CN1239742C - 磷酸盐处理锌系镀覆钢板 - Google Patents

磷酸盐处理锌系镀覆钢板 Download PDF

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CN1239742C
CN1239742C CNB008081409A CN00808140A CN1239742C CN 1239742 C CN1239742 C CN 1239742C CN B008081409 A CNB008081409 A CN B008081409A CN 00808140 A CN00808140 A CN 00808140A CN 1239742 C CN1239742 C CN 1239742C
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phosphate
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石塚清和
新头英俊
林公隆
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Nippon Steel Corp
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Abstract

本发明提供耐蚀性、涂装性优异的磷酸盐处理镀锌钢板。本发明特征是:在锌或锌合金的镀锌钢板表面上形成含有Mg 2wt%以上、Ni和/或Mn 0.5wt%以上,而且,Mg以及Ni和/或Mn共计4wt%以上的磷酸盐皮膜0.5g/m2以上;在锌或锌合金的镀锌钢板表面上形成含有Mg 2wt%以上,Ni和/或Mn 0.5wt%以上,而且,Mg以及Ni和/或Mn共计5wt%以上的磷酸盐皮膜0.3g/m2以上,最好1g/m2以上。

Description

磷酸盐处理锌系镀覆钢板
技术领域
本发明涉及用于汽车、家电、建材等的耐蚀性、涂装性优异的磷酸盐处理锌系镀覆钢板。
背景技术
在汽车、家电、建材等用途上所用的锌系镀覆钢板历来多施以磷酸盐处理、铬酸盐处理,还有施以有机被覆处理,以便提高耐蚀性、涂装性的附加价值而使用。近年从环境上的问题考虑,特别是经铬酸盐处理的钢板存在涉嫌含6价铬的可能性的倾向,故对于磷酸盐处理的期望正目益高涨。
然而,在锌系镀覆钢板的历来磷酸盐处理中,因为未必能得到充分的耐蚀性、涂装性,因此,各种改善的方法被提出。例如,特公昭60-34912号公报中公开了在形成磷酸盐皮膜之后,用缓蚀剂处理的方法。还有,在特开昭60-50175号公报、特开平8-13154号公报中公开了在磷酸盐皮膜中使Ni、Mn等共存的方法。
在以上的方法中,尽管有一定的效果,但如考虑到最近更苛刻的耐蚀性要求,则是不充分的,特别是裸钢的耐蚀性的改善效果则几乎没有。
又,在特开平1-312081号公报、特开平3-107469号公报中公开了含Mg的磷酸锌皮膜,但在此场合下耐蚀性的改善效果也不充分,并且涂装性是不够的。另外,在特开平9-49086公报中公开了含Ni和Mg的磷酸锌皮膜的形成方法,但在此情况下也有耐蚀性不充分的问题。
发明的公开
本发明的目的在于提供解决上述缺点的耐蚀性、涂装性优越的磷酸盐处理锌系镀覆钢板。
本发明人首先在对锌系镀覆钢板上施加磷酸盐处理中,使在处理浴中共存大量的镁离子和镍离子,试图形成历来技术未曾有的Mg和Ni含有率高的磷酸盐皮膜,结果发现:如使磷酸盐皮膜中的Mg和Ni双方的含有率增加,则可同时改善耐蚀性和涂装性。还发现:在形成含有Mg和Ni的磷酸盐皮膜之后,涂布含有Mg和/或Ni的磷酸盐水溶液,不水洗而进行干燥,则可进一步得到含有高Mg和Ni的磷酸盐皮膜,如将如此所得的磷酸盐皮膜中的Mg和Ni各自的含有率定在特定的范围,则可得到历来不曾知道的极为良好的耐蚀性、涂装性。又得知以Mn代替Ni也可得到同样效果。
本发明就是基于以上的新知识而完成的。其要旨是提供耐蚀性、涂装性优越的磷酸盐处理锌系镀覆钢板,其特征在于:在锌或锌系合金镀覆钢板的表面上形成含有Mg 2wt%以上、Ni和/或Mn 0.5wt%以上,而且Mg以及Ni和/或Mn共计4wt%以上的磷酸盐皮膜0.5g/m2以上;还提供耐蚀性、涂装性优越的磷酸盐处理锌系镀覆钢板,其特征在于:在锌或锌系合金镀覆钢板的表面上形成含有Mg 2wt%以上、Ni和/或Mn 0.5wt%以上,而且,Mg以及Ni和/或Mn共计5wt%以上的磷酸盐皮膜0.3g/m2以上,最好1g/m2以上。
为实施本发明的最佳形态
对于在本发明中所用的锌系镀覆钢板没有特殊的限制,纯锌镀覆或锌合金镀覆中的任一种均可使用。另外对于纯锌镀覆和锌合金镀覆的方法来说,不管电镀、热浸镀、真空镀膜等手段均可。
在本发明的锌系镀覆层上所形成的磷酸盐皮膜中,通常含有从镀层溶出的和磷酸盐处理浴中存在的锌,此外,还必须含有Mg以及Ni和/或Mn,这些金属对磷酸盐皮膜全体重量的含有比例必须是:Mg为2wt%以上、Ni和/或Mn为0.5wt%以上;而且,Mg以及Ni和/或Mn共计为4wt%以上,如小于任何一个下限,其耐蚀性、涂装性都显著地恶化。Mg以及Ni和/或Mn如共计为5wt%以上则更好。
又,就上限来说,并无特定的限制,Mg和Ni的单独一种或其合计量以约10wt%左右为界限;Mg以及Mn和/或Ni的合计量以约15wt%左右为界限,其含量如超过此界限,则在技术上有困难。
含有上述Mg以及Ni和/或Mn合计为4wt%以上的磷酸盐皮膜的重量必须是0.5g/m2以上,如不满此值,则耐蚀性不足;另外,含有上述Mg以及Ni和/或Mn合计为5wt%以上的磷酸盐皮膜的重量必须是0.3g/m2以上,如不满此值,则耐蚀性不足,更好是1g/m2以上。另外,就上限来说,没有特别限定,如考虑焊接性,一般则以2.5g/m2左右以下为令人满意。
由于Ni和Mn有同等效果,所以以下的叙述仅用Ni作为代表而不用Mn。
本发明的含Mg和Ni的磷酸盐处理皮膜可以通过利用含有Mg离子和Ni离子的磷酸盐处理浴处理而获得。在这样的处理之前,最好进行钛胶体处理和洗刷处理等公知的前处理。作为磷酸盐处理浴可示例的有在含有Zn离子、磷酸离子、氟化物、氧化剂(硝酸盐、亚硝酸盐、氯酸盐等)等的处理浴中添加Mg离子和Ni离子的处理浴,此时的各金属离子浓度比(重量比)对1个Zn离子而言以约10~50个Mg离子;约1~10个左右的Ni离子为令人满意。使用这样的处理浴,作为上述的处理方法可列举的有例如喷涂法或浸渍法,通过这些方法,可在锌系镀覆钢板上形成磷酸锌处理皮膜。再者,在这些方法中,当使Mg和Ni共存时,所形成的皮膜中的两种金属的合计的重量比例在工业上是以5%左右为界限,要以这个界限以上多的比例含有时,不仅非常困难,而且,还易引起皮膜的折出不良和发生大量淤泥等,因而不理想。
当使更多量的Mg和Ni共存时,用上述那样的方法,用含Mg和Ni的磷酸盐浴一次处理;或者,宜在用通常的不含Mg、Ni的磷酸浴处理之后,将含Mg和/或Ni的磷酸盐水溶液涂布,不进行水洗地干燥,使到达板温度为90~150℃,从而形成复合磷酸盐皮膜,这样是理想的。作为上述所涂布的水溶液希望是各金属的亚磷酸盐(也可说是磷酸二氢盐、磷酸氢盐)。作为涂布的方法希望是滚涂法。该涂布可在两面进行;也可在一面上进行,例如,当像汽车钢板那样的更重视其内面的耐蚀性时,仅在相当于内面的面上涂布也是适宜的。当涂布磷酸盐水溶液时,本发明中的磷酸盐皮膜的总重量是最初的磷酸盐处理皮膜与其后以磷酸盐水溶液涂布所形成的皮膜的合计重量。Mg和Ni的各自的含有率是将最初的磷酸盐处理皮膜和其后所涂布的磷酸盐皮膜中的各自含量的合计含量除以两种皮膜总重量所得的百分率值。而且,各自的含有率和皮膜总重量如在本发明范围内,则同样可得到良好的耐蚀性和涂装性。
如以上所述那样,用Mn代替Ni也可;另外,Ni和Mn并用也可得到同样效果。
实施例
以下示出本发明的实施例。
作为试料,在任何实施例中均使用单位面积量为30g/m2(单面)的电镀镀锌钢板。
调整试料
(实施例1~8)
使用市售钛胶体系处理剂(日本帕喀来井有限公司制的PL-Zn)将镀锌钢板进行前处理后,用喷涂法以表1的磷酸盐处理浴进行磷酸盐处理。将喷涂时间调节在1.5秒~10秒;将处理浴温度调节在60℃~70℃之间,按照各实施例形成干燥后重量为0.2~1.7g/m2的磷酸盐皮膜。处理后水洗一次,干燥后,再用滚涂器通过改变其旋转数涂布磷酸氢镁水溶液(将米山化学工业有限公司所制的磷酸氢镁50%水溶液稀释5倍使用),使涂布的皮膜干燥后重量调节成为0.3~1.5g/m2,再进行干燥,使到达板温度为110℃。
       表1磷酸盐处理浴组成①
  浓度
  磷酸离子   10g/l
  Zn离子   2g/l
  Ni离子   4G/l
  Mg离子   1g/l
  硝酸离子   10g/l
  F   0.3g/l
  全酸度/游离酸度   15
(实施例9)
与上述一样,使用表1的磷酸盐处理浴,喷涂时间为2秒,处理浴温度为60℃,形成干燥后重量为0.7g/m2的磷酸盐皮膜。水洗并干燥后,再在磷酸氢镁水溶液(使用米山化学工业有限公司制磷酸氢镁50%水溶液)中将磷酸氢锰(米山化学工业有限公司制磷酸二氢锰四水合物)混合,使其固体成分重量比为2∶1,用水稀释,调整成固体成分浓度为10%的水溶液,用滚涂器将其调整成涂布皮膜的干燥后重量为1g/m2后再进行涂布,干燥之,使到达板温度为110℃。
(实施例10)
在表1所示的磷酸盐处理浴中,添加取代Ni离子的Mn离子4g/l,同样地在喷涂时间为2秒,处理浴温度为65℃的条件下,形成干燥后重量为1g/m2的磷酸盐皮膜。水洗并干燥后,再将磷酸氢镁水溶液(将米山化学工业有限公司制的磷酸氢镁50%水溶液稀释5倍使用),用滚涂器调整到使其涂布皮膜的干燥后重量为0.7g/m2后涂布,干燥之,使其到达板温度为110℃。
(实施例11)
使用表2的磷酸盐处理浴进行喷涂处理以完成磷酸盐处理。喷涂时间为1.5秒,处理浴温度为60℃,形成干燥后重量为1.0g/m2的磷酸盐皮膜。水洗并干燥后,再在磷酸氢镁水溶液(使用米山化学工业有限公司制磷酸氢镁50%水溶液)中混合磷酸氢锰(使用米山化学工业有限公司制磷酸二氢锰四水合物),使其固体成分重量比为2∶1,用水稀释,调制成固体成分浓度为10%的水溶液,用滚涂器涂布,干燥之,使到达板温度为110℃,得到干燥后重量为1g/m2的涂布皮膜。
     表2磷酸盐处理浴组成②
  浓度
  磷酸离子   10g/l
  Zn离子   2g/l
  Ni离子   0.2g/l
  硝酸离子   10g/l
  F   0.2g/l
  全酸度/游离酸度   15
(实施例12~13)
用表3的磷酸盐处理浴喷涂于钢板上进行磷酸盐处理。喷涂时间为4秒和2秒,处理浴温度为70℃,形成干燥后重量分别为1.4g/m2(实施例12)和0.6g/m2(实施例13)的磷酸盐皮膜。处理后水洗并干燥。
      表3磷酸盐处理浴组成③
  浓度
  磷酸离子   6g/l
  Zn离子   1g/l
  Ni离子   4g/l
  Mg离子   30g/l
  硝酸离子   80g/l
  F   0.3g/l
  全酸度/游离酸度   15
(实施例14)
进行了与实施例13完全相同的处理后,再将磷酸氢镁溶液(米山化学工业有限公司制磷酸氢镁50%水溶液稀释5倍后使用)用滚涂器涂布,使其涂布皮膜的干燥后重量为1g/m2,干燥之,使其到达板温度为110℃。
(实施例15)
使用表3的磷酸盐处理浴,进行以喷涂处理的磷酸盐处理。喷涂时间为2秒,处理浴温度为65℃,形成干燥后重量为0.4g/m2的磷酸盐皮膜,处理后水洗并干燥。
(实施例16)
使用表3的磷酸盐处理浴,进行用喷涂处理的磷酸盐处理。喷涂时间为1.5秒,处理浴温度为60℃,形成干燥后重量为0.2g/m2的磷酸盐皮膜。水洗、干燥后,再将使磷酸氢镁和磷酸氢锰的固体成分重量比调整到1∶1的水溶液调节成涂布皮膜的干燥后重量为0.1g/m2那样进行涂布,干燥之,使到达板温度为110℃。
(比较例1)
使用除了Ni离子浓度为0g/l之外与表3相同浓度组成的处理浴,以喷涂处理进行磷酸盐处理。喷涂时间为6秒,处理浴温度为65℃,形成干燥后重量为1.5g/m2的磷酸盐皮膜。处理后水洗并干燥。
(比较例2)
使用表1的处理浴,喷涂时间为0.5秒,浴温度为55℃,形成干燥后重量为0.1g/m2的磷酸盐皮膜。水洗并干燥后,再用滚涂器将磷酸氢镁水溶液(使用将米山化学工业有限公司制磷酸氢镁50%水溶液稀释10倍稀释溶液)调节并涂布,使涂布皮膜的干燥后重量为0.1g/m2,再干燥之,使到达板温度为110℃。
(比较例3)
除磷酸处理后不涂布磷酸氢镁水溶液之外,其它与实施例5相同,形成磷酸盐皮膜。
(比较例4)
用表4的磷酸盐处理浴作喷涂处理,以进行磷酸盐处理。喷涂时间为4秒,处理浴温度为70℃,形成干燥后重量1.5g/m2的磷酸盐皮膜。处理后水洗并干燥。
       表4磷酸盐处理浴组成④
  浓度
  磷酸离子   15g/l
  Zn离子   1g/l
  Ni离子   3.5g/l
  Mn离子   2g/l
  硝酸离子   18g/l
  F   1g/l
  全酸度/游离酸度   30
(比较例5)
用表5的磷酸盐处理浴作喷涂处理,以进行磷酸盐处理。喷涂时间为4少,处理浴温度为65℃,形成干燥后重量为1.5g/m2的磷酸盐皮膜。处理后水洗并干燥。
       表5磷酸盐处理浴组成⑤
  浓度
  磷酸离子   15g/l
  Zn离子   1g/l
  Ni离子   3.5g/l
  Mg离子   8g/l
  Mn离子   2g/l
  硝酸离子   28g/l
  F   1g/l
  全酸度/游离酸度   30
[性能评价方法]
皮膜重量:在铬酸氢铵20g/l和25%氨490g/l的混合水溶液(剥离液)中将试料浸渍,将磷酸盐皮膜完全剥离。从剥离前后的试料重量差算出皮膜量。
皮膜成份(Mg、Ni、Mn):在含上述皮膜的剥离液中加入硝酸,升温后,根据ICP将Mg、Ni、Mn定量,算出占全皮膜量中的重量%。
涂装粘合性(一次):对试料进行碱脱脂(使用日本佩因特有限公司制SD 280MZ);化学处理(日本佩因特有限公司制SD 2500MZL);阳离子电淀积涂装(日本佩因特制V-20,膜厚20μm)。经放置一日后,用NT切割器刻划2mm间隔的直达基体铁的划痕,形成方格(100个方块),再在用埃立克森试验机(Erichsen tester)7mm挤出后,用赛璐玢带剥离。(评价:××:剥离100个方块;×:剥离99~6个方块;△:剥离1~5个方块;○:方块剥不下来,但在划痕周边部有剥离;◎:完全不剥离。)
涂装粘合性(二次):与上述同样地处理直到进行电淀积涂装之后,在50℃温水中浸渍10日后,与上述一样进行评价。
涂装后耐蚀性:与上述涂装粘合性评价相同地进行到电淀积涂装之后,经放置1日后,用NT切割器交叉刻划直达基体铁的划痕,进行20天的JIS-Z-2371的盐水喷雾试验,然后用赛璐珞带进行剥离,评价从交叉刻痕部的涂膜剥离宽度(一侧)的最大值。(×:大于10mm;△:3~10mm;○:小于3mm)。
裸钢耐蚀性:在用带将试料边缘和背面密封后,用JIS-Z-2371的盐水喷雾试验测定直到红锈5%发生的日数。(××:1日之内;×:2日之内;△:2日~5日;○:5日~10日;◎:10天或10天以上)。
评价结果示于表6,在本发明实施例中可得良好的涂装性和耐蚀性,与此相反,就本发明范围之外的比较例而言,无论哪一个性能都恶化了。
                                 表6评价结果
  No   皮膜重量g/m2   皮膜成分   涂装粘合性   涂装后耐蚀性   裸耐蚀性
  Mg%   Ni%   Mn%   Ni+Mn%   Mg+Ni+Mn%
  一次   二次
  实施例   1   0.5   6.4   1.2   0   1.2   7.6   ◎   ◎   ○   ○
  2   1   5.3   1.6   0   1.6   6.9   ◎   ◎   ○   ◎
  3   1.2   8.8   0.5   0   0.5   9.3   ◎   ◎   ○   ◎
  4   1.5   3.6   2.0   0   2.0   5.6   ◎   ◎   ○   ◎
  5   2.2   2.5   2.5   0   2.5   4.9   ◎   ◎   ○   ◎
  6   2.1   2.1   4.0   0   4.0   6.1   ◎   ◎   ○   ◎
  7   2.5   6.3   1.6   0   1.6   7.9   ◎   ◎   ○   ◎
  8   2.5   4.3   1.8   0   1.8   6.1   ◎   ◎   ○   ◎
  9   1.7   4.2   1.2   3.4   4.6   8.8   ◎   ◎   ○   ◎
  10   1.7   4.4   0.0   2.1   2.1   6.5   ◎   ◎   ○   ◎
  11   2   3.5   0.1   2.9   2.9   6.4   ◎   ◎   ○   ◎
  12   1.4   3.0   1.4   0   1.4   4.4   ◎   ◎   ○   ○
  13   0.6   2.9   2.7   0   2.7   5.6   ◎   ◎   ○   ○
  14   1.6   7.7   1.0   0   1.0   8.7   ◎   ◎   ○   ◎
  比较例   1   1.5   4.0   0.0   0   0.0   4.0   △   ×   ×   ○
  2   0.2   5.4   2.0   0   2.0   7.4   ○   ○   △   △
  3   1.2   0.3   5.0   0   5.0   5.3   ◎   ◎   ○   ×
  4   1.5   0.0   2.5   2   4.5   4.5   ◎   ◎   △   ××
  5   1.5   1.0   2.0   2   4.0   5.0   ◎   ◎   ○   △
  实施例   15   0.4   4.5   0.8   0   0.8   5.3   ◎   ◎   ○   ○
  16   0.3   2.9   0.3   2.5   2.8   5.7   ◎   ◎   ○   ○
产业上利用可能性
按照本发明可得到历来未曾有的具有耐蚀性或涂装性的磷酸盐处理锌系镀覆钢板。本发明钢板不用6价铬等有害物质,制造方法简易,成本也低廉,适用于汽车、家电、建材等各种用途。

Claims (2)

1.一种磷酸盐处理锌系镀覆钢板,它是表面上形成有磷酸盐皮膜的锌或锌系合金镀覆钢板,其特征在于:该磷酸盐皮膜中Mg的含量为2wt%至10wt%、Ni和/或Mn的含量为0.5wt%以上,而且,当该磷酸盐皮膜的重量为0.5g/m2以上时,Mg以及Ni和/或Mn的共计含量为4wt%以上,当磷酸盐皮膜的重量为0.3-0.5g/m2时,Mg以及Ni和/或Mn的共计含量为5wt%以上。
2.权利要求1的磷酸盐处理锌系镀覆钢板,其中磷酸盐皮膜的重量为1g/m2以上。
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