CN107779084A - 一种建筑外墙水性超疏水涂料及其制备方法与应用 - Google Patents
一种建筑外墙水性超疏水涂料及其制备方法与应用 Download PDFInfo
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Abstract
本发明公开了一种建筑外墙水性超疏水涂料,其特征在于:所述的涂料按照如下方法进行制备:将去离子水和无机微纳米颗粒混合,室温下搅拌均匀,然后再加入建筑外墙涂料乳液和含氟丙烯酸树脂,搅拌均匀,得到建筑外墙水性超疏水涂料;所述的建筑外墙涂料乳液为硅丙乳液、苯丙乳液、纯丙乳液或有机硅乳液中的一种或二种及以上任意比例的混合;所述的无机微纳米颗粒为二氧化硅、碳酸钙或二氧化钛中的一种或二种及以上的组合。本发明所述的制备工艺简单,操作简便,利用建筑外墙涂料乳液提供基底结合力,含氟丙烯酸树脂往表面自迁移形成低表面能,微纳米颗粒提供微粗糙度,使涂层具有较好的超疏水性能。
Description
一、技术领域
本发明涉及涂料技术领域,特别是指一种含微纳米颗粒的外墙水性超疏水涂料及其制备方法与应用。
二、背景技术
我国目前正处于城镇化建设高峰期,高品质的外墙涂料有着广阔的需求空间和发展潜力。而涂层耐沾污能力不足是外墙涂料普遍存在的共性问题。超亲水和超疏水均能实现表面雨水自清洁。过去20年,超疏水表面备受重视,但如何量产低成本、易涂覆、能室温固化、且涂层较耐水浸或雨淋的外墙用超疏水涂料仍然颇具挑战性,尤其是研制能与现有外墙涂料(丙烯酸、苯丙、硅丙乳液等)配方和施工工艺相衔接或匹配的超疏水涂料,极具工程应用价值。市场上很多打着超疏水旗号的涂料,并未达到超疏水效果,充其量是高度疏水。文献中提到的超疏水涂层大多以含氟硅溶胶和纳米颗粒为主成分,与现有外墙涂料并不兼容。
周绍忠等通过硅树脂、钛白粉、超细重钙粉、聚醚改性硅氧烷等制备了一种纳米自清洁外墙涂料(专利申请号:201210423418.4)。王嘉龙等通过将纯丙乳液、聚有机硅氧烷、有机硅消泡剂、云母粉、碳酸钙等搅拌分散研磨,再加入纤维素增强,发明了一种自清洁外墙涂料(专利申请号:201610678473.6)。这些发明配方复杂,且涂层并未超疏水。如果能基于现有的外墙涂料,通过往里添加疏水性聚合物的方式实现涂层超疏水,那将非常有利于该类涂料的市场推广。
三、发明内容
为解决现有技术存在的问题,本发明的目的之一在于提供一种建筑外墙用水性超疏水涂料及其制备方法,并通过超疏水涂料来实现外墙自清洁。
本发明的目的通过以下技术方案来实现:
一种建筑外墙水性超疏水涂料,其特征在于:所述的建筑外墙水性超疏水涂料按照如下方法进行制备:
将去离子水和无机微纳米颗粒混合,室温下搅拌均匀,然后再加入建筑外墙涂料乳液和含氟丙烯酸树脂,搅拌均匀,得到建筑外墙水性超疏水涂料;所述的建筑外墙涂料乳液为硅丙乳液、苯丙乳液、纯丙乳液或有机硅乳液中的一种或二种及以上任意比例的混合;所述的无机微纳米颗粒为二氧化硅、碳酸钙或二氧化钛中的一种或二种及以上的组合;所述的无机微纳米颗粒加入量以去离子水的体积计为 0.033~0.5g/mL;所述的建筑外墙涂料乳液的加入量以去离子水的体积计为0.0167~0.3g/mL;所述的含氟丙烯酸树脂的加入量以去离子水的体积为0.0167~0.3mL/mL。
进一步,所述的二氧化硅的粒径为10nm-200nm,优选20-100nm。
进一步,所述的碳酸钙粒径为800目-4000目,优选1200-2000目。
进一步,所述的二氧化钛的粒径为10nm-200nm,优选20-100nm。
本发明的目的之二在于提供一种建筑外墙水性超疏水涂料用于制备超疏水涂层。
进一步,所述的应用为:将上述建筑外墙水性超疏水涂料均匀涂覆于基底上,在10-180℃(优选20-60℃)下固化,得到超疏水涂层。
再进一步,所述的涂覆方式为喷涂、淋涂、浸涂、滚涂或刷涂(优选为喷涂)。
再进一步,所述的基底为玻璃、水泥外墙、水泥地、石材或木材。
与现有技术相比,本发明的有益效果在于:
本发明所述的制备工艺简单,操作简便,利用建筑外墙涂料乳液提供基底结合力,含氟丙烯酸树脂往表面自迁移形成低表面能,微纳米颗粒提供微粗糙度,使涂层具有较好的超疏水性能。
四、附图说明
图1为超疏水涂层微观形貌及接触角。
图2为超疏水涂层浸泡在水中静态接触角随时间变化图。
图3为有机硅乳液/含氟丙烯酸树脂乳液制得的疏水涂层表面元素在10nm内的分布图。
五、具体实施方式
下面将对本发明实施例中的技术方案进行清楚、完整的描述。显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
实施例1
(1)将1g SiO2(浙江万景新材料有限公司,SP-30,平均粒径30nm,下同)加入到30mL水中,并在磁力搅拌下混合均匀,然后加入2.5g有机硅乳液(上海向岚化工有限公司,ESASIL 505,固含量约50%)和1mL聚含氟丙烯酸树脂(太仓中化环保化工有限公司,EG616G),搅拌均匀,得到超疏水涂料。
(2)将此超疏水涂料喷涂在玻璃表面,120℃下干燥固化20min,形成超疏水涂层(图1),其静态接触角为154.2°,滚动角6.1°。其它性能同实施例1。将涂层浸没在去离子水中,发现12h后,涂层的接触角仍然达到147.7°,滚动角小于10°,仍具有超疏水性能(实际应用中,极少有连着下12h雨的情况)(图2)。继续浸泡,虽然滚动角变化较大,但是作为外墙涂料,涂层是竖直的,所以影响不大。并且将浸泡2天的涂层放入120℃的烘箱2h,涂层彻底恢复到超疏水性能,接触角和滚动角恢复到151.7°、8.4°,或者室温下放置27h 也可恢复。
涂层硬度采用涂膜硬度铅笔测定法GB/T6739-1996测试,涂层附着力采用色漆和清漆漆膜的划格试验GB/T9286-1998操作方法测试。测试结果表明,上述超疏水涂层硬度为3B,涂层附着力等级为3。具有一定的力学性能。
涂层耐沾污(自清洁)性能采用建筑涂料涂层耐沾污性试验方法 GB/T9780-2013中建筑外墙浸渍法测试,通过与基本灰卡的色差进行比色评定等级。具体是将制备好的超疏水涂料喷涂在水泥纤维板上,在120℃下烘干30min,然后将其倒扣放置浸没在石墨与水的混合悬浮液中5s,取出在60℃烘箱中烘干30min,然后进行耐沾污表征,发现耐沾污性等级为0级,污染程度为无。
实施例2
(1)将2g CaCO3(1200目,重钙,一般市售)加入到10mL水中,并在搅拌条件下混合均匀,然后加入1g有机硅乳液(上海向岚化工有限公司,ESASIL 505,固含量约50%)和1mL含氟丙烯酸乳液 (太仓中化环保化工有限公司,EG616G),搅拌均匀,得到超疏水涂料。
(2)将此超疏水涂料刷涂在玻璃表面,120℃下干燥固化20min,形成超疏水涂层。其静态接触角为154.4°,滚动角9.6°,将该涂层浸没在去离子水中,10h内其接触角和滚动角基本无变化。涂层力学及自清洁性能同实施例1。
实施例3
(1)将5g CaCO3(2000目,轻钙,一般市售)加入到50mL水中,并在搅拌条件下混合均匀,然后加入5g丙烯酸乳胶漆(优涂保耐久外墙墙面漆,上海紫荆花制漆有限公司)和2.5mL含氟丙烯酸乳液(同上),搅拌均匀,得到超疏水涂料。
(2)将此超疏水涂料滴涂或刷涂在玻璃/铝板表面,120℃下干燥固化20min,形成超疏水涂层,其静态接触角为156.4°,滚动角10°。涂层力学及自清洁性能同实施例1。
实施例4
将1g SiO2加入到20mL水中,并在磁力搅拌下混合均匀,然后加入1g硅丙乳液(上海保立佳化工有限公司),得到外墙涂料。将此涂料喷涂在水泥墙面上,120℃下固化20min后,再在其表面喷涂含氟丙烯酸乳液(同上,但20倍稀释),120℃下干燥20min,得到自清洁外墙(静态接触角为153.4°,滚动角8.1°)。涂层力学及自清洁性能同实施例1。
实施例5
其它同实施例1,但不加纳米SiO2颗粒,对该有机硅涂层进行转角XPS(X射线光电子能谱)测试,分析该涂层表面元素在10nm内的分布情况(见图3),发现疏水的F元素富集在表面(越深含量越低),而亲水的O元素则分布在底部(越深含量越高),呈现梯度分布,证明该涂膜在干燥固化过程中,含氟丙烯酸树脂大分子链有往涂层表面迁移,从而为涂层提供了低表面能和高基底结合力。
实施例6
取上述实施例1所制备的外墙自清洁涂料,喷涂在水泥板面上,探讨其固化方式对涂层性能的影响。发现在120℃下烘干30min,其表面接触角达到150°,并且随着温度升高,其所需时间缩短,在180℃下烘5min即可达到表面超疏水化。而在50℃下其固化时间则延长到2 h。不仅如此,此涂料在室温下也可以完成固化,在30℃室温晴天下放置1天,其接触角也大大上升,变成了超疏水(接触角150°)。所以此涂料可以在一个很宽的温度范围内完成固化。
实施例7
取上述实施例1所制备的涂料,分别喷涂、滚涂和刷涂在玻璃上, 120℃下烘干20min干后均可固化,水滴接触角155°,滚动角为5°,可见涂装方式对超疏水性能影响不大。
Claims (8)
1.一种建筑外墙水性超疏水涂料,其特征在于:所述的建筑外墙水性超疏水涂料按照如下方法进行制备:
将去离子水和无机微纳米颗粒混合,室温下搅拌均匀,然后再加入建筑外墙涂料乳液和含氟丙烯酸树脂,搅拌均匀,得到建筑外墙水性超疏水涂料;所述的建筑外墙涂料乳液为硅丙乳液、苯丙乳液、纯丙乳液或有机硅乳液中的一种或二种及以上任意比例的混合;所述的无机微纳米颗粒为二氧化硅、碳酸钙或二氧化钛中的一种或二种及以上的组合;所述的无机微纳米颗粒加入量以去离子水的体积计为0.033~0.5g/mL;所述的建筑外墙涂料乳液的加入量以去离子水的体积计为0.0167~0.3g/mL;所述的含氟丙烯酸树脂的加入量以去离子水的体积计为0.0167~0.3mL/mL。
2.按权利要求1所述的建筑外墙水性超疏水涂料,其特征在于:所述的二氧化硅的粒径为10nm-200nm。
3.按权利要求1所述的建筑外墙水性超疏水涂料,其特征在于:所述的碳酸钙的目数为800目-4000目。
4.按权利要求1所述的建筑外墙水性超疏水涂料,其特征在于:所述的二氧化钛的粒径为10nm-200nm。
5.一种如权利要求1所述的建筑外墙水性超疏水涂料用于制备超疏水涂层。
6.如权利要求5所述的应用,其特征在于:所述的应用为:将上述建筑外墙水性超疏水涂料均匀涂覆于基底上,在10-180℃下固化,得到超疏水涂层。
7.如权利要求6所述的应用,其特征在于:所述的涂覆方式为喷涂、淋涂、浸涂、滚涂或刷涂。
8.如权利要求6所述的应用,其特征在于:所述的基底为玻璃、水泥外墙、水泥地、石材或木材。
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