ABSTRACT
Increasing the security by the multilevel authentication mechanism was the most significant challenge in recent years for the development of anticounterfeiting inks based on photoluminescent nanomaterials. For this purpose, the greatest strategy is the use of multicomponent organic materials and a combination of Förster resonance energy transfer (FRET) with the intelligent behavior of photochromic compounds like spiropyran. Here, the hydroxyl-functionalized polymer nanoparticles were synthesized by emulsion copolymerization of methyl methacrylate (MMA) and 2-hydroxyethyl methacrylate (HEMA) in different compositions (0-30 wt % of HEMA). Results illustrated that the size of the nanoparticles changed from 64 to 204 nm, and a morphology evolution from spherical to Janus shape was observed by increasing the concentration of HEMA. Photoluminescent inks with red, green, and blue (RGB) fluorescence emissions were prepared by modification of nanoparticles containing 15 wt % of HEMA with spiropyran, fluorescein, and coumarin, respectively. To develop dual-color and multicolor photoluminescent inks that display static and dynamic emission, RGB latex samples were mixed together in different ratios and printed on cellulosic paper. Results display that the fluorescence emission of developed inks can be photoswitched between different statuses, including white to blue, green to blue, green to red/orange, purple to pink, and white to pink, utilizing the FRET phenomenon, photochromism, and a combination of both phenomena. Samples containing spiropyran displayed dynamic color changes in the emission to red, orange, and pink depending on the composition. Hence, developed dual-color and multicolor photoluminescent inks were used for printing of security tags and also painting of some hand-drawn artworks, which obtained results indicating high printability, maximum fluorescence intensity, high resolution, and fast responsivity upon UV-light irradiations of 254 nm (for static mode) and 365 nm (for dynamic mode). In addition, the multilevel authentication mechanism by a static emission under UV-light irradiation of 254 nm, a dynamic emission under UV-light irradiation of 365 nm, and photochromic color change was observed, resulting in increasing the security of developed inks. Actually, developed multicolor photoluminescent inks are the most efficient candidates for developing a new category of chameleon-like high-security anticounterfeiting inks that have tunable optical properties and complex multilevel authentication mechanisms.
ABSTRACT
Increasing the security of anticounterfeiting materials has been the most important challenge in recent years, and the development of dual-color photoluminescent inks with multi-level security, static/dynamic emission, and dynamic color change is an important solution to overcome this problem. In this study, the multi-functionalized copolymer nanoparticles containing different functional groups (with a concentration of 20 wt %), including ester, carboxylic acid, hydroxyl, epoxide, amide, and amine groups were synthesized successfully by the emulsion polymerization method. The results showed that the particle size and morphology of nanoparticles are affected by the polarity of functional groups. The prepared multi-functionalized copolymer nanoparticles were modified physically with spiropyran (photochromic and red fluorescence emission) and coumarin (cyan emission) derivatives to develop dual-color photoluminescent polymer nanoparticles with application in static-dynamic photoluminescent anticounterfeiting inks, which have multi-level security. The investigation of optical properties indicates that the kinetics of photochromism and photoluminescence properties of samples containing spiropyran is dependent on the local polarity on the surface of polymer nanoparticles. Hence, an increase in the polarity (functionalization with amide, carboxylic acid, and hydroxyl groups) has resulted in fast photochromism, high-intensity photoluminescence emission and increased the efficiency of the photoswitchable color change of emission from cyan to pink. Dual-color photoluminescent anticounterfeiting inks were prepared by mixing polymer nanoparticles containing spiropyran with polymer nanoparticles containing coumarin, in different ratios (1:1, 1:3, 1:5, 1:8, and 1:10). Obtained results showed that prepared samples have cyan emission under UV light of 254 nm (static mode), and a dynamic photoswitching of fluorescence emission from cyan to pink (as a function of irradiation time) was also observed under UV-light irradiation of 365 nm, which is well known as a dynamic mode of emission. The responsivity and intensity of dynamic photoluminescence emission are dependent on the local polarity of the surface functional groups, in which the samples based on amide functionalized copolymer nanoparticles displayed high-intensity emission in the static mode and high-intensity photoswitchable dual-color emission in the dynamic mode, in the case of all ratios of colloid solution mixtures. Printing security tags on cellulose paper by dual-color photoluminescent inks indicates advantages such as maximum printability, resolution, brightness, and static-dynamic photoluminescence emission with high intensity for inks based on amide functionalized nanoparticles. The static-dynamic dual-color photoluminescent anticounterfeiting ink with unique properties and multi-level security was reported for the first time by the collaboration of spiropyran and coumarin. This study can open a new approach and window to the future of advanced and high-security anticounterfeiting technologies.
