CN108410266B - Novel invisible anti-counterfeiting two-dimensional code based on nano metal organic framework material - Google Patents
Novel invisible anti-counterfeiting two-dimensional code based on nano metal organic framework material Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/50—Sympathetic, colour changing or similar inks
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G83/008—Supramolecular polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/36—Inkjet printing inks based on non-aqueous solvents
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- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06K—GRAPHICAL DATA READING; PRESENTATION OF DATA; RECORD CARRIERS; HANDLING RECORD CARRIERS
- G06K19/00—Record carriers for use with machines and with at least a part designed to carry digital markings
- G06K19/06—Record carriers for use with machines and with at least a part designed to carry digital markings characterised by the kind of the digital marking, e.g. shape, nature, code
- G06K19/06009—Record carriers for use with machines and with at least a part designed to carry digital markings characterised by the kind of the digital marking, e.g. shape, nature, code with optically detectable marking
- G06K19/06037—Record carriers for use with machines and with at least a part designed to carry digital markings characterised by the kind of the digital marking, e.g. shape, nature, code with optically detectable marking multi-dimensional coding
Abstract
A novel invisible anti-counterfeiting two-dimensional code based on a nano metal organic framework material. The novel invisible anti-counterfeiting two-dimensional code is formed by printing nano metal organic framework material ink into invisible coding blocks with adjustable quantity and equal size and three black vertex positioning blocks, and the fluorescent color of the coding blocks under the excitation of specific wavelength is used as an information storage unit. The fluorescent color of the coding block bears coding information, and almost infinite fluorescent colors can be obtained by mixing tricolor fluorescent emission ink through an ink-jet printer, so that infinite coding information is realized. Also, the size of the coded information capacity can be achieved by adjusting the number of coding blocks of a unit. In order to realize the novel invisible anti-counterfeiting two-dimensional code, the preparation of nano invisible ink with three primary colors and fluorescence emission is required; meanwhile, the three primary colors and the mixed color ink thereof do not display colors under sunlight, and emit fluorescence of different colors under the excitation of single-wavelength light.
Description
Technical Field
The invention belongs to the field of application of ink-jet printing invisible anti-counterfeiting two-dimensional codes, and particularly relates to an anti-counterfeiting code based on fluorescence color as information storage content. The content relates to preparation of tricolor fluorescence emission ink under single excitation, and the full-color ink-jet printing of the invisible fluorescence anti-counterfeiting two-dimensional code is realized according to the tricolor principle.
Background
Counterfeiting has become a global problem threatening business, government, finance and even human health. Therefore, there is an urgent need to develop anti-counterfeit technologies that are difficult to copy and easy to authorize to protect important documents, luxury goods, money, drugs, certificates, etc. In recent years, two-dimensional codes based on photolithography, laser engraving, screen printing, and inkjet printing have been applied to marking and forgery prevention. Among them, the ink jet printing technology is widely used due to its remarkable advantages of strong designability, low cost, high yield, simple and convenient fabrication, etc. The two-dimensional code is a kind of data symbol information recorded by black and white patterns distributed on a plane (two-dimensional direction) according to a certain rule by using a certain specific geometric figure, and has the characteristics of large information capacity, high reliability, easy manufacture, low cost and the like, thereby being widely used. Meanwhile, due to the defects that the existing visible two-dimensional code is easy to copy, and is easy to be loaded with trojan viruses by criminals, the security of the two-dimensional code faces a great challenge. Therefore, the development of encrypted two-dimensional codes is a problem to be solved urgently at present. To solve this problem, it has been reported that two-dimensional code encryption is performed by modifying fluorescent organic dyes, quantum dots, up-conversion nanoparticles, and the like.
Currently, the fluorescent anti-counterfeiting two-dimensional codes have the following types: rare earth metal up-conversion nanoparticles, which are a luminescent material with adjustable fluorescence, high resolution and strong light stability, such as 1) Meraga, J.M., Baride, A., Cross, W., Kellar, J.J & May, P.S.Red-green-blue printing using luminescence-conversion inks. journal of Materials Chemistry C2014, 2,2221, are complex and difficult to overcome, and require a long wavelength laser which is difficult to use in daily life; carbon Dots or quantum Dots or fluorescent organic dyes are easy to prepare, e.g., 2) Jiang, K.et al.triple-Mode Emission of Carbon Dots for Applications for Advanced Anti-coupling.Angewandte Chemie 2016,55, 7231-7235; 3) hou, X. et al. tunable solid-state fluorescent materials for supra molecular encryption. Nature Communications 2015,6, 6884; 4) kumar, P., Singh, S. & Gupta, B.K. future projections of fluorescent based security inputs from synthesis to anti-calibration applications, Nanoscale 2016,8, 14297-. However, such materials have limitations in the emission wavelength and are prone to photobleaching. The materials are complex to synthesize and complicated in steps, and the application of the materials in ink-jet printing of anti-counterfeiting two-dimensional codes is limited. Therefore, the development and synthesis of the nano fluorescent material which is simple, high in luminous intensity, strong in light stability and easy to obtain in excitation wavelength for the ink-jet printing of the anti-counterfeiting two-dimensional code has important academic value and practical application significance.
The invention aims to develop a novel invisible anti-counterfeiting two-dimensional code which is high in anti-counterfeiting degree and simple to operate. The method is characterized in that a red, green and blue three-primary-color fluorescent nano metal organic frame material which is simple to synthesize and high in universality is used as an ink raw material, fluorescent colors are used as a signal storage unit, information storage is realized through design and arrangement of the fluorescent colors of coding blocks of the storage unit, and two-dimensional code information extraction is realized through single-wavelength excitation of an ultraviolet lamp. The fluorescent invisible anti-counterfeiting two-dimensional code provided by the invention fully utilizes the characteristics of proper size, tricolor fluorescence emission and single excitation wavelength of a nano metal organic framework material, and realizes multiple anti-counterfeiting functions of the novel invisible two-dimensional code through ink-jet printing.
Disclosure of Invention
Aiming at the problems, the invention provides a novel encrypted anti-counterfeiting two-dimensional code taking the fluorescent color as a signal identification unit. The novel two-dimensional code is composed of invisible coding blocks with equal size and adjustable quantity and three black vertex positioning blocks, and the fluorescent color of each invisible coding block bears one piece of coding information. The novel encrypted anti-counterfeiting two-dimensional code only displays the black positioning block under sunlight, realizes information decryption under the excitation of ultraviolet light with specific wavelength, and displays the coded information which is the same as the input information. The single-excited three-primary-color invisible fluorescent nano MOFs is designed and synthesized, and is modified to prepare three-primary-color ink suitable for ink-jet printing, and invisible anti-counterfeiting two-dimensional codes or multiple applications of personalized anti-counterfeiting are developed.
The technical scheme of the invention is as follows:
the novel encrypted anti-counterfeiting two-dimensional code takes the fluorescence color as a signal identification unit. The novel two-dimensional code is composed of invisible coding blocks with equal size and adjustable quantity and three black vertex positioning blocks, and the fluorescent color of each invisible coding block bears one piece of coding information. And only the black positioning block is displayed under sunlight, information decryption is realized under the excitation of ultraviolet light with specific wavelength, and the coded information which is the same as the input information is displayed.
The novel encrypted anti-counterfeiting two-dimensional code is a novel invisible anti-counterfeiting two-dimensional code based on nanometer metal organic framework material fluorescent ink. The preparation steps of the ink are as follows:
1) adding anhydrous lanthanide chloride, 1, 3-terephthalic acid and 3, 5-dicarboxyphenylboronic acid into N, N-dimethylformamide and water, and ultrasonically dissolving for 10min to obtain a uniform and transparent mixed solution;
2) adding the mixed solution into a polytetrafluoroethylene inner container, sleeving the polytetrafluoroethylene inner container into a reaction kettle, putting the reaction kettle into an oven, heating the mixture at 120 ℃ for reaction for 6 hours to obtain a reaction solution, and separating out white precipitate at the bottom;
3) centrifuging the precipitate and the supernatant, washing with N, N-dimethylformamide and ethanol for 2 times respectively, and drying to obtain nanometer metal organic framework material Ln-NMOFs;
in one embodiment, the anhydrous lanthanide chloride is europium chloride, resulting in Eu-NMOFs that fluoresces red when irradiated with 275nm laser light;
in one embodiment, the anhydrous lanthanide chloride is terbium chloride, and Tb-NMOFs is obtained and shows green fluorescence under the irradiation of laser with the wavelength of 275 nm;
in one embodiment, the anhydrous lanthanide chloride is dysprosium chloride to obtain Dy-NMOFs which exhibit blue fluorescence under the irradiation of laser with the wavelength of 275 nm;
the dosage ratio of the anhydrous lanthanide chloride, the 1, 3-terephthalic acid, the 3, 5-dicarboxyphenylboronic acid, the N, N-dimethylformamide and the water is 0.02mmol:0.01mmol:0.01mmol:7mL:3 mL.
Uio-66-NH2The synthesis of (a) is as follows:
1) adding 77mg of zirconium chloride, 48mg of amino terephthalic acid and 600mg of benzoic acid into 6mL of N, N-dimethylformamide and 55L of HCl, and ultrasonically dissolving for 10min to obtain a uniform and transparent mixed solution;
2) adding the mixed solution into a reaction kettle with a 30mL polytetrafluoroethylene inner container, putting the reaction kettle into an oven, and heating and reacting the mixture for 24 hours at 120 ℃ to obtain reaction liquid with white precipitate at the bottom;
3) centrifuging the precipitate and the supernatant, washing with N, N-dimethylformamide and ethanol for 2 times, and freeze drying to obtain nanometer metal organic skeleton material Uio-66-NH emitting stronger blue fluorescence2；
The modification preparation steps of the invisible fluorescent ink are as follows:
A) the dried fluorescent NMOFs material was added to ethanol and ultrasonically dispersed for 15min and stirred at room temperature for 0.5 h.
B) Adding ink solvent including ethylene glycol, glycerol, diethylene glycol, and surfactant SDS, ultrasonic treating for 15min, and rapidly stirring at room temperature for 2 hr.
In one embodiment, in step A), Eu-NMOFs powder is 20mg, and ethanol is 450L; in step B), ethylene glycol was 450L, glycerin was 50L, diethylene glycol was 50L, and surfactant SDS (3mg/mL) was 500L.
In one embodiment, in step a), the Tb-NMOFs powder is 10mg, and the ethanol is 450L; in step B), ethylene glycol was 450L, glycerin was 50L, diethylene glycol was 50L, and surfactant SDS (3mg/mL) was 500L.
In one embodiment, Uio-66-NH is added in step A)230mg of powder and 450L of ethanol; in step B), ethylene glycol was 450L, glycerin was 50L, diethylene glycol was 50L, and surfactant SDS (3mg/mL) was 500L.
The synthesized tricolor fluorescence emission ink is respectively filled in an ink box of an ink-jet printer, the preset color anti-counterfeiting two-dimensional code is printed on A4 paper, the ink is smoothly discharged in the printing process, no blockage occurs, the A4 paper is placed under an ultraviolet light source with the wavelength of 275nm, the color fluorescence two-dimensional code can be clearly seen, and the imaging is accurate.
The synthesized nano metal organic framework material respectively emits red, green and blue tricolor fluorescence, and the tricolor fluorescence ink for ink-jet printing is prepared by modifying the three materials. The novel anti-counterfeiting two-dimensional code with the fluorescent color as the signal identification unit is provided, one fluorescent color corresponds to one piece of coded information, rich stored information can be obtained through mixed printing of three primary colors, the anti-counterfeiting function is realized, and the invisible anti-counterfeiting function is realized because the color of ink under sunlight is nearly colorless. In addition, the information capacity of the two-dimensional code can be adjusted by designing the number of the color information unit blocks in the two-dimensional code.
The invention has the advantages that: the fluorescent color is used as a signal identification unit to realize multiple anti-counterfeiting functions of two-dimensional code position and information, and the invisible anti-counterfeiting ink is prepared by a one-pot solvothermal method, and has the advantages of simple process, low cost and easy implementation. The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, and therefore should not be construed as limiting the scope of the present invention. On the premise of the conception of the invention, any coding mode for realizing the invisible anti-counterfeiting two-dimensional code by using the tricolor fluorescent ink belongs to the protection scope of the invention.
Drawings
Fig. 1 is a design schematic diagram of a novel invisible anti-counterfeiting two-dimensional code, wherein: a is a schematic diagram of the preparation process of the nanometer MOFs ink respectively emitting red, green and blue tricolor fluorescence; b is a schematic diagram of the ink-jet printer cartridge refitting process; c is a printing process schematic diagram; and D is a schematic diagram of the encryption and decryption processes of the printed anti-counterfeiting information.
FIG. 2 is a scanning electron microscope image of lanthanide series nano MOFs as a matrix material of three primary colors ink, wherein: a is Eu-NMOFs emitting red fluorescence; b is Tb-NMOFs emitting green fluorescence; c is Dy-NMOFs emitting blue fluorescence; the inset is the corresponding transmission electron micrograph.
Fig. 3 is a graph showing the luminescence property of a three primary color ink matrix material, wherein: a is a fluorescence emission diagram of Eu-NMOFs emitting red fluorescence under the excitation of 275nm wavelength; b is a fluorescence emission diagram of Tb-NMOFs emitting green fluorescence under 275nm excitation; c is a fluorescence emission diagram of blue fluorescence Dy-NMOFs under 275nm excitation; d is the position of the emission colors of the three fluorescent MOFs in the CIE.
FIG. 4 is a diagram of the emission spectra and the coordinate positions in CIE of Eu-NMOFs, Tb-NMOFs and Dy-NMOFs mixed in pairs of 1:0,1:2,1:1,2:1,0:1, respectively, in which: a is a luminescence spectrum diagram of mixed red fluorescent ink Eu-NMOFs and green fluorescent ink Tb-NMOFs; b is a luminescence spectrum diagram of the mixed red fluorescent ink Eu-NMOFs and blue fluorescent ink Dy-NMOFs; c is a luminescence spectrum diagram of the mixed green fluorescent ink Tb-NMOFs and blue fluorescent ink Dy-NMOFs; d is a coordinate diagram of the mixed light emission spectrum in CIE.
FIG. 5 shows three primary color inks Eu-NMOFs, Tb-NMOFs and Uio-66-NH2The light emission spectra obtained after mixing two by two according to the ratio of 1:0,1:2,1:1,2:1,0:1 and a coordinate position diagram in CIE, wherein: a is a luminescence spectrum diagram of mixed red fluorescent ink Eu-NMOFs and green fluorescent ink Tb-NMOFs; b is a luminescence spectrum diagram of the mixed red fluorescent ink Eu-NMOFs and blue fluorescent ink Dy-NMOFs; c is a luminescence spectrum diagram of the mixed green fluorescent ink Tb-NMOFs and blue fluorescent ink Dy-NMOFs; d is a coordinate diagram of the mixed light emission spectrum in CIE.
FIG. 6 shows the emission spectra and CIE coordinate positions obtained by mixing the red fluorescent ink Eu-NMOFs and the green fluorescent ink Tb-NMOFs at a ratio of 1:0,0:1, 1:1,1:1.001,1:1.01,1:1.1,1:2,1:1.3,1:1.4 and 1:1.5, respectively.
Table 1 shows the coordinate positions of the mixed emission spectra of the red fluorescent ink Eu-NMOFs and the green fluorescent ink Tb-NMOFs in CIE according to the ratio of 1:0,0:1, 1:1,1:1.001,1:1.01,1:1.1,1:2,1:1.3,1:1.4 and 1:1.5, respectively.
Fig. 7 is a diagram of writing effect of a pen core made of tricolor ink, wherein: A. b is Eu-NMOFs, Tb-NMOFs and Uio-66-NH respectively2The ink is filled in the refill to make a picture of the fountain pen under a fluorescent lamp and an ultraviolet lamp; C. d is respectively red fluorescent ink Eu-NMOFs, green fluorescent ink Tb-NMOFs and blue fluorescent ink Uio-66-NH2Photographs of the acronyms "N", "K", "U" written "Nankai University" under fluorescent light and ultraviolet light, respectively; and E is the surface appearance of the square frame in the picture C under a scanning electron microscope, and uniform and complete particles of the nano MOFs can be clearly seen.
FIGS. 8A-C are photographs of a two-dimensional code printed under fluorescent light and under a 275nm UV lamp, illustrating the pattern of the input two-dimensional code; FIG. 8D is a bar code designed to identify the color and location of the fluorescence as information under excitation by fluorescent and ultraviolet lamps. FIG. 8E shows the information printed on RMB under the fluorescent lamp and UV lamp, respectively, for a designed heart and crescent overlay.
Detailed Description
Example (b):
the preparation method comprises the steps of preparing the nano metal organic framework material emitting red, green and blue fluorescence, modifying the nano metal organic framework material to prepare the three-primary-color ink suitable for ink-jet printing, and using the fluorescence color as a novel two-dimensional code anti-counterfeiting technology of a signal identification unit.
The novel two-dimensional code is a novel encrypted anti-counterfeiting two-dimensional code taking fluorescent color as a signal identification unit and comprises invisible coding blocks with equal size and adjustable quantity and three black vertex positioning blocks. The color of the fluorescence of each invisible coding block carries one piece of coding information. The novel encrypted anti-counterfeiting two-dimensional code only displays the black positioning block under sunlight, realizes information decryption under the excitation of ultraviolet light with specific wavelength, and displays the coded information which is the same as the input information.
The novel encrypted anti-counterfeiting two-dimensional code is a novel invisible anti-counterfeiting two-dimensional code based on nanometer metal organic framework material fluorescent ink. The nano metal organic framework material is prepared by a hydrothermal method, and comprises the following steps:
1) 0.02mmol of lanthanide chloride (EuCl)3，TbCl3And DyCl3) Adding 0.01mmol of 1, 3-terephthalic acid and 0.01mmol of 3, 5-dicarboxyphenylboronic acid into 7mLN, N-dimethylformamide and 3mL of water, and ultrasonically dissolving for 10min to obtain a uniform and transparent mixed solution;
2) adding the mixed solution into a reaction kettle with a 30mL polytetrafluoroethylene inner container, putting the reaction kettle into an oven, and heating and reacting for 6 hours at 120 ℃ to obtain reaction liquid with white precipitate at the bottom;
3) centrifugally separating the precipitate from the supernatant, washing the precipitate with N, N-dimethylformamide and ethanol for 2 times respectively, and finally freeze-drying to obtain nano metal organic framework materials Ln-NMOFs which respectively emit red, green and blue fluorescence;
in one embodiment, the anhydrous lanthanide chloride is europium chloride, resulting in Eu-NMOFs 1, which fluoresces red under 275nm laser irradiation;
in one embodiment, the anhydrous lanthanide chloride is terbium chloride, and Tb-NMOFs 2 is obtained and shows green fluorescence under the irradiation of laser with the wavelength of 275 nm;
in one embodiment, the anhydrous lanthanide chloride is dysprosium chloride to obtain Dy-NMOFs 3; which exhibits blue fluorescence under the irradiation of laser with a wavelength of 275 nm;
in order to further verify the universality of the tricolor fluorescent ink and improve the luminescence property, the nanometer Uio-66-NH emitting blue fluorescence is synthesized through experiments2Respectively physically mixing with red fluorescent ink Eu-NMOFs and green fluorescent ink Tb-NMOFs, and verifying the potential of the ink-jet printing ink;
Uio-66-NH2the synthesis of (a) is as follows:
1) adding 77mg of zirconium chloride, 48mg of amino terephthalic acid and 600mg of benzoic acid into 6mL of N, N-dimethylformamide and 55 mu L of HCl, and ultrasonically dissolving for 10min to obtain a uniform and transparent mixed solution;
2) adding the mixed solution into a reaction kettle with a 30mL polytetrafluoroethylene inner container, putting the reaction kettle into an oven, and heating and reacting the mixture for 24 hours at 120 ℃ to obtain reaction liquid with white precipitate at the bottom;
3) centrifuging the precipitate and supernatant, washing with N, N-dimethylformamide and ethanol for 2 times, and freeze drying to obtain nanometer metal organic framework material Uio-66-NH2(ii) a The resulting material may emit more intense blue fluorescence.
The modification preparation steps of the invisible fluorescent ink are as follows:
A) the dried fluorescent NMOFs material was added to ethanol and ultrasonically dispersed for 15min and stirred at room temperature for 0.5 h.
B) Adding an ink solvent comprising ethylene glycol, glycerol, diethylene glycol and surfactant SDS, performing ultrasonic treatment for 15min again, and rapidly stirring for 2h at room temperature to obtain the tricolor fluorescent ink S @ NMOFs.
In one embodiment, in step A), Eu-NMOFs powder is 20mg, and ethanol is 450 μ L; in step B), 450. mu.L of ethylene glycol, 50. mu.L of glycerin, 50. mu.L of diethylene glycol, and 500. mu.L of SDS (3mg/mL) as a surfactant were added.
In one embodiment, in step a), the Tb-NMOFs powder is 10mg, and the ethanol is 450 μ L; in step B), 450. mu.L of ethylene glycol, 50. mu.L of glycerin, 50. mu.L of diethylene glycol, and 500. mu.L of SDS (3mg/mL) as a surfactant were added.
In one embodiment, Uio-66-NH is added in step A)2Powder 30mg, ethanol 450 μ L; in step B), 450. mu.L of ethylene glycol, 50. mu.L of glycerin, 50. mu.L of diethylene glycol, and 500. mu.L of SDS (3mg/mL) as a surfactant were added.
The design of the novel invisible anti-counterfeiting two-dimensional code is as follows: the color of fluorescence under the excitation of specific wavelength is used as a signal storage unit, and the color of the fluorescence of each coding block bears one piece of coding information. A two-dimensional code is composed of invisible coding blocks with different colors, the same size and adjustable quantity and three black visible positioning blocks. The two-dimensional code picture printed and output only displays three black positioning blocks under a fluorescent lamp, but decryption is realized under the excitation of an ultraviolet lamp with a specific wavelength, and two-dimensional code information identical to a designed input graph is displayed, namely, the two-dimensional code picture has a multiple information encryption anti-counterfeiting function. Because the fluorescent color is generated by mixing the ink with three-primary-color fluorescent emission through an ink-jet printer, almost infinite fluorescent colors can be generated, and infinite coded information is realized. The size of the amount of coded information can also be adjusted by the number of coding blocks of a unit. In order to realize the novel invisible anti-counterfeiting two-dimensional code, a three-primary-color nanoscale fluorescent material is required to be obtained so as to prepare ink; mixing the tricolor fluorescent ink by a printer and then printing to obtain fluorescence of different colors; the tricolor and mixed color ink thereof do not display color under sunlight; since information storage and reading is achieved by fluorescence, the three primary colors and their mixed color fluorescence must be emitted under a single excitation.
Fig. 1 is a design schematic diagram of a novel invisible anti-counterfeiting two-dimensional code, wherein: a is a schematic diagram of the preparation process of the nanometer MOFs ink respectively emitting red, green and blue tricolor fluorescence; b is a schematic diagram of the ink-jet printer cartridge refitting process; c is a printing process schematic diagram; and D is a schematic diagram of the encryption and decryption processes of the printed anti-counterfeiting information.
Fig. 2 is a scanning electron microscope image of a matrix lanthanide series nano metal organic framework material of three primary color ink, wherein: a is Eu-NMOFs emitting red fluorescence; b is Tb-NMOFs emitting green fluorescence; c is Dy-NMOFs emitting blue fluorescence; the inset is the corresponding transmission electron micrograph. The results show that: the prepared nano metal organic framework material has uniform particle size and appearance, the size is about 200nm, and the particle size is smaller than 1/50 of the diameter of a nozzle of an ink-jet printing ink box, so that the nano metal organic framework material cannot block the nozzle and has the potential of being prepared into ink-jet printing ink.
Fig. 3 is a luminescent property of a substrate lanthanide series nano metal organic framework material of three primary color ink, wherein: a is a fluorescence emission diagram of Eu-NMOFs emitting red fluorescence under the excitation of 275nm wavelength; b is a fluorescence emission diagram of Tb-NMOFs emitting green fluorescence under 275nm excitation; c is a fluorescence emission diagram of Dy-NMOFs emitting blue fluorescence under 275nm excitation; d is the position of the emission colors of the three fluorescent MOFs in CIE chromaticity coordinates. Illustrated in the figure are: the prepared three lanthanide series nanometer metal organic frame materials respectively emit red, green and blue fluorescence, and have narrow spectrums, and the colors are respectively positioned in red, green and blue regions in CIE.
FIG. 4 shows the emission spectra and the coordinate positions in CIE obtained by physically mixing Eu-NMOFs, Tb-NMOFs and Dy-NMOFs in pairs in the volume ratio of 1:0,1:2,1:1,2:1 and 0:1, respectively, wherein: a is a luminescence spectrum diagram of mixed red fluorescent ink Eu-NMOFs and green fluorescent ink Tb-NMOFs; b is a luminescence spectrum diagram of the mixed red fluorescent ink Eu-NMOFs and blue fluorescent ink Dy-NMOFs; c is a luminescence spectrum diagram of the mixed green fluorescent ink Tb-NMOFs and blue fluorescent ink Dy-NMOFs; d is the coordinate position of the mixed luminescence spectrum in the CIE chromaticity. Illustrated in the figure are: the fluorescence spectra emitted by the two mixed inks are exactly positioned in the middle of the three primary color fluorescence color coordinates in the CIE chromaticity coordinates, the spectra obtained by mixing the whole proportion form a triangle covering various colors in a wider range in the CIE chromaticity coordinates, and the red, green and blue emissions are respectively positioned at three vertexes of the triangle.
FIG. 5 shows three primary color inks Eu-NMOFs, Tb-NMOFs and Uio-66-NH2The luminescence spectra and the coordinate position diagram in CIE obtained after mixing two by two according to 1:0,1:2,1:1,2:1,0:1 respectively, wherein: a is a luminescence spectrum diagram of mixed red fluorescent ink Eu-NMOFs and green fluorescent ink Tb-NMOFs; b is a luminescence spectrum diagram of the mixed red fluorescent ink Eu-NMOFs and blue fluorescent ink Dy-NMOFs; c is a luminescence spectrum diagram of the mixed green fluorescent ink Tb-NMOFs and blue fluorescent ink Dy-NMOFs; d is the coordinate of the mixed luminescence spectrum in the CIE. Illustrated in the figure are: uio66-NH2Compared with Dy-NMOFs, the blue fluorescent light emitted under 275nm excitation has higher intensity and is in a deeper blue region in CIE chromaticity coordinates, so that better mixed fluorescent color is obtained. The results also indicate that the fluorescent ink material is not limited to lanthanide metal nanometal organic framework materials, and other materials satisfying particle size, excitation wavelength and emission position can be used in the technology.
FIG. 6 shows the emission spectra and coordinate positions in CIE of the red fluorescent ink Eu-NMOFs and the green fluorescent ink Tb-NMOFs mixed at 1:0,0:1, 1:1,1:1.001,1:1.01,1:1.1,1:2,1:1.3,1:1.4 and 1:1.5, respectively. Illustrated in the figure are: in the case where the difference in the mixing ratio is small, the spectra after mixing are similar, and there is only a slight difference in intensity, which is difficult to distinguish by the naked eye, but the positions in the CIE chromaticity coordinates are different.
Table 1 shows the coordinate positions of the mixed emission spectra of the red fluorescent ink Eu-NMOFs and the green fluorescent ink Tb-NMOFs in CIE according to the ratio of 1:0,0:1, 1:1,1:1.001,1:1.01,1:1.1,1:2,1:1.3,1:1.4 and 1:1.5, respectively. The following are illustrated in the table: even if the volume difference in the case of ink mixing is only 0.001, the images can be distinguished by the coordinate values of the spectrum in the CIE chromaticity diagram, and the distinguishing accuracy of 0.0002 for Δ x and 0.0006 for Δ y can be achieved. The good distinguishing capability of the similar fluorescent colors indicates the feasibility of information coding by taking the fluorescent colors as the signal identification unit, and also indicates that the novel anti-counterfeiting two-dimensional code coding strategy has huge information capacity so as to realize a safer encryption function.
TABLE 1
Fig. 7 is a diagram of writing effect of a pen core made of tricolor ink, wherein: A. b is Eu-NMOFs, Tb-NMOFs and Uio-66-NH respectively2The ink is filled in the refill to make a picture of the fountain pen under a fluorescent lamp and an ultraviolet lamp; C. d is respectively red fluorescent ink Eu-NMOFs, green fluorescent ink Tb-NMOFs and blue fluorescent ink Uio-66-NH2Photographs of the acronyms "N", "K", "U" written "Nankai University" under fluorescent light and ultraviolet light, respectively; and E is the surface appearance of the circle in the graph C under a scanning electron microscope, and complete particles of the nano MOFs can be clearly seen. Illustrated in the figure are: after the ink is prepared, the luminescent property of the luminescent material is well reserved; the ink has excellent fluid performance and particle size stability as can be seen by writing feeling and scanning electron microscope pictures.
FIGS. 8A-C are photographs of a two-dimensional code printed under fluorescent light and under a 275nm UV lamp, illustrating the pattern of the input two-dimensional code; FIG. 8D is a photograph of a bar code designed to have a fluorescent color and position as identification bars under excitation by fluorescent and ultraviolet lamps. And FIG. 8E shows a designed heart and crescent superposition pattern printed on Renminbi for recruitment under a fluorescent lamp and an ultraviolet lamp, respectively. Illustrated in the figure are: the two-dimensional code picture output by ink-jet printing only displays three black position blocks under common light, and two-dimensional code coding information which is the same as an input figure is displayed under the excitation of a specific 275nm ultraviolet lamp, so that a novel invisible anti-counterfeiting two-dimensional code coding technology is realized. Meanwhile, the information capacity of the two-dimensional code can be adjusted by designing the size and the number of the color blocks of the information units in the input two-dimensional code. In addition, the prepared invisible fluorescent ink can also be used for invisible anti-counterfeiting pattern marks.
Claims (9)
1. A novel invisible anti-counterfeiting two-dimensional code based on a nano metal organic framework material is characterized in that: the novel invisible anti-counterfeiting two-dimensional code is formed by printing nanometer metal organic frame materials emitting red, green and blue fluorescence into different coding squares and three vertex black positioning blocks, wherein the fluorescent color of the squares under the excitation of specific wavelength is determined by the proportion of three different fluorescent color inks, and the fluorescent colors of the different coding squares are used as information storage units and bear coding information;
the average particle size of the metal organic framework material Ln-NMOFs emitting red, green and blue fluorescence is 200nm, and the particle size and the appearance of the metal organic framework material are uniform;
the synthesis method of three lanthanide Ln-MOFs comprises the following steps:
the anhydrous lanthanide chloride emitting red fluorescence is europium chloride to obtain Eu-NMOFs which shows red fluorescence under the irradiation of laser with the wavelength of 275 nm;
the anhydrous lanthanide chloride emitting green fluorescence is terbium chloride, Tb-NMOFs are obtained, and the Tb-NMOFs display green fluorescence under the irradiation of laser with the wavelength of 275 nm;
the anhydrous lanthanide chloride emitting blue fluorescence is dysprosium chloride to obtain Dy-NMOFs which exhibit blue fluorescence under the irradiation of laser with the wavelength of 275 nm.
2. The novel invisible anti-counterfeiting two-dimensional code based on the nano metal organic framework material as claimed in claim 1, is characterized in that: the fluorescence color and arrangement are used as information storage units, which is different from QD codes using square block size and black and white arrangement as information units and different from bar codes using line width and interval size as information units.
3. The novel invisible anti-counterfeiting two-dimensional code based on the nano metal organic framework material as claimed in claim 1, is characterized in that: the fluorescent ink is formed by printing tricolor fluorescent ink of a nanometer metal organic framework material which emits red, green and blue fluorescence, the ratio of three different fluorescent color inks determines the fluorescent colors of different coding blocks, and the tricolor and mixed color fluorescence thereof are generated under the excitation of light with the same wavelength.
4. The novel invisible anti-counterfeiting two-dimensional code based on the nano metal organic framework material as claimed in claim 3, is characterized in that: the preparation steps of the tricolor fluorescent ink are as follows:
1) adding anhydrous lanthanide chloride, 1, 3-terephthalic acid and 3, 5-dicarboxyphenylboronic acid into N, N-dimethylformamide and water, and ultrasonically dissolving for 10min to obtain a uniform and transparent mixed solution;
2) adding the mixed solution into a polytetrafluoroethylene inner container, sleeving the polytetrafluoroethylene inner container into a reaction kettle, putting the reaction kettle into an oven, and heating and reacting for 6 hours at 120 ℃ to obtain reaction liquid with white precipitates separated out at the bottom;
3) centrifuging the precipitate and the supernatant, washing with N, N-dimethylformamide and ethanol for 2 times respectively, and drying to obtain metal organic framework material Ln-NMOFs with average particle size of 200nm capable of emitting red, green and blue fluorescence respectively;
4) adding the dried fluorescent NMOFs material into ethanol, ultrasonically dispersing for 15min, and stirring at room temperature for 0.5 h;
5) adding the mixed solvent, ethylene glycol, glycerol, diethylene glycol and surfactant SDS, performing ultrasonic treatment again for 15min, and rapidly stirring for 2h at room temperature to obtain the fluorescent inks S @ NMOFs respectively emitting red, green and blue colors.
5. The novel invisible anti-counterfeiting two-dimensional code based on the nano metal organic framework material as claimed in claim 4, is characterized in that: in the step 1), the dosage ratio of anhydrous lanthanide chloride, 1, 3-terephthalic acid, 3, 5-dicarboxyphenylboronic acid, N-dimethylformamide and water is 0.02mmol:0.01mmol:0.01mmol:7mL:3 mL.
6. The novel invisible anti-counterfeiting two-dimensional code based on the nano metal organic framework material as claimed in claim 4, is characterized in that: ZrCl in step 4)4The dosage ratio of the amino terephthalic acid, the benzoic acid, the N, N-dimethylformamide and the hydrochloric acid is 0.33mmol to 0.26mmol to 5mmol to 6mL to 55 mu L.
7. The novel invisible anti-counterfeiting two-dimensional code based on the nano metal organic framework material as claimed in claim 4, is characterized in that: the dosage ratio of ethanol, glycol, glycerol, diglycol and surfactant SDS in the steps 7) and 8) is as follows: 450 μ L, 50 μ L, 500 μ L.
8. The novel invisible anti-counterfeiting two-dimensional code based on the nano metal organic framework material as claimed in claim 4, is characterized in that: the purpose of the synthesis of the Ln-NMOFs is to obtain three kinds of Ln-NMOFs which respectively emit red, green and blue fluorescence under the excitation of a single wavelength, and other fluorescent luminophors which can emit red, green and blue fluorescence under the same excitation wavelength, and the method can also be used for realizing the novel invisible fluorescent anti-counterfeiting two-dimensional code.
9. Use of the fluorescent ink S @ NMOFs prepared as described in claim 4, wherein: by filling the ink into an ink box of an ink-jet printer, the anti-counterfeiting two-dimensional code which takes fluorescent color as a signal identification unit is designed, a black block which only displays positioning under a fluorescent lamp is obtained after printing, and a novel invisible anti-counterfeiting two-dimensional code which displays coded information under an ultraviolet lamp with specific wavelength of 275nm is obtained.
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| CN109830174A (en) * | 2019-03-21 | 2019-05-31 | 赖正俊 | Paper base group of the lanthanides intelligent anti-counterfeiting device |
| CN110569942B (en) * | 2019-07-17 | 2023-05-23 | 浙江工业大学 | Preparation method of multiple anti-counterfeiting fluorescent two-dimensional code device |
| CN110668974A (en) * | 2019-09-12 | 2020-01-10 | 河南大学 | Organic nano-particle with multiple stimulus response characteristics and preparation method and application thereof |
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| CN113881285A (en) * | 2021-11-09 | 2022-01-04 | 山西聚微天成科技有限公司 | MOF fluorescent ink and application thereof in ion identification |
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| CN113913050A (en) * | 2021-11-09 | 2022-01-11 | 清华大学 | Preparation of MOF fluorescent ink and application of MOF fluorescent ink in ion concentration detection |
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