of the processing stable. However, when the electrolytic treatment in the regeneration tank 108 is performed, the regeneration reaction of the etching treatment liquid is regenerated, and a side reaction that generates insoluble sludge is also caused. For example, when an aqueous permanganate solution is used as the etching solution, when Mn7 + is reduced to Mn + in the etching treatment tank 104, the surface of the resin substrate 102 is roughened. The etching solution containing Mn6 + generated in the ㈣ treatment tank 1 () 4 enters the regeneration tank 108, and the electrolytic treatment of the electrode ιι, ιιο ～ is oxidized to Mn7 +, and then returned to the rice carving processing tank again. When the electrodes 110 and 110 are used for electrolytic treatment, the broken 6+ is oxidized to 7 7 and regenerated. However, based on the regeneration efficiency, _ part of Mn6 + will not be regenerated to form manganese dioxide (Μη02). 7 Jiuqiao bath · The slag that was born in the slag (hereinafter referred to as ulcer) and circulated in the remaining treatment tank 104 and the regeneration tank 108, 20 200302881 玖, the description of the invention and gradually accumulated, it is easy to become a blockage of piping, etc. This may cause adverse effects on the surface roughening of the resin substrate 102. Therefore, the electrolytic treatment apparatus 100 shown in FIG. 5 is provided with a slag removal tank 200 for removing the last name engraved processing solution from the slag sinking hall. The slag removal tank 200 and the regeneration tank in the 5 slag removal tank 200 are equipped with a circulation system 204,206㈣, so that the ⑽ in the regeneration tank 与 can flow with the etched treatment liquid to the Yufeng removal tank 200, The treatment liquid from which Yu Feng has been removed can also be returned to the regeneration tank 108. In the electrolytic treatment apparatus ⑽ shown in FIG. 5, the sludge caused by the etching treatment liquid can be removed by setting the slag removal tank 10200, so that the sludge can be prevented from being in the etching treatment tank 104 and the regeneration tank 108. Accumulation. However, the sludge accumulated and accumulated in the sludge removal tank 200 must be removed regularly, and the removal operation of the hydration is very complicated, and the accumulation of the sediment in the hall is very hard, which further increases the difficulty of the removal operation of the sludge. 15 In addition, if the sludge removal tank 200 is provided in parallel, the size of the electrolytic treatment apparatus 100 will increase. Therefore, it is necessary to have a scheme to reduce as much as possible during production and achieve a regeneration tank 108 without the need to set a sludge removal tank 200. [Explanation of content]-0 The subject of the present invention is to reduce as much as possible when providing an electrolytic regeneration treatment device 'when the treatment solution containing metal ions is engraved in a regeneration tank provided with electrodes. The generated insolubility in the slag does not require a special sludge removal mechanism such as a sludge removal tank. The present inventors kept reviewing in order to solve the above-mentioned problems, and found that 200302881 (1), the invention explains that the etching treatment solution flowing into the regeneration tank flows upward or downward alternately, and an electrode is provided to contact the etching treatment solution flowing upward. The agitated portion of the etching treatment liquid is further stirred, so that the amount of sludge generated in the regeneration = can be reduced as much as possible, and the present invention has been completed. 5, that is, with the present month, an electrolytic regeneration processing device can be provided, which can regenerate an etching treatment solution containing metal ions, including: a regeneration tank, the interior of which is divided into a plurality of regions, so that the supply side The above-mentioned remaining processing liquid-surface interaction changes the flow direction upwards or downwards, and one side sequentially flows to the outlet side direction; 10 poles are provided in the above-mentioned #etching liquid in the above-mentioned area among the above-mentioned areas; And a stirring mechanism, which is provided in a portion where the etching solution precipitates in the aforementioned area and is used to stir the aforementioned etching solution. In the present invention, it is preferable to use an electrode having a larger anode area than the cathode area, especially an electrode formed of a cylindrical mesh body and an electrode formed of a rod body inserted into the mesh body. The electrode is preferably used in a state in which the aforementioned mesh body and rod body are arranged upright along the flow direction of the processing liquid. In addition, by setting the stirring mechanism in the vicinity of a portion where the flow direction of the etching treatment liquid is changed from downward to upward, it is possible to prevent insolubility from accumulating in a portion where the flow direction of the treatment liquid is changed by 20 °. It is preferable that the stirring mechanism is a nozzle having a nozzle for spraying the radon treatment liquid in the regeneration tank. In the present invention, a circulation path is provided, and the engraving treatment liquid can be taken out from the foregoing regeneration tank, and the rest of the treatment liquid can be returned to the regeneration tank again, and the circulation path is preferably provided with the aforementioned nozzle. 200302881 发明 Description of the invention With the electrolytic regeneration device of the present invention, the amount of insoluble sludge generated in the regeneration tank can be greatly reduced compared with the conventional device. In addition, electrodes that are insoluble in the slag, such as MnO2, are formed in a state in contact with the etching treatment liquid flowing upward, and a puppet mechanism is provided in the part of the sink of the treatment liquid with the last name 5 Because the ridges generated by the electrodes are not substantially accumulated in the regeneration tank, it can be set by
循衣配S中述之過滤器等簡易之於逢除去機構而輕易地除 去。 1 結果，由於關於本發明之電解再生處理裝置中，不需 10特別併設於逢除去槽等齡潰除去機構，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。 \ 5 h 第2圖是第1圖所示之電解再生處理裝置之平面圖。The filter and other filters described in S are easily removed by the removal mechanism. 1 As a result, the electrolytic regeneration processing apparatus of the present invention does not need to be provided in a special age-removing mechanism such as a removal tank, so that the size of the electrolytic regeneration apparatus can be reduced. Brief Description of the Drawings Fig. 1 is an explanatory diagram illustrating an example of an electrolytic regeneration processing apparatus according to the present invention. \ 5 h Figure 2 is a plan view of the electrolytic regeneration processing device shown in Figure 1.
第3圖疋第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5兒明第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钕刻處理液喷出之喷 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錳酸之再生率之圖 形0 10 200302881 玖、發明說明 【實施方式;1 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側方向 · 5區分為多數個區域12&〜1211，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。 該區域12a〜12h係各自藉由2種類之隔板14a，l4b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。 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之姓刻處理液，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i2a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i4b與隔板i4a所形成之區域 20 12c ’因此|虫刻處理液在區域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-l2b—12c—12d—12e—12f-l2g—I2h 之順 11 200302881 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 上之區域12b，12d，12f之各區域中設置有電極16。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& 10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 值會因姓刻處理液之處理置如何設定而不同，不過處理二 氧化I孟（Mn〇2)時，如後所述地將陽極陰極面積比設定為 20 : 1較為適當。 15 又，設於區域l2b，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。 隹 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)。 10 該餘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，姓刻處理液之流速會變得極為緩慢而 產生阻塞。蝕刻處理液中所含淤渣即容易在該阻塞部分沉 澱。 這一點，第1圖所示之再生槽12中，在蝕刻處理液之 12 200302881 玖、發明說明 机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㈣㈣處理液之_手段。該攪拌手段中，沿再生 乜12底面6又置配管2〇’而位於姓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。 之形成於再生槽12底面側之噴嘴孔取族將流入區域 之業已再生之再生麵刻液以栗18昇壓而喷出，搜掉再 生中之蝕刻處理液。Figures 3 and 3 are perspective views of electrodes used in the electrolytic regeneration processing apparatus shown in Figure 1. Fig. 4 is a nozzle 20 for spraying the neodymium-etched treatment liquid in the regeneration tank in the electrolytic regeneration treatment device shown in Fig. 5 and Fig. 1 as a mixing mechanism. Fig. 5 is an explanatory diagram for explaining a conventional electrolytic treatment device. Fig. 6 is a graph showing an increase rate of permanganic acid with respect to time. Fig. 7 is a graph showing the regeneration rate of permanganic acid relative to the current density. 0, 10, 2003, 02, 881, Description of the invention [Embodiment; 1] An example of the electrolytic regeneration treatment device according to the present invention is shown in Fig. 1. The regeneration tank 12 constituting the electrolytic regeneration processing device 10 shown in FIG. 1 is: from the supply side to the outlet side where the etching treatment liquid containing metal ions is supplied, and 5 is divided into a plurality of regions 12 & 1211, and the The etching solution is formed by using an etching solution containing metal ions such as permanganate, aqueous solution and the like to perform a roughening treatment on the surface of a resin substrate. The regions 12a to 12h are separated by two types of partitions 14a, 14b. The upper end of the partition 14a protrudes from the water surface of the etching treatment liquid, and the lower end of 10 is formed between the lower end of the partition 14a and the bottom surface of the regeneration tank 12. The path through which the etching treatment liquid can pass. On the other hand, the partition plate 14b is provided such that its lower end is in close contact with the bottom surface of the regeneration tank 12, and the etchant can flow over the upper end to the next area. In the regeneration tank 12 shown in FIG. 1, the treatment liquid engraved on the inner wall surface of the regeneration tank 12 and the region 12 a formed by the partition plate 14 a is formed between the lower end of the partition plate 15 a and the bottom surface of the regeneration tank 12. Since the gap flows into the region 12b, in the region i2a, the flow direction of the etching treatment liquid is downward. · The region 12b is formed by the partition 14a and the partition 14b. Therefore, the etching treatment solution flowing into the region 12b from the gap on the lower end side of the partition 14a will pass over the upper end of the partition 14b and flow into the partition i4b and the partition i4a. The region 20 12c 'so | the flow direction of the insect-etching treatment liquid in the region 12b is upward. In this way, the regions 12a to 12h are separated by two types of separators 14a and 14b, respectively, so that the etching solution flowing into the region 12a changes the flow direction interactively upward or downward while facing the exit direction (direction of the region 12h). That is, in order of 12a-l2b—12c—12d—12e—12f—12g—I2h 11 200302881 玖, the description of the invention flows 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 is upward. The electrode 16 is an electrode composed of an anode formed of a cylindrical mesh body 16a and a cathode formed of a rod body 16b inserted into the mesh body 16a, as shown in FIG. _ The rod body 16b is, for example, a portion of the surface of the conductor covered with a tube made of polytetrafluoroethylene. The cylindrical mesh body 16 is formed of a metal slat or mesh. Therefore, in the electrode 16, the anode system formed of the mesh body 16a is formed to have an area larger than that of the cathode formed of the rod body 16b. The electrode 16 shown in FIG. 3 is a mesh body 16 & 10 and a rod body 16b which are arranged upright in each of the regions 12b, 12d, and 12f along the upward flow direction of the etching treatment liquid. The area ratio of the anode to the cathode or the current value will vary depending on how the treatment solution of the engraved treatment solution is set. However, when treating I2O (MnO2), the anode-cathode area ratio is set to 20 as described later: 1 is more appropriate. 15. The electrodes 16 provided in the regions 12b, 12d, and 12f are shown in FIG. 2, and a plurality of electrodes 16, 16, 16 may be provided.再生 In the regeneration tank 12 shown in Fig. 1, the etching treatment liquid flowing into the region 12a changes the flow direction alternately upward or downward, and sequentially flows through each region toward the exit direction (region 12h). 10 When the flow direction of the treatment liquid is changed from upward to downward, or from downward to upward, the flow velocity of the treatment liquid of the last name will become extremely slow and cause blockage. The sludge contained in the etching treatment liquid is liable to be deposited on the blocked portion. In this regard, in the regeneration tank 12 shown in FIG. 1, in the vicinity of the etching treatment liquid 12 200302881 发明, description of the invention, the maneuvering direction is changed from upward to downward or from downward to upward. means. In this stirring means, the pipe 20 is placed along the bottom surface 6 of the regeneration cylinder 12 and the portion of the pipe 20 located in the vicinity of the change in the flow direction of the engraved treatment liquid is shown in Fig. 4 from the pipe 2. The nozzle hole formed on the bottom surface side of the regeneration tank 12 ejects the already-regenerated regeneration surface engraving solution that has flowed into the area by pumping up the chestnut 18, and searches for the etching treatment solution during regeneration.
再生㈣液從該噴嘴孔施，加朝再生槽12底面侧喷 出，如此亦可防止於逢在再生槽12之底面沉搬蓄積。 1〇 対嘴孔2Ga，2Ga所形成之配管2G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叫朴 而略平行地、且設於再生槽12底面之㈣。之所以將配管 20如此設置，W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。The regeneration solution is sprayed from the nozzle hole and sprayed toward the bottom surface side of the regeneration tank 12, so that it can be prevented from accumulating in the bottom surface of the regeneration tank 12. The piping 2G formed by the nozzle holes 2Ga and 2Ga is shown in FIG. 2. The partition wall between each area and the area where the etching treatment solution flows next is called simple but slightly parallel and is provided in the regeneration tank 12. Bottom ㈣. The piping 20 is set in such a manner that the flow direction of the etching treatment liquid is changed from downward to 15 near the partitions 14a and 14b and near the bottom surface of the regeneration tank 12, and the sludge is liable to settle in the vicinity. Accumulated sake.
又，從配管20之喷嘴孔20a，20a噴出之噴出液攪拌入 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2〇之噴嘴孔 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3〇内。兮产理 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#刻之過锰酸鹽水溶液等含有八屬 13 200302881 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10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 液之一部分作為蝕刻處理液送到電解再生處理裝置1Q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内之電解使蝕刻處理液再生之際，淤渣之產 生極少，相較於第5圖所示之習知蝕刻處理槽104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之配管之途中設置過 2〇濾器42,即可充分作為除去業經再生之再生蝕刻液及蝕刻 液中之於逢之機構，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30及電解再生裝置 1 〇中’以過處器42之交換程度即足以作為於逢除去作業 14 200302881 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。 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 過猛酸率 (%) 過錳酸上昇 率 (%) 於渣量 (g) 5V/96A Oh 72.02 0.00 1 無喷嘴 67L/分 5V/96A 2h 75.18 3.16 丄 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 2 無喷嘴 150L/分 5V/96A 2h 72.77 1.74 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 有噴嘴 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 4 有喷嘴 150L/分 5V/96A 2h 74.38 2.89 縱隔板 (27mm/秒） 5V/96A 4h 78.69 7.20 5V/96A 6h 84.70 13.21 0.002gIn addition, the ejection liquid sprayed from the nozzle holes 20a and 20a of the piping 20 is stirred into the regenerating etching treatment liquid to prevent the sediment from accumulating and accumulating on the bottom surface of the regeneration tank 12, so it can also be regenerated as shown by the dotted line in FIG. The etching treatment liquid accumulated in the region other than the region 12h of the groove 12 is ejected from the nozzle holes 20 20a, 20a of the pipe 20. The electrolytic regeneration device 10 shown in Fig. 1 is installed in a processing device 30 for performing a roughening process such as roughening the surface of a resin substrate. In the production and processing device 30, a processing tank 32 is provided for storing a roughened surface of the resin substrate. The permanganate aqueous solution such as the engraving, etc. contains an etchant containing eight genus 13 200302881 发明, the ion of the invention An overflow tank 34 is provided on the outer periphery of the processing tank 32 to receive the etching solution overflowing from the processing tank 32. The regenerated etching solution that has been regenerated from the area 12h of the electrolytic regeneration processing apparatus 10 is returned to the overflow tank 34 through the pipe 36. 5 The etching solution and regenerated etching solution flowing into the overflow tank 34 are returned to the processing tank 32 through the pipe 38, the pump 40, and the filter 42. The filter 42 is used to separate the resin powder from the etching solution flowing into the overflow tank 34 and the regenerated etching solution. In addition, the processing tank 32 is provided with a pipe 44 for sending a part of the stored etching solution as an etching treatment solution to the regeneration tank 12 of the electrolytic regeneration processing apparatus 1Q. The pipe 44 is provided with a liquid feeding pump 46 and a filter.器 48。 48. The filter 48 is used to separate 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 device 30 and electrolytic regeneration processing device 1015 shown in FIG. 1 are used, and the etching treatment liquid is regenerated by electrolysis in the regeneration tank 12, the generation of sludge is extremely small, compared with the practice shown in FIG. 5. It is known that the amount of sludge generated in the etching treatment tank 104 can be suppressed to about 1/10. Therefore, in the processing device 30 and the electrolytic regeneration processing device 10 shown in FIG. I, a 20 filter 42 is installed on the way to return the etching solution flowing into the overflow tank 34 and the regeneration etching solution to the piping of the processing tank 32. That is, it can be fully used as a mechanism for removing the regenerated etching solution and the etching solution in the etching solution, and it is not necessary to install a special device such as the sludge removal tank 200 shown in FIG. 5 in the regeneration tank 12. Therefore, the exchange degree of the processor 42 in the processing device 30 and the electrolytic regeneration device 10 shown in FIG. 1 is sufficient as the removal operation 14 200302881 玖, the description of the invention, and therefore, the accumulation of the sediment in the The operation of removing the sludge block in the sludge removal tank 200 can also achieve miniaturization of the device. Next, the effects of the present invention will be described with reference to Tables 1 and 2, and Figs. 6 and 7. These graphs show the experimental results when the electrolytic regeneration treatment apparatus shown in Fig. 1 was used and the etching solution containing an aqueous solution of a permanganate was used as the metal ions. Table 1: Regeneration efficiency based on stirring conditions · Conditioning stirring amount (passing speed) Voltage / current electrolysis time Excessive acid rate (%) Permanganic acid rise rate (%) Slag amount (g) 5V / 96A Oh 72.02 0.00 1 Nozzle 67L / min 5V / 96A 2h 75.18 3.16 丄 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 2 No nozzle 150L / min 5V / 96A 2h 72.77 1.74 vertical partition (27mm / second) 5V / 96A 4h 74.27 3.24 5V / 96A 6h 75.22 4.19 1.63g 5V / 96A Oh 78.80 0.00 with nozzle 67L / min 5V / 96A 2h 80.27 1.47 j vertical partition (12mm / second ) 5V / 96A 4h 80.70 1.90 5V / 96A 6h 83.68 4.88 0.04g 5V / 96A Oh 71.49 0.00 4 with nozzle 150L / min 5V / 96A 2h 74.38 2.89 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 彳匕（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同樣是無噴嘴 15 200302881 玖、發明說明 20a，20b、而通過流速提升為15〇L/分時之情況，條件3是 有喷嘴20a，20b、通過流速為67L/分時之情況，條件$ $ 樣是有噴嘴20a，20b、而通過流速提升為15〇L/分時之情況 。第6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，藉噴嘴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 1 ·· 10 陽極電流密度 (A/dm2) 23 ^ 電流 (A) 1.75 電壓 (V) 3.01 電解前 (g/L) 18 電解後 (g/L) 17 過猛酸再生率 __(g/AH) 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 广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（陰極丨6b與陽極丨6a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 貫質差異’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 : 2〇為佳。 16 200302881 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；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】Table 1 shows the manganese per manganese per electrolysis time (initial state, 2 hours, 4 hours, and 6 hours) when the presence or absence of the nozzles 20a, 20b and the stirring amount (10 flow rate of the etching solution through the device) are changed. Changes in acid content (rising rate) and changes in sludge amount. In each condition, there are separators 14a and 14b in the vertical direction. However, condition 1 is the case where there are no nozzles 20a and 20b and the flow rate is 67 L / min. Condition 2 is also the case where there is no nozzle 15 200302881 发明, invention description 20a, 20b, when the flow rate is increased to 150L / min, condition 3 is with a nozzle 20a, 20b, when the flow rate is 67L / min, the condition is $ 20, such that there are nozzles 20a, 20b, and the flow rate is increased. In the case of 15 liters / minute. Fig. 6 is a graph showing the results of Table 1. It can be seen from the experimental results that the regeneration rate, that is, the increase rate of permanganic acid, will increase due to the passage velocity of the regeneration electrode and the stirring of the stagnant part. However, in this case, only the stirring generated by the passage velocity of the regeneration electrode is used. It is impossible to remove the sludge sufficiently. On the other hand, by using the nozzles 20a and 20b to stir, the amount of sludge can be significantly reduced. Table 2: Regeneration efficiency and current density range by using the electrode ratio NO cathode: anode ratio 1 ·· 10 anode current density (A / dm2) 23 ^ current (A) 1.75 voltage (V) 3.01 before electrolysis (g / L) 18 After electrolysis (g / L) 17 Permanganic acid regeneration rate __ (g / AH) 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 Guang 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 shows the regeneration efficiency generated by the experimental results when changing the pole ratio (the ratio of the electrode area of the cathode 丨 6b to the anode 丨 6a) and the anode current density. The graph shows the results, and shows the regeneration rate of permanganic acid 15 with respect to the current density. The peak value of the regeneration rate has no consistency difference between the extreme ratio of 1:20 and 1:10. However, since the range of the density of the available current can be expanded as practically as possible, the extreme ratio is 1:20. good. 16 200302881 发明, description of the invention The industrial applicability is as described above. With the electrolytic regeneration treatment device of the present invention, when the etching treatment liquid containing metal ions is electrolytically regenerated, it can be reduced as much as possible; Occurs, therefore, not only can the sludge removal mechanism be 5 simplified, the sludge removal operation can be simplified, but also the device can be miniaturized. [Schematic description]
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@。 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噴出之喷 15 嘴孔。Fig. 1 is an explanatory diagram illustrating an example of an electrolytic regeneration processing apparatus according to the present invention. 10 FIG. 2 is a plan view of the electrolytic regeneration processing apparatus shown in FIG. 1. Fig. 3 is a three-dimensional view of the electrodes used in the electrolytic regeneration processing apparatus shown in Fig. 1. Fig. 4 illustrates the 15 nozzle holes used in the electrolytic regeneration processing apparatus shown in Fig. 1 as a stirring mechanism for ejecting the etching treatment liquid in the regeneration tank.
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錳酸之再生率之圖 形。 20 【囷式之主要元件代表符號表】 10…電解再生處理裝置 12…再生槽 12a〜12h…區域 …隔板 16…電極 16a···陽極（筒狀網體16a) 16b···陰極（棒體16b) 18···泵 17 200302881 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…蝕刻處理槽 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…過濾、器 200…於潰除去槽 44···配管 202···循環泵 46…送液泵 204,206···循環配管 48···過渡器Fig. 5 is an explanatory diagram for explaining a conventional electrolytic treatment apparatus. Fig. 6 is a graph showing an increase rate of permanganic acid with respect to time. Fig. 7 is a graph showing the regeneration rate of permanganic acid with respect to the current density. 20 [Representative symbols for main components of the formula] 10 ... Electrolytic regeneration processing device 12 ... Regeneration tank 12a ~ 12h ... Area ... Separator 16 ... Electrode 16a ... Anode (Cylinder-shaped mesh body 16a) 16b ... Cathode ( Rod 16b) 18 ... Pump 17 200302881 881, Description of Invention 20 ... Piping 100 ... Electrolytic processing device 20a ... Nozzle hole 102 ... Resin substrate 30 ... Processing device 104 ... Etching processing tank 32 ... Processing tank 106 ... pipe 34 ... overflow tank 108 ... regeneration tank 36 ... pipe 110 ... many electrodes 38 ... pipe 112 ... circulation pipe 40 ... pump 114 ... circulation pump 42 ... filter 200 200 ... Piping 202 ... Circulation pump 46 ... Liquid delivery pumps 204,206 ... Circulation piping 48 ... Transitioner
1818