CN-118085641-B - Water-based rare earth complex invisible fluorescent ink capable of being printed by ink jet, photon glass, and preparation method and application thereof

Abstract

The invention relates to an ink-jet printable aqueous rare earth complex invisible fluorescent ink, photon glass, and a preparation method and application thereof. Firstly adding microspheres into a rare earth complex solution for ultrasonic oscillation and then centrifuging to obtain aqueous rare earth complex photonic glass, wherein ligands in the rare earth complex are selected from potassium hydrogen tris (3-phenyl-5-methylpyrazole-1-yl) borate, bipyridine, 2-phenylpyridine, 4-trifluoro-1- (2-thienyl) -1, 3-butanedione, 4-trifluoro-1- (2-furyl) -1, 3-butanedione, 4-dibromo-bipyridine, terpyridine and phenanthroline. Then the obtained aqueous rare earth complex photon glass is ultrasonically dispersed in water to obtain a solution, namely the aqueous rare earth complex invisible fluorescent ink which can be used for ink-jet printing and can be applied to the fields of information encryption, optical anti-counterfeiting or specific identification. The preparation method is simple and convenient, the raw materials are cheap and easy to obtain, expensive instruments are not needed, the cost is low, and the method is suitable for industrial preparation and has good practical popularization and application values.

Inventors

• HONG WEI
• Mo Wanqi
• ZHENG YUEWEI

Assignees

• 中山大学

Dates

Publication Date

20260512

Application Date

20240129

Claims (8)

1. 1. The preparation method of the water-based rare earth complex photonic glass capable of being subjected to ink-jet printing is characterized by adding microspheres into a rare earth complex solution for ultrasonic oscillation, and then centrifuging to obtain the water-based rare earth complex photonic glass; The rare earth complex is any one of di [ potassium hydrogen tris (3-phenyl-5-methylpyrazol-1-yl) borate ] cerium (III), (bipyridine) di [ 2-phenylpyridine ] terbium (III), (4, 4-dibromo-bipyridine) tris [4, 4-trifluoro-1- (2-thienyl) -1, 3-butanedione ] europium (III), (phenanthroline) tris [4, 4-trifluoro-1- (2-furyl) -1, 3-butanedione ] europium (III) and di [ terpyridine ] dysprosium (III), and the mass ratio of the microsphere to the rare earth complex is1 (0.005-0.2); The microsphere is a submicron polymer microsphere with a cross-linked structure.
2. 2. The method of claim 1, wherein the ultrasound is at a frequency of 20-60 KHz for 1-3 hours.
3. 3. The method according to claim 1, wherein the shaking is shaking at a rotational speed of 30-70 r/min for 20-28 hours.
4. 4. The aqueous rare earth complex photonic glass prepared by the preparation method of any one of claims 1-3.
5. 5. An ink-jet printable invisible fluorescent ink of an aqueous rare earth complex, which is characterized by comprising the aqueous rare earth complex photonic glass solution of claim 4.
6. 6. The invisible fluorescent ink of claim 5, wherein the solvent is water and the mass to volume ratio of the photonic glass of the aqueous rare earth complex to the water is (0.001-0.1): 1.
7. 7. The application of the aqueous rare earth complex photon glass of claim 4 or the aqueous rare earth complex invisible fluorescent ink of claim 5 in the field of information encryption or specific identification.
8. 8. The use of claim 7, wherein the specific identification comprises optical security.

Description

Water-based rare earth complex invisible fluorescent ink capable of being printed by ink jet, photon glass, and preparation method and application thereof Technical Field The invention belongs to the technical field of optical anti-counterfeiting ink. More particularly, relates to an ink-jet printable invisible fluorescent ink of an aqueous rare earth complex, an aqueous rare earth complex photon glass, and a preparation method and application thereof. Background The adoption of advanced technologies that are simple, economical and have good security capabilities in information storage/transmission, product authentication and tamper detection is an increasingly serious challenge facing the research community. The anti-counterfeit labels with various fluorescent colors play an important role in information encryption and decryption, and the fluorescent ink anti-counterfeit technology is adopted for paper money, tickets and trademarks in various countries due to the advantages of simple operation, low cost, convenient inspection, strong reproducibility and the like. The invisible ink belongs to one of anti-counterfeiting ink, has the characteristics of better concealment and stronger anti-counterfeiting force, and has been widely applied to anti-counterfeiting printing of various tickets, documents, trademarks, logos and the like. In recent years, various materials including small molecular fluorescent substances, rare earth oxides, rare earth complexes, carbon dots and the like are widely applied to invisible anti-counterfeiting printing ink. Compared with invisible fluorescent substances such as small molecular fluorescent substances, carbon dots and the like, the rare earth complex has the advantages of large Stokes shift, weak visible light absorption and high quantum efficiency, and compared with inorganic luminescent powder of rare earth oxide, the rare earth complex has the advantages of being capable of being dissolved and high in compatibility with printing modes. However, the level of security provided by a single fluorescent property is still very limited. Photon glass refers to a material capable of generating non-rainbow coherent scattering, compared with rainbow structural colors generated by photon crystals, gratings and liquid crystals, the photon glass has special non-rainbow structural color characteristics, and structural resonance changes along with the included angle between the incidence direction and the observation direction so as to respectively show angle dependence and structural colors without angle dependence. However, a series of problems exist in the application of single photon glass material in anti-counterfeiting, such as easy cracking of anti-counterfeiting information, low information content and the like. However, no report is made on the realization of high-safety anti-counterfeiting application by compounding the photonic glass with the rare earth complex luminescent substances and applying the structural color characteristics and the fluorescence luminescence characteristics of the photonic glass, and in addition, the water-based rare earth complex photonic glass ink which is simple to prepare, low in cost and suitable for industrial preparation and can be printed by ink-jet printing is lacking in the market. Disclosure of Invention The invention aims to provide ink capable of being printed by ink jet, which has a rare earth fluorescence effect and a structural color effect. The submicron polymer microsphere with a certain crosslinking structure is prepared, the crosslinking structure and the size are precisely controlled, the permeability of the rare earth complex is adjusted, and the ultraviolet excited multicolor fluorescent submicron photon glass is realized by doping different rare earth complexes. The first object of the invention is to provide a preparation method of rare earth complex photonic glass capable of being printed by ink jet. The second purpose of the invention is to provide the rare earth complex photon glass prepared by the preparation method. The third purpose of the invention is to provide an ink-jet printing invisible photonic glass anti-counterfeiting ink. The fourth purpose of the invention is to provide the application of the rare earth complex photon glass and the ink-jet printing invisible photon glass anti-counterfeiting ink. The above object of the present invention is achieved by the following technical scheme: The invention provides a preparation method of rare earth complex photon glass capable of being printed by ink jet, which comprises the steps of adding microspheres into rare earth complex solution for ultrasonic oscillation, enabling the rare earth complex to be spontaneously doped into the microspheres by a solid phase extraction method, and obtaining the rare earth complex photon glass after centrifugation; Preferably, the ligand in the rare earth complex is any one or more of potassium hydrogen tris (3-phenyl-5-methylpyrazol-1-y