CN103108988A - 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
CN103108988A
CN103108988A CN2011800440612A CN201180044061A CN103108988A CN 103108988 A CN103108988 A CN 103108988A CN 2011800440612 A CN2011800440612 A CN 2011800440612A CN 201180044061 A CN201180044061 A CN 201180044061A CN 103108988 A CN103108988 A CN 103108988A
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China
Prior art keywords
steel plate
layer
amount
mulch film
plating
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CN2011800440612A
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CN103108988B (zh
Inventor
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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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/82—After-treatment
    • C23C22/83—Chemical after-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B1/00—Layered products having a non-planar shape
    • B32B1/08—Tubular products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—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
    • B32B15/08—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 synthetic resin
    • B32B15/09—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 synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/18—Layered products comprising a layer of metal comprising iron or steel
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    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0205—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips of ferrous alloys
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
    • C21D8/0226—Hot rolling
    • C—CHEMISTRY; METALLURGY
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    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
    • C21D8/0236—Cold rolling
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    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
    • C21D8/0263—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment following hot rolling
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0278—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips involving a particular surface treatment
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    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
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    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
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    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
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Abstract

本发明的目的在于提供高膜密合性优异的容器用钢板及其制造方法。本发明的容器用钢板在钢板上具有金属Zr量为1～100mg/m2、P量为0.1～50mg/m2、F量为0.1mg/m2以下的化学生成覆盖膜，在该化学生成覆盖膜上具有C量为0.1～50mg/m2的酚醛树脂层。本发明的容器用钢板的制造方法是获得本发明的容器用钢板的容器用钢板制造方法，通过在含有Zr离子、磷酸根离子、F离子的处理液中的浸渍处理或使用了该处理液的电解处理而在上述钢板上形成上述化学生成覆盖膜，接着，将形成有上述化学生成覆盖膜的上述钢板浸渍于含有酚醛树脂的水溶液中，或者在上述化学生成覆盖膜上涂布该水溶液，其后进行干燥。

Description

容器用钢板及其制造方法
技术领域
本发明涉及一种容器用钢板及其制造方法。
背景技术
以往，在任何罐类中，均对罐所使用的钢板（容器用钢板）进行涂覆，但从地球环境保护的观点出发，近年来层压膜的技术作为代替涂覆的技术备受瞩目，并得到了迅速的发展。
然而，以往在层压膜的基底中使用的钢板上形成铬酸盐覆盖膜，而随着近年来的对铅和镉等有害物质的使用限制及对制造工厂劳动环境的关心的呼吁，已开始要求不使用铬酸盐覆盖膜。
另外，在饮料容器市场中，罐在成本、质量方面处于与PET瓶、瓶、纸袋等容器的竞争中，对于层压容器用钢板也开始要求更优异的制罐加工性（特别是膜密合性、加工膜密合性、耐腐蚀性等）。
作为满足这样的要求的容器用钢板，例如，专利文献1中公开了“一种容器用钢板，其特征在于，具有通过在含有Zr离子、F离子、铵离子、硝酸根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，上述Zr化合物覆盖膜的附着量以金属Zr量计为1～100mg/m2、以F量计为0.1mg/m2以下”（［权利要求1］）。
专利文献1:日本特开2010-13728号公报
发明内容
如上所述，近年来，在饮料容器市场中，随着质量竞争的激烈化，对层压容器用钢板也要求更优异的膜密合性。特别是罐进行缩颈加工后的颈部分的膜通常容易剥离，所以期待在严酷的条件下该部分也不发生剥离的容器用钢板。
本发明者人等，使用专利文献1中公开的容器用钢板，针对颈部分的膜密合性（以下，也称为“高膜密合性”）进行了研究，结果得知尚未达到现今所要求的水平，需要改进。
因此，本发明的目的在于提供一种高膜密合性优异的容器用钢板及其制造方法。
本发明人为解决上述课题进行了深入研究，结果发现在形成于钢板上的规定的化学生成覆盖膜上设有规定的酚醛树脂层的容器用钢板的高膜密合性优异，从而完成了本发明。
即，本发明提供以下的（1）～（7）。
（1）一种容器用钢板，其在钢板上具有金属Zr量为1～100mg/m2、P量为0.1～50mg/m2、F量为0.1mg/m2以下的化学生成覆盖膜，在该化学生成覆盖膜上具有C量为0.1～50mg/m2的酚醛树脂层。
（2）如上述（1）所述的容器用钢板，是通过在含有Zr离子、磷酸根离子、F离子的处理液中的浸渍处理或使用了该处理液的电解处理而在上述钢板上形成上述化学生成覆盖膜，接着，将形成有上述化学生成覆盖膜的上述钢板浸渍于含有酚醛树脂的水溶液中，或者在上述化学生成覆盖膜上涂布该水溶液，其后进行干燥而得的。
（3）如上述（1）或（2）所述的容器用钢板，上述钢板至少在单面具有含有以金属Ni量计10～1000mg/m2的Ni，或以金属Sn量计100～15000mg/m2的Sn的表面处理层。
（4）如上述（1）或（2）所述的容器用钢板，其中，对上述钢板，在其表面实施镀Ni或镀Fe-Ni合金而形成基底Ni层，在上述基底Ni层上实施镀Sn，并利用熔融熔锡处理使该镀Sn的一部分与上述基底Ni层的一部分或全部合金化而形成含有岛状Sn的镀Sn层，并且，上述基底Ni层含有以金属Ni量计5～150mg/m2的Ni，上述镀Sn层含有以金属Sn量计300～3000mg/m2的Sn。
（5）一种容器用钢板的制造方法，是获得上述（1）～（4）中任一项所述的容器用钢板的容器用钢板制造方法，其通过在含有Zr离子、磷酸根离子、F离子的处理液中的浸渍处理或使用该处理液的电解处理而在上述钢板上形成上述化学生成覆盖膜，接着，将形成有上述化学生成覆盖膜的上述钢板浸渍于含有酚醛树脂的水溶液中，或者在上述化学生成覆盖膜上涂布该水溶液，其后进行干燥。
（6）如上述（5）所述的容器用钢板的制造方法，其中，上述干燥的温度为70℃以上。
（7）如上述（5）或（6）所述的容器用钢板的制造方法，其中，在上述干燥之后进一步以80℃以上温度的水清洗并再次进行干燥。
根据本发明，可提供高膜密合性也优异的容器用钢板及其制造方法。
具体实施方式
＜容器用钢板＞
本发明的容器用钢板是在钢板上具有金属Zr量为1～100mg/m2、P量为0.1～50mg/m2、F量为0.1mg/m2以下的化学生成覆盖膜，在该化学生成覆盖膜上具有C量为0.1～50mg/m2的酚醛树脂层的容器用钢板。
以下，对本发明的容器用钢板的构成进行详细说明。
＜钢板＞
作为本发明中使用的钢板没有特别限定，通常，可使用作为容器材料而使用的钢板原板。另外，该钢板原板的制造方法、材质等也没有特别限制，可使用从通常的钢片制造工序经热轧、酸洗、冷轧、退火、调质轧制等各工序而制造的钢板原板。
作为本发明中使用的钢板，可以是至少在单面具有含有镍（Ni）和/或锡（Sn）的表面处理层的钢板。
这样的表面处理层为镀Ni层、镀Sn层、镀Sn-Ni合金层等。
Ni对于涂料密合性、膜密合性、耐腐蚀性、焊接性等可发挥其效果。此时，从使这些特性更优异的理由和经济的观点出发，在表面处理层中金属Ni量优选为10～1000mg/m2。
Sn对于加工性、焊接性、耐腐蚀性等可发挥其效果。此时，从使这些特性更优异的理由和经济的观点出发，在表面处理层中金属Sn量优选为100～15000mg/m2，从使焊接性更优异的理由出发，优选为200～15000mg/m2，从使加工性更优异的理由出发，进一步优选为1000～15000mg/m2。
作为形成表面处理层（镀层）的方法，没有特别限定，例如，可以使用电镀法、浸镀法、真空蒸镀法、溅射法等公知的方法，并且，为了形成扩散层也可以组合加热处理。
作为镀Ni层，除实施镀金属Ni而形成的层之外，也可以是实施镀铁（Fe）-镍（Ni）合金而形成的镀Fe-Ni合金层。
镀Sn层是通过实施利用金属Sn的镀覆（镀Sn）而形成，但本发明的“镀Sn”包括在金属Sn中混入不可逆的杂质的情况以及在金属Sn中添加微量元素的情况。
另外，在本发明中，可以形成含有岛状Sn的镀Sn层。此时，对钢板的表面实施镀Ni或镀Fe-Ni合金而形成基底Ni层，在基底Ni层上实施镀Sn，利用熔融熔锡处理使该镀Sn的一部分与基底Ni层的一部分或全部合金化，从而形成含有岛状Sn的镀Sn层。
通过熔融熔锡处理（回流焊处理），Sn溶解，与钢板、基底Ni层合金化，形成Sn-Fe合金层或Sn-Fe-Ni合金层，提高合金层的耐腐蚀性，并且形成岛状的Sn合金。岛状的Sn合金可通过适当控制熔融熔锡处理来形成。
Ni为高耐腐蚀金属，所以能够提高通过熔融熔锡处理而形成的含有Fe和Sn的合金层的耐腐蚀性。
从体现耐腐蚀性的观点和经济的观点出发，基底Ni层中的金属Ni量优选为5～150mg/m2。
作为基底Ni层，在实施加热处理而形成扩散层时，可以在加热处理的前后或与加热处理同时进行氮化处理。
Sn的优异的耐腐蚀性因金属Sn量为300mg/m2以上而显著提高，并且Sn的含量越多，耐腐蚀性的提高程度越增加。因此，含有岛状Sn的镀Sn层中的金属Sn量优选为300mg/m2以上。另外，如果金属Sn量超过3000mg/m2，则耐腐蚀性提高效果饱和，所以从经济的观点出发，Sn含量优选为3000mg/m2以下。
另外，电阻低的Sn柔软，在焊接时通过在电极间对Sn加压而使其扩展，能够确保稳定的通电区域，所以可发挥特别优异的焊接性。只要金属Sn量为100mg/m2以上，就可发挥出该优异的焊接性。另外，在显示上述优异的耐腐蚀性的金属Sn量的范围内，该焊接性的提高效果并未饱和。因此，为了确保优异的耐腐蚀性和焊接性，优选使金属Sn量为300mg/m2～3000mg/m2。
应予说明，表面处理层中的金属Ni量或金属Sn量，例如，可利用荧光X射线法测定。此时，使用金属Ni量已知的Ni附着量样本，预先特定金属Ni量相关的检量线，使用该检量线相对地特定金属Ni量。对于金属Sn量，也同样地使用金属Sn量已知的Sn附着量样本，预先特定金属Sn量相关的检量线，使用该检量线相对地特定金属Sn量。
＜化学生成覆盖膜＞
本发明的容器用钢板具有形成于上述钢板上的金属Zr量为1～100mg/m2、P量为0.1～50mg/m2、F量为0.1mg/m2以下的化学生成覆盖膜。
作为形成化学生成覆盖膜的方法，例如可举出利用在溶解有Zr离子、磷酸根离子、F离子的处理液（酸性溶液）中浸渍钢板的浸渍处理来进行的方法；利用在含有Zr离子、磷酸根离子、F离子的处理液中的阴极电解处理来进行的方法等，从可得到均匀的覆盖膜的理由出发，优选利用阴极电解处理来进行的方法。
并且，特别是在阴极电解处理中，优选在处理液中使硝酸根离子和铵离子共存。由此，能够实现数秒～数十秒程度的短时间处理，另外，能够形成耐腐蚀性、密合性的提高效果优异的化学生成覆盖膜。
应予说明，进行阴极电解处理时，从覆盖膜的形成效率、成本、形成的覆盖膜组织的均匀性等观点出发，阴极电解处理的浴温优选为10～40℃（低温阴极电解处理）。另外，从抑制覆盖膜附着量的降低、形成稳定的覆盖膜、处理时间、抑制覆盖膜特性的降低等观点出发，阴极电解处理的电解电流密度优选为0.05～50A/dm2。并且，从抑制覆盖膜附着量的降低、形成稳定的覆盖膜、处理时间、抑制覆盖膜特性的降低等观点出发，阴极电解处理的通电时间优选为0.01～5秒。
化学生成覆盖膜含有Zr化合物。此处，Zr化合物的作用是确保耐腐蚀性和密合性。Zr化合物可认为是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。应予说明，“Zr水合氧化物”是指Zr氧化物与Zr氢氧化物混在的状态。
如果化学生成覆盖膜中的金属Zr量为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。另外，如果金属Zr量超过100mg/m2，则化学生成覆盖膜本身的密合性劣化，并且电阻上升焊接性劣化。因此，化学生成覆盖膜中的金属Zr量为1～100mg/m2，优选为1～20mg/m2，更优选为1～10mg/m2。
另外，如果增加Zr磷氧化物，则可发挥更优异的的耐腐蚀性和密合性，可清楚确认其效果的是在P量为0.1mg/m2以上时。另外，如果P量超过50mg/m2，则密合性劣化，并且电阻上升焊接性劣化。因此，化学生成覆盖膜中的P量为0.1～50mg/m2，优选为0.1～20mg/m2，更优选为0.1～10mg/m2。
处理液中含有F，所以与Zr化合物一起混入覆盖膜中。覆盖膜中的F不影响涂料和膜的通常的密合性，但蒸煮处理等高温杀菌处理时成为使密合性、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溶出到水蒸气和腐蚀液中，使与有机覆盖膜的结合分解，或者腐蚀基底钢板。
化学生成覆盖膜中的F量如果超过0.1mg/m2，则这些各特性开始显著劣化，所以为0.1mg/m2以下。
为了使化学生成覆盖膜中的F量为0.1mg/m2以下，只要在形成化学生成覆盖膜之后，利用温水中的浸渍处理或喷雾处理来进行清洗处理即可。此时，可通过提高处理温度或者延长处理时间来减少F量。
例如，为了使化学生成覆盖膜中的F量为0.1mg/m2以下，只要以40℃以上的温水进行0.5秒以上的浸渍处理或喷雾处理即可。
化学生成覆盖膜中的金属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。
处理液中的铵离子的浓度为100～10000ppm左右，硝酸根离子的浓度为1000～20000ppm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。
＜酚醛树脂层＞
本发明的容器用钢板具有形成于化学生成覆盖膜上的、含有酚醛树脂的酚醛树脂层。
作为酚醛树脂成分，例如可举出N,N-二乙醇胺改性的水溶性酚醛树脂。
酚醛树脂本身为有机物，所以具有酚醛树脂层的本发明的容器用钢板对于层压膜可得到非常优异的密合性。
此时，如果酚醛树脂层中的C量小于0.1mg/m2，则无法确保实用水平的密合性。另一方面，如果C量超过50mg/m2，则电阻上升焊接性劣化，另外，有时因酚醛树脂层中的凝集破坏而导致密合性降低。
相对于此，如果C量为0.1～50mg/m2，则可确保实用上没有问题的水平的密合性，并且，也可抑制电阻的上升。因此，酚醛树脂层中的C量为0.1～50mg/m2，优选为0.1～10mg/m2，更优选为0.1～8mg/m2。
应予说明，酚醛树脂层中的C量可使用TOC（总有机体碳分析仪），通过减去存在于钢板中的C量来测定。
作为形成酚醛树脂层的方法，没有特别限定，例如可举出将形成有化学生成覆盖膜的钢板浸渍于含有酚醛树脂的水溶液后进行干燥的方法；将含有酚醛树脂的水溶液涂布于形成于钢板上的化学生成覆盖膜上后进行干燥的方法等。
浸渍时，浸渍时间没有特别限定，但优选为1秒以上。
应予说明，不论是哪种方法，均优选干燥的温度为70℃以上。
＜清洗＞
在本发明中，从使容器用钢板的高膜密合性更优异的理由出发，可在形成酚醛树脂层之后，将得到的容器用钢板进一步用水，优选用80℃以上温度的水清洗，其后进行干燥。
认为通过进行这样的清洗，使酚醛树脂层的表面适度地粗糙化，使高膜密合性更良好。
另外，通过进行这样的清洗，在除去化学生成覆盖膜中存在的F而减少F量方面也有效。
此时，作为清洗的方法没有特别限定，例如可举出将得到的容器用钢板浸渍于水中的方法；使用喷雾器等将水涂布于得到的容器用钢板上的方法等。
浸渍时，浸渍时间优选为1秒以上。
另外，干燥的温度优选为70℃以上。
实施例
以下，例举实施例具体说明本发明，但本发明并不限定于此。
＜表面处理层＞
使用以下的处理法（1-0）～（1-7）的方法，在板厚0.17～0.23mm的钢板上形成表面处理层。
（1-0）对冷轧后进行了退火、调压的原板实施脱脂、酸洗，制作钢板。
（1-1）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。
（1-2）将冷轧后进行了退火、调压的原板脱脂、酸洗后，使用瓦特浴实施镀Ni，制作镀Ni钢板。
（1-3）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。
（1-4）将冷轧后进行了退火、调压的原板脱脂、酸洗后，使用费洛斯坦浴实施镀Sn，制作镀Sn钢板。
（1-5）将冷轧后进行了退火、调压的原板脱脂、酸洗后，使用费洛斯坦浴实施镀Sn，其后，进行熔融熔锡处理（回流焊处理），制作具有Sn合金层的镀Sn钢板。
（1-6）冷轧后，将原板脱脂、酸洗后，使用瓦特浴实施镀Ni，退火时形成Ni扩散层，脱脂、酸洗后，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合金层的镀Ni、Sn钢板。
（1-7）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，然后，使用费洛斯坦浴实施镀Sn，其后，进行熔融熔锡处理（回流焊处理），制作具有Sn合金层的镀Ni、Sn钢板。
应予说明，进行（1-6）和（1-7）的处理时，用光学显微镜观察表面，评价了岛状Sn的情况的结果，确认到整体上形成有岛。
＜化学生成覆盖膜＞
利用上述处理形成表面处理层后，用以下处理法（2-1）～（2-3）形成化学生成覆盖膜。
（2-1）在使K2ZrF6（4.3g/L）和磷酸（1.2g/L）溶解并添加硝酸铵而将pH调节为2.65的处理液中，浸渍上述钢板，以浴温30℃，以第1表所示的条件进行阴极电解形成化学生成覆盖膜。
（2-2）在使K2ZrF6（4.3g/L）、磷酸（1.2g/L）和酚醛树脂（0.7g/L）溶解并添加硝酸铵而将pH调节为2.65的处理液中，浸渍上述钢板，以浴温30℃，以第1表所示的条件进行阴极电解形成化学生成覆盖膜。
（2-3）在使K2ZrF6（4.3g/L）和磷酸钠（1.4g/L）溶解并添加磷酸而使pH调节为2.65的处理液中，浸渍上述钢板，以浴温30℃，以第1表所示的条件进行阴极电解形成化学生成覆盖膜。
（水洗处理）
利用上述处理形成化学生成覆盖膜后，用以下处理法（3-1）进行水洗处理，控制化学生成覆盖膜中的F量。
（3-1）在40℃的温水中浸渍1秒钟。
＜酚醛树脂层＞
利用上述处理形成化学生成覆盖膜并利用上述处理进行水洗处理之后，用以下处理（4-1）～（4-5）形成酚醛树脂层。
（4-1）将溶解有酚醛树脂0.1g/L的水溶液用辊涂机涂布后，以75℃干燥，形成酚醛树脂层。
（4-2）在溶解有酚醛树脂0.5g/L的水溶液中，将上述钢板浸渍1秒钟后，用辊滚压，以75℃干燥，形成酚醛树脂层。
（4-3）将溶解有酚醛树脂3.0g/L的水溶液用辊涂机涂布后，以75℃干燥，形成酚醛树脂层。
（4-4）在溶解有酚醛树脂0.01g/L的水溶液中，将上述钢板浸渍1秒钟后，用辊滚压，以75℃干燥，形成酚醛树脂层。
（4-5）将溶解有酚醛树脂10.0g/L的水溶液用辊涂机涂布后，以75℃干燥，形成酚醛树脂层。
应予说明，不论在哪种方法中，均使用上述N,N-二乙醇胺变性的水溶性酚醛树脂（重均分子量：5000）作为酚醛树脂。
＜清洗＞
利用上述的处理形成酚醛树脂层后，用以下处理法（5-1）进行清洗。
（5-1）在85℃的水中浸渍1秒钟后，以75℃干燥。
应予说明，在所有实施例和比较例中，表面处理层中的金属Ni量和金属Sn量均利用荧光X射线法测定并使用检量线特定。另外，化学生成覆盖膜中含有的金属Zr量、P量、F量均利用荧光X射线分析等定量分析法测定。另外，化学生成覆盖膜和酚醛树脂层中含有的C量均使用TOC（总有机体碳分析仪），通过减去钢板中存在的C量来测定。
＜性能评价＞
对进行了上述处理的试验材料进行高膜密合性的评价。
首先，在实施例和比较例的各试验材料的两面以200℃层压厚度为20μm的PET膜后，进行冲拔拉伸加工制作罐体，对制作的罐体实施缩颈加工形成颈部。将该罐体以120℃进行30分钟的蒸煮处理，评价颈部的膜的剥离情况。
具体而言，将完全没有剥离的情况评价为“◎”，将发生实用上没有问题的程度的极微的剥离的情况评价为“○”，将部分地发生剥离并在实用上存在问题的情况评价为“△”，将大部分发生剥离的情况评价为“×”。将结果在第1表中示出。
Figure BDA00002913991900121
从第1表所示的结果可知，比较例1～11的高膜密合性均差。
特别是可知即使是化学生成覆盖膜中含有酚醛树脂的比较例9，也得不到充分的高膜密合性。
另外，可知具有酚醛树脂层但其C量在本发明的范围外的比较例10、11也得不到充分的高膜密合性。
与此相对，可知实施例1～9的高膜密合性均优异。此时，形成酚醛树脂层后进行了清洗的实施例2，与未进行清洗的实施例1相比，高膜密合性更优异。

Claims (7)

1.一种容器用钢板，是在钢板上具有金属Zr量为1～100mg/m2、P量为0.1～50mg/m2、F量为0.1mg/m2以下的化学生成覆盖膜，在该化学生成覆盖膜上具有C量为0.1～50mg/m2的酚醛树脂层的容器用钢板。
2.根据权利要求1所述的容器用钢板，是通过在含有Zr离子、磷酸根离子、F离子的处理液中的浸渍处理或使用了该处理液的电解处理而在所述钢板上形成所述化学生成覆盖膜，接着，将形成有所述化学生成覆盖膜的所述钢板浸渍于含有酚醛树脂的水溶液中，或者，在所述化学生成覆盖膜上涂布该水溶液，其后进行干燥而得的。
3.根据权利要求1或2所述的容器用钢板，其中，所述钢板至少在单面具有含有以金属Ni量计含量为10～1000mg/m2的Ni或以金属Sn量计含量为100～15000mg/m2的Sn的表面处理层。
4.根据权利要求1或2所述的容器用钢板，其中，对所述钢板，在其表面上实施镀Ni或镀Fe-Ni合金而形成基底Ni层，在所述基底Ni层上实施镀Sn，利用熔融熔锡处理使该镀Sn的一部分与所述基底Ni层的一部分或者全部合金化而形成含有岛状Sn的镀Sn层，
所述基底Ni层含有以金属Ni量计含量为5～150mg/m2的Ni，
所述镀Sn层含有以金属Sn量计含量为300～3000mg/m2的Sn。
5.一种容器用钢板的制造方法，是获得权利要求1～4中任一项所述的容器用钢板的容器用钢板制造方法，
通过在含有Zr离子、磷酸根离子、F离子的处理液中的浸渍处理或使用了该处理液的电解处理而在所述钢板上形成所述化学生成覆盖膜，接着，将形成有所述化学生成覆盖膜的所述钢板浸渍于含有酚醛树脂的水溶液中，或者，在所述化学生成覆盖膜上涂布该水溶液，其后进行干燥。
6.根据权利要求5所述的容器用钢板的制造方法，其中，所述干燥的温度为70℃以上。
7.根据权利要求5或6所述的容器用钢板的制造方法，其中，在所述干燥之后，进一步用80℃以上温度的水清洗并再次进行干燥。
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CN107683351B (zh) * 2015-06-23 2019-05-28 新日铁住金株式会社 容器用钢板及容器用钢板的制造方法

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