CN116463042A - 一种基于纳米粒子的聚氨酯仿皮涂层耐久性功能整理方法 - Google Patents
一种基于纳米粒子的聚氨酯仿皮涂层耐久性功能整理方法 Download PDFInfo
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Abstract
本发明公开了一种基于纳米粒子的聚氨酯仿皮涂层耐久性功能整理方法，解决了聚氨酯本体接枝功能整理剂时聚合过程难以控制，操作复杂的问题，以及功能整理剂与聚氨酯共混时或涂覆于聚氨酯表面时功能耐久性差的问题。该方法主要是将纳米粒子分散均匀的整理液喷涂到聚氨酯涂层表面，通过预热处理驱动底层聚氨酯与表层的纳米粒子融合，然后通过热固化过程驱动聚氨酯链段相互靠近，同时将纳米粒子以全包覆或半包覆方式坚牢地固着于聚氨酯仿皮涂层中，实现聚氨酯仿皮涂层的功能耐久性。
Description
技术领域
本发明属于纺织品聚氨酯功能涂层领域，具体涉及了一种基于纳米粒子的聚氨酯仿皮涂层耐久性功能整理方法。
背景技术
聚氨酯仿皮涂层是一种高性能的涂层材料，具有优异的附着力、耐磨性、抗污性等优点。目前，聚氨酯仿皮面料通常是通过聚氨酯涂层的方式制得，广泛应用于汽车座椅、家具器材、纺织服装等众多领域。为满足不同应用的需求，研究技术人员开发了一系列聚氨酯涂层功能整理的方法。
CN102304852B将抗菌有效成分竹醋液添加到聚氨酯涂层剂中，并通过柔软剂和增稠剂调控涂层的性能，制得抗菌整理液，在75～95℃下焙烘3～5min定形，再采用120～180℃焙烘3～5min交联，制得抗菌型聚氨酯涂层。
CN103696265A将浸轧防迁移剂水溶液的织物焙烘后，浸轧防水防油剂乳液，随后将其进行焙烘处理，最后将焙烘织物的反面进行聚氨酯涂层整理，制得聚氨酯功能涂层。
CN115449255A通过在单体形态的原硅酸四甲酯水解时添加三甲基氯硅烷，水解的原硅酸四甲酯缩合时添加六甲基二硅氮烷、醇溶剂和甲基三甲氧基硅烷制得超疏水改性二氧化硅纳米颗粒，随后将改性二氧化硅纳米颗粒、乙二醇、二羟基聚酯、4，4'-二苯基甲烷二异氰酸酯与聚氨酯溶液混合制得超疏水聚氨酯涂层涂布液。
以上方法主要是通过机械共混或先施加功能组分再涂覆聚氨酯的方式，将功能整理剂引进聚氨酯涂层内部或覆盖在表面，从而赋予聚氨酯涂层功能性，该方法操作简易。但是这些方式难以兼顾聚氨酯涂层性能与功能耐久性，其中先施加功能组分再涂覆聚氨酯的方式虽不影响聚氨酯涂层的成膜，但其功能组分没有额外的交联，其耐久性较差。而机械共混的方式往往通过增加其涂覆量提高其功能耐久性，但易造成聚氨酯涂层成膜不匀，导致其机械性能下降，手感变差。
此外，CN112646110A合成了具有抗菌特性的双子季铵盐二醇单体，随后通过双子季铵盐二醇与二异腈酸酯等聚氨酯预聚体的加成反应将其以扩链剂的形式在分子水平上引入到聚氨酯中，制得了一种由含有功能性单体聚合而成的抗菌型聚氨酯涂层材料。该方法虽然巧妙地解决了聚氨酯涂层功能耐久性的问题，但其功能性单体的合成复杂，不易量产，且其聚合过程难以控制。针对现有聚氨酯涂层功能整理技术存在的功能耐久性差、功能组分制备复杂等问题，开发一种工艺简单、环境友好、功能耐久性优异且具有抗紫外、抗菌等功能的聚氨酯仿皮涂层耐久性整理方法，对纺织品聚氨酯功能涂层领域具有实际应用意义。
发明内容
本发明旨在提供一种基于纳米粒子的聚氨酯仿皮涂层耐久性功能整理方法，针对现有技术中的缺陷，开发一种工艺简单、环境友好、功能耐久性优异且具有抗紫外、抗菌等功能的聚氨酯仿皮涂层耐久性整理方法。
为了解决上述技术问题，采用如下技术方案：
一种基于纳米粒子的聚氨酯仿皮涂层耐久性功能整理方法，其特征在于包括如下步骤：
(1)将纳米粒子添加到含有分散剂的极性溶剂中，超声20～60min后制得分散均匀的功能整理液；
(2)设置喷枪压力为0.3～0.6MPa，将功能整理液喷涂在铺展均匀的水性聚氨酯表面，制得功能聚氨酯仿皮涂层前驱体；
(3)在一定湿度条件下，对功能聚氨酯仿皮涂层前驱体进行预热处理，驱动底层聚氨酯与表层纳米粒子相互融合；
(4)对预热处理后的功能聚氨酯仿皮涂层前驱体进行热固化，通过溶剂蒸发驱动聚氨酯链段相互靠近，完成聚氨酯涂层对纳米粒子的全包覆或半包覆，制得具有功能耐久性的聚氨酯仿皮涂层。
优选后，所述的纳米粒子为亲水性纳米粒子，其粒径为8～100nm，选自纳米氧化钛粒子、纳米氧化锌粒子、纳米硅胶粒子、羟基化碳纳米管粒子、羧基化碳纳米管粒子、纳米银粒子、纳米碱式硫酸铜粒子、纳米硫化铜粒子、纳米氧化铁粒子中的一种或多种，其中纳米氧化钛粒子和纳米氧化锌粒子可赋予整理液抗紫外、抗菌、自清洁等功能；纳米硅胶粒子可赋予整理液抗老化性、防水性等功能且可提高其聚氨酯涂层等基体的机械性能和吸附性能；羟基化碳纳米管粒子和羧基化碳纳米管粒子可赋予整理液热传导功能且可提高其聚氨酯涂层等基体的机械性能和导电性能；纳米银粒子和纳米碱式硫酸铜粒子可赋予整理液抗菌功能；纳米硫化铜粒子可赋予整理液防腐性能和导电性能；纳米氧化铁粒子可赋予整理液耐酸碱和抗紫外性能。
优选后，所述的分散剂选自十二烷基苯磺酸钠、聚甲基丙烯酸、月桂醇醚磷酸酯、柠檬酸钠、聚乙烯毗咯酮、聚丙烯酰胺、脂肪醇聚氧乙烯醚、乙二胺四乙酸钠中的一种或多种。
优选后，所述的极性溶剂选自乙醇、乙二醇、丙二醇、丙三醇、异丙醇、水中的一种或多种。
优选后，所述的功能整理液为纳米粒子的分散液，纳米粒子的用量为极性溶剂的0.2～1wt％，分散剂的用量为极性溶剂的0.1～0.5wt％。
优选后，所述的铺展均匀的水性聚氨酯是由刮刀或丝棒刮涂制得，涂覆量为20～60g/m2。
优选后，所述的水性聚氨酯选自水性聚氨酯9580C、水性聚氨酯H130D、水性聚氨酯2019B、水性聚氨酯209N、水性聚氨酯WPU-2426、水性聚氨酯AE-12、水性聚氨酯树脂AH-1618、水性聚氨酯树脂AH-1604F、水性聚氨酯树脂AH-1619、水性聚氨酯树脂AH-1605B、水性聚氨酯树脂AH-1739中的一种或多种。
优选后，所述的预热处理湿度为40％～80％，温度为30～50℃，时间为10～20min。
优选后，所述的热固化条件为60～80℃下焙烘20～40min。
由于采用上述技术方案，具有以下有益效果：
1、本发明提供了一种基于纳米粒子的聚氨酯仿皮涂层耐久性功能整理方法，该方法可适用于不同类型的纳米粒子以实现涂层不同的功能性。通过功能整理液的分散制备以及喷涂手段可实现功能纳米粒子的高分散性，提升功能整理效果。
2、本发明所述的聚氨酯仿皮涂层耐久性功能整理方法无需添加额外的交联剂，通过特定湿度和预热温度处理，驱动底层聚氨酯大分子对功能纳米粒子的牢固包覆，实现其功能的耐久性，具有过程操作简单、调控便捷的优点。
具体实施方式
本发明旨在提供一种基于纳米粒子的聚氨酯仿皮涂层耐久性功能整理方法，其原理为将亲水性的功能纳米粒子超声分散在极性溶剂中配制成功能整理液，随后将功能整理液喷涂到铺展均匀的水性聚氨酯表面，制得功能聚氨酯仿皮涂层前驱体，然后在一定湿度条件下对其进行预热处理驱动底层聚氨酯与表层的纳米粒子融合，最后对其进行热固化驱动聚氨酯链段相互靠近，形成聚氨酯膜将纳米粒子牢固地全包覆或半包覆于聚氨酯膜中，提高聚氨酯涂层的功能耐久性。
下面结合具体的实施例的对本发明的技术方案作进一步说明：
实施例1
(1)将0.06g纳米硅胶粒子添加到含有0.02g柠檬酸钠的乙醇溶剂中，超声30min后制得分散均匀的防水整理液，其中乙醇用量为10g；
(2)用丝棒将水性聚氨酯H130D均匀地刮涂到离型纸上，其涂覆量为30g/m2，随后设置喷枪压力为0.4MPa，将制备的防水整理液喷涂在铺展均匀的水性聚氨酯表面，制得功能聚氨酯仿皮涂层前驱体；
(3)在湿度为50％，温度为40℃的条件下对功能聚氨酯仿皮涂层前驱体预热处理10min，驱动底层水性聚氨酯H130D与表层的纳米粒子融合；
(4)在60℃下焙烘40min，对预热处理后的功能聚氨酯仿皮涂层前驱体进行热固化，使聚氨酯链段相互靠近形成聚氨酯膜，将纳米硅胶粒子全包覆或半包覆，制得具有防水功能耐久性的聚氨酯仿皮涂层。
实施例2
(1)将0.02g纳米二氧化钛粒子和0.06g纳米银粒子添加到含有0.04g聚乙烯毗咯酮的异丙醇溶剂中，超声60min后制得分散均匀的抗菌整理液，其中异丙醇用量为20g；
(2)用刮刀将水性聚氨酯AE-12均匀地刮涂到离型纸上，其涂覆量为40g/m2，随后设置喷枪压力为0.5MPa，将制备的抗菌整理液喷涂在铺展均匀的水性聚氨酯表面，制得功能聚氨酯仿皮涂层前驱体；
(3)在湿度为60％，温度为30℃的条件下对功能聚氨酯仿皮涂层前驱体预热处理20min，驱动底层水性聚氨酯AE-12与表层的的纳米粒子融合；
(4)在70℃下焙烘30min，对预热处理后的功能聚氨酯仿皮涂层前驱体进行热固化，使聚氨酯链段相互靠近形成聚氨酯膜，将纳米硅胶粒子全包覆或半包覆，制得具有抗菌功能耐久性的聚氨酯仿皮涂层。
实施例3
(1)将0.05g羟基化碳纳米管粒子添加到含有0.03g聚丙烯酰胺的乙二醇溶剂中，超声20min后制得分散均匀的导电整理液，其中乙二醇用量为10g；
(2)用刮刀将水性聚氨酯AH-1604F均匀地刮涂到离型纸上，其涂覆量为60g/m2，随后设置喷枪压力为0.6MPa，将制备的导电整理液喷涂在铺展均匀的水性聚氨酯表面，制得功能聚氨酯仿皮涂层前驱体；
(3)在湿度为60％，温度为40℃的条件下对功能聚氨酯仿皮涂层前驱体预热处理10min，驱动底层水性聚氨酯AH-1604F与表层的纳米粒子融合；
(4)在80℃下焙烘30min，对预热处理后的功能聚氨酯仿皮涂层前驱体进行热固化，使聚氨酯链段相互靠近形成聚氨酯膜，将纳米硅胶粒子全包覆或半包覆，制得具有导电功能耐久性的聚氨酯仿皮涂层。
实施例4
(1)将0.12g纳米氧化锌粒子添加到含有0.06g月桂醇醚磷酸酯的丙三醇溶剂中，超声30min后制得分散均匀的抗紫外整理液，其中丙三醇用量为30g；
(2)用丝棒将水性聚氨酯AH-1619均匀地刮涂到离型纸上，其涂覆量为30g/m2，随后设置喷枪压力为0.5MPa，将制备的抗紫外整理液喷涂在铺展均匀的水性聚氨酯表面，制得功能聚氨酯仿皮涂层前驱体；
(3)在湿度为60％，温度为50℃的条件下对功能聚氨酯仿皮涂层前驱体预热处理20min，驱动底层水性聚氨酯AH-1619与表层的纳米粒子融合；
(4)在80℃下焙烘20min，对预热处理后的功能聚氨酯仿皮涂层前驱体进行热固化，使聚氨酯链段相互靠近形成聚氨酯膜，将纳米硅胶粒子全包覆或半包覆，制得具有抗紫外功能耐久性的聚氨酯仿皮涂层。
实施例5
(1)将0.06g纳米氧化铁粒子添加到含有0.05g脂肪醇聚氧乙烯醚的异丙醇溶剂中，超声30min后制得分散均匀的耐酸碱整理液，其中异丙醇用量为20g；
(2)用丝棒将水性聚氨酯2019B均匀地刮涂到离型纸上，其涂覆量为30g/m2，随后设置喷枪压力为0.4MPa，将制备的耐酸碱整理液喷涂在铺展均匀的水性聚氨酯表面，制得功能聚氨酯仿皮涂层前驱体；
(3)在湿度为50％，温度为60℃的条件下对功能聚氨酯仿皮涂层前驱体预热处理10min，驱动底层水性聚氨酯2019B与表层的纳米粒子融合；
(4)在80℃下焙烘30min，对预热处理后的功能聚氨酯仿皮涂层前驱体进行固化，使聚氨酯链段相互靠近形成聚氨酯膜，将纳米硅胶粒子全包覆或半包覆，制得具有耐酸碱功能耐久性的聚氨酯仿皮涂层。
实施例6
(1)将0.05g纳米碱式硫酸铜粒子和0.01g纳米银粒子添加到含有0.03g柠檬酸钠的乙二醇溶剂中，超声30min后制得分散均匀的防水整理液，其中乙二醇用量为10g；
(2)用刮刀将水性聚氨酯WPU-2426均匀地刮涂到离型纸上，其涂覆量为30g/m2，随后设置喷枪压力为0.5MPa，将制备的抗菌整理液喷涂在铺展均匀的水性聚氨酯表面，制得功能聚氨酯仿皮涂层前驱体；
(3)在湿度为80％，温度为60℃的条件下对功能聚氨酯仿皮涂层前驱体预热处理10min，驱动底层水性聚氨酯WPU-2426与表层的纳米粒子融合；
(4)在70℃下焙烘30min，对预热处理后的功能聚氨酯仿皮涂层前驱体进行热固化，使聚氨酯链段相互靠近形成聚氨酯膜，将纳米硅胶粒子全包覆或半包覆，制得具有抗菌功能耐久性的聚氨酯仿皮涂层。
以上仅为本发明的具体实施例，但本发明的技术特征并不局限于此。任何以本发明为基础，为解决基本相同的技术问题，实现基本相同的技术效果，所作出地简单变化、等同替换或者修饰等，皆涵盖于本发明的保护范围之中。
Claims (10)
1.一种基于纳米粒子的聚氨酯仿皮涂层耐久性功能整理方法，其特征在于包括如下步骤：
(1)将纳米粒子添加到含有分散剂的极性溶剂中，超声20～60min后制得功能整理液；
(2)设置喷枪压力为0.3～0.6MPa，将功能整理液喷涂在铺展的水性聚氨酯表面，制得功能聚氨酯仿皮涂层前驱体；
(3)在一定湿度条件下，对功能聚氨酯仿皮涂层前驱体进行预热处理，驱动底层聚氨酯与表层纳米粒子相互融合；
(4)对预热处理后的功能聚氨酯仿皮涂层前驱体进行热固化，通过溶剂蒸发驱动聚氨酯链段相互靠近，完成聚氨酯涂层对纳米粒子的全包覆或半包覆，制得具有功能耐久性的聚氨酯仿皮涂层。
2.根据权利要求1所述的一种基于纳米粒子的聚氨酯仿皮涂层耐久性功能整理方法，其特征在于：所述纳米粒子为亲水性纳米粒子，其粒径为8～100nm。
3.根据权利要求1所述的一种基于纳米粒子的聚氨酯仿皮涂层耐久性功能整理方法，其特征在于：所述纳米粒子选自纳米氧化钛粒子、纳米氧化锌粒子、纳米硅胶粒子、羟基化碳纳米管粒子、羧基化碳纳米管粒子、纳米银粒子、纳米碱式硫酸铜粒子、纳米硫化铜粒子、纳米氧化铁粒子中的一种或多种。
4.根据权利要求1所述的一种基于纳米粒子的聚氨酯仿皮涂层耐久性功能整理方法，其特征在于：所述分散剂选自十二烷基苯磺酸钠、聚甲基丙烯酸、月桂醇醚磷酸酯、柠檬酸钠、聚乙烯毗咯酮、聚丙烯酰胺、脂肪醇聚氧乙烯醚、乙二胺四乙酸钠中的一种或多种。
5.根据权利要求1所述的一种基于纳米粒子的聚氨酯仿皮涂层耐久性功能整理方法，其特征在于：所述极性溶剂选自乙醇、乙二醇、丙二醇、丙三醇、异丙醇、水中的一种或多种。
6.根据权利要求1所述的一种基于纳米粒子的聚氨酯仿皮涂层耐久性功能整理方法，其特征在于：所述功能整理液为纳米粒子的分散液，纳米粒子的用量为极性溶剂的0.2～1wt％，分散剂的用量为极性溶剂的0.1～0.5wt％。
7.根据权利要求1所述的一种基于纳米粒子的聚氨酯仿皮涂层耐久性功能整理方法，其特征在于：所述铺展的水性聚氨酯涂层是由刮刀或丝棒刮涂制得，涂覆量为20～60g/m2。
8.根据权利要求1所述的一种基于纳米粒子的聚氨酯仿皮涂层耐久性功能整理方法，其特征在于：所述的水性聚氨酯选自水性聚氨酯9580C、水性聚氨酯H130D、水性聚氨酯2019B、水性聚氨酯209N、水性聚氨酯WPU-2426、水性聚氨酯AE-12、水性聚氨酯树脂AH-1618、水性聚氨酯树脂AH-1604F、水性聚氨酯树脂AH-1619、水性聚氨酯树脂AH-1605B、水性聚氨酯树脂AH-1739中的一种或多种。
9.根据权利要求1所述的一种基于纳米粒子的聚氨酯仿皮涂层耐久性功能整理方法，其特征在于：所述预热处理湿度为40％～80％，温度为30～50℃，时间为10～20min。
10.根据权利要求1所述的一种基于纳米粒子的聚氨酯仿皮涂层耐久性功能整理方法，其特征在于：所述热固化条件为60～80℃下焙烘20～40min。
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