CN103097580A - 耐蚀性优良的罐用钢板 - Google Patents

耐蚀性优良的罐用钢板 Download PDF

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CN103097580A
CN103097580A CN2011800390223A CN201180039022A CN103097580A CN 103097580 A CN103097580 A CN 103097580A CN 2011800390223 A CN2011800390223 A CN 2011800390223A CN 201180039022 A CN201180039022 A CN 201180039022A CN 103097580 A CN103097580 A CN 103097580A
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steel plate
rete
corrosion
alloy layer
tanks
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平野茂
河端诚
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Abstract

本发明提供一种耐蚀性、密合性、焊接性优良的罐用钢板，该罐用钢板具备：钢板、形成在所述钢板的至少一方表面上的Ni-Cu合金镀层、形成在所述Ni-Cu合金镀层的表面上的铬酸盐被膜层，在所述Ni-Cu合金镀层中，Ni附着量为0.30～3.0g/m2，且Cu含量为0.5～20质量%，在所述铬酸盐被膜层中，Cr附着量按Cr换算量计为1.0～40mg/m2。

Description

耐蚀性优良的罐用钢板
技术领域
本发明涉及罐用钢板，特别是涉及2片罐及3片罐中使用的钢板，即耐蚀性、密合性、焊接性优良的罐用钢板。
本申请基于2010年8月18日提出的日本专利申请第2010-182661号公报并主张其优先权，这里引用其内容。
背景技术
在主要用于饮料罐领域的铁制的容器中，有2片罐和3片罐。所谓2片罐，是罐底和罐筒部为一体的罐体，已知有DrD罐、DI罐等，通过深冲加工、减径拉拔加工、弯曲-返弯加工或者通过组合这些加工进行成形。这些罐体所用的钢板，有镀锡钢皮（镀Sn钢板）或TFS（电解铬酸处理钢板（无锡钢板）），根据用途及加工方法而分别使用。
3片罐是罐筒部和底部分开的罐体，通过焊接制造罐筒部的焊接罐为主流。作为罐筒部的材料，使用薄的镀Sn钢板或镀Ni钢板。此外，作为底部的材料，使用TFS等。
无论在2片罐中还是在3片罐中，为了向消费者宣传商品价值，而在罐外表面实施印刷。此外，在罐内表面，为了确保耐蚀性而涂敷树脂。以往的2片罐在进行了罐体的成形后，通过喷涂等涂装罐内表面侧，对罐外表面侧实施曲面印刷。此外，最近，将预先层叠了PET薄膜的钢板成形成罐的层叠2片罐正在兴起（专利文献1、专利文献2）。此外，关于构成3片罐的焊接罐，以往，通过对罐内表面实施了涂装、同时罐外表面实施了印刷的钢板进行焊接来制造罐体，但取代涂装加工而采用层叠有预先印刷过的PET薄膜的层叠钢板制造的3片罐也在兴起（专利文献3、专利文献4）。
在制造2片罐时，对罐用钢板实施深冲加工及减径拉拔加工、弯曲-返弯加工，此外，在制造3片罐时也对罐用钢板实施收口加工及凸缘加工，根据情况实施用于设计性的扩径加工。所以对于用作罐用钢板的层叠钢板，要求能够追随这些加工的优良的薄膜密合性。
镀Sn钢板虽通过Sn的优良的替代防腐作用即使对酸性的内装物也具有优良的耐蚀性，但因在其最表层存在脆弱的Sn氧化物而使薄膜的密合性不稳定。因此，在接受上述加工时，存在薄膜发生剥离、或薄膜与钢板的密合力不足的地方成为发生腐蚀的起点等问题。
因而，一直在使用加工性及密合性优良、而且可焊接的镀Ni钢板作为容器用的层叠钢板（专利文献5）。镀Ni钢板很早就有公开（例如专利文献9）。作为镀Ni钢板，已知有如镀Sn钢板那样表面无光泽的钢板，另一方面已知有采用添加了光泽剂的镀Ni方法实施了光泽镀的钢板（专利文献6、专利文献7）。
可是，已知：Ni在酸性溶液中不具有Sn那样的替代防腐作用，因此对于酸性饮料等腐蚀性高的内装物，从Ni镀层的针孔等缺陷部开始，发生腐蚀向板厚方向扩展的穿孔腐蚀，在短时间内达到开孔。因此，要求提高镀Ni钢板的耐蚀性。为了减轻穿孔腐蚀，还发明了为使要镀敷的钢板的电位向高的方向靠近而调整了钢成分的镀Ni钢板（专利文献8）。
现有技术文献
专利文献
专利文献1：日本特开2000-263696号公报
专利文献2：日本特开2000-334886号公报
专利文献3：日本专利3060073号公报
专利文献4：日本专利2998043号公报
专利文献5：日本特开2007-231394号公报
专利文献6：日本特开2000-26992号公报
专利文献7：日本特开2005-149735号公报
专利文献8：日本特开昭60-145380号公报
专利文献9：日本特开昭56-169788号公报
发明内容
发明要解决的问题
在上述专利文献8所述的发明中，对于减轻穿孔腐蚀取得了一定的效果，但希望进一步提高耐蚀性。此外，专利文献8所述的发明因限定钢成分而只适用于一部分用途。因而，一直要求可适用于多类内装物或罐形状的镀Ni钢板。本发明是鉴于上述情况而完成的，其课题是提供一种耐蚀性、密合性、焊接性优良的罐用钢板。
用于解决课题的手段
本发明为了完成上述课题而采用以下手段。
（1）本发明的第一方式是一种耐蚀性、密合性、焊接性优良的罐用钢板，其具备钢板、形成在所述钢板的至少一方表面上的Ni-Cu合金镀层、形成在所述Ni-Cu合金镀层的表面上的铬酸盐被膜层；在所述Ni-Cu合金镀层中，Ni附着量为0.30～3.0g/m2，且Cu含量为0.5～20质量%；在所述铬酸盐被膜层中，Cr附着量按Cr换算量计为1.0～40mg/m2。
（2）本发明的第二方式是一种耐蚀性、密合性、焊接性优良的罐用钢板，其具备钢板、形成在所述钢板的至少一方表面上的Ni-Cu合金镀层、形成在所述Ni-Cu合金镀层的表面上的含Zr被膜层；在所述Ni-Cu合金镀层中，Ni附着量为0.30～3.0g/m2，且Cu含量为0.5～20质量%；在所述含Zr被膜层中，Zr附着量按Zr换算量计为1.0～40mg/m2。
发明效果
根据本发明，可得到耐蚀性优良的、而且与层叠的树脂薄膜的密合性及焊接性优良的罐用钢板。
附图说明
图1是表示Ni镀层中的Cu含有率（质量%）与穿孔腐蚀深度的关系的曲线图。
图2是表示本发明的实施方式的罐用钢板的结构的一个例子的概略图。
图3是表示本发明的实施方式的罐用钢板的结构的另一个例子的概略图。
具体实施方式
本发明者们发现了下述现象：为了应对减轻穿孔腐蚀，通过使Cu含在Ni镀层中，在腐蚀从Ni镀层的针孔等缺陷部开始扩展时，穿孔腐蚀速度下降（参照图1）。
推测此现象是通过以下的机理进行的。在酸性溶液中，与Ni相比Cu的溶出速度快，容易被腐蚀，由此认为对于含Cu的Ni镀层也产生同样的效果，Ni镀层和基底金属的电位差变小，腐蚀速度下降。本发明者们利用此现象，达成发明了密合性、耐蚀性、焊接性优良的罐用钢板。
以下，对基于上述发现的本发明的实施方式的耐蚀性、密合性、焊接性优良的罐用钢板进行详细说明。
如图2所示，本发明的实施方式的罐用钢板1具备钢板11、形成在钢板11的至少一方表面上的Ni附着量为0.30～3.0g/m2且Cu含量为0.5～20质量%的范围的Ni-Cu合金镀层12、和形成在Ni-Cu合金镀层12的表面上的铬酸盐被膜层13A。
另外，如图3所示，在所述Ni-Cu合金镀层12的表面，也可以取代铬酸盐被膜层13A而形成含Zr被膜层13B。
铬酸盐被膜层13A按Cr换算量计以1.0～40mg/m2的附着量形成在Ni-Cu合金镀层12上。此外，含Zr被膜层13B按Zr量计以1.0～40mg/m2的附着量形成在Ni-Cu合金镀层12上。
钢板11为罐用钢板1的镀敷原板，能够采用从通常的钢坯制造工序经过热轧、酸洗、冷轧、退火、调质轧制等工序制造的钢板11。钢板11的板厚只要在0.15mm～0.23mm的范围就可以。在作为镀敷原板的钢板11上，为了确保耐蚀性、密合性、焊接性，形成有Ni-Cu合金镀层12。Ni是同时具有对钢板11的密合性和锻接性（在熔点以下的温度下接合的特性）的金属，因此通过将对钢板11进行镀敷时的附着量按Ni量计规定为0.30g/m2以上，开始发挥实用的密合性或焊接性。Ni附着量在0.40g/m2以上时，发挥优良的密合性及焊接性，但如果Ni附着量超过1.0g/m2，则焊接部的接合强度开始缓慢下降，如果超过3.0g/m2，则焊接部的结合强度开始缓慢下降，如果超过3.0g/m2，焊接部的实用上的接合强度下降，焊接性劣化。所以，需要将Ni附着量规定为0.30～3.0g/m2，优选规定为0.40～1.0g/m2。
此外，如果Ni-Cu合金镀层12中的Cu含有率过低，则促进穿孔腐蚀，因此不优选。在Ni-Cu合金镀层12中的Cu含有率为0.5%以上时，开始抑制穿孔腐蚀速度。另一方面，如果Ni-Cu合金镀层12中的Cu含有率过剩，则损害Ni的锻接性，其结果是，焊接性劣化。所以，需要使Ni-Cu合金镀层12中的Cu含有率在20%以下。此外，在Ni-Cu合金镀层12中，除Cu以外，还含有不可避免的杂质。
作为在钢板11上形成上述Ni-Cu合金镀层12的方法，以在由硫酸镍或氯化镍构成的公知的酸性镀镍溶液中溶解有硫酸铜或氯化铜的溶液作为镀液进行阴极电解的方法在工业上是有用的，但也不特别限定于这些方法。
在Ni-Cu合金镀层12上，为了提高耐蚀性、与树脂薄膜的密合性、特别是加工后的二次密合性，进行铬酸盐处理。通过铬酸盐处理，形成由水合氧化Cr构成的、或由水合氧化Cr和金属Cr构成的铬酸盐被膜层13A。
构成铬酸盐被膜层13A的金属Cr或水合氧化Cr具有优良的化学稳定性，所以罐用钢板1的耐蚀性与铬酸盐被膜量成正比地提高。此外，水合氧化Cr通过与树脂薄膜的官能团形成强固的化学键，即使在加热水蒸汽气氛下也可发挥优良的密合性，因此铬酸盐被膜层13A的附着量越大，与树脂薄膜的密合性越提高。要在实用上发挥充分的耐蚀性及密合性，按金属Cr换算量计为1.0mg/m2以上的铬酸盐被膜层13A是必要的。
通过增加铬酸盐被膜层13A的附着量，耐蚀性、密合性的提高效果也增大，但由于铬酸盐被膜层13A中的水合氧化Cr是电绝缘体，所以如果铬酸盐被膜层13A的附着量增大，则罐用钢板1的电阻非常高，成为使焊接性劣化的主要原因。具体地讲，如果铬酸盐被膜层13A的附着量按金属Cr换算量计超过40mg/m2，则焊接性严重劣化。所以，需要将铬酸盐被膜层13A的附着量按金属Cr换算计规定在40mg/m2以下。
铬酸盐处理方法可以采用各种Cr酸的钠盐、钾盐、铵盐的水溶液的浸渍处理、喷涂处理、电解处理等中的任一种方法进行。在向Cr酸中添加了作为镀敷助剂的硫酸离子、氟化物离子（包含络离子）或它们的混合物的水溶液中实施阴极电解处理，在工业上也是优选的。
此外，也可以取代上述铬酸盐被膜层13A而在Ni-Cu合金镀层12上形成含Zr被膜层13B。含Zr被膜层13B是含有氧化Zr、磷酸Zr、氢氧化Zr、氟化Zr等Zr化合物的被膜或是它们的复合被膜。如果作为金属Zr量以1.0mg/m2以上的附着量形成含Zr被膜层13B，则可以确认与树脂薄膜的密合性及耐蚀性与上述的铬酸盐被膜层13A同样地飞跃般地提高。另一方面，如果含Zr被膜层13B的附着量以金属Zr量计超过40mg/m2，则焊接性及外观性劣化。特别是，Zr被膜层因是电绝缘体而使电阻非常高，所以成为使焊接性劣化的主要原因，如果附着量按金属Zr换算计超过40mg/m2，则焊接性严重劣化。所以，需要将Zr被膜层的附着量按金属Zr量计规定在1.0～40mg/m2。
关于形成含Zr被膜层13B的方法，例如，可以采用将形成Ni-Cu合金镀层12后的钢板11在以氟化Zr、磷酸Zr、氟酸为主成分的酸性溶液中进行浸渍处理、或进行阴极电解处理的方法等。
根据本实施方式，可提高罐用钢板1的耐穿孔腐蚀性，同时提高焊接性、与树脂薄膜的密合性及加工后与树脂薄膜的密合性。
实施例
通过实施例对本发明进行更详细的说明。
首先，对本发明的发明例及比较例进行论述，其结果见表1。用以下的（1）所示的方法制作试样，对（2）的（a）～（d）各项目进行性能评价。
（1）试样制作方法
钢板（镀敷原板）：
使用板厚0.2mm的回火等级3（T-3）的镀锡用冷轧钢板作为镀敷原板。
Ni-Cu合金镀敷条件：在含有浓度20%的硫酸镍、浓度15%的氯化镍、1%的硼酸、调整到pH＝2的水溶液中，添加1～10%的硫酸铜，按5A/dm2进行阴极电解，在钢板上形成Ni-Cu合金镀层。利用电解时间控制Ni附着量。
铬酸盐处理条件：在含有浓度10%的氧化铬（VI）、浓度0.2%的硫酸、浓度0.1%的氟化铵的水溶液中，进行10A/dm2的阴极电解，水洗10秒钟，在Ni镀层上形成铬酸盐被膜层。利用电解时间控制铬酸盐被膜层的Cr附着量。
含Zr被膜层的处理条件：
在含有浓度5%的氟化锆、浓度4%的磷酸、浓度5%的氟酸的水溶液中，进行10A/dm2的阴极电解，在Ni镀层上形成含Zr被膜层。利用电解时间控制含Zr被膜层的Zr附着量。
（2）试样评价方法
（a）焊接性
在试验片上层叠厚度15μm的PET薄膜，在搭接量0.5mm、加压力45kgf、焊丝速度80m/min的条件下，变更电流，实施焊接，根据由可得到充分焊接强度的最小电流值及喷溅等焊接缺陷开始显著的最大电流值构成的适当电流范围的宽度和焊接稳定状态来综合判断适宜焊接条件的范围，以4阶段（A：非常宽、B：宽、C：实用上无问题、D：窄）进行评价。
（b）密合性
在试样上层叠15μm厚的PET薄膜，用DrD压力机制作筒头（cup）。用DI机械将该筒头成形成DI罐。观察成形后的DI罐的罐壁部的薄膜的剥离状况，以4阶段（A：完全没有发现剥离、B：发现稍微的薄膜鼓起、C：发现大的剥离、D：薄膜在DI成形中剥离，以至破体）进行综合评价。
（c）二次密合性
在试样上层叠15μm厚的PET薄膜，用DrD压力机制作筒头。在用DI机械将该筒头成形成DI罐后，在超过PET薄膜的熔点的温度（240℃左右）下进行10分钟的热处理，再在125℃、30分钟的加热水蒸汽气氛下进行处理（蒸煮处理）。然后，观察蒸煮处理后的DI罐的罐壁部的薄膜的剥离状况，以4阶段（A：完全没有发现剥离、B：发现稍微的薄膜鼓起、C：发现大的剥离、D：薄膜在DI成形中剥离，以至破体）进行综合评价。
（d）耐蚀性
制作层叠有PET薄膜的焊接罐，在焊接部涂布修补涂料，将含有1.5%柠檬酸-1.5%食盐混合液的试验液填充在焊接罐中，装上盖，在55℃下在恒温室内放置1个月。然后，分4阶段（A：没有发现穿孔腐蚀、B：发现实用上无问题的程度的轻微穿孔腐蚀、C：发现穿孔腐蚀扩展、D：因穿孔腐蚀发生开孔）判断评价焊接罐内部的薄膜缺陷部的腐蚀状况。
对于变更了Ni-Cu合金镀层的Ni附着量及Cu含有率、且变更了铬酸盐被膜层或含Zr被膜层的附着量的发明例1～11及比较例1～8，表1中示出了焊接性、密合性、二次密合性及耐蚀性的评价结果。表1中，将本发明范围外的数值附加下划线。
表1
Figure BDA00002829417700081
如表1所示，得知：发明例1～11的钢板都是焊接性、密合性、二次密合性及耐蚀性优良。
比较例1因Ni-Cu合金镀层的Ni附着量低，而使焊接性和耐蚀性特别下降。
比较例2、3因Ni-Cu合金镀层中的Cu含有率在本发明的范围外，因而在比较例2中耐蚀性下降，在比较例3中焊接性下降。
比较例4、5因铬酸盐被膜层的附着量在本发明的范围外，而在比较例4中二次密合性下降，在比较例5中焊接性下降。
在比较例6、7中，因含Zr被膜层的附着量在本发明的范围外，而在比较例6中二次密合性下降，在比较例7中焊接性下降。
比较例8，因Ni-Cu合金镀层的Ni附着量高而使焊接性下降。
接着，作为镀敷原板，准备多个板厚0.2mm的回火等级3（T-3）的镀锡用冷轧钢板，在与上述同样的镀Ni条件下进行镀敷，在各钢板上形成Ni-Cu合金镀层。Ni附着量统一为0.7g/m2。
接着，在与上述同样的铬酸盐处理条件下，在Ni-Cu合金镀层上形成铬酸盐被膜层。铬酸盐被膜层的Cr附着量统一为8g/m2。
对得到的各种钢板，与上述同样地进行耐蚀性试验，测定穿孔腐蚀的深度。结果见图1。
如图1所示，得知：Ni-Cu合金镀层中的Cu含有率在0.5～20%的范围，穿孔腐蚀深度为0.02～0.05mm的范围，对穿孔腐蚀的耐蚀性大幅度提高。在Cu含有率为0.5～20%的范围时，腐蚀沿着Ni-Cu合金镀层与基底金属的界面扩展。另一方面，在Cu含有率低于0.5%的范围时，腐蚀沿着钢板的厚度方向扩展。
通过上述实施例，确认了本发明的效果。
产业上的利用可能性
根据本发明，可得到耐蚀性优良的、而且与层叠的树脂薄膜的密合性及焊接性优良的罐用钢板。
符号说明
1－罐用钢板，11－钢板，12－Ni-Cu合金层，13A－铬酸盐被膜层，13B－含Zr被膜层。

Claims (2)

1.一种耐蚀性、密合性、焊接性优良的罐用钢板，其特征在于，具备：
钢板、
形成在所述钢板的至少一方表面上的Ni-Cu合金镀层、
形成在所述Ni-Cu合金镀层的表面上的铬酸盐被膜层；
在所述Ni-Cu合金镀层中，Ni附着量为0.30～3.0g/m2，且Cu含量为0.5～20质量%；
在所述铬酸盐被膜层中，Cr附着量按Cr换算量计为1.0～40mg/m2。
2.一种耐蚀性、密合性、焊接性优良的罐用钢板，其特征在于，具备：
钢板、
形成在所述钢板的至少一方表面上的Ni-Cu合金镀层、
形成在所述Ni-Cu合金镀层的表面上的含Zr被膜层；
在所述Ni-Cu合金镀层中，Ni附着量为0.30～3.0g/m2，且Cu含量为0.5～20质量%；
在所述含Zr被膜层中，Zr附着量按Zr换算量计为1.0～40mg/m2。
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