461833 A7 __B7_____ 五、發明説明（】） 〔產業上之利用領域〕 本發明係關於低氧銅之製造方法，尤指有關於連續鑄 造出自熔融爐之熔銅，連續地製造抑制含氧量的低氧銅之 製造方法者。 〔先行技術〕 大凡於坊間所產製，將含氧量抑制在2 0 P pm，理 想上爲1〜1 0 p pm ( PartsperMillion )以下之低氧銅 (亦稱爲「無氧銅」），係具種種不同形態，即有所謂長 錠和結塊等鑄塊狀，或經過輥軋，拉伸後呈線狀，短錠形 狀者。就此種低氧銅之製造方法而言，屬較一般者乃使用 槽型感應電爐和坩堝式感應電爐等電感應式爐產製熔銅， 并將該熔銅，於移送過程中仍然維持其氣密性直到連續鑄 造機而鑄造之方法。 如此使用電感應式爐製造之時候，可藉簡便的操作容 易獲得高溫，又，產製熔銅時因爲未同時發生化學反應之 故，具有可保其品質穩定等優點《但其反面，亦具有建造 成本和運轉成本高，生產性低等之缺點。 〔發明所欲解決之課題〕 凡欲以低成本大量製造低氧銅時，雖以使用高爐等氣 體爐製造之方法爲理想，惟若使用該類氣體爐之時候’爲 了要在爐內燃燒，即產生氧化反應之需，必須進行熔銅之 還原處理不可。此係採用電感應爐時沒有之缺點。因此， 本紙張尺度適用中國國家標準（CNS ) A4规格（2I0X297公* ) I T 裳 訂 I I Hi 泛 (請先閲讀背面之注意事今再填寫本頁} -4- 46 183 3 A7 B7 五、發明説明（2) 若不將產生之熔銅，於其移送過程中藉還原氣體及/或是 惰性氣體予以還原處理，降低含氧濃度後，再移送至連續 鑄造機時，無法製出低氧銅。 但，若僅進行這樣之脫氧處理的話，則在低氧銅中會 產生鑄孔，致產生腫脹等之缺陷，終究讓低氧銅之品質劣 化。尤其，於欲將其製成銅線之情形下，該鑄孔於輥軋時 構成瑕疵，成爲表面品質低劣之銅線成品。因此之故，一 般咸認使用氣體爐製造高品質之低氧銅，乃屬非常困難之 事，實際上低氧銅乃專門用電感應爐予以製造者。 如斯之鑄孔，乃於熔銅凝固時，由於熔銅中之氫與氧 之溶解度降低之故，結合而產生之水蒸汽（h2〇)氣泡爲 起因者。該氣泡，在熔銅之冷卻，凝固時被捕捉，殘存於 低氧銅內，以致產生鑄孔也6在熱力學中，熔銅中之氫與 氧的濃度|有如次式表示之關係。 [H] 2 [Ο] = ρΗ2〇· Κ ......式（A) 此處， 〔H〕：熔銅中之含氫濃度 〔◦〕：熔銅中之含氧濃度 PH2。：周遭氣體中之水蒸汽分壓 K :平衡定數 者。 平衡定數K，係溫度之函數，因在一定之溫度下成爲 本紙張尺度適用中國國家揉牟（CNS > A4*L格（210X29?公釐） —.1 ^^1 l_i n 1/ an Λ3 .«a (請先《讀背面之注意事項再填疼本頁) 經濟部智慧財4笱負工消费合作社印製 -5- 4 6 183 3 A7 B7_ 五、發明説明（3) --------—裝------訂 {請先閱讀背面之注意事項再填寫本頁) 定數之故，熔銅中之含氧濃度與含氫濃度呈反比之關係。 因此，越是藉還原進行脫氧處理，其含氫濃度將愈高，不 但於凝固時容易形成鑄孔外，僅能製造出低品質之低氧銅 鑄塊。換言之，不只需要脫氧處理，倘若忽略脫氫處理而 不做時，於凝固時將形成大量鑄孔，致無法製造出高品質 之低氧銅。 另一方面，藉由做爲一般性脫氣方法之氧化還原法， 有可能在幾乎呈完全燃燒狀態使其熔融而獲得含氫濃度低 之熔銅，惟尙須爲後續進行之脫氧處理確保相當長之移送 距離不可，故並不實際。 本發明乃鑑於前述狀況所做，其目的在於提供：不須 確保長的移送距離亦能進行脫氫處理，可抑制凝固時產生 之鑄孔|獲得表面品質良好之高品質低氧銅的低氧銅之製 造方法。 〔用以解決課題之手段〕 申請專利範圍第1項之發明，係以涵蓋：在熔融爐之 還原性氣體環境中進行燃燒生產熔銅之熔銅生產工序：將 由前述熔融爐送來之熔銅，使用可藉非氧化氣體環境密封 之鑄造流出槽移送至餵槽之熔銅移送工序；對通過設於該 鑄造流出槽中之脫氣手段的熔銅進行脫氫處理之脫氣工序 ;將該熔銅供給與連續鑄造機而連續生產鑄造銅材之連續 鑄造工序；和將該鑄造銅材依規定之長度截斷做成低氧銅 鑄塊之切斷工序而成者爲其特徵之從熔銅做爲鑄塊而連續 本紙張尺度通用中國國家櫺準（CNS ) A4現格（210X297公釐） -6 - 461833 A7 _B7_ 五、發明説明（4) 製造低氧銅之製造方法。 申請專利範圍第2項之發明·係屬申請專利範圍第1 項的低氧銅之製造方法，其中於前述脫氣工序，係藉對前 述熔銅加以攪拌之舉進行脫氫處理者。 申請專利範圍第3項之發明，係屬申請專利範圍第2 項的低氧銅之製造方法，其中前述攪拌手段，乃使前述熔 銅通過之流路做成蛇行之舉達成攪拌者。 申請專利範圍第4項之發明係指有關連續製造做爲銅 線的低氧銅之製造方法，其特徵爲該製造方法係以涵蓋： 在熔融爐之還原性氣體環境中進行燃燒生產熔銅之熔銅生 產工序；和將由前述熔融爐送來之熔銅，使用可藉非氧化 氣體環境密封之鑄造流出槽移送至餵槽之熔銅移送工序； 和對通過設於該鑄造流出槽中之脫氣手段的熔銅加以脫氫 處理之脫氣工程；和將該熔銅供給與環帶鑄造式連續鑄造 機而連續生產鑄造鋼材之連續鑲造工序；和輥軋該鑄造銅 材做成低氧銅線之輥軋工序在內者。 經濟部智慧时4苟負工消*合作社印3|} it I— It m «I ^1 ^1— T (請先《讀背面之注意Ϋ項再填寫本頁) 申請專利範圍第5項之發明，係屬申請專利範圍第4 項的低氧銅之製造方法，其中前述脫氣工序，乃以攪拌前 述熔銅進行脫氫處理者。 申請專利範圍第6項之發明，係颶申請專利範圍第5 項的低氧銅之製造方法，其中前述脫氣工序係使前述熔銅 通過之流路做成蛇行而達成攪拌者》 申請專利範圍第7項之發明，係連續製造做爲銅合金 線的低氧銅之製造方法，其特徵爲：該製造方法係以涵蓋 本紙張尺度逋用中團國家橾準（CNS } Α4坑格（2丨0X297公嫠） 4 6 183 3 A7 _B7 五、發明説明（） 0 ，在熔融爐之還原性氣體環境中進行燃燒而生產熔銅之熔 銅生產工序；和將由前述熔融爐送來之熔銅，使用可藉非 氧化氣體環境密封之鑄造流出^移送至餵槽之熔銅移送工 ;和對通過設於該鑄造流出槽中之脫氣手段的熔銅施予脫 氫處理之脫氫工序；和添加銀至經該脫氫處理後之熔銅的 銀添加工序：和將該熔銅供給與環帶鑄造式連續鑄造機而 連續生產鑄造銅合金材之連續鑄造工序；和輥軋該鑄造銅 合金材做成低氧銅合金線之輥軋工序在內者。 申請專利範圍第8項之發明，係屬申請專利範圍第7 項的低氧銅之製造方法，其中前述脫氣工序，乃以攪拌前 述熔銅進行脫氫處理者。 申請專利範圍第9項之發明，係屬申請專利範圍第8 項的低氧銅之製造方法，其中前述脫氣工序，係使前述熔 銅通過之流路做成蛇行而達成攪拌者。 申請專利範圍第1 0項之發明，係屬連續製造做爲鍍 銅用含磷銅母材的低氧銅之製造方法，其特徵爲：該製造 方法係以涵蓋，在熔融爐之還原性氣體環境中進行燃燒而 生產熔銅之熔銅生產工序，和將由前述熔融爐送來之熔銅 ，使用可藉非氧化氣體環境密封之鑄造流出槽移送至餵槽 之熔銅移送工序：和對通過設於該鑄造流出槽中之脫氣手 段的熔銅施予脫氫處理之脫氣工序：和添加磷至經該脫氫 處理後之熔銅的磷添加工序，和將該熔銅供給與環帶鑄造 式連續鑄造機而連續生產鑄造母線材之連續鑄造工序；和 輥軋該鑄造母線材做成鍍銅用含磷銅母材之輥軋工序在內 本紙張尺度適用中國國家梂準（CNS > A4規格（2丨0X297公釐） ---------^------tr------^ (請先s讀背面之注意事項再填窝本頁) -8 - 4 6 1 8 3 3 A7 B7 五、發明说明（6) 者。 申請專利範圍第1 1項之發明，係屬申請專利範圍第 1 〇項的低氧銅之製造方法，其中前述脫氣工序’乃係以 攪拌前述熔銅進行脫氫處理者。 申請專利範圍第1 2項之發明，係屬申請專利範圍第 1 1項的低氧銅之製造方法，其中前述脫氣工序’係使前 述通過之熔銅流路做成蛇行而達成攪拌者。 申請專利範圍第1 3項之發明’係靥申請專利範圍第 1 2項的低氧銅之製造方法，其中包含將前述經輥軋後之 鍍銅用含磷銅母材截斷爲規定長度之短錠化工序’藉此連 續製造短錠狀之鍍銅用含磷銅母材者° 申請專利範圍第1 4項之發明’係屬申請專利範圍第 1 3項的低氧銅之製造方法，其中包含洗滌前述短錠狀鍍 銅用含磷銅母材之洗淨工序在內者。 〔作用〕 於如此的低氧銅之製造方法中'在藉還原性之氣體環 境中進行燃燒之熔融爐裡’使熔銅脫氧。被脫氧之熔銅’ 在鑄造流出槽中以非氧化氣體環境密封并移送至餵槽。於 熔融爐裡經脫氧後之熔銅’由於含氧濃度與含氫濃度係具 有反比之關係，故其含氫濃度增高。該含氫濃度提高之熔 銅，於通過鑄造流出槽之際’藉由脫氣手段接受脫氫處理 。由是，鑄造時之氣體釋放量減少’抑制產生於鑄造銅材 中之鑄孔，減低在低氧銅表面形成之鑄疵。 本纸張尺度適用中國國家揉準（CNS } A4规格（210X297公釐） ^^1- ^^1 ^^1 ^^1 ^^1 ^^1 ^^1 fr I <請先《讀背面之注意事項再填寫本頁) 訂 绶濟部智慧时4笱8工消步合泎钍印 -9- 461833 A7 B7 五、發明説明（7) (請先《讀背面之注意事項再填寫本頁) 又，於脫氣工序裡，若對熔銅加以攪拌時，則將熔銅 中之氫氣強制逐出，可進行脫氫處理。就是由於在鑄造流 出槽中設有接觸到熔銅之攪拌手段，故移送至餵槽以前之 熔銅將接觸到攪拌手段而被攪拌，使爲了形成非氧化氣體 環境用而吹進之惰性氣體與熔銅之接觸性提昇。此時，對 熔銅之氫氣分壓而言惰性氣體中之氫氣分壓極小之故，熔 銅中之氫被惰性氣體所吸收，得能進行熔銅之脫氫處理。 更且*於脫氣工序裡，若藉由堰使通過鑄造流出槽之 熔銅蛇行時，則因可構成激流而被攪拌。即，可藉熔銅本 身之流動，自動攪拌之。這樣，熔銅即藉堰形成上下或左 右之激流，使流經鑄造流出槽之熔銅與惰性氣體有普遍接 觸之機會，更能提高脫氫處理之效率。 在此情形下，以譬如設於熔銅流路上呈棒狀，板狀之 堰爲理想者。又，該堰，於往熔銅之流動方向設置多數， 或朝垂直於熔銅之流動方向設置多數者，皆屬可行。更且 ，若以譬如說碳做成該堰時，可藉熔銅與碳間之接觸，能 更有效地進行脫氧處理者。 〔實施例〕 茲佐以參考圖面就本發明有關低氧銅之製造方法的實 施形態詳細說明之如下。又，文中之「低氧銅」係指含氧 量2 0 p pm以下，最好抑制在1〜1 0 P pm範圍內之 銅或銅合金之謂也。 本紙張尺度適用中國國家揉率（CNS ) Α4ϋΙ格（2I0X297公釐） -10- 4 6 18 3 3 A7 _B7_ 五、發明说明（8) 〔第1種實施形態〕 I ^^1 ^^1 —^1. ^^1 ϋ p In m KVK -* (請先w讀背面之注意事項再填寫本頁) 茲就第1及2圖將第1種實施形態說明之。本實施形 態，係有關將低氧銅做爲鑄塊予以製造之製造方法者。 第1圖係將使用於本實施形態中的低氧銅鑄塊之製造 裝置大略表示之構成圖，第2圖係以平面俯視（a) ’側 面正視（b )表示第1圖中鑄造流出槽主要部之放大圖。 該低氧銅鑄塊之製造裝置（低氧銅之製造裝置） i〇l，係備置：熔融爐A，和保溫爐B，和鑄造流出槽 C，和連續鑄造機D，和切斷手段E，和搬出手段F所構 成。 熔融爐A爲具有圓筒形爐本體之氣體爐，譬如高爐係 適合於採用者。於熔融爐A下部*往圓周方向裝設多數燃 燒器（未圖示），并按熔融量呈多段狀設置之。於該熔融 爐Α裡，以還原性氣體環境進行燃燒，產生熔銅（熔態金 屬）。還原性氣體環境，譬如說，可在天然氣和空氣的混 合氣體中，藉提高燃料心而得之。更具體地說，一般在排 氣中之C0 (―氧化碳）濃度，係維持在〇 . 2〜0 . 6 %範圍者比較，空氣燃料比將其調整到2〜5%之範圍者 。如前述情形，由於熔融爐A中進行在還原性氣體環境下 之燃燒，故熔銅即接受脫氧處理。 保溫爐B，除暫時貯存從熔融爐A送來之熔態金屬外 ，尙爲使其保持規定溫度轉送至鑄造流出槽之目的所設。 鑄造流出槽C，係以非氧化氣體環境密封自保溫爐B 送來之熔態金屬并移送至餵槽5 a所用者。所指之密封， 本纸張尺度通用中S國家橾率（CNS ) A4说格（210X297公釐） -11 - 461333 A7 B7 一· '"' 五、發明説明（9) 則如於第2圖所示，係以遮蓋8覆住鑄造流出槽C之熔銅 流路（熔銅之流路）3 1上面而達成。該非氧化氣體環境 ,乃例如，將氮與一氧化碳之混合氣體和氬等之惰性氣體 ，吹入鑄造流出槽C內而形成。 鑄造流出槽C之熔銅流路3 1處，係如於第2圖所示 ，設置對所通過之熔態金屬施予包含脫氫處理之脫氣處理 所用攪拌手段（脫氣手段）33。該攪拌手段33，乃由 堰33a，33b，33c，33d所構成，俾使熔態金 屬於流通中被激烈地攪拌。 堰3 3 a設置於熔銅流路3 1上側，即遮蓋8處=又 ，堰3 3 b在熔銅流路3 1之下側，堰3 3 c在熔銅流路 3 1左側，堰3 3 d在熔銅流路3 1之右側，分別設置之 。藉該等腹33a，33b，33c，33d，熔態金屬 即朝上下左右蛇行而朝第2圖中箭頭所指方向流通并形成 激流而被攪拌，得能進行脫氣處理者。又，於第2圖（b )中，圖號3 2係表示熔態金屬面。 堰33c，33d，係對熔銅流路31之實際長度再 予加長形成熔態金屬之流路|假若鑄造流出槽C雖屬於尺 寸短者，亦能提昇脫氣處理之效率者=又，堰33a ， 3 3 b係爲能儘防止在脫氣處理前後之熔銅和環境氣體相 混合之任務所設。 又，該攪拌手段3 3，雖主以進行脫氫處理爲目的所 設，惟由於熔態金屬接受攪拌之故，尙能逐出殘存於熔態 金屬中之氧氣者。就是說，做爲脫氣處理，能進行脫氫處 本紙張尺度逍用中國國家揉準（CNS )八4*1格（2丨0X297公釐） (請先閲讀背面之注意事項再填寫本页) 訂 經濟部皙慧时4苟具工合作社印奴 -12- 46 183 3 A7 ____B7_ 五、發明説明（j (請先《讀背面之注意^項再填寫本頁) 理和第2次脫氧處理之雙方也。該等堰3 3a，3 3b， 33c，33d，例如以碳等做成時，可藉熔銅與碳之接 觸，能有效進行脫氧處理。 該脫氣處理，有必要於該保溫爐B以後之移送過程中 進行。其理由係·爲能獲得低氧銅鑄塊，在保溫爐B內進 行在還原性氣體環境裡之燃燒，或者藉還原劑進行之脫氧 處理故，據前述之平衡式（A)的關係，其含氫濃度必然 會昇高也。 再者，就進行脫氣處理之位置而論 > 不宜在鑄造直前 之餵槽5 a內進行脫氣處理。因爲若在餵槽5 a內進行熔 態金屬激烈攪拌之動作，例如起泡動作時，液面將激烈地 振動，使從後述澆鑄口（未圖示）流出之熔態金屬壓力頭 變動，無法使穩定之熔銅供給與連續鑄造機D之故也。另 一方面，液面未達激烈振動之程度時，則無法期望有脫氣 之效果。從此點可瞭解，以自保溫爐B至餵槽5 a間之移 送過程中進行脫氣處理者最爲理想。 經濟部智慧財I局員工消費合作钍印裂 餵槽5 a上，朝熔態金屬流動方向之終端設有澆鑄口 (未圖示），俾能從餵槽5 a供給熔態金屬與連續鑄造機 者。 與保溫爐B以鑄造流出槽C爲介，連結著連續鑄造機 D。該連續鑄造機D屬於所謂直立式鑄造機，係備置可一 面冷卻所供給之熔銅一面將其朝略垂直方向下側抽製成規 定截面形狀之鑄造銅材2 1 a所用之鑄模4 1 ，與捏縮輥 4 2而成。該等鑄模4 1及捏縮輥4 2之形狀及配置，乃 i紙張尺度適用中國國家標準（CNS ) ( 2丨Ο X 297公釐） -13 - Α7 Β7 4 6 丨 83 3 五、發明説明（j (請先W讀背面之注意事項再填寫本頁) 按照做爲製品之低氧銅鑄塊（低氧銅）2 3 a之形狀，適 當地挑選。例如，於欲將低氧銅鑄塊2 3 a，做成略呈圓 柱形狀之長錠時，使鑄模4 1之截面呈圓形而捏縮輥4 2 亦做成對應於該形狀者，又，若欲製成略呈直方體形狀之 結塊時，則將鑄模4 1之截面形狀做成矩形而捏縮輥4 2 亦做成相對應之形狀即可。於第1圖中之低氧銅鑄塊 2 3 a係以結塊爲一例所表示者。 又，於本實施之形態中雖以使用直立式連續鑄造機者 爲例說明，惟使用將鑄塊朝橫方向鑄造之臥式連續鑄造機 時，亦屬可行也。 切斷手段E，乃將出自連續鑄造機D之鑄造銅材 2 1 a ，截斷成規定長度者。就該切斷手段E之一例而言 ，雖可舉出呈圓盤狀之刀刃旋轉之快速圓鋸，惟只要能截 斷鑄造銅材2 1 a者，採用其他之構成亦無不可。 搬出手段F，係備置盛籃51，與升降機52，與輸 送機5 3，所成。 盛籃5 1位於連續鑄造機D之略正下方處，接受經由 切斷手段E截斷成規定長度之低氧銅鑄塊2 3 a ，再將其 裝載至升降機5 2上者。 升降機5 2則將藉盛籃5 1所裝載之低氧銅鑄塊 2 3 a搬上輸送機5 3之位置者。 輸送機5 3係爲搬送來自升降機5 2之低氧銅鑄塊 2 3 a而設β 茲就使用按照前述情形所構成低氧銅鑄塊之製造裝置 本紙張尺度遴用中困國家標準（CNS ) Α4Λ格（2丨Ο X 297公釐） -14- 4 6 1 83 3 A7 B7 五、發明説明（j 1 0 1的低氧銅鑄塊之製造方法予以說明之= 首先，於熔融爐A內以還原性氣體環境進行燃燒，一 面將熔銅予以脫氧處理一面產製熔銅（熔銅生產工序）。 經過脫氧處理後之熔銅，再經保溫爐B，并於鑄造流出槽 C中以非氧化氣體環境密封，而移送至餵槽5 a (熔銅移 送工序）。於熔融爐A中經脫氧處理之熔銅，由於含氧濃 度和含氫濃度係呈反比之關係故，其含氫濃度提高。該含 氫濃度提高之熔銅，於通過鑄造流出槽C之際，即藉攪拌 手段33進行脫氫處理（脫氣工序）。 藉此，熔銅即被調整至含氣量2 0 p pm以下，含氫 量1 p pm以下。靠該措施，鑄造時所釋出之氣體減少| 可抑制鑄造銅材2 1 a內產生鑄孔。 另，從平衡式（A)之關係，得由降低水蒸汽分壓之 舉減低熔銅之氣體濃度故，藉完全分離脫氫處理前之熔銅 和脫氫處理後之熔銅，而有可能得到進一步之脫氣效果。 該事項，譬如說於熔銅移送工序中，以設置如前述之攪拌 手段33而能實現。即，該攪拌手段33，亦可善盡防止 脫氫處理前後之氣體環境相混合，與熔銅之混合的任務者 〇 自熔融爐A移送至保溫爐B之熔銅，於昇溫後，經過 鑄造流出槽C，餵槽5 a而供給與連續鑄造機D。又從鑄 模4 1藉捏縮輥4 2朝下方抽取再被冷卻、凝固而連續鑄 造成爲鑄造銅材21a (連續鑄造工序）。 該鑄造銅材2 1 a，乃藉切斷手段E予以截斷，循序 本紙张尺度遢用中國困家標準（仁阳）厶4洗格（210父297公釐} (請先聞讀背面之注意事項再填寫本頁 訂 -15- A7 461833 B7 五、發明説明（^ 連續製造出具規定長度之低氧銅鑄塊2 3 a (切斷工序） 〇 I ^^1 —i I ^^1 ^^1 -I— I— I m----t— 1^1 HI t^n (請先《讀背面之注意事項再填寫本頁) 被截斷之鑄造銅材2 1 a，係做爲低氧銅鑄塊2 3 a 藉搬出手段下所搬出（搬出工序）。即，低氧銅鑄塊 2 3 a乃被位於略在正下方處之盛籃5 1所接受，并裝載 於升降機5 2往上搬運至輸送機5 3之位置，再藉該輸送 機5 3予以搬送之。 經濟部智楚財夜笱8工消費合作社印製 於本實施形態有關，使用低氧銅鑄塊製造裝置1 0 1 之製造方法中，在熔融爐A內以還原性之氣體環境進行燃 燒，將熔銅予以脫氧處理，該熔銅乃於鑄造流出槽C中藉 非氧化氣體環境密封并移送至餵槽5 a =又該熔銅，由於 其含氧濃度與含氫濃度係呈反比之關係故其含氫濃度提高 ，惟在後續之脫氣工序中藉攪拌手段3 3做脫氫處理。藉 此，即不需確保長的熔銅移送距離，就能減低因以還原方 式脫氧處理時提高之含氫濃度，進而抑制熔銅中產生之氣 泡。因此，可以使用在燈內進行燃燒之氣體爐，以低成本 連續的大量製造能於冷卻，凝固時抑制鑄孔產生之高品質 的低氧銅鑄塊2 3 a。 又，由於將脫氣手段，以攪拌熔銅之攪拌手段3 3做 成，可在短時間內進行強制性脫氫處理，故能以簡易的構 成有效地進行脫氫處理者。 更且，若將攪拌手段3 3，藉由能使通過通路之熔銅 蛇行之堰所構成時，由於可憑熔銅本身之流動自行攪拌， 無需特別裝用攪拌器等，除能以更簡易的構成有效進行脫 本紙張尺度逍用中國國家標準（CNS > A4规格（210X297公釐） -16- a 6 t 83 3 A7 ______B7__ 五、發明説明（j 氫處理外’尙能使低氧銅鑄塊之製造裝置1 ο 1的運轉管 理容易而能以更低的成本製造之。 I I I - I . 1- - I I - —1— - - I n (請先閎讀背面之注意事項再填寫本頁) 又’藉由該攪拌手段3 3所做之分離，並未僅侷限於 單一處所，而可按移送過程之長度適宜地設置。又，在整 體範圍內亦未僅限於低氧銅鑄塊，而有可能尙以混合恰當 之添加元素製得低氧銅合金鑄塊也。 又，本例中雖舉在熔銅流路3 1之上下左右分別設置 堰33a，33b，33c，33d做爲攪拌手段33之 例，惟視鑄造流出槽C之長度和寬度適宜地變更該等堰之 個數和配置者亦無不可》 又，本例中雖使用所謂直立式之連續鑄造機D而加以 說明，惟使用朝橫向連續鑄造之所謂臥式連續鑄造機亦屬 可行。在此情形下，即不需要如升降機5 2等之升降手段 〔第2種實施之形態〕 繼而，就第2種實施形態，依照所附第3及4圖說明 之。本實施形態，係有關將低氧銅做爲銅線製造之製造方 法者。 第3圖係槪略表示在本實施形態中所用低氧銅線之製 造裝置的構成圖。該低氧銅線之製造裝置（低氧銅之製造 裝置）1 0 2，其大致區分之主要部係由：熔融爐A ’與 保溫爐B，與鑄造流出槽C 2，與環帶鑄造式連續鑄造機 G，與輥軋機Η，與纏卷裝置I等所構成。 本紙張尺度適用中國國家揲準（CNS ) A4洗格（210X297公釐） -17- 461833 A7 __B7____ 五、發明説明（j (請先閱讀背面之注意事項再填寫本頁) 另，於本實施形態中之熔融爐及保溫爐’係與前述第 1種實施形態裡所說明之各該爐等屬同一構成之故’對其 附與同一符號并省略其詳細說明。 鑄造流出槽C 2，係將從保溫爐B送來之熔態金屬以 非氧化氣體環境密封并移送至餵槽5 b。在餵槽5 b ’於 熔態金屬流通方向終端設有澆鑄噴管9 ’俾將來自簾槽. 5 b之熔態金靥供給與環帶鑄造式連續鑄造機G ° 另，該鑄造流出槽C 2及餵槽5 b，如與前述第1種 實施形態中之鑄造流出槽C及餵槽5 a比較時，僅因欲適 用於低氧銅線之製造而在形狀等上有若干差異外，其大致 之構成係互相屬於同一者。即，於鑄造流出槽（：2上’沒 有如於第2圖中所示之攪拌手段3 3。 經濟部智慧时4'"員工消旁合作社印製 保溫爐B乃以鑄造流出槽C 2爲介，與環帶鑄造式連 續鑄造機G連結。該環帶鑄造式連續鑄造機G係由週旋移 動之無接端環帶11，與將其圓周之一部分接觸在無接端 環帶1 1上旋轉之鑄造輪1 3所構成，俾連續生產鑄造銅 材2 1 b者。該環帶鑄造式連續鑄造機g ’更與輥軋機Η 相連結之。 輥軋機Η，係將出自環帶鑄造式連續鑄造機G之桿狀 鑄造銅材2 1 b加以輥軋，做成低氧銅線（低氧銅） 23b者。該輥軋機又以剪切機（切斷手段）15及 手探傷器19介於中間，與纏卷裝置I相連結。 剪切機1 5，具備一對旋轉刃16，16，係用來截 斷經過輥軋機Η所輥軋之鑄造銅材2 1 b，即低氧銅線 本紙張尺度逍用中國國家標準（CNS)A4现格（210X297公釐） ~ ~ 4 6 183 3 A7 B7 五、發明説明（d (請先閱讀背面之注意事項苒填寫本頁) 2 3 b，截成短錠狀者。例如，於環帶鑄造式連續鑄造機 G之運轉伊始等時*鑄造銅材2 1 b之內部組織呈不穩定 之狀態，在此狀態下製得之低氧銅線2 3 b，不可能成爲 品質穩定之製品。在此情形下，將從輥軋機Η製出之低氧 銅線2 3 b藉剪切機1 5依序截斷，直到其品質穩定以前 暫不送至探傷器1 9及纏卷裝置I。而待鑄造銅材2 1 b 之品質穩定後，將旋轉刃1 6，1 6從低氧銅線2 3 b移 開，并將低氧銅線23b送至探傷器19及纏卷裝置I。 茲就使用具如此構成之低氧銅線製造裝匱1 0 2的低 氧銅線製造方法說明之。 首先，於熔融爐A中藉還原性氣體環境進行燃燒，一 面對熔銅做脫氧處理一面生產熔銅（熔銅生產工序經 脫氧處理後之熔銅|通過保溫爐B，並於鑄造流出槽C 2 中藉非氧化氣體環境密封，而移送至餵槽5b(熔銅移送 工序）。在熔融燫A中接受脫氧處理之熔銅，由於其含氧 濃度與含氫濃度呈反比之關係故，含氫濃度提高。該含氫 濃度提高之熔銅，於通過鑄造流出槽C 2之際，藉攪拌手 段3 3加以脫氫處理（脫氣工序）。 於是乎，熔銅之含氧量被調整至2 0 p pm以下，含 氫量則爲1 P pm以下。藉此措施，鑄造時之釋氣量減少 ，而能抑制鑄造銅材2 1 b內產生之鑄孔。 又，依照平衡式（Α)之關係，因可藉由降低水蒸汽 分壓減低熔銅中所含氣體濃度故，將實施脫氣處理前之熔 銅和實施脫氫處理後之熔銅予以完全分離之舉，有可能得 本紙張尺度通用中國a家棣準（CNS ) A4^ ( 2丨0X297公釐} -19- 461833 A7 ___B7 五、發明説明（^ t請先《讀背面之注意事項再填寫本頁) 到更進一步之脫氣效果。其法爲，例如於熔銅移送工序中 ，設置如前述之攪拌手段3 3即能實現。就是，該攪拌手 段3 3，亦能盡到防止經脫氫處理前後之環境氣體的混合 ，與熔銅之混合的任務者。 從熔融爐A移送至保溫爐B之熔銅，經昇溫之後，通 過鑄造流出槽C 2，餵槽5 b，再自澆鑄噴管9供給與環 帶鑄造式連續鑄造機G，并於環帶鑄造式連續鑄造機G中 予以連續鑄造，然後在剛從環帶鑄造式連續鑄造機G之排 料處成形爲鑄造銅材2 1b (連續鑲造工序）。 該鑄造銅材2 lb，乃以輥軋機Η予以輥軋，做成表 面品質良好的低氧銅線（低氧銅）2 3 b (輥軋工序）。 該低氧銅線2 3 b，若品質呈穩定狀態時，藉探傷器1 9 檢測有無瑕疵後，一面塗敷蠟等之潤滑油被纏卷裝置I所 卷取，并以該狀態送往後續工序。 此種低氧銅線之製造方法，係將熔銅之含氣量調整至 氧20ppm以下，氫lppm以下之後，進行鑄造。輥 軋之舉使鑄造時之釋出氣體減少，抑制產生於鑄造銅材 2 1 b內之鑄孔，減低在低氧銅線2 3 b上之表面瑕疵。 又，按照此種製造方法所製造之低氧銅線2 3 b，其 氣體釋出特性亦爲卓越者。第4圖中，分別表示按本實施 形態有關之製造方法所製造低氧銅線之氣體釋出特性（曲 線a)與已往藉浸漬成形法所製造低氧銅之氣體釋出特性 (曲線b)。於該圖中，橫軸表示自開始實驗起之經過時 間（秒）*縱軸表示被釋出之氣體量。 本紙張尺度適用中國國家橾準（CNS ) A4規格（210X297公釐) ~ 4 6 18 3 3 A7 _B7___ 五、發明说明（j 如於該圖所示，可知按本實施形態有關之製造方法所 製造之低氧銅線的氣體釋出量，較藉浸漬成形法所製出之 低氧銅線的氣體釋出量甚少者至爲明顯》 當氣體釋出量多之低氧銅線或低氧銅合金線，在所謂 高真空或者高溫的條件下使用之時候*即有產生表面膨脹 而降低表面品質，或將氣體放出外部而污染環境之慮》 按本實施形態有關之製造方法所製造之低氧銅線，由 於其氣體釋出量已非常少，故正好可使用在例如呈高真空 之粒子加速器，呈高溫之微波爐等者。 於使用本實施形態有關之低氧銅線製造裝置1 0 2的 製造方法中，在熔融爐A內以還原性之氣體環境進行燃燒 ，使熔銅接受脫氧處理，該熔銅復於鑄造流出槽C 2中藉 非氧化氣體環境密封并移送至餵槽5 b。然後，該熔銅由 於其含氧濃度與含氫濃度呈反比之關係故，其含氫濃度提 高，惟在後續之脫氣工序中藉攪拌手段3 3進行脫氫處理 。藉此，即不需確保長的熔銅移送距離，就能減低因藉還 原方式脫氧處理時提高之含氫濃度，連同抑制熔銅中產生 之氣泡。因此|可使用在爐內進行燃燒的氣體爐，連續鑲 造可抑制冷卻，凝固時所產生氣孔之高品質鑄造銅材 2 1 b，更以使用環帶鑄造式連續鑄造機，連續製造低成 本高品質的低氧銅線2 3 b。 另，由於將攪拌熔銅之攪拌手段3 3，做爲脫氣手段 之故，可在短時間內進行強制性脫氫處理，故能以簡易的 構成有效完成脫氫處理。 本纸張尺度適用中S國家揉準（CNS ) (2f0X297公釐} (請先Μ讀背面之注—項再填寫本頁) 訂 • 21 - 46 183 3 at __B7____ 五、發明説明（^ 更且，若將擾拌手段3 3，藉由能使通過通路之溶銅 蛇行之堰構成時，由於可憑熔銅本身之流動自行攪样’故 無需特別地裝用攪拌器等，除能以更簡易的構成有效進行 脫氫處理後，尙能使低氧銅線之製造裝置的運轉管理容易 a 又爲能穩定熔態金屬之溫度，亦可在保溫爐B和餵槽 5 b之間設置電爐。 且，在自鑄造流出槽C 2終端部以后至餵槽5 b終端 止之間，設置對熔銅添加銅以外之元素用的手段亦無不可 也。 〔第3種實施形態〕 繼之，就第3種實施形態，按所附第5及6圖說明如 次。本實施形態，係有關將低氧銅製成含有銀（A g )之 低氧銅合金線的製造方法者。 茲經本發明者等專心檢討之結果發現，在熔銅中添加 少量之銀時’可將形成於該含銀之鑲造銅合金材之鑄孔微 細地分散，成爲輥軋時即消失而不形成瑕疵之程度的超微 細孔’而達成抑制低氧銅合金線中產生有害鑄孔之目的者 。該添加銀之方法，又其有可抑制製得之低氧銅合金線之 導電率減低之優點。 第5圖係槪略地表示在本實施形態中所用低氧銅合金 線之製造裝置的構成圖。該低氧銅合金線之製造裝置（低 氧銅之製造裝置）1 0 3，與前述第2種實施形態中之低 本紙乐尺度適用中a國家螵準（CNS ) A4洗格（21 OX297公釐） (请先閱讀背面之注意事項再填寫本頁)461833 A7 __B7_____ V. Description of the invention ()) [Application fields in the industry] The present invention relates to a method for manufacturing low-oxygen copper, especially to continuous casting of molten copper from a melting furnace, and continuously manufacturing low-oxygen content that suppresses oxygen content. Method of making copper. [Advanced technology] Low-oxygen copper (also known as "oxygen-free copper") produced by Dafan in the workshop, which suppresses the oxygen content to 20 P pm, ideally 1 to 10 p pm (Partsper Million), There are various forms of the system, that is, ingot-like shapes such as long ingots and agglomerates, or those that are rolled and stretched into linear and short ingot shapes. As for the production method of such low-oxygen copper, the more common ones use molten induction copper such as trough-type induction furnaces and crucible-type induction furnaces to produce molten copper, and the molten copper still maintains its airtightness during the transfer process. Method of casting until continuous casting machine. In this way, when using an electric induction furnace to manufacture, high temperature can be easily obtained by simple operation. In addition, because no chemical reaction occurs at the same time when producing molten copper, it has the advantages of maintaining its quality and stability. "But its reverse side also has construction Disadvantages such as high cost and running cost, and low productivity. [Problems to be Solved by the Invention] When a large amount of low-oxygen copper is to be produced at a low cost, it is ideal to use a gas furnace such as a blast furnace. However, when using such a gas furnace, 'to burn in the furnace, That is to say, the oxidation reaction is required, and reduction treatment of molten copper must be performed. This system does not have the disadvantages when using an electric induction furnace. Therefore, this paper size applies the Chinese National Standard (CNS) A4 specification (2I0X297 male *) IT Chang II II Hi Pan (please read the note on the back before filling this page today) -4- 46 183 3 A7 B7 V. Invention Note (2) If the molten copper produced is not reduced during the transfer process by reducing gas and / or inert gas, the oxygen concentration will be reduced and then transferred to the continuous casting machine, the low oxygen copper cannot be produced. However, if only such deoxidation treatment is performed, cast holes will be generated in the low-oxygen copper, causing defects such as swelling, and the quality of the low-oxygen copper will eventually be deteriorated. In particular, when it is intended to be made into copper wire This cast hole constitutes a flaw during rolling and becomes a finished copper wire with poor surface quality. Therefore, it is generally recognized that it is very difficult to use a gas furnace to produce high-quality low-oxygen copper. In fact, low-oxygen Copper is specially manufactured by an electric induction furnace. Such a cast hole is caused by the combination of water vapor (h2〇) bubbles generated when the molten copper solidifies due to the reduced solubility of hydrogen and oxygen in the molten copper. .The bubble, The cooling of molten copper is captured during solidification and remains in low-oxygen copper, so that cast holes are also produced. In thermodynamics, the concentration of hydrogen and oxygen in molten copper has a relationship as expressed by the following formula. [H] 2 [Ο] = ρΗ2〇 · Κ ...... Formula (A) Here, [H]: hydrogen concentration in molten copper [◦]: oxygen concentration in molten copper PH2: partial pressure K of water vapor in surrounding gas: Those who are in equilibrium. The equilibrium in K is a function of temperature, because it becomes the standard of this paper at a certain temperature. It is applicable to Chinese national standards (CNS > A4 * L (210X29? Mm) —.1 ^^ 1 l_i n 1 / an Λ3. «a (Please read the" Notes on the back side and fill in this page first ") Printed by the Ministry of Economic Affairs and Intellectual Property 4 笱 Consumer Cooperatives -5- 4 6 183 3 A7 B7_ V. Description of the invention ( 3) ---------- Packing ------ Order {Please read the notes on the back before filling this page) For a fixed number, the oxygen concentration in the molten copper is inversely proportional to the hydrogen concentration Therefore, the more the deoxidation treatment is carried out by reduction, the higher the hydrogen concentration will be. It will not only easily form cast holes during solidification, but also only produce low-quality low-oxygen copper ingots. In other words, Not only deoxidation treatment is needed, but if dehydrogenation treatment is ignored and not done, a large number of cast holes will be formed during solidification, making it impossible to produce high-quality low-oxygen copper. On the other hand, as a general degassing method, The redox method is likely to melt in a nearly complete combustion state to obtain molten copper with a low hydrogen concentration, but it is not practical to ensure a considerable distance for the subsequent deoxidation treatment. The present invention is based on the fact that The purpose of the foregoing situation is to provide: a dehydrogenation treatment can be performed without ensuring a long transfer distance, and cast holes generated during solidification can be suppressed | a method for manufacturing a low-oxygen copper that obtains high-quality low-oxygen copper with a good surface quality . [Means to solve the problem] The invention of item 1 of the scope of patent application covers the following steps: copper melting production process of burning copper to produce molten copper in the reducing gas environment of the melting furnace: the molten copper sent from the foregoing melting furnace can be used. A molten copper transfer process that is transferred to a feeding tank by a casting outflow tank sealed in a non-oxidizing gas environment; a degassing process for dehydrogenating the molten copper through a degassing means provided in the casting outflow tank; supplying the molten copper and continuous casting Continuous casting process of continuous production of cast copper material by a machine; and the cutting process of cutting the cast copper material into a low-oxygen copper ingot according to a specified length, which is characterized by continuous melting from molten copper as an ingot. Paper size is in accordance with China National Standard (CNS) A4 (210X297 mm) -6-461833 A7 _B7_ V. Description of the invention (4) Manufacturing method of low oxygen copper. The invention of the second scope of the patent application is a method of manufacturing low-oxygen copper that belongs to the first scope of the patent application, wherein in the aforementioned degassing step, the dehydrogenation treatment is performed by stirring the molten copper. The invention in the third scope of the patent application is a method for manufacturing low-oxygen copper in the second scope of the patent application, in which the aforementioned stirring means is to make the flow path through which the molten copper passes meandering to achieve agitation. The invention in item 4 of the scope of patent application refers to a method for continuously manufacturing low-oxygen copper as a copper wire, which is characterized in that the manufacturing method is to cover: copper fused copper produced by burning in a reducing gas environment of a melting furnace A production process; and a molten copper transfer process of transferring the molten copper sent from the melting furnace to a feeding tank by a casting outflow tank sealed by a non-oxidizing gas environment; and a molten copper passing through a degassing means provided in the casting outflow tank A degassing process for dehydrogenation; a continuous inlaying process for continuously producing cast steel by supplying the molten copper to an endless continuous casting machine; and a rolling process for rolling the cast copper material into a low-oxygen copper wire Inside. When the Ministry of Economic Affairs is wise, it will take 4 years to work * Cooperative Press 3 |} it I—It m «I ^ 1 ^ 1— T (please read the“ Notes on the back ”before filling out this page) The invention belongs to the manufacturing method of low-oxygen copper according to item 4 of the scope of patent application, in which the aforementioned degassing step is performed by stirring the molten copper for dehydrogenation treatment. The invention with the scope of patent application No. 6 is the manufacturing method of low-oxygen copper in the scope of patent application No. 5 with the aforementioned degassing process making the molten copper flow path meandering to achieve agitation. " The invention of 7 items is a method for continuously manufacturing low-oxygen copper as a copper alloy wire, which is characterized in that the manufacturing method is to cover the paper standard (CNS) Α4 pit grid (2 丨0X297 Gong) 4 6 183 3 A7 _B7 V. Description of the invention () 0, the production process of copper melting by burning in the reducing gas environment of the melting furnace to produce molten copper; and the molten copper sent from the foregoing melting furnace can be borrowed. A non-oxidizing gas environment sealed casting outflow ^ a molten copper transferer transferring to a feeding tank; and a dehydrogenation step for subjecting the molten copper to a dehydrogenation process by a degassing means provided in the casting outflow tank; and adding silver to the Silver adding process of molten copper after dehydrogenation: and a continuous casting process of continuously producing a cast copper alloy material by supplying the molten copper to a continuous casting type continuous casting machine; and rolling the cast copper alloy material The rolling process of the low-oxygen copper alloy wire is included. The invention in the eighth aspect of the patent application is a method for manufacturing low-oxygen copper in the seventh aspect of the patent application, wherein the degassing step is performed by stirring the molten copper. The dehydrogenation process. The invention in the ninth scope of the patent application is a method of manufacturing low-oxygen copper in the eighth scope of the patent application, wherein the degassing step is to make the molten copper flow path meandering to achieve agitation. The invention of item 10 in the scope of patent application is a method for continuously manufacturing low-oxygen copper as a phosphorus-containing copper base material for copper plating, and is characterized in that the manufacturing method is to cover the reduction in a melting furnace. The copper smelting copper production process of burning copper in a gas atmosphere to produce molten copper, and the copper smelting copper transfer process that transfers the copper smelt from the melting furnace to a feeding tank using a casting outflow tank sealed by a non-oxidizing gas environment: Degassing step of applying dehydrogenation treatment to the molten copper in the degassing means in the casting outflow tank: and a phosphorus addition step of adding phosphorus to the molten copper after the dehydrogenation treatment, and supplying the molten copper Continuous casting process for continuous production of cast bus bar with endless belt casting continuous casting machine; and rolling process of rolling the cast bus bar to make phosphorous copper base material for copper plating. This paper is applicable to Chinese standards (CNS > A4 specification (2 丨 0X297 mm) --------- ^ ------ tr ------ ^ (Please read the precautions on the back before filling the book (Page) -8-4 6 1 8 3 3 A7 B7 V. Description of invention (6) The invention in the 11th scope of the patent application is a method for manufacturing low-oxygen copper in the 10th scope of the patent application, of which The aforementioned degassing step is a method for dehydrogenating the molten copper by stirring. The invention in the patent application No. 12 is a method for manufacturing low-oxygen copper in the patent application No. 11 in the aforementioned degassing step. The molten copper flow path passing through is made serpentine to achieve agitator. The invention of item 13 in the scope of patent application 'is the method for manufacturing low-oxygen copper in item 12 of the scope of patent application, which includes cutting the aforementioned phosphorus-containing copper base material for copper plating after rolling to a short length of a predetermined length The ingot forming process is used to continuously manufacture short ingot-shaped phosphorous copper base materials for copper plating. ° The invention claimed in item 14 of the patent scope is a method for manufacturing low-oxygen copper in the scope of patent application No. 13; This includes a washing step of washing the phosphorous copper base material for short ingot-like copper plating. [Operation] In such a method for producing low-oxygen copper, the molten copper is deoxidized 'in a melting furnace which burns in a reducing gas environment'. The deoxidized molten copper 'is sealed in a casting outflow tank in a non-oxidizing gas environment and transferred to a feeding tank. After the deoxidation of the molten copper in the melting furnace 'has an inversely proportional relationship between the oxygen concentration and the hydrogen concentration, the hydrogen concentration increases. This molten copper having an increased hydrogen concentration is subjected to a dehydrogenation treatment by a degassing means when it flows out of a casting tank. Therefore, the reduction of the amount of gas released during casting 'suppresses the casting holes generated in the cast copper material, and reduces the casting defects formed on the surface of the low-oxygen copper. This paper size applies to the Chinese national standard (CNS) A4 (210X297 mm) ^^ 1- ^^ 1 ^^ 1 ^^ 1 ^^ 1 ^^ 1 ^^ 1 fr I < Please read the “Notes on the back page before filling out this page.” Order the Ministry of Economic Affairs ’wisdom and the 4 steps and 8 steps. -9-461833 A7 B7 V. Description of the invention (7) (Please read the“ back page first ” (Please note this page before filling in this page) Also, in the degassing process, if the molten copper is stirred, the hydrogen in the molten copper is forcibly expelled to perform dehydrogenation treatment. It is because the stirring means for contacting the molten copper is provided in the casting outflow tank, so the molten copper before being transferred to the feeding tank will be contacted and stirred by the stirring means, so that the inert gas and molten copper blown in for the purpose of forming a non-oxidizing gas environment. Improved contact. At this time, the hydrogen partial pressure in the inert gas is extremely small in terms of the hydrogen partial pressure of the molten copper, and the hydrogen in the molten copper is absorbed by the inert gas, so that the dehydrogenation treatment of the molten copper can be performed. Furthermore, in the degassing step, if the molten copper flowing through the casting outflow trough through the weir meanders, it can be stirred because it can form a torrent. That is, it can be automatically stirred by the flow of molten copper itself. In this way, the molten copper is formed by the weir to form an up-and-down or left-right turbulent flow, so that the molten copper flowing through the casting outflow groove has a chance of universal contact with the inert gas, and the efficiency of the dehydrogenation treatment can be improved. In this case, for example, a bar-shaped or plate-shaped weir provided on a molten copper flow path is preferable. Moreover, it is feasible to provide a large number of the weirs in the direction of the flow of molten copper, or a plurality of the weirs in a direction perpendicular to the flow of the molten copper. Moreover, if the weir is made of carbon, for example, the contact between molten copper and carbon can be used to perform a deoxidation treatment more effectively. [Embodiment] The following is a detailed description of the embodiment of the method for producing low oxygen copper according to the present invention with reference to the drawings. The term "low-oxygen copper" in the text refers to copper or copper alloys that have an oxygen content of 20 p pm or less, and is preferably suppressed in the range of 1 to 10 P pm. This paper size is applicable to China National Kneading Rate (CNS) Α4ϋΙ (2I0X297 mm) -10- 4 6 18 3 3 A7 _B7_ V. Description of the Invention (8) [First Embodiment] I ^^ 1 ^^ 1 — ^ 1. ^^ 1 ϋ p In m KVK-* (Please read the precautions on the back before filling out this page) The first embodiment will be described with reference to Figures 1 and 2. This embodiment is related to a manufacturing method for manufacturing low-oxygen copper as an ingot. FIG. 1 is a schematic diagram showing a manufacturing apparatus of a low-oxygen copper ingot used in this embodiment. FIG. 2 is a plan view (a) and a side elevation view (b) showing a casting outflow groove in FIG. 1 Enlarged view of main parts. The manufacturing device of the low-oxygen copper ingot (the manufacturing device of the low-oxygen copper) i01 is equipped with: a melting furnace A, a holding furnace B, a casting outflow tank C, a continuous casting machine D, and a cutting means E , And moving out means F. The melting furnace A is a gas furnace having a cylindrical furnace body. For example, a blast furnace system is suitable for users. A plurality of burners (not shown) are installed in the lower part of the melting furnace A * in the circumferential direction, and are arranged in multiple stages according to the melting amount. In this melting furnace A, combustion is performed in a reducing gas atmosphere to produce molten copper (molten metal). The reducing gas environment, for example, can be obtained by improving fuel in a mixed gas of natural gas and air. More specifically, in general, the CO (-carbon oxide) concentration in the exhaust gas is maintained in the range of 0.2 to 0.6%, and the air-fuel ratio is adjusted to the range of 2 to 5%. As described above, since the melting in the melting furnace A is performed in a reducing gas atmosphere, the molten copper is subjected to a deoxidizing treatment. In addition to temporarily storing the molten metal sent from the melting furnace A, the holding furnace B is provided for the purpose of keeping it at a predetermined temperature and transferring it to the casting outflow tank. The casting outflow tank C is a non-oxidizing gas environment that seals the molten metal sent from the holding furnace B and transfers it to the feeding tank 5a. The seals referred to in this paper are commonly used in the S countries (CNS) A4 scale (210X297 mm) -11-461333 A7 B7 I. '"' V. The description of the invention (9) is as in the second As shown in the figure, it is achieved by covering the molten copper flow path (flow path of molten copper) 3 1 of the casting outflow tank C with a cover 8. The non-oxidizing gas environment is formed, for example, by blowing a mixed gas of nitrogen and carbon monoxide and an inert gas such as argon into the casting outflow tank C. The molten copper flow path 31 at the casting outflow tank C is provided with a stirring means (deaeration means) 33 for applying degassing treatment including dehydrogenation treatment to the molten metal passing therethrough as shown in FIG. 2. The stirring means 33 is composed of weirs 33a, 33b, 33c, and 33d, so that molten gold is vigorously stirred while it is in circulation. Weir 3 3 a is located on the upper side of molten copper flow path 3 1, that is, it covers 8 places. Again, weir 3 3 b is on the lower side of molten copper flow path 3 1, weir 3 3 c is on the left side of molten copper flow path 3 1, and weir 3 3 d These are arranged on the right side of the molten copper flow path 31 respectively. By means of the abdomen 33a, 33b, 33c, and 33d, the molten metal is meandering up, down, left, and right, and flows in the direction indicated by the arrow in Fig. 2 to form a turbulent current and is stirred, so that it can be degassed. In Fig. 2 (b), the reference numeral 32 denotes a molten metal surface. The weirs 33c, 33d are the actual length of the molten copper flow path 31, which is then lengthened to form a molten metal flow path. If the casting outflow groove C is of a short size, it can also improve the efficiency of the degassing treatment. = Weir 33a 3 3 b is designed to prevent the mixing of molten copper and ambient gas before and after degassing. In addition, although the stirring means 3 and 3 are mainly provided for the purpose of performing dehydrogenation treatment, since the molten metal is stirred, it is possible to expel the oxygen remaining in the molten metal. In other words, as a degassing treatment, the paper can be dehydrogenated. The paper size can be used in China National Standards (CNS) 8 4 * 1 grid (2 丨 0X297 mm) (Please read the precautions on the back before filling this page. ) Order the Ministry of Economic Affairs Xi Hui Shi 4 Gou Gong Cooperative Co., Ltd. -12- 46 183 3 A7 ____B7_ V. Description of the invention (j (please read "Notes on the back ^ before filling this page). The two sides also. The weirs 3 3a, 3 3b, 33c, 33d, for example, when made of carbon, can be effectively deoxidized by contact between molten copper and carbon. The degassing treatment is necessary for the holding furnace It will be carried out during the transfer process after B. The reason is that in order to obtain low-oxygen copper ingots, combustion in a reducing gas environment or deoxidation treatment by a reducing agent is performed in the holding furnace B. According to the foregoing balance, For the relationship of formula (A), the hydrogen concentration will inevitably increase. Moreover, in terms of the position for performing degassing treatment, it is not appropriate to perform degassing treatment in the feeding tank 5a before casting. Because In the tank 5a, the molten metal is stirred vigorously. It will vibrate violently, causing the molten metal pressure head flowing out of a casting port (not shown) to be described later to change, so that stable molten copper supply and continuous casting machine D cannot be achieved. On the other hand, the liquid level does not reach the level of intense vibration. The degree of degassing cannot be expected. From this point, it can be understood that the degassing process is most ideal during the transfer process from the holding furnace B to the feeding tank 5a. The staff of the Ministry of Economic Affairs and the Intelligent Finance Bureau's consumer cooperation There is a casting port (not shown) on the end of the seal-feeding tank 5a toward the end of the flowing direction of the molten metal, and it can supply molten metal and continuous casting machine from the feeding tank 5a. The outflow tank C is connected to a continuous casting machine D. The continuous casting machine D is a so-called vertical casting machine, which is provided with a molten copper that can be cooled while being supplied and drawn down to a slightly vertical direction to a predetermined cross-sectional shape. The copper mold 2 1 a is used for the mold 4 1 and the pinch roller 4 2. The shape and configuration of the molds 4 1 and the pinch roller 4 2 are in accordance with the Chinese national standard (CNS) for paper size (2丨 〇 X 297 mm) -13-Α7 Β7 4 6 丨 8 3 3 V. Description of the invention (j (please read the precautions on the reverse side before filling out this page). Choose the shape of the low-oxygen copper ingot (low-oxygen copper) 2 3 a as the product, and select it appropriately. For example, in When the low-oxygen copper ingot 2 3 a is to be made into a long cylindrical ingot with a slightly cylindrical shape, the cross-section of the mold 41 is rounded and the pinch roller 4 2 is also made to correspond to the shape. When the agglomerate with a slightly rectangular shape is made, the cross-sectional shape of the mold 41 can be made rectangular, and the pinch roller 4 2 can also be made into a corresponding shape. The low-oxygen copper ingot in the first figure 2 3 a is shown by taking agglomerates as an example. In the embodiment, although a vertical continuous casting machine is used as an example, a horizontal continuous casting machine that casts ingots in a horizontal direction is used. It is also feasible. The cutting means E is to cut the cast copper 2 1 a from the continuous casting machine D to a predetermined length. As an example of this cutting means E, although a circular saw with a disk-shaped blade rotating can be mentioned, as long as it can cut the cast copper 2 1 a, other configurations are not indispensable. The removal means F is made by placing a basket 51, an elevator 52, and a conveyor 53. The basket 51 is located just below the continuous casting machine D, and accepts the low-oxygen copper ingot 2 3 a cut to a predetermined length by the cutting means E, and then loads it into the lifter 52. The lifter 5 2 will carry the low-oxygen copper ingot 2 3 a loaded in the basket 5 1 to the position of the conveyor 53. Conveyor 5 3 is designed to transport low-oxygen copper ingots 2 3 a from elevator 5 2. Β is used to manufacture the low-oxygen copper ingots constructed in accordance with the foregoing situation. ) Α4Λ lattice (2 丨 〇 X 297mm) -14- 4 6 1 83 3 A7 B7 V. Description of the invention (The manufacturing method of the low oxygen copper ingot of j 1 0 1 is explained first. In the melting furnace A The combustion is performed in a reducing gas environment, and the molten copper is deoxidized while producing molten copper (copper melting production process). The molten copper after the deoxidation treatment is passed through a holding furnace B, and a non-oxidizing gas environment is used in the casting outflow tank C. It is sealed and transferred to the feeding tank 5 a (melt copper transfer process). The deoxidized copper in the melting furnace A has an inverse relationship between the oxygen concentration and the hydrogen concentration, so the hydrogen concentration increases. The hydrogen content When the molten copper having an increased concentration passes through the casting and flows out of the tank C, the dehydrogenation treatment (degassing step) is performed by the stirring means 33. With this, the molten copper is adjusted to a gas content of less than 20 p pm and a hydrogen content of 1 p Below pm. By this measure, released during casting Gas reduction | It is possible to suppress the occurrence of casting holes in the cast copper 2 a. In addition, from the relationship of the balance type (A), the gas concentration of the molten copper can be reduced by reducing the partial pressure of water vapor, so by completely separating the dehydrogenation treatment The former molten copper and the molten copper after dehydrogenation treatment may have a further degassing effect. This matter can be achieved, for example, by providing the aforementioned stirring means 33 in the molten copper transfer process. That is, the stirring means 33 It is also possible to prevent the mixing of the gas environment before and after the dehydrogenation treatment, and the tasker who mixes with the molten copper. 0 The molten copper is transferred from the melting furnace A to the holding furnace B. After the temperature is raised, it flows out of the casting tank C and is fed to the tank The supply and continuous casting machine D. It is drawn down from the mold 41 by the pinch roller 4 2 and then cooled and solidified to continuously cast into a cast copper material 21a (continuous casting process). This cast copper material 2 1 a is It is cut off by cutting means E, and the paper size in this order is in accordance with Chinese standards (Renyang) 厶 4 washers (210 father 297 mm) (Please read the precautions on the back before filling in this page to order-15- A7 461833 B7 V. Description of the invention (^ Continuous production of low-oxygen copper ingots with specified length 2 3 a (cutting process) 〇I ^^ 1 —i I ^^ 1 ^^ 1 -I— I— I m ---- t— 1 ^ 1 HI t ^ n (Please read the “Notes on the back side before filling out this page”) The cut-off copper material 2 1 a is used as the low-oxygen copper ingot 2 3 a. It is removed by the removal method (the removal process). The low-oxygen copper ingot 2 3 a was accepted by the basket 5 1 located just below, and was loaded on the lifter 5 2 and moved up to the position of the conveyor 5 3, and then borrowed by the conveyor 5 3 Move it. Printed in this embodiment by the Ministry of Economic Affairs, the Intellectual Property Co., Ltd., in a manufacturing method using a low-oxygen copper ingot manufacturing device 110, the furnace is burned in a reducing gas environment in the melting furnace A, and The molten copper is deoxidized. The molten copper is sealed in the casting outflow tank C by a non-oxidizing gas environment and transferred to the feeding tank. 5 a = The molten copper, because its oxygen concentration and hydrogen concentration are inversely proportional, its hydrogen content The concentration is increased, but in the subsequent degassing process, the dehydrogenation treatment is performed by stirring means 3 3. This eliminates the need to ensure a long molten copper transfer distance, which can reduce the hydrogen concentration that is increased during deoxidation by reduction, thereby suppressing the generation of bubbles in the molten copper. Therefore, a high-quality low-oxygen copper ingot 2 3 a capable of cooling and suppressing the generation of cast holes during solidification can be produced continuously and in large quantities at low cost by using a gas furnace that burns in a lamp. In addition, since the degassing means is made by the stirring means 33 for stirring molten copper, the forced dehydrogenation treatment can be performed in a short time, so the dehydrogenation treatment can be effectively performed with a simple structure. In addition, if the stirring means 33 is constituted by a weir capable of causing the molten copper to snake through the passage, it can be stirred by the flow of the molten copper itself, so there is no need to install a special stirrer, etc. Effectively carry out the paper size and use the Chinese national standard (CNS > A4 size (210X297mm) -16- a 6 t 83 3 A7 ______B7__ V. Description of the invention (j Hydrogen treatment outside '尙 can make low oxygen copper ingots The manufacturing equipment 1 ο 1 is easy to operate and manage and can be manufactured at a lower cost. III-I. 1--II-—1—--I n (Please read the precautions on the back before filling this page) Also, the separation made by the stirring means 33 is not limited to a single place, but can be appropriately set according to the length of the transfer process. Moreover, it is not limited to low-oxygen copper ingots in the overall scope, and It is also possible to produce low-oxygen copper alloy ingots by mixing appropriate addition elements. In this example, although weirs 33a, 33b, 33c, and 33d are provided above and below the molten copper flow path 31 as the stirring means 33, respectively. For example, depending on the length and width of the casting outflow groove C, The number and configuration of these weirs are not indispensable. "Also, in this example, although the so-called vertical continuous casting machine D is used for illustration, it is also feasible to use the so-called horizontal continuous casting machine that continuously casts in the lateral direction. In this case, no lifting means such as a lifter 5 2 [the second implementation form] is needed, and the second implementation form is explained in accordance with the attached figures 3 and 4. This embodiment is related to A person who uses low-oxygen copper as a manufacturing method of copper wire. Fig. 3 is a diagram showing the structure of a low-oxygen copper wire manufacturing apparatus used in this embodiment. The low-oxygen copper wire manufacturing apparatus (low-oxygen copper) Manufacturing equipment) 102, the main parts of which are roughly distinguished are: melting furnace A 'and holding furnace B, and casting outflow groove C 2, and endless casting continuous casting machine G, and rolling mill Η, and winding Roll device I, etc. This paper size is applicable to China National Standards (CNS) A4 wash case (210X297 mm) -17- 461833 A7 __B7____ 5. Description of the invention (j (Please read the precautions on the back before filling this page) ) In addition, the melting furnace in this embodiment The heat-retaining furnace is the same structure as that of each of the furnaces described in the first embodiment described above. The same reference numerals are attached to the furnace and the detailed description is omitted. The casting outflow tank C 2 will be sent from the heat-retaining furnace B. The coming molten metal is sealed with a non-oxidizing gas environment and transferred to the feeding tank 5b. A casting nozzle 9 'is provided at the end of the feeding tank 5b' in the direction of the molten metal flow direction, and will come from the curtain tank. 5 b 的 fused state Golden supply and continuous belt casting type continuous casting machine G ° In addition, the casting outflow groove C 2 and the feeding groove 5 b are only compared with the casting outflow groove C and the feeding groove 5 a in the first embodiment described above. There are some differences in shape and the like because they are suitable for the manufacture of low-oxygen copper wires, and their approximate structures belong to each other. That is, in the casting outflow groove (: 2, there is no stirring means 3 3 as shown in FIG. 2). The Ministry of Economic Affairs's wisdom 4 '" The staff consumer cooperative prints the holding furnace B by casting outflow groove C 2 It is connected to the endless belt casting continuous casting machine G. The endless belt casting continuous casting machine G is an endless endless belt 11 which is moved by a circle and contacts a part of its circumference on the endless endless belt 1 1 It consists of a rotating casting wheel 1 and 3, and 俾 continuously produces cast copper 2 1 b. The endless belt casting type continuous casting machine g 'is connected to the rolling mill Η. The rolling mill Η will be produced by the endless belt casting. The rod-shaped cast copper 2 1 b of the continuous casting machine G is rolled to form a low-oxygen copper wire (low-oxygen copper) 23 b. The rolling machine is further cut by a shearing machine (cutting means) 15 and a hand flaw detector 19 is in the middle, and is connected with the winding device I. Shearing machine 1, 5, with a pair of rotating blades 16, 16, is used to cut off the cast copper 2 1 b rolled by the rolling mill, that is, low oxygen Copper wire paper standard Chinese standard (CNS) A4 standard (210X297 mm) ~ ~ 4 6 183 3 A7 B7 V. Description of the invention ( d (Please read the precautions on the reverse side and fill in this page) 2 3 b, cut into short ingots. For example, at the beginning of the operation of the endless belt continuous casting machine G * Casting the inside of copper 2 1 b The structure is unstable, and the low-oxygen copper wire 2 3 b made in this state cannot be a stable product. In this case, the low-oxygen copper wire 2 3 b drawn from the rolling mill It will be cut in order by the shearing machine 15 until the quality is stable. It will not be sent to the flaw detector 19 and the winding device I until the quality of the cast copper 2 1 b is stable. Remove from the low-oxygen copper wire 2 3 b and send the low-oxygen copper wire 23 b to the flaw detector 19 and the winding device I. Hereby, the low-oxygen copper wire with such a structure is used to manufacture the low-oxygen copper 1 2 The manufacturing method is explained. First, the melting furnace A is burned by a reducing gas environment, while the molten copper is deoxidized, and the molten copper is produced (the molten copper after the deoxidation of the copper production process | passes through the holding furnace B, and is cast The outflow tank C 2 is sealed by a non-oxidizing gas environment and transferred to the feed tank 5b (melt copper transfer process). The molten copper subjected to deoxidation treatment in molten A has an inversely proportional relationship between the oxygen concentration and the hydrogen concentration. Therefore, the hydrogen concentration is increased. The molten copper having the increased hydrogen concentration is stirred while flowing out of the tank C 2 through casting. Means 33 are dehydrogenated (degassing process). Therefore, the oxygen content of the molten copper is adjusted to less than 20 p pm, and the hydrogen content is less than 1 p pm. By this measure, the amount of gas released during casting is reduced. It can suppress the casting holes generated in the cast copper 2 1 b. In addition, according to the relationship of the equilibrium formula (A), because the gas concentration in the molten copper can be reduced by reducing the partial pressure of water vapor, a degassing treatment will be implemented The former copper smelting and the copper smelting after the dehydrogenation treatment are completely separated, it is possible to obtain the paper standard GM China Standard (CNS) A4 ^ (2 丨 0X297 mm) -19- 461833 A7 ___B7 V. Invention Instructions (^ t Please read the “Notes on the back side before filling out this page”) to further degassing effect. The method is, for example, provided in the molten copper transfer process by providing the stirring means 33 as described above. That is, the stirring means 33 can also avoid the task of preventing the mixing of the ambient gas before and after the dehydrogenation treatment and the mixing of the molten copper. The molten copper transferred from the melting furnace A to the holding furnace B is heated, and then flows out of the tank C 2 and feeds the tank 5 b through the casting, and then is supplied from the casting nozzle 9 to the continuous belt casting type casting machine G, and is cast on the continuous belt. The continuous casting machine G is continuously cast, and then is formed into a cast copper material 2 1b just after the discharge from the endless belt continuous casting machine G (continuous inlaying process). This cast copper material 2 lb was rolled with a rolling mill to form a low-oxygen copper wire (low-oxygen copper) 2 3 b with good surface quality (rolling process). If the quality of the low-oxygen copper wire 2 3 b is stable, the lubricating oil coated with wax or the like is taken up by the winding device I after the flaw detector 19 detects the flaw, and it is sent to the follow-up state in this state. Procedure. The manufacturing method of such a low-oxygen copper wire is to adjust the gas content of molten copper to 20 ppm or less of oxygen and 1 ppm or less of hydrogen before casting. The rolling action reduces the gas released during casting, suppresses the casting holes generated in the cast copper 2 1 b, and reduces surface defects on the low oxygen copper wire 2 3 b. In addition, the low-oxygen copper wire 2 3 b manufactured by such a manufacturing method is also excellent in gas release characteristics. Figure 4 shows the gas release characteristics (curve a) of the low-oxygen copper wire manufactured by the manufacturing method related to this embodiment and the gas release characteristics (curve b) of the low-oxygen copper wire manufactured by the dip forming method. . In the figure, the horizontal axis represents the elapsed time (seconds) since the start of the experiment. The vertical axis represents the amount of gas released. This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) ~ 4 6 18 3 3 A7 _B7___ V. Description of the invention (j As shown in the figure, it can be seen that it is manufactured according to the manufacturing method related to this embodiment The amount of gas released from low-oxygen copper wire is significantly less than the amount of gas released from low-oxygen copper wire produced by the dipping forming method. When the amount of gas released is low-oxygen copper wire or low-oxygen Copper alloy wire, when used under so-called high vacuum or high temperature conditions *, may cause surface swelling to reduce surface quality, or release gas to the outside to pollute the environment. Oxygen copper wire has a very small amount of gas released, so it can be used in, for example, particle accelerators with high vacuum, microwave ovens with high temperature, etc. The low-oxygen copper wire manufacturing device related to this embodiment is used. In the manufacturing method, combustion is performed in a reducing gas environment in the melting furnace A, and the molten copper is subjected to deoxidation treatment. The molten copper is sealed in the casting outflow tank C 2 by a non-oxidizing gas environment and transferred to the feeding tank 5 b. Then, due to the inverse relationship between the oxygen concentration and the hydrogen concentration of the molten copper, the hydrogen concentration of the molten copper is increased, but in the subsequent degassing process, the dehydrogenation treatment is performed by the stirring means 3 3. Thus, there is no need to ensure The long molten copper transfer distance can reduce the hydrogen concentration increased during deoxidation by reduction and suppress the bubbles generated in the molten copper. Therefore, a gas furnace that can be used for combustion in the furnace can be used. Continuous inlaying can suppress cooling. The high-quality cast copper 2 1 b with pores generated during solidification, and the continuous casting machine using an endless belt casting type, continuously manufactures low-cost and high-quality low-oxygen copper wires 2 3 b. In addition, because of the stirring means for stirring the molten copper 3 3. As a means of degassing, mandatory dehydrogenation treatment can be performed in a short period of time, so the dehydrogenation treatment can be effectively completed with a simple structure. This paper is applicable to S countries (CNS) (2f0X297) Mm} (please read the note on the back—item first, then fill out this page) Order • 21-46 183 3 at __B7____ V. Description of the invention (^ Moreover, if the disturbance means 3 3 are used, the passage can be passed Welded Copper Snake Weir Structure At the time of completion, the sample can be stirred by the flow of the molten copper itself, so there is no need to install a stirrer, etc. In addition to the effective dehydrogenation treatment with a simpler structure, the operation of the low-oxygen copper wire manufacturing equipment can be enabled It is easy to manage a. In order to stabilize the temperature of the molten metal, an electric furnace can be installed between the holding furnace B and the feeding tank 5 b. Also, from the end of the casting outflow tank C 2 to the end of the feeding tank 5 b It is also necessary to provide means for adding elements other than copper to molten copper. [Third Embodiment] Next, the third embodiment will be described as follows according to the attached Figures 5 and 6. This embodiment, This is a method for manufacturing low-oxygen copper into a low-oxygen copper alloy wire containing silver (Ag). As a result of intensive review by the inventors, it was found that when a small amount of silver is added to the molten copper, the casting holes formed in the silver-containing inlaid copper alloy material can be finely dispersed, and disappear when rolling, without forming defects. To the extent that ultra-fine pores are used, the purpose of suppressing the generation of harmful cast holes in low-oxygen copper alloy wires is achieved. The method of adding silver has the advantage of suppressing the decrease in the conductivity of the produced low-oxygen copper alloy wire. Fig. 5 is a block diagram schematically showing a device for manufacturing a low-oxygen copper alloy wire used in this embodiment. The low oxygen copper alloy wire manufacturing device (low oxygen copper manufacturing device) 103 is compatible with the national standard (CNS) A4 washing grid (21 OX297) for the low paper music scale in the second embodiment described above. Li) (Please read the notes on the back before filling in this page)
-22- 461833 經濟部智慧財4笱貝工消費合作社印製 A7 B7___ 五、發明説明（2() 氧銅線製造裝置1 〇 2相較，僅其鑄造流出槽之構成不同 而己。因此之故，對其他之構成要素，只附與和前述第2 種實施形態者相同之符號而省略其詳細說明。 在該低氧銅合金線之製造裝置1 〇 3備置鑄造流出槽 C 3，以替代低氧銅線之製造裝置1 〇 2所備置之鑄造流 出槽C 2。 於鑄造流出槽C 3之終端部附近，設有銀添加手段3 ，俾能將銀添加到熔態金屬中者《藉該銀添加手段3，可 對完成脫氧處理及脫氫處理後之熔態金屬添加銀，再藉接 著於餵槽5 b中產生之亂流，可使銀與熔銅做良好的混合 〇 且，設置該銀添加手段3之場所，並不限定於鑄造流 出槽C 3之終端部附近。就是，只要屬於添加於完成脫氫 處理後之熔態金屬中而能充分擴散之處即可，故從鑄造流 出槽3之終端部以后至餵槽5 b之終端止，其間皆屬可設 置之場所也。 又，鑲造流出槽C 3，除備置銀添加手段3之點以外 的構成，皆與鑄造流出槽C 2相同。即，鑄造流出槽C 3 ，亦設有如於第2圖中所示之攪拌手段3 3。 茲就使用具備此構成之低氧銅合金線製造裝置1 0 3 的低氧銅合金線之製造方法加以說明。 首先，於熔融爐A中藉還原性氣體環境進行燃燒，一 面對溶銅做脫氧裝置一面生產熔銅（熔銅生產工序）。經 脫氧處理後之熔銅|通過保溫壚B ’并於鑄造流出槽C 3 (請先聞讀背面之注意事項再填寫本頁}-22- 461833 Wisdom from the Ministry of Economic Affairs 4 Printed by Ai Bong Consumer Cooperative A7 B7___ 5. Description of the Invention (2 () Oxygen copper wire manufacturing equipment 1 〇 Compared with the only one, the structure of the cast outflow groove is different. Therefore, Therefore, the other constituent elements are given the same symbols as those in the second embodiment, and detailed descriptions are omitted. A casting outflow groove C 3 is provided in the manufacturing device 1 of the low-oxygen copper alloy wire to replace it. The casting outflow groove C 2 provided in the low oxygen copper wire manufacturing device 1 02. Near the terminal portion of the casting outflow groove C 3, a silver adding means 3 is provided, which can add silver to the molten metal. The silver adding means 3 can add silver to the molten metal after the deoxidation treatment and dehydrogenation treatment are completed, and then by using the turbulent flow generated in the feeding tank 5 b, the silver and the molten copper can be well mixed. The location of the silver addition means 3 is not limited to the vicinity of the terminal portion of the casting outflow tank C 3. That is, as long as it is a place that can be sufficiently diffused by being added to the molten metal after the dehydrogenation treatment is completed, From the end of the outflow tank 3 to the feeding tank The terminal 5b is only a place that can be installed in between. The structure of the outflow groove C 3 is the same as that of the outflow groove C 2 except that the silver adding means 3 is provided. That is, the outflow groove is cast. C 3 is also provided with a stirring means 3 3 as shown in Fig. 2. A method for manufacturing a low-oxygen copper alloy wire using the low-oxygen copper alloy wire manufacturing apparatus 103 having this configuration will be described. First, Combustion is carried out in the melting furnace A by using a reducing gas environment, and molten copper is produced while the dissolved copper is used as a deoxidizing device (copper fused copper production process). The molten copper after the deoxidation treatment | Please read the notes on the back before filling out this page}
本紙乐尺度逍用中國國家揉準（CNS ) A4現格（2I0X297公釐} -23· 461833 A7 B7 五、發明説明（21) (請先閲讀背面之注意事項再填寫本頁) 中藉非氧化氣體環境所密封，而移送至餵槽5b(熔銅移 送工序）。在熔融爐A中接受脫氧處理之熔銅，由於其含 氧濃度與含氣濃度呈反比之關係故，含氣濃度會提高。該 含氫濃度提高之熔銅，於通過鑄造流出槽C 3之際’藉攢 拌手段3 3施予脫氫處理（脫氣工序）。 藉此，熔銅經調整其含氧童至1〜1 0 p P m以下， 含氫量則爲1 P pm以下者。并且，自銀添加手段3添加 銀與經過調整含氧濃度及含氫濃度後之熔銅，俾讓熔銅中 之銀含量在0 . 005〜0 . 2wt%範圔內者（銀添加 工序）。 若含銀量小於0.005wt%時，幾乎無法期望將 鑄孔微細化，就是說不能得到抑制表面瑕疵之功效。反之 ，若含銀量大於0 . 2w t %時，雖然抑制瑕疵產生之作 用并無太大變化，惟因低氧銅合金線之強度增高，致影響 鑄造銅合金材之輥軋，後續加工等不易順利地進行。 基於該原因，理想上以維持含銀量於前述範圍內爲宜 〇 經濟部智S財產苟员工消費合作社印製 如前所述，自熔融爐A移送至保溫爐B之含銀熔銅， 經昇溫之後，通過鑄造流出槽C 3，餵槽5 b而供給與環 帶鑄造式連續鑄造機G，復在環帶鑄造式連續鑄造機G中 予以連續鑄造，而於剛出環帶鑄造式連續鑄造機G處成形 爲鑄造銅合金材2 1c (連續鑄造工序）。 該鑄造銅合金材2 1 c，復經輥軋機Η予以輥軋，製 成含有規定量之銀且表面品質良好的低氧銅合金線（低氧 本紙張尺度遙用中國國家揉率（CNS ) Α4规格（210Χ297公釐} -24- 46 1 83 3 A7 ____B7_ 五、發明説明（j 銅）23c，并被纏卷裝置I所卷取。 (請先Μ讀背面之注意事項再填寫本頁) 依前所述，將經調整含氧濃度及含氫濃度’并且添加 規定量之銀以後的熔銅予以鑄造，輥軋’使鑄造時之釋出 氣體減少，抑制產生於鑄造銅合金材2 1 c內之鑄孔’減 低在低氧銅合金線2 3 c表面之瑕疵。 第6圖表示使用如前述低氧銅合金線之製造裝置 1 ◦ 3的製造方法所得低氧銅合金線2 3 c表面探傷檢査 結果。該探傷檢查，係選用銅線用旋轉位相型渦電流探傷 裝置製造廠商名：（株）ESTEK，機型名：R P -7000)，以旋轉位相型渦電流探傷法進行者。 於第6圖中，分別表示對，（a)未含銀者；（b) 含有O.Olwt%之銀者；（c)含有0.03wt% 之銀者；（d)含有0 . 0 5wt%之銀者，探傷之圖表 。各該圖表中分別表示縱軸爲時間•橫軸爲對應於瑕疵之 數量及大小產生之渦電流電壓（V )。 如該第圖中所示，可知在低氧銅合金線2 3 c中之含 銀量越多時，即對熔銅之銀的添加量越多，低氧銅合金線 4i濟部智慧574¾負工消費合汴社印^ 2 3 c表面之瑕疵越會減少之情形。 此乃表示，若能添加可使銅之結晶粒微細化之元素而 增加粒界時，每單位粒界之氣體成分濃度將減少1而當考 慮鑄造銅合金材2 1 c中之氫，氧，水蒸汽局部性之平衡 時，外表上之氣體成分濃度，與粒界增大之情形相較降低 甚多，結果據推測係難於形成大鑄孔之故也。 依照本發明者等所檢討，適於做爲該添加元素者爲銀 本紙張尺度適用中困困家橾準（CNS ) A4规格（2丨0X297公釐） -25- 461833 A7 B7 五、發明说明（ ，若使之含有0 . ◦ 0 5w t %以上之銀後，可將形成於 鑄造銅合金材2 1 c中之鑄孔微細地分散成超微鑄孔，能 夠減少將該鑄造銅合金材21c輥軋而製得之低氧銅合金 線23c表面的瑕疵。而，使其含有0.03wt%以上 時，則能顯著地減少瑕疵，含有0 . 0 5 w t %以上時， 更可顯著地減少瑕疵。 於使用本實施形態有關之低氧銅合金線製造裝置 1 0 3的製造方法中，在熔融爐A內以還原性之氣體環境 進行燃燒，將熔銅予以脫氧處理，該熔銅乃於鑄造流出槽 C 3中藉非氧化氣體環境密封并移送至餵槽5。然後，該 熔銅由於其含氧濃度與含氫濃度呈反比之關係，故其含氫 濃度提高，惟在後續之脫氣工序中藉攪拌手段3 3進行脫 氣處理。藉此，就能減低因藉還原方式脫氧裝置時提高之 含氫濃度，抑制凝固時產生之鑄孔。而且，更從銀添加手 段3添加銀於經過脫氧處理及脫氧處理而難於產生鑄孔之 熔銅中，可使鑄孔微細地分散，形成超微鑄孔。 經濟部智慧財產局8工消費合作社印製 ^^1 ^^^1 — ：· - 1.- ^^1 .^^1 ^^1 I · ^^1· m tui ^^^1 ,f*J (請先w讀背面之注意事項再填寫本頁) 是以，可使用環帶鑄造式連續鑄造機G，將能抑制導 電率之降低，而且有害鑄孔少之長錠狀鑄造銅合金材，并 以低成本連續地製造。又，雖將脫氣工序簡略化，亦可獲 得表面瑕疵顯著地減少，表面品質良好之低氧銅合金線。 藉此，即無必要使用爲進行脫氫處理之裝置，譬如真空脫 氣裝置等高價且特別之裝置，除使裝置之構成簡易化，同 時尙能以低成本製造出低氧銅合金線者。 又，因以攪拌熔銅用之攪拌手段3 3做爲脫氣手段之 本纸張尺度適用中國國家揉率（CNS ) A4規格（2丨0X297公釐） -26- 461833 A7 __B7 _ _ 五、發明説明（ 故，可在短時間內完成強制性脫氫處理，能以簡易的構成 有效進行脫氫處理。 (請先聞讀背面之注意事項再填寫本買) 更且，若將攪拌手段3 3，藉由能使通過通路之熔銅 蛇行之堰構成時，由於可憑熔銅本身之流動自行攪拌，故 無需特別裝用攪拌器等，除能以更簡易的構成有效進行脫 氫處理外*尙能使低氧銅合金線之製造裝置的運轉管理容 易。 又，所製成之低氧銅合金線2 3 c含有〇 . 〇 0 5〜 0 . 2w t %之銀，除能抑制導電率之降低外，尙能做成 表面瑕疵少，表面品質良好，就是說高品質之成品者。 〔第4種實施之形態〕 茲參照所附第7及8圖，就第4種實施形態說明之如 次。本實施形態，係有關製造做爲低氧銅并含有磷（P ) 之鍍銅用含磷銅母材之製造方法者》 矬濟部智慧財4笱員工消費合作社印製 如此之鍍銅用含磷銅母材，乃被成形爲桿狀，線狀或 者球（Ball )狀等之形狀，正好可使用於譬如說在印刷電 路基板上之配線圖案中的鍍銅用陽極。就是說，此種印刷 電路基板上之配線圖案，可藉鍍銅，特別是鍍硫酸銅等適 當地形成，而該鎪硫酸銅中之陽極即使用含磷銅（含有約 0 . 0 4%磷的低氧銅）所成。含有磷時，可促進陽極銅 順利的溶解，當使用未含磷的鍍銅用陽極時，將降低鍍膜 均勻之密接性。 第7圖係槪略地表示在本實施形態中所用鍍銅用含磷 本紙伕尺度逍用中國國家標準（CNS ) A4規格（210X297公釐） -27- 461833 A7 __B7_ 五、發明说明（^ 銅母材之製造裝置的構成圖。該鍍銅用含磷銅母材之製造 裝置（低氧銅之製造裝置）1 0 4，與前述第2種實施形 態中之低氧銅線製造裝置1 0 2比較，僅其鑄造流出槽之 構成不同而已。因此，對其他之構成要素，只附與和前述 第2種實施形態者相同之符號并省略其詳細說明。 在該鍍銅用含磷銅母材之製造裝置1 0 4，備置鑄造 流出槽C 4，以替代低氧銅線之製造裝置1 0 2所備置之 鑄造流出槽C 2。 於鑄造流出槽C 4之終端部附近，設有磷添加手段4 ，俾添加磷於熔態金屬之內β藉該磷添加手段4，可對完 成脫氧處理及脫氫處理後之熔態金屬添加磷，并防止磷和 氧之反應，再藉其後產生在餵槽5 b中之亂流，使磷與熔 銅做良好的混合。 又，設置該磷添加手段4之場所，並不限定於鑄造流 出槽C 4之終端部附近。就是，只要添加於完成脫氫處理 後之熔態金屬中并能充分擴散者即可，故從鑄造流出槽 C 4之終端部以后至餵槽5 b之終端止，其間皆屬可設置 經濟部智慧时產局貝工消費合作社印製 I ^ I ---- 裝——---"—訂 (請先聞讀背面之注f項再填寫本頁) 之場所也。 又，鑄造流出槽C 4 |除備置磷添加手段4之點以外 的構成，皆與鑄造流出槽C 2者相同。就是，在鑄造流出 槽C 4，亦設有如於第2圖中所示之攪拌手段3 3。 茲就使用具備此構成之鍍銅用含磷銅母材製造裝置 1 0 4的鍍銅用含磷銅母材之製造方法說明之。 首先，於熔融爐A中藉還原性氣體環境進行燃燒，一 本紙浪尺度適用中國國家揉率（CNS ) A4规格（210X29?公釐） -28- ^ b183 3 A7 B7 五、發明説明（d 面對熔銅做脫氧處理一面生產熔銅（熔銅生產工序）》經 脫氧處理後之熔銅，通過保溫爐B，并於鑄造流出槽C 4 中藉非氧化氣體環境所密封，而移送至餵槽5 (熔銅移送 工序）。在熔融爐A中接受脫氧處理之熔銅，由於其含氧 濃度與含氫濃度呈反比之關係故，含氫濃度會提高。該含 氫濃度提高之熔銅，於通過鑄造流出槽C 4之際，藉攪拌 手段3 3進行脫氫處理。 藉此，調整熔銅之含氧量於2 0 p pm以下，含氫量 則爲1 P pm以下者.并且，對經過調整含氧濃度及含氫 濃度後之熔銅，自磷添加手段4添加磷（磷添加工序）， 俾使溶銅之含隣率在4 0〜1，〇 〇 〇 p pm範圍內者。 於此，假如含氧濃度，含氫濃度，含磷率等在前述範 圍以外之時候，將發生下述不良之狀況。就是說，含氧量 不在2 0 p pm以下時，其加工性不良，并會在鑄造母線 材產生裂痕。當含氫量不在1 p pm以下時，釋出之氣體 多，使鑄造母線材產生裂痕。含磷量不在4 0 p pm以上 時，於當做陽極使用之際無法得到均勻之溶解性，不能成 爲做銅球之素材。又，若含磷量不在1,0 0 0 P pm以下 時，其加工性不良。 如此，進行調整含氧濃度及含氫濃度，并對添加磷以 後之熔銅予以鑄造，輥軋，即可使鑄造時之氣體釋出量減 少，抑制產生於鑄造母線材2 1 d之鑄孔，并減低線材表 面之瑕疵也。 如前所述，自熔融爐A移送至保溫爐B之熔銅，經昇 本紙乐尺度遴用中國國家樣率（CMS ) A4規格（210X297公釐） ----------裝-- (請先閲讀背面之注$項再填寫本頁) -,tr 經濟邹皙慧时4"員工消費合作社印发 -29 4 6 18 3 3 A7 __B7 五、發明说明（ (請先Μ讀背面之注意事項再填寫本頁) 溫後，通過鑄造流出槽C 4，餵槽5 b供給與環帶鑄造式 連續鑄造機G，於環帶鑄造式連續鑄造機G中予以連續鑄 造，而於剛出環帶鑄造式連續鑄造機G處成形爲鑲造母線 材21d。該鑄造母線材21d，復藉輥軋機Η輥軋，製 成含有規定量之磷且表面品質良好之鍍銅用含磷銅母材（ 低氧銅）2 3 d »該鍍銅用含磷銅母材2 3 d，於藉探傷 器1 9檢測有無瑕疵之後，一面塗以蠟等之潤滑油一面被 纏卷裝置I所卷取。該鍍銅用含磷銅母材2 3 d，再送至 別的工序，而適當地成形爲例如銅球等者。 經濟部智慈財產局員工消費合作社印製 於使用本實施形態有關之鍍銅用含磷銅母材的製造裝 置1 0 4進行之基板方法中，在熔融爐A內以還原性之氣 體環境進行燃燒，使熔銅接受脫氧處理，該熔銅乃於鑄造 流出槽C 4中藉非氧化氣體環境密封并移送至餵槽5 b。 然後，該熔銅由於其含氧濃度與含氫濃度呈反比之關係故 ，其含氫濃度提高，惟於後續之脫氣工序中藉攪拌手段 3 3進行脫氫處理。藉此，即不需確保長的熔銅移送距離 ，就能減低因藉還原方式脫氧處理時提高之含氫濃度，連 同抑制熔銅中產生之氣泡。因此之故，可使用環帶鑄造式 連續鑄造機G，將表面瑕疵少之高品質鑄造母線材2 1 d >以低成本連續製造。又因能夠減少釋放氣體，抑制形成 鑄孔而減低表面之瑕疵，故可得無裂縫之鑄造母線材 2 1 d進而製得表面品質良好之鍍銅用含磷銅母材2 3 d 。更因可製得抗彎力強之鑄造母線材2 1 d，對於製造球 狀之鍍銅用陽極時可防止裂縫產生。更由於使用環帶鑄造 本紙張尺度適用中國國家橾準（CNS Μ4現格（210X297公釐） -30- 461833 A7 B7 經濟部智慧財4馬ΜΚ工消費合作杜印製 五、發明説明（d 式連續鑄造機G，鑄造後即進行加熱輥軋工序，故可消除 當直接鑄造鍍銅用陽極時發生之殘留鑄造組織，并且藉由 再結晶獲得組織均勻之鍍銅用陽極。 結果，能夠廉價且大量的生產高品質之鏤銅用陽極也 又，如以攪拌熔銅用之攪拌手段3 3做爲脫氣手段時 ，能在短時間及強制完成脫氫處理，故可以簡易的構成有 效完成脫氫處理。 更且*若將攪拌手段3 3，藉由能使通過通路之熔銅 蛇行之堰構成時，由於可憑熔銅本身之流動自行攪拌，故 無需特別裝用攪拌器等，除能以更簡易的構成有效進行脫 氫處理外，尙能容易施行鍍銅用含磷銅母材之製造裝置 1 0 4的運轉管理- 又，有別於此種製造方法，使用剪切機1 5，直接製 造截成短錠狀之鍍銅用含磷銅母材2 3 e亦可，茲就本製 造方法，做爲本實施形態中之其他一例，加以說明如下。 於本製造方法中使用之鍍銅用含磷銅母材之製造裝置 1 0 4 b，係具有於前述鍍銅用含磷銅母材製造裝置 1 0 4所屬剪切機1 5下方附加乙醇浴（洗淨手段）1 8 之構成。 於使用該鍍銅用含磷銅母材製造裝置1 0 4 b之製造 方法中，如於第8圖所示，將從輥軋機Η所出連續長錠狀 之鍍銅用含磷銅母材2 3 d，藉剪切機1 5之旋轉刃1 6 所屬刃部1 6 a，依序將鍍銅用含磷銅母材2 3 e按規定 -II-------裝 1 1 (請先Η讀背面之注$項再填寫本頁) 訂 本紙張尺度逍用中國國家橾準（CNS ) Α4说格（21〇Χ；Ζ97公釐） -31 - 4 6 丨 83 3 绶濟部智慧財4局8工消费合作社印製 A7 £7_五、發明説明（j 長度截成短錠狀（短錠化工序）。然後，將短錠狀鍍銅用 含磷銅母材2 3 e |投入設於剪切機1 5下方盛有乙醇 1 8 a之乙醇浴1 8內，藉酒精1 8 a進行洗淨（洗淨工 序）。就是說，在該製造方法中，不使用探傷器19及纏 卷裝置I。 出自輥軋機Η之鍍銅用含磷銅母材2 3 d，依然保有 高溫，其表面被空氣所氧化而形成氧化薄膜。然而，由於 短錠狀鍍銅用含磷銅母材2 3 e之投入乙醇1 8 a中，除 可洗淨其表面之同時，其氧化薄膜尙被還原，使表面品質 ，尤其是表面光澤變好。該所用之乙醇18a ，以IPA (異乙醇）爲理想者。 又於本例中，雖以各設四個刃部1 6 a構成旋轉刃 1 6，1 6者，惟該第刃部1 6 a之數量乃可適當地予以 改變者。 使用該鍍銅用含磷銅母材製造裝置1 0 4 b之製造方 法中，由於將鍍銅用含磷銅母材2 3 d截成規定長度，直 接製造短錠狀鍍銅用含磷銅母材2 3 e，故不需如於欲得 長錠狀之鍍銅用含磷銅母材2 3 d之情形時所必要之卷取 在纏卷裝置I上的工序，得以謀求工序數之削減，結果， 可將例如銅球等更廉價且容易地製造。 又，因不需在卷取爲卷筒狀時必要時蠟等潤滑油，可排 除顯著地降低銅球甚至鍍銅用陽極之品質的畏懼*製造高 品質之銅球，明顯地提高品質穩定性。 進而，若將短錠狀鍍銅用含磷銅母材2 3 e，藉如 m ^^1 11- I I I - 1. m I I --. I n ^^1 (請先H讀背面之注意事項再填寫本頁) 本纸張尺度適用中國國家揉率（CNS ) A4規格（210X297公釐） -32 - 46 183 3 硬身部皙慧时4笱_工消费合作社印製 五、發明说明（3() 1 P A (異乙醇 品質，尤其是表 2 3 e。 做爲洗淨溶 和處理難易之觀 又，於前述 輪式之連續鑄造 若採用其他形態 環帶鑄造式連續 成之雙環帶式連 A7 B7 )等之乙醇1 8 a洗淨時，將可獲得表面 面光澤良好的短錠狀鍍銅用含磷銅母材 液，除乙醇之外亦可使用酸。惟基於操作 點，以使用乙醇較酸爲理想。 第2至4種實施形態中，係使用環帶與轉 機做爲環帶鑄造式連續鑄造機之例者，惟 之環帶鑄造式連續鑄造機時亦屬可行。就 鑄造機而言，此外尙有由兩條無縫環帶構 續鑄造機等。 〔發明之效果〕 如前之詳細說明，按本發明有關之低氧銅的製造方法 時，能不必確保長的移送距離即可進行脫氫處理，抑制於 凝固時產生之鏡孔，而獲得表面品質良好之高品質低氧銅 〔圖面之簡單說明〕 第1圖爲槪略表示本發明有關之低氧銅製造方法所屬 第1種實施形態中所用低氧銅鑄塊製造裝置之構成圖- 第2圖係將鑄造流出槽由平面俯視（a ),側面正視 (b )表示之主要部分放大圖。 第3圖爲槪略表示本發明有關之低氧銅製造方法所屬 第2種實施形態中所用低氧銅線製造裝置之構成圖。 本紙張尺度適用中國國家標率（CNS ) A4规格（210X297公釐） 請 先 Μ 背 之 注 意 事 項 再 旁 >33- 4 6 183 3 A7 B7 五、發明说明（3ί 第4圖表示從本發明有關之低氧銅製造方法所屬第2 種實施形態所製造之低氧銅線，與藉已往之浸漬成形法所 製造之低氧銅銅線兩者間氣體釋放特性加以比較之圖表》 第5圖係槪略表示本發明有關之低氧銅製造方法所屬 第3種實施形態中所用，低氧銅合金線製造裝置之構成圖 〇 第6圖係表示按照本發明有關之低氧銅製造方法所屬 第3種實施形態所製造低氧銅合金線之表面瑕疵狀態圖。 第7圖係槪略表示本發明有關之低氧銅製造方法所屬 第4種實施形態中所用，鍍銅用含磷銅母材製造裝置之構 成圖。 第8圖係槪略表示本發明有關之低氧銅製造方法所屬 第4種實施形態的其他一例中所用含磷銅母材製造裝置之 主要部放大圖。 〔圖號說明〕 10 1 低氧銅鑄塊之製造裝置（低氧銅之製造裝置） 10 2 低氧銅線之製造裝置（低氧銅之製造裝置） 103 低氧銅合金線之製造裝匱（低氧銅之製造裝置 ) 1 0 4，1 0 4b 鍍銅用含磷銅母材之製造裝置（低氧 銅之製造裝置） 3 銀添加手段 4 磷添加手段 本紙張尺度適用中國國家標率（CNS ) ( 2丨0X297公釐） ^^1 —^ϋ i m m ap (請先閲讀背面之注意事項再填寫本頁) -34 - 461833 A7 B7 五、發明説明（ 5 a ，5 b 餵槽 1 5 剪切機（切 斷 手 段 ) 1 8 乙醇浴（洗 淨 手 段 ) 1 8 a 乙醇 2 1 a 鑄造銅材 2 1 b 鑄造銅材 2 1 c 鑄造銅合金 材 2 1 d 鑄造母線材 2 3 a 低氧銅鑄塊 ( 低 氧 銅 ) 2 3 b 低氧銅線（ 低 氧 銅 ) 2 3 c 低氧銅合金 線 ( 低 氧 銅 ) 2 3 d 鍍銅用含磷 銅 母 材 ( 低 氧 銅 ) 2 3 e 短錠狀鍍銅 用 含 磷 銅 母 材 ( 低氧銅） 3 1 熔銅流路（ 熔 銅 之 流路 ) 3 3 攪拌手段（ 脫 氣 手 段 ) 3 3 a，3 3 b，3 3 C 3 3 d 堰 A 熔融爐 B 保溫爐 C ， C 2， C 3，C 4 鑄 流 出 槽 D 連續鑄造機 E 切斷手段 F 搬出手段 G 環帶鑄造式 連 續 鑄 1Ξ. 機 Η 輥軋機 本紙伕尺度適用中國國家揉準（CNS)A4C^( 210X297公釐） -35- 4 6 183 3 A7 B7 五、發明説明（^ I 纏卷裝置。 (請先閲讀背面之注意事項再填寫本頁) 裝· 訂 經濟部智«-財產局8工消費合作社印製 本紙張尺度通用中國國家揉準（CNS > A4規格（2丨0X297公嫠） -36-The scale of this paper is free to use Chinese National Standard (CNS) A4 (2I0X297 mm) -23 · 461833 A7 B7 V. Description of the invention (21) (Please read the precautions on the back before filling this page) Non-oxidized The gas environment is sealed and transferred to the feeding tank 5b (melt copper transfer process). The molten copper subjected to deoxidation treatment in the melting furnace A has an inverse relationship between the oxygen concentration and the gas concentration, so the gas concentration will increase. The molten copper with an increased hydrogen concentration is subjected to a dehydrogenation treatment (degassing step) by the mixing method 3 3 when it flows out of the tank C 3 through casting. By this, the molten copper is adjusted to have an oxygen content of 1 to 10 p P m or less, the hydrogen content is 1 P pm or less. And, since the silver addition means 3 is added silver and the molten copper after adjusting the oxygen concentration and hydrogen concentration, so that the silver content in the molten copper is 0.005 ~ 0.2% by weight (in the silver addition process). If the silver content is less than 0.005wt%, it is almost impossible to miniaturize the cast holes, that is, the effect of suppressing surface defects cannot be obtained. On the contrary, if the silver content is greater than 0. 2w t%, although the effect of suppressing the occurrence of defects is not The large change, but because the strength of the low-oxygen copper alloy wire is increased, it affects the rolling of the cast copper alloy material, and subsequent processing is not easy to proceed smoothly. For this reason, it is ideal to maintain the silver content within the aforementioned range. Printed by the Ministry of Economic Affairs, the Intellectual Property Co-operative Consumer Cooperative, as mentioned above, the silver-containing molten copper transferred from the melting furnace A to the holding furnace B. After heating, it is cast out of the tank C 3 and fed to the tank 5 b to be supplied to the belt. The casting type continuous casting machine G is continuously cast in the endless belt casting type continuous casting machine G, and is formed into a cast copper alloy material 2 1c at the end of the endless belt casting type continuous casting machine G (continuous casting process). The copper alloy material 2 1 c is cast and rolled by a rolling mill to form a low-oxygen copper alloy wire containing a specified amount of silver and having a good surface quality (the low-oxygen paper size is remotely used in China's national kneading rate (CNS) Α4 Specifications (210 × 297 mm) -24- 46 1 83 3 A7 ____B7_ V. Description of the invention (j copper) 23c, and was taken up by the winding device I. (Please read the precautions on the back before filling in this page) As mentioned above, the oxygen concentration and Concentration ', molten copper after adding a prescribed amount of silver is cast, and rolling' reduces the gas released during casting and suppresses the occurrence of cast holes in the cast copper alloy 2 1 c 'to reduce to low oxygen copper alloy wires 2 3 c Defects on the surface. Figure 6 shows the results of the surface flaw inspection of the low-oxygen copper alloy wire 2 3 c obtained using the manufacturing method of the low-oxygen copper alloy wire manufacturing device 1 ◦ 3 described above. The flaw detection is performed by using copper wire for rotation. Phase-type eddy current flaw detection device manufacturer name: ESTEK Co., Ltd., model name: RP-7000), performed by rotating phase-type eddy current flaw detection method. In Figure 6, respectively, it means that (a) those without silver; (b) those with 0.01% by weight of silver; (c) those with 0.03% by weight of silver; (d) those with 0.05% by weight Silver person, flaw detection chart. Each of these graphs indicates that the vertical axis is time and the horizontal axis is the eddy current voltage (V) generated according to the number and size of defects. As shown in the figure, it can be seen that when the silver content in the low-oxygen copper alloy wire 2 3 c is larger, that is, the more the amount of silver is added to the molten copper, the low-oxygen copper alloy wire 4i is the Ministry of Wisdom 574¾. Consumption Cooperative Press ^ 2 3 c The surface defects will decrease. This means that if the grain boundary can be increased by adding elements that can refine the crystal grains of copper, the concentration of gas components per unit grain boundary will decrease by 1 and when considering the hydrogen and oxygen in the cast copper alloy 2 1 c, When the local balance of water vapor, the concentration of gas components on the external surface is much lower than that when the grain boundary is increased. As a result, it is presumed that it is difficult to form large cast holes. According to the review by the present inventors, those who are suitable as the added element are silver paper standards (CNS) A4 specification (2 丨 0X297 mm) -25- 461833 A7 B7 V. Description of the invention (If the silver content is more than 0. ◦ 0 5 w t%, the cast holes formed in the cast copper alloy material 2 1 c can be finely dispersed into ultra-fine cast holes, which can reduce the cast copper alloy material. Defects on the surface of the low-oxygen copper alloy wire 23c obtained by rolling 21c. When it contains 0.03 wt% or more, the flaws can be significantly reduced, and when it contains 0.05 wt% or more, it can be significantly reduced. In the manufacturing method using the low-oxygen copper alloy wire manufacturing device 103 according to this embodiment, the molten copper is burned in a reducing gas environment in the melting furnace A, and the molten copper is deoxidized, and the molten copper flows out of the casting. The tank C 3 is sealed by a non-oxidizing gas environment and transferred to the feeding tank 5. Then, the molten copper concentration increases due to the inverse relationship between the oxygen concentration and the hydrogen concentration, but in the subsequent degassing process Degassing by stirring means 3 3 It can reduce the hydrogen concentration increased by the reduction method deoxidation device and suppress the cast holes generated during solidification. In addition, the silver addition means 3 adds silver to the molten copper that is difficult to produce cast holes after deoxidation treatment and deoxidation treatment. It can make the casting holes finely dispersed to form ultra-micro casting holes. Printed by the 8th Industrial Cooperative Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs ^^ 1 ^^^ 1 —: ·-1.- ^^ 1. ^^ 1 ^^ 1 I · ^^ 1 · m tui ^^^ 1, f * J (please read the precautions on the back before filling in this page) So, you can use the endless belt casting continuous casting machine G, which can suppress the conductivity Long ingot-shaped copper alloy material with reduced and harmful cast holes and continuously manufactured at low cost. In addition, although the degassing process is simplified, surface defects can be significantly reduced and the surface quality of low-oxygen copper can be obtained. Alloy wire. This means that it is not necessary to use expensive and special equipment such as vacuum degassing equipment for dehydrogenation treatment. In addition to simplifying the structure of the equipment, it is also possible to produce low-oxygen copper alloys at low cost. In addition, because the stirring means for stirring molten copper 3 3 is used as a degassing hand Duan Zhiben's paper scale is applicable to Chinese National Kneading Rate (CNS) A4 specification (2 丨 0X297 mm) -26- 461833 A7 __B7 _ _ V. Description of the invention (Therefore, the mandatory dehydrogenation treatment can be completed in a short time, It can effectively perform dehydrogenation treatment with a simple structure. (Please read the precautions on the back before filling in this purchase.) Furthermore, if the stirring means 3 3 is constituted by a weir that can melt copper through the passage, It can be stirred by the flow of molten copper itself, so there is no need to install a special stirrer, etc. In addition to being able to effectively perform dehydrogenation treatment with a simpler structure *, it can make the operation and management of the low-oxygen copper alloy wire manufacturing equipment easy. In addition, the manufactured low-oxygen copper alloy wire 2 3 c contains 0.005 to 0.2 wt% of silver. In addition to suppressing the decrease in electrical conductivity, it can be made into fewer surface defects and good surface quality. That means high-quality finished products. [The fourth embodiment] The fourth embodiment will be described as follows with reference to the attached figures 7 and 8. This embodiment relates to a method for manufacturing a phosphorus-containing copper base material for copper plating as a low-oxygen copper and containing phosphorus (P). " The phosphorous copper base material is formed into a rod shape, a wire shape, or a ball shape, and can be used as a copper plating anode in a wiring pattern on a printed circuit board, for example. That is to say, the wiring pattern on this printed circuit board can be appropriately formed by copper plating, especially copper sulfate plating, etc., and the anode in the rhenium copper sulfate uses phosphorous copper (containing about 0.4% phosphorous). Of low oxygen copper). When phosphorus is contained, it can promote the smooth dissolution of anode copper. When a copper-based anode that does not contain phosphorus is used, the uniform adhesion of the coating will be reduced. Figure 7 shows the phosphorus-containing paper used for copper plating in this embodiment. The standard is the Chinese National Standard (CNS) A4 specification (210X297 mm) -27- 461833 A7 __B7_ 5. Description of the invention (^ Copper Structure diagram of the base material manufacturing equipment. The manufacturing equipment for the phosphorous copper base material for copper plating (manufacturing equipment for low-oxygen copper) 1 0, and the low-oxygen copper wire manufacturing equipment 1 in the second embodiment described above. 2Comparison, only the structure of the casting outflow groove is different. Therefore, the other constituent elements are given the same symbols as those in the second embodiment described above, and detailed descriptions thereof are omitted. The phosphorous copper base used for this copper plating Material manufacturing device 104 is equipped with a casting outflow groove C 4 to replace the casting outflow groove C 2 provided in the low oxygen copper wire manufacturing equipment 104. Near the terminal portion of the casting outflow groove C 4 is provided phosphorus Adding means 4, 俾 adds phosphorus to the molten metal. Β By this phosphorus adding means 4, it can add phosphorus to the molten metal after deoxidation and dehydrogenation treatment, and prevent the reaction between phosphorus and oxygen, and then borrow it. Turbulent flow in the feeding tank 5 b, making phosphorus and molten copper good Good mixing. The place where the phosphorus addition means 4 is installed is not limited to the vicinity of the terminal part of the casting outflow tank C 4. That is, as long as it is added to the molten metal after the dehydrogenation treatment and can sufficiently diffuse, Yes, so from the end of the casting outflow tank C 4 to the end of the feeding tank 5 b, in the meantime, it can be printed by the Ministry of Economic Affairs, the Bureau of Intelligent Production, Shellfish Consumer Cooperatives, and I ^ I ---- installed --- -" —Order (please read the note f on the back side before filling out this page). Also, the casting outflow tank C 4 | Except for the point where the phosphorus addition means 4 is provided, it is the same as the casting outflow tank. C 2 is the same. That is, the casting outflow tank C 4 is also provided with a stirring means 3 3 as shown in Fig. 2. A phosphorous copper base material manufacturing apparatus for copper plating having this structure is used. The manufacturing method of the phosphorus-containing copper base material for copper plating is explained. First, in the melting furnace A, a reducing gas environment is used for combustion. A paper scale is applicable to the Chinese National Kneading Rate (CNS) A4 specification (210X29? Mm). -28- ^ b183 3 A7 B7 V. Description of the invention (d. Copper smelting (copper smelting production process)》 After the deoxidation treatment, the copper smelting passes through the holding furnace B and is sealed by the non-oxidizing gas environment in the casting outflow tank C 4 and is transferred to the feeding tank 5 (copper smelting copper transfer process). The molten copper subjected to deoxidation treatment in A will have an increased hydrogen concentration due to the inverse relationship between the oxygen concentration and the hydrogen concentration. The molten copper with an increased hydrogen concentration is agitated while flowing out of the tank C 4 through casting. 3 3 Perform dehydrogenation treatment. With this, adjust the oxygen content of the molten copper to less than 20 p pm, and the hydrogen content to less than 1 p pm. Also, for the molten copper after adjusting the oxygen concentration and hydrogen concentration, Phosphorus is added from the phosphorus addition means 4 (phosphorus addition step), so that the ortho ratio of the dissolved copper is within the range of 40 to 1,000 p pm. Here, if the oxygen concentration, hydrogen concentration, and phosphorus content are outside the above ranges, the following problems will occur. That is, when the oxygen content is less than 20 p pm, the workability is poor, and cracks are generated in the cast bus bar. When the hydrogen content is less than 1 p pm, more gas is released, causing cracks in the casting bus bar. When the phosphorus content is not more than 40 p pm, when the anode is used as an anode, uniform solubility cannot be obtained, and it cannot be used as a material for copper balls. When the phosphorus content is less than 1,000 P pm, the workability is poor. In this way, by adjusting the oxygen concentration and hydrogen concentration, and casting the molten copper after adding phosphorus, and rolling, the gas release amount during casting can be reduced, and the casting holes generated in the casting bus bar 2 1 d can be suppressed. And reduce the flaws on the wire surface. As mentioned above, the molten copper transferred from melting furnace A to holding furnace B is selected from the China National Sample Rate (CMS) A4 specification (210X297 mm) after the paper scale is upgraded. -(Please read the note on the back before filling in this page)-, tr Economy Zou Xihuishi 4 " Issued by Employee Consumer Cooperatives-29 4 6 18 3 3 A7 __B7 V. Description of the invention ((Please read the notes on the back first Fill in this page again) After warming, the outflow tank C 4 and feed tank 5 b are supplied to the endless belt continuous casting machine G, which is continuously cast in the endless belt continuous caster G, and the endless belt The cast continuous casting machine G is formed into an inlay bus bar 21d. The cast bus bar 21d is rolled by a roll mill and rolled to produce a phosphorus-containing copper base material for copper plating with a predetermined amount of phosphorus and good surface quality ( Low oxygen copper) 2 3 d »The phosphorous copper base metal used for copper plating was 2 3 d. After being inspected for flaws by the flaw detector 19, the lubricating oil coated with wax or the like was taken up by the winding device I. This copper-containing phosphorous copper base material for copper plating is then fed to another process, and is suitably formed into, for example, a copper ball. Bureau Consumer Cooperative Co., Ltd. printed it on the substrate method using the manufacturing equipment 104 of the copper-containing phosphorous copper base material for copper plating according to this embodiment, and burned it in a reducing gas environment in the melting furnace A to receive molten copper. In the deoxidation treatment, the molten copper is sealed in the casting outflow tank C 4 by a non-oxidizing gas environment and transferred to the feeding tank 5 b. Then, the molten copper has a hydrogen concentration because of an inverse relationship between its oxygen concentration and hydrogen concentration. It is increased, but in the subsequent degassing process, the dehydrogenation treatment is performed by the stirring means 33. By this, it is not necessary to ensure a long molten copper transfer distance, which can reduce the increased hydrogen concentration during deoxidation by the reduction method. Suppresses the air bubbles generated in the molten copper. Therefore, the ring-shaped continuous casting machine G can be used to continuously manufacture high-quality cast bus bars 2 1 d > with low surface defects at a low cost. Because it can reduce the release of gas, Suppresses the formation of cast holes and reduces surface defects, so the crack-free cast bus bar 2 1 d can be obtained, and the phosphor-containing copper base metal for copper plating with good surface quality 2 3 d can be obtained. The strong casting bus bar 2 1 d can prevent cracks from occurring when manufacturing spherical anodes for copper plating. It is also applicable to the national standard of China (CNS Μ4 standard (210X297 mm)) due to the use of ring casting. 30- 461833 A7 B7 Ministry of Economic Affairs, Intellectual Property, Malaysia, Malaysia, Japan, Japan, Japan, Japan, Japan, Japan, Japan, Japan, Japan, Japan, Japan, Japan, Japan, etc. V. Invention Description (d-type continuous casting machine G, after the casting, the heating and rolling process is performed, so it can be eliminated when directly casting copper anodes The remaining cast structure is generated, and a copper-plated anode having a uniform structure can be obtained by recrystallization. As a result, it is possible to inexpensively and mass-produce a high-quality copper-plated anode, such as a stirring means for stirring molten copper 3 3 In the degassing means, the dehydrogenation treatment can be completed in a short time and forcibly, so the dehydrogenation treatment can be effectively completed with a simple structure. In addition, if the stirring means 3 3 is formed by a weir that allows the molten copper to pass through the passage, it can be stirred by the flow of the molten copper itself, so there is no need to install a special stirrer, etc. In addition to the effective dehydrogenation treatment, it is easy to implement the operation and management of the manufacturing equipment for the copper-containing phosphorous copper base material for copper plating 104. Also, unlike this manufacturing method, a shearing machine 15 is used to directly produce the cut The short ingot-like copper-containing copper base material 2 3 e for copper plating may be used. This manufacturing method is described as another example in this embodiment, and is described below. The manufacturing device 1 0 4 b of the phosphorous copper base material for copper plating used in this manufacturing method is provided with an ethanol bath under the shearer 15 belonging to the aforementioned copper phosphorous copper base material manufacturing device 1 0 4 for copper plating. (Cleaning means) Composition of 1-8. In the manufacturing method using the phosphorous copper base material manufacturing apparatus 1 0 4 b for copper plating, as shown in FIG. 8, the continuous long ingot-shaped phosphorous copper base material for copper plating is rolled out from a rolling mill. 2 3 d, using the rotating blade 1 5 of the shearing machine 1 6 belonging to the cutting edge portion 16 a, the phosphorous copper base material for copper plating 2 3 e is installed in accordance with the regulations -II ------- 1 1 (Please read the note on the back of the page before filling in this page.) The paper size of the book is free of the Chinese National Standards (CNS) Α4 grid (21〇 ×; Z97 mm) -31-4 6 丨 83 3 A7 £ 7_ printed by the Ministry of Wisdom 4 Bureau and 8 Industrial Cooperatives Fifth, the description of the invention (j length is cut into short ingots (short ingot process). Then, the short ingot-shaped copper-containing copper base material for copper plating 2 3 e | Put into the ethanol bath 18 containing ethanol 18 a under the shearing machine 15 and wash it with alcohol 18 a (washing process). That is, in this manufacturing method, no flaw detection is used 19 and winding device I. The phosphorous copper-containing copper base material for copper plating from the rolling mill was still maintained at a high temperature, and its surface was oxidized by air to form an oxidized film. However, since the short ingot-like copper plating contains Input of Phosphor Copper Base Metal 2 3e In ethanol 18a, in addition to cleaning the surface, the oxidized film 尙 is reduced to improve the surface quality, especially the surface gloss. The ethanol 18a used is preferably IPA (isoethanol). In this example, although the rotating blades 16 and 16 are constituted by providing four blade portions 16 a each, the number of the first blade portions 16 a can be appropriately changed. In the manufacturing method of the phosphor copper base material manufacturing device 104 b, the phosphorous copper base material 2 3 d for copper plating is cut to a predetermined length, and the short ingot-like copper base material 2 3 e for copper plating is directly manufactured. Therefore, it is not necessary to take up the winding process on the winding device I, which is necessary when obtaining a long ingot-like phosphorous copper base metal 2 3 d for copper plating. As a result, the number of steps can be reduced. As a result, the number of steps can be reduced. For example, copper balls and the like are cheaper and easier to manufacture. In addition, since lubricating oil such as wax is not necessary when winding into a roll shape, the fear of significantly reducing the quality of copper balls and even copper anodes can be eliminated. * High manufacturing Quality copper balls, significantly improving quality stability. Furthermore, if the short ingot-like copper-containing copper base material for copper plating 2 3 e is used, m ^^ 1 11- III-1. m II-. I n ^^ 1 (Please read the precautions on the back before filling this page) This paper size applies to China National Kneading (CNS) A4 size (210X297 (Mm) -32-46 183 3 Hard body part Xihuishi 4 笱 _Printed by Industrial Consumer Cooperatives V. Description of invention (3 () 1 PA (Isoethanol quality, especially Table 2 3e. As a washing solvent In view of the difficulty of handling, if the continuous casting of the aforementioned wheel type adopts other forms of endless belt casting type, such as double endless belt type with A7 B7) and other ethanol 1 8 a, it will obtain a good surface gloss. Phosphorus-containing copper base metal liquid for short ingot-like copper plating can use acids other than ethanol. However, based on the operating point, the use of ethanol is more acidic. In the second to fourth embodiments, an endless belt casting machine and an endless belt conveyor are used as examples of the endless belt casting type continuous casting machine, but the endless belt casting type continuous casting machine is also feasible. As for the casting machine, there is also a continuous casting machine composed of two seamless endless belts. [Effects of the Invention] As described in detail above, according to the method for producing low-oxygen copper according to the present invention, dehydrogenation treatment can be performed without ensuring a long transfer distance, and mirror holes generated during solidification can be suppressed to obtain a surface. High-quality low-oxygen copper with good quality [Simplified description of the drawing] FIG. 1 is a diagram showing the structure of a low-oxygen copper ingot manufacturing device used in the first embodiment of the method for manufacturing a low-oxygen copper related to the present invention- Figure 2 is an enlarged view of the main part of the casting outflow groove as viewed from the plane (a) and the front side (b). Fig. 3 is a block diagram schematically showing a low-oxygen copper wire manufacturing apparatus used in a second embodiment of the method for manufacturing low-oxygen copper according to the present invention. This paper size is applicable to China National Standards (CNS) A4 specifications (210X297 mm) Please note the back of the M first >> 33- 4 6 183 3 A7 B7 V. Description of the invention (3ί Figure 4 shows the results from the invention Chart showing comparison of gas release characteristics between low-oxygen copper wires manufactured in the second embodiment of the related low-oxygen copper manufacturing method and low-oxygen copper wires manufactured by the conventional dip forming method "Figure 5 FIG. 6 shows the structure of a low-oxygen copper alloy wire manufacturing device used in the third embodiment of the method for manufacturing low-oxygen copper related to the present invention. FIG. 6 shows the first section of the low-oxygen copper manufacturing method according to the present invention. The surface defect state diagram of the low-oxygen copper alloy wire manufactured in the three embodiments. Figure 7 is a diagram showing the fourth embodiment of the manufacturing method of the low-oxygen copper related to the present invention, and the phosphorus-containing copper base material for copper plating is used. FIG. 8 is an enlarged view of a main part of a manufacturing apparatus for phosphorous copper base material used in another example of the fourth embodiment of the method for manufacturing low-oxygen copper according to the present invention. [Figure No. Ming] 10 1 Manufacturing device of low oxygen copper ingot (manufacturing device of low oxygen copper) 10 2 Manufacturing device of low oxygen copper wire (manufacturing device of low oxygen copper) 103 Manufacturing device of low oxygen copper alloy wire (low oxygen Copper manufacturing equipment) 1 0 4, 1 0 4b Manufacturing equipment for phosphorous copper base materials for copper plating (manufacturing equipment for low-oxygen copper) 3 Means for adding silver 4 Means for adding phosphorus This paper applies China National Standards (CNS) (2 丨 0X297mm) ^^ 1 — ^ ϋ imm ap (Please read the precautions on the back before filling this page) -34-461833 A7 B7 V. Description of the invention (5 a, 5 b Feed trough 1 5 Shear Machine (cutting means) 1 8 Ethanol bath (cleaning means) 1 8 a Ethanol 2 1 a Cast copper 2 2 b Cast copper 2 1 c Cast copper alloy 2 1 d Cast bus bar 2 3 a Low oxygen copper Ingot (low oxygen copper) 2 3 b Low oxygen copper wire (low oxygen copper) 2 3 c Low oxygen copper alloy wire (low oxygen copper) 2 3 d Phosphorous copper base material for copper plating (low oxygen copper) 2 3 e Phosphorous copper base material for short ingot-like copper plating (low Copper) 3 1 Copper melting flow path (flow path of copper melting) 3 3 Stirring means (degassing means) 3 3 a, 3 3 b, 3 3 C 3 3 d Weir A Melting furnace B Holding furnace C, C 2, C 3 , C 4 casting outflow groove D continuous casting machine E cutting means F removal method G endless belt casting type continuous casting 1. MachineΗ Rolling mill paper size 适用 Applicable to China National Standard (CNS) A4C ^ (210X297 mm) -35 -4 6 183 3 A7 B7 V. Description of the invention (^ I Winding device. (Please read the precautions on the back before filling this page) Binding and ordering printed by the Ministry of Economic Affairs «-Property Bureau 8 Industrial Consumer Cooperative Co., Ltd. This paper is printed in accordance with the standard of the Chinese state (CNS > A4 size (2 丨 0X297) 嫠-36-