壳聚糖荧光防伪印花涂料的制备及其应用性能  

Preparation and application properties of chitosan fluorescent anti-counterfeiting printing coating

作　　者：李曼丽 季志浩 龙柱 王益峰 金恩琪[3] LI Manli;JI Zhihao;LONG Zhu;WANG Yifeng;JIN Enqi(College of Textile Science and Engineering,Jiangnan University,Wuxi,Jiangsu 214122,China;Zhejiang Furun Co.,Ltd.,Shaoxing,Zhejiang 311800,China;Key Laboratory of Clean Dyeing and Finishing Technology of Zhejiang Province,Shaoxing University,Shaoxing,Zhejiang 312000,China)

机构地区：[1]江南大学纺织科学与工程学院,江苏无锡214122 [2]浙江富润数字科技股份有限公司,浙江绍兴311800 [3]绍兴文理学院浙江省清洁染整技术研究重点实验室,浙江绍兴312000

出　　处：《纺织学报》2024年第3期114-121,共8页Journal of Textile Research

基　　金：浙江省公益技术研究计划项目(LGG21E030005,LGG22E030002);浙江省清洁染整技术研究重点实验室开放基金项目(QJRZ1902);浙江省博士后科研择优资助项目(276089)。

摘　　要：为解决纺织品印染中常用有机荧光防伪印花涂料发光强度低、耐光漂白性弱等问题,以壳聚糖(CS)为生物基高分子涂料代表,采用不同物质的量的聚集诱导发光(AIE)分子四苯基乙烯(TPE)对CS进行荧光标记,制备出一系列具有不同标记率的TPE-CS荧光涂料。测定了TPE-CS防伪涂料的荧光强度、耐光漂白性、热稳定性等,并对棉织物进行防伪印花。结果表明:与目前较常用的聚集诱导荧光猝灭(ACQ)分子标记CS荧光涂料相比,TPE-CS显示出优异的荧光发射性能和耐光漂白性能;当TPE-CS的标记率仅为1.43%(摩尔分数)时,该防伪涂料溶液(1 000 mg/L)的相对荧光强度超过1 090;溶液在强紫外光下曝露1 h后,相对荧光强度仍能达到光漂白前的94.9%。Objective In order to tackle the low fluorescence intensity and photobleaching resistance of organic fluorescent anti-counterfeiting printing coatings commonly used in textile printing and dyeing industry,aggregation-induced emission(AIE)fluorophore-tetraphenyl ethylene(TPE)labeled chitosan(CS)fluorescent anti-counterfeiting coatings were prepared and their application properties were investigated.Method The typical AIE monomer-tetraphenyl ethylene-isothiocyanate(TPE-ITC)was synthesized initially.The TPE-ITC product was characterized by Fourier transform infrared spectroscopy(FT-IR)and MALDI-TOF mass spectrometry(MS).The study took CS as the representative of bio-based polymer paints,labeled different amounts of TPE fluorophores onto CS using the TPE-ITC as fluorescent monomers,and prepared a series of TPE-CS fluorescent paints with different degrees of labeling(DL).The series of TPE-CS products were characterized by FT-IR and 1H-nuclear magnetic resonance(1 H-NMR)to confirm the labeling of TPE fluorophores.Main application properties of the TPE-CS paints,such as fluorescence intensity,photobleaching resistance and thermal stability,were evaluated.Anti-counterfeit printing on cotton fabric was carried out using the TPE-CS coatings and the common color fastness of the printed fabric was tested systematically according to the national standards.Results FT-IR and MS spectra confirmed that the synthetic product was the expected AIE fluorescent monomer TPE-ITC.FT-IR and ^(1)H-NMR spectra proved that TPE fluorophores were successfully grafted onto the molecular chain of CS.The higher was the feed concentration of TPE-ITC monomers,the higher was the DL of TPE-CS.TGA thermograms illustrated that TPE-CS(DL of 2.56%)had nearly the same thermal stability with unlabeled CS.With the increase in the DL,the fluorescence intensity of TPE-CS showed a gradual increase,reflecting its unique AIE advantage.The TPE-CS coating was colorless and thus its printing pattern on the fabric had good concealment in the sunlight.On the contrary

关 键 词：四苯基乙烯 壳聚糖 荧光涂料 印花涂料 荧光发射性能 耐光漂白性能 热稳定性 荧光防伪印花 

分 类 号：TS194.2[轻工技术与工程—纺织化学与染整工程]