201233853 六、發明說明： 【發明所屬之技術領域】 本發明係關於蝕刻液之維持管理方法及使用其之系統 ，更詳細而言，係關於一種於因進行蝕刻而造成銅離子蓄 積，而使性能降低的蝕刻液中，藉由將該蝕刻液中之銅離 子濃度維持在一定的範圍，而可將該蝕刻液處理性能安定 化，並使壽命飛躍地延長之蝕刻液之維持管理方法及使用 其之系統。 【先前技術】 於最近之可撓性印刷配線板之領域中，爲了能將配線 圖型高密度化，而使用有濺鍍法二層CCL作爲貼銅層合板 (CCL)。該濺鍍法二層CCL，主要是藉由下述方式所製 作，即：在藉由濺鍍來將鎳-鉻合金形成於聚醯亞胺薄膜 上後進行銅濺鏟，進而形成銅電鎪層。 雖藉由上述鎳-鉻合金層的存在，能提昇聚醯亞胺薄 膜與銅層之間的密著性，但若在電路形成中，於經去除不 必要之銅電鍍層的部分殘存鎳-鉻合金層，則會在該部分 引起金屬析出，而有配線部分（銅電鍍的殘存部分）分流 的可能性，因此於濺鍍法二層C C L中，必須蝕刻去除鎳-鉻 合金層。 以往，關於鎳-鉻合金層之蝕刻劑，係已知有一些先 前技術（專利文獻1及2 )。然而，此等蝕刻液，即使最初 的性能優異，但由於在蝕刻處理過程於溶液中每次少量溶 -5- 201233853 解、蓄積的銅離子，因此有處理性能緩緩降低的問題，且 在實際的現場，伴隨著上述問題而產生了必須要調整處理 時間等之繁雜的操作之問題。 而且，在上述蝕刻液中，除了銅離子以外也有鎳離子 或鉻離子等所蓄積的物質，在此等的存在下僅將銅經濟性 地去除之方法仍未被發現，因此會將銅已達到特定濃度之 溶液廢棄，而成爲經濟方面成本上昇的主要因素。 此外，於多層印刷配線板的領域中，多數是藉由半加 成法來形成外層的銅電路。於該半加成法中，主要是在利 用無電解銅電鍍作爲種晶層的最終步驟中，蝕刻去除多餘 的無電·解銅電鍍層。 然而，由於在已去除無電解銅電鏟層的樹脂表面，係 附著有欲形成無電解銅電鍍被膜所使用的鈀觸媒等之金屬 的情況爲多，且因其影響而有配線間之絕緣性降低等的問 題，因此必須蝕刻去除鈀觸媒等。 以往，關於鈀觸媒之蝕刻劑，係已知有一些先前技術 (專利文獻3 )。然而，此等蝕刻液，即使最初的性能優 異，但由於在蝕刻處理過程於溶液中每次少量溶解、蓄積 的銅離子，因此有處理性能緩緩降低的問題，且在實際的 現場，伴隨著上述問題而產生了必須要調整處理時間等之 繁雜的操作之問題。 而且，在上述蝕刻液中，除了銅離子以外也有鈀離子 等所蓄積的物質，在此等的存在下僅將銅經濟性地去除之 方法仍未被發現，因此會將銅已達到特定濃度之溶液廢棄 -6- 201233853 ，而成爲經濟方面成本上昇的主要因素。 〔先前技術文獻〕 〔專利文獻〕 [專利文獻1]日本特開2004- 1 90054號公報 [專利文獻2]國際專利公開W02007/040046號公報 [專利文獻3]日本專利第41 1 3846號公報 【發明內容】 〔發明所欲解決課題〕 因此，本發明之課題爲提供一種鈾刻液之維持管理方 法，其係將會對蝕刻性能造成較大影響的銅離子，從在可 撓性印刷配線板、多層印刷配線板等之印刷配線板之銅電 路的形成所利用的蝕刻液中去除，藉此可達成該蝕刻液之 安定化，並延長其壽命，且有助於成本降低與廢棄物的削 減，或環境資源的保護。 〔解決課題之手段〕 本發明者們發現：僅將銅離子從因進行蝕刻而造成銅 離子蓄積的蝕刻液中選擇性地去除的方法，且經進行銳意 硏究的結果得知：藉由利用隔膜電解法，而可將銅離子選 擇性地去除一事。接著發現：利用該方法，將蝕刻液進行 連續地處理，並將銅濃度維持在一定的範圍，藉此可達成 該蝕刻液之處理性能的安定化，並飛躍地延長該蝕刻液的 壽命，而完成了本發明。 201233853 亦即，本發明係一種蝕刻液之維持管理方法，其係包 含：將因進行蝕刻而造成銅離子蓄積而使性能降低的蝕刻 液，從蝕刻槽送至以陽離子交換膜作區隔的電解槽之陰極 室並進行電解的步驟；與使經電解的陰極室之陰極液返回 蝕刻槽的步驟，該蝕刻液之維持管理方法，其特徵爲：於 電解槽之陽極槽中加入有酸性溶液，且使前述蝕刻液中之 銅離子的濃度維持在〇.lg/L〜10g/L之範圍進行電解。 此外，本發明係一種鎳-鉻合金用蝕刻液之維持管理 方法，其係包含：將蝕刻槽之鎳-鉻合金用蝕刻液送至具 有陽離子交換膜之電解槽的陰極室並進行電解的步驟；與 使經電解的陰極室之陰極液返回蝕刻槽的步驟，該鎳-鉻 合金用蝕刻液之維持管理方法，其特徵爲：於電解槽之陽 極室中加入有酸性溶液，且使前述鈾刻液中之銅離子的濃 度維持在〇.lg/L〜l〇g/L之範圍進行電解。 再者，本發明係一種鈀用蝕刻液之維持管理方法，其 係包含：將蝕刻槽之鈀用蝕刻液送至具有陽離子交換膜之 電解槽的陰極室並進行電解的步驟：與使經電解的陰極室 之陰極液返回蝕刻槽的步驟，該鈀用蝕刻液之維持管理方 法，其特徵爲：於電解槽之陽極室中加入有酸性溶液，且 使前述蝕刻液中之銅離子的濃度維持在〇.lg/L〜10g/L之範 圍進行電解。 此外，本發明係一種蝕刻液之維持管理系統，其係具 備：蝕刻槽，係設置有銅分析裝置；電解槽，係藉由陽離 子交換膜來區隔設置有陰極的陰極室與設置有陽極的陽極 -8- .201233853 室；蝕刻液送液配管，係將前述蝕刻槽與前述電解槽之陰 極室作連通，使蝕刻液能在彼等之間循環；供電設備，係 用來將電流供給至前述陰極及陽極：以及電腦，係用來控 制銅分析裝置、蝕刻液送液配管及供電設備。 〔發明效果〕 依據本發明，係藉由利用簡單的裝置，而可達成將因 進行蝕刻而造成銅離子蓄積，而使性能降低的蝕刻液之蝕 刻性能安定化，並且延長其壽命。因此，本發明，係有助 於作業性的提昇與成本降低以及廢棄物的削減者。 〔實施發明之最佳形態〕 本發明方法，係藉由電解去除因進行蝕刻而造成銅離 子蓄積之蝕刻液中所含的銅離子，而使蝕刻性能安定化， 並延長其壽命。 因本發明所致之成爲維持、管理之對象的蝕刻液’係 只要是將因進行蝕刻而造成銅離子蓄積，而使性能或作業 性降低者便無特別限制。上述之飩刻液，係可列舉例如： 用來將可撓性印刷配線板、多層印刷配線板等之印刷配線 板之銅電路的形成中所利用的各種金屬、觸媒、樹脂等， 去除或剝離的蝕刻液。 具體的蝕刻液之例示，係可列舉：用來剝離鎳-鉻合 金層的鎳-鉻合金用蝕刻液，該鎳-鉻合金層，係殘存在使 用濺鍍二層CCL而進行了電路形成的基板之已去除銅電鍍 -9 - 201233853 層的部分（空間部分）。 上述的鎳-鉻合金用蝕刻液之例示，雖可列舉：含有 氫氯酸及/或氯化物、與硫酸及/或硫酸鹽、以及亞硝酸及/ 或亞硝酸鹽者；含有氫氯酸及/或氯化物、與硫酸及/或硫 酸鹽及/或磺酸化合物及/或磺酸化合物鹽者；含有氫氯酸 及/或氯化物、與硝酸及/或硝酸鹽、與硫酸及/或硫酸鹽及 /或磺酸化合物及/或磺酸化合物鹽者；含有氫氯酸及/或氯 化物、與硝酸及/或硝酸鹽' 以及亞硝酸及/或亞硝酸鹽者 :含有氫氯酸及/或氯化物、與硝酸及/或硝酸鹽、與磷酸 及/或磷酸鹽、與亞硝酸及/或亞硝酸鹽者等，但亦可爲此 外之組成者。此外，於該等之鎳-鉻合金用蝕刻液中，亦 可視需要添加界面活性劑、含硫有機化合物等。 在此’氯化物，係指例如：氯化鈉、氯化鉀、氯化銨 、氯化鈣、氯化鋰' 氯化銅、氯化鎳、氯化鐵、氯化鋅、 氯化錫、氯化鉛等。硫酸鹽，係指例如：硫酸鈉、硫酸鉀 、硫酸銨、硫酸鈣、硫酸鋰、硫酸銅、硫酸鎳、硫酸鐵' 硫酸鋅、硫酸錫 '硫酸鉛等。硝酸鹽，係指例如：硝酸鈉 、硝酸鉀、硝酸銨、硝酸鈣、硝酸鋰、硝酸銅、硝酸鎳、 硝酸鐵、硝酸鋅、硝酸錫、硝酸鉛等。磷酸鹽，係指例如 :磷酸鈉'磷酸鉀、磷酸銨、磷酸鈣、磷酸鋰、磷酸銅、 磷酸鎳、磷酸鐵、磷酸鋅、磷酸錫、磷酸鉛等。亞硝酸鹽 ’係指例如：亞硝酸鈉、亞硝酸鉀、亞硝酸銨、亞硝酸鈣 等。擴酸化合物’係指例如：甲磺酸'乙磺酸、羥基甲磺 酸、經基乙磺酸等。磺酸化合物鹽，係指例如：甲磺酸鈉 -10- 201233853 、甲磺酸鉀、甲磺酸銨、甲磺酸甲酯、乙磺酸鈉、羥甲磺 酸鈉、羥乙磺酸鈉等。 此外，界面活性劑，係指例如：聚氧乙稀聚氧丙稀嵌 段聚合物、乙二胺之聚氧乙稀聚氧丙稀嵌段聚合物、聚氧 乙稀烷基醚、聚氧乙稀烷基苯基醚、聚乙烯乙二醇、聚氧 乙稀烷基胺、烷基烷醇醯胺等之非離子界面活性劑；烷基 苯磺酸鹽、α烯烴磺酸鹽、醚羧酸鹽、烷基磷酸鹽等之陰 離子界面活性劑；四級銨鹽、烷基胺鹽等之陽離子界面活 性劑；烷基甜菜鹼、烷基胺氧化物等之兩性界面活性劑。 含硫化合物，係指含有硫原子，且排除上述之硫酸、硫酸 鹽、磺酸化合物、磺酸化合物鹽之化合物，例如：硫脲、 二乙基硫脲、四甲基硫脲、1-苯基-2-硫脲、硫乙烯胺等之 硫脲化合物、2-酼基咪唑' 2-锍基噻唑啉、3-锍基-1,2,4-三唑、巯基苯倂咪唑、锍基苯倂噁唑、锍基苯併噻唑、锍 基吡啶、硫代乙醇酸、毓基丙酸、硫代蘋果酸、L-光胱胺 酸等之硫醇化合物、2-胺苯基二硫化物、硫蘭、硫代二乙 醇酸（thiodi glycolic acid )等之二硫化物化合物、L-(-)胱胺酸、二吡啶基二硫化物、二硫代二乙醇酸等之二硫 化物化合物、硫氰酸鈉、硫氰酸鉀、硫氰酸銨等之硫氰酸 鹽、磺胺酸、磺胺酸銨、磺胺酸鈉、磺胺酸鉀等之磺胺酸 或其鹽。 另外，上述的鎳-鉻合金用蝕刻液，可利用例如：曰 本特開2004-190054號公報、日本特開2005-154899號公報 、曰本特開2006-229196號公報、日本特開2005-350708號 -11 - 201233853 公報等所記載者。 上述鎳-鉻合金用蝕刻液中’係以含有氫氯酸及/或氯 化物、與硫酸及/或硫酸鹽、以及亞硝酸及/或亞硝酸鹽者 爲佳，特別是以酸濃度爲0.2〜13N、氯離子濃度爲0.1〜 13質量％、硫酸離子濃度爲0.5〜30質量％、亞硝酸離子爲 0.0001〜0.5質量％，且視需要添加有0.001〜5質量％之界 面活性劑之組成者爲佳。 此外，蝕刻液之其他例示，係可列舉：用來剝離鈀觸 媒層的鈀用蝕刻液，該鈀觸媒層，係將無電解銅電鍍作爲 種晶層，並殘存在藉由半加成法而進行了電路形成的基板 之已去除銅電鍍層的部分（空間部分）。 上述的鈀用蝕刻液之例示，雖可列舉：含有氫氯酸及 /或氯化物者；含有氫氯酸及/或氯化物、與硝酸及/或硝酸 鹽者；含有氫氯酸及/或氯化物、與硝酸及/或硝酸鹽、與 硫酸及/或硫酸鹽及/或磺酸化合物及/或磺酸化合物鹽者： 含有氫氯酸及/或氯化物、與亞硝酸及/或亞硝酸鹽者；含 有氫氯酸及/或氯化物、與硝酸及/或硝酸鹽、與磷酸及/或 磷酸鹽、與亞硝酸及/或亞硝酸鹽者；含有氫氯酸及/或氯 化物、與亞硝酸及/或亞硝酸鹽、與硫酸及/或硫酸鹽及/或 磺酸化合物及/或磺酸化合物鹽者等，但亦可爲此外之組 成者。此外，於此等之鈀用蝕刻液中，亦可視需要添加界 面活性劑、含硫有機化合物等。另外，氯化物、硝酸鹽、 氯化物、硫酸鹽、磺酸化合物、磺酸化合物鹽、亞硝酸鹽 、磷酸鹽、界面活性劑、含硫有機化合物，係可使用與上 -12- 201233853 述鎳-鉻合金用蝕刻液相同者。 另外，上述之蝕刻液，係可利用例如：日本特開 2008- 1 063 54號公報、日本專利第4 1 1 3846號公報、日本特 開2005-1 54899號公報、日本特開2009-24220號公報、日本 特開2005-3 50708號公報、日本特開2006-2291 96號公報等 所記載者。 上述鈀用蝕刻液中，係以含有氫氯酸及/或氯化物、 與硝酸及/或硝酸鹽者爲佳，特別是以酸濃度爲0.2〜1 0N 、氯離子濃度爲0.1〜20質量％、硝酸離子爲1〜17質量％， 且視需要添加有0.001〜5質量％之界面活性劑之組成者爲 佳。 - 本發明方法，係藉由下述方式進行，即：將因上述銅 離子蓄積而使性能降低的蝕刻液，從蝕刻槽送至藉由陽離 子交換膜來作區隔的電解槽之陰極室，在此將銅於陰極析 出去除，並使銅離子濃度已降低的蝕刻液，再度返回蝕刻 槽。 於該電解中之陰極電流密度，係只要是在以銅作爲金 屬而有效地析出之範圍內則無特別限制，較佳爲〇. 1〜 ΙΟΑ/dm2，更佳爲0.2〜3 A/dm2之範圍。此外，相對於蝕刻 液量之電流量，亦無特別限制，一般而言，相對於蝕刻液 1L，以在0.01〜5A下進行者爲佳，在0.02〜1A之電流下進 行者爲更佳。 再者，上述電解，係以在25〜55t之溫度，特別是在 30〜50°C之溫度下進行者爲佳，此外，電解中之攪拌方式 -13- 201233853 雖無特別指定，但以不在陰極室內造成蝕刻液停滯部位的 方式進行充分攪拌者爲佳。 另外，於上述電解中，將酸性溶液’例如：硫酸或甲 磺酸、乙磺酸、羥基甲磺酸、羥基乙磺酸等之磺酸化合物 之溶液，加入電解槽之陽極室中。如此一來便可通過隔膜 之陽離子交換膜，將充足量的質子供給至電解槽之陰極室 。加入陽極室之酸性溶液的濃度，係只要是可將充足量之 質子供給至陰極室的濃度便無特別限制’但爲了防止氯離 子的浸透，以高於陰極室所含有之蝕刻液的酸濃度爲佳。 上述，加入陽極室之酸性溶液的酸濃度之範圍，較佳爲 0.1N〜14N、特別佳爲0.5N〜.12N。 如以上方式所言，雖進行用以去除蝕刻液中之銅離子 的電解，但於本發明方法中重要的觀點，並非將蝕刻液中 之銅離子完全地去除，而是設在特定的濃度範圍中。亦即 ，若蝕刻液中之銅離子濃度過高，則於殘存之銅部分（配 線部分），會產生腐蝕的問題，但相反地，當銅離子濃度 過低時，會產生蝕刻性能降低之電流效率降低的問題。因 此，於本發明方法中，必須將蝕刻液中之銅離子濃度維持 在適當的範圍，亦即，〇.lg/L〜10 g/L之範圍。再者，所 維持之銅離子濃度的範圍爲上述範圍，且蝕刻液之蝕刻性 能得以發揮之銅離子濃度，係以設爲±40%以內，較佳爲土 20%以內，特別佳爲±10%以內較佳。例如，於銅離子濃度 爲1 .Og/L左右且蝕刻性能得以發揮之蝕刻液的情況，係維 持在0.6〜1.4 g/L，較佳爲0.8〜1.2 g/L，特別佳爲0.9〜 -14- 201233853 1.1g/L 。 於將蝕刻液中之銅離子維持在上述之適當的範圍中， 係只要是在測量蝕刻槽中銅離子濃度，並對應於該數値的 強度或者是頻率下實施電解處理即可。電解處理時，係使 蝕刻槽內之蝕刻液在充足交替的流量下循環者較爲理想。 —般而言，以使蝕刻槽內的蝕刻液，在1小時交替2次以上 的流量下循環者爲佳。 接著，列舉用以實施本發明方法之系統的一態樣，對 本發明作更詳細地說明》 第1圖係模式性地顯示本發明之蝕刻液之維持管理系 統的附圖。圖中，1係表示維持管理系統，2係表示鈾刻槽 ，3係表示電解槽’ 3 a係表示陰極室，3b係表示陽極室，4 係表示陽離子交換膜，5係表示供電裝置，5 a係表示陰極 ’ 5b係表示陽極’ 6係表示銅離子測量裝置，7係表示電腦 ’ 8係表示蝕刻液配管，9係表示酸性溶液配管，1 〇係表示 送液泵。 本發明之系統’係藉由：蝕刻槽2、電解槽3及藉由蝕 刻液配線管8來使蝕刻槽2與電解槽3之陰極室3a之間連通 而構成。於該蝕刻液配線管8中，係視需要而配置有用來 送液之泵10。另外’於電解槽3中，係爲了清掃等之維護 ，亦可設有暫時溶液抽出路徑或排水路徑。 此外’電解槽3，係藉由陽離子交換膜4來區隔陰極室 3a與陽極室3b’且分別配設有陰極5a與陽極5b。此處所使 用的陰極5a，係用來使銅離子析出者，且可利用經銅或銅 -15- 201233853 合金、鎳或鎳合金、鈦、鈾族、鉑族或其之氧化物所 的鈦等之原料。另一方面，陽極係用來供給質子者， 利用經鉑族、鉑族或其之氧化物所被覆之鈦等之不溶 電極者。陽極與陰極，係可利用具有使所需的電流量 流動的面積，且呈平板、波紋板、網狀等之形狀者》 ，將陰極室3a與陽極室3b作區隔的陽離子交換膜4, 特別限制，但可利用全氟磺酸聚合物（Nafion膜；Du 公司製）等者。 如上所述，雖於陰極室3a中加入有蝕刻液，但於 室3b中加入有酸性溶液。該酸性溶液，係以可視需要 或抽取酸性成分或水分的方式來設置酸性溶液配管9a 者爲佳。 另一方面，於陰極室3a中之陰極5a及陽極室3b中 極5b中，係藉由供電裝置5而施加電壓，並進行電解 外’於蝕刻槽2中，係安裝有銅離子測量裝置6，以測 刻液中之銅離子濃度。 如上所述，經測量之銅離子濃度的資訊，係被傳 電腦7，且當該濃度偏離管理範圍（例如上述之特定 )時，會啓動泵1 〇而輸送蝕刻液，且使供電裝置5啓 進行電解，藉此使蝕刻液中之銅離子回到管理範圍內 外’在以自然流下的方式使蝕刻液返回蝕刻槽的情況 亦可省略泵1 Ob。此外，亦可將以電腦來控制的動作 動進行。 藉由上述方式，便可不變更蝕刻操作的條件，而 被覆 且可 解性 充分 再者 雖無 Pont 陽極 補充 及9b 之陽 。此 量蝕 送至 濃度 動而 。另 下， 以手 安定 -16- 201233853 地去除或剝離於印刷配線板等之銅電路的形成中所利用的 各種金屬、觸媒、樹脂等，並且可延長所使用的蝕刻液之 焉命。 【實施方式】 〔實施例〕 接著雖列舉實施例，並對本發明作更詳細地說明，但 本發明並不受該等實施例所限制。 實施例1〜5及比較例1〜4 準備有浴量500L的蝕刻槽及浴量200L的隔膜電解裝置 (陰極室：陽極室=180L: 20L)。於該隔膜電解裝置中， 係使用全氟磺酸聚合物（Nafion35〇 ; Du Pont公司製）作 爲隔膜，陰極係使用特定面積之鈦或銅板，陽極係使用有 效面積60dm2之可擴充形狀的鉑被覆鈦。 另一方面，建浴680L之下述組成的鎳-鉻用蝕刻液， 並使lg/L之Cu溶解，而調製出試驗用Ni-Cr合金用蝕刻液 (以下，簡稱爲「蝕刻液1」）。 <蝕刻液1 > 組成： H2S〇4 : 2 5質量％ HC1 : 1 0質量％ NaN02 ： 0.02質量％ -17- 201233853 陽離子系界面活性劑* : 0.2質量％ *聚醚陽離子 (ADEKA COL CC-15;ADEKA 公司製） 使上述蝕刻液1加入蝕刻槽中，由此開始透過泵，於 隔膜電解槽之陰極室與蝕刻槽作循環。另一方面，於隔膜 電解槽之陽極室中，加入5質量％之硫酸水溶液。一邊使蝕 刻槽與電解裝置24小時循環一邊進行電解，然後，以下述 方法來調查：因電解所致之Cu析出性、蝕刻液1之Cu配線 腐蝕性及Ni-Cr合金層去除性。另外，循環中，補給特定 量之Cu於蝕刻液1中。將電解條件顯示於表1中，並將Cu之 析出性、蝕刻液1之Cu配線腐蝕性及Ni-Cr合金層去除性之 試驗結果顯示於表2中。 (1 )因電解所致之Cu析出性： 因電解所致之Cu析出性，係根據蝕刻液1之電解前和 24小時電解後之Cu濃度變化與Cu之總補給量，而求出Cu 之析出量，並計算出與Cu之析出相關的電流效率。 (2 )蝕刻性能： 藉由濺鍍，於聚醯亞胺薄膜的單面，形成約25nm之 川-(：1：((：1：含量20質量％)合金層，接著，形成約1〇〇11111之 Cu層。其後，藉由半加成法，於聚醯亞胺薄膜上，形成Cu 配線高度約ΙΟμπι、線/空間=15μηι/15μιη之Cu配線圖型，並 -18- .201233853 將其作爲試驗片。另外，於經該半加成法所形成之 間之聚醯亞胺薄膜上，係整面皆殘留有Ni-Cr合金 該試驗片，以24小時電解後之蝕刻液1進行處理， Cu配線腐蝕性與Ni-Cr合金層去除性。201233853 VI. Description of the Invention: [Technical Field] The present invention relates to a method for maintaining and managing an etching solution and a system using the same, and more particularly to a method for accumulating copper ions due to etching In the reduced etchant, by maintaining the copper ion concentration in the etchant in a certain range, the etchant treatment performance can be stabilized, and the etchant maintenance management method and the use thereof can be prolonged The system. [Prior Art] In the field of recent flexible printed wiring boards, in order to increase the density of wiring patterns, a two-layer CCL having a sputtering method is used as a copper clad laminate (CCL). The two-layer CCL of the sputtering method is mainly produced by forming a nickel-chromium alloy on a polyimide film by sputtering, and then performing a copper splashing shovel to form a copper electrode. Floor. Although the adhesion between the polyimide film and the copper layer can be improved by the presence of the above-mentioned nickel-chromium alloy layer, if nickel is left in the portion where the unnecessary copper plating layer is removed in the circuit formation. In the chrome alloy layer, metal is precipitated in this portion, and there is a possibility that the wiring portion (the remaining portion of the copper plating) is shunted. Therefore, in the two-layer CCL of the sputtering method, the nickel-chromium alloy layer must be etched and removed. Conventionally, some prior art has been known as an etchant for a nickel-chromium alloy layer (Patent Documents 1 and 2). However, even if the initial performance is excellent, the etching liquid has a problem that the processing performance is gradually lowered due to a small amount of copper ions dissolved and accumulated in the solution during the etching process. At the scene, along with the above problems, there has been a problem that complicated operations such as processing time have to be adjusted. Further, in the above etching liquid, in addition to copper ions, there are substances accumulated by nickel ions or chromium ions, and in the presence of these, only the method of economically removing copper is not found, so that copper has been reached. A certain concentration of the solution is discarded, which becomes a major factor in the economic cost increase. Further, in the field of multilayer printed wiring boards, a copper circuit of an outer layer is mostly formed by a semi-additive method. In the semi-additive method, the excess electroless copper-free plating layer is etched away mainly in the final step of electroless copper plating as a seed layer. However, since the surface of the resin on which the electroless copper shovel layer has been removed is adhered to a metal such as a palladium catalyst used to form an electroless copper plating film, and there is insulation between wirings due to the influence thereof. There is a problem such as a decrease in properties, and therefore it is necessary to etch and remove a palladium catalyst or the like. Conventionally, some prior art has been known as an etchant for a palladium catalyst (Patent Document 3). However, even if the initial etching performance is excellent, the etching liquid has a problem that the processing performance is gradually lowered due to a small amount of copper ions dissolved and accumulated in the solution during the etching process, and the actual site is accompanied by The above problem has caused a problem that it is necessary to adjust the complicated operation such as processing time. Further, in the etching liquid, in addition to copper ions, a substance accumulated by palladium ions or the like is present, and in the presence of these, only the method of economically removing copper is not found, so that copper has reached a certain concentration. The solution was discarded -6- 201233853 and became a major factor in the economic cost increase. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. 2004- 190054 [Patent Document 2] International Patent Publication No. WO2007/040046 (Patent Document 3) Japanese Patent No. 41 1 3846 DISCLOSURE OF THE INVENTION [Problem to be Solved by the Invention] Therefore, an object of the present invention is to provide a method for maintaining and managing uranium engraving, which is a copper ion which will greatly affect etching performance, from a flexible printed wiring board. The etching liquid used for forming the copper circuit of the printed wiring board such as the multilayer printed wiring board can be removed, thereby achieving the stability of the etching liquid, extending the life thereof, and contributing to cost reduction and waste reduction. , or the protection of environmental resources. [Means for Solving the Problem] The inventors of the present invention have found that only copper ions are selectively removed from an etching solution in which copper ions are accumulated by etching, and as a result of intensive research, it is known that Diaphragm electrolysis, which selectively removes copper ions. Then, it was found that by using this method, the etching liquid is continuously processed, and the copper concentration is maintained within a certain range, whereby the treatment performance of the etching liquid can be stabilized, and the life of the etching liquid is prolonged, and the life of the etching liquid is prolonged. The present invention has been completed. In the meantime, the present invention relates to a method for maintaining and managing an etching solution, which comprises: an etching liquid which reduces the performance of copper ions accumulated by etching, and is sent from an etching bath to an electrolysis separated by a cation exchange membrane. a step of electrolyzing the cathode chamber of the tank; and a step of maintaining the catholyte of the electrolyzed cathode chamber back to the etching bath, the method for maintaining and maintaining the etching liquid, characterized in that an acidic solution is added to the anode tank of the electrolytic cell, Further, the concentration of the copper ions in the etching liquid is maintained in a range of 〇.lg/L to 10 g/L for electrolysis. Further, the present invention provides a method for maintaining and managing an etching solution for a nickel-chromium alloy, which comprises the steps of: feeding an etching solution of a nickel-chromium alloy in an etching bath to a cathode chamber of an electrolytic cell having a cation exchange membrane and performing electrolysis. And a step of maintaining the catholyte of the electrolyzed cathode chamber back to the etching bath, the method for maintaining the etching solution for the nickel-chromium alloy, characterized in that an acidic solution is added to the anode chamber of the electrolytic cell, and the uranium is added The concentration of copper ions in the etchant is maintained in the range of 〇.lg/L to l〇g/L for electrolysis. Furthermore, the present invention provides a method for maintaining and managing an etching solution for palladium, which comprises the steps of: feeding an etched bath of palladium to an anode of an electrolytic cell having a cation exchange membrane and performing electrolysis; The step of returning the catholyte of the cathode chamber to the etching bath, the method for maintaining and maintaining the palladium etching solution, characterized in that an acidic solution is added to the anode chamber of the electrolytic cell, and the concentration of copper ions in the etching solution is maintained. Electrolysis was carried out in the range of 〇.lg/L 1010 g/L. Further, the present invention is an etchant maintenance management system comprising: an etching tank provided with a copper analysis device; and an electrolytic cell which is provided by a cation exchange membrane to partition a cathode chamber provided with a cathode and an anode provided Anode-8-.201233853 chamber; etching liquid feeding pipe, the etching tank is connected with the cathode chamber of the electrolytic cell to enable the etching liquid to circulate between them; the power supply device is used for supplying current to The cathode and the anode: and the computer are used to control the copper analysis device, the etching liquid supply pipe, and the power supply device. [Effect of the Invention] According to the present invention, by using a simple device, copper ions can be accumulated by etching, and the etching performance of the etching liquid can be stabilized and the life can be prolonged. Therefore, the present invention contributes to improvement in workability, cost reduction, and waste reduction. [Best Mode for Carrying Out the Invention] In the method of the present invention, copper ions contained in an etching liquid in which copper ions are accumulated by etching are removed by electrolysis, whereby etching performance is stabilized and the life thereof is prolonged. The etching liquid which is a target for maintenance and management according to the present invention is not particularly limited as long as copper ions are accumulated by etching, and performance or workability is lowered. For example, the various metals, catalysts, resins, and the like used for forming a copper circuit of a printed wiring board such as a flexible printed wiring board or a multilayer printed wiring board are removed or Stripped etchant. Specific examples of the etching liquid include an etching liquid for a nickel-chromium alloy for peeling off a nickel-chromium alloy layer, and the nickel-chromium alloy layer is left with a circuit formed by sputtering a two-layer CCL. The substrate has been removed from the copper plating -9 - 201233853 layer part (space part). Examples of the above-described etching solution for a nickel-chromium alloy include those containing hydrochloric acid and/or chloride, sulfuric acid and/or sulfate, and nitrous acid and/or nitrite; and hydrochloric acid and / or chloride, and sulfuric acid and / or sulfate and / or sulfonic acid compounds and / or sulfonic acid compound salts; containing hydrochloric acid and / or chloride, with nitric acid and / or nitrate, and sulfuric acid and / or Sulfate and / or sulfonic acid compound and / or sulfonic acid compound salt; containing hydrochloric acid and / or chloride, and nitric acid and / or nitrate ' and nitrous acid and / or nitrite: containing hydrochloric acid And / or chloride, and nitric acid and / or nitrate, and phosphoric acid and / or phosphate, and nitrous acid and / or nitrite, etc., but can also be a component. Further, in such an etching solution for a nickel-chromium alloy, a surfactant, a sulfur-containing organic compound, or the like may be added as needed. Here, 'chloride' means, for example, sodium chloride, potassium chloride, ammonium chloride, calcium chloride, lithium chloride 'copper chloride, nickel chloride, ferric chloride, zinc chloride, tin chloride, Lead chloride, etc. Sulfate means, for example, sodium sulfate, potassium sulfate, ammonium sulfate, calcium sulfate, lithium sulfate, copper sulfate, nickel sulfate, iron sulfate 'zinc sulfate, tin sulfate 'lead sulfate, and the like. The nitrate refers to, for example, sodium nitrate, potassium nitrate, ammonium nitrate, calcium nitrate, lithium nitrate, copper nitrate, nickel nitrate, iron nitrate, zinc nitrate, tin nitrate, lead nitrate, and the like. Phosphate means, for example, sodium phosphate 'potassium phosphate, ammonium phosphate, calcium phosphate, lithium phosphate, copper phosphate, nickel phosphate, iron phosphate, zinc phosphate, tin phosphate, lead phosphate, and the like. "Nitrite" means, for example, sodium nitrite, potassium nitrite, ammonium nitrite, calcium nitrite, and the like. The acid-expanding compound 'is for example: methanesulfonic acid 'ethanesulfonic acid, hydroxymethanesulfonic acid, peryleneethanesulfonic acid, and the like. Sulfonic acid compound salt means, for example, sodium methanesulfonate-10-201233853, potassium methanesulfonate, ammonium methanesulfonate, methyl methanesulfonate, sodium ethanesulfonate, sodium hydroxymethanesulfonate, sodium isethionate Wait. In addition, the surfactant refers to, for example, a polyoxyethylene polyoxypropylene block polymer, a polyethylene dioxyethylene polyoxypropylene block polymer, a polyoxyethylene alkyl ether, a polyoxygen. Nonionic surfactants such as ethylene alkyl phenyl ether, polyethylene glycol, polyoxyethylene alkyl amine, alkyl alkanohydrin; alkyl benzene sulfonate, alpha olefin sulfonate, ether An anionic surfactant such as a carboxylate or an alkyl phosphate; a cationic surfactant such as a quaternary ammonium salt or an alkylamine salt; or an amphoteric surfactant such as an alkylbetaine or an alkylamine oxide. Sulfur-containing compound means a compound containing a sulfur atom and excluding the above-mentioned sulfuric acid, sulfate, sulfonic acid compound, or sulfonic acid compound salt, for example, thiourea, diethylthiourea, tetramethylthiourea, 1-benzene Thiourea compound of thiourea, thioethyleneamine, etc., 2-mercaptoimidazole '2-mercaptothiazoline, 3-mercapto-1,2,4-triazole, mercaptobenzimidazole, fluorenyl a thiol compound such as benzoxazole, mercaptobenzothiazole, mercaptopyridine, thioglycolic acid, mercaptopropionic acid, thiomalic acid, L-photocysteine, 2-aminophenyl disulfide a disulfide compound such as thiolan, thiodi glycolic acid, or a disulfide compound such as L-(-) cystamine, dipyridyl disulfide or dithiodiglycol, a sulfinic acid such as thiocyanate, potassium thiocyanate or ammonium thiocyanate, sulfamic acid, ammonium sulfamate, sodium sulfamate or potassium sulfamate or a salt thereof. In addition, the above-mentioned etching liquid for a nickel-chromium alloy can be used, for example, in JP-A-2004-190054, JP-A-2005-154899, JP-A-2006-229196, and JP-A-2005- No. 350708-11 - 201233853. Preferably, the etchant for the nickel-chromium alloy contains hydrochloric acid and/or chloride, sulfuric acid and/or sulfate, and nitrous acid and/or nitrite, especially at an acid concentration of 0.2. ～13N, a chloride ion concentration of 0.1 to 13% by mass, a sulfate ion concentration of 0.5 to 30% by mass, a nitrite ion of 0.0001 to 0.5% by mass, and, if necessary, a composition of 0.001 to 5% by mass of a surfactant. It is better. Further, other examples of the etching liquid include an etching solution for palladium for separating the palladium catalyst layer, and the palladium catalyst layer is electroless copper plating as a seed layer, and remains by semi-addition. The portion (space portion) of the substrate on which the copper plating layer has been removed is formed by the circuit. Examples of the above-mentioned palladium etching solution include those containing hydrochloric acid and/or chloride; those containing hydrochloric acid and/or chloride, and nitric acid and/or nitrate; and containing hydrochloric acid and/or Chloride, and nitric acid and / or nitrate, and sulfuric acid and / or sulfate and / or sulfonic acid compounds and / or sulfonic acid compound salts: containing hydrochloric acid and / or chloride, and nitrous acid and / or Asia Nitrate; containing hydrochloric acid and / or chloride, and nitric acid and / or nitrate, and phosphoric acid and / or phosphate, and nitrous acid and / or nitrite; containing hydrochloric acid and / or chloride And nitrous acid and/or nitrite, sulfuric acid and/or sulfate and/or sulfonic acid compound and/or sulfonic acid compound salt, etc., but may be other components. Further, in such an etching solution for palladium, an surfactant, a sulfur-containing organic compound or the like may be added as needed. In addition, chlorides, nitrates, chlorides, sulfates, sulfonic acid compounds, sulfonic acid compound salts, nitrites, phosphates, surfactants, sulfur-containing organic compounds, can be used with the nickel described in -12-201233853 - The etchant for chrome alloy is the same. In addition, for the above-mentioned etching liquid, for example, JP-A-2008- 1 063 54, Japanese Patent No. 4 1 1 3846, JP-A-2005-1 54899, and JP-A-2009-24220 Japanese Unexamined Patent Publication No. Hei No. Hei. No. Hei. The palladium etching solution preferably contains hydrochloric acid and/or chloride, and nitric acid and/or nitrate, and particularly has an acid concentration of 0.2 to 10 N and a chloride ion concentration of 0.1 to 20% by mass. The nitrate ion is preferably 1 to 17% by mass, and preferably 0.001 to 5% by mass of a surfactant is added as needed. - the method of the present invention is carried out by transferring an etching liquid having a reduced performance due to accumulation of the copper ions from an etching bath to a cathode chamber of an electrolytic cell partitioned by a cation exchange membrane, Here, the copper is precipitated and removed at the cathode, and the etching liquid having a reduced copper ion concentration is returned to the etching bath again. The cathode current density in the electrolysis is not particularly limited as long as it is effectively precipitated by using copper as a metal, and is preferably 〇1 to ΙΟΑ/dm2, more preferably 0.2 to 3 A/dm2. range. Further, the amount of current with respect to the amount of etching liquid is not particularly limited. Generally, it is preferably carried out at 0.01 to 5 A with respect to 1 L of the etching liquid, and more preferably at a current of 0.02 to 1 A. Further, the above electrolysis is preferably carried out at a temperature of 25 to 55 t, particularly at a temperature of 30 to 50 ° C, and the stirring method in the electrolysis - 13 - 201233853 is not specified, but is not It is preferred that the cathode chamber is sufficiently agitated in such a manner that the etchant is stagnant. Further, in the above electrolysis, a solution of an acidic solution, for example, sulfuric acid or a sulfonic acid compound such as methanesulfonic acid, ethanesulfonic acid, hydroxymethanesulfonic acid or hydroxyethanesulfonic acid, is added to the anode chamber of the electrolytic cell. In this way, a sufficient amount of protons can be supplied to the cathode chamber of the electrolytic cell through the cation exchange membrane of the separator. The concentration of the acidic solution added to the anode chamber is not particularly limited as long as it can supply a sufficient amount of protons to the cathode chamber. However, in order to prevent the permeation of chloride ions, the acid concentration of the etching solution contained in the cathode chamber is higher. It is better. The acid concentration of the acidic solution added to the anode chamber is preferably 0.1 N to 14 N, particularly preferably 0.5 N to 12.12 N. As described above, although electrolysis for removing copper ions in the etching liquid is performed, an important point in the method of the present invention is not to completely remove copper ions in the etching liquid, but to set a specific concentration range. in. That is, if the concentration of copper ions in the etching solution is too high, corrosion may occur in the remaining copper portion (wiring portion), but conversely, when the copper ion concentration is too low, a current having reduced etching performance may occur. The problem of reduced efficiency. Therefore, in the method of the present invention, the concentration of copper ions in the etching solution must be maintained in an appropriate range, i.e., in the range of 〇.lg/L 1010 g/L. Further, the range of the copper ion concentration to be maintained is in the above range, and the copper ion concentration at which the etching performance of the etching liquid is exerted is set to within ±40%, preferably within 20% of the soil, particularly preferably ±10. Less than %. For example, in the case of an etching solution in which the copper ion concentration is about 1.0 g/L and the etching performance is exerted, it is maintained at 0.6 to 1.4 g/L, preferably 0.8 to 1.2 g/L, particularly preferably 0.9 to - 14- 201233853 1.1g/L. The copper ions in the etching solution are maintained in an appropriate range as described above, and the electrolytic treatment may be carried out by measuring the copper ion concentration in the etching bath and corresponding to the intensity or frequency of the number. In the electrolytic treatment, it is preferred that the etching liquid in the etching bath is circulated at a sufficiently alternating flow rate. In general, it is preferred that the etching liquid in the etching bath is circulated at a flow rate alternately twice or more per hour. Next, the present invention will be described in more detail with reference to an aspect of the system for carrying out the method of the present invention. Fig. 1 is a view schematically showing the maintenance management system of the etching liquid of the present invention. In the figure, 1 indicates the maintenance management system, 2 indicates the uranium groove, and 3 indicates the electrolytic cell '3 a indicates the cathode chamber, 3b indicates the anode chamber, 4 indicates the cation exchange membrane, and 5 indicates the power supply device. a indicates that the cathode '5b indicates an anode' and 6 indicates a copper ion measuring device, and 7 indicates that the computer '8 indicates an etching liquid pipe, 9 indicates an acidic solution pipe, and 1 indicates a liquid feeding pump. The system of the present invention is constructed by etching the groove 2, the electrolytic cell 3, and the etching liquid pipe 8 to connect the etching bath 2 to the cathode chamber 3a of the electrolytic cell 3. In the etching liquid wiring pipe 8, a pump 10 for supplying liquid is disposed as needed. Further, in the electrolytic cell 3, a temporary solution extraction path or a drainage path may be provided for maintenance such as cleaning. Further, in the electrolytic cell 3, the cathode chamber 3a and the anode chamber 3b' are partitioned by the cation exchange membrane 4, and the cathode 5a and the anode 5b are disposed, respectively. The cathode 5a used herein is used for the precipitation of copper ions, and may be made of copper or copper-15-201233853 alloy, nickel or nickel alloy, titanium, uranium, platinum group or oxide thereof. Raw materials. On the other hand, the anode is used to supply a proton, and an insoluble electrode such as titanium coated with a platinum group, a platinum group or an oxide thereof is used. The anode and the cathode are cation exchange membranes 4 which partition the cathode chamber 3a from the anode chamber 3b by using an area having a flow of a desired current amount and being in the shape of a flat plate, a corrugated plate, a mesh or the like. It is particularly limited, but a perfluorosulfonic acid polymer (Nafion membrane; manufactured by Du) can be used. As described above, although the etching liquid is added to the cathode chamber 3a, an acidic solution is added to the chamber 3b. The acidic solution is preferably one in which the acidic solution piping 9a is provided as needed or by extracting an acidic component or moisture. On the other hand, in the cathode 5a of the cathode chamber 3a and the pole 5b of the anode chamber 3b, a voltage is applied by the power supply device 5, and electrolysis is performed. In the etching tank 2, a copper ion measuring device 6 is attached. To measure the concentration of copper ions in the solution. As described above, the measured copper ion concentration information is transmitted to the computer 7, and when the concentration deviates from the management range (for example, the above specific), the pump 1 is activated to deliver the etching liquid, and the power supply device 5 is activated. Electrolysis is performed to return the copper ions in the etching solution to the inside and outside of the management range. The pump 1 Ob may be omitted in the case where the etching liquid is returned to the etching bath in a natural flow manner. In addition, it is also possible to perform actions controlled by a computer. By the above method, it is possible to cover without omitting the conditions of the etching operation, and the solvability is sufficient, and there is no Pont anode supplement and 9b anode. This eclipse is sent to the concentration. In addition, various metals, catalysts, resins, and the like used in the formation of a copper circuit such as a printed wiring board are removed or peeled off by hand - 16 - 201233853, and the life of the etching liquid to be used can be prolonged. [Embodiment] [Embodiment] The present invention will be described in more detail with reference to examples, but the present invention is not limited by the examples. Examples 1 to 5 and Comparative Examples 1 to 4 An etching bath having a bath volume of 500 L and a diaphragm electrolyzer having a bath volume of 200 L were prepared (cathode chamber: anode chamber = 180 L: 20 L). In the separator electrolysis apparatus, a perfluorosulfonic acid polymer (Nafion 35®; manufactured by Du Pont Co., Ltd.) was used as a separator, a cathode was used for a specific area of titanium or a copper plate, and an anode was used as an expandable shape platinum coating having an effective area of 60 dm 2 . titanium. On the other hand, an etchant for nickel-chromium having the following composition of 680L is formed, and lg/L of Cu is dissolved to prepare an etching solution for a Ni-Cr alloy for testing (hereinafter, simply referred to as "etching liquid 1") ). <etching solution 1 > Composition: H2S〇4 : 2 5 mass% HC1 : 10 mass% NaN02 : 0.02 mass% -17- 201233853 Cationic surfactant*: 0.2 mass% *polyether cation (ADEKA COL CC -15; manufactured by ADEKA Co., Ltd.) The etching liquid 1 is introduced into the etching bath, thereby starting the permeation pump and circulating the cathode chamber and the etching bath of the diaphragm electrolysis cell. On the other hand, a 5 mass% aqueous sulfuric acid solution was added to the anode chamber of the separator electrolytic cell. Electrolysis was carried out while circulating the etching tank and the electrolysis apparatus for 24 hours, and then Cu deposition property due to electrolysis, Cu wiring corrosion of the etching liquid 1, and Ni-Cr alloy layer removal property were examined by the following methods. Further, in the cycle, a specific amount of Cu is supplied to the etching liquid 1. The electrolysis conditions are shown in Table 1, and the test results of Cu precipitation, Cu wiring corrosivity of etching liquid 1, and Ni-Cr alloy layer removability are shown in Table 2. (1) Cu precipitation due to electrolysis: Cu precipitation due to electrolysis is determined by Cu change in Cu concentration before electrolysis and electrolysis after electrolysis for 24 hours and total replenishment of Cu. The amount of precipitation was calculated and the current efficiency associated with the precipitation of Cu was calculated. (2) Etching property: On the single side of the polyimide film by sputtering, an alloy layer of about 25 nm was formed, and then an alloy layer of about 20 nm was formed, followed by formation of about 1 Å. a Cu layer of 〇11111. Thereafter, a Cu wiring pattern having a Cu wiring height of about ΙΟμπι, line/space=15μηι/15μηη is formed on the polyimide film by a semi-additive method, and -18-.201233853 This was used as a test piece. In addition, on the polyimide film formed by the semi-additive method, the test piece of Ni-Cr alloy remained on the entire surface, and the etching liquid after electrolysis for 24 hours was used. The treatment was performed, and the Cu wiring was corrosive and the Ni-Cr alloy layer was removed.
Cu配線 層。將 並調査 [銅配線腐蝕性J 將試驗片，在以24小時電解後之蝕刻液1電解 溫、60秒的條件下進行處理後，以掃描式電子顯 SEM )觀察Cu配線的狀態，並與處理前之試驗片作 且以下述之評價基準作評價。 < Cu配線腐蝕性評價基準> 時的液 微鏡（ 比較， (評價） (內容） ◎ : 無變化 〇 ： 大致上無變化 Δ : 有些微腐蝕 X : 有腐蝕 [Ni-Cr合金層去除性] 將試驗片，在以24小時電解後之蝕刻液1電解 溫、1 0〜2 5秒的條件下進行處理後，以金屬顯微鏡 觀察Cu配線間之聚醯亞胺薄膜上，並以下述之評價 對Ni-Cr合金的存在作評價。 時的液 、SEM 基準來 -19- 201233853 < Ni-Cr合金層去除性評價基準> (評價） (內容） 〇 : 完全被去除 Δ : 雖大部分被去除，但有些許殘留 X : 幾乎全部未被去除 另外，調製與剛建浴後之蝕刻液1相同狀況之蝕刻液 及與經蝕刻液1複數次去除Ni_Cr合金層後相同狀況（Cu濃 度已上昇者）之蝕刻液作爲比較，使用此等而對Cu配線腐 蝕性及Ni-Cr合金層去除性作試驗（比較例1及2 )。此外 ，也對不改變蝕刻液1之電解條件者進行了與實施例相同 的試驗（比較例3及4) ° [表1] 陰極材質 陰極面積 (dm2) 電流 (A) 陰極電流密度 (A/d m2) 浴溫 (X) 銅補給量 (g/h) 實施例1 T i 50 50 1. 0 3 5 3 3 實施例2 Cu 50 50 1. 0 3 5 3 3 實施例3 T i 30 50 1. 7 3 5 3 3 實施例4 τ i 1 20 5 0 0. 4 3 5 33 實施例5 T i 30 50 1 . 7 45 33 比較例Ί ( 不電解 ) 3 5 0 比較例2 ( 不電解 ) 35 33 比較例3 T i 50 20 0. 4 35 33 比較例4 T i 90 150 1. 7 3 5 33 -20- 201233853 [表2] 因電解所致之Cu析出性 顧性能 |濃度U/L) 電解前 電解後 析出量 (g) 電流 效率 (%) C u配線 臟性 •C r·^層去除性 10秒 15秒 20秒 25秒 實施例1 實施例2 實施例3 實施例4 實施例5 03 07 9 7 0 2 9 8 0· 9 5 02 93 08 848 827 820 7 50 764 59. 7 58. 2 57.7 52. 8 5 3.8 ooooo ooooo ooooo △ Δ Δ ΔΟ 比較例1 比較例2 比較例3 比較例4 05 1 2 9 9 0 2Cu wiring layer. The copper wiring corrosion resistance J was measured and the test piece was treated under the conditions of electrolysis temperature of the etching liquid 1 after electrolysis for 24 hours for 60 seconds, and the state of the Cu wiring was observed by a scanning electron SEM. The test piece before the treatment was prepared and evaluated on the basis of the following evaluation criteria. <Liquid Micro-mirror of Cu wiring Corrosion Evaluation Criteria> (Comparative, (Evaluation) (Content) ◎: No change 〇: There is substantially no change Δ: Some micro-etching X: Corrosion [Ni-Cr alloy layer removal The test piece was treated under the conditions of electrolyzing temperature of the etching solution 1 after electrolysis for 24 hours, for 10 to 25 seconds, and then observed on a polyimide film between Cu wiring lines by a metal microscope, and the following Evaluation of the presence of the Ni-Cr alloy. The liquid and the SEM standard are used. -19-201233853 <Ni-Cr alloy layer removal evaluation criteria> (evaluation) (Content) 〇: Completely removed Δ : Most of them are removed, but some residual X: Almost all are not removed. The etching solution of the same condition as the etching solution 1 immediately after the bath is prepared and the same condition as the etching solution 1 after removing the Ni_Cr alloy layer (Cu concentration) The etching liquid of the ascending liquid was used as a comparison, and the Cu wiring corrosion property and the Ni-Cr alloy layer removal property were tested using these (Comparative Examples 1 and 2). Moreover, the electrolytic conditions of the etching liquid 1 were not changed. Performed the same as the embodiment Test (Comparative Examples 3 and 4) ° [Table 1] Cathode Material Cathode Area (dm2) Current (A) Cathode Current Density (A/d m2) Bath Temperature (X) Copper Replenishment (g/h) Example 1 T i 50 50 1. 0 3 5 3 3 Example 2 Cu 50 50 1. 0 3 5 3 3 Example 3 T i 30 50 1. 7 3 5 3 3 Example 4 τ i 1 20 5 0 0. 4 3 5 33 Example 5 T i 30 50 1 . 7 45 33 Comparative Example 不 (without electrolysis) 3 5 0 Comparative Example 2 (without electrolysis) 35 33 Comparative Example 3 T i 50 20 0. 4 35 33 Comparative Example 4 T i 90 150 1. 7 3 5 33 -20- 201233853 [Table 2] Cu precipitation due to electrolysis; concentration U/L) Precipitation after electrolysis (g) Current efficiency (%) C u wiring dirty • C r · layer removal 10 sec 15 sec 20 sec 25 sec Example 1 Example 2 Example 3 Example 4 Example 5 03 07 9 7 0 2 9 8 0· 9 5 02 93 08 848 827 820 7 50 764 59. 7 58. 2 57.7 52. 8 5 3.8 ooooo ooooo ooooo △ Δ Δ ΔΟ Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 05 1 2 9 9 0 2
ΔΟΔ ΟΟΟΔ oooo 如表2所示般，於實施例1〜4中，具有與銅離子爲一 定的情況（比較例1 )大致相等的Cu配線腐蝕性、Ni-Cr合 金層去除性，此外，如實施例5般，即使在浴溫高的情況 下也可維持Cu之濃度，顯示出可進行以本發明方法所安定 的蝕刻處理一事。另一方面，於銅離子濃度已上昇的情況 (比較例2 )中，Ni-Cr合金層去除性雖良好，但發生了腐 触基板之Cu配線部分的問題。該問題，係與在電解不充分 下銅離子濃度變得較管理範圍更高者有相同的結果（比較 例3 )。相.對於此，於過度電解而使銅離子濃度變得較管 理範圍更低者（比較例4 )中，雖基板的Cu配線部分之腐 齡性低，但Ni-Cr合金層去除性不佳，且電流效率降低， 而降低作業性。 由此結果可理解：使用本發明之電解裝置，而將Cu離 子維持在特定的濃度，藉此可在高電流效率（50%以上） 下’於陰極板析出Cu，且幾乎不會腐蝕Cxi配線，而可迅速 -21 - 201233853 地將Ni-Cr合金層完全地去除一事。 實施例6〜9及比較例5〜8 準備有浴量500L之蝕刻槽及浴量200L之隔膜電解裝置 (陰極室：陽極室=180L:20L)。於該隔膜電解裝置中， 係使用全氟磺酸聚合物（Nafion350; Du Pont公司製）作 爲隔膜，陰極係使用特定面積之鈦或銅板，陽極係使用有 效面積60dm2之可擴充形狀的鉑被覆鈦。 另一方面，建浴680L之下述組成之鈀用蝕刻液，並使 lg/L之Cu溶解，調製出試驗用鈀用蝕刻液（以下，簡稱爲 「蝕刻液2」）。 <蝕刻液2 > 組成： HC1 : 5質量％ HN〇3 ： 5質量 ％ΔΟΔ ΟΟΟΔ oooo As shown in Table 2, in Examples 1 to 4, Cu wiring corrosion property and Ni-Cr alloy layer removal property were substantially equal to those in the case where copper ions were constant (Comparative Example 1), and In the same manner as in the fifth embodiment, the concentration of Cu can be maintained even when the bath temperature is high, and it is shown that the etching treatment which is stabilized by the method of the present invention can be performed. On the other hand, in the case where the copper ion concentration has increased (Comparative Example 2), the Ni-Cr alloy layer has good removability, but a problem occurs in the Cu wiring portion of the substrate. This problem is the same as the case where the copper ion concentration becomes higher than the management range when electrolysis is insufficient (Comparative Example 3). In this case, in the case where the copper ion concentration is lower than the management range by excessive electrolysis (Comparative Example 4), although the etch age of the Cu wiring portion of the substrate is low, the Ni-Cr alloy layer is poorly removed. And the current efficiency is lowered, and the workability is lowered. From this result, it can be understood that the Cu ion is maintained at a specific concentration by using the electrolysis device of the present invention, whereby Cu can be precipitated on the cathode plate at a high current efficiency (50% or more), and the Cxi wiring is hardly corroded. , and the Ni-Cr alloy layer can be completely removed quickly - 21 - 201233853. Examples 6 to 9 and Comparative Examples 5 to 8 An etching bath having a bath volume of 500 L and a diaphragm electrolysis apparatus having a bath volume of 200 L (cathode chamber: anode chamber = 180 L: 20 L) were prepared. In the separator electrolysis apparatus, a perfluorosulfonic acid polymer (Nafion 350; manufactured by Du Pont Co., Ltd.) was used as a separator, a cathode was used for a specific area of titanium or a copper plate, and an anode was used as an expandable shape of a platinum-coated titanium having an effective area of 60 dm 2 . . On the other hand, an etchant for palladium having the following composition of 680L was formed, and lg/L of Cu was dissolved to prepare an etching solution for palladium for testing (hereinafter, simply referred to as "etching liquid 2"). <etching solution 2 > Composition: HC1 : 5 mass% HN〇3 : 5 mass %
LiCl ： 10質量 ％ 非離子系界面活性劑* : 0.5質量％ *聚氧乙稀-聚氧丙稀縮合物 (ADEKA Pluronic L-64;ADEKA 公司製） 使上述蝕刻液2加入蝕刻槽中，由此開始透過栗，於 隔膜電解槽之陰極室與蝕刻槽作循環。另一方面，於隔膜 電解槽之陽極室中’加入5質量％之硫酸水溶液。一邊使貪虫 -22- 201233853 刻槽與電解裝置24小時循環一邊進行電解，然後，以下述 方法來調查：因電解所致之Cu的析出性、蝕刻液2之Cu配 線腐蝕性及鈀觸媒去除性。另外，循環中，補給特定量之 Cu於蝕刻液2中。將電解條件顯示於表3中，並將Cu之析出 性、蝕刻液2之Cu配線腐蝕性及鈀觸媒去除性之試驗結果 顯示於表4中。 (1 )因電解所致之Cu析出性： 因電解所致之Cu析出性，係根據蝕刻液2之電解前和 24小時電解後之Cu濃度變化與Cu之總補給量，求出Cu之 析出量，並計算出與Cu之析出相關的電流效率。 (2 )蝕刻性能： 藉由以下的方法來調査：24小時電解後之蝕刻液2的 Cu配線腐蝕性與鈀觸媒去除性。 [Cu配線腐蝕性] 於尺寸5x5cm之環氧樹脂製之基材，形成約〇.3/zm之 無電解Cu電鍍。其後，藉由半加成法，於環氧樹脂製之基 材上，形成Cu配線高度約20 y m、線/空間=20 v m/20 μ m 之Cu配線圖型，並將其作爲試驗片。將試驗片，在以蝕刻 液2電解時的液溫、60秒的條件下進行處理後，以掃描式 電子顯微鏡（SEM )觀察Cu配線的狀態，並與處理前之試 驗片作比較，以下述之評價基準作評價。 -23- 201233853 < Cu配線腐蝕性評價基準> (評價） (內容） ◎ • Arr . 撕 變 化 〇 : 大 致 上 m 變化 Δ : 有 ifcb 微 腐 蝕 X : 有 腐 蝕 [鈀觸媒去除性] 藉由以下的步驟，於尺寸5x1 0cm之環氧樹脂之基材， 形成約0.3 μιη之無電解Cu電鍍，其後，浸漬於7質量％ H2S04、2質量％ H202之水溶液中，將無電解Cu電鍍被膜 剝離，作成於環氧樹脂製之基材上殘存有鈀觸媒的狀態者 ，並將其作爲試驗片。將試驗片在以蝕刻液2電解時之液 溫、60秒的條件下進行處理後，測量鈀殘留量，並將與未 處理之試驗片的鈀殘留量之差，作爲鈀去除率而計算並評 價。鈀殘留量的測量，係將試驗片，浸漬於約50mL之以3 :1的容量比進行混合37質量％ HC1與68% ΝΗ03所作成之 王水中5分鐘，並將該王水於i〇〇mL量瓶中進行取樣，接著 以離子交換水來洗淨該試驗片，也將該洗淨水於100mL量 瓶中進行取樣，最後，藉由原子吸光分析裝置（AA240FS ;Varian公司製），來分析經準確定量爲1 OOmL之水溶液 中的鈀濃度。 -24- 201233853 <試驗片之無電解Cu電鍍處理步驟> 清潔/調節（PB-117S)50°C，5分鐘LiCl : 10% by mass of nonionic surfactant*: 0.5% by mass * Polyoxyethylene-polyoxypropylene condensate (ADEKA Pluronic L-64; manufactured by ADEKA CORPORATION) The etching liquid 2 is added to the etching bath, This begins through the pump, circulating in the cathode chamber of the diaphragm cell and the etching bath. On the other hand, a 5 mass% aqueous sulfuric acid solution was added to the anode chamber of the separator electrolytic cell. Electrolysis was carried out while circulating the worm-22-201233853 groove and the electrolysis apparatus for 24 hours, and then investigation was carried out by the following methods: precipitation of Cu due to electrolysis, corrosion of Cu wiring of the etching solution 2, and palladium catalyst. Removeability. Further, in the cycle, a specific amount of Cu is supplied to the etching liquid 2. The electrolysis conditions are shown in Table 3, and the test results of the precipitation properties of Cu, the Cu wiring corrosivity of the etching solution 2, and the palladium catalyst removal property are shown in Table 4. (1) Cu precipitation due to electrolysis: Cu precipitation due to electrolysis is based on the change in Cu concentration before and after electrolysis of the etching solution 2 and the total replenishment amount of Cu, and the precipitation of Cu is determined. The amount and calculate the current efficiency associated with the precipitation of Cu. (2) Etching property: The Cu wiring corrosivity and palladium catalyst removal property of the etching solution 2 after 24 hours of electrolysis were investigated by the following method. [Cu wiring corrosion property] An electroless Cu plating of about 〇3/zm was formed on a substrate made of an epoxy resin having a size of 5 x 5 cm. Thereafter, a Cu wiring pattern having a Cu wiring height of about 20 μm and a line/space = 20 vm/20 μm was formed on the epoxy resin substrate by a semi-additive method, and this was used as a test piece. . The test piece was treated under the conditions of a liquid temperature at the time of electrolysis of the etching liquid 2 for 60 seconds, and the state of the Cu wiring was observed by a scanning electron microscope (SEM), and compared with the test piece before the treatment, the following The evaluation criteria are evaluated. -23- 201233853 <Cu wiring corrosion evaluation standard> (Evaluation) (Content) ◎ • Arr. Tear change 〇: Approximate m change Δ: Ifcb Micro-etching X: Corrosion [Palladium catalyst removal] The following steps were carried out to form an electroless Cu plating of about 0.3 μm on a substrate of an epoxy resin having a size of 5×10 0 cm, and thereafter, immersed in an aqueous solution of 7 mass% H 2 SO 4 and 2 mass % H 202 to electroless Cu plating. The film was peeled off, and a state in which a palladium catalyst remained on a substrate made of an epoxy resin was prepared, and this was used as a test piece. The test piece was treated under the condition of liquid temperature at the time of electrolysis of the etching liquid 2, and the residual amount of palladium was measured, and the difference from the palladium residual amount of the untreated test piece was calculated as the palladium removal rate. Evaluation. The amount of palladium residue was measured by immersing the test piece in a volume ratio of about 50 mL at a capacity ratio of 3:1 by 37% by mass of HC1 and 68% of ΝΗ03 for 5 minutes, and the aqua regia was The sample was taken in an mL volumetric flask, and then the test piece was washed with ion-exchanged water. The washed water was also sampled in a 100 mL volumetric flask, and finally, by an atomic absorption spectrometer (AA240FS; manufactured by Varian). The palladium concentration in an aqueous solution accurately quantified to be 100 mL was analyzed. -24- 201233853 <Electroless Cu plating treatment step of test piece> Cleaning/adjustment (PB-117S) 50 ° C, 5 minutes
I 水洗 軟蝕刻（PB-228) 30 °c、2分鐘I Washing Soft Etching (PB-228) 30 °c, 2 minutes
I 水洗 預浸漬（氫氯酸）30°c、1分鐘I Washing pre-impregnation (hydrochloric acid) 30 ° C, 1 minute
I 賦予Pd觸媒（PB-318)30°C、5分鐘 加速器（PB-445)3 0°C、5分鐘I Pd catalyst (PB-318) 30 ° C, 5 minutes Accelerator (PB-445) 30 ° C, 5 minutes
I 水洗I wash
I 無電解Cu電鍍（PB-503F)3(TC、15分鐘 (氫氯酸以外之藥品，係皆由EBARA UDYLITE CO.， LTD 製） 另外，調製與剛建浴後之蝕刻液2相同狀況之蝕刻液 及與經蝕刻液2複數次去除鈀觸媒層後相同狀況（Cu濃度 已上昇者）之蝕刻液作爲比較，使用該等來對Cu配線腐蝕 -25- 201233853 性及鈀觸媒去除性作試驗（比較例5及6 )。此外，也對不 改變蝕刻液2之電解條件者進行了與實施例相同的試驗（ 比較例7及8)。 [表3] 陰極材質 陰極面積 (drrf) 電流 (A) 陰極電流密度 (A/dirf) 浴溫 (°C) 銅補給量 (g/h) 實施例6 Ti 50 30 0. 60 50 25 實施例7 Cu 50 30 0.60 50 25 實施例8 Ti 30 30 1.00 50 25 實施例9 Ti 120 30 0. 25 50 25 比較例5 (不電解 ） 50 0 比較例6 ( 不電解 ） 50 25 比較例7 Ti 50 15 0.30 50 25 比較例8 Ti 90 90 1.00 50 25 [表4] 因電解所致之Cu析出性 蝕刻性能 Cu 濃度(g/L) Cu析出量 電流效率 Cu配線 Pd去除率 電解前 電解後 (g) (%) 腐蝕性 (%) 實施例6 1.05 0. 99 640.5 75. 1 〇 98.4 實施例7 0.98 0.91 652.4 76.5 〇 99.2 實施例8 1.03 1.02 609.8 71.5 〇 98.4 實施例9 1.05 1.01 625.1 73. 3 〇 99.2 比較例5 0.99 一 — — 〇 98.4 比較例6 1.80 — — — X 99.2 比較例7 1.01 1.44 299.8 70.3 Δ 99.2 比較例8 1.05 0.37 1077. 1 42. 1 ◎ 88.4 -26- 201233853 如表4所示般，於實施例6〜9中，具有與銅離子爲一 定的情況（比較例5 )大致相等的Cu配線腐蝕性、鈀殘渣 去除性，且顯示出可進行以本發明方法所安定的蝕刻處理 一事。另一方面，於銅離子濃度已上昇的情況（比較例6 )中，鈀觸媒去除性雖良好，但發生了腐蝕基板之Cu配線 部分的問題》此問題，係與在電解不充分下銅離子濃度變 得較管理範圍更高者有相同的結果（比較例7)。相對於 此，於過度電解而使銅離子濃度變得較管理範圍更低者（ 比較例8 )中，雖基板的Cu配線部分之腐蝕性低，但鈀觸 媒去除性不佳，且電流效率降低，而降低作業性。 · 由此結果可理解：藉由使用本發明之電解裝置，將Cu 離子維持在特定的濃度，而可在高電流效率（70%以上） 下，於陰極板析出Cu，且幾乎不會腐蝕Cu配線，而可迅速 地將鈀觸媒完全地去除。 〔產業上之可利用性〕 依據本發明之蝕刻液之維持管理方法及系統，係可藉 由所謂簡單的電解之手段，而可達成將蝕刻液之蝕刻性能 安定化，並且延長其壽命。 因此，本發明，係於可撓性印刷配線板之領域中，特 別是於使用濺鏟法二層CCL之領域中，對於作業性的提昇 、成本降低及廢棄物的削減有很大的貢獻。 此外，本發明，係於印刷配線板之領域中，特別是在 -27- 201233853 以無電解銅電鍍作爲種晶層，而藉由半加成法來進行電路 形成的領域中，對於作業性的提昇、成本降低及廢棄物的 削減有很大的貢獻。 【圖式簡單說明】 [第1圖]係顯示本發明之蝕刻液之維持管理系統的模式 圖。 【主要元件符號說明】 1 :液維持管理系統 2 :蝕刻槽 3 :電解槽 3a :陰極室 3b :陽極室 4 :陽離子交換膜 5 :供電裝置 5a :陰極 5 b _陽極 6 :銅離子測量裝置 7 :電腦 8 :蝕刻配線管 9 :酸性溶液配線管 10 :泵 -28-I Electroless Cu plating (PB-503F) 3 (TC, 15 minutes (drugs other than hydrochloric acid, manufactured by EBARA UDYLITE CO., LTD) In addition, the etching is performed in the same condition as the etching solution 2 immediately after the bath is built. The liquid and the etching solution in the same condition (the Cu concentration has risen) after the removal of the palladium catalyst layer by the etching liquid 2 are used as a comparison, and the Cu wiring is corroded by the etching method and the palladium catalyst removal property is used. Tests (Comparative Examples 5 and 6). The same tests as in the examples (Comparative Examples 7 and 8) were carried out without changing the electrolysis conditions of the etching solution 2. [Table 3] Cathode material cathode area (drrf) current (A) Cathodic current density (A/dirf) Bath temperature (°C) Copper replenishment (g/h) Example 6 Ti 50 30 0. 60 50 25 Example 7 Cu 50 30 0.60 50 25 Example 8 Ti 30 30 1.00 50 25 Example 9 Ti 120 30 0. 25 50 25 Comparative Example 5 (without electrolysis) 50 0 Comparative Example 6 (without electrolysis) 50 25 Comparative Example 7 Ti 50 15 0.30 50 25 Comparative Example 8 Ti 90 90 1.00 50 25 [Table 4] Cu precipitation etchability due to electrolysis Cu concentration (g/L) Cu deposition amount Current efficiency Cu wiring Pd removal After electrolysis before electrolysis (g) (%) Corrosivity (%) Example 6 1.05 0. 99 640.5 75. 1 〇98.4 Example 7 0.98 0.91 652.4 76.5 〇99.2 Example 8 1.03 1.02 609.8 71.5 〇98.4 Example 9 1.05 1.01 625.1 73. 3 〇99.2 Comparative Example 5 0.99 1 - 〇 98.4 Comparative Example 6 1.80 — — — X 99.2 Comparative Example 7 1.01 1.44 299.8 70.3 Δ 99.2 Comparative Example 8 1.05 0.37 1077. 1 42. 1 ◎ 88.4 -26- As shown in Table 4, in Examples 6 to 9, the Cu wiring corrosion property and the palladium residue removal property which are substantially equal to the case where the copper ions are constant (Comparative Example 5) are shown, and it is shown that the present invention can be carried out. On the other hand, in the case where the copper ion concentration has increased (Comparative Example 6), the palladium catalyst removal property is good, but the problem of etching the Cu wiring portion of the substrate has occurred. The same result was obtained as the copper ion concentration became higher than the management range when electrolysis was insufficient (Comparative Example 7). On the other hand, in the case where the copper ion concentration is lower than the management range by excessive electrolysis (Comparative Example 8), the corrosion resistance of the Cu wiring portion of the substrate is low, but the palladium catalyst removal property is poor, and the current efficiency is low. Reduce, and reduce workability. From this result, it can be understood that by using the electrolysis device of the present invention, Cu ions are maintained at a specific concentration, and Cu can be precipitated on the cathode plate at a high current efficiency (70% or more), and Cu is hardly corroded. Wiring can quickly remove the palladium catalyst completely. [Industrial Applicability] According to the method and system for maintaining and maintaining the etching liquid of the present invention, the etching performance of the etching liquid can be stabilized and the life thereof can be prolonged by means of simple electrolysis. Therefore, the present invention is in the field of a flexible printed wiring board, and particularly in the field of using a two-layer CCL using a spatter method, it contributes greatly to improvement in workability, cost reduction, and waste reduction. Further, the present invention is in the field of printed wiring boards, particularly in the field of electroless copper plating as a seed layer in -27-201233853, and in the field of circuit formation by semi-additive method, for workability Improvements, cost reductions and waste reductions have contributed significantly. BRIEF DESCRIPTION OF THE DRAWINGS [Fig. 1] is a schematic view showing a maintenance management system for an etching solution of the present invention. [Main component symbol description] 1 : Liquid maintenance management system 2 : etching tank 3 : electrolytic cell 3 a : cathode chamber 3 b : anode chamber 4 : cation exchange membrane 5 : power supply device 5 a : cathode 5 b _ anode 6 : copper ion measuring device 7: Computer 8: Etched wiring tube 9: Acid solution wiring tube 10: Pump-28-