CN1890089B - 具有优异耐腐蚀性和很小环境影响的预涂金属板 - Google Patents
具有优异耐腐蚀性和很小环境影响的预涂金属板 Download PDFInfo
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- CN1890089B CN1890089B CN2004800364040A CN200480036404A CN1890089B CN 1890089 B CN1890089 B CN 1890089B CN 2004800364040 A CN2004800364040 A CN 2004800364040A CN 200480036404 A CN200480036404 A CN 200480036404A CN 1890089 B CN1890089 B CN 1890089B
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Abstract
一种涂覆的金属板,其包含金属板并在该金属板的至少一个表面上形成有包含金属氧化物和/或金属氢氧化物作为主要成分的涂膜,其中金属种类不包括铬,并且其中涂膜具有裂纹和/或下方金属板具有凹坑,并且其进一步在上述无机涂膜上包含有机涂层。该涂覆的金属板无铬酸盐并且具有优异的耐腐蚀性、优异的涂料附着性和降低的环境影响。
Description
技术领域
本发明涉及预涂金属板,更具体地,涉及具有优异的涂料附着性和耐腐蚀性、由于不含六价铬(其被视为对环境具有重大影响)而对全球环境友好并适合用于汽车、建筑材料和家电的预涂金属板。
背景技术
为了提高设计性能和耐腐蚀性,对许多用于家电、建筑材料和汽车的金属板进行预涂。对于这种金属板,在许多情况下使用被称作铬酸盐处理的化学转化处理作为对涂层的预处理,因为铬酸盐处理由于膜中所含的六价铬的自修复功能而提供了优异的耐腐蚀性,并由于含六价铬的水合氧化物而提供了优异的涂料附着性。
然而,随着近来对全球环境关注度的提高,要求抑制六价铬的洗脱并在可能的情况下不使用铬酸盐处理。
在这种背景下,在JP 5-230666A中提出了使用通过使有机树脂与铬酸盐化合获得的树脂铬酸盐的技术。使用该技术,确实可以降低但不能完全防止六价铬的洗脱。
另一方面,最近已经开发出性能与铬酸盐处理相当的各种无铬酸盐处理。其典型例子是用有机树脂覆盖金属表面的技术,该有机树脂具有形成螯合物的能力以加强覆盖膜与金属表面之间的结合力,从而提高耐腐蚀性。
例如,JP 11-29724A公开了一种使用含有含硫代羰基的化合物和磷酸根离子并进一步含有水分散性二氧化硅的含水树脂进行的无铬酸盐处理。这种无铬酸盐处理确实在一定程度上提高了耐腐蚀性,但是,在进行剧烈加工的用途中,涂料附着性未必令人满意。JP 8-73775A公开了一种含有两种硅烷偶联剂的酸性表面处理剂。这种处理剂确实在一定程度上提高了涂料附着性,但是耐腐蚀性未必令人满意。
如上所述,还没有开发出具有高水平的涂料附着性和耐腐蚀性的无铬酸盐处理,急需进行开发。
发明内容
在这些情况下,产生了本发明,并且本发明的目的是提供一种具有优异的涂料附着性和耐腐蚀性、无六价铬并对环境影响极小的预涂金属板。
为解决上述问题,本发明人进行了深入的研究,发现当在金属板的至少一个表面上提供主要含金属氧化物和/或金属氢氧化物的膜并在物理构造上具有膜裂纹和/或金属板表面凹坑时,预涂金属板表现出与铬酸盐处理过的金属板相同的涂料附着性和耐腐蚀性。基于此发现完成了本发明。
也就是说,本发明的要点如下。
(1)一种具有优异耐腐蚀性和很小环境影响的预涂金属板,其包含金属板,该金属板在至少一个表面上具有无机膜和其上的有机涂层,其中所述无机膜是主要含各自使用铬以外的金属种类的金属氧化物和/或金属氢氧化物的膜,并且所述膜中有裂纹。
(2)一种具有优异耐腐蚀性和很小环境影响的预涂金属板,其包含金属板,在该金属板表面上形成有凹坑,该金属板在至少一个表面上具有无机膜和其上的有机涂层,其中所述无机膜是主要含各自使用铬以外的金属种类的金属氧化物和/或金属氢氧化物的膜。
(3)一种具有优异耐腐蚀性和很小环境影响的预涂金属板,其包含金属板,在该金属板表面上形成有凹坑,该金属板在至少一个表面上具有无机膜和其上的有机涂层,其中所述无机膜是主要含各自使用铬以外的金属种类的金属氧化物和/或金属氢氧化物的膜,并且所述膜中有裂纹。
(4)如(1)或(3)所述的预涂金属板,其中裂纹尺寸为宽0.1至10微米,深0.5至10微米且长3微米或更高。
(5)如(2)或(3)所述的预涂金属板,其中凹坑尺寸为短轴0.5至10微米且深0.5至10微米。
(6)如(1)至(5)任一项所述的预涂金属板,其中构成金属氧化物或金属氢氧化物的金属种类是一种或多种选自钛、锆和硅的元素。
按照本发明,不使用含六价铬的铬酸盐就可以提供具有优异的涂料附着性和耐腐蚀性且对环境影响极小的预涂金属板。
本发明的最佳实施方式
现在将详细描述本发明。
用于本发明的金属板在其表面上含有以各自使用铬以外的金属种类的金属氧化物和/或金属氢氧化物为主要成分的膜,并且在膜中有裂纹和/或在下方金属板上有凹坑。
一般而言,公知的是,当金属板在其表面上具有金属氧化物和/或金属氢氧化物作为主要成分时,与完全不进行这种处理的情况相比,涂布之后的涂料附着性和耐腐蚀性在一定程度上提高。至于其机理,据解释是金属氧化物或金属氢氧化物与涂在其上的有机树脂形成强结合,而这带来上述提高。
经过广泛的研究,本发明人进一步发现,当在金属板表面上的金属氧化物或金属氢氧化物膜中形成裂纹时,涂料附着性和耐腐蚀性会进一步提高,并且这种效果与铬酸盐处理时相当。并不清楚地了解其机理,但是据估计涂料进入裂纹以产生所谓的锚效应,由此提高涂料附着性,并且由于涂料附着性的提高,阻止了腐蚀因素侵入涂膜与金属氧化物或金属氢氧化物之间的界面,从而提高耐腐蚀性。
裂纹优选具有宽0.1至10微米、深0.5至10微米且长3微米或更高的尺寸。如果宽度低于0.1微米,深度低于0.5微米或长度低于3微米,涂料附着性和耐腐蚀性略差。大量宽度超过10微米或深度超过10微米的大裂纹的存在是不优选的,因为会产生下述现象——裂纹内残留的空气在烘焙涂料时产生体积膨胀,同时逸出涂膜表面,这可能导致粗糙的涂膜表面。至于裂纹的长度,长度越大,提高附着性的效果就越高。裂纹的尺寸更优选为宽0.3至10微米、深1至10微米且长4微米或更高。
类似地,已经发现,当在表面上含有金属氧化物和/或金属氢氧化物作为主要成分的金属板具有凹坑时,也会提高涂料附着性和耐腐蚀性。还不清楚地了解其机理,但是据估计,与金属氧化物或金属氢氧化物膜中的裂纹类似地,涂料进入凹坑部分以产生所谓的锚效应,由此提高涂料附着性,并且阻止了腐蚀因素侵入涂膜与金属氧化物或金属氢氧化物之间的界面,从而提高耐腐蚀性。凹坑优选具有短轴0.5至10微米且深0.5至10微米的尺寸。如果短轴小于0.5微米或深度小于0.5微米,涂料附着性和耐腐蚀性略差。另一方面,短轴超过10微米或深度超过10微米的大量大凹坑的存在是不优选的,因为会产生下述现象——凹坑内残留的空气在烘焙涂料时产生体积膨胀并逸出涂膜表面,这可能导致粗糙的涂膜表面。凹坑的尺寸更优选为短轴1至10微米且深1至10微米。至于长轴,长轴越大,提高附着性的效果就越高。
此外,当具有表面凹坑的金属板上存在含金属氧化物和/或金属氢氧化物并具有裂纹的无机膜时,与在物理构造上仅具有凹坑或仅具有裂纹的情况相比,金属板表现出更优异的涂料附着性和耐腐蚀性。还不清楚地了解其机理,但是据估计,由于凹坑和裂纹产生的协同锚效应,提高了涂料附着性,并阻止了腐蚀因素侵入涂膜与金属氧化物或金属氢氧化物之间的界面,并且提高了耐腐蚀性。
作为在本发明的金属板上形成的涂膜的金属物类,对构成金属氧化物或金属氢氧化物的金属物类(不包括铬)没有特别限制,但是其例子包括铁、镁、铌、钽、铝、镍、钴、钛、锆和硅。这些金属物类可以单独使用,或可以两种或多种混合使用。在这些金属中,特别优选钛、锆和硅。这是由于钛、锆或硅的氧化物或氢氧化物与有机材料形成良好的结合。
在金属板上形成金属氧化物和/或金属氢氧化物(各自使用铬以外的金属物类)的方法不受特别限制,并且可以使用公知的方法。其例子包括使用氟化物离子(例如金属的氟基络合离子)的液相沉积法、气相沉积法(例如溅射或CVD)和镀覆法(例如置换镀、无电镀、电镀或热浸镀)。
在金属板表面上形成的金属氧化物或金属氢氧化物的表面上形成裂纹的方法不受特别限制,但是其例子包括,例如,用砂纸等的机械打磨、热冲击(例如骤冷)和使用酸性水溶液、碱性水溶液或含氟化物离子的水溶液的化学蚀刻。
在金属板表面上形成凹坑的方法不受特别限制,但是其例子包括用砂纸等的机械打磨、使用酸性或碱性水溶液的化学蚀刻或使用氟化物离子的化学蚀刻。
对本发明中可用的金属板没有特别限制,但是,例如,不锈钢板、铝合金板和镀敷的金属板是合适的。不锈钢板的例子包括铁素体不锈钢板、马氏体不锈钢板和奥氏体不锈钢板。铝合金板的例子包括JIS 1000系列(纯Al型)、JIS 2000系列(Al-Cu型)、JIS 3000系列(Al-Mn型)、JIS 4000系列(Al-Si型)、JIS 5000系列(Al-Mg型)、JIS 6000系列(Al-Mg-Si型)、JIS 7000系列(Al-Zn型)。镀敷钢板的例子包括镀Zn钢板、镀Zn-Fe合金的钢板、镀Zn-Ni合金的钢板、镀Zn-Al合金的钢板、镀Zn-Al-Mg合金的钢板、镀Zn-Al-Mg-Si合金的钢板、镀Al-Si合金的钢板和镀Al-Zn-Si合金的钢板。
特别优选的金属板是主要含Zn或Al的镀合金钢板。通常,在镀合金钢板的表面上存在电化学碱性(base)部分和电化学惰性(noble)部分。当通过液相法,例如通过使用酸性或碱性水溶液或含氟化物离子的水溶液在这种镀敷钢板上生长金属氧化物或金属氢氧化物时,电化学碱性部分溶解且惰性部分保持不溶。因此,首先在下方的镀层上形成凹坑,同时在镀层上生长的金属氧化物或金属氢氧化物中形成裂纹。
例如,在热浸55%Al-43.4%Zn-1.6%Si合金镀敷的钢板上,富Zn相是碱性部分而富Al相是惰性部分。当用金属-六氟基络合离子处理这种镀敷金属板时,选择性溶解富Zn相以形成凹坑,而富Al相仍然几乎保持原样。然后,主要在富Al相上生长金属氧化物或金属氢氧化物,同时在富Zn相上的金属氧化物或金属氢氧化物中形成裂纹。在含Zn或Al作为主要成分的镀敷钢板(例如热浸Zn-5%Al-0.1%Mg合金镀敷的钢板、热浸Zn-11%Al-3%Mg-0.2%Si合金镀敷的钢板和热浸Al-9%Si合金镀敷的钢板)中发生同样的现象。在这种情况下,即使在下方钢板不是软钢而是不锈钢板时,也观察到相同的现象。不锈钢板的例子包括热浸Al-9%Si合金镀敷的不锈钢板。
可以通过简单浸渍由液相法进行上述反应,但是可以通过短接到标准电极电位比待处理的金属板低的金属上来加速待处理金属板表面上氧化物或氢氧化物的生长。此外,通过将不溶材料电连接到待处理的金属板上,可以控制该***以使不溶材料产生阳极反应且金属板产生阴极反应。
对用于本发明的预涂金属板的涂料没有特别限制,并且可以照原样使用常用于预涂金属板的涂料。对于树脂,可以根据用途使用公知的树脂。更具体地,其例子包括下述树脂:其中树脂组分(例如基于高分子聚酯的树脂、基于聚酯的树脂、基于丙烯酰基的树脂、基于环氧的树脂、基于氨基甲酸乙酯的树脂、基于氟的树脂、基于硅聚酯的树脂、聚酯氨基甲酸乙酯树脂、基于氯乙烯的树脂、基于聚烯烃的树脂、基于丁缩醛的树脂、基于聚碳酸酯的树脂、基于酚的树脂或它们的改性树脂)通过交联剂组分(例如丁醇改性三聚氰胺、甲基化三聚氰胺、丁基甲基混合的三聚氰胺、尿素树脂、异氰酸酯或它们的混合物)交联的树脂,并且还包括电子束固化型树脂和紫外线固化型树脂。
用于本发明的预涂金属板的涂料可以含有着色颜料或染料或光泽调节剂(例如二氧化硅),并且如果需要,还可以含有表面光滑剂、紫外线吸收剂、基于受阻胺的光稳定剂、粘度调节剂、固化催化剂、颜料分散剂、颜料沉淀抑制剂、色分离抑制剂等。
为了提高耐腐蚀性,涂层可以包括两层或多层。底涂层可以含有防锈颜料。关于防锈颜料,可以使用已知防锈颜料,并且可用防锈颜料的例子包括基于磷酸的防锈颜料,例如磷酸锌、磷酸铁、磷酸铝和亚磷酸锌;基于钼酸的防锈颜料,例如钼酸钙、钼酸铝和钼酸钡;基于钒的防锈颜料,例如氧化钒;基于离子交换型二氧化硅的防锈颜料,例如钙离子交换型二氧化硅;基于铬酸盐的防锈颜料,例如铬酸锶、铬酸锌、铬酸钙、铬酸钾和铬酸钡;细粒状二氧化硅,例如水分散的二氧化硅和火成二氧化硅;和铁合金,例如硅铁合金。这些可以单独使用或多种混合使用。此外,还可以添加炭黑粉末。然而,为了降低对环境的影响,优选避免使用基于铬酸盐的防锈颜料。
实施例
现在将参照实施例更详细地描述本发明,但是本发明并不限于这些实施例。
所用金属板是热浸55%Al-43.4%Zn-1.6%Si合金镀敷的钢板(两个表面上的镀层覆盖度:150克/平方米)、Zn-11%Al-3%Mg-0.2%Si合金镀敷的钢板(两个表面上的镀层覆盖度:120克/平方米)、不锈钢板(SUS304)和铝合金板(JIS A 3005(Al-Mn型))。这些金属板都具有0.8毫米的厚度。对各金属板样品进行碱法脱脂处理(用“SURFCLEANER155”,Nippon Paint Co.,Ltd.制造),然后进行实验。
为了对金属板提供金属氧化物或金属氢氧化物,使用液相法或气相法。
在液相法中使用的处理溶液是0.1摩尔/升六氟硅酸铵水溶液、0.1摩尔/升六氟钛酸铵水溶液、0.1摩尔/升六氟锆酸铵水溶液、0.05摩尔/升六氟钛酸铵水溶液与0.05摩尔/升六氟硅酸铵水溶液的混合水溶液(混合溶液A)、0.05摩尔/升六氟钛酸铵水溶液与0.05摩尔/升六氟锆酸铵水溶液的混合水溶液(混合溶液B)、0.05摩尔/升六氟锆酸铵水溶液与0.05摩尔/升六氟硅酸铵水溶液的混合水溶液(混合溶液C)、以及0.03摩尔/升六氟钛酸铵水溶液与0.03摩尔/升六氟硅酸铵水溶液和0.03摩尔/升六氟锆酸铵水溶液的混合水溶液(混合溶液D)。
将各金属板在脱脂后浸在处理溶液中并在下列条件下处理以形成金属氧化物或金属氢氧化物膜。
(a)通过简单浸渍形成金属氧化物或金属氢氧化物膜
成膜在室温下进行10分钟,并在成膜后,用水洗涤金属板并干燥。
(b)使用铂作为对电极通过阴极电解形成金属氧化物或金属氢氧化物膜
通过将电流密度控制在100毫安/平方厘米,成膜在室温下进行5分钟,并在成膜后,用水洗涤金属板并干燥。
在气相法中,使用Si、Ti或Zr作靶通过溅射处理金属板,从而在金属板基材上形成金属氧化物或金属氢氧化物膜。
通过X-射线光电能谱法和红外线光谱法对通过液相法或气相法形成的各膜进行分析,以证实金属氧化物或金属氢氧化物的生成。
在下列条件下涂布各金属板(其上已形成了金属氧化物膜或金属氢氧化物膜)以获得预涂金属板。首先,将作为无铬酸盐防锈颜料的含有总共30重量%的钙离子交换型二氧化硅(Shildex C303,Grace制造)与三聚磷酸二氢铝(Al2H2P3O10·2H2O)(K-WHITE#105,Tayaca制造)的1∶1混合物的基于改性环氧的底层预涂料(78 Primer,Kawakami ToryoK.K.制造)作为底层涂料涂布,以产生5微米的干燥厚度,并在其上进一步施用基于聚酯氨基甲酸酯的涂料(570T,Kawakami Toryo K.K.制造),以产生15微米的干燥厚度。
在下列条件下评测这些预涂金属板的涂料附着性和耐腐蚀性。
1)涂料附着性
将通过上述方法制成的预涂金属板在沸水中浸渍60分钟。此后,按照JIS K5400中描述的横切测试法在其上形成横切纹,并进一步进行Erichsen法,产生7毫米的Erichsen值。将压敏胶带(Nichiban Co.,Ltd.制造的玻璃纸)贴在处理过的部分上,然后朝45°的斜向拉,将其迅速剥离,并计算100个横切纹中剥落的横切纹数量。根据剥落程度以5个等级评定附着性。将得分为3或更高的样品评为“通过”。
表1:涂料附着性的得分
得分 | 分级标准 |
54321 | 无剥落小于5%的剥落面积比率5%至小于20%的剥落面积比率20%至小于70%的剥落面积比率70%或更高的剥落面积比率 |
2)耐腐蚀性测试
如下切割预涂金属板以制备用于耐腐蚀性测试的样品:使它们具有向上闪击(upward flash)的切头和向下闪击的切头。按照JIS H 8502中描述的中性盐喷洒循环试验(5重量%NaCl水溶液的喷洒(2小时)→干燥(60℃,相对湿度:20至30%,4小时)→润湿(50℃,相对湿度:95%或更高)),进行180循环的试验。评测来自切头的最大气泡宽度。根据气泡宽度将样品分为5个等级,并将得分为3或更高的样品评为“通过”。
表2:耐腐蚀性的得分
得分 | 分级标准 |
54321 | 无气泡3毫米或更低的最大气泡宽度大于3毫米至5毫米的最大气泡宽度大于5毫米至7毫米的最大气泡宽度大于7毫米的最大气泡宽度 |
通过涂料附着性试验以及耐腐蚀性试验的样品被综合评定为“通过”。
所得结果列在表3至6中。通过扫描电子显微镜观察样品表面或横截面的代表性部分,以5个裂纹或凹坑的平均值确定裂纹和凹坑的宽度、深度、长度和短轴。
当通过扫描电子显微镜观察金属氧化物或金属氢氧化物成膜后的外观时,在通过液相法处理55%Al-43.4%Zn-1.6%Si合金镀敷的钢板和Zn-11%Al-3%Mg-0.2%Si合金镀敷的钢板的情况下,在处理阶段后在下方金属板上形成凹坑,并在形成的金属氧化物或金属氢氧化物膜中形成裂纹。另一方面,在是铝合金板和不锈钢板的情况下,即使通过液相法处理,也不能形成凹坑和裂纹。
当通过气相法(溅射)处理时,在任何下方金属板条件或在任何金属氧化物或金属氢氧化物条件下,都既不能产生凹坑也不能产生裂纹。
对于不能在成膜阶段形成裂纹或凹坑的样品,还评测了下列样品:其中用金刚石研磨膏轻轻摩擦形成的金属氧化物或金属氢氧化物膜的表面以人工产生裂纹,和在成膜之前轻轻摩擦下方金属板的表面以人工形成凹坑。
表3:55%Al-43.4%Zn-1.6%Si合金镀敷钢板的下方金属板例子
编号 | 处理溶液(液相法)或靶(气相法) | 处理方法 | 裂纹 | 凹坑 | 耐腐蚀性 | 附着性 | 总评定 | 备注 | ||
宽度/微米 | 长度/微米 | 短轴/微米 | 深度/微米 | |||||||
1 | 六氟硅酸铵 | 简单浸渍 | 1 | 4 | 1 | 2 | 4 | 3 | 通过 | 发明 |
2 | 六氟硅酸铵 | 阴极电解 | 2 | 4 | 2 | 3 | 4 | 3 | 通过 | 发明 |
3 | 六氟钛酸铵 | 简单浸渍 | 1 | 5 | 1 | 2 | 4 | 4 | 通过 | 发明 |
4 | 六氟钛酸铵 | 阴极电解 | 1 | 8 | 1 | 3 | 4 | 4 | 通过 | 发明 |
5 | 六氟锆酸铵 | 简单浸渍 | 2 | 5 | 1 | 2 | 4 | 3 | 通过 | 发明 |
6 | 六氟锆酸铵 | 阴极电解 | 1 | 6 | 1 | 3 | 4 | 3 | 通过 | 发明 |
7 | 混合溶液A | 简单浸渍 | 1 | 4 | 1 | 2 | 4 | 3 | 通过 | 发明 |
8 | 混合溶液A | 阴极电解 | 2 | 6 | 1 | 2 | 4 | 3 | 通过 | 发明 |
9 | 混合溶液B | 简单浸渍 | 1 | 4 | 1 | 2 | 4 | 3 | 通过 | 发明 |
10 | 混合溶液B | 阴极电解 | 2 | 7 | 1 | 2 | 4 | 3 | 通过 | 发明 |
11 | 混合溶液C | 简单浸渍 | 1 | 4 | 1 | 2 | 4 | 3 | 通过 | 发明 |
12 | 混合溶液C | 阴极电解 | 1 | 4 | 1 | 2 | 4 | 3 | 通过 | 发明 |
13 | 混合溶液D | 简单浸渍 | 1 | 3 | 1 | 2 | 4 | 3 | 通过 | 发明 |
14 | 混合溶液D | 阴极电解 | 1 | 3 | 1 | 2 | 4 | 3 | 通过 | 发明 |
15 | Si | 溅射→抛光1) | 3 | 55 | 0 | 0 | 3 | 3 | 通过 | 发明 |
16 | Si | 抛光→溅射2) | 0 | 0 | 8 | 5 | 3 | 3 | 通过 | 发明 |
17 | Si | 溅射 | 0 | 0 | 0 | 0 | 2 | 2 | 未通过 | 对比 |
18 | Ti | 溅射→抛光1) | 2 | 60 | 0 | 0 | 3 | 3 | 通过 | 发明 |
19 | Ti | 抛光→溅射2) | 0 | 0 | 3 | 7 | 3 | 3 | 通过 | 发明 |
20 | Ti | 溅射 | 0 | 0 | 0 | 0 | 2 | 2 | 未通过 | 对比 |
21 | Zr | 溅射→抛光1) | 7 | 40 | 0 | 0 | 3 | 3 | 通过 | 发明 |
22 | Zr | 抛光→溅射2) | 0 | 0 | 5 | 8 | 3 | 3 | 通过 | 发明 |
23 | Zr | 溅射 | 0 | 0 | 0 | 0 | 2 | 2 | 未通过 | 对比 |
1)溅射形成膜,然后用金刚石研磨膏抛光。
2)用金刚石研磨膏抛光下方金属板,然后溅射形成膜。
表4:Zn-11%Al-3%Mg-0.2%Si合金镀敷钢板的下方金属板例子
编号 | 处理溶液(液相法)或靶(气相法) | 处理方法 | 裂纹 | 凹坑 | 耐腐蚀性 | 附着性 | 总评定 | 备注 | ||
宽度/微米 | 长度/微米 | 短轴/微米 | 深度/微米 | |||||||
1 | 六氟硅酸铵 | 简单浸渍 | 2 | 5 | 1 | 3 | 4 | 3 | 通过 | 发明 |
2 | 六氟硅酸铵 | 阴极电解 | 2 | 6 | 2 | 4 | 4 | 3 | 通过 | 发明 |
3 | 六氟钛酸铵 | 简单浸渍 | 2 | 7 | 1 | 2 | 4 | 4 | 通过 | 发明 |
4 | 六氟钛酸铵 | 阴极电解 | 3 | 9 | 2 | 5 | 4 | 4 | 通过 | 发明 |
5 | 六氟锆酸铵 | 简单浸渍 | 2 | 7 | 1 | 3 | 4 | 3 | 通过 | 发明 |
6 | 六氟锆酸铵 | 阴极电解 | 3 | 10 | 2 | 4 | 4 | 3 | 通过 | 发明 |
7 | 混合溶液A | 简单浸渍 | 2 | 6 | 1 | 2 | 4 | 3 | 通过 | 发明 |
8 | 混合溶液A | 阴极电解 | 2 | 8 | 1 | 3 | 4 | 3 | 通过 | 发明 |
9 | 混合溶液B | 简单浸渍 | 1 | 4 | 1 | 2 | 4 | 3 | 通过 | 发明 |
10 | 混合溶液B | 阴极电解 | 2 | 8 | 1 | 3 | 4 | 3 | 通过 | 发明 |
11 | 混合溶液C | 简单浸渍 | 3 | 6 | 1 | 2 | 4 | 3 | 通过 | 发明 |
12 | 混合溶液C | 阴极电解 | 1 | 4 | 1 | 3 | 4 | 3 | 通过 | 发明 |
13 | 混合溶液D | 简单浸渍 | 1 | 5 | 1 | 2 | 4 | 3 | 通过 | 发明 |
14 | 混合溶液D | 阴极电解 | 1 | 3 | 1 | 2 | 4 | 3 | 通过 | 发明 |
15 | Si | 溅射→抛光1) | 5 | 60 | 0 | 0 | 3 | 3 | 通过 | 发明 |
16 | Si | 抛光→溅射2) | 0 | 0 | 5 | 7 | 3 | 3 | 通过 | 发明 |
17 | Si | 溅射 | 0 | 0 | 0 | 0 | 2 | 2 | 未通过 | 对比 |
18 | Ti | 溅射→抛光1) | 3 | 75 | 0 | 0 | 3 | 3 | 通过 | 发明 |
19 | Ti | 抛光→溅射2) | 0 | 0 | 3 | 8 | 3 | 3 | 通过 | 发明 |
20 | Ti | 溅射 | 0 | 0 | 0 | 0 | 2 | 2 | 未通过 | 对比 |
21 | Zr | 溅射→抛光1) | 8 | 52 | 0 | 0 | 3 | 3 | 通过 | 发明 |
22 | Zr | 抛光→溅射2) | 0 | 0 | 6 | 8 | 3 | 3 | 通过 | 发明 |
23 | Zr | 溅射 | 0 | 0 | 0 | 0 | 2 | 2 | 未通过 | 对比 |
1)溅射形成膜,然后用金刚石研磨膏抛光。
2)用金刚石研磨膏抛光下方金属板,然后溅射形成膜。
表5:不锈钢(SUS304)的下方金属板例子
No. | 处理溶液(液相法)或靶(气相法) | 处理方法 | 裂纹 | 凹坑 | 耐腐蚀性 | 附着性 | 总评定 | 备注 | ||
宽度/微米 | 长度/微米 | 短轴/微米 | 深度/微米 | |||||||
1 | 六氟硅酸铵 | 简单浸渍 | 0 | 0 | 0 | 0 | 2 | 2 | 未通过 | 对比 |
2 | 六氟硅酸铵 | 简单浸渍→抛光3) | 5 | 70 | 0 | 0 | 3 | 3 | 通过 | 发明 |
3 | 六氟硅酸铵 | 阴极电解 | 0 | 0 | 0 | 0 | 2 | 2 | 未通过 | 对比 |
4 | 六氟硅酸铵 | 阴极电解→抛光3) | 8 | 65 | 0 | 0 | 3 | 3 | 通过 | 发明 |
5 | 六氟钛酸铵 | 简单浸渍 | 0 | 0 | 0 | 0 | 2 | 2 | 未通过 | 对比 |
6 | 六氟钛酸铵 | 简单浸渍→抛光3) | 10 | 70 | 0 | 0 | 3 | 3 | 通过 | 发明 |
7 | 六氟钛酸铵 | 阴极电解 | 0 | 0 | 0 | 0 | 2 | 2 | 未通过 | 对比 |
8 | 六氟钛酸铵 | 阴极电解→抛光3) | 8 | 55 | 0 | 0 | 3 | 3 | 通过 | 发明 |
9 | 六氟锆酸铵 | 简单浸渍 | 0 | 0 | 0 | 0 | 2 | 2 | 未通过 | 对比 |
10 | 六氟锆酸铵 | 简单浸渍→抛光3) | 6 | 80 | 0 | 0 | 3 | 3 | 通过 | 发明 |
11 | 六氟锆酸铵 | 阴极电解 | 0 | 0 | 0 | 0 | 2 | 2 | 未通过 | 对比 |
12 | 六氟锆酸铵 | 阴极电解→抛光3) | 0 | 0 | 0 | 0 | 3 | 3 | 通过 | 发明 |
13 | Si | 溅射 | 0 | 0 | 0 | 0 | 2 | 2 | 未通过 | 对比 |
14 | Si | 溅射→抛光1) | 3 | 52 | 0 | 0 | 3 | 3 | 通过 | 发明 |
15 | Si | 抛光→溅射2) | 0 | 0 | 3 | 5 | 3 | 3 | 通过 | 发明 |
16 | Si | 溅射 | 0 | 0 | 0 | 0 | 2 | 2 | 未通过 | 对比 |
17 | Ti | 溅射→抛光1) | 4 | 45 | 0 | 0 | 3 | 3 | 通过 | 发明 |
18 | Ti | 抛光→溅射2) | 0 | 0 | 2 | 5 | 3 | 3 | 通过 | 发明 |
19 | Ti | 溅射 | 0 | 0 | 0 | 0 | 2 | 2 | 未通过 | 对比 |
20 | Zr | 溅射→抛光1) | 3 | 40 | 0 | 0 | 3 | 3 | 通过 | 发明 |
21 | Zr | 抛光→溅射2) | 0 | 0 | 4 | 7 | 3 | 3 | 通过 | 发明 |
22 | Zr | 溅射 | 0 | 0 | 0 | 0 | 2 | 2 | 未通过 | 对比 |
1)溅射形成膜,然后用金刚石研磨膏抛光。
2)用金刚石研磨膏抛光下方金属板,然后溅射形成膜。
3)通过液相法形成膜,然后用金刚石研磨膏抛光。
表6:铝合金(JIS A 3005)的下方金属板例子
No. | 处理溶液(液相法)或靶(气相法) | 处理方法 | 裂纹 | 凹坑 | 耐腐蚀性 | 附着性 | 总评定 | 备注 | ||
宽度/微米 | 长度/微米 | 短轴微米 | 深度/微米 | |||||||
1 | 六氟硅酸铵 | 简单浸渍 | 0 | 0 | 0 | 0 | 2 | 2 | 未通过 | 对比 |
2 | 六氟硅酸铵 | 简单浸渍→抛光3) | 8 | 55 | 0 | 0 | 3 | 3 | 通过 | 发明 |
3 | 六氟硅酸铵 | 阴极电解 | 0 | 0 | 0 | 0 | 2 | 2 | 未通过 | 对比 |
4 | 六氟硅酸铵 | 阴极电解→抛光3) | 6 | 80 | 0 | 0 | 3 | 3 | 通过 | 发明 |
5 | 六氟钛酸铵 | 简单浸渍 | 0 | 0 | 0 | 0 | 2 | 2 | 未通过 | 对比 |
6 | 六氟钛酸铵 | 简单浸渍→抛光3) | 6 | 80 | 0 | 0 | 3 | 3 | 通过 | 发明 |
7 | 六氟钛酸铵 | 阴极电解 | 0 | 0 | 0 | 0 | 2 | 2 | 未通过 | 对比 |
8 | 六氟钛酸铵 | 阴极电解→抛光3) | 8 | 60 | 0 | 0 | 3 | 3 | 通过 | 发明 |
9 | 六氟锆酸铵 | 简单浸渍 | 0 | 0 | 0 | 0 | 2 | 2 | 未通过 | 对比 |
10 | 六氟锆酸铵 | 简单漫渍→抛光3) | 4 | 55 | 0 | 0 | 3 | 3 | 通过 | 发明 |
11 | 六氟锆酸铵 | 阴极电解 | 0 | 0 | 0 | 0 | 2 | 2 | 未通过 | 对比 |
12 | 六氟锆酸铵 | 阴极电解→抛光3) | 0 | 0 | 0 | 0 | 3 | 3 | 通过 | 发明 |
13 | Si | 溅射 | 0 | 0 | 0 | 0 | 2 | 2 | 未通过 | 对比 |
14 | Si | 溅射→抛光1) | 5 | 70 | 0 | 0 | 3 | 3 | 通过 | 发明 |
15 | Si | 抛光→溅射2) | 0 | 0 | 4 | 6 | 3 | 3 | 通过 | 发明 |
16 | Si | 溅射 | 0 | 0 | 0 | 0 | 2 | 2 | 未通过 | 对比 |
17 | Ti | 溅射→抛光1) | 5 | 80 | 0 | 0 | 3 | 3 | 通过 | 发明 |
18 | Ti | 抛光→溅射2) | 0 | 0 | 4 | 7 | 3 | 3 | 通过 | 发明 |
19 | Ti | 溅射 | 0 | 0 | 0 | 0 | 2 | 2 | 未通过 | 对比 |
20 | Zr | 溅射→抛光1) | 4 | 40 | 0 | 0 | 3 | 3 | 通过 | 发明 |
21 | Zr | 抛光→溅射2) | 0 | 0 | 3 | 5 | 3 | 3 | 通过 | 发明 |
22 | Zr | 溅射 | 0 | 0 | 0 | 0 | 2 | 2 | 未通过 | 对比 |
1)溅射形成膜,然后用金刚石研磨膏抛光。
2)用金刚石研磨膏抛光下方金属板,然后溅射形成膜。
3)通过液相法形成膜,然后用金刚石研磨膏抛光。
从表3至6可以看出,在本发明的范围内,在金属氧化物或金属氢氧化物具有裂纹和金属板具有凹坑的条件下,涂料附着性和耐腐蚀性良好。特别地,当如表3和4所示,使用55%Al-43.4%Zn-1.6 Si合金镀敷的钢板和Zn-11%Al-3%Mg-0.2%Si合金镀敷的钢板作为下方金属板并通过液相法处理时,同时形成裂纹和凹坑,这是有效的。
另一方面,当通过溅射之类的气相法形成膜或当下方金属板是不锈钢板等时,在下方金属板上没有形成凹坑,并且在制成的金属氧化物或金属氢氧化物膜上也没有形成裂纹。因此,在这些情况下,预涂金属板的涂料附着性和耐腐蚀性都不令人满意。然而,通过用例如金刚石研磨膏抛光之类的物理方法形成裂纹或凹坑,可以提高涂料附着性和耐腐蚀性。
Claims (6)
1.预涂金属板,其不含六价铬,并表现出与铬酸盐处理过的金属板相同的耐腐蚀性,所述预涂金属板包含金属板,该金属板在至少一个表面上具有无机膜和其上的有机涂层,其中所述无机膜是主要含选自由各自使用铬以外的金属种类的金属氧化物、金属氢氧化物、硅的氧化物和硅的氢氧化物组成的组中的至少一种物质的膜,并且所述膜中有裂纹,所述裂纹是通过使用液相法对金属板提供金属氧化物、金属氢氧化物、硅的氧化物或硅的氢氧化物而形成的。
2.预涂金属板,其不含六价铬,并表现出与铬酸盐处理过的金属板相同的耐腐蚀性,所述预涂金属板包含金属板,在该金属板表面上形成有凹坑,该金属板在至少一个表面上具有无机膜和其上的有机涂层,其中所述无机膜是主要含选自由各自使用铬以外的金属种类的金属氧化物、金属氢氧化物、硅的氧化物和硅的氢氧化物组成的组中的至少一种物质的膜,所述凹坑是通过使用液相法对金属板提供金属氧化物、金属氢氧化物、硅的氧化物或硅的氢氧化物而形成的。
3.预涂金属板,其不含六价铬,并表现出与铬酸盐处理过的金属板相同的耐腐蚀性,所述预涂金属板包含金属板,在该金属板表面上形成有凹坑,该金属板在至少一个表面上具有无机膜和其上的有机涂层,其中所述无机膜是主要含选自由各自使用铬以外的金属种类的金属氧化物、金属氢氧化物、硅的氧化物和硅的氢氧化物组成的组中的至少一种物质的膜,并且所述膜中有裂纹,所述凹坑和裂纹是通过使用液相法对金属板提供金属氧化物、金属氢氧化物、硅的氧化物或硅的氢氧化物而形成的。
4.如权利要求1或3所述的预涂金属板,其中所述裂纹尺寸为宽0.1至10微米,深0.5至10微米且长3微米或更高。
5.如权利要求2或3所述的预涂金属板,其中所述凹坑尺寸为短轴0.5至10微米且深0.5至10微米。
6.如权利要求1至3任一项所述的预涂金属板,其中构成所述金属氧化物或金属氢氧化物的金属种类是一种或多种选自钛和锆的元素。
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JP2001348678A (ja) * | 2000-04-03 | 2001-12-18 | Nisshin Steel Co Ltd | 耐久性の良好な塗装鋼板 |
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JPS5137168B2 (zh) * | 1972-12-29 | 1976-10-14 | ||
JPH0432577A (ja) * | 1990-05-25 | 1992-02-04 | Kobe Steel Ltd | 塗膜密着性及び耐食性に優れた塗装AlまたはAl合金材 |
JPH0825552A (ja) * | 1994-07-12 | 1996-01-30 | Nhk Spring Co Ltd | コーティング層を有する積層体とその製造方法 |
JPH08276533A (ja) * | 1995-04-07 | 1996-10-22 | Nippon Paint Co Ltd | 被覆金属板 |
JP3404286B2 (ja) * | 1998-04-16 | 2003-05-06 | 日本パーカライジング株式会社 | 金属の表面処理方法、および該表面処理方法により得られた表面を有する金属部材 |
US6465114B1 (en) * | 1999-05-24 | 2002-10-15 | Nippon Steel Corporation | -Zn coated steel material, ZN coated steel sheet and painted steel sheet excellent in corrosion resistance, and method of producing the same |
JPWO2003048416A1 (ja) * | 2001-12-04 | 2005-04-14 | 新日本製鐵株式会社 | 金属酸化物及び/又は金属水酸化物被覆金属材料とその製造方法 |
JP4344222B2 (ja) * | 2003-11-18 | 2009-10-14 | 新日本製鐵株式会社 | 化成処理金属板 |
JP4490677B2 (ja) * | 2003-12-03 | 2010-06-30 | 新日本製鐵株式会社 | 環境負荷の小さい塗装金属板 |
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2003
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2004
- 2004-12-07 WO PCT/JP2004/018538 patent/WO2005053949A1/ja active Application Filing
- 2004-12-07 KR KR1020067011177A patent/KR100775109B1/ko not_active IP Right Cessation
- 2004-12-07 US US10/582,123 patent/US20070122645A1/en not_active Abandoned
- 2004-12-07 CN CN2004800364040A patent/CN1890089B/zh not_active Expired - Fee Related
- 2004-12-07 EP EP04801684A patent/EP1693192A4/en not_active Withdrawn
- 2004-12-07 TW TW093137769A patent/TWI294825B/zh not_active IP Right Cessation
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JP2001348678A (ja) * | 2000-04-03 | 2001-12-18 | Nisshin Steel Co Ltd | 耐久性の良好な塗装鋼板 |
Also Published As
Publication number | Publication date |
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KR20060097757A (ko) | 2006-09-15 |
TW200531826A (en) | 2005-10-01 |
KR100775109B1 (ko) | 2007-11-09 |
EP1693192A4 (en) | 2010-06-16 |
TWI294825B (en) | 2008-03-21 |
JP2005169657A (ja) | 2005-06-30 |
CN1890089A (zh) | 2007-01-03 |
JP4414745B2 (ja) | 2010-02-10 |
EP1693192A1 (en) | 2006-08-23 |
MY137081A (en) | 2008-12-31 |
US20070122645A1 (en) | 2007-05-31 |
WO2005053949A1 (ja) | 2005-06-16 |
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