CN103097582A - 容器用钢板及其制造方法 - Google Patents

容器用钢板及其制造方法 Download PDF

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Publication number
CN103097582A
CN103097582A CN2011800442694A CN201180044269A CN103097582A CN 103097582 A CN103097582 A CN 103097582A CN 2011800442694 A CN2011800442694 A CN 2011800442694A CN 201180044269 A CN201180044269 A CN 201180044269A CN 103097582 A CN103097582 A CN 103097582A
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China
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steel plate
layer
amount
mulch film
container
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CN103097582B (zh
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铃木威
中村纪彦
宫本友佳
飞山洋一
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JFE Steel Corp
JFE Engineering Corp
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NKK Corp
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Abstract

本发明提供一种膜密合性高的容器用钢板，其具有化学生成覆盖膜和在该化学生成覆盖膜上的羟基酸处理层，所述化学生成覆盖膜通过在含有Zr离子、F离子的溶液中将钢板浸渍或进行电解处理而形成，且附着量以金属Zr量计为0.1～100mg/m2、以F量计为0.1mg/m2以下，所述羟基酸处理层的附着量以C量计为0.05～50mg/m2。

Description

容器用钢板及其制造方法
技术领域
本发明主要涉及加工成罐等容器而使用的金属板，特别是与塑料膜等有机树脂的密合性优异的容器用钢板及其制造方法。
背景技术
在饮料罐、食品罐、提桶或18升罐等各种金属罐中，使用镀锡钢板或被称为无锡钢板的电解铬酸处理钢板等金属板。其中，无锡钢板通过在含有6价铬的浴中对钢板进行电解处理而制造，其优点在于具有优异的与涂料等的树脂密合性。
近年来，随着环境意识的提高，开始世界范围限制6价铬的使用，在寻求制造时使用6价铬浴的无锡钢板的代替材料。作为不使用铬的无锡钢板的代替材料，例如专利文献1中公开了在钨酸溶液中实施了电解处理的容器用钢板。另外，专利文献2中提出了表面形成有以Zr、O、F为主成分且几乎不含有磷酸根离子的无机表面处理层的表面处理金属材料。
另一方面，以往以来，各种金属罐是对无锡钢板等金属板实施涂布之后加工成罐体而进行制造，而近年来为了抑制伴随制造而产生的废弃物，代替涂布大多使用将层压塑料膜等树脂而得的层压金属板（树脂被覆金属板）加工成罐体的方法。对于该层压金属板，树脂与金属板需要牢固地密合，特别是作为饮料罐、食品罐而使用的层压金属板，在颈部分进行冲拔拉伸加工，填充内容物后有时经蒸煮杀菌工序，所以要求即使在高温的湿润环境下，也不使加工率高的钢板与树脂的密合部发生剥离的强树脂密合性。加工率高的罐用钢板中，在寻求焊接性、耐腐蚀性、涂料密合性优异，并且膜密合性，特别是高加工部的膜密合性（以下，称为高膜密合性）优异的容器用钢板。
专利文献1:日本特开2004-285380号公报
专利文献2:日本特开2005-97712号公报
发明内容
本发明的目的在于进一步提供高膜密合性优异的容器用钢板。
本发明人为了实现上述目的进行了深入研究，结果发现在通过含有Zr离子、F离子的溶液中进行浸渍或电解处理而形成于钢板上的Zr化合物覆盖膜上具有羟基酸处理层的钢板的高膜密合性优异，从而完成了本发明。
即，本发明提供以下内容。
（1）一种容器用钢板，具有化学生成覆盖膜和该化学生成覆盖膜上的羟基酸处理层，所述化学生成覆盖膜通过在含有Zr离子、F离子的溶液中将钢板浸渍或进行电解处理而形成，且附着量以金属Zr量计为0.1～100mg/m2、以F量计为0.1mg/m2以下，所述羟基酸处理层的附着量以C量计为0.05～50mg/m2。
（2）如（1）所述的容器用钢板，其中，上述溶液中进一步含有磷酸根离子，上述化学生成覆盖膜的附着量以P量计还为0.1～50mg/m2。
（3）如（1）或（2）所述的容器用钢板，其中，上述羟基酸为选自柠檬酸、酒石酸、乙醇酸、乳酸、甘油酸以及扁桃酸中的至少1种。
（4）如（1）～（3）中任一项所述的容器用钢板，其中，上述钢板是至少在单面上具有以5～1000mg/m2含Ni或以100～15000mg/m2含Sn的表面处理层的表面处理钢板。
（5）如（1）～（4）中任一项所述的容器用钢板，其中，上述钢板是具有基底Ni层和岛状的镀Sn层的表面处理钢板，所述基底Ni层是以5～150mg/m2含Ni的、镀Ni或镀Fe-Ni合金相，上述岛状的镀Sn层是在上述基底Ni层上进行300～3000mg/m2的镀Sn，利用熔融熔锡处理使上述基底Ni层的一部分或者全部与上述镀Sn层的一部合金化，由上述镀Sn层的未合金化的剩余部分形成。
（6）一种容器用钢板的制造方法，是上述（1）～（5）中任一项所述的容器用钢板的制造方法，
在含有Zr离子、F离子的溶液中将钢板浸渍或进行电解处理，
在钢板上形成附着量以金属Zr量计为0.1～100mg/m2、以F量计为0.1mg/m2以下的化学生成覆盖膜，将具有该化学生成覆盖膜的钢板浸渍于含有羟基酸的水溶液中，或者在该化学生成覆盖膜上涂布含有羟基酸的水溶液并进行干燥。
（7）如（6）所述的容器用钢板的制造方法，其中，上述干燥工序的温度为70℃以上。
（8）如（6）或（7）所述的容器用钢板的制造方法，其特征在于，在上述干燥工序之后，用80℃以上温度的水清洗并进一步干燥。
根据本发明，能够提供焊接性、耐腐蚀性、涂料密合性优异且高膜密合性优异的容器用钢板、其制造方法以及使用该容器用钢板的金属罐、罐盖。
具体实施方式
以下，对本发明的容器用钢板进行详细说明。
1.本发明中使用的原板没有特别限制，通常，使用作为容器材料而使用的钢板。该原板的制造法、材质等也没有特别限制，可从通常的钢片制造工序经过热轧、酸洗、冷轧、退火、调质轧制等工序而制造。可以是该原板或对原板赋予了含有Ni、Sn中的1种以上的表面处理层。赋予的方法没有特别限定。
2.表面处理
对于表面处理钢板而言，钢板的至少一面具有含有Sn（锡）或Ni（镍）的表面处理层。表面处理层没有特别限定，但优选每单面以5～1000mg/m2含Ni或以100～15000mg/m2含Sn。
Sn发挥优异的加工性、焊接性、耐腐蚀性，为体现该效果，优选作为金属Sn为100mg/m2以上。为了确保充分的焊接性优选赋予200mg/m2以上，为了确保充分的加工性，优选赋予1000mg/m2以上。随着Sn附着量的增加，Sn的优异的加工性、焊接性的提高效果增加，但如果为15000mg/m2以上，则耐腐蚀性的提高效果饱和，在经济上不利。因此，Sn的附着量以金属Sn计优选为15000mg/m2以下。另外，在镀Sn后通过进行回流焊处理而形成Sn合金层，进一步提高耐腐蚀性。
Ni对于涂料密合性、膜密合性、耐腐蚀性、焊接性发挥其效果，因此，作为金属Ni优选5mg/m2以上的Ni。随着Ni的附着量的增加，Ni的优异的膜密合性、耐腐蚀性、焊接性的提高效果增加，但如果为1000mg/m2以上，则该提高效果饱和，在经济上不利。Ni的附着量以金属Ni计进一步优选为10mg/m2～1000mg/m2。
具体而言，优选为使用了Ni或Sn的镀层。从作为形成于其上的含有Zr的覆盖膜的化学生成覆盖膜的均匀覆盖性的观点出发，优选的镀层是包含使由Fe-Sn-Ni合金层或Fe-Sn合金层的单一层构成的中间层或者由在最下层是Fe-Ni合金层在其上表面是Fe-Sn-Ni合金层的复合层构成的中间层形成，进而在上述中间层的上表面形成了金属Sn层的镀层的钢板。
更具体而言，表面处理钢板是具有基底Ni层和岛状的镀Sn层的表面处理钢板，所述基底Ni层是以5～150mg/m2含Ni的、镀Ni或镀Fe-Ni合金相，上述岛状的镀Sn层是在上述基底Ni层上进行100～3000mg/m2的镀Sn，利用熔融熔锡处理使上述基底Ni层的一部分或全部与上述镀Sn层的一部分合金化，由未合金化的上述镀Sn层的剩余部分形成。
如果镀层的Sn附着量小于100mg/m2，则有耐腐蚀性劣化的趋势。另一方面，如果超过3000mg/m2，则镀层变过厚，有时成本的优点减少。应予说明，Sn附着量可以通过电解剥离法或利用荧光X射线的表面分析进行测定。
对钢板或实施了镍系的镀覆的镀覆钢板实施镀Sn之后进行的熔融熔锡处理也称为回流焊处理，是为了在镀Sn后通过将温度提高至作为Sn的熔点的232℃以上从而将表面的Sn熔融并呈现其表面光泽而进行的。另外，通过进行熔融熔锡处理，将表面的Sn熔融，与基底钢板、基底金属合金化，形成Sn-Fe合金层或Sn-Fe-Ni合金层，从而提高合金层的耐腐蚀性。另外，通过适当控制该熔融熔锡处理，从而能够形成岛状Sn。由此，能够制造具有露出了不存在金属Sn的、涂料和膜密合性优异的Fe-Ni合金镀层或Fe-Ni-Sn合金镀层的镀覆结构的表面处理钢板。
3.化学生成覆盖膜
在钢板上直接，或者，在含有这些Ni、Sn中的1种以上的表面处理层的上层赋予含有Zr化合物和F的化学生成覆盖膜，得到化学生成覆盖膜钢板。作为赋予这些覆盖膜的方法，有在溶解有Zr离子、F离子的酸性水溶液中将钢板浸渍的方法或进行阴极电解处理的方法。对于浸渍处理而言，是将基底蚀刻而形成各种覆盖膜，所以处理时间长，在工业生产上不利。另一方面，对于阴极电解处理而言，由强制的电荷移动以及钢板界面上产生的氢而引起的表面清洁化与由pH上升而产生的附着促进效果相互结合，能够得到均匀的覆盖膜。并且，在该阴极电解处理中，如果在处理液中使硝酸根离子与铵离子共存，则能够以从数秒到数十秒程度的短时间处理就能促进耐腐蚀性、密合性的提高效果优异的含有Zr氧化物或Zr磷氧化物的Zr化合物覆盖膜的析出，在工业上有利。因此，在化学生成覆盖膜的赋予中优选阴极电解处理，特别优选在使硝酸根离子与铵离子共存的处理液中的阴极电解处理。
另外，阴极电解处理的处理液中的铵离子的浓度为100～10000质量ppm左右，硝酸根离子的浓度为1000～20000质量ppm左右的范围，根据生产设备、生产速度（能力）进行适当调整即可。阴极电解处理可设为电流密度为0.05～50A/dm2，电解时间为0.01～10秒。
Zr化合物的作用是确保耐腐蚀性和密合性。可认为Zr化合物是由氧化Zr、氢氧化Zr构成的Zr水合氧化物和Zr磷氧化物，这些Zr化合物具有优异的耐腐蚀性和密合性。因此，如果Zr覆盖膜增加，则耐腐蚀性、密合性开始提高，如果成以金属Zr量计为0.1mg/m2以上，则可确保实用上没有问题的水平的耐腐蚀性和密合性。并且，虽然Zr覆盖膜量增加，则耐腐蚀性、密合性的提高效果也增加，但如果Zr覆盖膜量以金属Zr量计超过100mg/m2，则Zr覆盖膜变得过厚，Zr覆盖膜本身的密合性劣化，且电阻上升焊接性劣化。因此，Zr覆盖膜附着量以金属Zr量计为0.1～100mg/m2。
锆覆盖膜的附着量优选以金属锆量计为0.1mg/m2～9mg/m2。锆覆盖膜的附着量更优选以金属锆量计为1mg/m2～8mg/m2。通过使锆覆盖膜的附着量为该范围，从而能确保蒸煮后的耐腐蚀性，并且能够得到均质性高、加工性优异的覆盖膜。
另外，Zr磷氧化物增加，则可发挥更优异的耐腐蚀性合密合性，可明确识别其效果的是以金属P量计为0.1mg/m2以上。并且，虽然磷酸覆盖膜量增加，则耐腐蚀性、密合性的提高效果也增加，但如果磷酸覆盖膜量以P量计超过50mg/m2，则磷酸覆盖膜变得过厚，磷酸覆盖膜本身的密合性劣化，且电阻上升焊接性劣化。因此，磷酸覆盖膜附着量优选为以P量计0.1～50mg/m2。磷酸覆盖膜的附着量优选为以金属P量计0.1mg/m2～8mg/m2，更优选磷酸覆盖膜的附着量以金属P量计为1mg/m2～6mg/m2。通过使磷酸覆盖膜的附着量为1mg/m2～6mg/m2的范围，从而能够确保蒸煮后的耐腐蚀性，并且能够得到均质性高的化学生成覆盖膜。
F包含于形成化学生成覆盖膜的水溶液中，所以与Zr化合物一起混入覆盖膜中。覆盖膜中的F不影响涂料密合性、膜密合性（一次密合性），但会成为蒸煮处理等高温杀菌处理时使密合性（二次密合性）、耐锈性或涂膜下腐蚀性劣化的原因。其原因可认为是覆盖膜中的F溶出到水蒸气、腐蚀液中，分解与有机覆盖膜的结合，或者腐蚀基底钢板。如果覆盖膜中的F量超过0.1mg/m2，则这些各特性的劣化开始显著显现，所以优选使F量为0.1mg/m2以下。为了使F量为0.1mg/m2以下，在化学生成覆盖膜上形成羟基酸处理层，干燥后，利用在温水中的浸渍处理或喷雾处理进行清洗处理即可，可通过提高该处理温度或者延长处理时间来减少F量。因此，为了使覆盖膜中的F量为0.1mg/m2以下，优选进行在80℃以上的温水中的浸渍处理或喷雾处理。在清洗处理之后进行干燥。干燥温度没有限定但优选为70℃以上。
应予说明，本发明的化学生成覆盖膜中含有的金属Zr量、P量、F量，例如可利用荧光X射线分析等定量分析法测定。
4.羟基酸处理层
在如上所述地得到的化学生成覆盖膜上赋予羟基酸处理层。赋予的方法不受限定，但优选在羟基酸水溶液中浸渍化学生成覆盖膜钢板的方法或将羟基酸水溶液涂布于化学生成覆盖膜上的方法。浸渍或涂覆后进行干燥。干燥温度不受限定，但优选为70℃以上。原因是能够以短时间进行充分的干燥。
羟基酸是1分子中具有羧基和醇羟基的有机化合物的统称，在本发明中，可使用选自柠檬酸、酒石酸、乙醇酸、乳酸、甘油酸、扁桃酸等中的至少1种酸。羟基酸可以使用1种，也可以混合2种以上使用。另外，也可以在羟基酸中混合酚醛树脂使用。混合率小于有机物成分的50质量%。
作为该羟基酸处理层的形成方法，优选将上述羟基酸溶解于水或有机溶剂中，作为溶液涂布于钢板上后，进行干燥的方法。作为涂布的方法，可以使用各种公知的涂覆法。为了缩短干燥时间，可以根据需要来设置加热钢板的工序。应予说明，在利用干燥而形成覆盖膜之后，优选通过水洗工序来除去残留于金属上的过剩的羟基酸和/或F。此时，不需要特别强力的水洗，只要以在水槽中浸渍或用水喷雾的程度进行即可。水洗后再次干燥，供实用。
如果羟基酸处理层的附着量以C量计小于0.05mg/m2，则树脂密合性的改善效果不充分，如果超过50mg/m2，则在有机覆盖膜中产生凝集破坏，并且树脂密合性可能降低，所以优选为0.05～50mg/m2。应予说明，羟基酸处理层中含有的C量可以使用TOC（总有机体碳分析仪），减去钢板中存在的C量来测定。
对于在本发明的钢板上具有Zr化合物化学生成覆盖膜和羟基酸处理层的本发明的密合性覆盖膜而言，羟基酸处理层构成官能团多的界面，所以如果进一步在其上层形成树脂被覆层，则羟基酸处理层与其上层的膜密合性高。
5.有机树脂覆盖（层压）
对于本发明的容器用钢板而言，可在上述化学生成覆盖膜上覆盖树脂来制造树脂被覆钢板。如上所述，本发明的容器用钢板的高加工部的膜密合性（高膜密合性）优异。这可认为是因为羟基酸处理层具有多个官能团，与树脂膜（有机树脂）化学性地结合而导致的。
作为覆盖于容器用钢板原板或表面处理钢板的树脂，没有特别限定，可举出各种热塑性树脂、热固化性树脂。例如，可以是聚乙烯、聚丙烯、乙烯-丙烯共聚物、乙烯-乙酸乙烯酯共聚物、乙烯-丙烯酸酯共聚物、离聚物等烯烃系树脂膜，或者聚对苯二甲酸丁二醇酯等聚酯膜，或尼龙6、尼龙6,6、尼龙11、尼龙12等聚酰胺膜，聚氯乙烯膜，聚偏二氯乙烯膜等热塑性树脂膜的未拉伸或者双轴拉伸的膜。层叠时使用粘结剂时，优选使用聚氨酯系粘结剂、环氧系粘结剂、酸改性烯烃树脂系粘结剂、共聚酰胺系粘结剂、共聚酯系粘结剂（厚度:0.1～5.0μm）等。并且，也可将热固化性涂料以厚度0.05～2μm的范围涂布于表面处理钢板侧或膜侧，将其作为粘结剂。
并且，也可以是酚醛环氧树脂、氨基-环氧树脂等改性环氧涂料、氯乙烯-乙酸乙烯酯共聚物、氯乙烯-乙酸乙烯酯共聚物皂化物、氯乙烯-乙酸乙烯酯-马来酸酐共聚物、环氧改性-、环氧氨基改性-、环氧酚醛改性-乙烯涂料或改性乙烯涂料、丙烯酸涂料、苯乙烯-丁二烯系共聚物等合成橡胶系涂料等热塑性或热固化性涂料中的单独1中或2种以上的组合。
树脂被覆层的厚度优选为3～50μm，特别优选为5～40μm的范围。如果厚度低于上述范围，则耐腐蚀性不充分，如果厚度超过上述范围，则在加工性方面容易产生问题。
可用任意方法进行在本发明的羟基酸处理钢板上的树脂被覆层的形成。例如，可利用挤压涂覆法、流延膜热粘结法、双轴拉伸膜热粘结法等进行。为挤压涂覆法时，能够通过在表面处理钢板上将树脂以熔融状态进行挤压涂覆，进行热粘结来制造。即，用挤出机将树脂熔融混炼之后，从T-模以薄膜状挤出，将挤出的熔融树脂膜与表面处理钢板一起从一对层压辊间通过，在冷却下挤压使其一体化，接着进行急冷。对多层的树脂被覆层进行挤压涂覆时，使用多个各层用的挤出机，使来自各挤出机的树脂流在多重多层模内合流，之后与单层树脂的情况同样地进行挤压涂覆即可。另外，将表面处理钢板垂直地通过一对层压辊间，通过向其两侧供给熔融树脂带，从而能够在表面处理钢板两面形成树脂被覆层。
这样的树脂被覆钢板可适用于具有侧面接缝的三片罐、无缝罐（两片罐）。另外，可适用于留置式拉环的易开罐盖、全开式的易开罐盖等。
6.金属罐和罐盖
作为金属罐的制造方法，只要由上述树脂被覆钢板形成，就可以使用任意的制罐法。该金属罐也可以是具有侧面接缝的三片罐，但通常优选为无缝罐（两片罐）。该无缝罐可以用冲拔·再冲拔加工、利用冲拔·再冲拔的弯曲延展加工（拉伸缠绕加工）、利用冲拔·再冲拔的弯曲延展加工·拉伸加工、或者冲拔·拉伸加工、颈部的缩颈加工等以往公知的加工方法，以树脂被覆钢板的有机树脂的被覆面成为罐内面侧的方式制造。
另外，罐盖只要由上述树脂被覆钢板形成，就可以使用以往公知的任意的制盖法。通常可以利用留置式拉环的易开罐盖或全开式的易开罐盖的加工方法来制造。
上述说明仅说明了本发明的实施方式的一个例子，可在本发明的权利要求范围内施加各种变更。
实施例
以下示出实施例具体说明本发明。本发明并不限于此。
＜钢板上的表面处理层＞
使用以下处理法（1）～（6）的方法，在板厚0.17～0.23mm的钢板上赋予表面处理层。
（处理法1）将冷轧后进行了退火、调压的原板脱脂、酸洗后，使用费洛斯坦浴进行镀Sn，制作镀Sn钢板。
（处理法2）冷轧后，使用瓦特浴实施镀Ni，退火时形成Ni扩散层，制作镀Ni钢板。
（处理法3）将冷轧后进行了退火、调压的原板脱脂、酸洗后，使用费洛斯坦浴进行镀Sn，其后，进行回流焊处理，制作具有Sn合金层的镀Sn钢板。
（处理法4）将冷轧后进行了退火、调压的原板脱脂、酸洗后，使用硫酸-盐酸浴实施镀Fe-Ni合金，接着，使用费洛斯坦浴实施镀Sn，制作镀Ni、Sn钢板。
（处理法5）将冷轧后进行了退火、调压的原板脱脂、酸洗后，使用硫酸-盐酸浴实施镀Sn-Ni合金，制作镀Ni、Sn钢板。
（处理法6）
冷轧后，将厚度为0.17～0.23mm的钢基材（钢板）脱脂和酸洗后，使用瓦特浴实施镀Ni，利用退火形成Ni扩散层后，接着，使用费洛斯坦浴实施镀Sn，其后，进行熔融熔锡处理，制作具有Sn-Ni合金层的镀Sn钢板。
用光学显微镜观察表面而确认岛状Sn的形成情况，确认到实施例7、8中整体上形成有岛。
＜化学生成覆盖膜形成法＞
通过上述处理赋予表面处理层后，用以下处理法赋予化学生成覆盖膜。
（A法）在溶解有4000质量ppm的氟化Zr、300质量ppm的磷酸、0或700质量ppm的酚醛树脂、10000质量ppm的硝酸铵的处理液中，浸渍上述钢板，形成Zr化合物-酚醛树脂覆盖膜。
（B法）在溶解有1500质量ppm的氟化Zr、400质量ppm的磷酸、0或者500质量ppm的酚醛树脂、5000质量ppm的硝酸铵的处理液中，浸渍上述钢板、进行阴极电解，赋予Zr化合物-酚醛树脂覆盖膜。将阴极电解处理的电流密度（A/dm2）和时间（秒）在表1中示出。“-”表示未处理或未能检测。
（C法）在溶解有1500～4300质量ppm的氟化Zr钾、300～1500质量ppm的磷酸、1000～7000质量ppm的硝酸铵的处理液中，浸渍上述钢板，或进行阴极电解，赋予具有Zr化合物的化学生成覆盖膜（实施例）。将阴极电解处理的电流密度（A/dm2）和时间（秒）在表1中示出。
＜羟基酸处理层的赋予＞
在形成的化学生成覆盖膜上，使用辊涂机涂布表1所示的羟基酸的表1的浓度的水溶液。或者，浸渍并进行辊轧。
＜水洗处理＞
在通过上述处理赋予羟基酸处理层之后，用下述工序干燥，进行水洗处理，控制覆盖膜中的F量，其后干燥。
（W1法）以70℃干燥，在80℃的温水中浸渍，以40℃干燥。
（W2法）以40℃干燥，在85℃的温水中浸渍，以70℃干燥。
（W3法）以30℃干燥，在80℃的温水中浸渍，以40℃干燥。
（W4法）以70℃干燥，将80℃的温水喷雾，以70℃干燥。
应予说明，在本实施例中，表面处理层中的金属Ni量和金属Sn量利用荧光X射线法测定，使用检量线特定。另外，Zr化合物覆盖膜中含有的金属Zr量、P量、F量利用荧光X射线分析等定量分析法测定。羟基酸处理层中含有的C量使用TOC（总有机体碳分析仪），减去钢板中存在的C量来测定。
＜性能评价＞
对进行了上述处理的试件，进行以下所示的（A）～（G）的各项目的性能评价。关于（A）的高膜密合性，实施例的剥离面积率小于1%，膜密合性优异，而比较例的剥离面积率均为1%以上，高加工部的膜密合性存在问题。关于（B）～（G）的各项目，实施例和比较例同样地优异。
（A）用以下试验评价高膜密合性。
在试件的两面使用厚度20μm的拉伸倍率3.1×3.1、厚度25μm、共聚比12摩尔%、熔点224℃的对苯二甲酸共聚聚对苯二甲酸乙二醇酯膜，在膜的双轴取向度（BO值）成为150的层压条件下，即以钢板的进给速度：40m/min、橡胶辊的夹持长：17mm、压接后到水冷的时间：1sec的条件进行层压，制作实施例、比较例的树脂被覆钢板。此处，夹持长是指橡胶辊与钢板接触部分的搬运方向的长度。对得到的树脂被覆钢板进行冲拔拉伸加工，制作罐体，进行罐身的颈部的加工（缩颈加工），对该罐体进行120℃、30分钟的蒸煮处理，观察罐身的颈部的树脂膜的剥离情况，根据剥离面积率，以5个阶段（◎：剥离面积率0%、○：剥离面积率小于1%、△：剥离面积率1～2%、△×：剥离面积率超过2%～10%、×：剥离面积率超过10%）进行评价。将结果在表1中示出。
（B）加工性
在试件的两面以200℃对厚度20μm的PET膜进行层压，阶段性进行利用冲拔加工和拉伸加工的制罐加工，观察膜的瑕疵、突起、剥离，并根据它们的面积率评价成型，其结果未发现膜的瑕疵、突起、剥离。
（C）焊接性
使用线缝焊机，在焊丝速度80m/min的条件下，变更电流焊接试件，根据由得到充分的焊接强度的最小电流值和尘埃和焊接溅射等焊接缺陷开始变明显的最大电流值构成的适当电流范围的大小，进行综合判断，评价焊接性，其结果是二次侧的适当电流范围为1500A以上。
（D）一次涂料密合性
在试件上涂布环氧-酚醛树脂，以200℃、30min烘干后，以1mm间隔切割成到达基底铁的深度的棋盘格，用胶带剥离，观察剥离情况，根据剥离面积率进行评价，其结果是剥离面积率为0%。
（E）二次涂料密合性
在试件上涂布环氧-酚醛树脂，以200℃、30min烘干后，以1mm间隔切割成到达基底铁的深度的棋盘格，其后，进行125℃、30min的蒸煮处理，干燥后，用胶带剥离涂膜，观察剥离情况，根据剥离面积率以4个阶段进行评价，其结果是剥离面积率为0%。
（F）涂膜下耐腐蚀性
在试件上涂布环氧-酚醛树脂，以200℃、30min烘干后，进行切入到达基底铁的深度的交叉切割，在由1.5质量%柠檬酸-1.5质量%食盐混合液构成的试验液中进行45℃、72小时的浸渍，清洗、干燥后，进行胶带剥离，观察交叉切割部的涂膜下腐蚀情况和平板部的腐蚀情况，根据涂膜下腐蚀的宽度和平板部的腐蚀面积率这两个进行评价，其结果是涂膜下腐蚀宽度小于0.2mm，且平板部的腐蚀面积率为0%。
（G）蒸煮耐锈性
对试件进行125℃、30min的蒸煮处理，观察锈的产生情况，根据锈产生面积率来进行评价，其结果是锈产生面积率为0%。
Figure BDA00002918315200141

Claims (8)

1.一种容器用钢板，具有化学生成覆盖膜和在该化学生成覆盖膜上的羟基酸处理层，所述化学生成覆盖膜是通过在含有Zr离子、F离子的溶液中将钢板浸渍或电解处理而形成且附着量以金属Zr量计为0.1～100mg/m2、以F量计为0.1mg/m2以下，所述羟基酸处理层的附着量以C量计为0.05～50mg/m2。
2.根据权利要求1所述的容器用钢板，其中，所述溶液中进一步含有磷酸根离子，所述化学生成覆盖膜的附着量以P量计还为0.1～50mg/m2。
3.根据权利要求1或2所述的容器用钢板，其中，所述羟基酸为选自柠檬酸、酒石酸、乙醇酸、乳酸、甘油酸以及扁桃酸中的至少1种。
4.根据权利要求1～3中任一项所述的容器用钢板，其中，所述钢板是至少在单面具有以5～1000mg/m2的量含Ni或以100～15000mg/m2的量含Sn的表面处理层的表面处理钢板。
5.根据权利要求1～4中任一项所述的容器用钢板，其中，所述钢板是具有基底Ni层和岛状的镀Sn层的表面处理钢板，所述基底Ni层是以5～150mg/m2的量含Ni的、镀Ni或镀Fe-Ni合金相，所述岛状的镀Sn层是在所述基底Ni层上进行300～3000mg/m2的镀Sn，利用熔融熔锡处理使所述基底Ni层的一部分或者全部与所述镀Sn层的一部合金化，由所述镀Sn层的未合金化的剩余部分形成。
6.一种容器用钢板的制造方法，是权利要求1～5中任一项所述的容器用钢板的制造方法，
在含有Zr离子、F离子的溶液中将钢板浸渍或电解处理，
在钢板上形成附着量以金属Zr量计为0.1～100mg/m2、以F量计为0.1mg/m2以下的化学生成覆盖膜，将具有该化学生成覆盖膜的钢板浸渍于含有羟基酸的水溶液中，或者在该化学生成覆盖膜上涂布含有羟基酸的水溶液，进行干燥。
7.根据权利要求6所述的容器用钢板的制造方法，其中，所述干燥工序的温度为70℃以上。
8.根据权利要求6或7所述的容器用钢板的制造方法，其特征在于，在所述干燥工序之后，用80℃以上温度的水清洗并进一步干燥。
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