CN113621110A - Unclonable anti-counterfeiting material based on nanosphere self-assembly and preparation method and application thereof - Google Patents
Unclonable anti-counterfeiting material based on nanosphere self-assembly and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a non-clonable anti-counterfeiting material based on self-assembly of nanospheres, which is characterized in that monodisperse electronegative polymer nanospheres are used as a construction unit of a microcrystal region, acrylamide polymers obtained by polymerization reaction of acrylamide monomers are used as a base material, and the monodisperse electronegative polymer nanospheres are self-assembled in an acrylamide monomer reaction system to construct microcrystal light spots through static electricity. The non-clonable anti-counterfeiting material provided by the invention solves the problems of clonable property, weak information concealment, expensive identification equipment and easy aging and fading of the existing anti-counterfeiting material, has low preparation cost, can realize large-area preparation in a short time, has obvious color development of formed microcrystalline light spots, high color saturation and durability, has environmental friendliness, good display-hiding reversibility and high sensitivity, has high safety attribute of simple identification and multiple anti-counterfeiting, and has good application prospect in the field of anti-counterfeiting or information storage.
Description
Technical Field
The invention relates to the technical field of anti-counterfeiting materials, in particular to a non-clonable anti-counterfeiting material based on nanosphere self-assembly and a preparation method and application thereof.
Background
The anti-counterfeiting industry is developed vigorously in standardizing the economic order of the market and restraining counterfeit and shoddy products, and the product anti-counterfeiting plays an important role in preventing the counterfeiting or counterfeiting of the products and identifying the authenticity of the products. However, as the society is continuously deepened, the reliability and the safety of information are challenged by counterfeit markets, and the industries such as luxury goods, medicines, cosmetics and the like are 'disaster areas' of counterfeit commodities, so that the counterfeit markets must be pressed by adopting more complex, higher-level and safer anti-counterfeiting technologies to keep the stable development of market economy.
Photonic crystals with optical properties such as photonic band gap, low optical loss, and fluorescence enhancement have attracted a great deal of interest in a wide range of applications such as response sensors, optoelectronic devices, and biological detection. In particular, photonic crystals are attractive for optical encoding and information encryption due to their multiple advantages of tunable structural color, angle dependence, and colorfastness. Inspired by the random formation of scintillation microcrystals in natural precious opals, the natural strategy of information storage in the fossil can provide a novel anti-counterfeiting technology for anti-counterfeiting materials. For example: publication No. CN 104672733A discloses a humidity-sensitive color-changing anti-counterfeiting functional material, a preparation method and application thereof, wherein the humidity-sensitive color-changing anti-counterfeiting functional material consists of polyacrylamide and liquid gel of derivatives thereof and self-assembled photonic crystals. However, the photonic crystal is firstly self-assembled by a self-assembly method such as a vertical deposition method, an evaporation self-assembly method and the like, then the photonic crystal is added into an acrylamide monomer reaction system, and finally the monomer polymerization is initiated by ultraviolet light to obtain the humidity-sensitive color-changing anti-counterfeiting functional material. With the development of modern computer technology and the transparence of security tag preparation technology, the prepared security tag can still be cloned and forged due to the determined periodic structure and the predictable encoding/decoding mode of the photonic crystal. Therefore, it is highly desirable to develop photonic crystals with unpredictable and irreproducible coding/decoding properties to break through their current existing cloning and counterfeiting possibilities.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a non-clonable anti-counterfeiting material based on nanosphere self-assembly.
The second purpose of the invention is to provide a preparation method of the non-clonable anti-counterfeiting material based on the self-assembly of the nanospheres.
The above object of the present invention is achieved by the following technical solutions:
a non-cloning anti-counterfeiting material based on self-assembly of nanospheres is characterized in that monodisperse electronegative polymer nanospheres are introduced in the polymerization reaction process of acrylamide monomers to serve as a microcrystalline region construction unit, and the electronegative polymer nanospheres are self-assembled through static electricity to construct microcrystalline light spots.
The invention discloses a non-cloning anti-counterfeiting material based on self-assembly of nanospheres, wherein monodisperse electronegative polymer nanospheres are used as a building unit of a microcrystal region, microcrystalline light spots are automatically built in a reaction system of a positively charged acrylamide monomer through the electrostatic action of a built-in electric field of the monodisperse electronegative polymer nanospheres, and repulsive force and attractive force among molecules exist among the electronegative polymer nanospheres, an acrylamide monomer, a cross-linking agent and an initiator in the self-assembly system of the monodisperse electronegative polymer nanospheres. The intermolecular acting force can influence the regularity of the arrangement of the nanospheres, not only influences the shape and the forming position of the microcrystal area, but also influences the size of the microcrystal area, so that the formed light spot has smaller size and irregular shape, can show random light spots with different colors under the same humidity, has very high unclonability, and obviously improves the encryption performance of the anti-counterfeiting material.
Preferably, the electronegative polymer nanospheres include any one or more of poly (styrene-methacrylic acid) nanospheres, poly (methyl methacrylate-maleic acid) nanospheres, poly (styrene-methyl methacrylate-methacrylic acid) nanospheres, poly (styrene-maleic acid) nanospheres, poly (styrene-vinyl acetate-maleic acid) nanospheres, and poly (methyl methacrylate-methacrylic acid) nanospheres.
More preferably, the electronegative polymer nanospheres are any one or more of poly (styrene-vinyl acetate-maleic acid) nanospheres, poly (styrene-methyl methacrylate-methacrylic acid) nanospheres, poly (methyl methacrylate-methacrylic acid) nanospheres, and poly (styrene-methacrylic acid) nanospheres.
Preferably, the particle size of the electronegative polymer nanosphere is 120-230 nm.
Preferably, the preparation method of the electronegative polymer nanosphere comprises the following steps: and mixing reaction monomers, adding the mixture into a surfactant, stirring, introducing inert gas, heating to 70-90 ℃, adding an initiator, reacting for 7-9 hours, centrifugally precipitating and washing a product, and repeatedly washing for 10 times to obtain the electronegative polymer nanospheres.
More preferably, the surfactant is sodium lauryl sulfate; the initiator is potassium persulfate.
Preferably, the acrylamide polymer is obtained by reacting an acrylamide monomer, a cross-linking agent and an initiator.
Preferably, the acrylamide monomer comprises any one or more of acrylamide, methacrylamide, N-ethyl acrylamide, diacetone acrylamide, N-isopropyl acrylamide, N-hydroxyethyl acrylamide, N-dimethyl acrylamide and N-hydroxymethyl acrylamide.
More preferably, the acrylamide monomer is any one of diacetone acrylamide, N-hydroxyethyl acrylamide, acrylamide and N, N-dimethylacrylamide.
The invention also provides a preparation method of the non-clonable anti-counterfeiting material based on the self-assembly of the nanospheres, which comprises the following steps: adding the monodisperse electronegative polymer nanosphere aqueous solution into a reaction system formed by mixing acrylamide monomers, an initiator and a cross-linking agent, uniformly stirring, standing, carrying out polymerization reaction, and obtaining the polymer nanosphere after the reaction is finished.
Preferably, the mass fraction of the monodisperse electronegative polymer nanospheres in the aqueous solution is 10-70%.
More preferably, the mass fraction of the monodisperse electronegative polymer nanospheres in the aqueous solution is 15 to 40 wt%.
Preferably, the mass ratio of the electronegative polymer nanospheres, the acrylamide monomer, the cross-linking agent and the initiator is 1: (0.3-3): (0.001-0.03): (0.001-0.01).
More preferably, the mass ratio of the electronegative polymer nanospheres, the acrylamide monomer, the crosslinking agent and the initiator is 1: (0.375-2): (0.0036-0.015): (0.001-0.003).
Preferably, the initiator is a UV initiator including, but not limited to, 2-hydroxy-2-methyl propiophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-propanone; the polymerization reaction is carried out under the condition of ultraviolet irradiation.
Preferably, the crosslinking agent includes, but is not limited to, one of hexamethylene bisacrylamide, N-methylene bisacrylamide, and N, N-vinyl bisacrylamide.
Preferably, the standing time is 5-10 min; the reaction time is 0.5-1.5 h.
The invention also provides application of any one of the non-clonable anti-counterfeiting materials based on the self-assembly of the nanospheres in preparation of an anti-counterfeiting label. The anti-counterfeit label is affected by the shrinkage of the photonic crystal film under the condition of water loss, the distance between the nanospheres in the microcrystalline region is shrunk and closely arranged, the reflection wavelength is blue-shifted, the refractive indexes of the nanospheres and the photonic crystal film substrate are similar, and the anti-counterfeit label is in a transparent state. When the anti-counterfeit label meets water, the photonic crystal film absorbs water to expand, the distance between the nanospheres in the microcrystalline region is increased, the reflection wavelength is in red shift, and the photonic crystal film presents a multi-light-spot anti-counterfeit label with bright color and different colors. The photonic crystal film anti-counterfeiting label is endowed with the unclonable property by the disordered light spot pattern, and the anti-counterfeiting label can be identified and read by combining artificial intelligence.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a non-clonable anti-counterfeiting material based on self-assembly of nanospheres, which is characterized in that a physical non-clonable photonic crystal hydrogel, namely a non-clonable anti-counterfeiting material, is prepared by a new strategy of inducing self-assembly of nanospheres based on a built-in electric field effect, and the defects of clonable property, weak information hiding property, expensive identification equipment, easy aging and fading in the existing anti-counterfeiting material are overcome. The preparation cost of the non-clonable anti-counterfeiting material is low, large-area preparation can be realized in a short time, the formed microcrystalline light spots are obvious in color development, high in color saturation and durable, the environment-friendly property, good display-hiding reversibility and high sensitivity are realized, the high-grade safety attribute of simple and convenient identification and multiple anti-counterfeiting is realized, and the non-clonable anti-counterfeiting material has a good application prospect in the field of anti-counterfeiting or information storage.
Drawings
Fig. 1 is a schematic diagram of the synthesis steps of polystyrene-maleic acid nanospheres.
FIG. 2 is a schematic diagram of the synthesis steps of the anti-counterfeiting material.
FIG. 3 is an appearance view of the solutions of the electronegative polymer nanospheres of comparative example 1 and examples 1-5 under natural illumination, wherein the samples of the solutions of the electronegative polymer nanospheres of comparative example 1 and examples 1-5 are arranged from left to right.
FIG. 4 is a scanning electron microscope image of the electronegative polymer nanospheres of examples 1-5 (a-e).
Fig. 5 is a high-definition image of the anti-counterfeiting material with completely wet tiles in the industry, wherein fig. 5a to e are light spot images of the anti-counterfeiting materials of examples 1 to 5, and fig. 5f is a light spot image of the anti-counterfeiting material of comparative example 1.
FIG. 6 is a reflection spectrum of the anti-counterfeiting material of example 5 in different positions in a completely wet state.
Fig. 7 shows the light spot display transition process of the anti-counterfeiting material in a transparent state and a completely wet state under the completely dry state.
Detailed Description
The invention is further described with reference to the drawings and the following detailed description, which are not intended to limit the invention in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Unless otherwise indicated, reagents and materials used in the following examples are commercially available.
Example 1
S1, preparation of poly (styrene-methacrylic acid) nanospheres: weighing 15mL of styrene/methacrylic acid reaction monomer, adding the styrene/methacrylic acid reaction monomer into 80mL of deionized water, adding 50mg of sodium dodecyl sulfate, setting the stirring speed to 2000r/min, introducing inert gas for 30min, heating to 80 ℃, adding 0.1g of potassium persulfate, and reacting for 8h to obtain nanospheres with different particle sizes. And centrifuging and precipitating the obtained nanospheres in a centrifuge with the rotating speed of 21000r/min, adding deionized water for washing, repeating for 10 times, and finally obtaining 30 wt/% of poly (styrene-methacrylic acid) nanosphere solution with the average particle size of 120nm, namely the electronegative polymer nanosphere solution.
S2, preparation of the unclonable anti-counterfeiting material: taking 5mL of the electronegative polymer nanosphere solution (the dry weight of the poly (styrene-methacrylic acid) nanospheres is 1.5g) obtained in the step S1, adding 3g N-hydroxyethyl acrylamide reaction monomer, 15mg of N, N-methylene bisacrylamide crosslinking agent and 2.0mg of 2-hydroxy-2-methyl propiophenone initiator, standing for 5min after the reaction monomer, the crosslinking agent and the initiator are fully dissolved, injecting the mixture into a sandwich grinding tool with the interval of 0.1cm, and polymerizing for 0.5h under an ultraviolet lamp to obtain the unclonable anti-counterfeiting material.
Example 2
S1, preparation of a poly (methyl methacrylate-methacrylic acid) nanosphere: weighing 30mL of methyl methacrylate/methacrylic acid reaction monomer, adding the methyl methacrylate/methacrylic acid reaction monomer into 90mL of deionized water, adding 40mg of sodium dodecyl sulfate, setting the stirring speed to 2000r/min, introducing inert gas for 30min, heating to 70 ℃, adding 0.05g of potassium persulfate, and reacting for 8h to obtain nanospheres with different particle sizes. And centrifuging and precipitating the obtained nanospheres in a centrifuge with the rotating speed of 21000r/min, adding deionized water for washing, repeating for 10 times, and finally obtaining 25 wt/% poly (methyl methacrylate-methacrylic acid) nanosphere solution with the average particle size of 132nm, namely the electronegative polymer nanosphere solution.
S2, preparation of the unclonable anti-counterfeiting material: taking 10mL of the electronegative polymer nanosphere solution (the dry weight of poly (methyl methacrylate-methacrylic acid)) obtained in the step S1 is 2.5g, adding 1g of acrylamide reaction monomer, 9mg of N, N-methylene bisacrylamide crosslinking agent and 4.0mg of 2-hydroxy-2-methyl propiophenone initiator, standing for 10min after the reaction monomer, the crosslinking agent and the initiator are fully dissolved, injecting the solution into a sandwich grinding tool with the interval of 0.1cm, and polymerizing for 1.0h under an ultraviolet lamp to obtain the unclonable anti-counterfeiting material.
Example 3
S1, preparation of poly (styrene-methyl methacrylate-methacrylic acid) nanospheres: weighing 20mL of styrene/methyl methacrylate/methacrylic acid reaction monomer, adding the styrene/methyl methacrylate/methacrylic acid reaction monomer into 100mL of deionized water, adding 35mg of sodium dodecyl sulfate, setting the stirring speed at 2000r/min, introducing inert gas for 30min, heating to 80 ℃, adding 0.05g of potassium persulfate, and reacting for 8h to obtain nanospheres with different particle sizes. And centrifuging and precipitating the obtained nanospheres in a centrifuge with the rotating speed of 21000r/min, adding deionized water for washing, and repeating for 10 times to obtain a 20 wt/% poly (styrene-methyl methacrylate-methacrylic acid) nanosphere solution with the particle size of 150nm, namely the electronegative polymer nanosphere solution.
S2, preparation of the unclonable anti-counterfeiting material: taking 10mL of the electronegative polymer nanosphere solution (the dry weight of the poly (styrene-methyl methacrylate-methacrylic acid) nanospheres is 2.0g) obtained in the step S1, adding 1.5g of diacetone acrylamide reaction monomer, 30mg of hexamethylene bisacrylamide crosslinking agent and 2.0mg of 2-hydroxy-2-methyl propiophenone initiator, standing for 5min after the reaction monomer, the crosslinking agent and the initiator are fully dissolved, injecting the solution into a sandwich grinding tool with the distance of 0.1cm, and polymerizing for 1.5h under an ultraviolet lamp to obtain the unclonable anti-counterfeiting material.
Example 4
S1, preparation of poly (styrene-maleic acid) nanospheres: weighing 20mL of styrene/maleic acid reaction monomer, adding into 80mL of deionized water, adding 20mg of sodium dodecyl sulfate, setting the stirring speed at 2000r/min, introducing inert gas for 30min, heating to 80 ℃, adding 0.1g of ammonium persulfate, and reacting for 8h to obtain nanospheres with different particle sizes. And centrifuging and precipitating the obtained nanospheres in a centrifuge with the rotating speed of 21000r/min, then adding deionized water for washing, repeating for 10 times, and finally obtaining 20 wt/% polystyrene-maleic acid nanosphere solution with the average particle size of 186nm, namely the electronegative polymer nanosphere solution. The synthetic steps of the poly (styrene-maleic acid) nanosphere are schematically shown in fig. 1.
S2, preparation of the unclonable anti-counterfeiting material: taking 10mL of the electronegative polymer nanosphere solution (the dry weight of poly (styrene-maleic acid) obtained in the step S1 is 2.0g), adding 1.5g of diacetone acrylamide reaction monomer, 25mg of hexamethylene bisacrylamide crosslinking agent and 6.0mg of 1-hydroxycyclohexyl phenyl ketone initiator, standing for 5min after the reaction monomer, the crosslinking agent and the initiator are fully dissolved, injecting the solution into a sandwich grinding tool with the interval of 0.1cm, and polymerizing for 1.5h under an ultraviolet lamp to obtain the unclonable anti-counterfeiting material.
Example 5
S1, preparation of poly (styrene-polyvinyl acetate-maleic acid) nanospheres: weighing 16mL of styrene/vinyl acetate/maleic acid reaction monomer, adding the styrene/vinyl acetate/maleic acid reaction monomer into 85mL of deionized water, adding 20mg of sodium dodecyl sulfate, setting the stirring speed at 2000r/min, introducing inert gas for 30min, heating to 80 ℃, adding 0.1g of ammonium persulfate, and reacting for 8h to obtain nanospheres with different particle sizes. And centrifuging and precipitating the obtained nanospheres in a centrifuge with the rotating speed of 21000r/min, adding deionized water for washing, and repeating for 10 times to obtain 40 wt/% poly (styrene-vinyl acetate-maleic acid) nanosphere solution with the average particle size of 230nm, namely the electronegative polymer nanosphere solution.
S2, preparation of the unclonable anti-counterfeiting material: taking 10mL of the electronegative polymer nanosphere solution (the dry weight of poly (styrene-polyvinyl acetate-maleic acid) obtained in the step S1 is 4.0g), adding 1.5g N of N-dimethylacrylamide reaction monomer, 20mg of N, N-vinyl bisacrylamide crosslinking agent and 6.0mg of 1-hydroxycyclohexyl phenyl ketone initiator, standing for 5min after the reaction monomer, the crosslinking agent and the initiator are fully dissolved, injecting the solution into a sandwich grinding tool with the distance of 0.1cm, and polymerizing for 0.5h under an ultraviolet lamp to finally obtain the unclonable anti-counterfeiting material.
The schematic diagram of the synthetic steps of the anti-counterfeiting material prepared in the embodiments 1-5 of the invention is shown in FIG. 2. The first step in fig. 2 is a cleaning process of the solution of the electronegative polymer nanospheres, which form the microcrystalline region by self-assembly; the second step is the photo-initiated polymerization process of the material, and the liquid phase is converted into the solid phase, so that the non-cloning anti-counterfeiting material is finally prepared.
Comparative example 1
S1, preparation of poly (styrene-methacrylic acid) nanospheres: weighing 15mL of styrene/methacrylic acid reaction monomer, adding the styrene/methacrylic acid reaction monomer into 80mL of deionized water, adding 50mg of sodium dodecyl sulfate, setting the stirring speed to 2000r/min, introducing inert gas for 30min, heating to 80 ℃, adding 0.1g of potassium persulfate, and reacting for 8h to obtain nanospheres with different particle sizes. And centrifuging and precipitating the obtained nanospheres in a centrifuge with the rotating speed of 21000r/min, adding deionized water for washing, repeating for 10 times, and finally obtaining 15 wt/% of poly (styrene-methacrylic acid) nanosphere solution with the average particle size of 120nm, namely the electronegative polymer nanosphere solution.
S2, preparation of the unclonable anti-counterfeiting material: taking 10mL of the electronegative polymer nanosphere solution (the dry weight of the poly (styrene-methacrylic acid) nanospheres is 1.5g) obtained in the step S1, adding 2g of acrylate reaction monomer and 2.0mg of benzoin anisole initiator, standing for 5min after the reaction monomer, the crosslinking agent and the initiator are fully dissolved, injecting the mixture into a sandwich grinding tool with the interval of 0.1cm, and polymerizing for 0.5h under an ultraviolet lamp to obtain the anti-counterfeiting material.
The nanosphere solutions prepared in the embodiments 1-5 and the comparative example 1 of the invention are kept stand for 5min, under natural illumination, the appearance color is shown in fig. 3, and the samples in the figure are the electronegative polymer nanosphere solutions of the comparative examples 1 and the embodiments 1-5 from left to right. As can be seen from fig. 3, the nanospheres in the wet state show various colors under natural illumination, and have obvious color development and high color saturation. After the wet unclonable anti-counterfeiting material is placed for 6 months, the color, the saturation and the strength of the wet unclonable anti-counterfeiting material are almost not changed, which shows that the unclonable anti-counterfeiting material prepared by the invention cannot fade and is durable.
Test example 1
1. Scanning electron microscope
The experimental steps are as follows: 0.01mL of the 1 wt% nanosphere solution of examples 1-5 was applied dropwise to a conductive adhesive-coated electric microscope stage, dried in an oven at 60 ℃ for 6 hours, and finally observed under an electron scanning electron microscope for the microscopic morphology of the nanospheres (magnification 120K).
And (4) analyzing results: the surface morphologies of the electronegative polymer nanospheres of examples 1-5 are shown in sequence in FIGS. 4 a-e. As shown in FIG. 4, the nanospheres have regular morphology and uniform particle size, and the average particle size is 120nm to 230 nm.
2. Speckle effect map
The experimental steps are as follows: the completely wet anti-counterfeiting materials of the embodiments 1-5 and the comparative example 1 are placed on an observation table, and an industrial high-definition camera is used for shooting and storing under the irradiation of vertical light beams.
And (4) analyzing results: the anti-counterfeiting materials prepared in examples 1 to 5 and comparative example 1 were photographed by an industrial camera, and the photographed picture is shown in fig. 5. Wherein, fig. 5a to e are the unclonable anti-counterfeiting materials prepared in examples 1 to 5 in sequence, and fig. 5f is the anti-counterfeiting material prepared in comparative example 1. As can be seen from the figures, the anti-counterfeiting materials prepared by polymerization of acrylamide monomers in embodiments 1 to 5 have light spots of various colors, the size of the light spot in the anti-counterfeiting material prepared in the same embodiment is uniform, and the size of the light spot in the anti-counterfeiting materials prepared in different embodiments is different. And the anti-counterfeiting material prepared by adopting non-acrylamide monomers for polymerization reaction in the comparative example 1 does not appear or generate any light spots.
3. Reflectance spectrum testing
The experimental steps are as follows: the anti-counterfeiting material of example 5 was placed on a sample stage and tested using a spectrometer. And (4) analyzing results: the reflection spectrum of the security material of example 5 is shown in fig. 6. Under the condition of keeping the anti-counterfeiting material completely wet, reflection peaks with different wavelengths can be measured at different positions in a sample, and the fact that different positions have different colors in the anti-counterfeiting material is proved.
4. Appearance test of anti-counterfeiting material in dry and wet states
The appearance transition of the anti-counterfeiting material prepared in example 5 in a dry and wet state is shown in fig. 7. As can be seen from fig. 7, the dried anti-counterfeiting material is placed on the character surface, and the appearance is colorless and transparent when being observed, so that the character can be observed to the bottom through the anti-counterfeiting material; then the anti-counterfeiting material is completely wetted by water, the appearance of the anti-counterfeiting material can be observed to be opaque, a large number of colorful light spots are displayed on the surface of the anti-counterfeiting material, and the bottom characters are covered and cannot be observed. The principle is as follows: the anti-counterfeit label is affected by the shrinkage of the photonic crystal film under the condition of water loss, the distance between the nanospheres in the microcrystalline region is shrunk and closely arranged, the reflection wavelength is blue-shifted, the refractive indexes of the nanospheres and the photonic crystal film substrate are similar, and the anti-counterfeit label is in a transparent state. When the anti-counterfeit label meets water, the photonic crystal film absorbs water to expand, the distance between the nanospheres in the microcrystalline region is increased, the reflection wavelength is in red shift, and the photonic crystal film presents a multi-light-spot anti-counterfeit label with bright color and different colors. The photonic crystal film anti-counterfeiting label is endowed with the unclonable property by the disordered light spot pattern, and the anti-counterfeiting label can be identified and read by combining artificial intelligence.
Claims (10)
1. A non-cloning anti-counterfeiting material based on nanosphere self-assembly is characterized in that monodisperse electronegative polymer nanospheres are introduced as a microcrystalline region construction unit in the polymerization reaction process of acrylamide monomers, and microcrystalline light spots are constructed by the electronegative polymer nanospheres through electrostatic self-assembly.
2. The self-assembly nanosphere-based non-cloneable anti-counterfeiting material of claim 1, wherein the electronegative polymer nanospheres comprise any one or more of poly (styrene-methacrylic acid) nanospheres, poly (methyl methacrylate-maleic acid) nanospheres, poly (styrene-methyl methacrylate-methacrylic acid) nanospheres, poly (styrene-maleic acid) nanospheres, poly (styrene-vinyl acetate-maleic acid) nanospheres, and poly (methyl methacrylate-methacrylic acid) nanospheres.
3. The self-assembly nanosphere-based non-clonable anti-counterfeiting material according to claim 1, wherein the particle size of the electronegative polymer nanospheres is 120-230 nm.
4. The non-clonable anti-counterfeiting material based on the self-assembly of nanospheres according to claim 1, wherein the acrylamide monomer comprises any one or more of acrylamide, methacrylamide, N-ethyl acrylamide, diacetone acrylamide, N-isopropyl acrylamide, N-hydroxyethyl acrylamide, N-dimethyl acrylamide and N-hydroxymethyl acrylamide.
5. The preparation method of the non-cloning anti-counterfeiting material based on the self-assembly of the nanospheres as claimed in any one of claims 1 to 4, wherein a reaction system formed by mixing a monodisperse electronegative polymer nanosphere aqueous solution, an acrylamide monomer, an initiator and a cross-linking agent is stirred uniformly, then is kept stand for polymerization reaction, and is obtained after the reaction is finished.
6. The preparation method of claim 5, wherein the mass fraction of the monodisperse electronegative polymer nanospheres in the aqueous solution is 10-70%.
7. The preparation method according to claim 5, wherein the mass ratio of the electronegative polymer nanospheres to the acrylamide monomer to the crosslinking agent to the initiator is 1: (0.3-3): (0.001-0.03): (0.001-0.01).
8. The preparation method according to claim 6, wherein the mass ratio of the electronegative polymer nanospheres to the acrylamide monomer to the crosslinking agent to the initiator is 1: (0.375-2): (0.0036-0.015): (0.001-0.003).
9. The preparation method according to claim 5, wherein the standing time is 5-10 min; the reaction time is 0.5-1.5 h.
10. Use of the non-clonable anti-counterfeiting material based on the nanosphere self-assembly according to any one of claims 1 to 4 in the preparation of an anti-counterfeiting label.
Priority Applications (1)
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113990176A (en) * | 2021-11-19 | 2022-01-28 | 中山大学 | Preparation method and application of anti-counterfeit label based on temperature-induced phase-change hydrogel |
| CN114507401A (en) * | 2022-03-17 | 2022-05-17 | 河北师范大学 | Physical unclonable anti-counterfeiting material with decoration function, preparation method thereof and verification method of microcracks |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104672733A (en) * | 2013-12-02 | 2015-06-03 | 中国人民银行印制科学技术研究所 | Humidity-sensitive allochroic anti-counterfeiting functional material, and preparation method and application thereof |
| CN110569948A (en) * | 2019-09-23 | 2019-12-13 | 河北师范大学 | Physical unclonable structural color anti-counterfeiting label identified by artificial intelligence |
-
2021
- 2021-08-23 CN CN202110969732.1A patent/CN113621110B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104672733A (en) * | 2013-12-02 | 2015-06-03 | 中国人民银行印制科学技术研究所 | Humidity-sensitive allochroic anti-counterfeiting functional material, and preparation method and application thereof |
| CN110569948A (en) * | 2019-09-23 | 2019-12-13 | 河北师范大学 | Physical unclonable structural color anti-counterfeiting label identified by artificial intelligence |
| US20210091964A1 (en) * | 2019-09-23 | 2021-03-25 | Hebei Normal University | Physically unclonable structural-color anti-counterfeiting label with artificial intelligence authentication |
Non-Patent Citations (2)
| Title |
|---|
| CHEN, KE等: "Multicolor Printing Using Electric-Field-Responsive and Photocurable Photonic Crystals", 《ADVANCED FUNCTIONAL MATERIALS》, vol. 27, no. 43, 31 December 2017 (2017-12-31), pages 1 - 8 * |
| FATEMEH NADERI MEHR等: "Self-Assembly Behavior of Oppositely Charged Inverse Bipatchy Microcolloids", 《SMALL》, vol. 16, no. 14, 17 March 2020 (2020-03-17), pages 1 - 9 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113990176A (en) * | 2021-11-19 | 2022-01-28 | 中山大学 | Preparation method and application of anti-counterfeit label based on temperature-induced phase-change hydrogel |
| CN113990176B (en) * | 2021-11-19 | 2023-01-17 | 中山大学 | Preparation method and application of anti-counterfeit label based on temperature-induced phase-change hydrogel |
| CN114507401A (en) * | 2022-03-17 | 2022-05-17 | 河北师范大学 | Physical unclonable anti-counterfeiting material with decoration function, preparation method thereof and verification method of microcracks |
| CN114507401B (en) * | 2022-03-17 | 2023-08-29 | 河北师范大学 | Physical unclonable anti-counterfeiting material with decoration function, preparation method thereof and verification method of microcracks |
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