CN112898891A - 一种水性led光固化强耐腐蚀金属涂料及其制备方法 - Google Patents

一种水性led光固化强耐腐蚀金属涂料及其制备方法 Download PDF

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CN112898891A
CN112898891A CN201911217836.6A CN201911217836A CN112898891A CN 112898891 A CN112898891 A CN 112898891A CN 201911217836 A CN201911217836 A CN 201911217836A CN 112898891 A CN112898891 A CN 112898891A
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周建国
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Abstract

本发明涉及一种水性LED光固化强耐腐蚀金属涂料及其制备，由改性多功能树脂、光引发剂、助溶剂、色浆和去离子水等组成,树脂采用环氧丙烯酸酯类为基本共聚单体，同时引入多官能团的单体，通过特定的工艺合成水溶性羟基丙烯酸树脂。以质量百分数计，其原料配方为：改性多功能树脂70‑90份、光引发剂4‑6份、助溶剂3‑5份、色浆5‑7份、填料4‑6份和去离子水。此发明得到粒径较小的树脂，从而提高了成膜的致密程度，提升了附着力，同时也增强了涂料的硬度、耐腐蚀和耐盐雾性，可有效的保护金属，很大程度上提高了涂料产品的整体性能。

Description

一种水性LED光固化强耐腐蚀金属涂料及其制备方法
技术领域
本发明涉及一种水性LED光固化强耐腐蚀金属涂料及其制备方法，属于水性涂料领域。
背景技术
由于具备低VOC、干燥速度快等优点，UV光固化技术在蓬勃发展，但是传统的UV光固化技术普遍采用波长范围较宽的高压汞灯作为发光光源，导致此技术有一些难以克服的缺陷：高压汞灯的线谱很宽，其真正起到有效固化的紫外光谱波段只占其中的那一小部分，能源利用率不高，红外波段产生的热量会使承印物发生形变，限制了应用范围。LED光固化技术相比汞灯不仅效率高、还更可靠、体积小，寿命长。LED出光表面没有热辐射，芯片热量通过背部的散热结构排除，避免高压汞灯的高温表面带来的各种隐患。本发明的涂料采用LED光固化技术，快速高效成型；水性涂料由于采用水做为稀释剂，大幅度降低了挥发性有机化合物（VOC）排放，所得的涂层无异味残留、硬度高、附着能力强，应用十分广泛。
发明内容
本发明的目的在于提供一种水性LED光固化强耐腐蚀金属涂料及其制备方法。本发明制备的水性涂料采用LED光固化技术，快速高效成型；涂层具有优异的稳定性、防腐性能、低粘度以及低VOC含量的特征，不仅减小了施工难度，降低了对施工人员和环境的毒害，而且达到了溶剂型饱和聚酯涂料才能达到的饱满、高光泽的效果。分子中的长链基团可有效的增强柔韧性，使涂料与金属建材等结合更紧密。改性多功能树脂，一物多用，本身有很好的水溶性，成型后其可增强涂层的硬度、疏水性，待其成型后，不易溶于水等溶剂。合成的树脂可与金属等更紧密的结合，硬度高，耐水性、耐候性能更佳，有效的保护了金属。
一种改性多功能树脂水性金属涂料，配方由改性多功能树脂70-90份、光引发剂4-6份、助溶剂3-5份、色浆5-7份、填料4-6份和去离子水组成。
其中所述的改性多功能树脂水性金属涂料，由以下步骤制备：
a）、改性多功能树脂的制备：先将改性后的环氧丙烯酸酯、异佛尔酮二异氰酸酯和含有羧基或羟基的混合在80℃下搅拌1h,使之充分反应，合成二丙烯酸酯-单体的聚合物；
将上述聚合物、扩链剂、引发剂加入到装有温度计、磁力搅拌、回流装置的反应容器中，开启搅拌并升温到90℃，保温3h,降温至50℃左右，并加入中和剂中，得到水溶性改性多功能树脂。
b）、水性LED光固化强耐腐蚀金属涂料的制备：在容器中加入改性多功能树脂、助溶剂、色浆、填料搅拌均匀后加入光引发剂，最后加入去离子水搅拌成粘稠的均一流体，然后置于50℃水浴加热10min，即可得到所述的改性多功能树脂水性金属涂料。
所用的环氧丙烯酸酯类为环氧丙烯酸、环氧甲基丙烯酸及（甲基）丙烯酸丁酯、环氧甲基丙烯酸甲酯、环氧（甲基）丙烯酸乙酯、环氧甲基丙烯酸异冰酯中的一种或几种的组合。
所用的扩链剂为丙酸 、丁酸、戊酸、三羟基甲基丙烷、聚丙二醇、聚乙二醇、聚四氢呋喃二醇、聚己二酸1,6-己二醇酯中的一种或几种的组合。
所用的填料为钛白粉、云母粉、滑石粉、硫酸钡中的一种或几种的组合。
所用的引发剂为水溶性的亚硫酸钠、硫代硫酸钠、多元醇及多元胺过氧类过氧化二特丁基、过氧化二异丙苯和光引发自由基类2-甲基-1-（4-甲硫基苯基）-2-咖啡基-1-丙酮、2,4,6-三甲基苯甲酰基-而苯基氧化膦、1-羟基环己基苯基甲酮的一种或几种的组合。
所用的中和剂选自三乙胺、2-氨基-2-甲基-1-丙醇、三乙醇胺、N,N-二甲基乙醇胺、氨水、氢氧化钠中的一种或几种。
所用的多功能单体为甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯、丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、醋酸乙烯酯中的一种或几种的组合。
具体实施方式
实施例1
a）、改性多功能树脂的制备：先将改性后的环氧丙烯酸甲酯（60份）、异佛尔酮二异氰酸酯（30份）和甲基丙烯酸羟乙酯（30份）和甲基丙烯酸羟丙酯（30份）在80℃下搅拌1h,使之充分反应，合成二丙烯酸酯-单体的聚合物；
将上述聚合物、扩链剂丙酸（30份）、硫代硫酸钠（3份）加入到装有温度计、磁力搅拌、回流装置的反应容器中，开启搅拌并升温到90℃，保温3h,降温至50℃左右，并加入中和剂三乙醇胺中，得到水溶性改性多功能树脂。
b）、金属涂料的制备：在容器中加入改性多功能树脂（90份）、助溶剂（4份）、色浆（4份）、填料（4份）搅拌均匀后加入、过氧化二特丁基（3份），最后加入去离子水搅拌成粘稠的均一流体，然后置于50℃水浴加热10min，可得到所述的改性多功能树脂水性金属涂料coating-1. 得到25g/m2的涂层， 硬度2H, 耐盐雾600h不起泡，高低温循环可达7天。
实施例2
a）、改性多功能树脂的制备：先将改性后的环氧丙烯酸乙酯（55份）、异佛尔酮二异氰酸酯（30份）和甲基丙烯酸羟乙酯（30份）和甲基丙烯酸羟丙酯（30份）在80℃下搅拌1h,使之充分反应，合成二丙烯酸酯-单体的聚合物；
将上述聚合物、扩链剂丙酸（30份）、硫代硫酸钠（3份）加入到装有温度计、磁力搅拌、回流装置的反应容器中，开启搅拌并升温到90℃，保温3h,降温至50℃左右，并加入中和剂三乙醇胺中，得到水溶性改性多功能树脂。
b）、金属涂料的制备：在容器中加入改性多功能树脂（90份）、助溶剂（4份）、色浆（4份）、填料（4份）搅拌均匀后加入、过氧化二特丁基（3份），最后加入去离子水搅拌成粘稠的均一流体，然后置于50℃水浴加热10min，可得到所述的改性多功能树脂水性金属涂料coating-2. 得到的25g/m2的涂层，硬度2H, 耐盐雾700h不起泡，高低温循环可达7天。
实施例3
a）、改性多功能树脂的制备：先将改性后的环氧丙烯酸乙酯（60份）、异佛尔酮二异氰酸酯（30份）和甲基丙烯酸羟乙酯（30份）和甲基丙烯酸羟丙酯（30份）在80℃下搅拌1h,使之充分反应，合成二丙烯酸酯-单体的聚合物；
将上述聚合物、扩链剂丁酸（30份）、硫代硫酸钠（3份）加入到装有温度计、磁力搅拌、回流装置的反应容器中，开启搅拌并升温到90℃，保温3h,降温至50℃左右，并加入中和剂三乙醇胺中，得到水溶性改性多功能树脂。
b）、金属涂料的制备：在容器中加入改性多功能树脂（90份）、助溶剂（4份）、色浆（4份）、填料（4份）搅拌均匀后加入、过氧化二特丁基（3份），最后加入去离子水搅拌成粘稠的均一流体，然后置于50℃水浴加热10min，可得到所述的改性多功能树脂水性金属涂料coating-3。得到的25g/m2的涂层，硬度2H,耐盐雾800h不起泡，高低温循环可达7天。
下表为实施案例1-3制备的水性金属涂料的测试结果。
Figure 208473DEST_PATH_IMAGE001
由上表可见，本发明涂料具有附着力强、硬度高、耐腐蚀和耐盐雾性等特征，可有效的保护金属，很大程度上提高了涂料产品的整体性能。

Claims (9)

1.一种水性LED光固化强耐腐蚀金属涂料，其特征在于：配方中的改性多功能树脂70-90份、光引发剂4-6份、助溶剂3-5份、色浆5-7份、填料4-6份和去离子水组成；其中所述的改性多功能树脂水性金属涂料，由以下步骤制备：
a）、改性多功能树脂的制备：
先将改性后的环氧丙烯酸酯、异佛尔酮二异氰酸酯和含有羧基或羟基的混合物在80℃下搅拌1h,使之充分反应，合成二丙烯酸酯-单体的聚合物；
将上述聚合物、扩链剂、引发剂加入到装有温度计、磁力搅拌、回流装置的反应容器中，开启搅拌并升温到90℃，保温3h,降温至50℃左右，并加入中和剂中，得到水溶性改性多功能树脂；
b）、金属涂料的制备：在容器中加入改性多功能树脂、助溶剂、色浆、填料搅拌均匀后加入光引发剂，最后加入去离子水搅拌成粘稠的均一流体，然后置于50℃水浴加热10min， 即可得到所述的改性多功能树脂水性金属涂料。
2.根据权利要求1所述的水性LED光固化强耐腐蚀金属涂料，其特征在于环氧丙烯酸酯类为环氧丙烯酸、环氧甲基丙烯酸及（甲基）丙烯酸丁酯、环氧甲基丙烯酸甲酯、环氧（甲基）丙烯酸乙酯、环氧甲基丙烯酸异冰酯中的一种或几种的组合。
3.根据权利要求1所述的水性LED光固化强耐腐蚀金属涂料，其特征在于所述的扩链剂为丙酸 、丁酸、戊酸、三羟基甲基丙烷、聚丙二醇、聚乙二醇、聚四氢呋喃二醇、聚己二酸1,6-己二醇酯中的一种或几种的组合。
4.根据权利要求1所述的水性LED光固化强耐腐蚀金属涂料，其特征在于所述的填料为钛白粉、云母粉、滑石粉、硫酸钡中的一种或几种的组合。
5.根据权利要求1所述的水性LED光固化强耐腐蚀金属涂料，其特征在于所述的引发剂为水溶性的亚硫酸钠、硫代硫酸钠、多元醇及多元胺过氧类过氧化二特丁基、过氧化二异丙苯和光引发自由基类2-甲基-1-（4-甲硫基苯基）-2-咖啡基-1-丙酮、2,4,6-三甲基苯甲酰基-而苯基氧化膦、1-羟基环己基苯基甲酮的一种或几种的组合。
6.根据权利要求1所述的水性LED光固化强耐腐蚀金属涂料，其特征在于所述中和剂选自三乙胺、2-氨基-2-甲基-1-丙醇、三乙醇胺、N,N-二甲基乙醇胺、氨水、氢氧化钠中的一种或几种。
7.根据权利要求1所述的水性LED光固化强耐腐蚀金属涂料，其特征在于所述多功能单体为甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯、丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、醋酸乙烯酯中的一种或几种的组合。
8.根据权利要求1所述的水性LED光固化强耐腐蚀金属涂料，其特征在于所改性树脂的分子量为20000-60000。
9.根据权利要求1所述的水性LED光固化强耐腐蚀金属涂料在制备光固化金属涂料中的应用。
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