CN106283009A - 热镀锌板涂层液及其制备和使用方法 - Google Patents

热镀锌板涂层液及其制备和使用方法 Download PDF

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CN106283009A
CN106283009A CN201610663162.2A CN201610663162A CN106283009A CN 106283009 A CN106283009 A CN 106283009A CN 201610663162 A CN201610663162 A CN 201610663162A CN 106283009 A CN106283009 A CN 106283009A
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acid
coating solution
heat zinc
water
zinc coating
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董学强
郭太雄
冉长荣
张爱萍
徐权
周林
周一林
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Pangang Group Panzhihua Iron and Steel Research Institute Co Ltd
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Abstract

本发明属于热镀锌钢板领域,具体涉及一种热镀锌板涂层液及其制备和使用方法。针对现有技术中热镀锌板涂层液不环保、涂覆后膜层耐蚀性差等问题，本发明提供一种热镀锌板涂层液，其成分包括：按重量百分比计，每100份水中加入5～20份三价铬混合物、1～20份PH调节剂、1～10份成膜促进剂、5～20份胶体二氧化硅、10～30份水性树脂。本发明涂层液不含六价铬，不会对人体造成伤害，环保性好；本发明所述的涂层液，在热镀锌板表面涂覆后制备的热镀锌涂层板具有高耐蚀性，还具有良好的耐指纹性、耐水性、附着性等优良性能，为热镀钢板的钝化提供了一种全新的方法。

Description

热镀锌板涂层液及其制备和使用方法
技术领域
本发明属于热镀锌钢板领域,具体涉及一种热镀锌板涂层液及其制备和使用方法。
背景技术
热镀锌钢板由于具有优异的加工与使用性能，在家用电器、汽车、建筑等工业领域得到了广泛的应用。但在潮湿环境中，热镀锌板容易被腐蚀，因此一般采用镀层，将钢板作钝化处理。传统的铬酸盐钝化处理，工艺简单，膜结合力好，耐蚀性高，有自我修复能力。常用的铬酸盐中一般为六价铬,其是致癌物质，对人体和环境都有严重危害，因此，含有六价铬的产品受到了严格的限制。
为此，国内外大量研究了无铬钝化技术，但其耐蚀性等主要性能无法达到铬酸盐钝化工艺水准。
发明内容
本发明要解决的技术问题是传统的热镀锌板涂层液致癌、不环保、涂覆后膜层耐蚀性差等问题。
本发明解决该技术问题的技术方案为提供一种热镀锌板涂层液及其制备和使用方法，该涂层液环保安全，制备的热镀锌涂层板具有高耐蚀性、优良的耐指纹性、耐水性和附着性。
本发明提供一种热镀锌板涂层液，其原料包括以下成分：按重量份数计，每100份水中加入5～20份三价铬混合物、1～20份PH调节剂、1～10份成膜促进剂、5～20份胶体二氧化硅、10～30份水性树脂。
其中，上述热镀锌板涂层液中，所述的PH调节剂为硅酸钠、磷酸钠、磷酸钾、磷酸一氢钠、磷酸铵、磷酸一氢钾或四硼酸钠中的的至少一种。
其中，上述热镀锌板涂层液中，所述的成膜促进剂为钨酸钠、硫酸羟胺、硝酸钙、硝酸镍、亚硝酸钠、钼酸钠、钼酸钾、高锰酸钾或氯酸钠中的至少一种。
其中，上述热镀锌板涂层液中，所述的水性树脂为水性丙烯酸树脂、水性苯丙树脂、水性酚醛树脂、水性聚氨酯、水性有机硅树脂或水性环氧树脂中的至少一种。
其中，上述热镀锌板涂层液中，所述的三价铬混合物由六价铬化合物、有机物、酸性物质反应制备而成；制备方法为：每1～5mol六价铬化合物加入100mol水中，充分溶解后加入0.5～15mol有机物，溶解后再加入1～50mol酸性物质，搅拌反应2～10h。
其中，上述热镀锌板涂层液中，所述的六价铬化合物为三氧化铬、重铬酸钠、重铬酸钾或重铬酸氨中的至少一种；所述的酸性物质为氢氟酸、磷酸、硫酸、亚硫酸、氟钛酸、氟硅酸、亚硝酸、硝酸、磷酸二氢钠或磷酸二氢钾中的一种；所述的有机物为含有羧基的易溶于水的液体或固体有机物，所述的有机物为植酸、柠檬酸、草酸、乳酸、葡萄糖酸、苯甲酸、水杨酸、乙酸、丙酸、丁酸、马来酸、丁二酸、对羟基苯甲酸、氨基乙酸、氨基丙酸或己二酸中的至少一种。
特别的，当酸性物质为一元酸性物质(氢氟酸)时，六价铬化合物与一元酸性物质摩尔比为1﹕3～10；当酸性物质为二元酸性物质(亚磷酸、亚硝酸、亚硫酸、氟钛酸、氟硅酸、磷酸二氢钠或磷酸二氢钾中的一种)时，六价铬化合物与二元酸性物质摩尔比为1﹕1.5～5；当酸性物质为三元酸性物质(磷酸)时，六价铬与三元酸性物质摩尔比为1﹕1～4。
其中，上述热镀锌板涂层液中，所述涂层液的PH值为7.5～10。
本发明还提供一种上述热镀锌板涂层液的制备方法：将三价铬混合物、PH调节剂、成膜促进剂、胶体二氧化硅、水性树脂在水中溶解混合，搅拌均匀即可。
本发明还提供一种上述热镀锌板涂层液的使用方法：将涂层液涂覆于热镀锌板表面，60～100℃条件下烘干、固化10～30s，制得钝化的热镀锌板。
其中，上述热镀锌板涂层液的使用方法中，所述的涂覆厚度为0.2～1.5μm。
本发明还提供一种由上述使用方法制备得到的钝化的热镀锌板。
本发明的有益效果为：本发明提供一种热镀锌板涂层液，该涂层液通过将六价铬化合物还原成三价铬混合物,使涂层液中不含六价铬，不会对人体造成伤害，环保性好；本发明所述的涂层液，在热镀锌板表面涂覆后制备的热镀锌涂层板具有高耐蚀性，还具有良好的耐指纹性、耐水性、附着性等优良性能，为热镀钢板的钝化提供了一种全新的方法。
具体实施方式
本发明提供了一种热镀锌板涂层液，其原料包括以下成分：按重量份数计，每100份水中加入5～20份三价铬混合物、1～20份PH调节剂、1～10份成膜促进剂、5～20份胶体二氧化硅、10～30份水性树脂。
本发明采用三价铬混合物、胶体二氧化硅和水性树脂为主要原料制备热镀锌板涂层液，三价铬混合物主要与镀锌板反应，形成网状膜层骨架；此处的三价铬混合物由六价铬化合物还原而得，具体制备方法为：每1～5mol六价铬化合物加入100mol水中，充分溶解后加入0.5～15mol有机物，溶解后再加入1～50mol酸性物质，搅拌反应2～10h；通过六价铬化合物和有机物以及酸性物质的合适配比,在2～10h内,可以使六价铬化合物全部转化为三价铬,从而使涂层液中不含有六价铬,反应时间必须要在此范围内,才能完全的进行转化。
上述热镀锌板涂层液中，所述的六价铬化合物为三氧化铬、重铬酸钠、重铬酸钾或重铬酸氨中的至少一种；所述的酸性物质为氢氟酸、磷酸、硫酸、亚硫酸、氟钛酸、氟硅酸、亚硝酸、硝酸、磷酸二氢钠或磷酸二氢钾中的一种；所述的有机物为含有羧基的易溶于水的液体或固体有机物，所述的有机物为植酸、柠檬酸、草酸、乳酸、葡萄糖酸、苯甲酸、水杨酸、乙酸、丙酸、丁酸、马来酸、丁二酸、对羟基苯甲酸、氨基乙酸、氨基丙酸或己二酸中的至少一种。
发明人研究发现，当PH≤5时，六价铬可被有机酸全部还原成三价铬，最后稳定存在的涂层液不会含有六价铬，更环保健康。因此，在制备三价铬混合物时，为了使反应PH≤5，从而使六价铬全部还原成三价铬混合物，本发明的六价铬化合物与酸性物质的摩尔比为：当酸性物质为一元酸性物质时，六价铬化合物与一元酸性物质摩尔比为1﹕3～10；当酸性物质为二元酸性物质时，六价铬化合物与二元酸性物质摩尔比为1﹕1.5～5；当酸性物质为三元酸性物质时，六价铬与三元酸性物质摩尔比为1﹕1～4。
本发明涂层液中三价铬混合物加入量过多，则PH调节剂也要增加，涂层液的固含量会增大，进而使涂层中无机成分增加，易出现掉粉等不良现象；三价铬混合物加入量过少，涂层耐蚀性差。为了不掉粉和耐蚀性能好，本发明涂层中中适宜添加的三价铬混合物为：每100份水中加入5～20份三价铬混合物。
本发明中采用胶体二氧化硅作为填充，胶体二氧化硅粒径较小，可填充在膜层骨架中，起封闭作用。市场上的胶体二氧化硅粒径一般为1～50nm，都可达到好的效果。胶体二氧化硅含量过少时，涂层的耐蚀性和耐指纹性降低；胶体二氧化硅过高时，涂层易出现掉粉。为了使涂层不掉粉、且耐蚀性和耐指纹性增强，本发明涂层液的适宜胶体二氧化硅添加量为：每100份水中加入5～20份胶体二氧化硅。
本发明中水性树脂是指水性丙烯酸树脂、水性苯丙树脂、水性酚醛树脂、水性聚氨酯、水性有机硅树脂或水性环氧树脂中的至少一种；这类树脂水溶性强，且具有良好的粘附力，可粘附在热镀锌板表面，也可将胶体二氧化硅和三价铬混合物的膜层骨架结合在一起，水性树脂可显著提高涂层液的浓度，既降低了溶液中Cr含量，更环保，又有助于提升膜厚，即使镀锌机组速度较慢，也可使涂层的膜厚达到要求。水性树脂含量过高时，涂层的耐热性较差；含量过低时，涂层的附着性变差，易出现掉粉等不良现象。为了使涂层液耐热性优良、不掉粉，本发明涂层液中水性树脂的适宜添加量为：每100份水中加入10～30份水性树脂。
进一步的，为加快成膜速度，本发明加入了氧化性物质作为成膜促进剂，促进三价铬络合物与Zn的反应，所述的成膜促进剂为钨酸钠、硫酸羟胺、硝酸钙、硝酸镍、亚硝酸钠、钼酸钠、钼酸钾、高锰酸钾或氯酸钠中的至少一种。
进一步的，为了调整最后涂层液的PH值，本发明加入了PH调节剂，所述的PH调节剂为硅酸钠、磷酸钠、磷酸钾、磷酸一氢钠、磷酸铵、磷酸一氢钾或四硼酸钠中的的至少一种，优选的PH调节范围为7.5～10。
综上，为了得到环保、耐蚀性强的热镀锌板涂层液，本发明经过试验最终将涂层液的成分含量限定为：按重量份数计，每100份水中加入5～20份三价铬混合物、1～20份PH调节剂、1～10份成膜促进剂、5～20份胶体二氧化硅、10～30份水性树脂。
本发明还提供一种上述热镀锌板涂层液的制备方法：将三价铬混合物、PH调节剂、成膜促进剂、胶体二氧化硅、水性树脂在水中溶解混合，搅拌均匀即可。
本发明还提供一种上述热镀锌板涂层液的使用方法：将涂层液涂覆于热镀锌板表面，60～100℃条件下烘干、固化10～30s，制得钝化的热镀锌板。
其中，上述热镀锌板涂层液的使用方法中，所述的涂覆厚度为0.2～1.5μm。
本发明还提供一种由上述使用方法制备得到的钝化的热镀锌板。
下面将结合实施例对本发明的具体实施方式做进一步的解释说明，但不将专利的保护范围限制在实施例所述范围内。
实施例所述的胶体二氧化硅普通的粒径≤50nm的胶体二氧化硅，三氧化铬等产品均来至普通市售产品。
实施例1用本发明技术方法制备热镀锌板涂层液
制备三价铬混合物：
三价铬混合物由水、三氧化铬、柠檬酸、氢氟酸反应而成，其比例(以物质的量计)为：水100、三氧化铬2、柠檬酸2、氢氟酸6。制备方法为：首先将三氧化铬加入水中，溶解且搅拌均匀后加入柠檬酸，待完全溶解后，加入氢氟酸，在不断搅拌下，反应时间为5h。
制备热镀锌板涂层液：
制备热镀锌板涂层液，各原料含量(以重量份数计)为：水100，三价铬混合物10，硅酸钠5，钼酸钠6，胶体二氧化硅15，水性树脂20。在常温条件下，将其混合，搅拌均匀即可。
实施例2用本发明技术方法制备热镀锌板涂层液
制备三价铬混合物：
三价铬混合物由水、重铬酸钠、草酸、磷酸反应而成，其比例(以物质的量计)为：水100、重铬酸钠2、草酸5、磷酸9。制备方法为：首先将重铬酸钠加入水中，溶解且搅拌均匀后加入草酸，待完全溶解后，加入磷酸，在不断搅拌下，反应时间为3h。
制备热镀锌板涂层液：
制备热镀锌板涂层液，各原料含量(以重量份数计)为：水100，三价铬混合物15，磷酸钠10，高锰酸钾3，胶体二氧化硅10，水性树脂15。在常温条件下，将其混合，搅拌均匀即可。
实施例3用本发明技术方法制备热镀锌板涂层液
制备三价铬混合物：
三价铬混合物由水、重铬酸铵、植酸、磷酸二氢钠反应而成，其比例(以物质的量计)为：水100、重铬酸铵1.5、植酸1、磷酸二氢钠15。制备方法为：首先将重铬酸铵加入水中，溶解且搅拌均匀后加入植酸，待完全溶解后，加入磷酸二氢钠，在不断搅拌下，反应时间为6h。
制备热镀锌板涂层液：
制备热镀锌板涂层液，各原料含量(以重量份数计)为：水100，三价铬混合物20，四硼酸钠8，钨酸钠8，胶体二氧化硅20，水性树脂25。在常温条件下，将其混合，搅拌均匀即可。
实施例4用本发明技术方法制备热镀锌板涂层液
除三价铬混合物的制备含量为5外，其余步骤同实施例1。
实施例5用本发明技术方法制备热镀锌板涂层液
除钼酸钠制备含量为10外，其余步骤同实施例1。
实施例6用本发明技术方法制备热镀锌板涂层液
除胶体二氧化硅制备含量为5外，其余步骤同实施例1。
实施例7用本发明技术方法制备热镀锌板涂层液
除硅酸钠制备含量为10外，其余步骤同实施例1。
实施例8用本发明技术方法制备热镀锌板涂层液
水性树脂制备含量为10外，其余步骤同实施例1。
对比例1
除制备三价铬混合物时反应时间为1h外，其余步骤同实施例1。
对比例2
除不加入柠檬酸外，其余步骤同实施例1。
对比例3
除不加入氢氟酸外，其余步骤同实施例1。
对比例4
除不加入胶体二氧化硅外，其余步骤同实施例1。
对比例5
除不加入硅酸钠外，其余步骤同实施例1。
对比例6
除不加入钼酸钠外，其余步骤同实施例1。
对比例7
除不加入水性树脂外，其余步骤同实施例1。
制备钝化的热镀锌板
将实施例1～7和对比例1～6制备得到的涂层液分别辊涂涂覆在热镀锌钢带上，在80℃的固化温度(采用测温试纸测定固化温度)下固化20s分别得到高耐蚀性涂层1～7，以及对比例D1～D6。
涂层液及钝化的热镀锌板性能测试
涂层液稳定性测试：测试方法为：将配置好的涂层液在室温条件下放置，观察液体稳定储存(不出现颜色变化、沉淀、凝聚等不良现象)的时间和涂层液中六价铬的含量，结果见表1。
测定热镀锌涂层板的涂层的耐蚀性、耐指纹性、耐热性、耐水性、附着性，结果见表2。
其中，耐蚀性按照GB/T10125-1997中规定的方法和条件进行腐蚀试验，然后按照GB12335-90的规定对腐蚀结果进行评价(以120h、216h后的腐蚀面积占总面积的百分比表示)。其中，腐蚀面积越小越好(目前，热镀铝锌板涂层的耐蚀性一般要求为72h小于5％，120h小于20％)。
耐指纹性按照试样表面涂抹凡士林前后色差值的变化判定：若前后色差的变化小于1，则为A级；若前后色差的变化大于1，小于2，则为B级；若前后色差的变化大于2小于4，则为C级；若前后色差的变化大于4，则为D级。目前热镀锌涂层的耐指纹性一般要求为A和B级。
耐热性按照试样在300℃条件下20min的变化判定：若前后色差的变化小于4，且膜层未出现气泡、脱落、掉粉等现象，则为A级；若前后色差的变化大于4，小于8，且膜层未出现气泡、脱落、掉粉等现象，则为B级；若前后色差的变化大于8，且膜层未出现气泡、脱落、掉粉等现象，则为C级。若膜层出现气泡、脱落、掉粉等现象，则为D级。目前热镀锌涂层的耐热性一般要求为B级与C级。
耐水性是采用100℃去离子水滴于试样来测定：若试样完全无水迹，则为A级；有轻微水迹，则为B级；明显水迹，则为C级。目前热镀锌涂层的耐水性一般要求为B级。
附着性按照试样180°折弯后涂层的脱落掉粉程度判定：若涂层未出现脱落、掉粉等现象，则为A级；若出现掉粉但未出现脱落现象，则为B级；若出现脱落现象，则为C级。目前热镀锌涂层的附着性一般要求为A级。
表1热镀锌涂层稳定性及涂层中六价铬含量
涂层液 稳定时间(d) 是否含六价铬 涂层液 稳定时间(d) 是否含六价铬
实施例1 ≥180 无 对比例1 ≥180 有
实施例2 ≥180 无 对比例2 1(凝聚) 有
实施例3 ≥180 无 对比例3 1(凝聚) 有
实施例4 ≥180 无 对比例4 ≥180 无
实施例5 ≥180 无 对比例5 1(凝聚) 无
实施例6 ≥180 无 对比例6 ≥180 无
实施例7 ≥180 无 对比例7 ≥180 无
实施例7 ≥180 无
由表1可知，使用本发明方法的涂层液可以稳定存在180d以上，且在存放的过程中没有六价铬溢出，环保健康。对比例2、3、5中的涂层液不能稳定保存，发生凝聚反应，且对比例1～3中有六价铬溢出，达不到环保的要求。
表2钝化的热镀锌板性能指标
因对比例1～3中有六价铬溢出，不能用于涂层，故未对对比例1～3进行涂层性能测定。由表2可知，本发明涂层液涂覆的热镀锌板，具有较强的耐蚀性、优异的耐指纹性、耐水性、附着性。
综上，本发明涂层液环保、且涂覆后耐蚀性强、耐指纹和耐水性都较好，还具有高附着性，为热镀锌板涂层液提供了一种全新的选择。

Claims (10)

1.热镀锌板涂层液，其特征在于，原料包括以下成分：按重量份数计，每100份水中加入5～20份三价铬混合物、1～20份PH调节剂、1～10份成膜促进剂、5～20份胶体二氧化硅、10～30份水性树脂。
2.根据权利要求1所述的热镀锌板涂层液，其特征在于：所述的PH调节剂为硅酸钠、磷酸钠、磷酸钾、磷酸一氢钠、磷酸铵、磷酸一氢钾或四硼酸钠中的至少一种。
3.根据权利要求1或2所述的热镀锌板涂层液，其特征在于：所述的成膜促进剂为钨酸钠、硫酸羟胺、硝酸钙、硝酸镍、亚硝酸钠、钼酸钠、钼酸钾、高锰酸钾或氯酸钠中的至少一种。
4.根据权利要求1～3任一项所述的热镀锌板涂层液，其特征在于：所述的水性树脂为水性丙烯酸树脂、水性苯丙树脂、水性酚醛树脂、水性聚氨酯、水性有机硅树脂或水性环氧树脂中的至少一种。
5.根据权利要求1～4任一项所述的热镀锌板涂层液，其特征在于：所述的三价铬混合物由六价铬化合物、有机物、酸性物质反应制备而成，制备方法为：每1～5mol六价铬化合物加入100mol水中，充分溶解后加入0.5～15mol有机物，溶解后再加入1～50mol酸性物质，搅拌反应2～10h。
6.根据权利要求1～5任一项所述的热镀锌板涂层液，其特征在于：所述的六价铬化合物为三氧化铬、重铬酸钠、重铬酸钾或重铬酸氨中的至少一种；所述的酸性物质为氢氟酸、磷酸、硫酸、亚硫酸、氟钛酸、氟硅酸、亚硝酸、硝酸、磷酸二氢钠或磷酸二氢钾中的一种；所述的有机物为含有羧基的易溶于水的液体或固体有机物，所述的有机物为植酸、柠檬酸、草酸、乳酸、葡萄糖酸、苯甲酸、水杨酸、乙酸、丙酸、丁酸、马来酸、丁二酸、对羟基苯甲酸、氨基乙酸、氨基丙酸或己二酸中的至少一种。
7.权利要求1～6任一项所述的热镀锌板涂层液的制备方法，其特征在于：将三价铬混合物、PH调节剂、成膜促进剂、胶体二氧化硅、水性树脂在水中溶解混合，搅拌均匀即可。
8.权利要求1～6任一项所述的热镀锌板涂层液的使用方法，其特征在于：将涂层液涂覆于热镀锌板表面，60～100℃条件下烘干、固化10～30s，制得钝化的热镀锌板。
9.根据权利要求8所述的热镀锌板涂层液的使用方法，其特征在于：所述的涂覆厚度为0.2～1.5μm。
10.权利要求8或9所述的使用方法制备得到的钝化的热镀锌板。
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