CN111788334A - 镀Sn钢板及镀Sn钢板的制造方法 - Google Patents

镀Sn钢板及镀Sn钢板的制造方法 Download PDF

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Publication number
CN111788334A
CN111788334A CN201980016324.5A CN201980016324A CN111788334A CN 111788334 A CN111788334 A CN 111788334A CN 201980016324 A CN201980016324 A CN 201980016324A CN 111788334 A CN111788334 A CN 111788334A
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steel sheet
plated steel
zirconium oxide
zirconium
tin oxide
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CN111788334B (zh
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山中晋太郎
野田正和
佐藤恭彦
仲宗根信夫
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Nippon Steel Corp
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Nippon Steel and Sumitomo Metal Corp
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    • B32B15/043—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of metal
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    • B32B15/18—Layered products comprising a layer of metal comprising iron or steel
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Abstract

本发明提供一种镀Sn钢板，其具备：具有钢板、且在所述钢板的至少一面具有Sn镀层的母材镀敷钢板、以及位于所述母材镀敷钢板上、且含有锆氧化物和氧化锡的被膜层。该镀Sn钢板的相当于一面的Sn的附着量为0.1g/m2以上且15g/m2以下，所述被膜层中的所述锆氧化物的含量以金属Zr量计为1mg/m2以上且30mg/m2以下的范围内，所述被膜层中的所述氧化锡基于X射线光电子能谱法得到的Sn3d5/2的结合能的峰位置距离金属Sn的结合能的峰位置为1.4eV以上且小于1.6eV的范围内，所述氧化锡的还原所需的电量为大于5.0mC/cm2且20mC/cm2以下的范围内。

Description

镀Sn钢板及镀Sn钢板的制造方法
技术领域
本发明涉及镀Sn钢板及镀Sn钢板的制造方法。
本申请基于2018年3月1日在日本提交的日本特愿2018-036587号主张优先权，将其内容援引至此。
背景技术
镀锡(Sn)钢板作为“马口铁”而广为人知，在饮料罐、食品罐等罐用途及其它用途中广泛使用。这是由于，Sn对人体是安全的，而且是漂亮的金属。该镀Sn钢板主要利用电镀法进行制造。这是由于，为了将作为较昂贵金属的Sn的用量控制为所需最小限度的量，电镀法比熔融镀敷法更为有利。镀Sn钢板大多在通过镀敷后的加热熔融处理而赋予了漂亮的金属光泽后，通过使用6价铬酸盐溶液的电解处理、浸渍处理等铬酸盐处理，在Sn镀层上形成铬酸盐被膜。该铬酸盐被膜的效果有：通过抑制Sn镀层表面的氧化而防止外观黄变、防止在涂装而使用时由氧化锡的内聚破坏而导致的涂膜密合性变差、提高耐硫化黑变性等。
另一方面，近年来，由于对环境、安全的意识增强，因此不仅要求最终产品不含6价铬，而且要求不进行铬酸盐处理本身。然而，对于不存在铬酸盐被膜的镀Sn钢板而言，如上所述，会因氧化锡的增加而使外观产生黄变、涂膜密合性降低、耐硫化黑变性降低。
因此，提出了一些实施了代替铬酸盐被膜的被膜处理的镀Sn钢板。
例如，以下的专利文献1中提出了通过使用含有磷酸根离子和硅烷偶联剂的溶液的处理而形成了包含P和Si的被膜的镀Sn钢板。以下的专利文献2中提出了通过使用包含磷酸铝的溶液的处理而形成了被膜的镀Sn钢板，所述被膜包含Al和P、选自Ni、Co、Cu中的至少1种、以及硅烷偶联剂的反应物。另外，以下的专利文献3中提出了一种不具有铬酸盐被膜的镀Sn钢板的制造方法，该方法包括：在Sn镀层上镀Zn后，实施加热处理直至Zn单独镀层消失。另外，以下的专利文献4及专利文献5中提出了具有包含锆、磷酸、酚醛树脂等的化学转化处理被膜的容器用钢板。
现有技术文献
专利文献
专利文献1：日本特开2004-60052号公报
专利文献2：日本特开2011-174172号公报
专利文献3：日本特开昭63-290292号公报
专利文献4：日本特开2007-284789号公报
专利文献5：日本特开2010-13728号公报
非专利文献
非专利文献1：日本表面科学会编、《表面分析化学选书X射线光电子能谱法》(表面分析化学選書X線光電子分光法)、丸善株式会社、P.83
发明内容
发明所要解决的问题
然而，根据本发明人等研究的结果表明，上述专利文献1～专利文献5中提出的镀Sn钢板、其制造方法无法充分抑制随时间经过所引起的氧化锡的增加，有时耐黄变性、涂膜密合性不足。
本发明是鉴于上述问题而完成的，其目的在于不进行现有的铬酸盐处理而提供在耐黄变性、涂膜密合性及耐硫化黑变性方面更加优异的镀Sn钢板，并且提供镀Sn钢板的制造方法。
解决问题的方法
为了解决上述问题实现上述目的，本发明人等进行了深入研究。结果发现，通过在镀Sn钢板的表面形成含有锆氧化物和氧化锡的层，可以实现在耐黄变性、涂膜密合性及耐硫化黑变方面上更加优异的镀Sn钢板而不进行铬酸盐处理。基于上述见解而完成的本发明的主旨如下所述。
[1]本发明的一个方式的镀Sn钢板具备：
具有钢板、且在所述钢板的至少一面具有Sn镀层的母材镀敷钢板、以及
位于所述母材镀敷钢板上、且含有锆氧化物和氧化锡的被膜层，
所述镀Sn钢板的相当于一面的Sn的附着量为0.1g/m2以上且15g/m2以下，所述被膜层中的所述锆氧化物的含量以金属Zr量计为1mg/m2以上且30mg/m2以下的范围内，所述被膜层中的所述氧化锡基于X射线光电子能谱法得到的Sn3d5/2的结合能的峰位置距离金属Sn的结合能的峰位置为1.4eV以上且小于1.6eV的范围内，所述氧化锡的还原所需的电量为大于5.0mC/cm2且20mC/cm2以下的范围内。
[2]本发明的一个方式的镀Sn钢板的制造方法包括：第1工序，对于在钢板的至少一面形成有含有0.1g/m2以上且15g/m2以下的Sn的Sn镀层的母材镀敷钢板，实施在含有锆离子的溶液中的浸渍处理、或在含有锆离子的溶液中的阴极电解处理，由此形成含有锆氧化物的锆氧化物层；以及第2工序，在所述第1工序之后，在含氧气体氛围中，在同时满足以下的式1及式2的条件下，对形成有所述锆氧化物层的所述母材镀敷钢板进行加热处理，所述式1及式2中，加热温度T的单位为K，加热时间t的单位为小时。
0.11×exp(2400/T)＜t＜0.65×exp(2400/T)···(式1)
308＜T＜373···(式2)
[3]在上述[2]的方式中，所述第2工序中的所述加热处理可以在含有氧且水蒸气量为60体积％以上且90体积％以下的范围内的气体氛围中实施。
[4]在上述[2]或上述[3]的方式中，所述含有锆离子的溶液的锆离子浓度可以为100ppm以上且4000ppm以下，所述含有锆离子的溶液的pH值可以为3以上且5以下。
[5]在上述[2]～[4]中任一项所述的方式中，在所述第1工序中，可以通过阴极电解处理形成所述锆氧化物层，将所述阴极电解处理中的电流密度设为0.05A/dm2以上且50A/dm2以下。
发明的效果
如上所述，根据本发明的上述各方式，可以在不进行现有的铬酸盐处理的情况下提供在耐黄变性、涂膜密合性及耐硫化黑变性方面更加优异的镀Sn钢板及镀Sn钢板的制造方法。
附图说明
图1是示出本发明的一个实施方式的镀Sn钢板的图，是沿其板厚方向的剖面图。
图2是示出在实施例2中使加热处理时的温度和时间改变时的结果的图表。
符号说明
1 钢板
2 Sn镀层
3 母材镀敷钢板
4 被膜层
10 镀Sn钢板
具体实施方式
以下，对本发明的一个实施方式进行详细说明。
以下说明的本实施方式涉及在食品罐、饮料罐等罐用途及其它用途中广泛使用的镀Sn钢板及该镀Sn钢板的制造方法。更具体而言，涉及不进行现有的铬酸盐处理、且在耐黄变性、涂膜密合性及耐硫化黑变性方面更加优异的镀Sn钢板及该镀Sn钢板的制造方法。
(关于镀Sn钢板)
如图1所示，本实施方式的镀Sn钢板10在母材镀敷钢板3的表面具有被膜层4，所述母材镀敷钢板3在钢板1的至少一个表面1a形成有Sn镀层2，所述被膜层4含有给定量的锆氧化物和氧化锡。
更具体而言，本实施方式的镀Sn钢板1具有母材镀敷钢板3和被膜层4，所述母材镀敷钢板3在钢板1的至少一面形成有Sn镀层2，所述被膜层4位于该母材镀敷钢板3上、且含有锆氧化物和氧化锡，Sn镀层2的相当于一面的Sn的附着量为0.1g/m2以上且15g/m2以下。
需要说明的是，图1中示出了仅在钢板1的一面、即表面1a依次形成有Sn镀层2及被膜层4的情况，但并不仅限于该形态。即，还包括在上述结构的基础上，在钢板1的背面1b依次形成有Sn镀层2及被膜层4的情况。在这样于两面形成Sn镀层2的情况下，在表面1a形成的Sn镀层2的Sn的附着量可以为0.1g/m2以上且15g/m2以下，同时，在背面1b形成的Sn镀层2的Sn的附着量也可以为0.1g/m2以上且15g/m2以下。此外，在钢板1的两面形成Sn镀层2，可以是它们中的一者的Sn镀层2的Sn的附着量为0.1g/m2以上且15g/m2以下，而另一者的Sn镀层2的Sn的附着量为0.1g/m2以上且15g/m2以下的范围以外。
在本实施方式的镀Sn钢板10中，该被膜层4中的锆氧化物的含量以金属Zr量计为相当于一面1mg/m2以上且30mg/m2以下。另外，在本实施方式的镀Sn钢板10中，被膜层4中的氧化锡基于XPS(X-ray Photoelectron Spectroscopy：X射线光电子能谱法)得到的Sn3d5/2的结合能的峰位置距离金属Sn的结合能的峰位置为1.4eV以上且小于1.6eV的范围内，而且氧化锡的还原所需的电量为大于5.0mC/cm2且为20mC/cm2以下的范围内。
需要说明的是，在对被膜层4中的锆氧化物的含量及基于XPS的Sn3d5/2的结合能的峰位置进行测定时，需要排除因被膜层4的最表层的污物造成的对测定精度的影响。因此，优选对被膜层4的最表层进行蚀刻，在从被膜层4的稍靠内部的位置(例如距离蚀刻前的表层位置0.5nm的深度位置)至5nm深度位置的范围内进行测定。
以下，对具有上述结构的镀Sn钢板10进行详细说明。
<关于钢板1>
作为本实施方式的镀Sn钢板10的母材而使用的钢板1并没有特别限定，只要是通常的容器用的镀Sn钢板所使用的钢板即可，可以使用任意的钢板。作为这样的钢板1，例如可以举例出低碳钢、超低碳钢等。另外，对于使用的钢板1的制造方法、材质也没有特别限定，例如可以适当利用经过从铸造到热轧、酸洗、冷轧、退火、调质轧制等工序而制造的钢板。
<关于Sn镀层2>
在如上所述的钢板1的至少一面实施镀Sn，形成Sn镀层2。通过该Sn镀层2提高钢板1的涂装后耐腐蚀性。需要说明的是，本说明书中的“镀Sn”不仅包括基于金属Sn的镀敷，还包括金属Sn中混入有杂质的镀敷、金属Sn中含有微量元素的镀敷。
对钢板1的表面1a实施镀Sn的方法没有特别限定，例如优选为公知的电镀法，也可以使用通过将钢板1浸渍于熔融的Sn中而进行镀敷的熔融法。作为电镀法，例如可以利用使用了公知的费洛斯坦镀锡浴(Ferrostan Bath)、卤素浴、碱性浴等的电解法。
需要说明的是，在镀Sn后，可以实施将形成有Sn镀层2的钢板1加热至作为Sn的熔点的231.9℃以上的加热熔融处理。通过该加热熔融处理，使得镀Sn钢板10的表面出现光泽，并且在Sn镀层2与钢板1之间形成Sn和Fe的合金层，进一步提高涂装后耐腐蚀性。
<关于含有锆氧化物和氧化锡的被膜层4>
本实施方式的镀Sn钢板10在具有如上所述的Sn镀层2的母材镀敷钢板3的表面具有含有锆氧化物和氧化锡这两者的被膜层4。如上所述，该被膜层4中的锆氧化物的含量以金属Zr量计为相当于一面1mg/m2以上且30mg/m2以下的范围内。被膜层4中的氧化锡基于XPS得到的Sn3d5/2的结合能的峰位置距离金属Sn的结合能的峰位置为1.4eV以上且小于1.6eV的范围内，而且氧化锡的还原所需的电量为大于5.0mC/cm2且20mC/cm2以下的范围内。
需要说明的是，上述“Sn3d5/2”如上述非专利文献1中的记载那样是指Sn中的电子的能级。更具体而言，是指在Sn中自旋为平行的状态的3d电子的能级。
通过使本实施方式的镀Sn钢板10在Sn镀层2的表面2a上具有如上所述的锆氧化物和氧化锡共存的被膜层4，能够更进一步提高耐黄变性、涂膜密合性及耐硫化黑变性。需要说明的是，仅单独的锆氧化物或仅单独的氧化锡无法充分改善耐黄变性、涂膜密合性及耐硫化黑变性。其原因并未确定，但通过本发明人等的详细研究，考虑如下。
虽然氧化锡一直被认为是黄变的原因，但本发明人等进行的探讨的结果发现，在镀Sn钢板上生成均匀且足够量的氧化锡时，存在耐黄变性反而提高的倾向。而且还发现，在镀Sn钢板上生成均匀且足够量的氧化锡时，存在不仅耐黄变性提高、而且同时耐硫化黑变性也提高的倾向。可以认为这是由于，黄变是因镀Sn钢板上的微小金属锡的溶出和氧化现象反复发生而产生的，对于这一点，可以通过用氧化锡包覆Sn镀层表面来抑制微小金属锡的溶出。为了获得该效果，需要设为氧化锡的还原所需的电量在大于5.0mC/cm2且20mC/cm2以下的范围内的氧化锡量。在氧化锡的还原所需的电量大于20mC/cm2的情况下，涂膜密合性变差，因此不优选。氧化锡的还原所需的电量的下限值优选为7.0mC/cm2，进一步优选为8mC/cm2。另外，氧化锡的还原所需的电量的上限值优选为15mC/cm2，进一步优选为12mC/cm2。需要说明的是，“氧化锡的还原所需的电量”是指，以将镀Sn钢板10的被膜层4中的氧化锡还原去除所需的时间与电流值的乘积的形式求出的电量，是实质上与被膜层4的量(膜厚)对应的数值。
为了获得由氧化锡带来的上述效果，需要锆氧化物在被膜层4中共存。这是由于，锆氧化物可改善含有氧化锡的被膜的脆性，提高涂膜密合性。另外，锆氧化物自身也具有提高耐硫化黑变性的效果。为了获得该效果，需要使锆氧化物的含量以金属Zr量计为1mg/m2以上且30mg/m2以下的范围内。在金属Zr量小于1mg/m2的情况下，无法抑制包含氧化锡的被膜的脆化。另一方面，在金属Zr量大于30mg/m2的情况下，锆氧化物的含量过量，反而降低涂膜密合性。锆化合物的含量的下限值优选为3mg/m2，进一步优选为5mg/m2。另外，锆化合物的含量的上限值优选为10mg/m2，进一步优选为8mg/m2。
需要说明的是，氧化锡基于XPS得到的Sn3d5/2的结合能的峰位置需要为距离金属Sn的结合能的峰位置1.4eV以上且小于1.6eV的范围内。在氧化锡具有上述范围以外的结合能值的情况下，涂膜密合性不稳定。
含有上述锆氧化物和氧化锡的被膜层4既可以是两者的混合状态，也可以是氧化物的固溶体，其存在状态没有限制。另外，在这些氧化物中进一步含有诸如P、Fe、Ni、Cr、Ca、Na、Mg、Al、Si等的任何元素，也完全没有问题。即，作为被膜层4的成分，除了锆氧化物和氧化锡以外，还可以进一步含有其它成分(磷化合物、氟化物等)。
这里，上述Zr的附着量采用如下测得的值：将在表面形成有本实施方式的被膜层4的镀Sn钢板10浸渍于例如氢氟酸和硫酸等酸性溶液而将其溶解，通过高频电感耦合等离子体(Inductively Coupled Plasma：ICP)发射光谱法等化学分析对所得溶解液进行测定而测得的值。或者，上述Zr的附着量通过荧光X射线测定来求出也无妨。
氧化锡的还原所需的电量按如下方法进行测定。即，在通过氮气的鼓泡等而去除了溶解氧的0.001mol/L的氢溴酸水溶液中，利用0.06mA/cm2的恒定电流对本实施方式的镀Sn钢板10进行阴极电解。此时，根据将氧化锡还原去除所需的时间与电流值的乘积，可以求出氧化锡的还原所需的电量。
另外，基于XPS得到的Sn3d5/2的结合能的峰位置可以使用公知的XPS测定装置通过公知的方法进行测定。
<镀Sn钢板的Sn附着量>
在本实施方式的镀Sn钢板10中，相当于一面的Sn附着量以金属Sn量计为0.1g/m2以上且15g/m2以下。如以下的详细说明所述，本实施方式的镀Sn钢板10的被膜层4是通过在给定条件下对形成有锆氧化物层的镀Sn钢板(原材料)进行加热处理、使Sn镀层2中的Sn扩散到锆氧化物层中而形成的。因此，在本实施方式的镀Sn钢板10中，上述相当于一面的Sn附着量是Sn镀层2中存在的未扩散到被膜层4中的Sn的含量、和被膜层4中存在的氧化锡的换算为金属Sn量的总计值。
在本实施方式的镀Sn钢板10中，相当于一面的Sn附着量小于0.1g/m2时，涂装后耐腐蚀性差，是不优选的。另外，相当于一面的Sn附着量大于15g/m2时，由Sn带来的涂装后耐腐蚀性的提高效果充分，附着量的进一步增加从经济性的观点考虑是不优选的，而且还存在涂膜密合性降低的倾向。在本实施方式的镀Sn钢板10中，相当于一面的Sn附着量的下限值优选为1.0g/m2，进一步优选为2.0g/m2。另外，相当于一面的Sn附着量的上限值优选为10g/m2，进一步优选为7.0g/m2。
这里，如上所述的相当于一面的Sn的附着量例如采用通过JIS G 3303中记载的电解法、荧光X射线法测得的值。
(关于镀Sn钢板10的制造方法)
以下，对本实施方式的镀Sn钢板的制造方法进行详细说明。在本实施方式的镀Sn钢板的制造方法中，使用在钢板1的至少一面以相当于一面的Sn附着量为0.1g/m2以上且15g/m2以下的方式形成有Sn镀层2的母材镀敷钢板3作为原材料。
这里，对于母材镀敷钢板3的制造方法没有特别限定，可以通过利用公知的镀敷方法以相当于一面的镀Sn附着量为0.1g/m2以上且15g/m2以下的方式对具有希望的机械强度(例如拉伸强度等)的公知的钢板1实施镀Sn来制造。另外，也可以使用以相当于一面的附着量为上述范围内的方式预先实施了镀Sn的公知的镀Sn钢板(原材料)作为母材镀敷钢板3。
接着，对含有锆氧化物及氧化锡的被膜层4的形成方法进行详细说明。为了形成本实施方式的被膜层4，首先，在构成母材镀敷钢板3的Sn镀层2上形成含有锆氧化物的锆氧化物层。
对于含有锆氧化物的锆氧化物层而言，可以通过对形成有如上所述的Sn镀层2的母材镀敷钢板3实施在包含锆离子的溶液中的浸渍处理、或在包含锆离子的溶液中的阴极电解处理，从而在母材镀敷钢板3上形成。
但是，对于浸渍处理而言，由于通过对作为基底的母材镀敷钢板3的表面进行蚀刻来形成含有锆氧化物的锆氧化物层，因此其附着量容易不均匀，而且处理时间也长，因此在工业生产上是不利的。另一方面，对于阴极电解处理而言，由强制性的电荷移动及钢板界面处的氢产生所带来的表面清洁化与由pH值升高带来的附着促进效果相辅相成，可以得到均匀的被膜。此外，在该阴极电解处理中，通过在处理液中使硝酸根离子和铵离子共存，可以进行数秒钟至数十秒钟左右的短时间处理，因此在工业上是极为有利的。因此，本实施方式的含有锆氧化物的锆氧化物层的形成优选利用基于阴极电解的方法(阴极电解处理)。
以下，对进行阴极电解处理而形成锆氧化物层的情况进行详细说明，对于除电流密度等阴极电解处理所特有的条件以外的溶液相关的条件，也可以同样地适用于通过浸渍处理来形成锆氧化物层的情况。
这里，实施阴极电解处理的溶液中的锆离子的浓度可以根据生产设备、生产速度(能力)而适当调节。溶液中的锆离子浓度例如优选为100ppm以上且4000ppm以下。另外，在包含锆离子的溶液中包含氟离子、铵离子、硝酸根离子、硫酸根离子等其它成分也完全没有问题。
这里，进行阴极电解的溶液(阴极电解液)的液温没有特别限定，例如优选设为10℃以上且50℃以下的范围。通过在50℃以下进行阴极电解，可以形成由非常细小的粒子形成的致密且均匀的被膜组织。另一方面，在液温小于10℃的情况下，被膜的形成效率差，在夏季等外部气温高的情况下需要冷却溶液，不仅不经济，还有可能降低涂装后耐腐蚀性。另外，在液温大于50℃的情况下，形成的锆氧化物被膜组织变得不均匀，产生缺陷、破裂、微裂纹等而难以形成致密的被膜，有可能成为腐蚀等的起点，因此是不优选的。
另外，阴极电解液的pH值没有特别限定，优选为3以上且5以下。在pH值小于3的情况下，锆氧化物的生成效率可能降低，在pH值大于5的情况下，有可能在溶液中产生大量的沉淀，连续生产性降低。
需要说明的是，为了调节阴极电解液的pH值、提高电解效率，可以使阴极电解液中含有例如硝酸、氨水等。特别是为了实现阴极电解处理的短时间化，优选使阴极电解液中含有硝酸及氨水。
另外，阴极电解处理中的电流密度例如优选设为0.05A/dm2以上且50A/dm2以下的范围内。在电流密度小于0.05A/dm2的情况下，有可能导致锆氧化物的形成效率降低，难以稳定地形成含有锆氧化物的被膜层，不仅耐黄变性、耐硫化黑变性降低，而且涂装后耐腐蚀性也降低，因此是不优选的。另一方面，在电流密度大于50A/dm2的情况下，有可能使锆氧化物的形成效率过高，形成粗大且密合性差的锆氧化物，因此是不优选的。电流密度的范围的下限值更优选为1A/dm2，进一步优选为2A/dm2。电流密度的范围的上限值更优选为10A/dm2，进一步优选为6A/dm2。
需要说明的是，在形成锆氧化物层时，阴极电解的时间没有限制。对于作为目标的Zr附着量，根据电流密度而适当调整阴极电解的时间即可，例如在以如上所述的电流密度的范围进行阴极电解处理的情况下，通电时间可以设为0.3～5秒钟左右。
另外，作为阴极电解处理中使用的溶液的溶剂，例如可以使用蒸馏水等，但并不限定于蒸馏水等溶剂，可以根据待溶解的材料、形成方法等而适当选择。
阴极电解中的锆例如可以使用H2ZrF6这样的锆络合物作为锆的供给源。如上所述的锆络合物中的Zr随阴极电极界面的pH值的上升而形成Zr4+存在于阴极电解液中。这样的锆离子在阴极电解液中进一步反应，形成锆氧化物。在电解液中包含磷酸的情况下，还形成磷酸锆。
另外，作为进行阴极电解时的通电模式，无论是连续通电还是间歇通电均完全没有问题。
本实施方式的含有锆氧化物及氧化锡的被膜层4是通过在给定条件下对形成有如上所述的含有锆氧化物的锆氧化物层的母材镀敷钢板3进行加热处理而得到的。具体而言，在母材镀敷钢板3的Sn镀层2上形成锆氧化物层后，通过在含氧气体氛围中，在同时满足与温度T(单位：K)及时间t(单位：小时)相关的以下的式101及式102的条件下进行加热，可以得到本实施方式的镀Sn钢板10。即，通过利用以下详细说明的加热处理使Sn镀层2中的Sn扩散至锆氧化物层，扩散的Sn被氧化而形成氧化锡。通过该加热处理，使得氧化锡的生成量与如上所述的还原所需的电量相对应，且使得氧化锡基于XPS得到的Sn3d5/2的结合能的峰位置为如上所述的范围内。
0.11×exp(2400/T)＜t＜0.65×exp(2400/T)···(式101)
308＜T＜373···(式102)
上述的制造方法中的加热方法没有任何限定，例如可以应用气体氛围加热、感应加热、通电加热等公知的加热方法。这里，加热温度如上述式102所示，需要大于308K且小于373K(即大于35℃且小于100℃)。在加热温度为308K以下的情况下，不均匀地形成氧化锡，性能不提高。另一方面，在加热温度为373K以上的情况下，氧化锡的结构变化，外观变差，因此是不适当的。
这里，上述式101是本发明人等一边使加热处理时的加热温度和加热时间分别变化，一边验证得到的镀Sn钢板10是否落入本实施方式的范围内，从而通过实验得到的。即，本发明人等一边使加热处理时的加热温度T(K)和加热时间t(小时)分别变化，一边制造镀Sn钢板10，并验证得到的镀Sn钢板10是否落入本实施方式的范围内。在此基础上，对于由加热时间t(小时)及加热温度T(K)确定的坐标平面，在与各镀Sn钢板10的加热条件对应的位置对得到的验证结果进行描点。然后，为了得到给出作为本实施方式的范围内的区域的边界的曲线，对于坐标平面上的描点，在上述式102限定的加热温度T(K)的范围内，使用公知的数值计算应用程序应用非线性最小二乘法。通过这样的事先的验证，本发明人等得到了以上述式101表示的关系。
由本发明人等进行的上述的研究结果表明，加热处理工序的加热温度T[K]及加热时间t[小时]优选满足以下的式103，更优选满足以下的式104。
0.22×exp(2400/T)＜t＜0.55×exp(2400/T)···(式103)
0.33×exp(2400/T)＜t＜0.44×exp(2400/T)···(式104)
需要说明的是，对于加热处理工序的升温速度、冷却速度没有特别限定，可以根据公知的方法而适当设定。另外，如果为含氧气体氛围，则进行加热的气体氛围也没有特别限定，含氧气体氛围中的水蒸气量优选设为60～90体积％的范围内。可以认为通过在该范围内进行加热处理，可更均匀地生成氧化锡，性能变得良好。
实施例
接下来，一边示出实施例一边对本实施方式的镀Sn钢板10及镀Sn钢板10的制造方法进行具体说明。需要说明的是，以下所示的实施例仅是举例，本发明的镀Sn钢板及镀Sn钢板的制造方法并不仅限定于下述例子。
(实施例1)
<试验材料>
对于板厚0.2mm的低碳冷轧钢板(对应于钢板1)，作为前处理，进行了电解碱性脱脂、水洗、稀硫酸浸渍酸洗、水洗之后，使用苯酚磺酸浴实施电镀Sn，然后，进一步进行了加热熔融处理。镀Sn的附着量以相当于一面约2.8g/m2为标准，但一部分试验材料通过改变通电时间而使镀Sn的附着量发生了变化。另外，还一并制作了在电镀Sn后未进行加热熔融处理的试验材料。镀Sn附着量通过利用荧光X射线法(Rigaku公司制造的ZSX Primus)进行测定来确定。
在包含氟化锆的水溶液中对如上所述制作的镀Sn钢板进行阴极电解，在镀Sn钢板上形成了锆氧化物层。阴极电解液中的锆浓度设为1400ppm。另外，阴极电解液的浴温设为35℃，而且阴极电解液的pH值调整为3以上且5以下，并根据作为目标的Zr附着量而适当调整了电流密度及阴极电解时间。制作各试验材料时的电流密度及阴极电解时间如以下的表1所示。
另外，按照以下的表1所示的各种加热温度及加热时间保持形成有锆氧化物层的镀Sn钢板，形成了含有锆氧化物和氧化锡的被膜层。需要说明的是，作为比较，还一并制作了仅形成锆氧化物层而未进行加热处理的试验材料(No.1B、No.3B)、以及未形成锆氧化物而仅实施了加热处理的试验材料(No.7B)。另外，一部分试验材料在形成锆氧化物之前在碳酸钠水溶液中进行阳极电解处理，使氧化锡的结构发生了变化(No.5B、No.6B)。对于这样制作的镀Sn钢板进行了以下所示的各种评价。另外，一部分试验材料通过在包含氟化锆的水溶液中交替反复进行阴极电解和阳极电解的交替电解处理而形成了锆氧化物(No.9B)。
[Zr附着量]
各试验材料的被膜层的相当于一面的Zr附着量使用Rigaku公司制造的ZSXPrimus通过荧光X射线法进行了测定。将得到的Zr附着量一并示于以下的表1。
[氧化锡量]
对于各试验材料，在通过氮气鼓泡而去除了溶解氧的0.001mol/L的氢溴酸水溶液中，以0.06mA/cm2的恒定电流进行阴极电解，根据将氧化锡还原去除为止所需的时间与电流的乘积测定了氧化锡的还原所需的电量。将测得的电量一并示于以下的表1的“氧化锡量”一栏。
[XPS中的峰位置]
对于各试验材料，使用XPS(ULVAC-PHI制造的PHI Quantera SXM)测定Sn3d5/2的结合能的峰位置，计算出该峰位置距离金属Sn的结合能的峰位置的位移量。将得到的位移量一并示于以下的表1的“Sn3d5/2的结合能峰位置”一栏。
[耐黄变性]
耐黄变性如下进行评价。
对如上所述制作的各试验材料进行在保持40℃、相对湿度80％的恒温恒湿槽中放置4周的湿润试验，求出湿润试验前后的色坐标b*值的变化量Δb*，进行了评价。如果变化量Δb*为1以下则评价为3分，如果大于1且为2以下则评价为2分，如果为2～3则评价为1分，如果大于3则评价为0分，将评价为1分以上作为合格。需要说明的是，色坐标b*使用作为市售的色差计Suga Test Instruments公司制造的SC-GV5进行测定，色坐标b*的测定条件设为光源C、全反射、测定直径30mm。
[耐硫化黑变性]
耐硫化黑变性如下进行评价。
在如上所述制作的各试验材料的表面以干燥质量7g/m2涂布市售的罐用环氧树脂涂料，然后在200℃下烧结10分钟，在室温下放置24小时。然后，将得到的各试验材料切割成给定的尺寸，浸渍于分别含有0.3质量％的磷酸二氢钠、0.7质量％的磷酸氢钠、0.6质量％的L-半胱氨酸盐酸盐的水溶液中，在密封容器中进行121℃、60分钟的蒸煮处理，根据试验后的外观进行评价。如果在试验前后完全没有确认到外观的变化则评价为2分，如果确认到略微发生黑变(发生黑变的面积为10％以下)则评价为1分，如果在试验面的大于10％的区域确认到黑变则评价为0分，将评价为1分以上作为合格。
[涂膜密合性]
涂膜密合性如下进行评价。
对如上所述制作的各试验材料按上述[耐黄变性]中记载的方法进行湿润试验，然后在表面以干燥质量7g/m2涂布市售的罐用环氧树脂涂料，在200℃下烧结10分钟，在室温下放置24小时。然后，对于得到的各试验材料，以棋盘格状划出达到钢板表面的损伤(3mm间隔且纵横各7条的损伤)，进行该部位的胶带剥离试验，由此进行了评价。如果胶带粘贴部位的涂膜全部未剥离则评价为2分，如果在棋盘格的损伤部周围确认到涂膜剥离则评价为1分，如果在棋盘格的格内确认到涂膜剥离则评价为0分，将评价为1分以上作为合格。
[涂装后耐腐蚀性]
涂装后耐腐蚀性如下进行评价。
在按照上述[涂膜密合性]中记载的方法制作并进行了湿润试验的各试验材料的表面，以干燥质量7g/m2涂布市售的罐用环氧树脂涂料，然后在200℃下烧结10分钟，在室温下放置24小时。然后，将得到的各试验材料切割成40mm×40mm的尺寸，通过肉眼观察评价了60℃的温度环境下在市售的番茄汁中浸渍7天后有无生锈。如果完全没生锈则评价为2分，如果略微生锈(生锈的面积为5％以下)则评价为1分，如果生锈超过5％则评价为0分，将评价为1分以上作为合格。
[综合性能]
另外，作为综合性能，求出各种性能的评分的总和，将其总计值为8分或9分的情况评价为“优秀”，将6分或7分的情况评价为“良好”，将4分或5分的情况评价为“一般”，在任何一项性能中存在0分的情况下，将总计值记为0分并评价为“差”，将评分优秀、良好、一般作为合格。
Figure BDA0002658158080000151
根据上述表1可知，属于发明例的试验材料的任一项性能均良好。另一方面可知，属于比较例的试验材料的耐黄变性、涂膜密合性、耐硫化黑变性、涂装后耐腐蚀性中的任一项差。
(实施例2)
对于板厚0.2mm的低碳冷轧钢板，作为前处理，进行了电解碱性脱脂、水洗、稀硫酸浸渍酸洗、水洗之后，使用苯酚磺酸浴实施电镀Sn，然后，进一步进行了加热熔融处理。Sn的附着量设为相当于一面2.8g/m2。
在包含氟化锆的水溶液中对如上所述制作的镀Sn钢板进行阴极电解，在镀Sn钢板上形成锆氧化物层。阴极电解液中的锆浓度设为1400ppm。另外，阴极电解液的浴温设为35℃，而且阴极电解液的pH值调整为3以上且5以下，并适当调整了电流密度及阴极电解时间，使得Zr附着量为5mg/m2。
另外，以各种加热温度及加热时间保持形成有锆氧化物层的镀Sn钢板，形成含有锆氧化物和氧化锡的被膜层，将得到的各镀Sn钢板作为试验材料。
对于得到的各试验材料，与上述实施例1中记载的方法同样地评价各种性能，根据各评价项目的总计分进行综合性能的评价。综合性能的评价标准与实施例1相同。将结果汇总于以下的表2。另外，在由加热温度T[℃]及加热时间t[小时]确定的坐标平面中，在与各试验材料的加热温度及加热时间的组合相对应的位置，对得到的综合性能的评价结果进行描点绘图。将得到的图示于图2。
[表2]
Figure BDA0002658158080000171
需要说明的是，图2中一并示出了由上述式101、式103及式104的各自的最左边及最右边所确定的曲线。
根据图2可知，在本实施方式的范围内的条件下实施了加热处理的情况下，可以获得良好的性能，另一方面，在本实施方式的范围以外的条件下实施了加热处理的情况下，无法获得良好的性能。
以上，对本发明的优选的实施方式进行了详细说明，但本发明并不仅限定于上述例子。具有本发明所属技术领域的常识的人可以在权利要求书中记载的技术构思的范畴内显而易见地想到各种变更例或修正例，这些例子当然也属于本发明的技术范围。
工业实用性
如上所述，本发明的镀Sn钢板无需进行现有的铬酸盐处理，耐黄变性、涂膜密合性、耐硫化黑变性优异，因此可以作为环境友好的罐用材料而广泛用于食品罐、饮料罐等，工业上的利用价值极高。

Claims (5)

1.一种镀Sn钢板，其具备：
具有钢板、且在所述钢板的至少一面具有Sn镀层的母材镀敷钢板、以及
位于所述母材镀敷钢板上、且含有锆氧化物和氧化锡的被膜层，
所述镀Sn钢板的相当于一面的Sn的附着量为0.1g/m2以上且15g/m2以下，
所述被膜层中的所述锆氧化物的含量以金属Zr量计为1mg/m2以上且30mg/m2以下的范围内，
所述被膜层中的所述氧化锡基于X射线光电子能谱法得到的Sn3d5/2的结合能的峰位置距离金属Sn的结合能的峰位置为1.4eV以上且小于1.6eV的范围内，
所述氧化锡的还原所需的电量为大于5.0mC/cm2且20mC/cm2以下的范围内。
2.一种镀Sn钢板的制造方法，该方法包括：
第1工序，对于在钢板的至少一面形成有含有0.1g/m2以上且15g/m2以下的Sn的Sn镀层的母材镀敷钢板，实施在含有锆离子的溶液中的浸渍处理、或在含有锆离子的溶液中的阴极电解处理，由此形成含有锆氧化物的锆氧化物层；以及
第2工序，在所述第1工序之后，在含氧气体氛围中，在同时满足以下的式1及式2的条件下，对形成有所述锆氧化物层的所述母材镀敷钢板进行加热处理，所述式1及式2中，加热温度T的单位为K，加热时间t的单位为小时；
0.11×exp(2400/T)＜t＜0.65×exp(2400/T)···(式1)
308＜T＜373···(式2)。
3.根据权利要求2所述的镀Sn钢板的制造方法，其中，所述第2工序中的所述加热处理在含有氧且水蒸气量为60体积％以上且90体积％以下的范围内的气体氛围中实施。
4.根据权利要求2或3所述的镀Sn钢板的制造方法，其中，所述含有锆离子的溶液的锆离子浓度为100ppm以上且4000ppm以下，所述含有锆离子的溶液的pH值为3以上且5以下。
5.根据权利要求2～4中任一项所述的镀Sn钢板的制造方法，
在所述第1工序中，
通过阴极电解处理形成所述锆氧化物层，
将所述阴极电解处理中的电流密度设为0.05A/dm2以上且50A/dm2以下。
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