Department of Polymer Engineering , Sahand University of Technology , P.O. Box 51335-1996, Tabriz 51368 , Iran.
ACS Appl Mater Interfaces. 2018 Nov 14;10(45):39279-39292. doi: 10.1021/acsami.8b14865. Epub 2018 Oct 31.
Increase of safety in security documents by using anticounterfeiting inks based on fluorochromic and photochromic compounds has attracted a great deal of attention in the recent years. Herein, we developed novel functionalized stimuli-responsive latex particles containing spiropyran (1 wt %) by semicontinuous emulsifier-free emulsion polymerization, which are usable as anticounterfeiting inks for marking on security documents and also photopatterning on cellulosic papers. The size and morphology of the latex particles were characterized by scanning electron microscopy and dynamic light scattering and their functionality was characterized by Fourier-transform infrared spectroscopy. All the stimuli-responsive latexes are composed of spherical particles with different hydroxyl, epoxy, and carboxylic acid functional groups, and the size of the particles varies in the range of 400-900 nm. Additionally, the latex particles undergo a remarkable light-induced size variation (aggregation-disaggregation) upon UV illumination (365 nm), depending on the functional group type, as a result of π-π stacking interactions and also electrostatic attractions between the different particles. The photochromic behavior, kinetics of the SP ⇌ MC isomerization, photoswitchability, and photofatigue-resistant characteristics of the prepared latexes were extensively investigated. The results display that the photochromic behavior and SP ⇌ MC isomerization can significantly be influenced by the polar interactions between the functional groups and MC molecules. As a novel application, the prepared stimuli-responsive latexes were used as anticounterfeiting inks for writing on cellulosic paper and also security marking on several monies, where the written phrase displayed red fluorescence emission and coloration under and after UV illumination (365 nm), respectively. Additionally, the latexes were sprayed on cellulosic papers to prepare stimuli-responsive papers for investigation of their photopatterning ability under UV irradiation and different masking. The presence of functional groups and large particle sizes are the main effective factors for stabilization of the latex particles on cellulosic papers. This is the first report on application of functionalized stimuli-responsive latex particles containing spiropyran as anticounterfeiting inks for security marking and photopatterning on cellulosic papers, directly and without using further additives.
近年来,基于荧光和光致变色化合物的防伪油墨在安全文件中的应用安全性得到了极大的关注。在此,我们通过半连续无乳化剂乳液聚合方法开发了含有螺吡喃(1wt%)的新型功能化刺激响应乳胶粒子,可用作安全文件上的防伪油墨,也可用作纤维素纸上的光图案化。通过扫描电子显微镜和动态光散射对乳胶粒子的尺寸和形态进行了表征,并通过傅里叶变换红外光谱对其功能进行了表征。所有刺激响应乳胶均由具有不同羟基、环氧和羧酸官能团的球形粒子组成,粒径范围为 400-900nm。此外,乳胶粒子在紫外光(365nm)照射下会发生显著的光诱导粒径变化(聚集-解聚集),这取决于官能团类型,这是由于不同粒子之间的π-π堆积相互作用和静电吸引力。对制备的乳胶的光致变色行为、SP ⇌ MC 异构化动力学、光致开关性和光耐疲劳特性进行了广泛研究。结果表明,功能基团与 MC 分子之间的极性相互作用对光致变色行为和 SP ⇌ MC 异构化有显著影响。作为一种新的应用,制备的刺激响应乳胶被用作纤维素纸上的防伪油墨,也可用于几种货币上的安全标记,在紫外光(365nm)照射下和之后,所写的短语分别显示红色荧光发射和着色。此外,将乳胶喷涂在纤维素纸上,以制备刺激响应纸,研究其在紫外光照射下和不同掩蔽条件下的光图案化能力。功能基团和大粒径是乳胶粒子在纤维素纸上稳定存在的主要影响因素。这是首次报道将含有螺吡喃的功能化刺激响应乳胶粒子用作纤维素纸上的防伪油墨进行安全标记和光图案化,无需使用进一步的添加剂即可直接应用。