基于光固化墨水体系的反应型有机颜料结构构筑及其共价锚固机制

Photo-curing pigment digital ink-jet printing is a promising new technology nowadays. However, the common problems exist as the traditional pigment ink-jet printing: the poorer crock-fastness and washing-fastness due to the lack of high bonding strength between adhesive and pigment that was physically fixed in the curing film. To solve the problem, the vinyl double bonds were introduced onto the surface of the organic pigment, participating in the polymerization of bule-light curing system. The pigment would be anchored by covalent bonds in the integrated pigment-polymer film. Phthalocyanine blue was selected as the representative organic pigment. A series of reactive organic pigment with various grafting conditions were prepared via encapsulation and then grafting methods. The effects of grafting conditions (such as structure of graft chain, grafting ratio, grafting density and so on) on the polymerization properties of blue-light curing system were illuminated. The covalent bonding degrees between vinyl double bond under different grafting conditions and oligomer/monomer were clarified. The dispersed phase diagrams of reactive organic pigments in the color film were constructed. The relations among the grafting conditions of organic pigment, covalent bonding degrees and color film properties were revealed. The studies would provide not only new ideas and new methods for the modification of organic pigment, but also theoretical basis for covalent anchoring mechanism of reactive organic pigment.

光固化颜料数码喷墨印花技术是当今极具发展潜力的新技术。但是，该技术存在常规颜料喷墨印花的共性问题：有机颜料与高分子成膜物质之间缺乏牢固的结合力，仅依靠高分子成膜物质的物理包覆而固着，易造成印花织物的耐摩擦和耐水洗色牢度不佳。针对此问题，本课题将烯双键引入有机颜料表面，使其参与蓝光引发聚合固化反应以“共价键锚固”，形成有机颜料-高分子一体化色膜。拟选用酞菁蓝为代表性的蓝光固化颜料体系，采用包覆-接枝两步法，制备一系列表面接枝状态可单一调控的烯双键反应型有机颜料；阐明有机颜料表面接枝状态(接枝链结构、接枝率和接枝密度等)对蓝光固化体系聚合性能的影响规律以及不同接枝状态下烯双键与低聚物/单体的共价键合程度；构筑反应型有机颜料在色膜内的分散相图；揭示有机颜料表面接枝状态－共价键合程度－色膜性能的关系。研究成果不仅可为有机颜料的改性提供新思路和新方法，还可为反应型有机颜料的共价锚固机制提供理论依据。

光固化颜料数码喷墨印花技术存在常规颜料喷墨印花的共性问题：颜料仅依靠高分子成膜物质的物理包覆而固着，易造成印花织物的耐摩擦和耐水洗色牢度欠佳。项目创新性地提出构筑反应型颜料的新思路：将烯双键引入颜料粒子表面，使其参与蓝光引发聚合固化反应以“共价键锚固”于高分子交联网络结构中，形成牢固的颜料-高分子一体化色膜。主要研究内容包括：（1）反应型颜料的结构设计与可控构筑；（2）反应型颜料表面修饰状态与蓝光固化墨水性能的相关性研究；（3）蓝光固化反应型颜料墨水体系的印制特性研究。研究结果表明：反应型颜料构筑的一步法优化工艺为去离子水用量7mol/L，氨水用量0.15g，偶联剂KH570用量3×10-2mol/L；两步法优化包覆工艺为去离子水与乙醇的体积比1:16，pH 10，正硅酸乙酯与酞菁蓝颜料质量比0.8:1；与一步法相比，两步法可有效调控反应型颜料的表面修饰状态，且所制备的反应型颜料粒径相对较小，蓝光固化墨水的聚合性能和固化膜的物理机械性能均得以进一步提升；硅烷偶联剂溶剂化链链长及有机官能团类型决定了改性后颜料在蓝光固化墨水体系中的分散稳定性，链长对蓝光固化体系聚合性能影响较小，但链长太短会对固化膜性能造成负面影响；当颜料表面修饰基团为可参与聚合的双键或具有助引发作用的氨基时，有助于墨水聚合性能及固化膜物理机械性能的提升；随着KH570用量的增加，反应型颜料表面接枝率增加，蓝光固化墨水的各项性能均得以提升；蓝光固化反应型颜料墨水的优化配方为CQ/EDB=1%/1%、PUA/IBOA/HEA=60wt%/30wt%/10wt%、反应型颜料浓度0.5-2%，光照条件为光强大于16.9mW/cm2、光照时间5min、喷印压强20-100KPa，在模拟喷印设备上喷印流畅，印制织物的花纹轮廓清晰，颜色鲜艳，得色均匀，印制部位的手感柔软，耐干、湿摩擦色牢度均比未改性颜料的高0.5-1级。研究成果为颜料的改性提供了新思路和新方法，对解决颜料印花耐摩擦和耐水洗色牢度差的问题和推动颜料数码喷墨印花技术的发展具有重要的理论意义和实用价值。