CN110114484A - 铝合金箔及其层叠体以及它们的制造方法 - Google Patents

铝合金箔及其层叠体以及它们的制造方法 Download PDF

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CN110114484A
CN110114484A CN201780080814.2A CN201780080814A CN110114484A CN 110114484 A CN110114484 A CN 110114484A CN 201780080814 A CN201780080814 A CN 201780080814A CN 110114484 A CN110114484 A CN 110114484A
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mass
alloy foil
alloy
aluminium
laminated body
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新宫享
大八木光成
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Toyo Aluminum KK
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Toyo Aluminum KK
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    • C22C21/02—Alloys based on aluminium with silicon as the next major constituent
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22C21/00—Alloys based on aluminium
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
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Abstract

本发明提供一种具有优异的耐湿热性及耐蚀性，且具有充分的表面硬度的铝合金箔。所述铝合金箔在100质量％的铝合金箔中，含有96.9质量％以上的铝、0.4质量％以上3质量％以下的锰、0.03质量％以上0.08质量％以下的铁、0.00001质量％以上0.1质量％以下的硅、0.00001质量％以上0.03质量％以下的铜、0.00001质量％以上0.01质量％以下的锌、及0.00001质量％以上0.001质量％以下的镁。

Description

铝合金箔及其层叠体以及它们的制造方法
技术领域
本发明涉及一种铝合金箔及使用了该铝合金箔的层叠体、以及它们的制造方法。
背景技术
近年来，从降低对环境的负担的角度出发，对用于移动手段的飞机、铁路车辆或汽车要求进一步的轻量化。进一步，从操作性的角度出发，在各种机械零件、电气电子相关构件、建材、家庭用途等广泛的领域中，也要求构件的轻量化。
在这样的背景下，当在这些构件中使用金属材料时，正在通过不使用密度较大的铁钢材料或铜而使用密度更小的铝和/或铝合金来谋求构件的轻量化。
然而，通常铝合金存在因水、湿气、盐水等影响而容易腐蚀的缺点。因此，难以用于有受屋外、特别是海洋及沿岸等的盐水影响的可能性的用途，并且难以用于含有盐分的药品及含有盐分的食品的包装材料等用途。
因此，在专利文献1中，提出了一种以规定量含有锰、并相对抑制了除锰以外的各种元素含量的铝合金。通过以规定量含有锰，可提高强度而不损害铝合金的耐蚀性，并且通过采用规定的加工方法，能够得到用于使成型性良好的充分的拉伸度与用于得到薄箔的高压延性。
然而，例如在用作发电设施及汽车零件这样的被置于更严苛的高温多湿环境中的材料时，利用专利文献1所公开的铝合金而制作的铝合金箔无法获得在高温多湿环境下的耐蚀性(以下，称作耐湿热性)及耐蚀性，特别是在耐湿热性方面无法获得充分的性能。此外，在用于药品及食品的包装材料用途时，也不能说具有能够充分抑制因接触内容物及其他材料而造成的损伤的表面硬度。
此外，例如在电极电子相关构件中，在进行一个构件与另一个构件的接合及层叠等的工序中，更具体而言，在回流焊接(solder reflow)或热压(heat press)及加热成型等工序中，所述构件被暴露在加热环境中。在采用铝合金箔作为这样的构件时，铝合金箔的强度因热而下降。在专利文献1中，并未提及由上述工序中的热造成的铝合金箔的强度下降少、维持作为构件的充分强度的耐热强度。
像这样，谋求一种铝合金箔及使用了该铝合金箔的层叠体，该铝合金箔不仅具备在更严苛环境下的耐湿热性及耐蚀性，还具有充分的表面硬度及耐热强度。
现有技术文献
专利文献
专利文献1：日本专利第5116403号公报
发明内容
本发明要解决的技术问题
鉴于如上所述的情况，本发明的目的在于提供一种具有优异的耐湿热性及耐蚀性、且具有充分的表面硬度及耐热强度的铝合金箔。
解决技术问题的技术手段
为了达成上述目的，本申请的发明人反复进行了仔细研究，结果发现，通过使铝合金箔中含有规定量的锰并同时含有规定量的铁，能够提供一种不仅耐蚀性优异而且耐湿热性也优异，同时具有充分的表面硬度及耐热强度的铝合金箔。本申请的发明人根据该见解进一步进行反复研究，完成了本发明。
即，本发明提供以下的铝合金箔及其层叠体。
项1.一种铝合金箔，其在100质量％的铝合金箔中，含有96.9质量％以上的铝、0.4质量％以上3质量％以下的锰、0.03质量％以上0.08质量％以下的铁、0.00001质量％以上0.1质量％以下的硅、0.00001质量％以上0.03质量％以下的铜、0.00001质量％以上0.01质量％以下的锌、及0.00001质量％以上0.001质量％以下的镁。
项2.根据项1所述的铝合金箔，其厚度为5μm以上300μm以下。
项3.一种层叠体，其为在项1或2所述的铝合金箔的任一面或两面上层叠有树脂膜层及涂布层中的任一种或两种的层叠体，该层叠体的厚度为6μm以上301μm以下。
项4.一种铝合金箔的制造方法，其具有对铸块进行压延的工序，所述铸块含有96.9质量％以上的铝、0.4质量％以上3质量％以下的锰、0.03质量％以上0.08质量％以下的铁、0.00001质量％以上0.1质量％以下的硅、0.00001质量％以上0.03质量％以下的铜、0.00001质量％以上0.01质量％以下的锌、及0.00001质量％以上0.001质量％以下的镁。
项5.一种层叠体的制造方法，其具有在项4中得到的铝合金箔的任一面或两面上层叠树脂膜层及涂布层中的任一种或两种的工序。
发明效果
根据本发明的铝合金箔及其层叠体，能够提供一种具有优异的耐湿热性及耐蚀性、且具有充分的表面硬度及耐热强度的铝合金箔及其层叠体。
具体实施方式
本发明的铝合金箔的特征在于，在100质量％的该铝合金箔中，含有96.9质量％以上的铝、0.4质量％以上3质量％以下的锰、0.03质量％以上0.08质量％以下的铁、0.00001质量％以上0.1质量％以下的硅、0.00001质量％以上0.03质量％以下的铜、0.00001质量％以上0.01质量％以下的锌、及0.00001质量％以上0.001质量％以下的镁。
铝
在本发明的铝合金箔中，依据JIS H 2102:2011中记载的方法测定的铝纯度为96.9质量％以上。
锰
本发明的铝合金箔在100质量％的该铝合金箔中，含有0.4质量％以上3质量％以下的锰。锰为不使铝合金的耐蚀性大幅下降、使强度提高的元素。若锰的含有率小于0.4质量％，则不仅得不到充分的耐湿热性及耐蚀性，表面硬度及耐热强度也下降。此外，若锰的含有率超过3.0质量％，则虽然铝合金表面的硬度增高，但压延性下降，无法得到铝合金箔。为了兼具铝合金的耐蚀性、耐湿热性、表面硬度、耐热强度及压延性，优选将锰的含有率设为0.4质量％以上2.5质量％以下，更优选设为0.5质量％以上1.5质量％以下。
铁
本发明的铝合金箔在100质量％的该铝合金箔中，含有0.03质量％以上0.08质量％以下的铁。通过在铝合金箔中添加一定量的铁，能够使高温多湿气氛中的铝合金箔的耐蚀性提高。当100质量％的铝合金箔中的铁的含量不足0.03质量％时，高温多湿气氛中的铝合金箔的耐蚀性不充分。另一方面，若铁的含量超过0.08质量％，则-40～60℃下的、对盐水的耐蚀性显著下降。
若在铝合金箔中含有铁及锰，则可形成Al6(Fe、Mn)等铝-铁-锰的金属间化合物。与形成有铝-铁类金属间化合物的铝合金相比，通常形成有铝-铁-锰的金属间化合物的铝合金对盐分的耐蚀性优异。此外，通过使锰在铝合金箔中的含量为0.4质量％以上3质量％以下，易于形成铝-铁-锰的金属间化合物。另一方面，认为若铁的含量超过0.08质量％，则除了上述的铝-铁-锰的金属间化合物以外，还形成铝-铁类金属间化合物，因此-40～60℃下的、铝合金箔对盐水的耐蚀性显著下降。
此外，铁的含量越少，则铝合金箔的表面硬度变得越低。若参考上述的理由，则铁的含量更优选为0.04质量％以上0.07质量％以下。进一步优选为0.04质量％以上0.06质量％以下。
硅
若在铝合金中存在硅，则在酸性的环境下铝合金的耐蚀性下降，尤其会成为点腐蚀的原因。然而，通过含有硅，能够抑制高温多湿气氛下的耐蚀性的下降。另一方面，若减少硅的含有率，则铝合金的晶粒尺寸变小。由此，还能够提高铝合金的伸长率，即压延性。若考虑这些原因，则100质量％的铝合金箔中的硅的含有率需要设为0.00001质量％以上0.1质量％以下，更优选为0.001质量％以上0.08质量％以下。
铜
铜即使微量存在于铝合金中，也会使铝合金的耐蚀性下降。因此，需要使100质量％的铝合金箔中的铜的含有率为0.03质量％以下。铜的含量的下限值没有特别限定，通常为0.00001质量％左右。为了使铜的含有率小于0.00001质量％，还需要重复分步结晶法等，制造成本显著增高。此外，铜的含有率优选为0.02质量％以下，进一步优选为0.01质量％以下。
锌
锌即使微量存在于铝合金内，也会使铝合金的耐蚀性下降。因此，需要使100质量％的铝合金箔中的锌的含有率为0.01质量％以下。锌的含量的下限值没有特别限定，通常为0.00001质量％左右。为了使锌的含有率小于0.00001质量％，需要重复三层液电解法等，制造成本显著增高。
镁
由于镁容易浓缩于形成在铝表面上的氧化覆膜中，引起覆膜缺陷，因此使得铝合金的耐蚀性下降。因此，需要使100质量％的铝合金箔中的镁的含有率为0.001质量％以下。镁的含量的下限值没有特别限定，通常为0.00001质量％左右。为了使镁的含有率小于0.00001质量％，需要重复三层液电解法等，制造成本显著增高。
其他
除了上述的金属元素以外，本发明的铝合金箔也可含有选自由钒(V)、钛(Ti)、锆(Zr)、铬(Cr)、镍(Ni)等过渡元素、硼(B)、镓(Ga)及铋(Bi)等组成的组中的一种以上的元素。在100质量％的铝合金箔中，优选将所述各元素的含量分别设为0.05质量％以下。
另外，在本说明书中，铝合金箔的组成通过电感耦合等离子体发光分光分析法进行测定。作为测定装置，可列举出Thermo Fisher Scientific Inc.制造的iCAP 6500DUO或Shimadzu Corporation制造的ICPS-8100等。
铝合金箔的厚度
从强度及制造的容易性的角度出发，铝合金箔的厚度优选为5μm以上。此外，从铝合金箔的轻量化这一角度出发，优选将铝合金箔的厚度设为300μm以下。进一步优选设为5μm以上200μm以下。为了将铝合金箔的厚度设为上述范围，只要按照常规方法进行铸造、压延即可。此外，也可适当地进行热处理。
层叠体
此外，制成在本发明的铝合金箔的至少一侧的面上层叠有树脂膜层及涂布层中的任一种或两种的层叠体也为优选的实施方式。该层叠体适合用于要求对盐水的耐蚀性及高温多湿环境下的耐湿热性的环境下。此外，由于还具有高表面硬度，因此在含有盐分的饮料及食品的包装用、含有生理盐水的药品等包装材料用、隔热材料或防水片等的建材用、设置在海洋及沿岸部的设备(例如日光发电板)、船舶、航空、汽车及铁道车辆等的机械零件、以及将电气电子相关构件从紫外线、可见光、红外线、电波等电磁波、气体及湿气隔离的包覆用、家庭用及装饰用领域中也能够发挥充分的效果。
层叠于铝合金箔的树脂膜层及涂布层的层叠数及层叠顺序等根据该层叠体的使用用途等进行适当设定即可，没有限定。从强度的角度出发，优选将层叠体的厚度设为6μm以上，从轻量化的角度出发，优选设为301μm以下。进一步优选为10μm以上201μm以下。
作为用于树脂膜层的树脂膜，可广泛采用以公知的树脂为材料的膜，没有特别限定。具体而言，可使用选自聚乙烯、聚丙烯、聚丁烯、聚对苯二甲酸乙二醇酯、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、聚酰胺、聚酰亚胺及氯乙烯中的一种以上。树脂膜层的厚度只要以使层叠体的厚度为上述数值范围内的方式、并考虑铝合金箔的厚度及后文所述的涂布层的厚度进行适当设定即可。
作为将树脂膜层层叠于铝合金箔时对两者进行粘合的方法，可广泛采用公知的方法，没有特别限定。具体而言，可列举出使用聚酯氨基甲酸酯类、聚酯类等二液固化型粘合剂的干式层压法、共挤出法、挤出涂布法、挤出层压法、热封法及使用锚涂剂的热层压法等。
涂布层中可采用钛氧化物、硅氧化物、锆氧化物及铬组合物等的无机物涂布，丙烯酸酯、聚碳酸酯、硅树脂及氟树脂等的树脂涂布。此外，也可以适当地使用基于等离子体处理、脂肪酸、硅烷偶联剂等的表面修饰、以及利用酸和/或碱等而形成的改性物，没有特别限定。涂布层的厚度也以使层叠体的厚度为上述数值范围内的方式、并考虑铝合金箔及树脂膜层的厚度进行适当设定即可。
铝合金箔的制造方法
本发明的铝合金箔的制造方法的特征在于，具有对铸块进行压延的工序，所述铸块含有96.9质量％以上的铝、0.4质量％以上3质量％以下的锰、0.03质量％以上0.08质量％以下的铁、0.00001质量％以上0.1质量％以下的硅、0.00001质量％以上0.03质量％以下的铜、0.00001质量％以上0.01质量％以下的锌、及0.00001质量％以上0.001质量％以下的镁。
铸块例如可通过以下方式得到：溶解铝原料金属，并通过添加铁或铝-铁母合金及锰或铝-锰母合金而得到熔融金属，使该熔融金属凝固，进行铸造。铸造方法没有特别限定，可采用选自由半连续铸造、连续铸造及金属模铸造等组成的组中的方法。
也可对得到的铸块进行均匀化热处理。均匀化热处理例如优选在将加热温度设为400℃以上630℃以下、将加热时间设为1小时以上20小时以下的条件下进行。
作为用于进行压延的方法，可广泛采用公知的压延方法，没有特别限定。
其中，从容易调节铝合金箔的厚度这一角度出发，优选在热轧工序后设置冷轧工序。此外，热轧工序中的热轧次数及冷轧工序中的冷轧次数只要根据作为目的的最终厚度进行适当设定即可。
在实施多次冷轧时，优选实施中间退火。此时，优选以一次或多次的冷轧、中间退火、一次或多次的冷轧的顺序实施冷轧工序。优选将退火温度设定为50℃以上500℃以下、将退火时间设定为1秒以上20小时以下来实施中间退火。通过采用所述构成，能够容易地调节铝合金箔的厚度。
此外，也优选在热轧工序及冷轧工序后进一步设置箔压延工序。通过设置箔压延工序，更容易调节铝合金箔的厚度。箔压延工序可通过多层压延(multi-layer rolling)进行实施。
在箔压延工序后，也可进一步设置在50℃以上450℃以下的温度下实施1秒～50小时左右的热处理的热处理工序。通过设置热处理工序，能够调节因去除残留在铝合金箔表面的压延油而带来的湿润性提高、铝合金箔的机械特性。
层叠体的制造方法
还优选在上述得到的铝合金箔的任一面或两面上，层叠树脂膜层及涂布层中的任一种或两种，得到层叠体。作为此处的层叠的方法，可广泛采用公知的方法。具体而言，可采用选自由干式层压法、挤出层压法、湿式层压法及热层压法等组成的组中的方法。此外，将树脂膜层及涂布层均层叠在铝合金箔的任一面或两面上时，优选以涂布层及树脂膜层这一顺序层叠涂布层及树脂膜层。
以上对本发明的实施方式进行了说明，但本发明并不受这些例子的任何限定，当然，在不脱离本发明主旨的范围中，可通过各种方式实施。
实施例
以下，根据实施例，对本发明的实施方式进行更具体的说明，但本发明并不受这些实施例限定。
根据表1所示的组成，通过以约102℃/秒的冷却速度对铝合金进行溶解铸造，得到厚度为6mm的铝合金板。在400℃下对得到的铝合金板进行5小时热处理。从炉中取出板后，进行压延，得到实施例1～7及比较例1～8的、厚度为100μm的铝合金箔。
并且，根据表1所示的组成，通过以约102℃/秒的冷却速度对铝合金进行溶解铸造，得到厚度为500mm的铝合金板。在610℃下对得到的铝合金板进行10小时的均匀化热处理。从炉中取出板后，实施热轧，得到厚度为7mm的热轧板，然后进行冷轧，得到具有表1中记载的厚度的实施例8～11及比较例9的铝合金箔。
称取1.00g的铝合金箔，通过电感耦合等离子体发光分析法(装置名称：ShimadzuCorporation制造的ICPS-8100)进行测定，得到铝合金箔的组成信息。
(耐湿热性评价试验)
将各实施例及比较例的铝合金箔切成40mm×40mm作为试验片，在温度120℃下、在施加压力直至湿度为100％为止的气氛中放置12小时，测量放置前后的质量，计算由表面的氧化腐蚀造成的质量增加率。将质量增加率小于1.0％的试验片评价为具有充分的耐湿热性。另外，对于实施例8～11及比较例9，由于试验片质量不同，因此通过以下的式1、以100μm厚度的质量增加率的形式进行评价。
(式1)
质量增加率[％]＝(放置后质量-放置前质量)/(放置前质量×100/试验片厚度[μm])×100
(耐蚀性评价试验)
将各实施例及比较例的铝合金箔切成40mm×40mm作为试验片，在40℃下、在含有3质量％的氯化钠与3质量％的乙酸的水溶液中浸渍336小时，测量浸渍前后的质量，测量并计算由溶解腐蚀造成的质量减少率。将质量减少率小于12.0％的试验片评价为具有充分的耐蚀性。另外，对于实施例8～11及比较例9，由于试验片质量不同，因此通过以下的式2、以100μm厚度的质量减少率的形式进行评价。
(式2)
质量减少率[％]＝(浸渍前质量-浸渍后质量)/(浸渍前质量×100/试验片厚度[μm])×100
(维氏硬度(Vickers Hardness)测定试验)
测定得到的各实施例及比较例的维氏硬度。维氏硬度以表面的损伤难易度为指标，使用Shimadzu Corporation制造的维氏硬度计HMV-1，以金刚石压头进行下压，进行以490mN的试验力挤压5秒后的维氏硬度测定试验。将维氏硬度HV0.05为55.0以上的试验片评价为具有充分的表面硬度。
(耐热性试验)
在250℃下对得到的各实施例及比较例的铝合金箔进行3小时加热，测定加热前后的拉伸强度。拉伸强度为使用TOYOSEIKI Co.,Ltd.制造的AUTOGRAPH VES5D，将各铝合金箔切成压延宽度方向15mm、压延方向200mm，以标距长度为100mm、拉伸速度为20mm/分钟的条件进行拉伸试验时的最大拉伸强度。将加热后的拉伸强度为150N/mm2以上的试验片评价为具有充分的耐热性。
(试验结果)
如表1所示，各实施例的铝合金箔在耐湿热性、耐蚀性、表面硬度及耐热强度方面均表现出良好的结果。与此相比，各比较例的铝合金箔在耐湿热性、耐蚀性及表面硬度中的至少一种以上的评价中未得到令人满意的结果。

Claims (5)

1.一种铝合金箔，其在100质量％的铝合金箔中，含有96.9质量％以上的铝、0.4质量％以上3质量％以下的锰、0.03质量％以上0.08质量％以下的铁、0.00001质量％以上0.1质量％以下的硅、0.00001质量％以上0.03质量％以下的铜、0.00001质量％以上0.01质量％以下的锌、及0.00001质量％以上0.001质量％以下的镁。
2.根据权利要求1所述的铝合金箔，其厚度为5μm以上300μm以下。
3.一种层叠体，其为在权利要求1或2所述的铝合金箔的任一面或两面上层叠有树脂膜层及涂布层中的任一种或两种的层叠体，该层叠体的厚度为6μm以上301μm以下。
4.一种铝合金箔的制造方法，其具有对铸块进行压延的工序，所述铸块含有96.9质量％以上的铝、0.4质量％以上3质量％以下的锰、0.03质量％以上0.08质量％以下的铁、0.00001质量％以上0.1质量％以下的硅、0.00001质量％以上0.03质量％以下的铜、0.00001质量％以上0.01质量％以下的锌、及0.00001质量％以上0.001质量％以下的镁。
5.一种层叠体的制造方法，其具有在权利要求4中得到的铝合金箔的任一面或两面上层叠树脂膜层及涂布层中的任一种或两种的工序。
CN201780080814.2A 2016-12-27 2017-12-25 铝合金箔及其层叠体以及它们的制造方法 Pending CN110114484A (zh)

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