201144075 六、發明說明： 【發明所屬之技術領域】 本發明係關於將鋁合金製的鋁形狀體和銅合金製的銅 形狀體透過樹脂形狀體接合成一體之鋁-樹脂-銅複合品及 其製造方法，主要是關於適用於密閉型電池用蓋構件之密 合強度及氣密性優異的鋁-樹脂-銅複合品及其製造方法。 【先前技術】 在鋰電池等的電池容器，讓貫穿其蓋構件而設之正極 端子和負極端子分別與蓋構件絕緣，防止容器內部的電解 液和從容器內部產生的氣體等之洩漏，防止水分等從容器 的外部滲入內部，謀求嚴苛環境下之耐久性和耐熱性的提 昇、氣密性的提昇等，都是重要的課題。 以往，作爲鋁-樹脂-銅複合品製之密閉型電池用蓋構 件，爲了確保蓋體和電極端子間之氣密性，是採用讓樹脂 固接於鋁合金製的蓋體和金屬製的電極端子之嵌入成形的 方法等。又爲了使金屬零件和樹脂間的接合更低成本地進 行且更加提昇接合力，在要和樹脂接合之金屬零件的表面 進行既定表面處理的方法也是已知的。 例如，在專利文獻1提出一種密閉型電池用蓋體，係 具備絕緣密閉構件，其嵌入成形於蓋體和電極間，用來將 蓋體與電極予以絕緣並固定成一體。 此外，專利文獻2提出一種具備端子之電氣電子零件 的構造體，是由金屬製的端子、金屬製的基體及熱塑性樹 -5- 201144075 脂組成物所構成；該金屬製的端子，是具有朝長邊方向延 伸的形狀，在外周部的面實施表面處理；該金屬製的基體 包含平板部和凸狀部，該凸狀部，是在該平板部豎設一個 以上，形成有可保有既定間隔讓前述端子貫穿之內周部， 在前述內周部的面實施表面處理；該熱塑性樹脂組成物， 當前述金屬製的端子和前述金屬製的基體嵌入射出成形用 的模具後，是朝前述金屬製的端子之前述外周部和前述金 屬製的基體之前述內周部間所形成之模穴內射出，藉此將 前述金屬製的端子和前述金屬製的基體接合成一體化。 再者，在專利文獻3提出一種電池容器用封口板，是 將至少一個電極端子和蓋體藉由絕緣密封材料予以一體化 而構成。該電極端子，是藉由三嗪二硫醇化合物或矽烷偶 合劑進行表面處理之金屬所構成。該蓋體，是藉由進行該 表面處理之金屬所構成。該絕緣密封材料，是由含有彈性 模數55MPa以下的彈性體樹脂之聚苯硫組成物所構成。 再者’專利文獻4提出一種雙電層電容器的蓋體，是 將收容有電極元件之有底筒狀容器的開口部予以遮蔽閉蓋 ，且具備連接於各電極之1對的電極端子。該電極元件， 是讓透過分隔件而呈相對置之正極及負極含浸電解液而構 成。 然而’在上述任一者的情況都是，當曝露於嚴苛的環 境下時’金屬-樹脂界面之密合強度及氣密性不夠充分， 而要求開發出具備更優異的密合強度及氣密性之金屬·樹 脂複合體。 -6- 201144075 於是’本發明人等，首先就金屬材料而言是著眼於鋁 合金，爲了在該鋁合金製的鋁形狀體和一體地設置於其表 面之樹脂形狀體之間具備極高的密合強度及氣密性，又縱 使在嚴苛的環境下仍能發揮優異的密合強度及氣密性且能 發揮優異的耐久性及耐熱性，針對該鋁-樹脂複合品深入 探討的結果發現，藉由在鋁形狀體的表面形成凹凸部（具 有特定表面形狀的凹狀部），可顯著地提昇鋁形狀體和樹 脂形狀體間之密合性和氣密性，根據所獲得的成果提出日 本特願2008-153805號及特願2008-153806號的申請。 [專利文獻1]日本特開2007-179793號公報 [專利文獻2 ]日本特開2 0 0 8 - 1 3 1 0 0 5號公報 [專利文獻3]日本特開2008-27823號公報 [專利文獻4]日本特許第3 9675 5 1號公報 【發明內容】 本發明人，除了上述成果以外，針對鋁合金製的鋁形 狀體和銅合金製的銅形狀體透過樹脂形狀體接合成一體之 鋁-樹脂-銅複合品，爲了製造並提供一種縱使在振動多且 冷熱衝擊大的環境下仍能保持優異的鋁-樹脂-銅接合面之 密合強度及氣密性之鋁-樹脂-銅複合品，進行深入探討的 結果發現，藉由蝕刻處理而在鋁形狀體及銅形狀體的表面 形成凹凸部（具有特定表面形狀的凹狀部），如此可將鋁 形狀體和樹脂形狀體間及銅形狀體和樹脂形狀體間的密合 性、氣密性、以及耐久性、耐熱性予以顯著地提昇，而完 201144075 成本發明。 因此，本發明的目的是爲了提供一種鋁-樹脂-銅複合 品，能使鋁合金製的鋁形狀體和樹脂形狀體間及銅合金製 的銅形狀體和樹脂形狀體間的界面具有極高的密合強度及 氣密性，在溫度、濕度'粉塵等之嚴苛的環境下能保持優 異的密合強度及氣密性，特別是縱使在振動多且冷熱衝擊 大的環境下仍能發揮優異的耐久性、耐熱性。 此外，本發明的其他目的是爲了提供一種鋁-樹脂-銅 複合品之製造方法，其所製造出的鋁-樹脂-銅複合品，能 使鋁形狀體和樹脂形狀體間及銅形狀體和樹脂形狀體間的 界面具有極高的密合強度及氣密性，在嚴苛的環境下能保 持優異的密合強度及氣密性，特別是縱使在振動多且冷熱 衝擊大的環境下仍能發揮優異的耐蝕性、耐久性、耐熱性 的性能。 亦即，本發明之鋁-樹脂-銅複合品，其特徵在於，藉 由表面凹凸化蝕刻處理而在表面的一部分或全面具有凹凸 部之鋁合金製的鋁形狀體、和藉由表面凹凸化蝕刻處理而 在表面的一部分或全面具有凹凸部之銅合金製的銅形狀體 ，是透過樹脂形狀體而以互不接觸的狀態接合成一體。 此外，本發明之鋁-樹脂-銅複合品，其特徵在於，是 藉由表面凹凸化蝕刻處理而在表面的一部分或全面具有凹 凸部之鋁合金製的鋁形狀體、和藉由表面凹凸化蝕刻處理 而在表面的一部分或全面具有凹凸部之銅合金製的銅形狀 體’透過樹脂成形體而以互不接觸的狀態接合成一體之 -8- 201144075 鋁-樹脂-銅複合品； 在具有前述凹凸部之前述鋁形狀體及銅形狀體的表面 ，起因於前述凹凸部而形成複數個凹狀部； 前述各凹狀部，在前述鋁形狀體及銅形狀體各個的厚 度方向截面上，在與該厚度方向正交且位於通過凹凸部的 最高部之頂線和通過最深部的底線間之中間線（half line )上，藉由掃描型電子顯微鏡觀察而測定出之開口寬度爲 Ο.ίμιη以上30μηι以下的大小，其深度爲Ο.ίμηι以上30μηι以 下的大小； 在該等凹狀部內讓前述樹脂進入並固化而形成樹脂成 形體的嵌入部； 利用前述凹狀部和嵌入部，使前述鋁形狀體和樹脂成 形體間及銅形狀體和樹脂成形體間互相卡止。 此外’本發明之鋁-樹脂-銅複合品之製造方法，是將 鋁合金製的鋁形狀體和銅合金製的銅形狀體透過樹脂形狀 體以互不接觸的狀態接合成一體之鋁-樹脂-銅複合品之製 造方法，其特徵在於：在前述鋁形狀體及銅形狀體，藉由 將鋁合金材及銅合金材分別實施蝕刻處理而在表面的一部 分或全面形成起因於凹凸部之複數個凹狀部；在樹脂形狀 體之成形時’在前述鋁形狀體及銅形狀體之各凹狀部內讓 樹脂進入並固化而形成樹脂形狀體的嵌入部；讓鋁形狀體 及銅形狀體的凹狀部和樹脂形狀體的嵌入部互相卡止，藉 此將鋁形狀體和銅形狀體透過樹脂形狀體以互不接觸的狀 態接合成一體。 -9- 201144075 在本發明’作爲形成鋁形狀體之鋁合金材，具體而言 可列舉：將純A1系的1 000系、Al-Cu系的2000系' Al-Mn 系的3 000系、Al-Si系的4000系、Al-Mg系的5000系、 ADC5' ADC6、AUMg-Si 系的 6000 系、A卜Zn-Mg 系的 7000 系、Al-Fe 系的 8000 系、Al-Si-Mg 系的 ADC3' A卜 Si-Cu 系 的 ADC10、ADC10Z ' ADC12、ADC12Z、Al-Si-Cu-Mg 系 的ADC14等的材質所構成的材料適當地加工成期望的形狀 而得的加工材’進一步將該等加工材適當地組合而得之組 合材等。 在本發明’作爲形成銅形狀體之銅合金材，具體而言 可歹丨J 舉：C 1 1 00 ' c 1 020 ' C1220、C2700、C2801、C3604 ' C4641 、 C5191 、 C5210 、 C6782等。 此外，在本發明，起因於鋁形狀體及銅形狀體表面的 凹凸部而形成於該鋁形狀體及銅形狀體的表面之複數個凹 狀部，可以是其開口緣部爲無端周緣部之穴狀或孔狀者（ 具有無端開口緣部之凹狀部），此外，也可以是其開口緣 部具有兩端部之狹縫狀或溝槽狀者（具有有端開口緣部之 凹狀部），再者，也可以是混合存在著具有無端開口緣部 之穴狀或孔狀者和具有有端開口緣部之狹縫狀或溝槽狀者 〇 而且，關於鋁形狀體及銅形狀體之複數個凹狀部’較 佳爲在其一部分或全部’形成從凹狀部的開口緣部的—部 分或全體朝向開口寬度方向中心呈雪籍狀突出之突出部’ 藉此使凹狀部之開口寬度比其內部的寬度尺寸更窄’讓進 -10- 201144075 入該凹狀部內而固化後之樹脂形狀體的嵌入部和凹狀部間 形成彼此無法脫離的卡止構造，只要不破壞鋁形狀體及銅 形狀體的凹狀部或樹脂形狀體的嵌入部之任一方或雙方就 不會脫離，因此可更加提昇鋁形狀體及銅形狀體和樹脂形 狀體間的密合強度和氣密性。 再者，若如此般在鋁形狀體及銅形狀體之複數個凹狀 部之一部分或全部的開口緣部形成上述雪簷狀的突出部， 樹脂形狀體不一定要以密合狀態嵌合於該等的凹狀部內， 例如因爲鋁形狀體及銅形狀體和樹脂形狀體間之線膨脹係 數的差異和環境溫度，縱使該等鋁形狀體及銅形狀體和樹 脂形狀體間產生不可避免的極微小的間隙，仍能在該等鋁 形狀體及銅形狀體和樹脂形狀體間維持優異的密合強度和 氣密性。 在本發明，起因於鋁形狀體及銅形狀體表面的凹凸部 所形成之複數個凹狀部’若參照示意顯示該鋁形狀體及銅 形狀體的截面之第1圖做說明，在鋁形狀體及銅形狀體各 個的厚度方向截面上，在與該厚度方向正交且位於通過凹 凸部的最高部之頂線和通過最深部的底線間之中間線上， 藉由掃描型電子顯微鏡觀察而測定出之開口寬度爲01μπ1 以上30μιη以下的大小’較佳爲〇·5μιη以上20μιη以下，更佳 爲Ιμηι以上1〇μηι以下；其深度爲〇 1μιη以上30μιη以下的大 小’較佳爲0·5μηι以上20μιη以下。若該凹狀部的開口寬度 比0.1 μιη窄’樹脂不容易進入，在鋁形狀體及銅形狀體和 樹脂形狀體的界面會產生微小空隙，難以獲得優異的密合 -11 - 201144075 強度和氣密性；相反地，若比30μπι更寬，在鋁形狀體及 銅形狀體的表面處理（蝕刻處理）時，溶解反應會過度地 進行，而發生材料表面的缺損或材料的板厚減少量增大等 問題，會產生材料強度不足的製品而成爲生產性降低的原 因。此外，關於深度也是，若比0.1 μιη淺，難以獲得充分 的樹脂形狀體之嵌入部；相反地，若比30μπι深，在鋁形 狀體及銅形狀體的表面處理（蝕刻處理）時，溶解反應會 過度地進行，而發生材料表面的缺損或材料的板厚減少量 增大等問題， 在本發明，關於起因於鋁形狀體及銅形狀體表面的凹 凸部所形成之複數個凹狀部的密度，每0.1 mm見方，開口 寬度0·5μηι〜20μπι及深度0.5μηι〜20μιη的範圍內之一種或兩 種以上的大小者能以5〜2 00個程度的範圍存在。 此外，在本發明的鋁形狀體及銅形狀體，在凹狀部所 形成之雪簷狀的突出部較佳爲，在鋁-樹脂-銅複合品之 鋁-樹脂及銅-樹脂一體成形部分的厚度方向截面，將從該 樹脂形狀體側朝向鋁形狀體側或銅形狀體側沿厚度方向延 伸之觀察線以互相隔著0.1 μιη的間隔拉設複數條時，可在 一條觀察線上形成樹脂-鋁-樹脂或樹脂-銅-樹脂所構成之 至少一個以上的積層部，且該積層部之鋁形狀體或銅形狀 體部分的厚度爲0.1 μιη以上3 Ομιη以下的範圍，在鋁-樹脂-銅複合品上，可在1 000條觀察線的範圍內存在一個以上的 雪簷狀的突出部。 此外，鋁形狀體及銅形狀體之複數個凹狀部，在其一 -12- 201144075 部分或全部，可在內部壁面形成至少一個以上的內部凹狀 部而具有雙重凹狀部構造’或可在內部壁面形成至少一個 以上的內部突起部而具有內部凹凸構造，再者，同時存在 有雙重凹狀部構造和內部凹凸構造亦可。在鋁形狀體及銅 形狀體之複數個凹狀部之一部分或全部，藉由存在上述雙 重凹狀部構造或內部凹凸構造，能使鋁形狀體及銅形狀體 的凹狀部和樹脂形狀體之嵌入部彼此更強固地接合，而在 在鋁形狀體和樹脂形狀體及銅形狀體和樹脂形狀體間發揮 更優異的密合強度和氣密性。 [關於鋁-樹脂-銅複合品之製造方法] 在本發明，要製造上述般的鋁-樹脂-銅複合品時，首 先，是在表面形成具有上述複數個期望凹狀部之鋁形狀體 及銅形狀體，作爲其方法，例如可列舉：對鋁合金材及銅 合金材實施蝕刻處理而在表面的一部分或全面形成凹凸部 ，藉此形成起因於該凹凸部而具有複數個凹狀部之鋁形狀 體及銅形狀體的方法。 該鋁合金材的蝕刻處理所使用的蝕刻液，例如可列舉 :鹽酸、磷酸、硫酸、醋酸、草酸、抗壞血酸、安息香酸 、酪酸、檸檬酸、甲酸、乳酸、異丁酸、蘋果酸、丙酸、 酒石酸等的酸水溶液所構成的蝕刻液；爲了形成具有期望 大小的開口寬度及深度之複數個凹狀部、或爲了在凹狀部 的一部分或全部的開口緣部形成朝開口寬度方向中心突出 之雪簷狀的突出部等，亦即爲了將形成於表面之凹狀部控 -13- 201144075 制成期望的形狀及大小，作爲酸水溶液是使用氧化力較弱 的酸水溶液，又在該氧化力較弱的酸水溶液中，爲了溶解 鋁合金材表面所形成之氧化被膜，必須使用含有既定濃度 鹵素離子之蝕刻液。 亦即，作爲蝕刻液，可使用的蝕刻液，是在氧化力較 弱的酸水溶液中，含有既定濃度範圍之選自氯離子（Cl~ )、氟離子（F·)及碘離子（1_)中任一種或兩種以上 的鹵素離子。使用如此般含有鹵素離子之氧化力較弱的酸 水溶液時，若在該蝕刻液中浸漬鋁合金材，首先蝕刻液中 的鹵素離子會將鋁合金材表面的氧化被膜溶解，然後將內 部的鋁合金溶解而進一步俊蝕至鋁合金材內部，這時，由 於內部的鋁合金比表面的氧化被膜更容易被侵蝕（容易溶 解），藉由設定蝕刻液的組成和蝕刻處理的條件等，對於 起因於表面所形成的凹凸部之凹狀部，即可將其開口寬度 和深度等控制成期望的大小，或是在其一部分或全部的開 口緣部形成朝開口寬度方向中心突出之雪簷狀的突出部。 基於上述目的所使用之蝕刻液，作爲酸水溶液可列舉 :酸濃度5重量％以上80重量％以下（較佳爲10重量％以上 50重量％以下）之鹽酸溶液、磷酸溶液、稀硫酸溶液、醋 酸溶液等，酸濃度5重量％以上30重量％以下（較佳爲10重 量。/〇以上20重11 %以下）之草酸溶液等；此外’爲了在該 等酸水溶液中導入鹵素離子而添加之鹵化物’例如可列舉 :氯化鈉、氯化鉀、氯化鎂、氯化鋁等的氯化物’氟化鈣 等的氟化物，溴化鉀等的溴化物等。考慮到安全性等較佳 -14- 201144075 爲氯化物，再者，蝕刻液中之鹵素離子，通常爲0.5 g/L以 上3 00g/L以下，較佳爲1 g/L以上100 g/L以下；若未達0.5 g/L，鹵素離子的效果小，在開口緣部無法形成具有雪簷 狀突出部之凹狀部，又在超過300 g/L的情況，在鋁形狀 體的表面處理（蝕刻處理）時，溶解反應會急劇地進行， 難以進行凹狀部的控制。 又在本發明，作爲用來在鋁形狀體表面形成期望的凹 狀部之蝕刻液，硝酸或濃度超過80重量％之濃硫酸等的強 氧化力酸水溶液、氫氧化鈉和氫氧化鉀等的鹼性溶液並不 適當。硝酸和濃硫酸等之氧化力較強的酸水溶液，對鋁合 金具有被膜生成能力，反而會在鋁形狀體表面形成強固的 氧化被膜，造成鹵素離子所進行之氧化被膜的溶解變困難 。此外，氫氧化鈉和氫氧化鉀等的鹼性溶液對鋁合金的溶 解機制是屬於全面溶解型，縱使是添加鹵素離子的情況此 傾向也不會改變，要形成期望的凹狀部是困難的。 在本發明，使用上述蝕刻液將鋁形狀體表面實施蝕刻 處理時的處理條件，是依所使用的蝕刻液的種類、酸濃度 、鹵素離子的濃度、在鋁形狀體上應形成之複數個凹狀部 的數目、大小等而有不同，通常，在鹽酸溶液的情況可採 用浴溫20〜80 °C、浸漬時間10分鐘的範圍，在磷酸溶液 的情況可採用浴溫30~80°C、浸漬時間1〜5分鐘的範圍，在 硫酸溶液的情況可採用浴溫40〜80°C、浸漬時間2〜8分鐘的 範圍，在草酸溶液的情況可採用浴溫50〜80 °C、浸漬時間 1〜3分鐘的範圍，在醋酸溶液的情況可採用浴溫50〜80°C、 -15- 201144075 浸漬時間1 ~3分鐘的範圍。所使用之蝕刻液的酸濃度、浴 溫越高則蝕刻效果越顯著，而能進行短時間處理。關於浴 溫，未達20°C時溶解速度慢而要生成充分大小（開口寬度 及深度）之凹狀部需花费長時間，此外，在超過80°C的浴 溫，溶解反應會急劇進行而使凹狀部的開口寬度及深度的 控制變困難；又關於浸漬時間，未達1分鐘時凹狀部的開 口寬度及深度之控制困難，相反地超過10分鐘的浸漬時間 會成爲生產性降低的原因。 此外，作爲銅合金材的蝕刻處理所使用的蝕刻液，可 使用以下組成的酸水溶液：含有選自硫酸及草酸中任一種 酸之酸濃度0.1重fi%以上60重量％以下，較佳爲0.5重量％ 以上50重量％以下，且含有鹵素離子0.01g/L以上1.0g/L以 下，較佳爲〇.〇5 g/L以上0.5g/L以下的範圍，含有過氧化 氫或硝酸〇.lg/L以上300g/L以下，較佳爲10 g/L以上 100g/L以下的範圍內。 在此，當酸濃度未達0.】重量％的情況，溶解反應變得 極慢，而發生幾乎無法進行蝕刻的問題；若超過60重量％ ，溶解反應變得過快，而發生無法控制的問題。此外，當 過氧化氫或硝酸的濃度未達0.1 g/L的情況’添加過氧化氫 或硝酸以促進銅溶解反應的效果不彰，相反地，若超過 3 00g/L，溶解反應變得過快，而發生無法控制的問題。再 者，當鹵素離子濃度未達〇.〇1 g/L的情況，會發生無法控 制（一定化）溶解速度的問題，若超過l.〇g/L則發生溶解 反應顯著降低的問題。 -16- 201144075 又鹵素離子，是用來在銅表面生成保護性低的氯化銅 層後，在其上方形成保護性高的氧化亞銅被膜。另一方面 ，由於氧化亞銅被膜不緻密而到處具有缺陷部，能使銅表 面的一部分溶解而形成凹凸部。再者，在所形成的凹部內 也會產生同樣的反應，最終形成的凹部會具有其開口寬度 比內部的寬度尺寸窄之特殊構造。因此，若鹵素離子的含 量比上述既定量更多，由於保護性高的氧化被膜覆蓋住銅 表面，使蝕刻速度變得極低；另一方面在含量比既定量少 的情況，相反地無法形成保護性高的被膜，會變得均一溶 解而難以在表面形成凹凸部。 作爲添加於蝕刻液用的酸水溶液中之鹵素離子，可列 舉選自氯離子（cr)、氟離子（F-)及碘離子（I-)中 任一種或兩種以上，蝕刻液可含有既定濃度範圍之該等鹵 素離子。爲了在該酸水溶液中導入鹵素離子所添加之鹵化 物，例如可列舉氯化鈉、氯化鉀、氯化鎂、氯化鋁等的氯 化物，氟化鈣等的氟化物，溴化鉀等的溴化物等。考慮到 安全性等較佳爲氯化物。 此外，作爲上述銅合金材的蝕刻液所使用之酸水溶液 ，爲了溶解氧化後的銅，按照需要，能在0.01 g/L以上 100g/L以下的範圍內（較佳爲0.1g/L以上80g/L以下）添加 一種或兩種以上的有機酸。基於此目的而添加於蝕刻液中 的有機酸，例如可列舉：乙醇酸、甲酸、醋酸、丙酸、草 酸、丙二醇酸。其中特佳爲乙醇酸。 再者，在銅合金材的鈾刻液中，爲了防止粗面化後的 -17- 201144075 銅表面發生氧化，能在〇.〇lg/L以上100g/L以下的範圍內 (較佳爲O.lg/L以上80g/L以下）添加一種或兩種以上的 唑系化合物。基於此目的而添加於蝕刻液中的唑系化合物 ，例如爲苯并三唑、甲苯并三唑等，其中特佳爲苯并三唑 〇 在此，在銅合金材的蝕刻液中，當上述有機酸的添加 量未達0.01 g/L的情況，氧化後的銅之溶解性降低而存在 氧化銅殘存物，如此會降低樹脂接合性而不理想。另一方 面在超過100g/L的情況，銅的溶解穩定性變差，在銅表面 會發生再氧化的問題。此外，當上述唑系化合物的添加量 未達0.0 1 g/L的情況，無法抑制粗化後的銅表面氧化，會 有發生變色的情況，另一方面在l〇〇g/L以上的情況，銅的 溶解反應被明顯地抑制，而發生溶解反應無法進展的問題 〇 在本發明，使用上述蝕刻液將銅形狀體的表面實施蝕 刻處理時的處理條件，可採用浴溫20〜80 °C、浸漬時間 0.5〜30分鐘的範圍。所使用之蝕刻液的酸濃度、浴溫越高 則蝕刻效果越顯著，而能進行短時間處理。關於浴溫，未 達20t時溶解速度慢而要生成充分大小（開口寬度及深度 )之凹狀部需花費長時間，此外，在超過8 0°C的浴溫，溶 解反應會急劇進行而使凹狀部的開口寬度及深度的控制變 困難；又關於浸漬時間，未達0.5分鐘時凹狀部的開口寬 度及深度之控制困難，相反地超過3 0分鐘的浸漬時間會成 爲生產性降低的原因。 -18- 201144075 在本發明，如上述般對鋁合金材及銅合金 處理而形成具有凹狀部之鋁形狀體及銅形狀體 需要（爲了脫脂、表面調整、除去表面附著物 )，在該蝕刻處理前之鋁合金材及/或銅合金 施前處理，該前處理包含：使用酸水溶液進行 /或使用鹼性溶液進行鹼處理。 在此，作爲前處理所使用的酸水溶液，例 市售的酸性脫脂劑所調製而成的、用酸試藥所 ;該酸試藥包含：硫酸、硝酸、氫氟酸、磷酸 ，醋酸、檸檬酸等的有機酸，由該等酸混合而 等。此外，作爲鹼性水溶液，例如可使用：由 脫脂劑所調製而成的，由氫氧化鈉等的鹼性試 成的，或是由該等的混合物所調製而成的。 使用上述酸水溶液及/或鹼性水溶液而進 的操作方法及處理條件，可與習知之使用這種 鹼性水溶液而進行之前處理的操作方法及處理 例如可藉由浸漬法、噴霧法等的方法來進行。 另外，在銘合金材及/或銅合金材的表面 處理後，或實施用來形成凹狀部之蝕刻處理後 要實施水洗處理，該水洗處理可使用工業用水 自來水、離子交換水等，可按照要製造的銅形 地選擇。再者，實施前處理或蝕刻處理後之銅 按照需要進行乾燥處理，關於該乾燥處理也是 於室溫之自然乾燥以外，也能使用吹氣、乾燥 材實施蝕刻 時，可按照 、污染物等 材的表面實 酸處理，及 如可使用由 調製而成的 等的無機酸 得之混合酸 市售的鹼性 藥所調製而 行之前處理 酸水溶液或 條件相同， 實施上述前 ，可按照需 、地下水、 狀體而適當 合金材’可 ，除了放置 器、烘箱等 -19- 201144075 進行強制乾燥。 藉由上述蝕刻處理、或前處理及蝕刻處理所獲得之鋁 形狀體及銅形狀體的表面，是形成蝕刻處理後的凹凸部， 其表面之60度表面光澤度（使用SUGA試驗機公司製攜帶 型光澤計測定）的測定値宜爲60度以下，或表面粗糙度測 定器（使用東京精密公司製SURFCOM 590A-DTP測定）或 雷射顯微鏡（使用Lasertec公司製1LM21W測定）之測定 値宜爲表面粗糙度（Rz) Ιμιη以上。當表面光澤度超過60 的情況或表面粗糙度（Rz ) 1 μιη以下的情況，樹脂無法充 分地進入鋁形狀體及銅形狀體的凹狀部內，鋁形狀體及銅 形狀體和樹脂形狀體之間無法獲得充分的接合強度。 此外，將藉由上述蝕刻處理、或前處理及蝕刻處理所 獲得之鋁形狀體及銅形狀體的表面，用SEM或光學顯微鏡 以倍率1 000倍進行截面觀察，關於所獲得的截面相片，較 佳爲鋁形狀體及銅形狀體的表面積，是藉由蝕刻處理來形 成凹凸部前之鋁合金材或銅合金材的表面積之1.2倍以上 1 〇倍以下。該表面積增加率未達1 . 2倍或超過1 0倍的情況 ’樹脂無法充地進入鋁形狀體及銅形狀體的凹狀部內，鋁 形狀體及銅形狀體和樹脂形狀體間無法獲得充分的接合強 度。 此外，爲了獲得本發明的鋁-樹脂-銅複合品，可在如 此般製得之鋁形狀體及銅形狀體的表面塗布黏著劑後，讓 金屬或樹脂接合；或在所製得的鋁形狀體和銅形狀體和金 屬間介入樹脂，藉由熱壓機施加熱和壓力而進行接合；或 -20- 201144075 是將所製得的鋁形狀體及銅形狀體置入射出成形模具內， 朝該模具內將熔融後的既定熱塑性樹脂射出而使其固化， 藉此將鋁形狀體及銅形狀體經由樹脂的複合化，而製造出 目的之鋁形狀體及銅形狀體和樹脂的複合品。 在此，用來製造本發明的鋁-樹脂-銅複合品之熱塑性 樹脂，可將各種熱塑性樹脂予以單獨地使用，考慮到本發 明的鋁-樹脂-銅複合品所要求之物性、用途、使用環境等 ，作爲熱塑性樹脂宜使用：例如聚丙烯樹脂、聚乙烯樹脂 、丙烯腈-丁二烯-苯乙烯共聚物（ABS )、聚碳酸酯樹脂 、聚醯胺樹脂、聚苯硫（PPS)等的聚芳基硫醚樹脂、聚 縮醛樹脂、液晶性樹脂、聚對苯二甲酸乙二醇酯（PET ) 和聚對苯二甲酸丁二醇酯（PBT )等的聚酯系樹脂、聚甲 醛樹脂、聚醯亞胺樹脂、對位性聚苯乙烯樹脂等，以及該 等熱塑性樹脂之兩種以上的混合物。此外，爲了更加地改 善鋁形狀體及銅形狀體和樹脂形狀體間的密合性、機械強 度、耐熱性、尺寸穩定性（耐變形、彎曲等）、電氣性質 等的性能，更佳爲在該等熱塑性樹脂中添加纖維狀、粉粒 狀、板狀等的塡充劑，或各種的彈性體成分。 此外，作爲添加於熱塑性樹脂中的塡充劑，可例示出 :玻璃纖維、碳纖維、金屬纖維、石綿纖維、硼纖維等的 無機質纖維塡充劑，聚醯胺、氟樹脂、丙烯酸樹脂等的高 熔點有機纖維塡充劑，石英粉末、玻璃珠、玻璃粉、以碳 酸鈣爲首之無機粉體類等的粉狀塡充劑，玻璃薄片、滑石 、雲母等的矽酸鹽類的板狀塡充劑等，相對於熱塑性樹脂 -21 - 201144075 1 〇〇重量份’其添加il爲25 0重量份以下，較佳爲0重量份 以上200重量份以下，更佳爲〇重量份以上100重量份以下 的範圍。若該塡充劑的添加量超過250重量份，流動性降 低而變得難以進入鋁形狀體及銅形狀體的凹部內，無法獲 得良好的密合強度，而會發生機械特性變差的問題。 此外，作爲添加於熱塑性樹脂中的彈性體成分，可例 示出：聚胺酯系 '核殻型、烯烴系、聚酯系、醯胺系、苯 乙烯系等的彈性體，可考慮射出成形時熱塑性樹脂的熔融 溫度等來選擇，此外，相對於熱塑性樹脂100重量份，其 添加量爲30重量份以下，較佳爲3〜25重量份的範圍。若該 彈性體成分的添加S超過30重量份，看不出進一步的密合 強度提高效果，且會產生機械特性變差等的問題。該彈性 體成分的配合效果，當使用聚酯系樹脂作爲熱塑性樹脂的 情況特別的顯著。 再者，用來製造本發明的鋁·樹脂-銅複合品之熱塑性 樹脂中，可按照所要求的性能而適當地添加：一般添加於 熱塑性樹脂中之公知的添加劑，亦即難燃劑、染料和顏料 等的著色劑、抗氧化劑和紫外線吸收劑等的穩定劑、可塑 劑、潤滑劑、滑劑、脫模劑、結晶化促進劑、結晶核劑等 〇 在本發明，將鋁形狀體及銅形狀體置入射出成形用模 具內而進行熱塑性樹脂之射出成形時，雖可採用該熱塑性 樹脂所要求的成形條件，但在射出成形時讓熔融後的熱塑 性樹脂確實地進入鋁形狀體及銅形狀體的凹狀部內而固化 -22- 201144075 是重要的，因此宜將模具溫度、圓筒溫度在熱塑性樹脂的 種類、物性、成形循環所容許的範圍內設定成較高，特別 是關於模具溫度，下限溫度必須設定成9〇t以上，較佳爲 1 3 0 °C以上；上限溫度，可按照所使用熱塑性樹脂的種類 ’設定在1 0 0 °c〜比該熱塑性樹脂的熔點或軟化點（添加彈 性體成分的情況’是何者較高的溶點或軟化點）低2 01左 右的溫度範圍。此外，下限模具溫度較佳爲設定成：不要 比熱塑性樹脂的熔點低1 4 0 °C以上。 再者’用來製造本發明的鋁-樹脂-銅複合品之樹脂， 除上述的熱塑性樹脂以外，也能使用熱固性樹脂、常溫硬 化性樹脂、各種黏著劑等。作爲熱固性樹脂可列舉環氧系 樹脂等’又作爲常溫硬化性樹脂可列舉聚酯系樹脂等。再 者’作爲黏著劑可列舉：腈橡膠系、合成橡膠系、環氧系 、氰基丙烯酸系、氯乙烯系、塑膠系、熱熔系等。 在此’關於本發明的方法所製造之銘-樹脂-銅複合品 構成的製品’只要是在鋁合金製的鋁形狀體和銅合金製的 銅形狀體間透過樹脂形狀體接合成一體的構造即可，不管 是任何製品皆可，但基於鋁形狀體和樹脂形狀體間的界面 (鋁/樹脂界面）及銅形狀體和樹脂形狀體間的界面（銅/ 樹脂界面）之密合強度和氣密性極高的特性，較佳爲密閉 型電池用蓋構件。 作爲該密閉型電池用蓋構件，例如是具備鋁合金製的 鋁封孔蓋構件、鋁合金製的鋁合金端子和銅合金製的銅合 金端子、以及封孔絕緣樹脂；該鋁封孔蓋構件，是具有互 -23- 201144075 相隔著既定間隔之一對的貫通孔；該端子’是在該鋁封孔 蓋構件的各貫通孔內，與其周緣部維持既定的間隙而形成 貫穿；該封孔絕緣樹脂，是將前述鋁封孔蓋構件的各貫通 孔周緣部和各端子間的間隙予以密封。該密閉型電池用蓋 構件，是鋁-樹脂-銅複合品，其是將前述鋁封孔蓋構件及 鋁合金端子分別實施表面凹凸化蝕刻處理而具有起因於表 面的一部分或全面所形成的凹凸部之複數個凹狀部；前述 銅合金端子是藉由凹凸化蝕刻處理而具有起因於表面的一 部分或全面所形成的凹凸部之複數個凹狀部；該鋁-樹脂-銅複合品是由一方的樹脂形狀體和另一方的樹脂形狀體所 構成，該一方的樹脂形狀體，是具有前述封孔絕緣樹脂進 入前述鋁封孔蓋構件（鋁形狀體）及鋁合金端子（鋁形狀 體）的各凹狀部內而固化成的複數個嵌入部，藉此將該等 鋁封孔蓋構件和鋁合金端子間結合成一體；該另一方的樹 脂形狀體，是具有前述封孔絕緣樹脂進入前述鋁封孔蓋構 件（鋁形狀體）及銅合金端子（銅形狀體）的各凹狀部內 而固化成的複數個嵌入部，藉此將該等鋁封孔蓋構件和銅 合金端子間結合成一體。 本發明的鋁-樹脂-銅複合品，在鋁形狀體和樹脂形狀 體間的界面（鋁/樹脂界面）及銅形狀體和樹脂形狀體間 的界面（銅/樹脂界面）之密合強度及氣密性極高，即使 曝露於嚴苛環境下仍能保持其優異的密合強度及氣密性， 可長期維持高可靠性。因此，本發明之鋁-樹脂-銅複合品 ’主要適用於密閉型電池用蓋構件，特別適用於：樹脂形 • 24 · 201144075 狀體從鋁形狀體的一部分及銅形狀體的表面以對接狀態突 出而要求高結合強度之金屬-樹脂複合品。 此外’依據本發明之鋁-樹脂-銅複合品之製造方法， 藉由在製造時測定鋁形狀體的表面光澤度或是鋁形狀體及 銅形狀體的表面粗糙度，可預測所獲得的製品之密合強度 ’因此其製造時的品質管理變容易，且每個製品幾乎沒有 密合強度的差異，而能製造出高可靠性的製品。 【實施方式】 以下，基於實施例及比較例來具體說明本發明的較佳 實施形態。又本發明並不限定於以下所記載的例子。 [實施例1] [鋁形狀體的調製] 將兩個錯製的posiTEST試驗用端子（Dolly，DeFelsko 公司製，尺寸20mm(|)，JISA 1100)，首先在30wt%硝酸溶 液中以常溫浸漬5分鐘後，用離子交換水進行充分地水洗 ’接著在5wt%氫氧化鈉溶液中以50t浸漬1分鐘後進行水 洗’進一步在30wt%硝酸溶液中以常溫浸漬3分鐘後進行 水洗，藉此實施前處理。 接著，將上述前處理後的端子，在蝕刻液（在2.5 wt % 鹽酸溶液中添加54g/L的氯化銨六水合物而調製成）中以 66 °C浸漬4分鐘後水洗，藉此實施蝕刻處理，進一步在 3 Owt%硝酸溶液中以常溫浸漬3分鐘後進行水洗，使用120 -25- 201144075 澧 狀 形。 鋁品 ( 樣 片 價 驗評 試的 鋁用 個驗 兩試 出α 作測 製重 , 荷 鐘伸 分拉 5 成 燥作 乾來 風用 熱是 的其 [銅形狀體的調製] 從厚度lmm的銅合金（C1100)板裁切出大小50mmx 50mm的兩片銅片（銅合金材），關於該銅片，首先在 1 Owt%鹽酸溶液中浸漬1分鐘後用離子交換水充分地水洗 ，接著在5wt%氫氧化鈉溶液中以50°C浸漬1分鐘後進行水 洗，藉此實施前處理。 接著，將上述前處理後的銅片，在Alpha-prep PC-7030溶液 （ Mel tex公司製 ） 中以 40°C 浸漬 1分鐘後 水洗， 使用120 °C的熱風乾燥5分鐘，製作出兩個銅試驗片（銅形 狀體），其是用來作成拉伸荷重測定試驗用的評價樣品。 [鋁試驗片（鋁形狀體）和銅試驗片（銅形狀體）的 表面凹狀部觀察] 對於所獲得的鋁試驗片和銅試驗片，將其厚度方向截 面當中某區域的截面，使用掃描型電子顯微鏡（日立製 FE-SEM，S-45 00型）觀察，在鋁形狀體或銅形狀體之厚 度方向截面上，決定出與該厚度方向正交且通過凹凸部的 最高部之頂線，接著與上述大致相同地決定出與鋁形狀體 或銅形狀體之厚度方向正交且通過凹凸部的最深部之底線 ，接下來，從頂線朝底線拉出垂直方向的線，再拉出通過 該線的中間部且與頂線（或底線）平行的中間線，以存在 •26- 201144075 於該中間線上之鋁形狀體和鋁形狀體間或銅形狀體和銅形 狀體間的空隙部的距離作爲凹狀部的開口寬度，觀察起因 於鋁試驗片及銅試驗片表面的凹凸部而形成之凹狀部的形 狀和大小（開口寬度及深度）並進行測定。 在所觀察之鋁試驗片及銅試驗片之某區域的截面上， 例如第1圖的截面示意圖所示，可從該第1圖意識出之凹狀 部形狀的典型例，如第2圖所示包括：具有從開口緣部的 一部分朝開口寬度方向中心呈雪簷狀突出的突出部之凹狀 部（形狀a，參照第2 ( a )圖），具有從開口緣部的整體 朝開口寬度方向中心呈雪簷狀突出的突出部之凹狀部（形 狀b，參照第2(b)圖），在內部進一步形成凹狀部而具 有雙重凹部構造的凹狀部（形狀c，參照第2(c)圖）， 在內部壁面形成內部突起部而具有內部凹凸構造之凹狀部 (形狀d，參照第2 ( d )圖），在該實施例1中可觀察到所 有的形狀a〜d的凹狀部。此外，關於上述凹狀部的形狀， 即使改變觀察場所也是同樣的。 又關於實施例1〜5及比較例1〜3之凹狀部形狀的評價， 在具有上述形狀a~d任一者之一或兩個以上的情況評價爲 良好（〇），在形狀a〜d任一者都不存在的情況評價爲不 良（X )。 此外，在所測定之鋁試驗片及銅試驗片之某區域截面 上所觀察到的凹狀部之大小（開口寬度及深度）以及比例 ，在每o.lmm見方，開口寬度0.1μιη〜1μπι的凹狀部有 10〜100個，開口寬度Ιμπι〜10 μηι的凹狀部有1〜10個，開口 -27- 201144075 寬度Ιίμιη〜30μιη的凹狀部有1〜3個’深度在Ο.ίμηι〜30μηι的 範圍內。此外，雙重凹狀部構造的內部凹狀部之大小（開 口寬度及深度）以及比例也是’與上述大致同樣地’在每 0.1mm見方，開口寬度Ο.ίμιη〜Ιμπι的凹狀部有1〇~5〇個，開 口寬度Ιμπι〜ΙΟμηι的凹狀部有1〜50個’開口寬度 Ιίμηι〜30μιη的凹狀部有1〜2個，深度在Ο.ίμιη〜20μηι的範圍 內。關於該凹狀部的大小也是，縱使改變觀察場所也幾乎 不會變化。 又關於實施例1~5及比較例1〜3之凹狀部大小的評價， 在開口寬度〇. 1〜30μπι且深度0· 1~30μηι的範圍內的情況評 價爲良好（〇），超出該範圍的情況評價爲不良（X )。 [鋁試驗片及銅試驗片之表面光澤度的評價] 對於所獲得的鋁試驗片及銅試驗片各兩個，使用攜帶 型光澤計（SUGΑ試驗機公司製）測定表面的60度光澤度 ，算出兩個的平均値，作爲鋁試驗片及銅試驗片之60度光 澤度。鋁試驗片爲30,銅試驗片爲10。 [鋁試驗片（鋁形狀體）及銅試驗片（銅形狀體）之 表面積增加率的評價] 關於所獲得的兩個鋁試驗片及三個銅試驗片，分別用 SEM或光學顯微鏡以倍率1〇〇〇倍觀察截面，對於所獲得的 截面觀察相片，使用影像處理軟體（ImageJ )測定鋁形狀 體及銅試驗片之表面的表面積。相對於未處理的鋁合金材 -28- 201144075 ，求出各鋁試驗片表面的表面積增加的比例；相對於未處 理的銅合金材，求出各銅試驗片表面的表面積增加的比例 ，算出求得的兩數値的平均値而定義爲表面積增加率。結 果，鋁試驗片爲3.3倍，銅試驗片爲1.9倍。 [評價用試驗體[利用黏著劑進行之樹脂（黏著劑）的 接合]之調製] 如第3圖所示，將所獲得的銅試驗片（銅形狀體）1和 鋁試驗片（鋁形狀體）端子5，透過二液混合型的環氧系 急速硬化黏著劑（Huntsman Advanced Materials公司製， 商品名Aral dite Rapid ) 4進行接合後，使用熱壓機（AS ONE製AH-2003 )以按壓力〇. 1 Μ P a實施常溫加壓，保持2 4 小時而進行接壓，接著將從銅試驗片1和鋁試驗片端子5間 的接合面擠出之多餘的黏著劑4，當黏著劑固化後使用切 刀從接合面分離，調整成接合面爲3.14 cm2，製作出鋁試 驗片-黏著劑-銅試驗片（評價用試驗體）。 [評價用試驗體（利用加熱壓接進行之樹脂的接合） 的調製] 如第4圖所示，在所獲得的銅試驗片（銅形狀體）1上 ，以單位面積重〇.〇4g/cm2的方式載置聚苯硫樹脂（ Polyplastics公司製）的顆粒（樹脂）6，在其上方配置鋁 試驗片端子5，使用熱壓機（AS ONE製AH-2003)以按壓 力O.IMPa、板溫度300 °C進行熱壓接，製作出樹脂以 -29- 201144075 3. 14cm2的接合面積進行固接之鋁試驗片-樹脂-銅試驗片 (評價用試驗體）。 [利用posi TEST試驗機進行之接合面的拉伸強度評價] 對於上述各個評價用試驗體，使用posiTEST試驗機（ DeFelsko 公司製），依 ASTM D454 1 ( ISO 4624 )試驗法 測定鋁-樹脂接合面的拉伸強度（端子尺寸：20ιηιηφ，解 析能力：±0.01MPa，精度：±1%，測定範圍：0~20MPa) 。在該posiTEST試驗中，如第6圖所示，在posiTEST試驗 機的致動器8上，透過鋁試驗片端子固定用治具9來連結評 價用試驗體的鋁試驗片端子5 (或7)部分後，藉由泵施加 壓力，而測定端子5 (或7 )從銅試驗片（銅形狀體）1剝 離時的荷重（剝離荷重），又調查剝離後之鋁試驗片端子 5和銅試驗片1的接合部之剝離狀態。 評價用試驗體之剝離荷重，在鋁試驗片-黏著劑-銅試 驗片的情況爲5.5MPa，在鋁試驗片-樹脂-銅試驗片的情況 爲6.7MPa。又關於所觀察到的剝離狀態，在鋁試驗片或銅 試驗片的接合面上黏著劑或樹脂是遍及全面殘存的情況評 價爲良好（〇），在鋁試驗片或銅試驗片側僅一部分殘存 的情況評價爲局部良好（Δ )，在鋁試驗片側未殘存的情 況（界面剝離）評價爲不良（X );評價的結果都是良好 (〇）的》 [鋁-樹脂-銅稂層部的觀察評價] -30- 201144075 此外，如第7圖所示，關於所調製出之兩種的評價用 試驗體，亦即鋁試驗片·黏著劑-銅試驗片、鋁試驗片-樹 脂-銅試驗片，分別從鋁試驗片朝向積層於其上方之樹脂 (黏著劑）沿厚度方向切斷，將厚度方向截面用SEM或光 學顯.微鏡以倍率1〇〇〇倍觀察，關於所獲得之截面觀察相片 ，將從樹脂形狀體2側朝向鋁形狀體1側沿厚度方向延伸之 觀察線（OL )以互相隔著0.1 μιη的間隔拉設複數條時，在 一條觀察線（OL )存在由樹脂（黏著劑）-鋁-樹脂（黏著 劑）所構成之至少一個以上的積層部，且該積層部之鋁形 狀體部分的厚度爲Ο.ίμηι以上30μπι以下的範圍，將1 000條 觀察線（OL )的範圍內以一個以上的比例存在的情況評 價爲良好（〇），將1 000條觀察線（〇L )的範圍內連一 個積層部也不存在的情況評價爲不良（X )，結果所有的 情況都是良好（〇）的。此外，對於銅試驗片側也是以同 樣的手法進行測定，結果所有的情況都是良好（〇）的。 又關於以下的實施例1〜5及比較例1〜3也是以同樣的基準進 行評價。 [實施例2] 除了在銅的蝕刻處理是使用MoldPrep LF溶液（ ATOTECH公司製）以外，與上述實施例1同樣地製作出鋁 試驗片（鋁形狀體）及銅試驗片（銅形狀體），接著使用 與實施例1同樣的黏著劑及樹脂分別製作出鋁試驗片-樹脂 (黏著劑）-銅試驗片，與上述實施例1的情況同樣地實施 -31 - 201144075 :上述鋁試驗片及銅試驗片的表面之凹狀部觀察及光澤度 測定、posiTEST試驗、鋁-樹脂·銅的積層部之觀察評價。 結果是和實施例1的結果一起顯示於表1。 [實施例3] 除了作爲切出銅片的銅合金板是使用C 1 020以外’與 上述實施例1同樣地製作出鋁試驗片（鋁形狀體）及銅試 驗片（銅形狀體），接著使用與實施例1同樣的黏著劑及 樹脂分別製作出鋁試驗片·樹脂（黏著劑）-銅試驗片，與 上述實施例1的情況同樣地實施：上述鋁試驗片及銅試驗 片的表面之凹狀部觀察及光澤度測定、posiTEST試驗、 鋁-樹脂-銅的積層部之觀察評價。 結果是和實施例1的結果一起顯示於表1。 [贲施例4] 在400g/L硫酸溶液中添加硝酸溶液150g/L、氯化鈉 0.2g/L、苯并三唑l〇g/L、5-胺基四唑l〇g/L而調製成蝕刻 液（氯離子濃度〇.〇8g/L )，除了將銅的蝕刻處理變更成 在該蝕刻液中以60 °C浸漬1分鐘後水洗以外，與上述實施 例1同樣地製作出鋁試驗片（鋁形狀體）及銅試驗片（銅 形狀體），接著使用與實施例1同樣的黏著劑及樹脂分別 製作出鋁試驗片-樹脂（黏著劑）-銅試驗片，與上述實施 例1的情況同樣地施：上述鋁試驗片及銅試驗片的表面 之凹狀部觀察及光澤度測定' posiTEST試驗、鋁-樹脂-銅 -32- 201144075 的積層部之觀察評價。 結果是和實施例1的結果一起顯示於表1。 [實施例.5]. 從厚度lmm的鋁合金（JIS A 1 05 0 )板裁切出大小 50mmx50mm之鋁片（鋁合金材），對該鋁片在蝕刻液（ 於2.5 wt%鹽酸溶液中添加54g/L的氯化銨六水合物而調製 成）中以66t浸漬4分鐘後水洗而實施蝕刻處理，接著， 在30wt%硝酸溶液中以常溫浸漬3分鐘後水洗，用120°C的 熱風乾燥5分鐘，製作成鋁試驗片（鋁形狀體）。 此外，與實施例1同樣地製作出實施蝕刻處理後的銅 試驗片（銅形狀體）。 接著，如第5圖所示，將所製得的鋁試驗片（鋁形狀 體）13及銅試驗片（銅形狀體）1設置於未圖示的射出成 形機（NISSEI公司製ST10R2V)的模具內，使用聚苯硫樹 脂（Polyplastics公司製）作爲熱塑性樹脂，以射出時間5 秒、射出速度80mm/秒、保壓力lOOMPa、成形溫度3 20 °C 、模具溫度1 60 °C的成形條件進行射出成形，在鋁試驗片 13及銅試驗片1的上面將樹脂製端子7 —體成形，而製作出 樹脂製端子7對於鋁試驗片13及銅試驗片1上面之接合面積 爲3.14cm2之鋁-樹脂試驗片及銅-樹脂試驗片（評價用試 驗體）。 與上述實施例1的情況同樣地實施：上述鋁試驗片及 銅試驗片的表面之凹狀部觀察及光澤度測定、posiTEST試 -33- 201144075 驗、樹脂-銅的積層部之觀察評價。 結果是和實施例1的結果—起顯示於表1。 [比較例1] 僅進行實施例1的前處理但未進行蝕刻處理而調製成 鋁試驗片端子及銅試驗片，與實施例1的情況同樣地，使 用樹脂及黏著劑分別製作出鋁試驗片-樹脂（黏著劑）-銅 試驗片，與上述實施例1的情況同樣地實施：上述鋁試驗 片及銅試驗片的表面之凹狀部觀察及光澤度測定、 posiTEST試驗、鋁-樹脂-銅的積層部之觀察評價。 關於鋁試驗片及銅試驗片表面的凹狀部形狀，並未觀 察到實施例1所示的形狀a〜d之任一者，又凹狀部的大小也 是，其開口寬度爲Ο.ΟΟΙμηι以上未達Ο.ίμιη» 結果是和上述苡施例1〜5的結果一起顯示於表1。 [比較例2 ] 在40wt%硫酸溶液中添加150g/L硝酸溶液而調製成蝕 刻液，除了將銅的蝕刻處理變更成在該蝕刻液中以60°C浸 漬1分鐘後水洗以外，與上述實施例1同樣地製作出鋁試驗 片（鋁形狀體）及銅試驗片（銅形狀體），接著使用與實 施例1同樣的黏著劑及樹脂分別製作出鋁試驗片-樹脂（黏 著劑）-銅試驗片，與上述實施例1的情況同樣地實施：上 述鋁試驗片及銅試驗片的表面之凹狀部觀察及光澤度測定 、posiTEST試驗、鋁-樹脂·銅的積層部之觀察評價。 -34- 201144075 關於銅試驗片表面的凹狀部形狀，並未觀察到實施例 1所示的形狀a〜d之任一者，又凹狀部的大小也是，其開口 寬度爲〇.〇〇10爪以上未達〇.4111。 結果是和比較例1的結果一起顯示於表1。 [比較例3] 取代銅的鈾刻處理而在濃度1 wt%的矽烷偶合劑處理 液（信越矽利康公司製，KBM303)中浸漬30秒後，用120 °C的熱風乾燥5分鐘，除此外是與上述實施例1同樣地製作 出鋁試驗片（鋁形狀體）及銅試驗片（銅形狀體），接著 使用與實施例1同樣的黏著劑及樹脂分別製作出鋁試驗片-樹脂（黏著劑）-銅試驗片，與上述實施例1的情況同樣地 實施：上述鋁試驗片及銅試驗片的表面之凹狀部觀察及光 澤度測定、posiTEST試驗 '鋁-樹脂-銅的積層部之觀察評 價。 結果是和比較例1的結果一起顯示於表1。 -35- 201144075 [表i][Technical Field] The present invention relates to an aluminum-resin-copper composite in which an aluminum-shaped body made of an aluminum alloy and a copper-shaped body made of a copper alloy are integrally joined to each other through a resin-shaped body. The method mainly relates to an aluminum-resin-copper composite which is excellent in adhesion strength and airtightness of a lid member for a sealed battery, and a method for producing the same. [Prior Art] In a battery container such as a lithium battery, the positive electrode terminal and the negative electrode terminal provided through the lid member are insulated from the lid member, and the electrolyte inside the container and the gas generated from the inside of the container are prevented from leaking to prevent moisture. It is an important issue to infiltrate the inside from the outside of the container, and to improve durability, heat resistance, and airtightness in a harsh environment. In order to ensure the airtightness between the lid body and the electrode terminal, the lid member for a sealed battery made of an aluminum-resin-copper composite is a lid made of an aluminum alloy and a metal electrode. A method of insert molding a terminal or the like. Further, in order to make the joining between the metal part and the resin lower in cost and to further improve the joining force, a method of performing a predetermined surface treatment on the surface of the metal part to be bonded to the resin is also known. For example, Patent Document 1 proposes a cover for a sealed battery, which is provided with an insulating sealing member which is insert-molded between a lid body and an electrode for insulating and fixing the lid body and the electrode. Further, Patent Document 2 proposes a structure including an electric and electronic component of a terminal, which is composed of a metal terminal, a metal base body, and a thermoplastic tree-5-201144075 grease composition; the metal terminal has a The shape extending in the longitudinal direction is subjected to a surface treatment on the surface of the outer peripheral portion; the metal base body includes a flat plate portion and a convex portion, and the convex portion is erected one or more on the flat plate portion to form a predetermined interval a surface treatment is performed on the inner peripheral portion of the inner peripheral portion through which the terminal is inserted; and the thermoplastic resin composition is formed in the metal after the metal terminal and the metal substrate are embedded in the mold for injection molding. The outer peripheral portion of the formed terminal and the inner peripheral portion formed between the inner peripheral portion of the metal base are ejected, whereby the metal terminal and the metal base are joined together to be integrated. Further, Patent Document 3 proposes a sealing plate for a battery container in which at least one electrode terminal and a lid are integrally formed by an insulating sealing material. The electrode terminal is made of a metal surface-treated with a triazine dithiol compound or a decane coupling agent. The cover is made of a metal that is subjected to the surface treatment. The insulating sealing material is composed of a polyphenylene sulfide composition containing an elastomer resin having an elastic modulus of 55 MPa or less. Further, Patent Document 4 proposes a lid body for an electric double layer capacitor in which an opening portion of a bottomed cylindrical container in which an electrode element is housed is shielded and closed, and a pair of electrode terminals connected to the respective electrodes are provided. The electrode member is formed by impregnating an electrolyte with a positive electrode and a negative electrode which are opposed to each other through a separator. However, in the case of any of the above, the adhesion strength and airtightness of the metal-resin interface are insufficient when exposed to a severe environment, and it is required to develop a more excellent adhesion strength and gas. A dense metal/resin composite. -6- 201144075 Then, the present inventors first focused on an aluminum alloy in terms of a metal material, and have an extremely high degree between the aluminum-shaped body made of the aluminum alloy and the resin-shaped body integrally provided on the surface thereof. The results of intensive investigation of the aluminum-resin composites, such as adhesion strength and airtightness, and excellent adhesion and airtightness in a severe environment, and excellent durability and heat resistance. It has been found that by forming the uneven portion (the concave portion having a specific surface shape) on the surface of the aluminum-shaped body, the adhesion and airtightness between the aluminum-shaped body and the resin-shaped body can be remarkably improved, and based on the obtained results, Japanese Patent Application No. 2008-153805 and Japanese Patent Application No. 2008-153806. [Patent Document 1] JP-A-2007-179793 [Patent Document 2] Japanese Patent Laid-Open Publication No. JP-A No. 2008-27823 [Patent Document 3] 4] Japanese Patent No. 3,675,5, 5, 1 (Invention) In addition to the above-mentioned results, the inventors of the present invention have integrated an aluminum-shaped body made of an aluminum alloy and a copper-shaped body made of a copper alloy into a single aluminum-resin. - A copper-based composite, in order to manufacture and provide an aluminum-resin-copper composite which maintains an excellent adhesion strength and airtightness of an aluminum-resin-copper joint even in an environment with high vibration and high thermal shock. As a result of intensive investigation, it has been found that an uneven portion (a concave portion having a specific surface shape) is formed on the surface of the aluminum-shaped body and the copper-shaped body by etching treatment, so that the aluminum-shaped body and the resin-shaped body and the copper shape can be formed. The adhesion between the body and the resin body, the airtightness, and the durability and heat resistance are remarkably improved, and the invention is completed in 201144075. Accordingly, an object of the present invention is to provide an aluminum-resin-copper composite which has an extremely high interface between an aluminum alloy body and a resin body and a copper alloy body and a resin body. The adhesion strength and airtightness can maintain excellent adhesion strength and air tightness in a harsh environment such as temperature and humidity, such as dust, especially in an environment with high vibration and high thermal shock. Excellent durability and heat resistance. Further, another object of the present invention is to provide a method for producing an aluminum-resin-copper composite which can produce an aluminum-resin-copper composite which can be formed between an aluminum body and a resin body and a copper body. The interface between the resin-shaped bodies has extremely high adhesion strength and airtightness, and can maintain excellent adhesion strength and airtightness under severe environments, especially even in an environment with high vibration and high thermal shock. It exhibits excellent corrosion resistance, durability and heat resistance. In other words, the aluminum-resin-copper composite of the present invention is characterized in that the aluminum-shaped aluminum alloy body having a concave-convex portion on a part or the entire surface thereof by surface roughening etching treatment and surface roughening The copper-shaped body made of a copper alloy having a part or the entire surface of the surface and having an uneven portion on the surface is integrally bonded to each other without being in contact with each other through the resin-shaped body. Further, the aluminum-resin-copper composite of the present invention is characterized in that it is an aluminum-shaped aluminum alloy body having a concave-convex portion in a part or the entire surface thereof by surface roughening etching treatment, and surface roughening a copper-shaped body made of a copper alloy having a part or the entire surface of the surface and having a concavo-convex portion is etched into a single body by a resin molded body without being in contact with each other. -8-201144075 aluminum-resin-copper composite; The surface of the aluminum-shaped body and the copper-shaped body of the uneven portion is formed by a plurality of concave portions due to the uneven portion, and each of the concave portions is in a thickness direction cross section of each of the aluminum body and the copper body. The opening width measured by scanning electron microscope observation is perpendicular to the thickness direction and is located on a half line between the top line passing through the highest portion of the uneven portion and the bottom line passing through the deepest portion. Ίμιη above 30μηι below the size, the depth is Ο. Ίμηι or more and a size of 30 μm or less; the embedded portion in which the resin is allowed to enter and solidify to form a resin molded body; and the concave portion and the embedded portion are used to form the aluminum shape and the resin molded body and the copper shape The body and the resin molded body are mutually locked. In addition, the aluminum-resin-copper composite of the present invention is a method in which an aluminum-shaped body made of an aluminum alloy and a copper-shaped body made of a copper alloy are bonded to each other through a resin-shaped body without being in contact with each other. In the method for producing a copper composite, the aluminum alloy and the copper alloy are subjected to an etching treatment, and a part of the surface or a total amount of the uneven portion is formed in the entire surface of the aluminum alloy and the copper alloy. a recessed portion; in the molding of the resin-shaped body, the resin is allowed to enter and solidify in each of the concave portions of the aluminum-shaped body and the copper-shaped body to form an embedded portion of the resin-shaped body; and the aluminum-shaped body and the copper-shaped body are concave. The fitting portion of the shape portion and the resin-shaped body are locked to each other, whereby the aluminum-shaped body and the copper-shaped body are integrally joined to each other through the resin-shaped body without being in contact with each other. -9-201144075 In the present invention, as the aluminum alloy material forming the aluminum-shaped body, specifically, a pure A1-based 1 000-series, Al-Cu-based 2000-series Al-Mn-based 3 000-series, Al-Si 4000 system, Al-Mg 5000 system, ADC 5' ADC6, AUMg-Si 6000 system, A Zn-Mg system 7000 system, Al-Fe system 8000 system, Al-Si- A material of a material such as an ADC 10' A-Si-Cu-based ADC 10, an ADC 10Z ' ADC 12 , an ADC 12 Z , an Al-Si-Cu-Mg-based ADC 14 or the like is appropriately processed into a desired shape. Further, the materials and the like which are obtained by appropriately combining the processed materials are used. In the present invention, as a copper alloy material for forming a copper-shaped body, specifically, C 1 00 ' c 1 020 'C1220, C2700, C2801, C3604 'C4641, C5191, C5210, C6782 and the like can be mentioned. Further, in the present invention, the plurality of concave portions formed on the surfaces of the aluminum body and the copper body due to the uneven portions on the surface of the aluminum body and the copper body may be such that the opening edge portion is an endless peripheral portion. a hole or a hole (a concave portion having an end opening edge), or a slit shape or a groove shape having an opening edge portion at both ends thereof (having a concave shape having an end opening edge portion) Further, it may be a hole-like or hole-like shape having an endless opening edge portion and a slit-like or groove-like shape having an end opening edge portion, and regarding the aluminum-shaped body and the copper shape. The plurality of concave portions ' of the body preferably have a projection portion that forms a snow-like shape from a portion or all of the opening edge portion of the concave portion toward the center of the opening width direction, thereby making the concave portion The width of the opening of the portion is narrower than the width of the inner portion of the portion of the inner portion of the resin-shaped body and the recessed portion of the resin-shaped body that has been solidified into the concave portion to form a locking structure that cannot be separated from each other, as long as it does not Destroy aluminum body and copper Either one of the concave portion fitted portion or the shape of the resin member body will not be disengaged or both, thereby further enhance the adhesion strength and air tightness between the aluminum shape and the shape of copper and a resin body shape. Further, in the above-described manner, the snow-like protruding portion is formed in part or all of the opening edge portions of the plurality of concave portions of the aluminum-shaped body and the copper-shaped body, and the resin-shaped body does not have to be fitted in the close contact state. In the concave portions, for example, the difference in linear expansion coefficient between the aluminum-shaped body and the copper-shaped body and the resin-shaped body and the ambient temperature are inevitable between the aluminum-shaped body and the copper-shaped body and the resin-shaped body. The extremely small gap can maintain excellent adhesion strength and airtightness between the aluminum body, the copper body and the resin body. In the present invention, the plurality of concave portions formed by the uneven portions on the surface of the aluminum-shaped body and the copper-shaped body are described with reference to the first drawing showing the cross section of the aluminum-shaped body and the copper-shaped body. The cross section in the thickness direction of each of the body and the copper body is measured by scanning electron microscope observation on the intermediate line between the top line passing through the highest portion passing through the uneven portion and the bottom line passing through the deepest portion in the thickness direction. The opening width of the opening width of 01 μπ 1 or more and 30 μm or less is preferably 〇·5 μm or more and 20 μm or less, more preferably Ιμηι or more and 1 〇μηι or less; and the depth is 〇1 μm or more and 30 μm or less or less, preferably 0·5 μηι or more. 20μιη below. If the concave portion has an opening width of 0. The 1 μm narrow N resin does not easily enter, and fine voids are formed at the interface between the aluminum body and the copper body and the resin body, and it is difficult to obtain excellent adhesion -11 - 201144075 strength and air tightness; conversely, if it is more than 30 μπι When the surface treatment (etching treatment) of the aluminum-shaped body and the copper-shaped body is wide, the dissolution reaction is excessively performed, and the problem of the surface defect or the decrease in the thickness of the material is increased, and the material strength is insufficient. The product is a cause of reduced productivity. In addition, regarding the depth is also, if it is 0. When 1 μm is shallow, it is difficult to obtain a sufficient embedded portion of the resin-shaped body; on the contrary, when it is deeper than 30 μm, in the surface treatment (etching treatment) of the aluminum-shaped body and the copper-shaped body, the dissolution reaction proceeds excessively, and the material is generated. In the present invention, the density of the plurality of concave portions formed by the uneven portions on the surface of the aluminum body and the copper body body is 0. 1 mm square, opening width 0·5μηι~20μπι and depth 0. One or more of the sizes of 5 μηι to 20 μιη can exist in the range of 5 to 200. Further, in the aluminum-shaped body and the copper-shaped body of the present invention, the ferrule-like projection formed in the concave portion is preferably an aluminum-resin and copper-resin integrally formed portion of the aluminum-resin-copper composite. The cross-sectional direction in the thickness direction is an observation line extending from the resin-shaped body side toward the aluminum-shaped body side or the copper-shaped body side in the thickness direction. When a plurality of strips are pulled at intervals of 1 μm, at least one or more laminated portions composed of a resin-aluminum-resin or a resin-copper-resin may be formed on one observation line, and the aluminum-shaped body or the copper-shaped body portion of the laminated portion may be formed. The thickness is 0. In the range of 1 μm or more and 3 Ομηη or less, in the aluminum-resin-copper composite, more than one snow-like projection may be present in the range of 1,000 observation lines. In addition, the plurality of concave portions of the aluminum shape body and the copper shape body may have at least one or more inner concave portions on the inner wall surface and have a double concave portion structure in part or all of a -12-201144075. At least one or more internal protrusions are formed on the inner wall surface to have an internal concavo-convex structure, and a double concave portion structure and an internal concavo-convex structure may be present at the same time. In part or all of a plurality of concave portions of the aluminum body and the copper body, the concave portion and the resin shape of the aluminum body and the copper body can be formed by the double recessed portion structure or the inner uneven structure. The embedded portions are joined to each other more strongly, and exhibit more excellent adhesion strength and airtightness between the aluminum body and the resin body, and between the copper body and the resin body. [Manufacturing Method of Aluminum-Resin-Copper Composite] In the present invention, in order to manufacture the above-described aluminum-resin-copper composite, first, an aluminum body having the plurality of desired concave portions is formed on the surface and In the copper-shaped body, for example, the aluminum alloy material and the copper alloy material are subjected to an etching treatment to form a concave-convex portion on a part or the entire surface of the surface, thereby forming a plurality of concave portions due to the uneven portion. A method of an aluminum shape body and a copper shape body. Examples of the etching liquid used for the etching treatment of the aluminum alloy material include hydrochloric acid, phosphoric acid, sulfuric acid, acetic acid, oxalic acid, ascorbic acid, benzoic acid, butyric acid, citric acid, formic acid, lactic acid, isobutyric acid, malic acid, and propionic acid. An etching solution comprising an aqueous acid solution such as tartaric acid; a plurality of concave portions having an opening width and a depth having a desired size; or a central portion protruding toward the opening width direction in order to form an opening edge portion of a part or all of the concave portion The snow-like protrusion or the like, that is, in order to form the concave shape of the surface formed in the surface - 13- 201144075 into a desired shape and size, as an acid aqueous solution, an aqueous acid solution having a weak oxidizing power is used, and the oxidation is performed. In the acid aqueous solution having a weak force, in order to dissolve the oxide film formed on the surface of the aluminum alloy material, it is necessary to use an etching liquid containing a predetermined concentration of halogen ions. That is, the etching liquid which can be used as the etching liquid is selected from the group consisting of chloride ion (Cl~), fluorine ion (F·), and iodide ion (1_) in an aqueous acid solution having a weak oxidizing power. Any one or two or more kinds of halogen ions. When an aqueous acid solution having a weak oxidizing power such as a halogen ion is used, if an aluminum alloy material is immersed in the etching liquid, first, the halogen ions in the etching liquid dissolve the oxide film on the surface of the aluminum alloy material, and then the aluminum inside is dissolved. The alloy is dissolved and further etched into the interior of the aluminum alloy. At this time, since the inner aluminum alloy is more easily eroded (easy to dissolve) than the surface oxide film, by setting the composition of the etching liquid and the conditions of the etching treatment, etc., The concave portion of the uneven portion formed on the surface can be controlled to have a desired width and depth, or a snow-like projection protruding toward the center in the opening width direction at a part or all of the opening edge portion. unit. The etching solution used for the above-mentioned purpose is, as an acid aqueous solution, a hydrochloric acid solution, a phosphoric acid solution, a dilute sulfuric acid solution, and an acetic acid having an acid concentration of 5 wt% or more and 80 wt% or less (preferably 10 wt% or more and 50 wt% or less). a solution or the like, an oxalic acid solution having an acid concentration of 5 wt% or more and 30 wt% or less (preferably 10 wt%/〇 or more and 20 wt% or less); and a halogenation added for introducing a halogen ion into the aqueous acid solution. Examples of the material include fluorides such as chlorides such as sodium chloride, potassium chloride, magnesium chloride, and aluminum chloride, and bromide such as potassium bromide. Considering safety, etc. -14- 201144075 is chloride, in addition, the halogen ion in the etching solution is usually 0. 5 g / L or more is less than 300 g / L, preferably 1 g / L or more and 100 g / L or less; if not up to 0. 5 g/L, the effect of the halogen ion is small, and the concave portion having the ferrule-like projection cannot be formed at the edge of the opening, and in the case of the surface treatment (etching treatment) of the aluminum-shaped body at a temperature exceeding 300 g/L The dissolution reaction proceeds abruptly, making it difficult to control the concave portion. Further, in the present invention, an etching solution for forming a desired concave portion on the surface of an aluminum-shaped body, a strong aqueous solution of oxidizing acid such as nitric acid or concentrated sulfuric acid having a concentration of more than 80% by weight, sodium hydroxide or potassium hydroxide, or the like. Alkaline solutions are not suitable. An aqueous acid solution having a strong oxidizing power such as nitric acid or concentrated sulfuric acid has a film forming ability for the aluminum alloy, and a strong oxide film is formed on the surface of the aluminum body, which makes it difficult to dissolve the oxide film by the halogen ions. In addition, the alkaline solution such as sodium hydroxide and potassium hydroxide is completely soluble in the dissolution mechanism of the aluminum alloy, and the tendency is not changed even in the case of adding a halogen ion, and it is difficult to form a desired concave portion. . In the present invention, the processing conditions when the surface of the aluminum-shaped body is subjected to an etching treatment using the etching liquid are a plurality of concaves to be formed on the aluminum-shaped body depending on the type of the etching liquid to be used, the acid concentration, the concentration of the halogen ions, and the concentration of the halogen ions. The number and size of the shapes may vary. Generally, in the case of a hydrochloric acid solution, a bath temperature of 20 to 80 ° C and an immersion time of 10 minutes may be employed, and in the case of a phosphoric acid solution, a bath temperature of 30 to 80 ° C may be employed. The immersion time is in the range of 1 to 5 minutes. In the case of the sulfuric acid solution, the bath temperature may be 40 to 80 ° C, and the immersion time may be in the range of 2 to 8 minutes. In the case of the oxalic acid solution, the bath temperature may be 50 to 80 ° C, and the immersion time may be employed. For the range of 1 to 3 minutes, in the case of an acetic acid solution, a bath temperature of 50 to 80 ° C, -15 to 201144075, and an immersion time of 1 to 3 minutes may be employed. The higher the acid concentration and the bath temperature of the etching liquid to be used, the more remarkable the etching effect, and the shorter the time. Regarding the bath temperature, it takes a long time to form a concave portion having a sufficient size (opening width and depth) when the dissolution rate is slow at 20 ° C, and the dissolution reaction proceeds rapidly at a bath temperature exceeding 80 ° C. It is difficult to control the width and depth of the opening of the concave portion; and with respect to the immersion time, it is difficult to control the width and depth of the opening of the concave portion in less than one minute, and the immersion time exceeding 10 minutes in the opposite direction may become a decrease in productivity. the reason. Further, as the etching liquid used for the etching treatment of the copper alloy material, an aqueous acid solution having an acid concentration of any one selected from the group consisting of sulfuric acid and oxalic acid can be used. 1% fi% or more and 60% by weight or less, preferably 0. 5 wt% or more and 50 wt% or less, and contains a halogen ion of 0. 01g/L or more 1. 0g/L or less, preferably 〇. 〇5 g/L or more 0. The range below 5g/L contains hydrogen peroxide or cerium nitrate. Lg/L or more is 300 g/L or less, preferably 10 g/L or more and 100 g/L or less. Here, when the acid concentration is less than 0. In the case of % by weight, the dissolution reaction becomes extremely slow, and the problem of almost impossible etching occurs; if it exceeds 60% by weight, the dissolution reaction becomes too fast, and an uncontrollable problem occurs. In addition, when the concentration of hydrogen peroxide or nitric acid is less than 0. In the case of 1 g/L, the effect of adding hydrogen peroxide or nitric acid to promote the copper dissolution reaction is not good. On the contrary, if it exceeds 300 g/L, the dissolution reaction becomes too fast, and an uncontrollable problem occurs. Furthermore, when the halogen ion concentration is not reached. In the case of 〇1 g/L, there is a problem that the dissolution rate cannot be controlled (constant), if it exceeds l. 〇g/L has a problem that the dissolution reaction is remarkably lowered. -16- 201144075 Further, a halogen ion is used to form a protective copper oxide layer on the copper surface, and a protective cuprous oxide film is formed thereon. On the other hand, since the cuprous oxide film is not dense and has defective portions everywhere, a part of the copper surface can be dissolved to form uneven portions. Further, the same reaction occurs in the formed concave portion, and the finally formed concave portion has a special structure in which the opening width is narrower than the inner width dimension. Therefore, if the content of the halogen ion is more than the above-mentioned amount, the etching film is covered with the copper film surface by the highly protective oxide film, and the etching rate is extremely low. On the other hand, when the content is less than the predetermined amount, the opposite cannot be formed. The highly protective film is uniformly dissolved and it is difficult to form uneven portions on the surface. The halogen ion to be added to the acid aqueous solution for the etching liquid may be any one or two or more selected from the group consisting of chloride ion (cr), fluoride ion (F-), and iodide ion (I-), and the etching liquid may contain a predetermined one. The halogen ions of the concentration range. Examples of the halide to which the halogen ion is added to the aqueous acid solution include a chloride such as sodium chloride, potassium chloride, magnesium chloride or aluminum chloride, a fluoride such as calcium fluoride, or a bromine such as potassium bromide. Compounds, etc. In view of safety, etc., it is preferably chloride. In addition, the acid aqueous solution used as the etching liquid of the above-mentioned copper alloy material, in order to dissolve the copper after oxidation, can be used as needed. 01 g / L or more in the range of 100g / L or less (preferably 0. One or two or more organic acids are added in an amount of 1 g/L or more and 80 g/L or less. Examples of the organic acid added to the etching solution for this purpose include glycolic acid, formic acid, acetic acid, propionic acid, oxalic acid, and propylene glycol acid. Among them, glycolic acid is particularly preferred. Furthermore, in the uranium engraving of copper alloy materials, in order to prevent oxidation of the surface of -17-201144075 copper after roughening, it can be smashed. 〇 lg / L or more in the range of 100g / L or less (preferably O. One or two or more kinds of azole compounds are added in an amount of lg/L or more and 80 g/L or less. The azole compound added to the etching solution for this purpose is, for example, benzotriazole, tolyltriazole or the like, and particularly preferably benzotriazolium, in the etching solution of the copper alloy material, when The amount of organic acid added is less than 0. In the case of 01 g/L, the solubility of copper after oxidation is lowered to cause the residual copper oxide, which is not preferable because the resin bondability is lowered. On the other hand, in the case of more than 100 g/L, the dissolution stability of copper is deteriorated, and reoxidation occurs on the copper surface. In addition, when the above azole compound is added in an amount of less than 0. In the case of 0 1 g/L, it is impossible to suppress oxidation of the copper surface after roughening, and discoloration may occur. On the other hand, in the case of l〇〇g/L or more, the dissolution reaction of copper is remarkably suppressed, and occurs. The problem that the dissolution reaction cannot progress is in the present invention, and the treatment conditions in the case where the surface of the copper-shaped body is subjected to an etching treatment using the above etching liquid can be carried out at a bath temperature of 20 to 80 ° C and an immersion time of 0. 5 to 30 minutes range. The higher the acid concentration and the bath temperature of the etching liquid to be used, the more remarkable the etching effect, and the shorter the time. Regarding the bath temperature, it takes a long time to form a concave portion having a sufficient size (opening width and depth) when the dissolution rate is slow at 20 t, and the dissolution reaction is rapidly performed at a bath temperature exceeding 80 ° C. The control of the opening width and depth of the concave portion becomes difficult; and the immersion time is less than 0. The control of the opening width and depth of the concave portion is difficult at 5 minutes, and the immersion time exceeding 30 minutes on the contrary may cause a decrease in productivity. -18- 201144075 In the present invention, it is necessary to form an aluminum-shaped body and a copper-shaped body having a concave portion as described above for the treatment of an aluminum alloy material and a copper alloy (for degreasing, surface conditioning, removal of surface deposits), in the etching Pre-treatment of the aluminum alloy material and/or copper alloy before treatment, the pretreatment comprises: using an aqueous acid solution or using an alkaline solution for alkali treatment. Here, as an acid aqueous solution used for the pretreatment, an acid reagent is prepared by a commercially available acidic degreaser; the acid reagent includes: sulfuric acid, nitric acid, hydrofluoric acid, phosphoric acid, acetic acid, lemon An organic acid such as an acid is mixed with the acids and the like. Further, as the alkaline aqueous solution, for example, it may be prepared by a degreasing agent, a basicity such as sodium hydroxide or the like, or a mixture of these. The operation method and treatment conditions using the above aqueous acid solution and/or alkaline aqueous solution can be carried out by a conventional method and treatment using an alkaline aqueous solution, for example, by a dipping method, a spray method, or the like. Come on. In addition, after the surface treatment of the alloy material and/or the copper alloy material, or after the etching treatment for forming the concave portion, a water washing treatment may be performed, and the water washing treatment may use industrial water tap water, ion exchange water, etc., according to The choice of copper to be made. Further, the copper after the pre-treatment or the etching treatment is subjected to a drying treatment as needed, and the drying treatment is also natural drying at room temperature, and when etching is performed using a blowing or drying material, the material can be used according to the contaminant. The surface is acid-treated, and if it is prepared by using an alkaline acid commercially available as a mixed acid derived from a prepared inorganic acid, the aqueous acid solution or the conditions are the same, and the groundwater can be used as needed. , the shape and the appropriate alloy material 'can be, except for the placer, oven, etc. -19- 201144075 for forced drying. The surface of the aluminum-shaped body and the copper-shaped body obtained by the above-described etching treatment, pretreatment, and etching treatment is a concave-convex portion after the etching treatment, and the surface glossiness of the surface is 60 degrees (used by the SUGA testing machine company) The measurement of the type of gloss meter is preferably 60 degrees or less, or the surface roughness measuring device (measured by SURFCOM 590A-DTP manufactured by Tokyo Seimitsu Co., Ltd.) or the laser microscope (measured by 1LM21W manufactured by Lasertec). Roughness (Rz) Ιμιη or more. When the surface glossiness exceeds 60 or the surface roughness (Rz) is 1 μm or less, the resin does not sufficiently enter the concave portions of the aluminum body and the copper body, and the aluminum body, the copper body, and the resin body Sufficient joint strength cannot be obtained. Further, the surface of the aluminum-shaped body and the copper-shaped body obtained by the above etching treatment, or pre-treatment and etching treatment was observed by a SEM or an optical microscope at a magnification of 1,000 times, and the obtained cross-sectional photograph was compared. The surface area of the aluminum-shaped body and the copper-shaped body is preferably a surface area of the aluminum alloy material or the copper alloy material before the uneven portion is formed by etching. 2 times or more 1 〇 or less. The surface area increase rate is less than one. When the resin is not doubled or more than 10 times, the resin does not sufficiently enter the concave portion of the aluminum-shaped body and the copper-shaped body, and sufficient bonding strength cannot be obtained between the aluminum-shaped body and the copper-shaped body and the resin-shaped body. Further, in order to obtain the aluminum-resin-copper composite of the present invention, the metal or resin may be bonded after the surface of the aluminum-shaped body and the copper-shaped body thus obtained are coated with an adhesive; or in the shape of the aluminum produced. a body and a copper-shaped body and an intermetallic intervening resin, which are joined by applying heat and pressure by a hot press; or -20-201144075, the obtained aluminum shape body and the copper shape body are placed into the forming mold, toward In the mold, a predetermined thermoplastic resin after melting is emitted and solidified, whereby an aluminum body and a copper body are combined by a resin to produce a desired aluminum body, a copper body, and a resin composite. Here, the thermoplastic resin used for producing the aluminum-resin-copper composite of the present invention can be used alone, in consideration of the physical properties, use, and use of the aluminum-resin-copper composite of the present invention. Environment and the like are preferably used as the thermoplastic resin: for example, a polypropylene resin, a polyethylene resin, an acrylonitrile-butadiene-styrene copolymer (ABS), a polycarbonate resin, a polyamide resin, a polyphenylene sulfide (PPS), or the like. Polyaryl sulfide resin, polyacetal resin, liquid crystalline resin, polyester resin such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT), poly A formaldehyde resin, a polyimide resin, a para-type polystyrene resin, or the like, and a mixture of two or more of these thermoplastic resins. Further, in order to further improve the adhesion between the aluminum-shaped body and the copper-shaped body and the resin-shaped body, mechanical strength, heat resistance, dimensional stability (resistance to deformation, bending, etc.), electrical properties, etc., it is more preferable To the thermoplastic resin, a filler such as a fibrous form, a powder form, or a plate form, or various elastomer components are added. In addition, examples of the chelating agent to be added to the thermoplastic resin include inorganic fiber entangled materials such as glass fiber, carbon fiber, metal fiber, asbestos fiber, and boron fiber, and high in polyamide, fluororesin, and acrylic resin. Melting point organic fiber enthalpy, quartz powder, glass beads, glass powder, powdered sputum such as inorganic powders such as calcium carbonate, bismuth silicates of glass flakes, talc, mica, etc. The filler or the like is added in an amount of 25 parts by weight or less, preferably 0 parts by weight or more and 200 parts by weight or less, more preferably 100 parts by weight or more to 100 parts by weight or less based on the thermoplastic resin - 21,044,075, 5% by weight. The following range. When the amount of the chelating agent added exceeds 250 parts by weight, the fluidity is lowered and it becomes difficult to enter the concave portion of the aluminum-shaped body and the copper-shaped body, and a good adhesion strength cannot be obtained, and the mechanical properties are deteriorated. In addition, as the elastomer component to be added to the thermoplastic resin, an elastomer such as a polyurethane-based core-shell type, an olefin type, a polyester type, a guanamine type, or a styrene type can be exemplified, and a thermoplastic resin at the time of injection molding can be considered. The melting temperature and the like are selected, and the amount thereof is 30 parts by weight or less, preferably 3 to 25 parts by weight, based on 100 parts by weight of the thermoplastic resin. When the addition S of the elastomer component exceeds 30 parts by weight, no further effect of improving the adhesion strength is observed, and problems such as deterioration of mechanical properties occur. The blending effect of the elastomer component is particularly remarkable when a polyester resin is used as the thermoplastic resin. Further, in the thermoplastic resin for producing the aluminum resin-copper composite of the present invention, a known additive which is generally added to a thermoplastic resin, that is, a flame retardant or a dye, may be appropriately added in accordance with the required properties. a coloring agent such as a pigment, a stabilizer such as an antioxidant or an ultraviolet absorber, a plasticizer, a lubricant, a lubricant, a mold release agent, a crystallization accelerator, a crystal nucleating agent, etc., in the present invention, an aluminum body and When the copper-shaped body is placed in the molding die and the thermoplastic resin is injection-molded, the molding conditions required for the thermoplastic resin can be used. However, the molten thermoplastic resin is surely entered into the aluminum-shaped body and copper during the injection molding. It is important to cure in the concave portion of the shape body -22- 201144075. Therefore, it is preferable to set the mold temperature and the cylinder temperature to be high within the range allowed by the type, physical properties, and molding cycle of the thermoplastic resin, particularly regarding the mold temperature. The lower limit temperature must be set to 9 〇t or more, preferably 1300 ° C or higher; the upper limit temperature can be set according to the type of thermoplastic resin used. The temperature range of 1 0 0 °c~ is lower than the melting point or softening point of the thermoplastic resin (which is the higher melting point or softening point in the case where the elastomer component is added). Further, the lower limit mold temperature is preferably set so as not to be lower than the melting point of the thermoplastic resin by 140 ° C or higher. Further, as the resin for producing the aluminum-resin-copper composite of the present invention, in addition to the above thermoplastic resin, a thermosetting resin, a room temperature hardening resin, various adhesives, or the like can be used. The thermosetting resin may, for example, be an epoxy resin. The room temperature curable resin may, for example, be a polyester resin. Further, examples of the adhesive include a nitrile rubber type, a synthetic rubber type, an epoxy type, a cyanoacrylic type, a vinyl chloride type, a plastic type, and a hot melt type. Here, the 'product of the resin-copper composite produced by the method of the present invention' is a structure in which an aluminum-shaped body made of an aluminum alloy and a copper-shaped body made of a copper alloy are integrally joined by a resin-shaped body. However, it is suitable for any product, but it is based on the interface between the aluminum body and the resin body (aluminum/resin interface) and the interface between the copper body and the resin body (copper/resin interface) and airtightness. The extremely high characteristics are preferably a cover member for a sealed battery. The cover member for a sealed battery includes, for example, an aluminum sealing cap member made of an aluminum alloy, an aluminum alloy terminal made of an aluminum alloy, a copper alloy terminal made of a copper alloy, and a sealing insulating resin; and the aluminum sealing cover member; a through hole having a pair of mutually spaced intervals of -23-201144075; the terminal ' is formed in each of the through holes of the aluminum sealing cover member, and a predetermined gap is formed with the peripheral portion thereof; the sealing is insulated In the resin, the peripheral edge portion of each of the through holes of the aluminum plug cover member and the gap between the terminals are sealed. The lid member for a sealed battery is an aluminum-resin-copper composite in which the aluminum plug cap member and the aluminum alloy terminal are subjected to surface roughening etching treatment to have a bump formed by a part or a whole of the surface. a plurality of concave portions of the portion; the copper alloy terminal is a plurality of concave portions having a concavo-convex portion formed by a part or a whole of the surface by the roughening etching treatment; the aluminum-resin-copper composite is One of the resin-shaped bodies and the other resin-shaped body, the one-to-one resin-shaped body having the above-mentioned plugging insulating resin into the aluminum sealing cap member (aluminum-shaped body) and the aluminum alloy terminal (aluminum-shaped body) a plurality of embedded portions that are solidified in each of the concave portions, thereby integrally joining the aluminum sealing cover members and the aluminum alloy terminals; and the other resin shaped body having the plugging insulating resin enters the foregoing a plurality of embedded portions which are solidified in each of the concave portions of the aluminum sealing cover member (aluminum shaped body) and the copper alloy terminal (copper shaped body), thereby forming the aluminum sealing cover The parts are integrated with the copper alloy terminals. The aluminum-resin-copper composite of the present invention has an adhesion strength between an interface between an aluminum body and a resin body (aluminum/resin interface) and an interface between a copper body and a resin body (copper/resin interface) and It has extremely high air tightness and maintains its excellent adhesion strength and air tightness even when exposed to harsh environments, maintaining high reliability for a long time. Therefore, the aluminum-resin-copper composite of the present invention is mainly applied to a cover member for a sealed battery, and is particularly suitable for: a resin shape. 24 · 201144075 A body is butted from a part of an aluminum body and a surface of a copper body A metal-resin composite that is outstanding and requires high bonding strength. Further, in the method for producing an aluminum-resin-copper composite according to the present invention, the obtained product can be predicted by measuring the surface gloss of the aluminum body or the surface roughness of the aluminum body and the copper body at the time of manufacture. The adhesion strength 'is therefore easy to manage quality at the time of manufacture, and each product has almost no difference in adhesion strength, and a highly reliable product can be produced. [Embodiment] Hereinafter, preferred embodiments of the present invention will be specifically described based on examples and comparative examples. Further, the present invention is not limited to the examples described below. [Example 1] [Modulation of aluminum shaped body] Two misaligned terminals for posiTEST test (Dolly, manufactured by DeFelsko Co., Ltd., size 20 mm (|), JISA 1100) were first impregnated at room temperature in a 30 wt% nitric acid solution. After a minute, it was sufficiently washed with ion-exchanged water. Then, it was immersed in a 5 wt% sodium hydroxide solution at 50 t for 1 minute, and then washed with water. Further, it was further immersed in a 30 wt% nitric acid solution at room temperature for 3 minutes, and then washed with water. deal with. Next, the above pre-treated terminals are placed in an etchant (at 2. 5 wt % hydrochloric acid solution was added to the solution of 54 g / L of ammonium chloride hexahydrate, and the mixture was immersed at 66 ° C for 4 minutes, and then washed with water, thereby performing an etching treatment, and further impregnating at room temperature in a 3 Owt% nitric acid solution. After a minute of water washing, use a 120-25-201144075 澧 shape. Aluminium products (samples for the evaluation of the sample price of the aluminum test with two test results for the measurement of the weight, the charge of the pendulum stretched 5 into dry for the wind to use the heat is its [modulation of the copper shape] from the thickness of lmm A copper alloy (C1100) plate was cut into two pieces of copper (copper alloy) having a size of 50 mm x 50 mm, and the copper piece was first immersed in a 1 wt% hydrochloric acid solution for 1 minute, and then sufficiently washed with ion-exchanged water, followed by The pretreatment was carried out by immersing in a 5 wt% sodium hydroxide solution at 50 ° C for 1 minute and then washing with water. Next, the pretreated copper sheet was placed in an Alpha-prep PC-7030 solution (manufactured by Meltex Co., Ltd.). After immersing at 40 ° C for 1 minute, it was washed with water and dried by hot air at 120 ° C for 5 minutes to prepare two copper test pieces (copper-shaped bodies) which were used for evaluation samples for tensile load measurement tests. Observation of the surface concave portion of the test piece (aluminum-shaped body) and the copper test piece (copper-shaped body)] For the obtained aluminum test piece and copper test piece, a section of a section in the thickness direction section was scanned using a scanning electron microscope ( Hitachi FE-SEM, S-45 00 type In the cross section in the thickness direction of the aluminum body or the copper body, the top line which is perpendicular to the thickness direction and passes through the highest portion of the uneven portion is determined, and then the aluminum body or the copper shape is determined in substantially the same manner as described above. The thickness direction of the body is orthogonal and passes through the bottom line of the deepest portion of the concave and convex portion. Next, the vertical line is drawn from the top line toward the bottom line, and then pulled out through the middle portion of the line and parallel to the top line (or the bottom line). In the middle line, the distance between the aluminum-shaped body and the aluminum-shaped body or the gap between the copper-shaped body and the copper-shaped body on the intermediate line is taken as the opening width of the concave portion, and the aluminum test piece and the aluminum test piece are observed. The shape and size (opening width and depth) of the concave portion formed on the surface of the copper test piece were measured and measured. In the cross section of the observed aluminum test piece and the copper test piece, for example, the first figure As shown in the schematic cross-sectional view, a typical example of the shape of the concave portion that can be recognized from the first figure includes, as shown in Fig. 2, a snowball shape from a portion of the opening edge portion toward the center of the opening width. The concave portion of the protruding portion (the shape a, see FIG. 2( a )) has a concave portion (shape b) which protrudes from the entire opening edge portion toward the center in the opening width direction. 2(b)), a concave portion having a double concave portion structure (a shape c, see FIG. 2(c)) in which a concave portion is further formed inside, and an internal protrusion portion is formed on the inner wall surface to have an internal concavo-convex structure In the concave portion (shape d, see Fig. 2(d)), all the concave portions having the shapes a to d can be observed in the first embodiment. Further, the shape of the concave portion is changed even if the observation position is changed. In the same manner, the evaluation of the shape of the concave portion of Examples 1 to 5 and Comparative Examples 1 to 3 was evaluated as good (〇) in the case of having one or two or more of the above-described shapes a to d. In the case where none of the shapes a to d existed, it was evaluated as defective (X). Further, the size (opening width and depth) and the ratio of the concave portion observed in the cross section of a certain area of the aluminum test piece and the copper test piece were measured at each o. Lmm square, opening width 0. The concave portion of 1μιη~1μπι has 10~100, the concave width of the opening width Ιμπι~10 μηι has 1~10, the opening -27- 201144075 The width Ιίμιη~30μιη of the concave part has 1~3 'depth in Hey. Ίμηι~30μηι range. Further, the size (opening width and depth) and the ratio of the inner concave portion of the double concave portion structure are also 'substantially the same as described above' at every 0. 1mm square, opening width Ο. Ίμιη~Ιμπι has a concave portion of 1〇~5〇, and the opening width Ιμπι~ΙΟμηι has a concave portion of 1~50' opening width Ιίμηι~30μιη has 1~2 concave portions, and the depth is Ο. Ίμιη~20μηι range. The size of the concave portion is also almost unchanged even when the observation position is changed. Further, regarding the evaluation of the size of the concave portion of Examples 1 to 5 and Comparative Examples 1 to 3, the opening width was 〇. The evaluation in the range of 1 to 30 μm and the depth of 0·1 to 30 μm was evaluated as good (〇), and the case where the range was exceeded was evaluated as defective (X). [Evaluation of Surface Gloss of Aluminum Test Piece and Copper Test Piece] For each of the obtained aluminum test piece and copper test piece, a 60-degree gloss of the surface was measured using a portable gloss meter (manufactured by SUG® Test Machine Co., Ltd.). The average enthalpy of the two was calculated as the 60 degree gloss of the aluminum test piece and the copper test piece. The aluminum test piece was 30 and the copper test piece was 10. [Evaluation of surface area increase rate of aluminum test piece (aluminum shape body) and copper test piece (copper shape body)] With respect to the obtained two aluminum test pieces and three copper test pieces, the magnification was 1 by SEM or an optical microscope, respectively. The cross section was observed twice, and the obtained cross-sectional observation photograph was measured for the surface area of the surface of the aluminum-shaped body and the copper test piece using an image processing software (ImageJ). The proportion of the surface area increase on the surface of each aluminum test piece was determined with respect to the untreated aluminum alloy material -28-201144075, and the ratio of the surface area increase of the surface of each copper test piece was determined with respect to the untreated copper alloy material, and the calculation was performed. The average number of turns obtained is defined as the rate of increase in surface area. As a result, the aluminum test piece was 3. 3 times, the copper test piece is 1. 9 times. [Preparation of Evaluation Test Body [Joining of Resin (Adhesive) Using Adhesive]] As shown in Fig. 3, the obtained copper test piece (copper shape) 1 and aluminum test piece (aluminum shape) The terminal 5 is joined by a two-liquid mixing type epoxy-based rapid-hardening adhesive (manufactured by Huntsman Advanced Materials, trade name: Aral dite Rapid) 4 and then pressed by a hot press (AH-2003 manufactured by AS ONE). Hey. 1 Μ P a is subjected to normal temperature pressurization, and is pressed for 24 hours, and then the excess adhesive 4 extruded from the joint between the copper test piece 1 and the aluminum test piece terminal 5 is used after the adhesive is cured. The cutter is separated from the joint surface and adjusted to a joint surface of 3. 14 cm2, an aluminum test piece-adhesive-copper test piece (test piece for evaluation) was produced. [Preparation of Test Test Body (Joining by Resin by Heating and Pressure Bonding)] As shown in Fig. 4, on the obtained copper test piece (copper-shaped body) 1, the unit area was doubled. A pellet (resin) 6 of a polyphenylene sulfide resin (manufactured by Polyplastics Co., Ltd.) was placed on a 〇4 g/cm2, and an aluminum test piece terminal 5 was placed thereon, and a hot press (AH-2003 manufactured by AS ONE) was used to press the pressure O. . IMPa, plate temperature 300 °C for thermocompression bonding, making resin to -29- 201144075 3. Aluminum test piece-resin-copper test piece (test piece for evaluation) which was bonded to a joint area of 14 cm 2 . [Evaluation of the tensile strength of the joint surface by the posi TEST tester] For each of the above-mentioned evaluation test bodies, the aluminum-resin joint surface was measured by the test method of ASTM D454 1 (ISO 4624) using a posiTEST tester (manufactured by DeFelsko Co., Ltd.). Tensile strength (terminal size: 20ιηιηφ, analytical ability: ±0. 01MPa, accuracy: ±1%, measuring range: 0~20MPa). In the posiTEST test, as shown in Fig. 6, the aluminum test piece terminal 5 (or 7) of the evaluation test piece is connected to the actuator 8 of the posiTEST tester through the aluminum test piece terminal fixing jig 9. After that, the load (the peeling load) when the terminal 5 (or 7) was peeled off from the copper test piece (copper-shaped body) 1 was measured by applying a pressure to the pump, and the aluminum test piece terminal 5 and the copper test piece 1 after peeling were examined. The peeling state of the joint. The peeling load of the test piece for evaluation was 5. In the case of the aluminum test piece-adhesive-copper test piece. 5 MPa, in the case of an aluminum test piece-resin-copper test piece. 7MPa. Further, regarding the observed peeling state, it was evaluated that the adhesive or the resin remained intact throughout the joint surface of the aluminum test piece or the copper test piece, and only a part remained on the side of the aluminum test piece or the copper test piece. The case was evaluated as local good (Δ), and the case where the aluminum test piece side did not remain (interfacial peeling) was evaluated as poor (X); the evaluation results were all good (〇) [Aluminum-resin-copper layer observation Evaluation] -30- 201144075 In addition, as shown in Fig. 7, the test bodies for evaluation of the two types prepared are aluminum test piece, adhesive-copper test piece, aluminum test piece-resin-copper test piece. The aluminum test piece is cut in the thickness direction from the resin (adhesive) laminated thereon, and the thickness direction cross section is SEM or optical. The micromirror was observed at a magnification of 1 〇〇〇. With respect to the obtained cross-sectional observation photograph, the observation line (OL) extending from the resin-shaped body 2 side toward the aluminum-shaped body 1 side in the thickness direction was separated from each other by 0. When a plurality of strips are drawn at intervals of 1 μm, at least one or more laminated portions composed of a resin (adhesive)-aluminum-resin (adhesive) are present on one observation line (OL), and the aluminum-shaped body of the laminated portion is present. The thickness of the part is Ο. Ίμηι is not more than 30μπι, and the case where one or more observation lines (OL) exist in one or more ratios is evaluated as good (〇), and a layer of 1 000 observation lines (〇L) is connected in a layer. The case where the department did not exist was evaluated as bad (X), and as a result, all cases were good (〇). Further, the copper test piece side was also measured in the same manner, and as a result, all cases were good (〇). Further, the following Examples 1 to 5 and Comparative Examples 1 to 3 were also evaluated on the same basis. [Example 2] An aluminum test piece (aluminum shape body) and a copper test piece (copper shape body) were produced in the same manner as in Example 1 except that a MoldPrep LF solution (manufactured by ATOTECH Co., Ltd.) was used for the etching treatment of copper. Then, an aluminum test piece-resin (adhesive)-copper test piece was produced using the same adhesive and resin as in Example 1, and was carried out in the same manner as in the above-described Example 1 -31 - 201144075: the above aluminum test piece and copper The concave portion of the surface of the test piece was observed, and the glossiness was measured, the posiTEST test, and the observation of the laminated portion of aluminum-resin and copper. The results are shown in Table 1 together with the results of Example 1. [Example 3] An aluminum test piece (aluminum shape body) and a copper test piece (copper shape body) were produced in the same manner as in the above Example 1 except that C 1 020 was used as the copper alloy sheet from which the copper sheet was cut out. An aluminum test piece/resin (adhesive)-copper test piece was produced using the same adhesive and resin as in Example 1, and the surface of the aluminum test piece and the copper test piece was carried out in the same manner as in the above-described Example 1. Observation of the concave portion, measurement of glossiness, posiTEST test, and observation and evaluation of the laminated portion of aluminum-resin-copper. The results are shown in Table 1 together with the results of Example 1. [Example 4] Adding a nitric acid solution of 150 g/L and sodium chloride in a 400 g/L sulfuric acid solution. 2g / L, benzotriazole l 〇 g / L, 5-aminotetrazole l 〇 g / L and prepared into an etching solution (chloride ion concentration 〇. 〇8g/L) An aluminum test piece (aluminum shape) and a copper test were produced in the same manner as in the above Example 1 except that the etching treatment of copper was changed to immersion in the etching solution at 60 ° C for 1 minute and then water washing. A sheet (copper-shaped body), and then an aluminum test piece-resin (adhesive)-copper test piece was produced using the same adhesive and resin as in Example 1, and the aluminum test was carried out in the same manner as in the case of the above-described Example 1. Observation of the concave portion of the surface of the sheet and the copper test piece and measurement of the glossiness of the posiTEST test, aluminum-resin-copper-32-201144075. The results are shown in Table 1 together with the results of Example 1. [Examples. 5]. An aluminum piece (aluminum alloy material) having a size of 50 mm x 50 mm was cut from an aluminum alloy (JIS A 1 0 0 0 ) plate having a thickness of 1 mm, and the aluminum piece was etched in an etching solution (at 2. 5 wt% hydrochloric acid solution was added to the solution of 54 g/L of ammonium chloride hexahydrate, and the mixture was immersed in 66 t for 4 minutes, and then washed with water to carry out an etching treatment. Then, it was immersed in a 30 wt% nitric acid solution at room temperature for 3 minutes, and then washed with water. It was dried by hot air at 120 ° C for 5 minutes to prepare an aluminum test piece (aluminum shaped body). Further, in the same manner as in Example 1, a copper test piece (copper-shaped body) subjected to an etching treatment was produced. Next, as shown in Fig. 5, the aluminum test piece (aluminum body) 13 and the copper test piece (copper shape) 1 were placed in a mold of an injection molding machine (ST10R2V manufactured by NISSEI Co., Ltd.) (not shown). In the inside, a polyphenylene sulfide resin (manufactured by Polyplastics Co., Ltd.) was used as the thermoplastic resin, and the injection was carried out under the molding conditions of an ejection time of 5 seconds, an injection speed of 80 mm/sec, a holding pressure of 100 MPa, a molding temperature of 3 20 ° C, and a mold temperature of 1, 60 °C. After molding, the resin terminal 7 was molded on the upper surface of the aluminum test piece 13 and the copper test piece 1, and the joint area of the resin terminal 7 on the aluminum test piece 13 and the copper test piece 1 was 3. 14 cm2 of aluminum-resin test piece and copper-resin test piece (test piece for evaluation). In the same manner as in the case of the above-mentioned Example 1, the concave portion of the surface of the aluminum test piece and the copper test piece was observed and the glossiness was measured, and the posiTEST test - 33 - 201144075 test and the evaluation of the laminated portion of the resin-copper were carried out. The results are shown in Table 1 together with the results of Example 1. [Comparative Example 1] Only the pretreatment of Example 1 was carried out, but the aluminum test piece terminal and the copper test piece were prepared without performing an etching treatment. Similarly to the case of Example 1, an aluminum test piece was produced using a resin and an adhesive, respectively. - Resin (adhesive)-copper test piece, similar to the case of the above-mentioned Example 1, the concave part observation of the surface of the said aluminum test piece and copper test piece, the gloss measurement, posiTEST test, aluminum-resin-copper Observation and evaluation of the layered part. Regarding the shape of the concave portion on the surface of the aluminum test piece and the copper test piece, any of the shapes a to d shown in the first embodiment was not observed, and the size of the concave portion was also ,. ΟΟΙμηι has not reached Ο. The results of ίμιη» are shown in Table 1 together with the results of the above Examples 1 to 5. [Comparative Example 2] A 150 g/L nitric acid solution was added to a 40 wt% sulfuric acid solution to prepare an etching solution, and the copper etching treatment was changed to a water immersion at 60 ° C for 1 minute in the etching solution, followed by water washing. In the same manner as in Example 1, an aluminum test piece (aluminum shape body) and a copper test piece (copper shape body) were produced, and then an aluminum test piece-resin (adhesive)-copper was produced using the same adhesive and resin as in Example 1. The test piece was subjected to the observation of the concave portion on the surface of the aluminum test piece and the copper test piece, the measurement of the glossiness, the posiTEST test, and the observation and evaluation of the laminated portion of the aluminum-resin and copper, in the same manner as in the case of the above-mentioned Example 1. -34- 201144075 Regarding the shape of the concave portion on the surface of the copper test piece, the shape a to d shown in the first embodiment was not observed, and the size of the concave portion was also the width of the opening. 〇〇10 claws or more did not reach 〇. 4111. The results are shown in Table 1 together with the results of Comparative Example 1. [Comparative Example 3] After immersion in copper for uranium engraving treatment, the mixture was immersed in a decane coupling agent treatment solution (KBM303, manufactured by Shin-Etsuka Co., Ltd.) at a concentration of 1 wt% for 30 seconds, and then dried by hot air at 120 ° C for 5 minutes. An aluminum test piece (aluminum-shaped body) and a copper test piece (copper-shaped body) were produced in the same manner as in the above-mentioned Example 1, and then an aluminum test piece-resin (adhesive) was produced using the same adhesive and resin as in Example 1. The copper test piece was subjected to the observation of the concave portion on the surface of the aluminum test piece and the copper test piece, the glossiness measurement, and the posiTEST test 'aluminum-resin-copper layered portion in the same manner as in the case of the first embodiment. Observe the evaluation. The results are shown in Table 1 together with the results of Comparative Example 1. -35- 201144075 [Table i]
實施例 比較例 1 2 3 4 5 1 2 3 鋁形狀體 蝕刻液(A1用) 2.5wt%HCl+AlCl3 僅前 處理 2.5wt°/〇HCl+AlCl3 凹狀 部 形狀 〇 〇 〇 〇 〇 X 〇 〇 大小 〇 〇 〇 〇 〇 X 〇 〇 60度光澤度 30 31 28 25 28 150 30 28 積層部評價 〇 〇 〇 〇 〇 X 〇 〇 表面積 增加率 3.3 3.1 2.8 3.3 2.9 1.01 3.0 2.8 銅形狀體 蝕刻液(Cu用) *1 *2 *1 *3 *1 僅前 處理 *4 *5 凹狀 部 形狀 〇 〇 〇 〇 〇 X X X 大小 〇 〇 〇 〇 〇 X X X 60度光澤度 10 11 12 9 10 110 66 77 積層部評價 〇 〇 〇 〇 〇 X X X 表面積 增加率 1.90 1.70 1.80 1.90 2.10 1.01 1.10 1.02 接合部的 剝離狀態 黏著劑 〇 〇 〇 〇 - 未接合 未接合 未接合 樹脂 〇 〇 〇 〇 〇 未接合 未接合 未接合 posiTEST 黏著劑-拉伸 強度（MPa) 5.5 5.4 5.2 5.3 - - 樹脂·拉伸強 度（MPa) 6.7 6.8 6.6 6.5 6.5 _ - - 判定 〇 〇 〇 〇 〇 X X XEXAMPLES Comparative Example 1 2 3 4 5 1 2 3 Aluminum-shaped body etching solution (for A1) 2.5 wt% HCl + AlCl3 Pretreatment only 2.5 wt ° / 〇 HCl + AlCl 3 Concave shape 〇〇〇〇〇 X 〇〇 Size 〇〇X 〇〇60 degree gloss 30 31 28 25 28 150 30 28 Evaluation of the 〇〇〇〇〇X 〇〇 surface area increase rate 3.3 3.1 2.8 3.3 2.9 1.01 3.0 2.8 Copper shape body etching solution (Cu Use) *1 *2 *1 *3 *1 Pre-processing only *4 *5 Concave shape 〇〇〇〇〇 XXX Size 〇〇〇〇〇 XXX 60 degree gloss 10 11 12 9 10 110 66 77 Multilayer Evaluation 〇〇〇〇〇XXX Surface area increase rate 1.90 1.70 1.80 1.90 2.10 1.01 1.10 1.02 Peeling state of joints Adhesive 〇〇〇〇 - Unbonded unjoined unbonded resin 〇〇〇〇〇 Unjoined unjoined unjoined posiTEST Adhesive - Tensile strength (MPa) 5.5 5.4 5.2 5.3 - - Resin · Tensile strength (MPa) 6.7 6.8 6.6 6.5 6.5 _ - - Judgment 〇〇〇〇〇XXX
(註）*1 : Alpha-prep PC-7030 *2 · MoldPrep LF *3 :硫酸溶液400g/L+硝酸溶液150g/L+氯化鈉0.2g/L+苯并三(Note) *1 : Alpha-prep PC-7030 *2 · MoldPrep LF *3 : Sulfuric acid solution 400g/L+Nitrate solution 150g/L+Sodium chloride 0.2g/L+Benzene
唑10g/L+5-胺基四唑10g/LAzo 10g/L+5-aminotetrazole 10g/L
*4 : 40wt%硫酸溶液+硝酸溶液150g/L *5 : lwt%矽烷偶合劑（信越矽利康公司製，KBM303 ) 【圖式簡單說明】 -36- 201144075 第1圖係示意顯示實施例1的鋁形狀體的厚度方向截面 而用來說明凹狀部之截面示意圖。 第2(a)〜（d)圖係從第1圖意識出之凹狀部形狀的 典型例之截面說明圖。 第3圖係使用鋁試驗片（鋁形狀體）及銅試驗片（銅 形狀體）而調製成之posiTEST試驗用的鋁-黏著劑-銅試驗 片（評價用試驗體）的前視圖及側視圖。 第4圖係使用鋁試驗片（鋁形狀體）及銅試驗片（銅 形狀體）而調製成之posiTEST試驗用的鋁-樹脂-銅試驗片 (評價用試驗體）的前視圖及側視圖。 第5圖係使用銅試驗片（銅形狀體）而調製成之 posiTEST試驗用的銅-樹脂試驗片（評價用試驗體）的前 視圖及側視圖。 第6圖是在posiTEST試驗時將評價用試驗體設置在 posiTEST試驗裝置的致動器部的狀態之截面說明圖。 第7圖係說明評價用試驗體之樹脂-鋁-樹脂的積層部 之觀察評價方法之截面說明圖。 第8圖係本發明的主要製品之密閉型電池用蓋構件之 說明圖。 【主要元件符號說明】 1:銅形狀體（銅試驗片） TL :頂線 BL :底線 -37- 201144075 HL :中間線 d :開口寬度 OL :觀察線 2 :樹脂形狀體 3 :凹狀部 4 :黏著劑 5 :鋁形狀體（鋁試驗片端子） 6 :樹脂 7 :樹脂端子 8 :致動器 9 :端子固定用治具 1 〇 :鋁形狀體或銅形狀體 1 1 :鋁合金蓋體 12:鋁合金製容器主體 1 3 :鋁形狀體（鋁試驗片） -38-*4 : 40wt% sulfuric acid solution + nitric acid solution 150g/L *5 : lwt% decane coupling agent (KBM303, manufactured by Shin-Etsu Chemical Co., Ltd.) [Simple description of the drawing] -36- 201144075 Figure 1 is a schematic view showing the embodiment 1. A cross section in the thickness direction of the aluminum body is used to explain a schematic cross section of the concave portion. The second (a) to (d) drawings are cross-sectional explanatory views of typical examples of the shape of the concave portion which is perceived from Fig. 1. Fig. 3 is a front view and a side view of an aluminum-adhesive-copper test piece (test piece for evaluation) prepared by using an aluminum test piece (aluminum shape body) and a copper test piece (copper shape body) for the posiTEST test. . Fig. 4 is a front view and a side view of an aluminum-resin-copper test piece (test piece for evaluation) prepared for the posiTEST test using an aluminum test piece (aluminum shape body) and a copper test piece (copper shape body). Fig. 5 is a front view and a side view of a copper-resin test piece (test piece for evaluation) prepared by using a copper test piece (copper-shaped body). Fig. 6 is a cross-sectional explanatory view showing a state in which the evaluation test body is placed in the actuator portion of the posiTEST test apparatus in the posiTEST test. Fig. 7 is a cross-sectional explanatory view showing a method for observing and evaluating a laminated portion of a resin-aluminum-resin of a test object for evaluation. Fig. 8 is an explanatory view showing a cover member for a sealed battery of a main product of the present invention. [Description of main component symbols] 1: Copper-shaped body (copper test piece) TL: Top line BL: Bottom line -37- 201144075 HL: Intermediate line d: Opening width OL: Observation line 2: Resin-shaped body 3: Concave portion 4 : Adhesive 5 : Aluminum-shaped body (aluminum test piece terminal) 6 : Resin 7 : Resin terminal 8 : Actuator 9 : Fixture for terminal fixing 1 〇: Aluminum-shaped body or copper-shaped body 1 1 : Aluminum alloy cover 12: Aluminum alloy container body 1 3 : Aluminum body (aluminum test piece) -38-