CN109627963A - 一种超耐磨自清洁涂层及其制备方法 - Google Patents

一种超耐磨自清洁涂层及其制备方法 Download PDF

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CN109627963A
CN109627963A CN201811542649.0A CN201811542649A CN109627963A CN 109627963 A CN109627963 A CN 109627963A CN 201811542649 A CN201811542649 A CN 201811542649A CN 109627963 A CN109627963 A CN 109627963A
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parts
monomer
mixing
acrylate
official
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CN109627963B (zh
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李新雄
李时珍
李辉
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Bonfurt new materials Co.,Ltd.
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HUNAN BANFERT NEW MATERIALS TECHNOLOGY Co Ltd
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Priority to CN201811542649.0A priority Critical patent/CN109627963B/zh
Publication of CN109627963A publication Critical patent/CN109627963A/zh
Priority to PCT/CN2019/120504 priority patent/WO2020125328A1/zh
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Priority to US16/919,261 priority patent/US11001717B1/en
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Abstract

本发明公开了一种超耐磨自清洁涂层，包括第一道弹性面漆和第二道自清洁面漆，所述第一道弹性面漆按质量份包括两官聚氨酯丙烯酸树脂A10‑60份、引发剂A2‑7份、丙烯酸酯单体A10‑60份和添加剂A3‑40份，所述第二道自清洁面漆按质量份包括丙烯酸改性的具有无机粉料亲和性的有机硅树脂2‑30份、高硬度微粉颗粒0.3‑3份、两官聚氨酯丙烯酸树脂B2‑20份、多官能度聚氨酯丙烯酸树脂B10‑40份、丙烯酸酯单体B15‑45份、引发剂B2‑7份和添加剂B3‑40份；本发明还包括上述超耐磨自清洁涂层的制备方法。本发明具有超耐磨、耐刮擦、耐表面磨损的性能，同时具有长效自清洁特点。

Description

一种超耐磨自清洁涂层及其制备方法
技术领域
本发明涉及建筑装饰材料技术领域，具体涉及一种超耐磨自清洁涂层及其制备方法。
背景技术
地材(包括塑胶地板、竹木地板、复合地板等)在使用过程中，由于易受外力反复刮擦从而造成表面破坏，例如美观度降低，防潮防水功能降低，抗脏污能力降低、不易清洁等，从而造成材料能源和人力资源的极大浪费。因此，开发一种超耐磨、长效自清洁功能的涂料意义重大。目前市面上涂层耐磨性多采用有机涂层中添加高硬度无机材料(硅微粉、陶瓷粉、氧化铝等)，利用无机材料的高硬度来达到耐磨、耐表面刮擦的目的，由于只是简单的物理混合，无机材料与有机涂层结合牢度有限，另外涂层中应用的普通无机材料硬度有限(莫氏硬度低于9)，从而导致涂层耐磨、耐刮擦程度和耐久性有限；市面上涂层耐污性多采用添加低表面能物质(有机硅树脂、氟碳树脂等)，利用低表面能物质迁移到涂层表面形成一个低表面张力的疏水层，从而使污染物质不易润湿表面，达到易清洁的目的，这种涂层不具有耐污持久性，低表面能物质经过多次洗刷后含量逐渐降低直至完全失去抗污能力。
发明内容
本发明要解决的技术问题是克服现有技术的不足，提供一种超耐磨自清洁涂层及其制备方法，由第一道弹性面漆和第二道自清洁面漆组成的涂层具有超耐磨、耐刮擦、耐表面磨损的性能，同时具有长效自清洁特点，可广泛应用于公共场所地材、家居地材的涂装及其它对耐磨损、耐久性有特殊应用需求的场所涂装。
为解决上述技术问题，本发明提出的技术方案为：一种超耐磨自清洁涂层，包括第一道弹性面漆和第二道自清洁面漆，所述第一道弹性面漆按质量份包括两官聚氨酯丙烯酸树脂A10-60份、引发剂A2-7份、丙烯酸酯单体A10-60份和添加剂A3-40份，所述第二道自清洁面漆按质量份包括丙烯酸改性的具有无机粉料亲和性的有机硅树脂2-30份、高硬度微粉颗粒0.3-3份、两官聚氨酯丙烯酸树脂B2-20份、多官能度聚氨酯丙烯酸树脂10-40份、丙烯酸酯单体B15-45份、引发剂B2-7份和添加剂B3-40份。
进一步，所述两官聚氨酯丙烯酸树脂A的软段结构单元玻璃化转变温度为-50～10℃，软段含量为40-80％，两官聚氨酯丙烯酸树脂A通过选择分子量在2000-6000的二元醇与异氰酸酯、单羟基丙烯酸酯单体聚合制备得到，所述二元醇为聚己内酯二元醇、聚酯二元醇、二聚酸改性二元醇、聚四氢呋喃二元醇之中的一种或几种混合；所述异氰酸酯为甲苯二异氰酸酯、异佛尔酮二异氰酸酯、4,4'-二环己基甲烷二异氰酸酯之中的一种或几种混合；所述单羟基丙烯酸酯单体为丙烯酸羟乙酯、甲基丙烯酸羟乙酯、丙烯酸羟丙酯之中的一种或几种混合；所述两官聚氨酯丙烯酸树脂A的含量为15-40份。
进一步，所述丙烯酸酯单体A为三官能度单体与两官或单官单体的混合物，其中三官能度丙烯酸单体质量分数为1-20％，优选为5-10％；两官或单官单体的质量分数为10-50％，优选为15-40％，所述三官能度丙烯酸单体为三羟甲基丙烷三丙烯酸酯、乙氧基化三羟甲基丙烷三丙烯酸酯中的一种或几种混合；所述两官或单官单体为甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯、丙烯酰吗啉、1,6-己二醇二丙烯酸酯、新戊二醇二丙烯酸酯、二丙二醇二丙烯酸酯、三丙二醇二丙烯酸酯、聚乙二醇二丙烯酸酯中的一种或几种混合。
进一步，所述丙烯酸改性的具有无机粉料亲和性的有机硅树脂的制备方法包括如下步骤：
i)选用羟基聚硅氧烷与异氰酸酯反应，得到有机硅预聚体；
ii)将有机硅预聚体与单羟基丙烯酸酯单体反应，制备丙烯酸改性有机硅低聚物；
iii)将丙烯酸改性有机硅低聚物与硅烷偶联剂反应，制备丙烯酸改性的具有无机粉料亲和性的有机硅树脂；
所述丙烯酸改性的具有无机粉料亲和性的有机硅树脂含量为8-14份。
进一步，所述高硬度微粉颗粒为莫氏硬度不小于9的粉料，所述高硬度微粉颗粒为金刚石微粉、碳化硅微粉、氧化铝颗粒中的一种或几种组合，优选金刚石微粉或碳化硅微粉；高硬度微粉颗粒粒径为1-100μm，优选为5-20μm。
进一步，所述两官聚氨酯丙烯酸树脂B的软段结构单元玻璃化转变温度为-50～10℃，软段含量为40-80％，两官聚氨酯丙烯酸树脂B通过选择分子量在2000-6000的二元醇与异氰酸酯、单羟基丙烯酸酯单体聚合制备得到，所述二元醇为聚己内酯二元醇、聚酯二元醇、二聚酸改性二元醇、聚四氢呋喃二元醇之中的一种或几种混合；所述异氰酸酯为甲苯二异氰酸酯、异佛尔酮二异氰酸酯、4,4'-二环己基甲烷二异氰酸酯中的一种或几种混合；所述单羟基丙烯酸酯单体为丙烯酸羟乙酯、甲基丙烯酸羟乙酯、丙烯酸羟丙酯中的一种或几种混合；所述两官聚氨酯丙烯酸树脂B的含量为5-10份。
进一步，所述多官能度聚氨酯丙烯酸树脂玻璃化转变温度为50～150℃，多官能度聚氨酯丙烯酸树脂通过多异氰酸酯与含羟基丙烯酸酯单体进行封端反应制备得到，所述多异氰酸酯为异佛尔酮二异氰酸酯、4,4'-二环己基甲烷二异氰酸酯、HDI二聚体、HDI三聚体、HDI缩二脲、IPDI三聚体中的一种或几种混合；所述含羟基丙烯酸酯单体为丙烯酸羟乙酯、甲基丙烯酸羟乙酯、丙烯酸羟丙酯、季戊四醇三丙烯酸酯、双季戊四醇五丙烯酸酯中的一种或几种混合；所述多官能度聚氨酯丙烯酸树脂含量为15-30份。
进一步，所述丙烯酸酯单体B的均聚物玻璃化转变温度为50℃至150℃，优选为80～150℃，所述丙烯酸酯单体B为多官能度丙烯酸酯单体与两官能度或单官能度单体的混合，所述多官能度丙烯酸酯单体质量分数为5-15％，所述两官能度或单官能度单体质量分数为10-30％；所述多官能度丙烯酸酯单体为季戊四醇三丙烯酸酯、季戊四醇四丙烯酸酯、二缩三羟甲基丙烷四丙烯酸酯、二季戊四醇六丙烯酸酯中的一种或多种混合；两官能度或单官能度单体为二丙二醇二丙烯酸酯、新戊二醇二丙烯酸酯、丙烯酰吗啉中的一种或多种混合。
进一步，所述引发剂A和引发剂B均为光引发剂，可以是本领域中现有技术中公开了的任何一种或多种光引发剂；所述添加剂A和添加剂B均为达到所需要性能的所有类型添加剂，均包括分散剂、消泡剂、流平剂、颜料、消光粉、阻燃剂和稳定剂，其中消光粉为无机或有机类消光粉。
一种超耐磨自清洁涂层的制备方法，包括如下步骤：
1)第一道弹性面漆的制备：将两官聚氨酯丙烯酸树脂、引发剂A、丙烯酸酯单体A和添加剂A在合适的设备中高速分散或研磨到要求的细度后涂覆于底材上，经辐射固化得到第一道弹性面漆涂层，所述辐射固化方式为UV、LED、EB中的一种或几种组合；
2)第二道自清洁面漆的制备：将丙烯酸改性的具有无机粉料亲和性的有机硅树脂和高硬度微粉颗粒进行分散得到有机硅良好包裹的高硬度颗粒，将上述有机硅良好包裹的高硬度颗粒与两官聚氨酯丙烯酸树脂B、多官能度聚氨酯丙烯酸树脂、丙烯酸酯单体B、引发剂B和添加剂B在合适的设备中高速分散或研磨到要求的细度后涂覆于第一道弹性面漆涂层上，经辐射固化得到超耐磨自清洁涂层，所述辐射固化方式为UV、LED、EB中的一种或几种组合。
与现有技术相比，本发明的优点在于：
1、本发明的第一道面漆涂层采用弹性体系，低玻璃化转变温度、高柔韧性的两官能度聚氨酯丙烯酸树脂A作为第一道涂膜结构，在涂层表面受到刮擦作用时涂膜会发生微观形态下的位移，从而缓冲所受的作用力，使涂层表面耐磨、耐刮擦性能显著提升；
2、本发明的第二道面漆涂层采用特殊配方设计，高玻璃化转变温度、高硬度、多官能度的聚氨酯丙烯酸树脂和丙烯酸酯单体B搭配少量低玻璃化转变温度、高柔韧性的两官能度聚氨酯丙烯酸树脂B，分子形态上形成硬段为主、软段为辅的嵌段聚合物结构，在达到高交联、高硬度的同时，低玻璃化转变温度、高柔韧性的两官能度聚氨酯丙烯酸树脂B在受外部应力时提供缓冲作用，从而提高耐磨、耐刮擦性能；
3、本发明中丙烯酸改性的有机硅树脂经过硅烷偶联剂改性后，亲颜料基团的硅氧烷基团可与无机粉料中含氢活性基团发生作用形成稳定的化学键，与其他原料共同制备出高交联、高硬度涂层，造就长效低表面能的涂层表面，显著降低微观形态下外力摩擦、破坏作用；
4、本发明中丙烯酸改性的具有无机粉料亲和性的有机硅树脂与无机粉料(特别是消光粉)通过包覆作用，降低了粉料的表面张力，形成了一层疏水抗污层，使产品具有抗污自清洁特性；
5、本发明利用同时具有辐射固化活性和无机粉料亲和性的有机硅树脂对高硬度微粉颗粒颗粒进行包覆处理，高硬度微粉颗粒颗粒提供超耐磨性，有机硅树脂一方面与有机涂层反应交联，提供长效自清洁性，一方面包裹高硬度微粉颗粒颗粒，使无机高硬度微粉颗粒颗粒与有机涂层结合牢固，提供长效耐磨、耐刮擦性；
6、本发明制备的超耐磨自清洁涂层可广泛应用于公共场所地材、家居地材的涂装及其它对耐磨损、耐久性有特殊应用需求的场所涂装(例如手机、水龙头、桌椅、地板等)，应用范围较广。
具体实施方式
为了便于理解本发明，下文将结合较佳的实施例对本发明作更全面、细致地描述，但本发明的保护范围并不限于以下具体的实施例。
实施例1：
一种超耐磨自清洁涂层，包括第一道弹性面漆和第二道自清洁面漆，第一道弹性面漆按质量份包括玻璃化转变温度为-50～10℃的两官聚氨酯丙烯酸树脂A20份、引发剂A5份、丙烯酸酯单体A50份和添加剂A25份，第二道自清洁面漆按质量份包括丙烯酸改性的具有无机粉料亲和性的有机硅树脂4份、高硬度微粉颗粒1份、玻璃化转变温度为-50～-10℃的两官聚氨酯丙烯酸树脂B4份、玻璃化转变温度为50～150℃的多官能度聚氨酯丙烯酸树脂30份、玻璃化转变温度为50～150℃的丙烯酸酯单体B35份、引发剂B4份和添加剂B22份。
本实施例中，两官聚氨酯丙烯酸树脂A通过选择分子量在2000-6000的二元醇与异氰酸酯、单羟基丙烯酸酯单体聚合制备得到，二元醇为聚己内酯二元醇；异氰酸酯为甲苯二异氰酸酯；单羟基丙烯酸酯单体为丙烯酸羟乙酯。
本实施例中，引发剂A为1-羟基环己基苯基甲酮(184)。丙烯酸酯单体A为7份的乙氧基化三羟甲基丙烷三丙烯酸酯、10份的甲基丙烯酸羟乙酯、33份的三丙二醇二丙烯酸酯的混合物。
本实施例中，添加剂A为4份的分散剂、15份的二氧化硅消光粉、0.5份的消泡剂、0.5份的润湿剂、5份的硅微粉。
本实施例中，丙烯酸酯单体A为三官能度单体与两官或单官单体的混合物，其中三官能度丙烯酸单体含量为3％；两官或单官单体的含量为20％，三官能度丙烯酸单体为三羟甲基丙烷三丙烯酸酯；两官或单官单体为甲基丙烯酸羟乙酯。
本实施例中，丙烯酸改性的具有无机粉料亲和性的有机硅树脂的制备方法包括如下步骤：
i)选用羟基聚硅氧烷与异氰酸酯反应，得到有机硅预聚体；
ii)将有机硅预聚体与单羟基丙烯酸酯单体反应，制备丙烯酸改性有机硅低聚物；
iii)将丙烯酸改性有机硅低聚物与硅烷偶联剂反应，制备丙烯酸改性的具有无机粉料亲和性的有机硅树脂；
本实施例中，高硬度微粉颗粒为粒径50μm的金刚石微粉。
本实施例中，两官聚氨酯丙烯酸树脂B通过选择分子量在2000-6000的二元醇与异氰酸酯、单羟基丙烯酸酯单体聚合制备得到，二元醇为聚己内酯二元醇；单羟基丙烯酸酯单体为丙烯酸羟乙酯。
本实施例中，多官能度聚氨酯丙烯酸树脂通过多异氰酸酯与含羟基丙烯酸酯单体进行封端反应制备得到，多异氰酸酯为异佛尔酮二异氰酸酯；含羟基丙烯酸酯单体为丙烯酸羟乙酯。
本实施例中，丙烯酸酯单体B为按质量份6份的二季戊四醇六丙烯酸酯、10份的丙烯酰吗啉、19份的二丙二醇二丙烯酸酯的混合物。
本实施例中，引发剂B为按质量份3份的1-羟基环己基苯基甲酮(184)、1份的二苯甲酮(BP)的混合物。
本实施例中，添加剂B为按质量份4份的分散剂、14份的二氧化硅消光粉、0.5份的消泡剂、0.5份的润湿剂、3份的硅微粉的混合物。
本实施例中，引发剂A和引发剂B均为光引发剂，此光引发剂可以是本领域中现有技术中公开了任何一种光引发剂。
本实施例中，添加剂A和添加剂B均包括分散剂、消泡剂、流平剂、颜料、消光粉、阻燃剂和稳定剂，其中消光粉为无机或有机类消光粉，其中消光粉为无机消光粉，上述各成分可以是本领域中现有技术公开的任何一种相对应的成分。
一种超耐磨自清洁涂层的制备方法，包括如下步骤：
1)第一道弹性面漆的制备：将玻璃化转变温度为-50～10℃的两官聚氨酯丙烯酸树脂、引发剂A、丙烯酸酯单体A和添加剂A在合适的设备中高速分散到要求的细度后涂覆于底材上，经辐射固化得到第一道弹性面漆涂层，辐射固化方式为UV；
2)第二道自清洁面漆的制备：将丙烯酸改性的具有无机粉料亲和性的有机硅树脂和高硬度微粉颗粒进行分散得到有机硅良好包裹的高硬度颗粒，将上述有机硅良好包裹的高硬度颗粒与玻璃化转变温度为-50～10℃的两官聚氨酯丙烯酸树脂B、玻璃化转变温度为50～100℃的多官能度聚氨酯丙烯酸树脂、玻璃化转变温度为50～150℃的丙烯酸酯单体B、引发剂B和添加剂B在合适的设备中高速分散到要求的细度后涂覆于第一道弹性面漆涂层上，经辐射固化得到超耐磨自清洁涂层，辐射固化方式为UV。
实施例2：
一种超耐磨自清洁涂层，包括第一道弹性面漆和第二道自清洁面漆，第一道弹性面漆按质量份包括玻璃化转变温度为-50～10℃的两官聚氨酯丙烯酸树脂A30份、引发剂A4.5份、丙烯酸酯单体A30.5份和添加剂A35份，第二道自清洁面漆按质量份包括丙烯酸改性的具有无机粉料亲和性的有机硅树脂8份、高硬度微粉颗粒0.3份、玻璃化转变温度为-50～-10℃的两官聚氨酯丙烯酸树脂B3份、玻璃化转变温度为50～150℃的多官能度聚氨酯丙烯酸树脂40份、玻璃化转变温度为50～150℃的丙烯酸酯单体B30.7份、引发剂B3份和添加剂B15份。
本实施例中，两官聚氨酯丙烯酸树脂A通过选择分子量在2000-6000的二元醇与异氰酸酯、单羟基丙烯酸酯单体聚合制备得到，二元醇为聚酯二元醇和二聚酸改性二元醇的混合；异氰酸酯为异佛尔酮二异氰酸酯；单羟基丙烯酸酯单体为丙烯酸羟乙酯、甲基丙烯酸羟乙酯、丙烯酸羟丙酯三种混合。
本实施例中，丙烯酸酯单体A为三官能度单体与两官或单官单体的混合物，其中三官能度丙烯酸单体为三羟甲基丙烷三丙烯酸酯，含量5％；两官或单官单体的含量为25.5％，两官或单官单体为5份的新戊二醇二丙烯酸酯、15.5份的二丙二醇二丙烯酸酯、5份的甲基丙烯酸羟乙酯三种混合。
本实施例中，添加剂A为质量份5份的分散剂、12份的二氧化硅消光粉、0.5份的消泡剂、0.2份的流平剂，0.5份的润湿剂、12.3的阻燃剂。
本实施例中，丙烯酸改性的具有无机粉料亲和性的有机硅树脂的制备方法包括如下步骤：
i)选用羟基聚硅氧烷与异氰酸酯反应，得到有机硅预聚体；
ii)将有机硅预聚体与单羟基丙烯酸酯单体反应，制备丙烯酸改性有机硅低聚物；
iii)将丙烯酸改性有机硅低聚物与硅烷偶联剂反应，制备丙烯酸改性的具有无机粉料亲和性的有机硅树脂。
本实施例中，高硬度微粉颗粒为粒径20μm的金刚石微粉。
本实施例中，两官聚氨酯丙烯酸树脂B通过选择分子量在2000-6000的二元醇与异氰酸酯、单羟基丙烯酸酯单体聚合制备得到，二元醇为二聚酸改性二元醇；异氰酸酯为4，4'-二环己基甲烷二异氰酸酯；单羟基丙烯酸酯单体为甲基丙烯酸羟乙酯与丙烯酸羟丙酯的混合。
本实施例中，多官能度聚氨酯丙烯酸树脂通过多异氰酸酯与含羟基丙烯酸酯单体进行封端反应制备得到，多异氰酸酯为4，4'-二环己基甲烷二异氰酸酯、HDI二聚体、HDI三聚体和HDI缩二脲四种混合；含羟基丙烯酸酯单体为甲基丙烯酸羟乙酯。
本实施例中，丙烯酸酯单体B按质量分为5份的季戊四醇三丙烯酸酯、5份的二缩三羟甲基丙烷四丙烯酸酯、4份的新戊二醇二丙烯酸酯、16.7份的二丙二醇二丙烯酸酯的混合物。
本实施例中，引发剂B为按质量份2份的1-羟基环己基苯基甲酮(184)、1份(2,4,6-三甲基苯甲酰基)二苯基氧化膦(TPO)的混合物。
本实施例中，添加剂B为按质量份3份的分散剂、10.5份的二氧化硅消光粉、0.5份的消泡剂、0.5份的润湿剂、0.5份的流平剂的混合物。
一种超耐磨自清洁涂层的制备方法，包括如下步骤：
1)第一道弹性面漆的制备：将玻璃化转变温度为-50～10℃的两官聚氨酯丙烯酸树脂、引发剂A、丙烯酸酯单体A和添加剂A在合适的设备中高速分散到要求的细度后涂覆于底材上，经辐射固化得到第一道弹性面漆涂层，辐射固化方式为LED；
2)第二道自清洁面漆的制备：将丙烯酸改性的具有无机粉料亲和性的有机硅树脂和高硬度微粉颗粒进行分散得到有机硅良好包裹的高硬度颗粒，将上述有机硅良好包裹的高硬度颗粒与玻璃化转变温度为-50～10℃的两官聚氨酯丙烯酸树脂B、玻璃化转变温度为50～100℃的多官能度聚氨酯丙烯酸树脂、玻璃化转变温度为50～150℃的丙烯酸酯单体B、引发剂B和添加剂B在合适的设备中高速分散到要求的细度后涂覆于第一道弹性面漆涂层上，经辐射固化得到超耐磨自清洁涂层，辐射固化方式为EB。
实施例3：
一种超耐磨自清洁涂层，包括第一道弹性面漆和第二道自清洁面漆，第一道弹性面漆按质量份包括玻璃化转变温度为-50～10℃的两官聚氨酯丙烯酸树脂A40份、引发剂A6份、丙烯酸酯单体A39份和添加剂A15份，第二道自清洁面漆按质量份包括丙烯酸改性的具有无机粉料亲和性的有机硅树脂20份、高硬度微粉颗粒2份、玻璃化转变温度为-50～-10℃的两官聚氨酯丙烯酸树脂B10份、玻璃化转变温度为50～150℃的多官能度聚氨酯丙烯酸树脂30份、玻璃化转变温度为50～150℃的丙烯酸酯单体B31份、引发剂B2份和添加剂B5份。
本实施例中，两官聚氨酯丙烯酸树脂A通过选择分子量在2000-6000的二元醇与异氰酸酯、单羟基丙烯酸酯单体聚合制备得到，二元醇为聚四氢呋喃二元醇；异氰酸酯为甲苯二异氰酸酯、异佛尔酮二异氰酸酯和4，4'-二环己基甲烷二异氰酸酯的混合；单羟基丙烯酸酯单体为丙烯酸羟乙酯和丙烯酸羟丙酯的混合。
本实施例中，引发剂A为按质量份3份的(2,4,6-三甲基苯甲酰基)二苯基氧化膦(TPO)和3份的1-羟基环己基苯基甲酮(184)的混合物。
本实施例中，丙烯酸酯单体A为按质量份5份的三羟甲基丙烷三丙烯酸酯、34份的丙烯酰吗啉的混合物。
本实施例中，添加剂A为按质量份2.7份的分散剂、12份的聚脲消光粉、0.3份的消泡剂的混合物。
本实施例中，丙烯酸酯单体A为三官能度单体与两官或单官单体的混合物，其中三官能度丙烯酸单体含量为15％；两官或单官单体的含量为30％，三官能度丙烯酸单体为乙氧基化三羟甲基丙烷三丙烯酸酯；两官或单官单体为1，6-己二醇二丙烯酸酯和新戊二醇二丙烯酸酯的混合。
本实施例中，丙烯酸改性的具有无机粉料亲和性的有机硅树脂的制备方法，包括如下步骤：
i)选用羟基聚硅氧烷与异氰酸酯反应，得到有机硅预聚体；
ii)将有机硅预聚体与单羟基丙烯酸酯单体反应，制备丙烯酸改性有机硅低聚物；
iii)将丙烯酸改性有机硅低聚物与硅烷偶联剂反应，制备丙烯酸改性的具有无机粉料亲和性的有机硅树脂。
本实施例中，高硬度微粉颗粒为按质量份1份粒径10μm的金刚石微粉、1份粒径60μm碳化硅微粉的混合。
本实施例中，两官聚氨酯丙烯酸树脂B通过选择分子量在2000-6000的二元醇与异氰酸酯、单羟基丙烯酸酯单体聚合制备得到，二元醇为聚酯二元醇和二聚酸改性二元醇的混合；异氰酸酯为4，4'-二环己基甲烷二异氰酸酯；单羟基丙烯酸酯单体为甲基丙烯酸羟乙酯和丙烯酸羟丙酯的混合。
本实施例中，多官能度聚氨酯丙烯酸树脂通过多异氰酸酯与含羟基丙烯酸酯单体进行封端反应制备得到，多异氰酸酯为IPDI三聚体；含羟基丙烯酸酯单体为季戊四醇三丙烯酸酯和双季戊四醇五丙烯酸酯的混合。
本实施例中，丙烯酸酯单体B为按质量份10份的季戊四醇三丙烯酸酯、21份的丙烯酰吗啉的混合物。
本实施例中，引发剂B为苯基双(2,4,6-三甲基苯甲酰基)氧化膦(819)。
本实施例中，添加剂B为按质量份4.5份的硅微粉、0.2份的消泡剂、0.3份的流平剂的混合。
一种超耐磨自清洁涂层的制备方法，包括如下步骤：
1)第一道弹性面漆的制备：将玻璃化转变温度为-50～10℃的两官聚氨酯丙烯酸树脂、引发剂A、丙烯酸酯单体A和添加剂A在合适的设备中高速分散到要求的细度后涂覆于底材上，经辐射固化得到第一道弹性面漆涂层，辐射固化方式为UV与LED的组合；
2)第二道自清洁面漆的制备：将丙烯酸改性的具有无机粉料亲和性的有机硅树脂和高硬度微粉颗粒进行分散得到有机硅良好包裹的高硬度颗粒，将上述有机硅良好包裹的高硬度颗粒与玻璃化转变温度为-50～10℃的两官聚氨酯丙烯酸树脂B、玻璃化转变温度为50～100℃的多官能度聚氨酯丙烯酸树脂、玻璃化转变温度为50～150℃的丙烯酸酯单体B、引发剂B和添加剂B在合适的设备中高速分散到要求的细度后涂覆于第一道弹性面漆涂层上，经辐射固化得到超耐磨自清洁涂层，辐射固化方式为LED与EB的组合。
实施例4：
一种超耐磨自清洁涂层，包括第一道弹性面漆和第二道自清洁面漆，第一道弹性面漆按质量份包括玻璃化转变温度为-50～10℃的两官聚氨酯丙烯酸树脂A60份、引发剂A2份、丙烯酸酯单体A28份和添加剂A10份，第二道自清洁面漆按质量份包括丙烯酸改性的具有无机粉料亲和性的有机硅树脂15份、高硬度微粉颗粒3份、玻璃化转变温度为-30～-10℃的两官聚氨酯丙烯酸树脂B13份、玻璃化转变温度为50～150℃的多官能度聚氨酯丙烯酸树脂20份、玻璃化转变温度为50～150℃的丙烯酸酯单体B17份、引发剂B5份和添加剂B30份。
本实施例中，两官聚氨酯丙烯酸树脂A通过选择分子量在2000-6000的二元醇与异氰酸酯、单羟基丙烯酸酯单体聚合制备得到，二元醇为二聚酸改性二元醇；异氰酸酯为甲苯二异氰酸酯、异佛尔酮二异氰酸酯和4，4'-二环己基甲烷二异氰酸酯的混合；单羟基丙烯酸酯单体为甲基丙烯酸羟乙酯。
本实施例中，引发剂A为按质量份苯基双(2,4,6-三甲基苯甲酰基)氧化膦(819)。
本实施例中，丙烯酸酯单体A为按质量份8份的乙氧基化三羟甲基丙烷三丙烯酸酯、9份的1,6-己二醇二丙烯酸酯、11份的甲基丙烯酸羟丙酯的混合物。
本实施例中，添加剂A为按质量份2份的分散剂、7.5份的二氧化硅消光粉、0.5份的消泡剂的混合物。
本实施例中，丙烯酸改性的具有无机粉料亲和性的有机硅树脂的制备方法，包括如下步骤：
i)选用羟基聚硅氧烷与异氰酸酯反应，得到有机硅预聚体；
ii)将有机硅预聚体与单羟基丙烯酸酯单体反应，制备丙烯酸改性有机硅低聚物；
iii)将丙烯酸改性有机硅低聚物与硅烷偶联剂反应，制备丙烯酸改性的具有无机粉料亲和性的有机硅树脂。
本实施例中，高硬度微粉颗粒为按质量份1份粒径10μm的金刚石微粉、1份粒径30μm碳化硅微粉、1份粒径30μm氧化铝和混合。
本实施例中，两官聚氨酯丙烯酸树脂B通过选择分子量在2000-6000的二元醇与异氰酸酯、单羟基丙烯酸酯单体聚合制备得到，二元醇为聚酯二元醇；异氰酸酯为异佛尔酮二异氰酸酯；单羟基丙烯酸酯单体为甲基丙烯酸羟乙酯。
本实施例中，多官能度聚氨酯丙烯酸树脂通过多异氰酸酯与含羟基丙烯酸酯单体进行封端反应制备得到，多异氰酸酯为4，4'-二环己基甲烷二异氰酸酯；含羟基丙烯酸酯单体为丙烯酸羟丙酯。
本实施例中，丙烯酸酯单体B为按质量份5份的二缩三羟甲基丙烷四丙烯酸酯、5份的新戊二醇二丙烯酸酯、7份的丙烯酰吗啉的混合物。
本实施例中，引发剂B为1份的苯基双(2,4,6-三甲基苯甲酰基)氧化膦(819)、2份的2-羟基-2-甲基-1-苯基-1-丙酮(1173)、1份的4-氯二苯甲酮、1份的活性胺的混合物。
本实施例中，添加剂B为按质量份5份的分散剂、15份的二氧化硅消光粉、8.5份的耐磨粉、0.5份的消泡剂、0.5份的润湿剂、0.5份的流平剂的混合物。
一种超耐磨自清洁涂层的制备方法，包括如下步骤：
1)第一道弹性面漆的制备：将玻璃化转变温度为-50～10℃的两官聚氨酯丙烯酸树脂、引发剂A、丙烯酸酯单体A和添加剂A在合适的设备中高速分散到要求的细度后涂覆于底材上，经辐射固化得到第一道弹性面漆涂层，辐射固化方式为UV和EB的组合；
2)第二道自清洁面漆的制备：将丙烯酸改性的具有无机粉料亲和性的有机硅树脂和高硬度微粉颗粒进行分散得到有机硅良好包裹的高硬度颗粒，将上述有机硅良好包裹的高硬度颗粒与玻璃化转变温度为-50～10℃的两官聚氨酯丙烯酸树脂B、玻璃化转变温度为50～100℃的多官能度聚氨酯丙烯酸树脂、玻璃化转变温度为50～150℃的丙烯酸酯单体B、引发剂B和添加剂B在合适的设备中高速分散到要求的细度后涂覆于第一道弹性面漆涂层上，经辐射固化得到超耐磨自清洁涂层，辐射固化方式为UV和EB的组合。

Claims (10)

1.一种超耐磨自清洁涂层，其特征在于：包括第一道弹性面漆和第二道自清洁面漆，所述第一道弹性面漆按质量份包括两官聚氨酯丙烯酸树脂A10-60份、引发剂A2-7份、丙烯酸酯单体A10-60份和添加剂A3-40份，所述第二道自清洁面漆按质量份包括丙烯酸改性的具有无机粉料亲和性的有机硅树脂2-30份、高硬度微粉颗粒0.3-3份、两官聚氨酯丙烯酸树脂B2-20份、多官能度聚氨酯丙烯酸树脂10-40份、丙烯酸酯单体B15-45份、引发剂B2-7份和添加剂B3-40份。
2.根据权利要求1所述的超耐磨自清洁涂层，其特征在于：所述两官聚氨酯丙烯酸树脂A的软段结构单元玻璃化转变温度为-50～10℃，软段含量为40-80％，两官聚氨酯丙烯酸树脂A通过选择分子量在2000-6000的二元醇与异氰酸酯、单羟基丙烯酸酯单体聚合制备得到，所述二元醇为聚己内酯二元醇、聚酯二元醇、二聚酸改性二元醇、聚四氢呋喃二元醇之中的一种或几种混合；所述异氰酸酯为甲苯二异氰酸酯、异佛尔酮二异氰酸酯、4,4'-二环己基甲烷二异氰酸酯之中的一种或几种混合；所述单羟基丙烯酸酯单体为丙烯酸羟乙酯、甲基丙烯酸羟乙酯、丙烯酸羟丙酯之中的一种或几种混合；所述两官聚氨酯丙烯酸树脂A的含量为15-40份。
3.根据权利要求1所述的超耐磨自清洁涂层，其特征在于：所述丙烯酸酯单体A为三官能度单体与两官或单官单体的混合物，其中三官能度丙烯酸单体质量分数为1-20％，优选为5-10％；两官或单官单体的质量分数为10-50％，优选为15-40％，所述三官能度丙烯酸单体为三羟甲基丙烷三丙烯酸酯、乙氧基化三羟甲基丙烷三丙烯酸酯中的一种或几种混合；所述两官或单官单体为甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯、丙烯酰吗啉、1,6-己二醇二丙烯酸酯、新戊二醇二丙烯酸酯、二丙二醇二丙烯酸酯、三丙二醇二丙烯酸酯、聚乙二醇二丙烯酸酯中的一种或几种混合。
4.根据权利要求1-3中任一项所述的超耐磨自清洁涂层，其特征在于：所述丙烯酸改性的具有无机粉料亲和性的有机硅树脂的制备方法包括如下步骤：
i)选用羟基聚硅氧烷与异氰酸酯反应，得到有机硅预聚体；
ii)将有机硅预聚体与单羟基丙烯酸酯单体反应，制备丙烯酸改性有机硅低聚物；
iii)将丙烯酸改性有机硅低聚物与硅烷偶联剂反应，制备丙烯酸改性的具有无机粉料亲和性的有机硅树脂；
所述丙烯酸改性的具有无机粉料亲和性的有机硅树脂含量为8-14份。
5.根据权利要求1-3中任一项所述的超耐磨自清洁涂层，其特征在于：所述高硬度微粉颗粒为莫氏硬度不小于9的粉料，所述高硬度微粉颗粒为金刚石微粉、碳化硅微粉、氧化铝颗粒中的一种或几种组合；高硬度微粉颗粒粒径为1-100μm，优选为5-20μm。
6.根据权利要求1-3中任一项所述的超耐磨自清洁涂层，其特征在于：所述两官聚氨酯丙烯酸树脂B的软段结构单元玻璃化转变温度为-50～10℃，软段含量为40-80％，两官聚氨酯丙烯酸树脂B通过选择分子量在2000-6000的二元醇与异氰酸酯、单羟基丙烯酸酯单体聚合制备得到，所述二元醇为聚己内酯二元醇、聚酯二元醇、二聚酸改性二元醇、聚四氢呋喃二元醇之中的一种或几种混合；所述异氰酸酯为甲苯二异氰酸酯、异佛尔酮二异氰酸酯、4,4'-二环己基甲烷二异氰酸酯中的一种或几种混合；所述单羟基丙烯酸酯单体为丙烯酸羟乙酯、甲基丙烯酸羟乙酯、丙烯酸羟丙酯中的一种或几种混合；所述两官聚氨酯丙烯酸树脂B的含量为5-10份。
7.根据权利要求1-3中任一项所述的超耐磨自清洁涂层，其特征在于：所述多官能度聚氨酯丙烯酸树脂玻璃化转变温度为50～150℃，多官能度聚氨酯丙烯酸树脂通过多异氰酸酯与含羟基丙烯酸酯单体进行封端反应制备得到，所述多异氰酸酯为异佛尔酮二异氰酸酯、4,4'-二环己基甲烷二异氰酸酯、HDI二聚体、HDI三聚体、HDI缩二脲、IPDI三聚体中的一种或几种混合；所述含羟基丙烯酸酯单体为丙烯酸羟乙酯、甲基丙烯酸羟乙酯、丙烯酸羟丙酯、季戊四醇三丙烯酸酯、双季戊四醇五丙烯酸酯中的一种或几种混合；所述多官能度聚氨酯丙烯酸树脂含量为15-30份。
8.根据权利要求1-3中任一项所述的超耐磨自清洁涂层，其特征在于：所述丙烯酸酯单体B的均聚物玻璃化转变温度为50℃至150℃，优选为80～150℃，所述丙烯酸酯单体B为多官能度丙烯酸酯单体与两官能度或单官能度单体的混合，所述多官能度丙烯酸酯单体质量分数为5-15％，所述两官能度或单官能度单体质量分数为10-30％；所述多官能度丙烯酸酯单体为季戊四醇三丙烯酸酯、季戊四醇四丙烯酸酯、二缩三羟甲基丙烷四丙烯酸酯、二季戊四醇六丙烯酸酯中的一种或多种混合；两官能度或单官能度单体为二丙二醇二丙烯酸酯、新戊二醇二丙烯酸酯、丙烯酰吗啉中的一种或多种混合。
9.根据权利要求1-3中任一项所述的超耐磨自清洁涂层，其特征在于：所述引发剂A和引发剂B均为光引发剂；所述添加剂A和添加剂B均包括分散剂、消泡剂、流平剂、颜料、消光粉、阻燃剂和稳定剂，其中消光粉为无机或有机类消光粉。
10.一种超耐磨自清洁涂层的制备方法，其特征在于，包括如下步骤：
1)第一道弹性面漆的制备：将两官聚氨酯丙烯酸树脂、引发剂A、丙烯酸酯单体A和添加剂A在合适的设备中高速分散或研磨到要求的细度后涂覆于底材上，经辐射固化得到第一道弹性面漆涂层，所述辐射固化方式为UV、LED、EB中的一种或几种组合；
2)第二道自清洁面漆的制备：将丙烯酸改性的具有无机粉料亲和性的有机硅树脂和高硬度微粉颗粒进行研磨以得到有机硅良好包裹的高硬度颗粒，将上述有机硅良好包裹的高硬度颗粒与两官聚氨酯丙烯酸树脂B、多官能度聚氨酯丙烯酸树脂、丙烯酸酯单体B、引发剂B和添加剂B在合适的设备中高速分散或研磨到要求的细度后涂覆于第一道弹性面漆涂层上，经辐射固化得到超耐磨自清洁涂层，所述辐射固化方式为UV、LED、EB中的一种或几种组合。
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