TWI743281B - 鋁合金箔及其積層體以及其製造方法 - Google Patents

鋁合金箔及其積層體以及其製造方法 Download PDF

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TWI743281B
TWI743281B TW106145764A TW106145764A TWI743281B TW I743281 B TWI743281 B TW I743281B TW 106145764 A TW106145764 A TW 106145764A TW 106145764 A TW106145764 A TW 106145764A TW I743281 B TWI743281 B TW I743281B
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mass
aluminum alloy
less
alloy foil
aluminum
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TW201825690A (zh
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新宮享
大八木光成
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日商東洋鋁股份有限公司
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Abstract

本發明提供一種具有優良耐濕熱性及耐蝕性，且具有充分表面硬度之鋁合金箔。
本發明之鋁合金箔，其特徵係，於鋁合金箔100質量%中，含有96．9質量%以上的鋁、0．4質量%以上3質量%以下的錳、0．03質量%以上0．08質量%以下的鐵、0．00001質量%以上0．1質量%以下的矽、0．00001質量%以上0．03質量%以下的銅、0．00001質量%以上0．01質量%以下的鋅、及0．00001質量%以上0．001質量%以下的鎂。

Description

鋁合金箔及其積層體以及其製造方法
本發明，係關於鋁合金箔及使用其之積層體，以及其製造方法。
近年來，從環境負荷減輕之觀點期望進一步輕量化移動手段所使用之飛機、鐵道車輛或汽車。進一步，從使用上之觀點於各種機械零件、電器電子關聯部材、建材、家庭用途等之廣泛的領域中，期望部材之輕量化。
其中，於此等之部材使用金屬材料之情形，藉由不用相對密度大的鋼鐵材料或銅，而使用密度較小的鋁及/或鋁合金，進行部材之輕量化。
然而，一般的鋁合金，有因水、濕氣、鹽水等之影響而容易腐蝕之缺點。因此，室外，特別是可能受到海洋及沿岸等之鹽水之影響之用途，及含有鹽分之藥品與含有鹽分之食品之包裝材料等之用途難以發展。
因此在專利文獻1中，提出鋁合金含有規定量的錳，以相對地抑制錳以外之各種元素含有量。藉由含有規定量的錳，則不損害鋁合 金之耐蝕性而提高強度，且藉由採用規定的加工方法，可得到為了使成形性良好的充分延伸，及為了得到薄的箔的高壓延性。
然而，例如發電設施及汽車零件般，作為置於更嚴苛的高溫多濕環境之材料而採用之情形，由引證文獻1所揭露之鋁合金製作之鋁合金箔，在高溫多濕環境下之耐蝕性(以下，稱作耐濕熱性)及耐蝕性，尤其是耐濕熱性方面無法得到充分的性能。此外，於藥品及食品之包裝材料用途使用之情形，亦難以說是具有能充分抑制與內容物及其他材料接觸所導致之傷痕的表面硬度。
此外，例如電機電子關聯部材，在進行一方的部材與另一方的部材之接合及積層等步驟，更具體而言，回流焊接或熱壓、及加熱成型等步驟中，前述部材暴露於施加熱量之環境。作為這般部材而採用鋁合金箔之情形，因熱導致鋁合金箔之強度下降。專利文獻1並未提及在上述步驟中因熱導致鋁合金箔之強度下降較少，作為部材維持充分強度之耐熱強度。
如上所述，現正要求具備在更嚴苛環境下之耐濕熱性及耐蝕性，且亦具有充分表面硬度及耐熱強度之鋁合金箔及使用其之積層體。
【先前技術文獻】 【專利文獻】
【專利文獻1】日本專利第5116403號公報。
有鑑於上述情事，本發明之目的在於，提供一種具有優良的耐濕熱性及耐蝕性，並且，具有充分的表面硬度及耐熱強度之鋁合金箔。
本發明者們為了達成上述目的深入研究的結果，發現藉由在鋁合金箔中含有規定量的錳及規定量的鐵，從而可提供不僅耐蝕性且耐濕熱性亦優良，並具有充分的表面硬度及耐熱強度之鋁合金箔。本發明者們，基於這樣的發現而深入研究，進而完成本發明。
亦即，本發明，提供以下鋁合金箔及其積層體。
項1．
一種鋁合金箔，其特徵係，於鋁合金箔100質量%中，含有96．9質量%以上的鋁、0．4質量%以上3質量%以下的錳、0．03質量%以上0．08質量%以下的鐵、0．00001質量%以上0．1質量%以下的矽、0．00001質量%以上0．03質量%以下的銅、0．00001質量%以上0．01質量%以下的鋅、及0．00001質量%以上0．001質量%以下的鎂。
項2．
如項1所記載之鋁合金箔，其中，厚度係5μm以上300μm以下。
項3．
一種積層體，其特徵係，其係於如項1或2所記載之鋁合金箔之任一 面或兩面，積層樹脂薄膜層及塗佈層之任一者或兩者；該積層體之厚度係6μm以上301μm以下。
項4．
一種鋁合金箔之製造方法，其特徵係，具有將含有96．9質量%以上的鋁、0．4質量%以上3質量%以下的錳、0．03質量%以上0．08質量%以下的鐵、0．00001質量%以上0．1質量%以下的矽、0．00001質量%以上0．03質量%以下的銅、0．00001質量%以上0．01質量%以下的鋅、及0．00001質量%以上0．001質量%以下的鎂之鑄塊壓延之步驟。
項5．
一種積層體之製造方法，其特徵係，具有於項4所得到的鋁合金箔之任一面或兩面，將樹脂薄膜層及塗佈層之任一者或兩者積層之步驟。
根據本發明之鋁合金箔及其積層體，可提供具有優良耐濕熱性及耐蝕性，並且，具有充分表面硬度及耐熱強度之鋁合金箔及其積層體。
本發明之鋁合金箔，其特徵係該鋁合金箔100質量%中，含有96．9質量%以上的鋁、0．4質量%以上3質量%以下的錳、0．03質量%以上0．08質量%以下的鐵、0．00001質量 %以上0．1質量%以下的矽、0．00001質量%以上0．03質量%以下的銅、0．00001質量%以上0．01質量%以下的鋅、及0．00001質量%以上0．001質量%以下的鎂。
鋁
本發明之鋁合金箔中，根據JIS H 2102：2011所記載之方法測量之鋁純度為96．9質量%以上。
錳
本發明之鋁合金箔，係於該鋁合金箔100質量%中，含有0．4質量%以上3質量%以下的錳。錳，係不會大幅降低鋁合金之耐蝕性，而提升強度之元素。錳之含有率為未滿0．4質量%時，則不僅無法得到充分的耐濕熱性及耐蝕性，表面硬度及耐熱強度亦降低。此外，錳之含有率超過3．0質量%時，雖鋁合金表面之硬度提高，但壓延性降低，無法得到鋁合金箔。為了兼具鋁合金之耐蝕性、耐濕熱性、表面硬度、耐熱強度及壓延性，錳之含有率在0．4質量%以上2．5質量%以下為佳，在0．5質量%以上1．5質量%以下為更佳。
鐵
本發明之鋁合金箔，係於該鋁合金箔100質量%中，含有0．03質量%以上0．08質量%以下的鐵。藉由在鋁合金箔中加入一定量的鐵，可提升高溫多濕環境之鋁合金箔之耐蝕性。鋁合金箔100質量%中之鐵之含有量不足0．03質量%之情形，高溫多濕環境之鋁合金箔之耐蝕性變得不充分。另一方面，若鐵之含有量超過0．08質量%，則對-40~60℃之鹽水之耐蝕性顯著地降低。
於鋁合金箔，若含有鐵及錳，則形成Al6(Fe、Mn)等之鋁-鐵-錳之金屬間化合物。形成鋁-鐵-錳之金屬間化合物之鋁合金，比起一般的鋁-鐵系金屬間化合物所形成之鋁合金，對於鹽分之耐蝕性較優良。此外，藉由鋁合金箔中錳之含有量為0．4質量%以上3質量%以下，鋁-鐵-錳之金屬間化合物變得容易形成。在另一方面，鐵之含有量超過0．08質量%，則除了上述鋁-鐵-錳之金屬間化合物以外，亦形成鋁-鐵系金屬間化合物，因此可預想對於-40~60℃之鹽水之鋁合金箔之耐蝕性顯著地降低。
此外，鐵之含有量越少則鋁合金箔之表面硬度越低。若考慮到上述理由，則鐵之含有量在0．04質量%以上0．07質量%以下為更佳。進一步更佳為0．04質量%以上0．06質量%以下。
矽
若矽存在於鋁合金中，則降低鋁合金在酸性環境之耐蝕性，尤其是引起孔蝕。然而藉由含有矽，從而可抑制高溫多濕環境之耐蝕性的降低。另一方面，若減少矽之含有率，則鋁合金之結晶粒徑縮小。藉此，鋁合金之延伸，亦即可提升壓延性。若考慮到此等特性，有需要將鋁合金箔100質量%中之矽之含有率設定為0．00001質量%以上0．1質量%以下，在0．001質量%以上0．08質量%以下為更佳。
銅
銅即使微量存在於鋁合金中亦降低鋁合金之耐蝕性。因此，於鋁合金箔100質量%中，需要使銅之含有率為0．03質量%以下。銅之含有量之下限值並無特別限定，但通常為0．00001質量%左右。為了使 銅之含有率未滿0．00001質量%，需要進一步反覆進行分化結晶法等，製造成本顯著地提高。此外，較佳為銅之含有率在0．02質量%以下，進一步較佳為0．01質量%以下。
鋅
鋅即使微量存在於鋁合金內亦降低鋁合金之耐蝕性。因此，於鋁合金箔100質量%中，需要使鋅之含有率為0．01質量%以下。鋅之含有量之下限值並無特別限定，但通常為0．00001質量%左右。為了使鋅之含有率未滿0．00001質量%，需要反覆進行三層電解法等，製造成本顯著地提高。
鎂
鎂，係容易濃縮於鋁之表面上所形成之氧化塗層中，引發塗層缺陷，因而降低鋁合金之耐蝕性。因此，需要將鋁合金箔100質量%中之鎂之含有率設定為0．001質量%以下。鎂之含有量之下限值並無特別限定，但通常為0．00001質量%左右。為了使鎂之含有率未滿0．00001質量%，需要反覆進行三層電解法等，製造成本顯著地提高。
其他
本發明之鋁合金箔，除了上述金屬元素以外，亦可含有選自釩(V)、鈦(Ti)、鋯(Zr)、鉻(Cr)、鎳(Ni)等之過渡元素、硼(B)、鎵(Ga)、及鉍(Bi)等所成群之一種以上之元素。此等各元素之含有量，於鋁合金箔100質量%中，各別為0．05質量%以下為佳。
又，本說明書中，鋁合金箔之組成，係藉由電感耦合電漿 體原子發射光譜法而測量者。測量裝置，可列舉賽默飛世爾科技股份公司製iCAP6500DUO、或島津製作所股份公司製ICPS-8100等。
鋁合金箔之厚度
鋁合金箔之厚度，從強度及製造容易性之觀點而言，在5μm以上為佳。此外，從鋁合金箔之輕量化之觀點而言，鋁合金箔之厚度在300μm以下為佳。進一步較佳為5μm以上200μm以下。要使鋁合金箔之厚度為上述範圍，依據通常的方法，進行鑄造、壓延即可。此外，亦可適當進行熱處理。
積層體
此外，於本發明之鋁合金箔之至少一側的面，積層樹脂薄膜層及塗佈層之任一者或兩者之積層體亦為較佳的實施態樣。此種積層體，在要求對鹽水之耐蝕性及高溫多濕環境下之耐濕熱性之環境下之使用為合適的。又，亦具有高的表面硬度，因此在含有鹽分之飲料及食品之包裝用、含有生理食鹽水之藥品等之包裝材用、隔熱材或防水片材等建材用、海洋及沿岸地區所設置之設備(例如太陽能發電面板)、船舶、航空、汽車、及鐵道車輛等之機械零件、以及電器電子關聯部材之作為遮蔽紫外線、可見光、紅外線、電波等電磁波、氣體、及濕氣之覆蓋用、家庭用及裝飾用領域亦可發揮充分的效果。
鋁合金箔所積層之樹脂薄膜層及塗佈層之積層數，以及積層之順序等，因應其積層體之使用用途等，適當設定即可，並無限定。積層體之厚度，從強度之觀點而言，在6μm以上為佳，從輕量化之觀點在 301μm以下為佳。進一步較佳為10μm以上201μm以下。
樹脂薄膜層所使用之樹脂薄膜，可廣泛採用習知的樹脂為材料所形成之薄膜，並無特別限定。具體而言，可使用選自聚乙烯、聚丙烯、聚丁烯、聚對苯二甲酸乙二酯、聚萘二甲酸乙二醇酯、聚氯乙烯、聚偏二氯乙烯、聚乙烯醇、乙烯乙酸乙烯酯共聚物、聚醯胺、聚醯亞胺及氯乙烯中1種以上。樹脂薄膜層之厚度，係積層體之厚度形成如上述數值範圍內，亦考慮到鋁合金箔之厚度及後述之塗佈層之厚度，而適當設定即可。
將樹脂薄膜層積層於鋁合金箔時接著兩者之方法，可廣泛採用習知的方法，並無特別限定。具體而言，可列舉使用聚酯胺基甲酸酯系、聚酯系等之2液硬化型接著劑之乾層壓法、共擠出法、擠出塗佈法、擠出層壓法、熱密封法、及使用錨塗(anchor coating)劑之熱層壓法等。
塗佈層，可採用鈦氧化物、矽氧化物、鋯氧化物、及鉻組成物等之無機物塗料、丙烯酸、聚碳酸酯、矽氧樹脂、及氟樹脂等之樹脂塗料。其他亦可適當地使用等離子處理、脂肪酸、矽烷偶聯劑等進行表面修飾、並且、藉由酸及/或鹼等而形成之改性材料等，並無特別限定。塗佈層之厚度，亦為積層體之厚度形成如上述數值範圍內，且考慮到鋁合金箔及樹脂薄膜層之厚度，而適當設定即可。
鋁合金箔之製造方法
本發明之鋁合金箔之製造方法，其特徵係，具有將含有96．9質量%以上的鋁、0．4質量%以上3質量%以下的錳、0．03質量%以上0．08質量%以下的鐵、0．00001質量%以上0．1質量%以下 的矽、0．00001質量%以上0．03質量%以下的銅、0．00001質量%以上0．01質量%以下的鋅、及0．00001質量%以上0．001質量%以下的鎂之鑄塊壓延之步驟。
鑄塊，例如，將藉由熔解鋁鑄錠，並添加鐵或鋁-鐵母合金，及錳或鋁-錳母合金而得到的熔融金屬凝固而鑄造，從而可得到。鑄造方法並無特別限定，可採用選自半連續鑄造、連續鑄造、及模鑄造等所成群之方法。
得到的鑄塊，亦可進行均質化熱處理。均質化熱處理，例如在加熱溫度為400℃以上630℃以下、加熱時間為1小時以上20小時以下之條件進行為佳。
壓延所用之方法，可廣泛採用習知的壓延方法，並無特別限定。
然而，從易於調整鋁合金箔之厚度之觀點而言，於熱軋步驟後，設置冷軋步驟為佳。此外，熱軋步驟之熱軋次數及冷軋步驟之冷軋次數因應作為目的之最終厚度而適當設定即可。
複數次實施冷軋之情形，實施中間退火亦佳。此情形，將冷軋步驟，依序實施1次或複數次的冷軋、中間退火、1次或複數次的冷軋為佳。中間退火，係將退火溫度設定於50℃以上500℃以下，退火時間設定於1秒以上20小時以下而實施為佳。藉由採用此種構成，可易於調整鋁合金箔之厚度。
此外，熱軋步驟及冷軋步驟之後，進一步設置箔壓延步驟亦佳。藉由設置箔壓延步驟，調整鋁合金箔之厚度變得更容易。箔壓延步 驟，亦可藉由重合壓延實施。
於箔壓延步驟之後，亦可進一步設置熱處理步驟，在50℃以上450℃以下之溫度實施1秒~50小時左右之熱處理。藉由設置熱處理步驟，除去於鋁合金箔表面殘留之壓延油而提升潤濕性且可調整鋁合金箔之機械特性。
積層體之製造方法
上述得到的鋁合金箔之任一面或兩面，積層樹脂薄膜層及塗佈層之任一者或兩者，而得到積層體亦佳。在此之積層方法，可廣泛採用習知的方法，具體而言，可採用選自乾層壓法、擠出層壓法、濕層壓法、及熱層壓法等所成群之方法。此外，鋁合金箔之任一面或兩面，積層樹脂薄膜層及塗佈層兩者之情形，依序積層塗佈層及樹脂薄膜層為佳。
以上，對於本發明之實施型態進行說明，但本發明並非為限定於此等示例者，不脫離本發明概念之範圍當然可實施各種的型態。
【實施例】
以下，基於實施例，更具體說明本發明之實施型態，但本發明並非限定於此。
基於表1所示之組成，藉由將鋁合金以約102℃/秒之冷卻速度熔解鑄造，從而得到厚度6mm之鋁合金之板。將得到的鋁合金之板在400℃進行5小時熱處理。從爐取出板後進行壓延，而得到實施例1~7及比較例1~8之厚度100μm之鋁合金箔。
此外，基於表1所示之組成，藉由將鋁合金以約102℃/ 秒之冷卻速度熔解鑄造，從而得到厚度500mm之鋁合金之板。將得到的鋁合金之板在610℃進行10小時均質化熱處理。從爐取出板後施予熱軋，得到厚度7mm之熱軋板後，進行冷軋，得到具有表1所記載之厚度之實施例8~11及比較例9之鋁合金箔。
鋁合金箔之組成情報，係測量1．00g鋁合金箔，藉由電感耦合電漿體原子發射光譜法(裝置名稱：島津製作所股份公司製ICPS-8100)進行測量而得。
(耐濕熱性評價試驗)
將各實施例及比較例之鋁合金箔，切出40mm×40mm作為試驗片，在溫度120℃持續施加壓力至濕度到100%為止之環境中放置12小時，並測量放置前後之質量，算出表面之氧化腐蝕所導致之質量增加率。質量增加率未滿1．0%者評價為具有充分耐濕熱性。又，實施例8~11及比較例9之試驗片質量不同，因此藉由以下之式1評價作為100μm厚度之質量增加率。
(式1)質量增加率[%]=(放置後質量-放置前質量)/(放置前質量×100/試驗片厚度[μm])×100
(耐蝕性評價試驗)
將各實施例及比較例之鋁合金箔，切出40mm×40mm作為試驗片，浸漬於40℃之含有3質量%之氯化鈉及3質量%之乙酸之水溶液336小時，測量浸漬前後之質量，並測量‧算出溶解腐蝕之質量減少率。質量減少率未滿12．0%者評價為具有充分耐蝕性。又，實施例8~1 1及比較例9之試驗片質量不同，因此藉由以下之式2評價作為100μm厚度之質量減少率。
(式2)質量減少率[%]=(浸漬前質量-浸漬後質量)/(浸漬前質量×100/試驗片厚度[μm])×100
(維氏硬度測量試驗)
測量得到各實施例及比較例之維氏硬度。維氏硬度，係將表面之傷害難度作為指標，使用島津製作所製維氏硬度計HMV-1，藉由金剛石壓頭壓下，以試驗力490mN壓入5秒之後而進行維氏硬度測量試驗。維氏硬度HV0．05在55．0以上者，評價為具有充分的表面硬度。
(耐熱性試驗)
將得到的各實施例及比較例之鋁合金箔在250℃加熱3小時，測量加熱前後之拉伸強度。拉伸強度係使用東洋精機製作所股份公司製AUTOGRAPH VES5D，並將各鋁合金箔切出壓延寬方向15mm、壓延方向200mm，以標點間距離100mm、拉伸速度20mm/分作為進行拉伸試驗時之最大拉伸強度。加熱後之拉伸強度在150N/mm2以上者，評價為具有充分的耐熱性。
(試驗結果)
如表1所示，各實施例之鋁合金箔，在耐濕熱性、耐蝕性表面硬度及耐熱強度全部皆顯示良好的結果。相較於此，各比較例之鋁合金箔，在耐濕熱性、耐蝕性及表面硬度之至少1個以上，得不到滿意的結果。
【表1】
Figure 106145764-A0202-12-0014-1

Claims (5)

  1. 一種鋁合金箔，其特徵係，於鋁合金箔100質量%中，含有96．9質量%以上的鋁、0．4質量%以上3質量%以下的錳、0．03質量%以上0．08質量%以下的鐵、0．00001質量%以上0．1質量%以下的矽、0．00001質量%以上0．03質量%以下的銅、0．0005質量%以上0．01質量%以下的鋅、及0．00001質量%以上0．001質量%以下的鎂。
  2. 如申請專利範圍第1項所記載之鋁合金箔，其中，厚度係5μm以上300μm以下。
  3. 一種積層體，其特徵係，其係於如申請專利範圍第1或2項所記載之鋁合金箔之任一面或兩面，積層樹脂薄膜層及塗佈層之任一者或兩者；該積層體之厚度係6μm以上301μm以下。
  4. 一種鋁合金箔之製造方法，其特徵係，具有將含有96．9質量%以上的鋁、0．4質量%以上3質量%以下的錳、0．03質量%以上0．08質量%以下的鐵、0．00001質量%以上0．1質量%以下的矽、0．00001質量%以上0．03質量%以下的銅、0．0005質量%以上0．01質量%以下的鋅、及0．00001質量%以上0．001質量%以下的鎂之鑄塊壓延之步驟。
  5. 一種積層體之製造方法，其特徵係，具有於申請專利範圍第4項所得到的鋁合金箔之任一面或兩面，將樹脂薄膜層及塗佈層之任一者或兩者積層之步驟。
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