Phosphorescent dyes and triple anti-counterfeiting photonic crystal films containing phosphorescent dyes, preparation and application

Abstract

The application discloses a phosphorescent dye and a triple anti-counterfeiting photonic crystal film containing the phosphorescent dye, and preparation and application of the triple anti-counterfeiting photonic crystal film. The photonic crystal film contains a new phosphorescent dye component, and the photonic crystal film is endowed with phosphorescent anti-counterfeiting characteristics and phosphorescent long-life anti-counterfeiting characteristics, and further endowed with the structural color anti-counterfeiting characteristics of the photonic crystal itself, so that the photonic crystal film exhibits triple anti-counterfeiting characteristics, effectively solves problems of easy counterfeiting, complex anti-counterfeiting equipment and single anti-counterfeiting mode of existing anti-counterfeiting technologies, and the prepared anti-counterfeiting pattern is simple and easy to identify and has strong anti-counterfeiting specificity.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of anti-counterfeiting materials. More particularly, it relates to a phosphorescent dye and a triple anti-counterfeiting photonic crystal film containing the phosphorescent dye, preparation and application. BACKGROUND

[0002] With the economic development of modern society, the commodity market is expanding, and the anti-counterfeiting mark with unique recognition can greatly improve the recognition of products and also has anti-counterfeiting function. Traditional anti-counterfeiting technologies such as holography, fluorescent ink, temperature change ink and photochromic ink have been widely used in the printing of anti-counterfeiting marks. Fluorescent ink often uses organic dyes, which produce visible patterns under ultraviolet or infrared light excitation. The anti-counterfeiting pattern can be directly recognized by the naked eye, and has the characteristics of convenience, speed and intuition. In addition, the single anti-counterfeiting commonly used in the prior art is gradually not suitable for the modern rapidly developing society. In order to further improve the anti-counterfeiting effect and reduce the probability of being imitated, a material capable of realizing multi-anti-counterfeiting needs to be researched. CN104194497A discloses a triple anti-counterfeiting ink with up-conversion, down-conversion and phosphorescence, and a preparation method and application thereof. Through the triple identification method, it has excellent anti-counterfeiting performance, and has the advantages of stable properties, good acid and alkali resistance and light bleaching performance. However, the anti-counterfeiting mode based on light excitation directly displays the anti-counterfeiting pattern, and the effect is not perfect enough, there are problems of less anti-counterfeiting pattern information, and the anti-counterfeiting identification effect cannot be enhanced at a specific angle. The ink is easy to be imitated, so a new process is needed to improve the anti-counterfeiting technology.

[0003] Photonic crystal film patterning provides a new anti-counterfeiting technology for researchers. The structural color of photonic crystal has angle dependence and will not fade. Ordinary ink printing cannot replicate the special structural color properties of photonic crystal, so photonic crystal material has natural advantages in anti-counterfeiting. At present, photonic crystal anti-counterfeiting is mainly prepared by holographic technology, but the processing equipment required by holographic technology is relatively complex, and the processing process is also relatively complex, which limits the development of photonic crystal in the field of anti-counterfeiting technology.

[0004] Therefore, it is very important to study a new anti-counterfeiting material with multi-anti-counterfeiting characteristics, which can realize the enhanced anti-counterfeiting characteristics at a specific angle and has a simple processing process, for the development of anti-counterfeiting materials. SUMMARY

[0005] In view of the above problems, the first object of the present application is to provide a phosphorescent dye. The present application provides a new type of phosphorescent dye composition, which is a kind of aromatic compound with boronic acid group and hydroxyl group. The phosphorescent dye has phosphorescent light emitting characteristics and long life light emitting characteristics, and is a potential raw material for the preparation of anti-counterfeiting materials.

[0006] The second object of the present application is to provide a triple anti-counterfeiting photonic crystal film containing the phosphorescent dye as described above.

[0007] The third object of the present application is to provide a method for preparing the triple anti-counterfeiting photonic crystal film as described above.

[0008] The fourth object of the present application is to provide an application of the triple anti-counterfeiting photonic crystal film as described above in preparing a multi-anti-counterfeiting material.

[0009] To achieve the first object, the present application adopts the following technical solution:

[0010] The present application discloses a phosphorescent dye, and the component of the phosphorescent dye is a compound as shown in formula I.

[0011]

[0012] wherein, R1-R3 are each independently selected from one of hydrogen, hydroxyl, methoxyl or aldehyde group, and R1-R3 are the same or different.

[0013] In the technical solution of the present application, a new type of phosphorescent dye component is provided, which is an aromatic compound with a boronic acid group and a hydroxyl group, thereby widening the selection of raw materials for the phosphorescent dye, and retaining the phosphorescent emission characteristics and long-life emission characteristics of the phosphorescent dye, which provides raw material support for subsequent preparation of multi-anti-counterfeiting materials. In subsequent research, the above-mentioned phosphorescent dye is combined with photonic crystal technology, and a photonic crystal film with triple anti-counterfeiting characteristics is successfully prepared. The triple anti-counterfeiting characteristics refer to phosphorescent emission anti-counterfeiting characteristics, phosphorescent long-life emission anti-counterfeiting characteristics and structural color anti-counterfeiting characteristics. The structural color pattern of the photonic crystal film can be directly observed by the naked eye, solving the problems of existing anti-counterfeiting technologies, such as easy counterfeiting, complex anti-counterfeiting equipment and single anti-counterfeiting mode. In order to further improve the specificity of the anti-counterfeiting material, laser engraving technology is used for patterning treatment of the photonic crystal film, so that the anti-counterfeiting pattern is easy to identify, and the anti-counterfeiting specificity is significantly enhanced.

[0014] In the preparation process, the problems of complex processing equipment in holographic technology are overcome. Only the two-phase polymer solution needs to be dropped on a glass sheet, and then heated at a specific temperature to obtain a photonic crystal film with a composite layer structure. Researchers can engrave the required photonic crystal anti-counterfeiting pattern according to the actual application needs, so as to present the effect of triple anti-counterfeiting characteristics.

[0015] The three anti-counterfeiting features specifically refer to: (1) a phosphorescent anti-counterfeiting feature: the photonic crystal film is excited to generate phosphorescence under ultraviolet light, and a phosphorescent pattern can be observed; (2) a phosphorescent long-life anti-counterfeiting feature: the phosphorescent pattern can emit light for several seconds or more under an ultraviolet light source, and has a long afterglow property; and (3) a structural color anti-counterfeiting feature: the upper layer of water-soluble polymer compound is prepared into a photonic crystal, the photonic crystal has anisotropy, and different structural colors can be generated in different plane directions, the photonic crystal film observed from the side appears a region with enhanced fan-shaped phosphorescent emission, and the anisotropy of the photonic crystal can be used to realize anti-counterfeiting identification of a special phosphorescent pattern at a specific angle.

[0016] Further, the phosphorescent dye component is selected from one of the following compounds:

[0017]

[0018]

[0019] Further, the phosphorescent dye component is selected from one of 3-formyl-4-methoxyphenyl boronic acid, 4-formylphenyl boronic acid or 4-methoxyphenyl boronic acid.

[0020] To achieve the above-mentioned second object, the application adopts the following technical scheme:

[0021] The application discloses a triple anti-counterfeiting photonic crystal film, which comprises:

[0022] an upper layer containing a water-soluble polymer compound;

[0023] and a lower layer containing a phosphorescent dye and a matrix layer material as described above.

[0024] The photonic crystal film has a two-layer composite structure, the upper layer contains a water-soluble polymer compound with a high elastic modulus, and the photonic crystal can be prepared after heat treatment; preferably, the water-soluble polymer compound includes but is not limited to one or a combination of at least two of polyacrylamide, polyacrylic acid, polyvinylpyrrolidone, polyvinyl alcohol, polymaleic anhydride, polyquaternary ammonium salt or polyethylene glycol; the lower layer contains a phosphorescent dye and a matrix layer material as described above, wherein the matrix layer material is a polysaccharide polymer compound with a plurality of hydroxyl functional groups; preferably, the matrix layer material includes but is not limited to one or a combination of at least two of sodium hyaluronate, sodium carboxymethyl cellulose, sodium carboxymethyl cellulose, starch, alginic acid or chitosan; and the phosphorescent dye with a double anti-counterfeiting feature is dispersed in the lower layer solution.

[0025] Further, the concentration of the water-soluble polymer compound in the upper layer solution is 0.03-0.2 mg / mL; for example, the concentration of the water-soluble polymer compound can be 0.03 mg / mL, 0.06 mg / mL, 0.1 mg / mL, 0.12 mg / mL, 0.15 mg / mL, 0.18 mg / mL, 0.2 mg / mL, or the like, and the interval range formed by any two of the above values.

[0026] Further, the concentration of the matrix layer material in the lower layer solution is 10-30 mg / mL; for example, the concentration of the matrix layer material can be 10 mg / mL, 15 mg / mL, 20 mg / mL, 25 mg / mL, 30 mg / mL, or the like, and the interval range formed by any two of the above values.

[0027] Preferably, the concentration of the phosphorescent dye in the lower layer solution is 0.025-0.1 mg / mL; for example, the concentration of the phosphorescent dye can be 0.025 mg / mL, 0.05 mg / mL, 0.075 mg / mL, 0.1 mg / mL, or the like, and the interval range formed by any two of the above values.

[0028] To achieve the third object, the application adopts the following technical solution:

[0029] The application discloses a method for preparing the photonic crystal film as described above, comprising the following steps:

[0030] The lower layer solution containing the phosphorescent dye and the matrix layer material is dropped on the glass sheet treated by the chromic acid solution, and then the upper layer solution containing the water-soluble polymer compound is dropped above the lower layer solution; after the double-layer solution is spread, it is placed on a heating table and dried by heating.

[0031] Further, the heating temperature is 75-95°C, and the heating time is 30-60 min.

[0032] To achieve the fourth object, the application discloses an application of the photonic crystal film as described above in preparing a multi-prevention-fake material.

[0033] In the application, the photonic crystal film has triple-prevention-fake characteristics and can be directly used as a prevention-fake material; in order to further improve the specificity of the prevention-fake material, the inventors perform patterning treatment on the photonic crystal film, and obtain a multi-prevention-fake material with stronger prevention-fake specificity.

[0034] Further, the patterning adopts laser engraving; for example, the conditions of the laser engraving are that the power of the laser is 3 W, and the scanning time is 10 min, but are not limited to the above conditions.

[0035] The application has the following beneficial effects:

[0036] The application discloses a phosphorescent dye and a triple anti-counterfeiting photonic crystal film containing the phosphorescent dye, and preparation and application thereof.

[0037] (1) The photonic crystal film is prepared by adopting double-layer polymer solution evaporation, so that the purpose of cheap, efficient and convenient production of the photonic crystal anti-counterfeiting material is achieved.

[0038] (2) The photonic crystal film has triple anti-counterfeiting features, including phosphorescent light anti-counterfeiting features, phosphorescent long-life light anti-counterfeiting features and structural color anti-counterfeiting features. After being patterned, the anti-counterfeiting pattern is more convenient to identify, and the anti-counterfeiting specificity is significantly enhanced.

[0039] (3) The structural color anti-counterfeiting performance of the photonic crystal film guarantees the stability and reliability of the anti-counterfeiting pattern, and the structural color of the film can exist stably for a long time.

[0040] (4) The structural color of the photonic crystal film and the phosphorescent light color are simple and adjustable: the regulation of the structural color of the film and the phosphorescent light color can be realized by changing the upper-layer polymer concentration and exchanging different phosphorescent dyes with different light wavelengths.

[0041] (5) The anisotropy of the upper-layer photonic crystal structure causes the structural color of the photonic crystal film to appear only in a specific region and angle, the photonic crystal film observed from the side appears a fan-shaped region with enhanced phosphorescent light emission, and the anisotropic structure of the photonic crystal film is difficult to counterfeit. The anisotropy of the photonic crystal film can be used for the identification of the anti-counterfeiting pattern at a specific angle or the encryption of the anti-counterfeiting pattern in a specific direction angle, based on the enhancement of the phosphorescent light at a specific angle. BRIEF DESCRIPTION OF DRAWINGS

[0042] The specific embodiments of the application are further described in detail below with reference to the accompanying drawings.

[0043] Figure 1 The luminescence spectrum of the photonic crystal film prepared in Example 1 is shown.

[0044] Figure 2 The phosphorescent light effect pictures of the pattern of the photonic crystal film prepared in Example 1 under sunlight and under an ultraviolet lamp at different angles are shown.

[0045] Among them, (a) is the effect picture observed under sunlight, and (b)-(f) are the phosphorescent light effect pictures under an ultraviolet lamp at different angles.

[0046] Figure 3 The SEM pictures of the upper-layer photonic crystal stripes under different PVA concentrations in Example 1 are shown.

[0047] Wherein, (a) is 0.03 mg / mL, (b) is 0.06 mg / mL, (c) is 0.1 mg / mL, (d) is 0.2 mg / mL.

[0048] Figure 4 The absorption spectrum of the photonic crystal film prepared in Example 1 at different concentrations of PVA is shown.

[0049] Figure 5 The different structural color effects of the photonic crystal film prepared in Example 1 at different concentrations of PVA under sunlight are shown.

[0050] Wherein, (a) is 0 mg / mL, (b) is 0.03 mg / mL, (c) is 0.06 mg / mL, (d) is 0.1 mg / mL, (e) is 0.15 mg / mL, (f) is 0.2 mg / mL. DETAILED DESCRIPTION

[0051] In order to more clearly illustrate the present application, the present application will be further described below in conjunction with preferred embodiments and drawings. Those skilled in the art should understand that the specific descriptions below are illustrative rather than limiting, and should not limit the protection scope of the present application. Any range described in the present application includes the end value and any numerical value between the end values, as well as any sub-range formed by the end value or any numerical value between the end value.

[0052] The raw materials used in this embodiment are known compounds, which can be obtained by commercial means or can be prepared according to known methods in the art. In the following examples, the physical and chemical parameters involved are determined by the following instruments:

[0053] The emission spectrum was tested by a Hitachi F-4600 fluorescence spectrometer;

[0054] The SEM photograph was tested by a Hitachi HITACHI S-4800;

[0055] The UV-Vis absorption spectrum was tested by a Japanese Shimadzu UV-1601PC;

[0056] Example 1

[0057] The hyaluronic acid sodium solution (MW=10000, 10 mg / mL) mixed with 3-formyl-4-methoxyphenylboronic acid (0.05 mg / mL) was dropped on 0.5 mL of a chromium acid solution treated glass sheet, and then 0.125 mL of PVA (MW=80000) aqueous solution with different concentrations was dropped on the hyaluronic acid sodium solution, respectively, the solution was spread into a circle with a radius of 0.5 cm, and the PVA concentration was 0 mg / mL, 0.03 mg / mL, 0.06 mg / mL, 0.1 mg / mL, 0.15 mg / mL and 0.2 mg / mL. Finally, the solution was placed on a hot stage at 85°C for 1 hour to obtain a triple anti-counterfeiting photonic crystal film. The prepared photonic crystal film was engraved with a desired pattern by a laser engraving machine (DIATOOLS k6). The laser power was 3W, the scanning time was 10 min, and the mode was relief.

[0058] The anti-counterfeiting detection method is as follows:

[0059] Phosphorescent anti-counterfeiting: the photonic crystal film is irradiated with a 365 nm ultraviolet lamp, and the photonic crystal film can emit phosphorescence to realize phosphorescent anti-counterfeiting. Figure 1 The phosphorescent emission spectrum of 3-formyl-4-methoxyphenylboronic acid is shown. It can be seen that the phosphorescent peak of 3-formyl-4-methoxyphenylboronic acid is located at 445 nm, and the photonic crystal film has blue phosphorescent emission. And from Figure 2 It can be seen that the photonic crystal film is silver white without excitation by a 365 nm ultraviolet lamp, and the film shows blue light emission after excitation, and the color changes before and after irradiation.

[0060] Lifetime anti-counterfeiting: the photonic crystal film is excited for 10 min using a 254 nm ultraviolet lamp, and after the ultraviolet lamp is turned off, the photonic crystal film can continuously emit phosphorescence for several seconds.

[0061] Different concentrations of PVA can regulate the photonic crystal stripe period of the photonic crystal film, as shown in Figure 3 , the photonic crystal stripe period increases with the increase of the PVA concentration. The increase of the photonic crystal stripe period will cause the red shift of the photonic crystal band gap peak wavelength.

[0062] Figure 4 The absorption spectrum of the photonic crystal film prepared under different concentrations of PVA is shown, and it can be seen that the absorption peak of the photonic crystal film red shifts with the increase of the PVA concentration. And it is also found that the structural color of the photonic crystal film can be changed by adjusting the PVA concentration, see Figure 5When no PVA is added, the photonic crystal film has no structural color and is a transparent film; as the PVA concentration increases, the structural color of the photonic crystal film can be seen to red-shift from blue to orange. By adjusting the PVA concentration, a photonic crystal film having a desired structural color can be obtained, and the structural color of the photonic crystal film is continuously adjustable, covering the entire visible light region.

[0063] Structural color angle dependence: Figure 2 Figures b-f are phosphorescent light emission effect diagrams of the photonic crystal film at different angles under ultraviolet light, and the naked eye can directly observe the change in the structural color of the film. Due to the anisotropy of the photonic crystal film structure, Figure 2 Figures c-d show that the fan-shaped light emission enhancement region always remains horizontal, and the pattern light emission in the horizontal direction is enhanced. By observing the photonic crystal film from the side, the pattern in the horizontal direction can be interpreted.

[0064] Example 2

[0065] A chitosan solution (MW = 8000, 10 mg / mL) mixed with 3-formyl-4-methoxyphenylboronic acid (0.05 mg / mL) was added dropwise to 0.5 mL on a chromium acid washing liquid treated glass sheet, and then 0.125 mL of a PVA (MW = 80000) aqueous solution with different concentrations was added dropwise on the chitosan solution, the solution spread into a circular shape with a radius of 0.5 cm, and the PVA concentration was 0.03 mg / mL, 0.06 mg / mL, 0.1 mg / mL and 0.2 mg / mL. Finally, the solution was placed on a hot stage at 85°C for 1 hour to obtain a triple anti-counterfeiting photonic crystal film. The prepared photonic crystal film was engraved with the required pattern using a laser engraving machine (DIATOOLS k6). The laser power was 3W, the scanning time was 10 min, and the mode was relief.

[0066] The following anti-counterfeiting detection methods were used for detection:

[0067] Phosphorescent anti-counterfeiting: a 365 nm ultraviolet lamp was used to irradiate the photonic crystal film, and the photonic crystal film could emit phosphorescence to achieve phosphorescent anti-counterfeiting.

[0068] Lifetime anti-counterfeiting: a 254 nm ultraviolet lamp was used to excite the photonic crystal film for 10 min, and after the ultraviolet lamp was turned off, the photonic crystal film could continuously emit phosphorescence for several seconds.

[0069] Structural color angle dependence: the photonic crystal film was tilted, and the naked eye could directly observe the change in the structural color of the film.

[0070] Example 3

[0071] The carboxymethylcellulose sodium solution (MW=2000, 10 mg / mL) mixed with 3-formyl-4-methoxyphenylboronic acid (0.05 mg / mL) was dropped on 0.5 mL of a glass sheet treated with chromic acid solution, and then 0.125 mL of PVA (MW=80000) aqueous solution with different concentrations was dropped on the carboxymethylcellulose sodium solution, respectively, and the solution was spread into a circle with a radius of 0.5 cm, and the PVA concentration was 0.03 mg / mL, 0.06 mg / mL, 0.1 mg / mL and 0.2 mg / mL. Finally, the solution was placed on a hot stage at 85°C for heating and drying for 1 hour to obtain a triple anti-counterfeiting photonic crystal film. The prepared photonic crystal film was engraved with a laser to form a pattern on a laser engraving machine (DIATOOLS k6). The laser power was 3W, the scanning time was 10 min, and the mode was relief.

[0072] The following anti-counterfeiting detection methods were used for detection:

[0073] Phosphorescent anti-counterfeiting: a 365 nm ultraviolet lamp was used to irradiate the photonic crystal film, and the photonic crystal film could emit phosphorescence to realize phosphorescent anti-counterfeiting.

[0074] Lifetime anti-counterfeiting: a 254 nm ultraviolet lamp was used to excite the photonic crystal film for 10 min, and after the ultraviolet lamp was turned off, the photonic crystal film could continuously emit phosphorescence for several seconds.

[0075] Structural color angle dependence: tilting the photonic crystal film, the structural color of the film could be directly observed to change by naked eye.

[0076] Example 4

[0077] The starch solution (MW=2800, 10 mg / mL) mixed with 3-formyl-4-methoxyphenylboronic acid (0.05 mg / mL) was dropped on 0.5 mL of a glass sheet treated with chromic acid solution, and then 0.125 mL of PVA (MW=80000) aqueous solution with different concentrations was dropped on the starch solution, respectively, and the solution was spread into a circle with a radius of 0.5 cm, and the PVA concentration was 0.03 mg / mL, 0.06 mg / mL, 0.1 mg / mL and 0.2 mg / mL. Finally, the solution was placed on a hot stage at 75°C for heating and drying for 30 min to obtain a triple anti-counterfeiting photonic crystal film. The prepared photonic crystal film was engraved with a laser to form a pattern on a laser engraving machine (DIATOOLS k6). The laser power was 3W, the scanning time was 10 min, and the mode was relief.

[0078] The following anti-counterfeiting detection methods were used for detection:

[0079] Phosphorescent anti-counterfeiting: a 365 nm ultraviolet lamp was used to irradiate the photonic crystal film, and the photonic crystal film could emit phosphorescence to realize phosphorescent anti-counterfeiting.

[0080] Lifetime Anti-counterfeiting: The photonic crystal film is excited by 254 nm UV light for 10 min, and after the UV light is turned off, the photonic crystal film can continue to emit phosphorescence for several seconds.

[0081] Structural color angle dependence: Tilt the photonic crystal film, and the structural color of the film can be directly observed by the naked eye.

[0082] Example 5

[0083] A sodium hyaluronate solution (MW = 10000, 10 mg / mL) mixed with 3-formyl-4-methoxyphenyl boronic acid (0.05 mg / mL) was dropped onto a 0.5 mL chromium acid solution treated glass sheet, and then 0.125 mL of a polyvinylpyrrolidone (MW = 1000) aqueous solution with different concentrations was dropped onto the sodium hyaluronate solution, the solution was spread into a circular shape with a radius of 0.5 cm, and the concentration of the polyvinylpyrrolidone was 0.03 mg / mL, 0.06 mg / mL, 0.1 mg / mL and 0.2 mg / mL. Finally, the solution was placed on a 95°C hot stage for heating and drying for 30 min to obtain a triple anti-counterfeiting photonic crystal film. The prepared photonic crystal film was laser engraved with the required pattern under a laser engraving machine (DIATOOLS k6). The laser power was 3W, the scanning time was 10 min, and the mode was relief.

[0084] The following anti-counterfeiting detection method was used for detection:

[0085] Phosphorescence Anti-counterfeiting: The photonic crystal film was irradiated with a 365 nm UV light, and the photonic crystal film emitted phosphorescence to achieve phosphorescence anti-counterfeiting.

[0086] Lifetime Anti-counterfeiting: The photonic crystal film was excited by 254 nm UV light for 10 min, and after the UV light was turned off, the photonic crystal film could continue to emit phosphorescence for several seconds.

[0087] Structural color angle dependence: Tilt the photonic crystal film, and the structural color of the film can be directly observed by the naked eye.

[0088] Example 6

[0089] Hyaluronic acid sodium solution (MW=10000, 10 mg / mL) mixed with 3-formyl-4-methoxyphenylboronic acid (0.05 mg / mL) was dropped on 0.5 mL of glass sheet treated with chromic acid solution, then 0.125 mL of different concentrations of polyethylene glycol (MW=8000) aqueous solution was dropped on the hyaluronic acid sodium solution, the solution spread into a circle with a radius of 0.5 cm, the concentration of the polyethylene glycol was 0.03 mg / mL, 0.06 mg / mL, 0.1 mg / mL and 0.2 mg / mL. Finally, the solution was placed on a hot stage at 95°C for heating and drying for 30 min to obtain a triple anti-counterfeiting photonic crystal film. The prepared photonic crystal film was engraved with the required pattern under a laser engraving machine (DIATOOLS k6).

[0090] Specific anti-counterfeiting detection method:

[0091] Phosphorescent anti-counterfeiting: irradiate the photonic crystal film with a 365 nm ultraviolet lamp, the photonic crystal film can emit phosphorescence to achieve phosphorescent anti-counterfeiting.

[0092] Lifetime anti-counterfeiting: excite the photonic crystal film with a 254 nm ultraviolet lamp for 10 min, after the ultraviolet lamp is turned off, the photonic crystal film can continue to emit phosphorescence for several seconds.

[0093] Structural color angle dependence: tilt the photonic crystal film, the structural color of the film can be directly observed to change by the naked eye.

[0094] Example 7

[0095] Hyaluronic acid sodium solution (MW=10000, 10 mg / mL) mixed with 3-formyl-4-methoxyphenylboronic acid (0.05 mg / mL) was dropped on 0.5 mL of glass sheet treated with chromic acid solution, then 0.125 mL of different concentrations of polyacrylamide (MW=2000) aqueous solution was dropped on the hyaluronic acid sodium solution, the solution spread into a circle with a radius of 0.5 cm, the concentration of the polyacrylamide was 0.03 mg / mL, 0.06 mg / mL, 0.1 mg / mL and 0.2 mg / mL. Finally, the solution was placed on a hot stage at 95°C for heating and drying for 30 min to obtain a triple anti-counterfeiting photonic crystal film. The prepared photonic crystal film was engraved with the required pattern under a laser engraving machine (DIATOOLS k6). The laser power was 3 W, the scanning time was 10 min, and the mode was relief.

[0096] Specific anti-counterfeiting detection method:

[0097] Phosphorescent anti-counterfeiting: irradiate the photonic crystal film with a 365 nm ultraviolet lamp, the photonic crystal film can emit phosphorescence to achieve phosphorescent anti-counterfeiting.

[0098] Lifetime anti-counterfeiting: the photonic crystal film is excited by 254 nm ultraviolet light for 10 min, and after the ultraviolet light is turned off, the photonic crystal film can continue to emit phosphorescence for several seconds.

[0099] Structural color angle dependence: tilt the photonic crystal film, and the structural color of the film can be directly observed by the naked eye.

[0100] Example 8

[0101] A sodium hyaluronate solution (MW = 10000, 10 mg / mL) mixed with 3-formyl-4-methoxyphenyl boronic acid (0.05 mg / mL) is dropped onto a 0.5 mL chromium acid solution treated glass sheet, and then 0.125 mL of an aqueous solution of polyacrylic acid (MW = 4000) with different concentrations is dropped onto the sodium hyaluronate solution, respectively, and the solution spreads into a circular shape with a radius of 0.5 cm, and the polyacrylamide concentration is 0.03 mg / mL, 0.06 mg / mL, 0.1 mg / mL and 0.2 mg / mL. Finally, the solution is placed on a hot plate at 85°C for drying for one hour to obtain a triple anti-counterfeiting photonic crystal film. The prepared photonic crystal film is engraved with the required pattern under a laser engraving machine (DIATOOLS k6). The laser power is 3W, the scanning time is 10 min, and the mode is relief.

[0102] Specific anti-counterfeiting detection method:

[0103] Phosphorescent anti-counterfeiting: the photonic crystal film is irradiated with a 365 nm ultraviolet lamp, and the photonic crystal film can emit phosphorescence to achieve phosphorescent anti-counterfeiting.

[0104] Lifetime anti-counterfeiting: the photonic crystal film is excited by 254 nm ultraviolet light for 10 min, and after the ultraviolet light is turned off, the photonic crystal film can continue to emit phosphorescence for several seconds.

[0105] Structural color angle dependence: tilt the photonic crystal film, and the structural color of the film can be directly observed by the naked eye.

[0106] Example 9

[0107] Hyaluronic acid sodium solution (MW=10000, 10 mg / mL) mixed with 3-formyl-4-methoxybenzene boronic acid (0.05 mg / mL) was dropped on 0.5 mL of glass sheet treated with chromic acid solution, then 0.125 mL of PVA (MW=80000) aqueous solution with different concentrations was dropped on the hyaluronic acid sodium solution, the solution spread into a circle with a radius of 0.5 cm, and the PVA concentration was 0.03 mg / mL, 0.06 mg / mL, 0.1 mg / mL and 0.2 mg / mL. Finally, the solution was placed on a hot stage at 85°C for 1 hour to obtain a triple anti-counterfeiting photonic crystal film. The prepared photonic crystal film was laser engraved with the required pattern under a laser engraving machine (DIATOOLS k6). The laser power was 3W, the scanning time was 10 min, and the mode was relief.

[0108] Specific anti-counterfeiting detection method:

[0109] Phosphorescent anti-counterfeiting: irradiate the photonic crystal film with a 365 nm ultraviolet lamp, and the photonic crystal film can emit phosphorescence to achieve phosphorescent anti-counterfeiting.

[0110] Lifetime anti-counterfeiting: excite the photonic crystal film with a 254 nm ultraviolet lamp for 10 min, and after the ultraviolet lamp is turned off, the photonic crystal film can continue to emit phosphorescence for several seconds.

[0111] Structural color angle dependence: tilt the photonic crystal film, and the structural color of the film can be directly observed by the naked eye.

[0112] Example 10

[0113] Hyaluronic acid sodium solution (MW=10000, 10 mg / mL) mixed with 3-formyl-4-methoxybenzene boronic acid (0.05 mg / mL) was dropped on 0.5 mL of glass sheet treated with chromic acid solution, then 0.125 mL of PVA (MW=80000) aqueous solution with different concentrations was dropped on the hyaluronic acid sodium solution, the solution spread into a circle with a radius of 0.5 cm, and the PVA concentration was 0.03 mg / mL, 0.06 mg / mL, 0.1 mg / mL and 0.2 mg / mL. Finally, the solution was placed on a hot stage at 85°C for 1 hour to obtain a triple anti-counterfeiting photonic crystal film. The prepared photonic crystal film was laser engraved with the required pattern under a laser engraving machine (DIATOOLS k6). The laser power was 3W, the scanning time was 10 min, and the mode was relief.

[0114] Specific anti-counterfeiting detection method:

[0115] Phosphorescent anti-counterfeiting: irradiate the photonic crystal film with a 365 nm ultraviolet lamp, and the photonic crystal film can emit phosphorescence to achieve phosphorescent anti-counterfeiting.

[0116] Lifetime anti-counterfeiting: the photonic crystal film is excited by 254nm UV light for 10min, and the photonic crystal film can emit phosphorescence for several seconds after the UV light is turned off.

[0117] Structural color angle dependence: tilt the photonic crystal film, and the structural color of the film can be directly observed by naked eye.

[0118] Example 11

[0119] A sodium hyaluronate solution (MW=10000, 10mg / mL) mixed with p-aminophenylboronic acid (0.05mg / mL) is dropped on a chromium acid solution treated glass sheet for 0.5mL, and then 0.125mL of PVA (MW=80000) aqueous solution with different concentrations is dropped on the sodium hyaluronate solution, respectively, the solution spreads into a circle with a radius of 0.5cm, and the PVA concentration is 0.03mg / mL, 0.06mg / mL, 0.1mg / mL and 0.2mg / mL. Finally, the solution is placed on a hot stage at 85℃ for heating and drying for 1 hour to obtain a triple anti-counterfeiting photonic crystal film. The prepared photonic crystal film is engraved with a required pattern by a laser engraving machine (DIATOOLS k6). The laser power is 3W, the scanning time is 10min, and the mode is relief.

[0120] Specific anti-counterfeiting detection method:

[0121] Phosphorescence anti-counterfeiting: the photonic crystal film is irradiated by 365nm UV light, and the photonic crystal film can emit phosphorescence to realize phosphorescence anti-counterfeiting.

[0122] Lifetime anti-counterfeiting: the photonic crystal film is excited by 254nm UV light for 10min, and the photonic crystal film can emit phosphorescence for several seconds after the UV light is turned off.

[0123] Structural color angle dependence: tilt the photonic crystal film, and the structural color of the film can be directly observed by naked eye.

[0124] Obviously, the above examples of the present application are only examples for clearly illustrating the present application, and are not intended to limit the embodiments of the present application. For those skilled in the art, other different forms of changes or variations can be made on the basis of the above description, and it is impossible to enumerate all the embodiments here. Any obvious changes or variations derived from the technical solutions of the present application still fall within the protection scope of the present application.

Claims

1. A triple anti-counterfeiting photonic crystal film, characterized in that, The photonic crystal film comprises: an upper layer containing an aqueous high molecular compound; and a lower layer containing a phosphor dye and a matrix layer material; the aqueous high molecular compound comprises one or a combination of at least two of polyacrylamide, polyacrylic acid, polyvinylpyrrolidone, polyvinyl alcohol, polymaleic anhydride, polyquaternary ammonium salt or polyethylene glycol; the matrix layer material comprises one or a combination of at least two of sodium hyaluronate, sodium carboxymethyl cellulose, sodium carboxyethyl cellulose, starch, alginic acid or chitosan; the phosphor dye component is a compound as described in Formula I; I； wherein R1-R3 are each independently selected from one of hydrogen, hydroxyl, methoxyl or aldehyde groups, and R1-R3 are the same or different.

2. The photonic crystal film according to claim 1, wherein the phosphor dye component is selected from one of the following compounds:

3. The photonic crystal film of claim 1, wherein, the phosphor dye component is selected from one of 3-methoxyl-4-formylphenylboronic acid, p-methoxylphenylboronic acid or p-aldehyde phenylboronic acid.

4. A method for producing the photonic crystal film according to any one of claims 1 to 3, characterized by comprising the following steps: a lower layer solution containing a phosphor dye and a matrix layer material is dropped onto a chromium acid solution treated glass sheet, and then an upper layer solution containing an aqueous high molecular compound is dropped above the lower layer solution, the double layer solution is spread and placed on a heating platform for heating and drying.

5. The preparation method according to claim 4, characterized in that, the concentration of the aqueous high molecular compound in the upper layer solution is 0.03-0.2 mg / mL.

6. The preparation method according to claim 4, characterized in that, the concentration of the matrix layer material in the lower layer solution is 10-30 mg / mL.

7. The preparation method according to claim 4, characterized in that, the concentration of the phosphor dye in the lower layer solution is 0.025-0.1 mg / mL.

8. The preparation method according to claim 4, characterized in that, the heating temperature is 75-95 °C, and the heating time is 30-60 min.

9. Use of the photonic crystal film according to any one of claims 1-3 in the preparation of a multi-prevention material.

10. The use according to claim 9, wherein the photonic crystal film is further patterned to obtain the multi-prevention material.

11. The use according to claim 9, wherein the patterning is performed by laser engraving, and the laser power is 3 W and the scanning time is 10 min.

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