CN111270230A - 热镀铝锌板环保表面处理液及热镀铝锌钝化板的制备方法 - Google Patents
热镀铝锌板环保表面处理液及热镀铝锌钝化板的制备方法 Download PDFInfo
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Abstract
本发明涉及热镀铝锌板环保表面处理液及热镀铝锌钝化板的制备方法,属于热镀锌钢板领域。本发明解决的技术问题是现有热镀铝锌钢板环保问题突出,无法满足电控柜、建筑等行业对其耐蚀性、涂装性、耐指纹性的要求。本发明提供的热镀铝锌板无铬钝化液以重量份计包括水100、含锆化合物0.5~2.5重量份,水性有机树脂20~50重量份,硅烷偶联剂2~15重量份,硫脲0.2~2重量份,含H缓蚀剂0.5~5重量份。本发明将热镀铝锌板表面处理液涂敷在热镀铝锌板表面,然后烘干固化得到热镀铝锌钝化板。本发明制备得到的热镀铝锌钝化板具有优异的耐蚀性、涂装性、耐指纹性、耐碱性、耐水性。
Description
技术领域
本发明属于热镀锌钢板领域,具体涉及热镀铝锌板环保表面处理液及热镀铝锌钝化板的制备方法。
背景技术
热镀铝锌板兼顾了热镀锌和热镀铝板的优点,具有优异的耐蚀性和良好的外观装饰性等质量性能特点。从节约材料、减少资源浪费,以及有利于环保等方面考虑,热镀铝锌板在国内外电控柜、建筑等行业获得了广泛应用。
热镀铝锌板在一些产品的使用过程中,一些部件需要进行喷涂作业,而其他部件要直接裸用,为确保表面质量的统一性,一般会采用相同的热镀铝锌板进行制定。因此,可涂装且直接裸用一体化的热镀铝锌耐指纹板是今后的发展方向。由于使用环境的要求,有些用户要求铝锌板既要具有良好耐蚀性又要具有环保性,且随着人们对健康和环境要求越来越高及欧盟在建材等方面环保指令的实施,环保性也是今后电控柜用热镀铝锌板的发展方向。
由于国内热镀铝锌板表面处理技术尚不成熟,目前大部分厂家生产的电控柜用热镀铝锌板主要为六价铬耐指纹板,不环保,且可涂装性较差,不能直接进行喷涂处理。为满足电控柜用热镀铝锌板环保和可涂装要求、提升电控柜用热镀铝锌板品质、优化电控柜用热镀铝锌板结构,开发一种可涂装用热镀铝锌板环保表面处理液及其热镀铝锌钝化板具有十分重要的意义。
发明内容
本发明解决的技术问题是现有热镀铝锌钢板环保问题突出,无法满足电控柜、建筑等行业对其耐蚀性、涂装性、耐指纹性的要求。
本发明解决上述问题的技术方案是提供热镀铝锌板无铬钝化液,钝化液的原料以100重量份水为基准,还包括含锆化合物0.5~2.5重量份,水性有机树脂20~50重量份,硅烷偶联剂2~15重量份,硫脲0.2~2重量份,含H缓蚀剂0.5~5重量份。
其中,含锆化合物、含H缓蚀剂的质量比为1:1~2。
其中,含锆化合物为氟锆酸、氟锆酸钠、氟锆酸钾、氟锆酸铵、氟锆酸钙中的至少一种。
其中,水性有机树脂包括水性丙烯酸树脂、水性苯丙树脂、水性氟碳树脂、水性酚醛树脂中的至少一种。
其中,硅烷偶联剂为乙烯基三乙氧基硅烷、乙烯基三甲氧基硅烷、氨丙基三乙氧基硅烷、甲基丙烯酰氧基硅烷、硫丙基三甲氧基硅烷中的至少一种。
其中,含H缓蚀剂为硼酸、磷酸一氢钠、磷酸氢二钾、柠檬酸钠、葡萄糖酸钠、乳酸、亚磷酸中的至少一种。
本发明还公开上述热镀铝锌板环保表面处理液的制备方法,首先将含锆化合物溶于水中,然后加入含H缓蚀剂,待溶解后加入硫脲、硅烷偶联剂,搅拌均匀后放置一定时间,最后加入水性有机树脂,搅拌均匀即得。
本发明进一步公开热镀铝锌钝化板的制备方法,将上述热镀铝锌板环保表面处理液涂敷在热镀铝锌板表面,然后烘干固化得到热镀铝锌钝化板。
其中,固化温度80~110℃,固化时间5~50s。
本发明还公开上述制备方法制备得到的热镀铝锌钝化板,热镀铝锌钝化板的表面处理液涂层厚度为0.2~2.0μm。
本发明的有益效果:
本发明提供的热镀铝锌板环保表面处理液液不含铬,不会对人体和环境造成危害,环保性好;本发明提供的热镀锌板表面处理液具有良好的稳定性,各种成分协同作用,涂敷固化后形成的热镀铝锌钝化板具有优异的耐蚀性、涂装性、耐指纹性、耐碱性、耐水性等性能。
具体实施方式
本发明提供热镀铝锌板环保表面处理液,钝化液的原料以100重量份水为基准,还包括含锆化合物0.5~2.5重量份,水性有机树脂20~50重量份,硅烷偶联剂2~15重量份,硫脲0.2~2重量份,含H缓蚀剂0.5~5重量份。
本发明设计热镀铝锌板环保表面处理液的思路是:以水性有机树脂为主成膜物质,构成膜层骨架结构,其他成分辅助成膜。其中硫脲和含H缓蚀剂具有协同作用,可与镀层反应,加快成膜速度及镀层与钝化膜层的结合力,提高膜层的耐蚀性、耐水性;硅烷偶联剂和含锆化合物填充在钝化膜层的空隙中和与膜层交联,增强封闭作用和膜层与有机物质的结合作用,从而使钝化膜层具有优异的耐蚀性、涂装性能、耐水性、耐碱性等性能。
本发明提供的热镀铝锌板环保表面处理液可在热镀铝锌板表面形成致密均匀的表面膜层,其中硅烷偶联剂和含锆化合物成膜后通过与镀层反应增强了膜层与镀层的结合力,膜层中剩余硅烷偶联剂增强了膜层表面的极性,即可与聚酯等有机漆直接发生反应增强了与涂装漆膜的附着力,也可与陶化剂中硅烷偶联剂再次发生交联作用,从而增强了涂装性能;且通过硅烷偶联剂的交联和填充作用,改善了钝化膜层的封闭作用,提高了热镀铝锌环保耐指纹板的耐蚀性、耐指纹性、耐碱性、耐水性等性能。
其中,含锆化合物、含H缓蚀剂的质量比为1:1~2。
其中,含锆化合物为氟锆酸、氟锆酸钠、氟锆酸钾、氟锆酸铵、氟锆酸钙中的至少一种。
其中,水性有机树脂包括水性丙烯酸树脂、水性苯丙树脂、水性氟碳树脂、水性酚醛树脂中的至少一种。
本发明表面处理液配方中水性有机树脂重量份指的是相应的乳液重量,根据产品性能需求其固含量通常控制在30-50%。
其中,硅烷偶联剂为乙烯基三乙氧基硅烷、乙烯基三甲氧基硅烷、氨丙基三乙氧基硅烷、甲基丙烯酰氧基硅烷、硫丙基三甲氧基硅烷中的至少一种。
其中,含H缓蚀剂为可电离出氢离子的试剂,作为优选的,含H缓蚀剂为硼酸、磷酸一氢钠、磷酸氢二钾、柠檬酸钠、葡萄糖酸钠、乳酸、亚磷酸中的至少一种。
本发明还公开上述热镀铝锌板环保表面处理液的制备方法,首先将含锆化合物溶于水中,然后加入含H缓蚀剂,待溶解后加入硫脲、硅烷偶联剂,搅拌均匀后放置一定时间,最后加入水性有机树脂,搅拌均匀即得。
本发明进一步公开热镀铝锌钝化板的制备方法,将上述热镀铝锌板环保表面处理液涂敷在热镀铝锌板表面,然后烘干固化得到热镀铝锌钝化板。
其中,固化温度80~110℃,固化时间5~50s。
本发明对热镀铝锌板可不作特殊的限定,作为优选的,热镀铝锌板的镀层化学成分为以重量百分数计为55%的Al,43.4%的Zn,1.6%的Si。
本发明还公开上述制备方法制备得到的热镀铝锌钝化板,热镀铝锌钝化板的表面处理液涂层厚度为0.2~2.0μm。
以下通过实施例、对比例、性能测试对本发明作进一步的解释和说明。
各实施例、对比例均包括热镀铝锌板环保表面处理液和热镀铝锌钝化板的制备。
热镀铝锌板环保表面处理液的制备方法,首先将含锆化合物溶于水中,然后加入含H缓蚀剂,待溶解后加入硫脲、硅烷偶联剂,搅拌均匀后放置30min,最后加入水性有机树脂乳液,搅拌均匀即得。
热镀铝锌钝化板的制备方法,将上述热镀铝锌板环保表面处理液辊涂涂覆在热镀铝锌钢带上,在95℃的固化温度(采用测温试纸测定固化温度)下固化15s分别得到高性能热镀铝锌钝化板1-9,以及对比例D1-D5,其中热镀铝锌板的镀层化学成分为以重量百分数计为55%的Al,43.4%的Zn,1.6%的Si。
实施例1-9、对比例1-5热镀铝锌板环保表面处理液中各原料用量如表1所示。
表1热镀铝锌板环保表面处理液中各原料组成/重量份
水 | 含锆化合物 | 硅烷偶联剂 | 含H缓蚀剂 | 硫脲 | 水性树脂乳液 | |
实施例1 | 100 | 2.0 | 6 | 3.0 | 0.8 | 40 |
实施例2 | 100 | 1.0 | 2 | 1.6 | 1.5 | 35 |
实施例3 | 100 | 0.5 | 15 | 0.8 | 2.0 | 50 |
实施例4 | 100 | 2.5 | 12 | 4.5 | 0.2 | 20 |
实施例5 | 100 | 1.5 | 9 | 2.0 | 1.0 | 30 |
对比例1 | 100 | 0 | 6 | 3.0 | 0.8 | 40 |
对比例2 | 100 | 2.0 | 0 | 3.0 | 0.8 | 40 |
对比例3 | 100 | 2.0 | 6 | 0 | 0.8 | 40 |
对比例4 | 100 | 2.0 | 6 | 3.0 | 0 | 40 |
对比例5 | 100 | 2.0 | 6 | 3.0 | 0.8 | 0 |
实施例6 | 100 | 2.0 | 6 | 3.0 | 0.8 | 40 |
实施例7 | 100 | 2.0 | 6 | 3.0 | 0.8 | 40 |
实施例8 | 100 | 2.0 | 6 | 3.0 | 0.8 | 40 |
实施例9 | 100 | 2.0 | 6 | 3.0 | 0.8 | 40 |
实施例1-9和对比例1-5中,各组分的具体选择如下:
实施例1-5、对比例1-5中,含锆化合物为氟锆酸钠,硅烷偶联剂为甲基丙烯酰氧基硅烷,含H缓蚀剂为硼酸,水性有机树脂乳液为水性酚醛树脂(固含量为45%)与水性丙烯酸树脂(固含量为35%)的混合液(水性酚醛树脂:水性丙烯酸树脂重量比为1:1)。
实施例6中,与实施例1不同的是,含锆化合物为氟锆酸。
实施例7中,与实施例1不同的是,硅烷偶联剂选用的乙烯基三甲氧基硅烷。
实施例8中,与实施例1不同的是,含H缓蚀剂选用的柠檬酸钠。
实施例9中,与实施例1不同的是,水性有机树脂为水性苯丙树脂(固含量为45%)。
性能测试
对实施例、对比例热镀铝锌板环保表面处理液进行稳定性测试,其测试方法为:将配置好的表面处理液放于室内通风处,观察液体稳定储存即不出现颜色变化、沉淀、凝聚等不良现象的时间,结果见表2。目前常用涂层处理液如普通的耐指纹处理液、环保自润滑处理液、环保耐指纹液等保质期为90d。
对热镀铝锌钝化板1-9和D1-D5的涂层的耐蚀性、涂装性、耐指纹性、耐热性、耐水性、耐碱性进行测试,结果见表3。
其中,耐蚀性按照GB/T10125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、240h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NSST/120h腐蚀面积≤5%)。
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。目前热镀铝锌板涂层的耐指纹性一般为B级及以上。
耐热性按照试样在200℃条件下30min的变化判定:若前后色差的变化小于4,则为A级;若前后色差的变化大于4,小于8,则为B级;若前后色差的变化大于8,则为C级。目前热镀铝锌板涂层的耐热性一般为A级、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。目前热镀铝锌板的耐水性一般为A级。
耐碱性按照试样在60℃的PH=12的NaOH溶液中浸泡10min的变化判定:若膜层未出现气泡、脱落、掉粉等异常现象,则为A级;若膜层出现气泡,但未出现脱落、掉粉等现象,则为B级;若膜层出现气泡、脱落、掉粉等现象,则为C级。为保证试样在用户涂装前的脱脂清洗工艺要求,要求涂层耐碱性为A级。
涂装性按照试样经陶化+喷涂后的喷涂涂层的附着性(划格试验)来判定:若喷涂涂层未见有脱落、翘起等现象,则为0级,若出现轻微翘起,则为1级,若出现少量脱落,则为2级,若出现大量脱落,则为3级。为满足喷涂要求,附着性需达到0级或1级。
表2实施例、对比例热镀铝锌板环保表面处理液稳定性测试结果
处理液 | 稳定时间(d) | 处理液 | 稳定时间(d) |
实施例1 | ≥180 | 实施例8 | ≥180 |
实施例2 | ≥180 | 实施例9 | ≥180 |
实施例3 | ≥180 | 对比例1 | 90(有沉淀) |
实施例4 | ≥180 | 对比例2 | ≥180 |
实施例5 | ≥180 | 对比例3 | ≥180 |
实施例6 | ≥180 | 对比例4 | ≥180 |
实施例7 | ≥180 | 对比例5 | ≥180 |
表3热镀铝锌钝化板涂层性能测试结果
通过表2和表3的数据,通过实施例1-9与对比例1-5的对比,可以看出,本发明提供的热镀铝锌环保表面处理液具有良好的稳定性,在涂敷固化后形成的热镀铝锌钝化板同时兼顾优良的耐蚀性、涂装性、耐指纹性、耐热性、耐水性、耐碱性等性能。
以上详细描述了本发明的优选实施方式,但是,本发明并不限于上述实施方式中的具体细节,在本发明的技术构思范围内,可以对本发明的技术方案进行多种简单变型,这些简单变型均属于本发明的保护范围。
另外需要说明的是,在上述具体实施方式中所描述的各个具体技术特征,在不矛盾的情况下,可以通过任何合适的方式进行组合。为了避免不必要的重复,本发明对各种可能的组合方式不再另行说明。
此外,本发明的各种不同的实施方式之间也可以进行任意组合,只要其不违背本发明的思想,其同样应当视为本发明所公开的内容。
Claims (10)
1.热镀铝锌板环保表面处理液,其特征在于:所述表面处理液的原料以100重量份水为基准,还包括含锆化合物0.5~2.5重量份,水性有机树脂20~50重量份,硅烷偶联剂2~15重量份,硫脲0.2~2重量份,含H缓蚀剂0.5~5重量份。
2.根据权利要求1所述的热镀铝锌板环保表面处理液,其特征在于:所述含锆化合物、含H缓蚀剂的质量比为1∶1~2。
3.根据权利要求1或2所述的热镀铝锌板环保表面处理液,其特征在于:所述含锆化合物为氟锆酸、氟锆酸钠、氟锆酸钾、氟锆酸铵、氟锆酸钙中的至少一种。
4.根据权利要求1~3任一项所述的热镀铝锌板环保表面处理液,其特征在于:所述水性有机树脂包括水性丙烯酸树脂、水性苯丙树脂、水性氟碳树脂、水性酚醛树脂中的至少一种。
5.根据权利要求1~4任一项所述的热镀铝锌板环保表面处理液,其特征在于:所述硅烷偶联剂为乙烯基三乙氧基硅烷、乙烯基三甲氧基硅烷、氨丙基三乙氧基硅烷、甲基丙烯酰氧基硅烷、硫丙基三甲氧基硅烷中的至少一种。
6.根据权利要求1~5任一项所述的热镀铝锌板环保表面处理液,其特征在于:所述含H缓蚀剂为硼酸、磷酸一氢钠、磷酸氢二钾、柠檬酸钠、葡萄糖酸钠、乳酸、亚磷酸中的至少一种。
7.如权利要求1~6任一项所述的热镀铝锌板环保表面处理液的制备方法,其特征在于:首先将含锆化合物溶于水中,然后加入含H缓蚀剂,待溶解后加入硫脲、硅烷偶联剂,搅拌均匀后放置一定时间,最后加入水性有机树脂,搅拌均匀即得。
8.热镀铝锌钝化板的制备方法,其特征在于:将权利要求1~6任一项所述的热镀铝锌板环保表面处理液涂敷在热镀铝锌板表面,然后烘干固化得到热镀铝锌钝化板;固化温度80~110℃,固化时间5~50s。
9.根据权利要求8所述的热镀铝锌钝化板的制备方法,其特征在于:所述热镀铝锌板的镀层化学成分为以重量百分数计为55%的A1,43.4%的Zn,1.6%的Si。
10.根据权利要求8或9制备得到的热镀铝锌钝化板,其特征在于:所述热镀铝锌钝化板的表面处理液涂层厚度为0.2~2.0μm。
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