CN110766119A - Physical unclonable structural color anti-counterfeiting label with multiple anti-counterfeiting modes - Google Patents
Physical unclonable structural color anti-counterfeiting label with multiple anti-counterfeiting modes Download PDFInfo
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- CN110766119A CN110766119A CN201910922291.2A CN201910922291A CN110766119A CN 110766119 A CN110766119 A CN 110766119A CN 201910922291 A CN201910922291 A CN 201910922291A CN 110766119 A CN110766119 A CN 110766119A
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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
- G06K19/06018—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 one-dimensional coding
- G06K19/06028—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 one-dimensional coding using bar codes
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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
- G06K19/02—Record carriers for use with machines and with at least a part designed to carry digital markings characterised by the selection of materials, e.g. to avoid wear during transport through the machine
- G06K19/022—Processes or apparatus therefor
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- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06Q—INFORMATION AND COMMUNICATION TECHNOLOGY [ICT] SPECIALLY ADAPTED FOR ADMINISTRATIVE, COMMERCIAL, FINANCIAL, MANAGERIAL OR SUPERVISORY PURPOSES; SYSTEMS OR METHODS SPECIALLY ADAPTED FOR ADMINISTRATIVE, COMMERCIAL, FINANCIAL, MANAGERIAL OR SUPERVISORY PURPOSES, NOT OTHERWISE PROVIDED FOR
- G06Q30/00—Commerce
- G06Q30/018—Certifying business or products
- G06Q30/0185—Product, service or business identity fraud
Abstract
The invention discloses a physical unclonable structural color anti-counterfeiting label with multiple anti-counterfeiting modes. The optical film is composed of a patterned surface layer with a disordered optical structure, a transparent white middle layer changing to water and a black background bottom layer. The white color caused by the incoherent scattering of the light by the disordered optical structure surface layer is matched with the white intermediate layer, and the disordered optical structure surface layer is hidden; when the anti-counterfeit label meets water, the white middle layer becomes transparent, the black bottom layer uniformly absorbs light, the color saturation of the structural color surface layer is improved, and the structural color surface layer pattern is displayed. This enables a first invisible security mode visible to the naked eye. After the structural color surface layer meets water, the reflection spectrum of the structural color surface layer generates red shift, so that a second spectrum anti-counterfeiting mode is realized. The random arrangement of the monodisperse microspheres in the disordered optical structure has the property of physical unclonable, and the monodisperse microspheres can be identified by means of artificial intelligence, so that a third physical unclonable anti-counterfeiting mode is realized.
Description
Technical Field
The invention relates to an anti-counterfeiting label based on structural colors, in particular to a physical unclonable structural color anti-counterfeiting label with multiple anti-counterfeiting modes, and belongs to the technical field of anti-counterfeiting materials and structural color materials.
Background
Counterfeiting and faking are global problems, which not only cause huge economic loss, but also bring huge harm to individuals, enterprises and even the whole society. Although a number of advanced anti-counterfeiting technologies are developed, such as fluorescence, thermochromic, plasma optics, watermarking, laser holography, etc., economic losses due to counterfeit goods are still rapidly increasing worldwide. Therefore, it is necessary to develop a more advanced, efficient and portable anti-counterfeit technology to reverse the growth situation. An ideal anti-counterfeiting strategy should have the characteristics of low cost, environmental protection, mass production, non-destructive identification, simplicity, and most importantly, the label itself cannot be physically cloned.
The structural color is caused by the action of a submicron-scale special physical structure on light, and compared with fluorescent molecules, quantum dots or plasma optical materials, the structural color has the congenital advantages of fastness, environmental friendliness and capability of being recognized by naked eyes by virtue of equipment in disorder. Thus, a large number of anti-counterfeiting technologies based on the iridescent effect of structural colors and intelligently tunable properties of colors with external stimuli have been developed by the sciences (y. Heo, h. Kang, j.s. Lee, y.k. Oh, s.h. Kim, Small 2016, 12, 3819; s.l. Wu, b.q. Liu, x. Su, s.f. Zhang, j. phys. chem. lett. 2017, 8, 2835; k. Zhong, j. Li, l. Liu, s. Van Cleuvenbergen, k. Song, k. claus, adv.mater. 2018, 30, e 1707246; r.y. Xuan, j.p. Ge 2012, j. mater. chem. 2012,22, 367; h. Chen, q. Chen, j. Tang, hux. y. h. Chen, 110h. 22, h. However, the long-range ordered periodic structures that give rise to iridescence still present the possibility of physical cloning by counterfeiters.
In contrast, disordered optical structures which give rise to non-iridescent structural colours are due to the random arrangement of monodisperse submicron particles therein (Y.F. Zhang, B.Q. Dong, A. Chen, X.H. Liu, L. Shi, J. Zi, adv. Mater.2015, 27, 4719; J.M. Zhang, P. Han, M.J. Liu, H.Y. Zhou, Y.X. Zhang, J. K.Jiang, P. Liu, Y. Wei, Y.L. Song, X. Yao, Angew. chem. Ed.2017, 56, 10462; D.Ge, E. Lee, L. Yang, Y. Cho, M. Li, D.S. Gianola, S. Yang, Adv.Mater. 89, Y.2458, Y.H. Yang, Y.J. Zhang, Y.S. Sho, U, Y.S. Sho, S. Yang, Adv.M.27, J.J. Yang, H.H.H.J. Zhang, Y.S. Sho, U, S. Sho, S. H.S. Sho, H.t. Sho, H.t.t.t.t. Sho, S. H.t. Sho, S. H.t, S. Sho, S. H.t.t.t, k, nuengnoraj, h, Nishihara, m, Teshima, y, ohtsuka, t, Seki, angelw, chem, int, ed, 2013, 52, 7261), then has a physical unclonable property. However, their weak, unobtrusive, non-iridescent structural colors have led to people who have ignored their use in the anti-counterfeiting field.
Disclosure of Invention
The invention aims to provide a physical unclonable structural color anti-counterfeiting label with multiple anti-counterfeiting modes.
The structural color anti-counterfeiting label comprises a disordered optical structure patterned surface layer, a middle white layer which becomes transparent when meeting water and a black bottom layer.
Wherein the disordered optical structure patterning surface layer is formed by randomly arranging monodisperse colloid particles; the middle white layer which becomes transparent when meeting water is formed by dispersing nano particles into a hydrophilic polymer framework; the black background bottom layer is one of plastic, ceramic, metal, cloth, glass, wood, paper and the like.
The monodisperse colloidal particles are selected from one of styrene colloidal microspheres, polymethyl methacrylate colloidal microspheres, polystyrene-polymethyl methacrylate-polyacrylic acid colloidal microspheres, silicon dioxide colloidal microspheres, titanium dioxide colloidal microspheres, ferric sulfide colloidal microspheres, sulfur simple substance colloidal microspheres, gold colloidal microspheres and silver colloidal microspheres, and the size of the monodisperse colloidal particles is 120 nm-1000 nm.
The nano particles are selected from one or a mixture of more of silicon dioxide nano particles, calcium fluoride nano particles, titanium dioxide nano particles, zinc oxide nano particles, indium oxide nano particles, tin oxide nano particles and indium tin oxide nano particles, and the particle size is 5-100 nm.
The hydrophilic polymer is one of acrylic acid modified polyurethane, polyacrylic resin, polyvinyl alcohol resin, polyphthalamide and polyhydroxyethyl methacrylate, and the mass ratio of the polyphthalamide to the nanoparticles is 0.1: 1-2: 1.
The spectral range corresponding to the structural color is 390-800 nm, and the whole visible light area is covered.
After the anti-counterfeiting label is in contact with water, the disordered optical structure patterned surface layer is displayed, and the red shift of the reflection spectrum of the anti-counterfeiting label is 10-50 nm.
The invention has the advantages that through the multi-coating design, the multi-anti-counterfeiting mode of the non-iridescent structural color anti-counterfeiting label is realized by utilizing the special transparent intermediate layer which changes when meeting water. Firstly, hiding a structural color surface layer pattern by utilizing the hue matching of a structural color optical surface layer and a white middle layer; after the middle layer becomes transparent when meeting water, the exposed black background bottom layer improves the saturation of the structural color, and the structural color surface layer pattern is displayed. This is the first visible invisible anti-counterfeiting mode. After meeting water, the reflection spectrum of the structural color surface layer generates unique red shift, which is a second anti-counterfeiting mode based on spectrum identification. The random arrangement of monodisperse colloidal particles in the disordered optical structure has the property of being physically unclonable, which is a third anti-counterfeiting mode. The anti-counterfeiting label has the safety attributes of simple and convenient identification and incapability of being cloned, and has important application prospect in a plurality of safety fields.
Drawings
FIG. 1 shows the hidden and water-exposed anti-counterfeit label with butterfly pattern in white intermediate coating layer in the embodiment 1 of the invention.
Fig. 2 shows reflection spectra before and after the disordered optical structure coating of the anti-counterfeit label in embodiment 1 of the present invention is in contact with water.
FIG. 3 is an SEM photograph of the disordered optical structure coating of the security label in example 1 of the invention.
Detailed Description
Example 1
First, 20 nm of SiO2Nanoparticles and SiO2The mass ratio of the nano particles is 0.8: 1 acrylic acid modified polyurethane ultrasonic dispersing water to form SiO2And the mass fraction of the nano particles is 10 percent. Secondly, spin-coating the dispersionAnd forming a middle white coating with the property of changing into transparent when meeting water on the black paperboard. Thirdly, spraying the emulsion containing 10% of monodisperse polystyrene-polymethyl methacrylate-polyacrylic acid colloidal microspheres with the particle size of 205 nm to the middle white to obtain the non-iridescent structural color anti-counterfeiting label with the butterfly pattern and the disordered optical structure. When dried, the white color of the disordered optical structure coating is close to the white color of the intermediate coating, and the butterfly pattern is hidden, as shown in fig. 1; upon encountering water, a green butterfly pattern appears (fig. 1). This achieves a first invisible anti-counterfeiting mode. Before and after water, the reflection spectrum of the disordered optical structure coating is shifted from 490nm to 510 nm and is red-shifted by 20 nm, as shown in figure 2, so that a second spectrum anti-counterfeiting mode is realized. The monodisperse colloidal particles in the disordered optical structure coating are arranged in a random manner (fig. 3), achieving a third, triple security mode with physical unclonable properties.
Example 2
Firstly, mixing 5 nm calcium fluoride nano-particles and polyacrylic resin accounting for 0.1:1 of the mass ratio of the calcium fluoride nano-particles, and ultrasonically dispersing neutral water to form a dispersion liquid with the mass fraction of the calcium fluoride nano-particles being 10%. Secondly, dip-coating the dispersion solution on black PVC plastic paper to form a middle white coating with the property of becoming transparent when meeting water. Thirdly, spraying the emulsion containing 10% of monodisperse silica colloidal microspheres with the particle size of 120 nm to the middle white color to obtain the non-iridescent structural color anti-counterfeiting label with the disordered optical structure of the two-dimensional code pattern. When the two-dimensional code is dried, the white color of the disordered optical structure coating is close to that of the middle coating, and the two-dimensional code pattern is hidden; and when the water is changed, the purple two-dimensional code pattern is displayed. This achieves a first invisible anti-counterfeiting mode. Before and after the coating meets water, the reflection spectrum of the disordered optical structure coating is shifted from 380 nm to 390 nm and is red-shifted by 10 nm, so that a second spectrum anti-counterfeiting mode is realized. The monodisperse colloidal particles in the disordered optical structure coating are arranged in a random mode, and a third triple anti-counterfeiting mode with physical unclonable property is realized.
Example 3
Firstly, the mass ratio of titanium dioxide nanoparticles with the particle size of 100 nm to titanium dioxide nanoparticles is 2:1, dispersing water in the polyvinyl alcohol resin by ultrasonic to form a dispersion liquid with the titanium dioxide nano particles of which the mass fraction is 10 percent. Secondly, dip-coating the dispersion liquid on a black metal sheet to form an intermediate white coating with the property of becoming transparent when meeting water. Thirdly, spraying the emulsion containing 10% of monodisperse polystyrene colloidal microspheres with the particle size of 1000nm to the middle white to obtain the non-iridescent structural color anti-counterfeiting label with the disordered optical structure of the bar code pattern. When dried, the white color of the disordered optical structure coating is close to the white color of the intermediate coating, and the bar code pattern is hidden; after the water changes, the red bar code pattern appears. This achieves a first invisible anti-counterfeiting mode. Before and after the coating meets water, the reflection spectrum of the disordered optical structure coating is shifted from 750 nm to 800 nm and is red-shifted by 50 nm, so that a second spectrum anti-counterfeiting mode is realized. The monodisperse colloidal particles in the disordered optical structure coating are arranged in a random mode, and a third triple anti-counterfeiting mode with physical unclonable property is realized.
Example 4
Firstly, mixing zinc oxide nano-particles with the particle size of 30nm with polyamide resin accounting for 1:1 of the mass ratio of the zinc oxide nano-particles, and ultrasonically dispersing water to form a dispersion liquid with the mass fraction of titanium dioxide nano-particles being 10%. Secondly, dip-coating the dispersion liquid on a black metal sheet to form an intermediate white coating with the property of becoming transparent when meeting water. Thirdly, spraying the emulsion containing 10% of monodisperse polystyrene colloidal microspheres with the particle size of 1000nm to the middle white to obtain the non-iridescent structural color anti-counterfeiting label with the disordered optical structure of the bar code pattern. When dried, the white color of the disordered optical structure coating is close to the white color of the intermediate coating, and the bar code pattern is hidden; after the water changes, the red bar code pattern appears. This achieves a first invisible anti-counterfeiting mode. Before and after the coating meets water, the reflection spectrum of the disordered optical structure coating is shifted from 750 nm to 800 nm and is red-shifted by 50 nm, so that a second spectrum anti-counterfeiting mode is realized. The monodisperse colloidal particles in the disordered optical structure coating are arranged in a random mode, and a third triple anti-counterfeiting mode with physical unclonable property is realized.
Example 5
Firstly, the mass ratio of indium oxide nanoparticles with the particle size of 30nm to indium oxide nanoparticles is 0.5:1 and ultrasonically dispersing the neutral water to form a dispersion liquid with the mass fraction of the indium oxide nano particles being 10%. Secondly, dip-coating the dispersion liquid on a black ceramic substrate to form an intermediate white coating with the property of changing into transparency when meeting water. Thirdly, spraying the emulsion containing the monodisperse polymethyl methacrylate microspheres with the particle size of 250 nm and the mass fraction of 20% to the middle white color to obtain the non-iridescent structural color anti-counterfeiting label with the disordered optical structure of the bar code pattern. When dried, the white color of the disordered optical structure coating is close to the white color of the intermediate coating, and the bar code pattern is hidden; after the water changes, the red bar code pattern appears. This achieves a first invisible anti-counterfeiting mode. Before and after the coating meets water, the reflection spectrum of the disordered optical structure coating is shifted from 720 nm to 750 nm and is red-shifted by 30nm, so that a second spectrum anti-counterfeiting mode is realized. The monodisperse colloidal particles in the disordered optical structure coating are arranged in a random mode, and a third triple anti-counterfeiting mode with physical unclonable property is realized.
Example 6
Firstly, the mass ratio of indium oxide nanoparticles with the particle size of 30nm to indium oxide nanoparticles is 0.5:1 and ultrasonically dispersing the neutral water to form a dispersion liquid with the mass fraction of the indium oxide nano particles being 10%. Secondly, dip-coating the dispersion liquid on a black ceramic substrate to form an intermediate white coating with the property of changing into transparency when meeting water. Thirdly, spraying the emulsion containing 10% of monodisperse polymethyl methacrylate microspheres with the particle size of 250 nm to the middle white to obtain the non-iridescent structural color anti-counterfeiting label with the disordered optical structure of the bar code pattern. When dried, the white color of the disordered optical structure coating is close to the white color of the intermediate coating, and the bar code pattern is hidden; after the water changes, the red bar code pattern appears. This achieves a first invisible anti-counterfeiting mode. Before and after the coating meets water, the reflection spectrum of the disordered optical structure coating is shifted from 720 nm to 750 nm and is red-shifted by 30nm, so that a second spectrum anti-counterfeiting mode is realized. The monodisperse colloidal particles in the disordered optical structure coating are arranged in a random mode, and a third triple anti-counterfeiting mode with physical unclonable property is realized.
Example 7
Firstly, the mass ratio of 30nm tin oxide nanoparticles to tin oxide nanoparticles is 0.5:1 and ultrasonically dispersing the neutral water to form a dispersion liquid with the mass fraction of tin oxide nano particles being 10%. Secondly, dip-coating the dispersion solution on a black wood substrate to form an intermediate white coating with the property of becoming transparent when meeting water. Thirdly, the emulsion containing the monodisperse titanium dioxide colloid microballoons with the particle size of 180 nm and the mass fraction of 10 percent is printed to be white in the middle by ink-jet printing to obtain the non-iridescent structural color anti-counterfeiting label with the disordered optical structure of the digital pattern. When dried, the white color of the disordered optical structure coating is close to the white color of the intermediate coating, and the digital pattern is hidden; when it is changed by water, the cyan bar code pattern is displayed. This achieves a first invisible anti-counterfeiting mode. Before and after the coating meets water, the reflection spectrum of the disordered optical structure coating is shifted from 480 nm to 490nm and is red-shifted by 10 nm, so that a second spectrum anti-counterfeiting mode is realized. The monodisperse colloidal particles in the disordered optical structure coating are arranged in a random mode, and a third triple anti-counterfeiting mode with physical unclonable property is realized.
Example 8
Firstly, the mass ratio of indium tin oxide nanoparticles with the particle size of 30nm to indium tin oxide nanoparticles is 0.5:1 and ultrasonically dispersing water to form a dispersion liquid with the mass fraction of indium tin oxide particles being 10%. Secondly, dip-coating the dispersion solution on a black glass substrate to form an intermediate white coating with the property of changing into transparency when meeting water. Thirdly, spraying the emulsion containing 10% of monodisperse ferric sulfide colloid microspheres with the particle size of 250 nm to the middle white to obtain the non-iridescent structural color anti-counterfeiting label with the disordered optical structure of the letter pattern. When the coating is dried, the white color of the disordered optical structure coating is close to that of the intermediate coating, and the letter patterns are hidden; after the water changes, the red letter code pattern appears. This achieves a first invisible anti-counterfeiting mode. Before and after the coating meets water, the reflection spectrum of the disordered optical structure coating is shifted from 720 nm to 750 nm and is red-shifted by 30nm, so that a second spectrum anti-counterfeiting mode is realized. The monodisperse colloidal particles in the disordered optical structure coating are arranged in a random mode, and a third triple anti-counterfeiting mode with physical unclonable property is realized.
Example 9
Firstly, the mass ratio of indium tin oxide nanoparticles with the particle size of 30nm to indium tin oxide nanoparticles is 0.5:1 and ultrasonically dispersing water to form a dispersion liquid with the mass fraction of indium tin oxide particles being 10%. Secondly, dip-coating the dispersion solution on a black glass substrate to form an intermediate white coating with the property of changing into transparency when meeting water. Thirdly, spraying the emulsion containing 5% of monodisperse gold colloid microspheres with the particle size of 250 nm to the middle white to obtain the non-iridescent structural color anti-counterfeiting label with the disordered optical structure of the letter pattern. When the coating is dried, the white color of the disordered optical structure coating is close to that of the intermediate coating, and the letter patterns are hidden; after the water changes, the red letter code pattern appears. This achieves a first invisible anti-counterfeiting mode. Before and after the coating meets water, the reflection spectrum of the disordered optical structure coating is shifted from 720 nm to 750 nm and is red-shifted by 30nm, so that a second spectrum anti-counterfeiting mode is realized. The monodisperse colloidal particles in the disordered optical structure coating are arranged in a random mode, and a third triple anti-counterfeiting mode with physical unclonable property is realized.
Example 10
Firstly, the mass ratio of indium tin oxide nanoparticles with the particle size of 30nm to indium tin oxide nanoparticles is 0.5:1 (mass ratio of 1: 1) and ultrasonically dispersing water to form a dispersion liquid with the mass fraction of indium tin oxide particles being 10%. Secondly, dip-coating the dispersion solution on a black leather substrate to form an intermediate white coating with the property of changing into transparency when meeting water. Thirdly, spraying the emulsion containing 5% of monodisperse silver colloid microspheres with the particle size of 250 nm to the intermediate white color to obtain the non-iridescent structural color anti-counterfeiting label with the disordered optical structure of the letter pattern. When the coating is dried, the white color of the disordered optical structure coating is close to that of the intermediate coating, and the letter patterns are hidden; after the water changes, the red letter code pattern appears. This achieves a first invisible anti-counterfeiting mode. Before and after the coating meets water, the reflection spectrum of the disordered optical structure coating is shifted from 720 nm to 750 nm and is red-shifted by 30nm, so that a second spectrum anti-counterfeiting mode is realized. The monodisperse colloidal particles in the disordered optical structure coating are arranged in a random mode, and a third triple anti-counterfeiting mode with physical unclonable property is realized.
Example 12
Firstly, the mass ratio of indium tin oxide nanoparticles with the particle size of 30nm to indium tin oxide nanoparticles is 0.5:1, mixing and ultrasonically dispersing water in a mixture (mass ratio of 1:1: 1) of poly (phthalamide), poly (hydroxyethyl methacrylate) and polyacrylic resin to form a dispersion liquid with the mass fraction of indium tin oxide particles being 10%. Secondly, dip-coating the dispersion solution on a black leather substrate to form an intermediate white coating with the property of changing into transparency when meeting water. Thirdly, spraying the emulsion containing 5% of monodisperse silver colloid microspheres with the particle size of 250 nm to the intermediate white color to obtain the non-iridescent structural color anti-counterfeiting label with the disordered optical structure of the letter pattern. When the coating is dried, the white color of the disordered optical structure coating is close to that of the intermediate coating, and the letter patterns are hidden; after the water changes, the red letter code pattern appears. This achieves a first invisible anti-counterfeiting mode. Before and after the coating meets water, the reflection spectrum of the disordered optical structure coating is shifted from 720 nm to 750 nm and is red-shifted by 30nm, so that a second spectrum anti-counterfeiting mode is realized. The monodisperse colloidal particles in the disordered optical structure coating are arranged in a random mode, and a third triple anti-counterfeiting mode with physical unclonable property is realized.
Example 11
Firstly, indium oxide of 30nm, silicon dioxide nanoparticles of 20 nm, zinc oxide nanoparticles of 10 nm (mass ratio of 1:1: 1) and a mixture of poly (acrylamide) and poly (hydroxyethyl methacrylate) (mass ratio of 1: 1) in a mass ratio of 0.5:1 to the nanoparticles are mixed, and water is ultrasonically dispersed to form a dispersion liquid with the mass fraction of the nanoparticles being 10%. Secondly, dip-coating the dispersion solution on black wood to form an intermediate white coating with the property of becoming transparent when meeting water. Thirdly, spraying the emulsion containing 5% of monodisperse silver colloid microspheres with the particle size of 250 nm to the intermediate white color to obtain the non-iridescent structural color anti-counterfeiting label with the disordered optical structure of the letter pattern. When the coating is dried, the white color of the disordered optical structure coating is close to that of the intermediate coating, and the letter patterns are hidden; after the water changes, the red letter code pattern appears. This achieves a first invisible anti-counterfeiting mode. Before and after the coating meets water, the reflection spectrum of the disordered optical structure coating is shifted from 720 nm to 750 nm and is red-shifted by 30nm, so that a second spectrum anti-counterfeiting mode is realized. The monodisperse colloidal particles in the disordered optical structure coating are arranged in a random mode, and a third triple anti-counterfeiting mode with physical unclonable property is realized.
Example 11
Firstly, mixing indium oxide with the thickness of 30nm and silicon dioxide nano particles with the thickness of 20 nm with the weight ratio of the nano particles of 0.5:1 (mass ratio of 1: 1) and ultrasonically dispersing water to form a dispersion liquid with the mass fraction of nanoparticles being 10%. Secondly, dip-coating the dispersion liquid on black cloth to form an intermediate white coating with the property of becoming transparent when meeting water. Thirdly, spraying the emulsion containing 5% of monodisperse silver colloid microspheres with the particle size of 250 nm to the intermediate white color to obtain the non-iridescent structural color anti-counterfeiting label with the disordered optical structure of the letter pattern. When the coating is dried, the white color of the disordered optical structure coating is close to that of the intermediate coating, and the letter patterns are hidden; after the water changes, the red letter code pattern appears. This achieves a first invisible anti-counterfeiting mode. Before and after the coating meets water, the reflection spectrum of the disordered optical structure coating is shifted from 720 nm to 750 nm and is red-shifted by 30nm, so that a second spectrum anti-counterfeiting mode is realized. The monodisperse colloidal particles in the disordered optical structure coating are arranged in a random mode, and a third triple anti-counterfeiting mode with physical unclonable property is realized.
Claims (5)
1. A physical unclonable structural color anti-counterfeiting label with multiple anti-counterfeiting modes is characterized in that: the optical film is composed of a disordered optical structure patterning surface layer, a middle white layer which becomes transparent when meeting water and a black background bottom layer;
wherein the disordered optical structure patterning surface layer is formed by randomly arranging monodisperse colloid particles; the middle white layer which becomes transparent when meeting water is formed by dispersing nano particles into a hydrophilic polymer framework; the black background bottom layer is one of plastic, ceramic, metal, cloth, glass, wood and paper.
2. The security label of claim 1, wherein the monodisperse colloidal particles are selected from one of styrene colloidal microspheres, polymethyl methacrylate colloidal microspheres, polystyrene-polymethyl methacrylate-polyacrylic acid colloidal microspheres, silica colloidal microspheres, titanium dioxide colloidal microspheres, iron sulfide colloidal microspheres, elemental sulfur colloidal microspheres, gold colloidal microspheres, and silver colloidal microspheres, and the size of the monodisperse colloidal particles is 120 nm to 1000 nm.
3. The security label of claim 1, wherein: the nano particles are selected from one or a mixture of more of silicon dioxide nano particles, calcium fluoride nano particles, titanium dioxide nano particles, zinc oxide nano particles, indium oxide nano particles, tin oxide nano particles and indium tin oxide nano particles, and the particle size is 5-100 nm.
4. The security label of claim 1, wherein: the hydrophilic polymer is one of acrylic acid modified polyurethane, polyacrylic resin, polyvinyl alcohol resin, polyphthalamide and polyhydroxyethyl methacrylate, and the mass ratio of the polyphthalamide to the nanoparticles is 0.1: 1-2: 1.
5. The security label of claim 1, wherein: the spectral range corresponding to the structural color is 390-800 nm, and the whole visible light area is covered.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113506508A (en) * | 2021-08-07 | 2021-10-15 | 河北师范大学 | Super-hydrophobic physical unclonable structural color anti-counterfeiting label and preparation method thereof |
| CN114409376A (en) * | 2022-01-24 | 2022-04-29 | 陕西科技大学 | Preparation method of high-saturation amorphous photonic crystal structure colored glaze |
| CN115232514A (en) * | 2022-07-20 | 2022-10-25 | 中山大学 | Structural color material capable of developing color in presence of water and preparation method thereof |
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| CN114409376A (en) * | 2022-01-24 | 2022-04-29 | 陕西科技大学 | Preparation method of high-saturation amorphous photonic crystal structure colored glaze |
| CN115232514A (en) * | 2022-07-20 | 2022-10-25 | 中山大学 | Structural color material capable of developing color in presence of water and preparation method thereof |
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