CN107513350B - 一种透明户外超疏水自洁涂料 - Google Patents
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Abstract
本发明公开了透明户外超疏水自洁涂料,它包括带溶剂疏水树脂和用六甲基二硅氮烷处理糙度固态粒子,所述用六甲基二硅氮烷处理糙度固态粒子的加入量为带溶剂疏水树脂固含量的1～5倍，所述带溶剂疏水树脂由2.84～5.68wt%的十七氟癸基三甲氧基硅烷，0.6～1.2wt%的苯基三甲氧基硅烷,0.45～0.9 wt%的正硅酸甲酯，其余为溶剂混合后部分水解缩合而成。本发明具有强劲的疏水、抗油污能力，灰尘等污物与涂层表面接触面积大大减少，具有无比优越的自动清洁特性；水在物体表面犹如在荷叶上一样滚落而不留水迹。本发明适用户外金属构件、公路护栏、输电铁塔、铁路沿线信号设施、城市户外公共设施等基材外表使用。
Description
技术领域
本发明涉及户外金属构件、公路护栏、输电铁塔、铁路沿线信号设施、城市户外公共设施等表面超疏水自洁涂料的合成技术，特别是一种用于玻璃、塑料、石材、陶瓷、金属、等基材表面的透明超疏水自洁涂料。
背景技术
户外金属构件、公路护栏、输电铁塔、铁路沿线信号设施、城市户外公共设施外表面由于接触雨水、雾、泥浆、空气中水汽、粉尘、汽车尾气等，表面都会逐渐变脏。清洗特别工作量巨大、清洗施工操作困难。特别是脏污沉积，会对基材造成侵蚀，影响使用寿命。目前大部分户外金属构件、公路护栏、输电铁塔、铁路沿线信号设施、城市户外公共设施外表都是使用普通油漆类涂料，虽然有一定的保护功能，但没有自洁功能，需要定期清洗和维护，造成额外工作量。也有一些疏水型涂料，但是很多都是不透明的，水接触角一般也只有100度左右，疏水效果一般，有的疏水涂料还需要高温固化，限制了使用环境。
发明内容：
本发明针对现有技术中普通油漆和疏水型涂料存在的不足，提供一种具有透明、超疏水、自洁，且常温下也可固化成膜的超疏水自洁涂料。
本发明要解决的技术问题所采取技术方案如下：所述透明户外超疏水自洁涂料包括带溶剂的疏水树脂和用六甲基二硅氮烷处理糙度固态粒子，所述用六甲基二硅氮烷处理糙度固态粒子的加入量为带溶剂疏水树脂固含量的1～5倍。
所述带溶剂疏水树脂由2.84～5.68wt%的十七氟癸基三甲氧基硅烷，0. 6～1.2wt%的苯基三甲氧基硅烷, 0.45～0.9 wt%的正硅酸甲酯、其余为溶剂混合，部分水解缩合而成。
所述带溶剂疏水树脂固化后折射率为1.45～1.47。
所述用六甲基二硅氮烷处理糙度固态粒子是用至少两种粒径不同的二氧化硅粒子与六甲基二硅氮烷混合搅拌后，加热并用真空抽出过量的六甲基二硅氮烷及副产物后所余下的物质。
所述带溶剂疏水树脂固含量是指带溶剂疏水树脂在规定条件下烘干后未挥发份物含量占带溶剂疏水树脂总量的百分数。
本发明所述透明户外超疏水自洁涂料水接触角能到150°，具有极低的表面张力，从而具有强劲的疏水、抗油污能力；灰尘等污物与涂层表面接触面积大大减少，从而具有无比优越的自动清洁特性；水在物体表面犹如在荷叶上一样滚落而不留水迹。所述透明户外超疏水自洁涂料用喷枪喷在在基材上。
所述透明户外超疏水自洁涂料可在常温下或升温下固化成膜，所述透明户外超疏水自洁涂料中还可添加催化剂或其他辅料。
所述透明户外超疏水自洁涂料带溶剂疏水树脂为侧链带有十七氟碳基团、苯基呈硅氧键主链的交联结构，十七氟碳基团为疏水疏油基团，引入苯基调整树脂折射率、正硅酸甲酯为四官能团，加入四官能团可以使树脂在常温固化。
所述透明户外超疏水自洁涂料所述的用六甲基二硅氮烷处理糙度固态粒子是六甲基二硅氮烷处理的疏水型纳米级或亚微米级、折射率为1.45~1.47的二氧化硅粒子。所述带溶剂疏水树脂的溶剂为非极性溶剂，如苯、甲苯、环己烷、醋酸酯、溶剂油等等类。溶剂可以是一种或多种复配。
所述透明户外超疏水自洁涂料喷涂时需要将固体基材表面清理干净，喷涂后涂抹液层裸露于空气中，挥发溶剂吸附空气中水分子发生交联反应一定时间后固化成膜。
本发明的有益效果：本发明提供的透明户外超疏水自洁涂料可以在基材上形成一层透明具有纳米、亚微米级糙度薄膜，其对水的接触角为120°到150°，具有极低的表面张力，从而具有强劲的疏水、抗油污能力，灰尘等污物与涂层表面接触面积大大减少，从而具有无比优越的自动清洁特性；水在物体表面犹如在荷叶上一样滚落而不留水迹。本发明适用户外金属构件、公路护栏、输电、铁塔、铁路沿线信号设施、城市户外公共设施等基材外表使用。
具体实施方式
为了使本领域技术人员更好地理解本发明的技术方案，下面通过具体实施例来进一步详细描述本发明。
1、透明户外超疏水自洁涂料包括带溶剂的疏水树脂和用六甲基二硅氮烷处理糙度固态粒子，所述的带溶剂疏水树脂第一种制备方法是：取十七氟癸基三甲氧基硅烷5.68g，苯基三甲氧基硅烷1.2g,正硅酸甲酯0.6g，二甲苯（溶剂）192克，加入到1000ml带恒温加热、搅拌和回流装置的四口烧瓶中，用氮气排出空气，开动搅拌，滴一滴浓盐酸，匀速滴加0.6g去离子水。升温至60℃用真空抽出产生的甲醇，释放真空，继续恒温反应24小时。冷却后获得固含量约为3.5%的带溶剂疏水树脂。
2、所述的带溶剂疏水树脂第二种制备方法：取十七氟癸基三甲氧基硅烷2.84g，苯基三甲氧基硅烷0.6g,正硅酸甲酯0.9g，二甲苯（溶剂）192克，加入到1000ml带恒温加热、搅拌和回流装置的四口烧瓶中，用氮气排出空气，开动搅拌，滴一滴浓盐酸，匀速滴加0.4g去离子水。升温至60℃用真空抽出产生的甲醇，释放真空，继续恒温反应24小时。冷却后获得固含量约为2.0%的带溶剂疏水树脂。
带溶剂疏水树脂固含量指将溶剂脱干后剩余固体含量。
3、透明户外超疏水自洁涂料用六甲基二硅氮烷处理糙度固态粒子制备：取粒径10~20nm 二氧化硅50g，粒径100~400nm 二氧化硅50g，加入六甲基二硅氮烷50g混合搅拌2小时，加热至130度，并用真空抽出过量的六甲基二硅氮烷及副产物，真空度为-90KPa，释放真空降温后所余下的物质即为六甲基二硅氮烷处理糙度固态粒子。
实施例1,先秤取上述固含量为3.5%的带溶剂疏水树脂20克（其中固含量为0.7g），加入六甲基二硅氮烷处理糙度固态粒子0.7g（即该糙度固态粒子加入量为带溶剂疏水树脂中固含量的1倍），采用超声波分散机进行混合后即制得透明户外超疏水自洁涂料。
实施例2, 先秤取上述固含量为2%的带溶剂疏水树脂20克（其中固含量为0.4g），加入六甲基二硅氮烷处理糙度固态粒子2.0g（即该糙度固态粒子加入量为带溶剂疏水树脂中固含量的5倍），采用超声波分散机进行混合后即制得透明户外超疏水自洁涂料。
实施例3, 先秤取上述固含量为3.5%的带溶剂疏水树脂20克（其中固含量为0.7g），加入六甲基二硅氮烷处理糙度固态粒子2.0g（即该糙度固态粒子加入量为带溶剂疏水树脂中固含量的3倍），加入催化剂有机锡一滴（约0.1毫升），采用超声波分散机进行混合后即制得透明户外超疏水自洁涂料。
实施例4, 先秤取上述固含量为2.0%的带溶剂疏水树脂二20克（其中固含量为0.4g），加入六甲基二硅氮烷处理糙度固态粒子2g（即该糙度固态粒子加入量为带溶剂疏水树脂中固含量的5倍），加入催化剂有机锡一滴（约0.1毫升），采用超声波分散机进行混合后即制得透明户外超疏水自洁涂料。
上述实施例1～4的透明户外超疏水自洁涂料，水接触角的测试采用日本协和界面科学公司CA-Z150型接触角测量仪来测量的。实施例1～ 3在性能实验中，制得透明户外超疏水自洁涂料。镀膜液涂抹方法采用喷枪喷涂。试验基材采用24×40mm载玻片，载玻片经过浓硫酸-铬酸钾洗液浸泡，用清水冲洗干净晾干，常温自然成膜5分钟至24小时不等，也可以加温成膜。水珠滚落效果是将试片倾斜45°，用滴头近距离滴水，每滴水约0.05g。测定接触角、透明度、水珠滚动肉眼观察。如列表所示：
实施例 对水接触角 水珠滚落效果 透明度 疏水性
实施例1 122° 良好 透明 良好
实施例2 151° 优秀 透明 优秀
实施例3 151° 优秀 透明 优秀
实施例4 151° 优秀 透明 优秀
注：疏水性：对水接触角﹥120°为良好、对水接触角150°为优秀。实施例3在实施例2增加了催化剂，成膜速度更快。在实际应用中，取实例3透明户外超疏水自洁涂料喷在公路护栏和街道路牌上，用泥水泼后不沾。一个月后观察，喷过透明户外超疏水自洁涂料部分明显比没喷的地方干净很多。
以上叙述有助于本领域技术人员理解本发明创造，但并非限制本发明创造的保护范围。任何没有脱离本发明创造实质内容的对以上叙述的同等替换、修饰
改进或删繁从简而进行的实施，均落入本发明申请请求专利保护的范围。
Claims (2)
1.透明户外超疏水自洁涂料,其特征在于:它包括带溶剂疏水树脂和用六甲基二硅氮烷处理糙度固态粒子, 所述用六甲基二硅氮烷处理糙度固态粒子的加入量为带溶剂疏水树脂固含量的1～5倍，所述带溶剂疏水树脂由2.84～5.68wt%的十七氟癸基三甲氧基硅烷，0. 6～1.2wt%的苯基三甲氧基硅烷,0.45～0.9 wt%的正硅酸甲酯，其余为溶剂混合后部分水解缩合而成，所述用六甲基二硅氮烷处理糙度固态粒子是用至少两种粒径不同的二氧化硅粒子与六甲基二硅氮烷混合搅拌后，加热并用真空抽出过量的六甲基二硅氮烷及副产物后所剩余的物质，所述带溶剂疏水树脂固化后折射率为1.45～1.47，所述用六甲基二硅氮烷处理糙度固态粒子的折射率为1.45～1.47。
2.根据权利要求1所述的透明户外超疏水自洁涂料,特征在于：所述透明户外超疏水自洁涂料中含有机锡。
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