Application of photocurable adhesive in improving the afterglow performance of organic long afterglow materials

Abstract

The present invention discloses the use of a photocurable adhesive for improving the afterglow performance of an organic long-afterglow material. The photocurable adhesive, a host material, a guest material, and a solvent are mixed and stirred at room temperature for at least 5 minutes to obtain a solution. The solution is allowed to stand for at least 2 hours to allow the solvent in the solution to completely evaporate, and then cured by ultraviolet light. The present invention enhances the afterglow performance of existing pure organic long-afterglow materials by introducing the photocurable adhesive into the host and guest materials for photocuring. The preparation method of the present invention enables solution processing, and the film obtained by the photocurable adhesive is smooth and flat, with good and stable afterglow performance. The present invention also discloses a novel non-destructive metal flaw detection technology and expands the application range of organic long-afterglow materials in information encryption and anti-counterfeiting.

Description

Technical Field

[0001] The present invention belongs to the technical field of organic long afterglow materials, and in particular relates to an application of a photocuring adhesive in improving the afterglow performance of an organic long afterglow material. Background Art

[0002] In recent years, the research and development of organic long-persistent luminescence materials (OLPLMs) have attracted widespread attention due to their green preparation process, tunable luminescence properties (color, brightness or duration, etc.) and more sensitive external environment response properties (pressure, temperature or humidity, temperature, etc.), showing unique performance advantages in the fields of biosensing and imaging, information encryption or anti-counterfeiting.

[0003] Numerous studies on OLPLMs (OLPLMs) have demonstrated that a rigid matrix facilitates the stabilization of the triplet state's radiative decay, thereby yielding room-temperature phosphorescent (RTP) materials with long-lasting luminescence. In particular, some crystalline OLPLMs with host-guest doped structures exhibit environmentally stable afterglow properties, with LPL durations ranging from seconds to tens of seconds. This is achieved by constructing a rigid host crystal structure to promote triplet state radiative decay and prolong the RTP lifetime in the presence of water and oxygen. However, due to the demanding crystal formation conditions and limited reproducibility, such crystalline OLPLMs are difficult to achieve solution processing and large-area uniform luminescence. Furthermore, by doping or copolymerizing phosphors into a specific rigid amorphous polymer matrix, molecular vibrations can be effectively suppressed, enabling targeted and efficient generation of persistent RTP and LPL emission. However, due to the lack of clear and effective strategies for constructing a rigid environment, research on utilizing a rigid environment to enhance the performance of amorphous OLPLMs remains relatively limited. This has prompted the development of a universal strategy to construct amorphous OLPLMs with rigidity to improve their reproducibility and processability for large-scale applications. Summary of the Invention

[0004] In view of the shortcomings of the prior art, the object of the present invention is to provide a method for improving the afterglow performance of organic long afterglow materials by using a photocurable adhesive.

[0005] Another object of the present invention is to provide a method for preparing the film.

[0006] Another object of the present invention is to provide a luminous body.

[0007] Another object of the present invention is to provide an application of an organic long afterglow material in metal flaw detection.

[0008] Another object of the present invention is to provide a use of light-curing adhesive in anti-counterfeiting.

[0009] Another object of the present invention is to provide a use of the light-curing adhesive in information encryption.

[0010] The purpose of the present invention is achieved through the following technical solutions.

[0011] A method for improving the afterglow performance of an organic long afterglow material by using a photocurable adhesive is method 1 or method 2:

[0012] Method 1: Evenly mix the light-curing adhesive, solvent, and organic long-lasting glow material, evaporate the solvent completely, and cure with ultraviolet light. The ratio of the light-curing adhesive to the organic long-lasting glow material is (4-6):1 by weight.

[0013] Method 2: Mix a photocurable adhesive, a host material, a guest material, and a solvent, stir at room temperature for at least 5 minutes to obtain a solution, let it stand for at least 2 hours to allow the solvent in the solution to evaporate completely, and cure it with ultraviolet light. The ratio of the host material, the guest material, and the photocurable adhesive is 100:1:(400-600) by mass.

[0014] In the above technical solution, the ratio of the mass fraction of the light-curing adhesive to the volume fraction of the solvent is 4:(5-15), the unit of mass fraction is g, and the unit of volume fraction is ml.

[0015] In the above technical solution, the solvent is dichloromethane.

[0016] In the above technical solution, the curing time is 20 to 40 seconds.

[0017] A method for preparing a thin film comprises: mixing a photocurable adhesive, a host material, a guest material, and a solvent; stirring the mixture at room temperature of 20-25°C for at least 5 minutes to obtain a solution; coating the solution on a substrate; and curing the solution by ultraviolet light after the solvent evaporates to obtain a thin film. The ratio of the host material, the guest material, and the photocurable adhesive is 100:1:(400-600) by mass.

[0018] In the above technical solution, the solvent is dichloromethane.

[0019] In the above technical solution, the ratio of the mass fraction of the photocurable adhesive to the volume fraction of the solvent is 4:(5-15), the unit of mass fraction is g, and the unit of volume fraction is mL.

[0020] In the above technical solution, the coating method is drip coating.

[0021] A luminous body comprises an organic long afterglow material and a cured light-curing adhesive, wherein the organic long afterglow material is located in the light-curing adhesive.

[0022] In the above technical solution, the object material is:

[0023] R1 is H, CH3, OCH3, O(CH2)5, CN, CHO, NO2 or CH═CH(C6H5), R2 is H, CH3, OCH3, O(CH2)5, CN, CHO, NO2 or CH═CH(C6H5), R3 is H, CH3, OCH3, O(CH2)5, CN, CHO, NO2 or CH═CH(C6H5), X═C, O, P or Si;

[0024] The main material is:

[0025]

[0026] Among them, X1, X2 and X3 are independent of each other, and X1, X2, X3 are H, C n H 2n+1 , OCH3, O(CH2)5, CN, CHO, NO2 and CH=CH(C6H5).

[0027] Application of organic long afterglow materials in metal flaw detection.

[0028] In the above technical solution, a photocurable adhesive, a main material, a guest material and a solvent are mixed and stirred at room temperature of 20 to 25°C for at least 5 minutes to obtain a solution. The solution is applied to a metal surface, excess solution on the metal surface is wiped off, and the metal surface is cured with ultraviolet light. The metal surface is then irradiated with ultraviolet light, and the position and size of the defect are judged by the afterglow. When an open defect exists on the metal surface, the open defect emits a long afterglow, and when no open defect exists on the metal surface, no long afterglow is emitted. The ratio of the main material, the guest material and the photocurable adhesive is 100:1:(400 to 600) by mass.

[0029] In the above technical solution, the ratio of the mass fraction of the light-curing adhesive to the volume fraction of the solvent is 4:(5-15), the unit of mass fraction is g, and the unit of volume fraction is ml.

[0030] In the above technical solution, the solvent is dichloromethane.

[0031] In the above technical solution, the curing time is 20 to 40 seconds.

[0032] The use of light-curing adhesive in anti-counterfeiting.

[0033] The use of light-curing adhesive in anti-counterfeiting is to illuminate the surface of the object to be tested with ultraviolet light when distinguishing authenticity. The authenticity of the object to be tested is determined based on whether the surface of the object to be tested emits long afterglow light or the afterglow time is long. The emission of long afterglow light on the surface of the object to be tested is achieved by the following method:

[0034] Step 1: mixing a photocurable adhesive, a host material, a guest material, and a solvent, and stirring at room temperature for at least 5 minutes to obtain a solution, wherein the ratio of the host material, the guest material, and the photocurable adhesive is 100:1:(400-600) by weight;

[0035] In the step 1, the solvent is dichloromethane.

[0036] In the step 1, the ratio of the mass fraction of the photocurable adhesive to the volume fraction of the solvent is 4:(5-15), the unit of the mass fraction is g, and the unit of the volume fraction is ml.

[0037] Step 2: Spray the solution onto the surface of the real object to be tested, wait for the solvent to evaporate, and then cure it with ultraviolet light.

[0038] In step 2, the curing time is 20 to 40 seconds.

[0039] The use of photocuring adhesive in information encryption, the method of improving the afterglow performance of organic long afterglow materials by using photocuring adhesive, extending the afterglow time of organic long afterglow materials, making different afterglow times and colors represent different meanings, and realizing information encryption.

[0040] The beneficial effects of the present invention are as follows:

[0041] 1. By introducing a photocurable adhesive into the host and guest materials for photocuring, the afterglow performance of existing pure organic long afterglow materials can be enhanced;

[0042] 2. The preparation method of the present invention can be processed in solution, and the obtained film is flat and smooth, with good and stable afterglow performance. The afterglow time of the obtained film is improved, and the conditions are mild and not harsh, which will be very beneficial to the application of LPL materials in various scenarios. It can achieve large-scale film preparation;

[0043] 3. The present invention discloses a novel non-destructive metal flaw detection technology.

[0044] 4. The present invention extends the afterglow time of the organic long afterglow material by introducing a photocurable adhesive, and can realize large-area film preparation, thereby expanding the application scope of the organic long afterglow material in information encryption and anti-counterfeiting. BRIEF DESCRIPTION OF THE DRAWINGS

[0045] Figure 1(a) Optical micrograph of the organic long afterglow material obtained in Comparative Example 1 (from left to right: upon excitation, 2 seconds after turning off the UV lamp, and 6 seconds after turning off the UV lamp); (b) Macroscopic LPL images of the film obtained in Example 1 at room temperature (from left to right: upon excitation, 4 seconds after turning off the UV lamp, and 9 seconds after turning off the UV lamp);

[0046] Figure 2 (a) XRD of the organic long afterglow material obtained in Comparative Example 1, (b) XRD of the thin film obtained in Example 1;

[0047] Figure 3 (a) Afterglow performance attenuation spectrum of the organic long afterglow material obtained in Comparative Example 1, (b) Afterglow performance attenuation spectrum of the film obtained in Example 1;

[0048] Figure 4 (a) Optical micrographs of the organic long afterglow material obtained in Comparative Example 2 (from left to right: upon excitation, 1 second after the UV lamp is turned off, and 3 seconds after the UV lamp is turned off); (b) Macroscopic LPL images of the film obtained in Example 2 at room temperature (from left to right: upon excitation, 3 seconds after the UV lamp is turned off, and 7 seconds after the UV lamp is turned off);

[0049] Figure 5 (a) Afterglow performance attenuation spectrum of the organic long afterglow material obtained in Comparative Example 2, (b) Afterglow performance attenuation spectrum of the film prepared in Example 2;

[0050] Figure 6 (a) Optical micrographs of the organic long afterglow material obtained in Comparative Example 3 (from left to right: upon excitation, 1 second after the UV lamp is turned off, and 3 seconds after the UV lamp is turned off); (b) Macroscopic LPL images of the film prepared in Example 3 at room temperature (from left to right: upon excitation, 3 seconds after the UV lamp is turned off, and 7 seconds after the UV lamp is turned off);

[0051] Figure 7 (a) Afterglow performance attenuation spectrum of the organic long afterglow material obtained in Comparative Example 3, (b) Afterglow performance attenuation spectrum of the film prepared in Example 3;

[0052] Figure 8 Macroscopic LPL images of the film in Example 4 at room temperature (from left to right: at the time of excitation, 4 seconds after the UV lamp is turned off, and 9 seconds after the UV lamp is turned off);

[0053] Figure 9 This is the afterglow performance attenuation spectrum of the film in Example 4;

[0054] Figure 10(a) Optical micrographs of the organic long afterglow material obtained in Comparative Example 5 (from left to right: upon excitation, 1 second after the UV lamp is turned off, and 2 seconds after the UV lamp is turned off); (b) Macroscopic LPL images of the film in Example 5 at room temperature (from left to right: upon excitation, 1 second after the UV lamp is turned off, and 3 seconds after the UV lamp is turned off);

[0055] Figure 11 (a) Afterglow performance attenuation spectrum of the organic long afterglow material obtained in Comparative Example 5, (b) Afterglow performance attenuation spectrum of the film in Example 5;

[0056] Figure 12 (a) Optical micrographs of the organic long afterglow material obtained in Comparative Example 6 (from left to right: upon excitation, 1 second after the UV lamp is turned off, and 2 seconds after the UV lamp is turned off); (b) Macroscopic LPL images of the film in Example 6 at room temperature (from left to right: upon excitation, 1 second after the UV lamp is turned off, and 3 seconds after the UV lamp is turned off);

[0057] Figure 13 (a) Afterglow performance attenuation spectrum of the organic long afterglow material obtained in Comparative Example 6, (b) Afterglow performance attenuation spectrum of the film in Example 6;

[0058] Figure 14 Macroscopic LPL images of the film in Example 7 at room temperature (from left to right: 1 second after the UV lamp is turned off and 2 seconds after the UV lamp is turned off);

[0059] Figure 15 This is the afterglow performance attenuation spectrum of the film in Example 7;

[0060] Figure 16 This is the afterglow performance attenuation spectrum of the film in Example 8;

[0061] Figure 17 (a) Afterglow performance attenuation spectrum of the organic long afterglow material obtained in Comparative Example 9, (b) Afterglow performance attenuation spectrum of the film in Example 9;

[0062] Figure 18 (a) Afterglow performance attenuation spectrum of the organic long afterglow material obtained in Comparative Example 10, (b) Afterglow performance attenuation spectrum of the film in Example 10;

[0063] Figure 19 This is the afterglow performance attenuation spectrum of the film in Example 11;

[0064] Figure 20 This is the afterglow performance attenuation spectrum of the film in Example 12;

[0065] Figure 21(a) Afterglow performance attenuation spectrum of the organic long afterglow material obtained in Comparative Example 13, (b) Afterglow performance attenuation spectrum of the film in Example 13;

[0066] Figure 22 (a) Afterglow performance attenuation spectrum of the organic long afterglow material obtained in Comparative Example 14, (b) Afterglow performance attenuation spectrum of the film in Example 14;

[0067] Figure 23 This is a photo of the application of the light-curing adhesive in metal flaw detection in Example 16;

[0068] Figure 24 This is a photo of the use of light-curing adhesive in information encryption and anti-counterfeiting in Example 17. DETAILED DESCRIPTION

[0069] The technical solution of the present invention is further described below with reference to specific embodiments.

[0070] In the following Examples 1 to 19 and the comparative examples, the main material and the guest material were purchased from Tianjin Xiens Biochemical Technology Co., Ltd. (purity: 98%); the photocuring adhesive was purchased from Shenzhou Pengketai Trading Co., Ltd., LOCTITE@AA3491, AA 3491 is a transparent, low viscosity, modified acrylate liquid adhesive that cures after a few seconds of exposure to 365nm UV light.

[0071] The instruments and models involved in the tests in the following examples are:

[0072] Leica DM2700M functional optical microscope;

[0073] Ocean Optics multi-band spectrometer;

[0074] Room temperature: 20~25℃.

[0075] The substrate may be a glass sheet or paper. In the following embodiments, the substrate is glass.

[0076] The power of the UV lamp in the following examples is 15W (365nm).

[0077] Examples 1 to 14

[0078] A photocurable adhesive is used to improve the afterglow performance of an organic long-afterglow material. The specific method is as follows: a photocurable adhesive, a host material, a guest material, and a solvent are mixed, stirred at room temperature of 20-25°C for 5 minutes to obtain a solution, 0.5 mL of the solution is dropwise coated on a substrate, and allowed to stand at room temperature for 2 hours to allow the solvent in the solution to evaporate completely (at which point the host material and the guest material form an organic long-afterglow material), and then cured with a 15W UV lamp for 30 seconds to obtain a thin film. The ratio of the host material, guest material, and photocurable adhesive is 100:1:400 by mass, the ratio of the mass of the photocurable adhesive to the volume of the solvent is 4:10, the units of mass are g and volume are mL, and the solvent is dichloromethane. The host and guest materials of different embodiments are shown in Table 1 ("1-14" in Examples 1-14 are indicated by the serial numbers in Table 1). The photocurable adhesive was purchased from Shenzhou Pengketai Trading Co., Ltd. (LOCTITE@AA3491).

[0079] Comparative Examples 1 to 14

[0080] A method for preparing an organic long afterglow material comprises: mixing a host material, a guest material and a solvent, stirring for 5 minutes at room temperature of 20 to 25°C to obtain a solution, applying 0.5 ml of the solution dropwise on a substrate, and standing for 2 hours at room temperature to allow the solvent in the solution to evaporate completely, thereby obtaining an organic long afterglow material, wherein the ratio of the host material to the guest material is 100:1 by mass, the ratio of the mass fraction of the host material to the volume fraction of the solvent is 1:10, the unit of mass fraction is g, the unit of volume fraction is mL, and the solvent is dichloromethane. The host materials and guest materials of different comparative examples are shown in Table 1 ("1 to 14" in comparative examples 1 to 14 are shown in the serial numbers in Table 1). The light-curing adhesive was purchased from: Shenzhou Pengketai Trading Co., Ltd. (LOCTITE@AA3491).

[0081] Table 1

[0082]

[0083]

[0084]

[0085] Organic long-lasting light (LPL) materials consist of a host material that forms regular flaky crystals, with the guest material uniformly and freely dispersed within the host material's flaky crystals. By introducing a photocurable adhesive and performing a light-curing process, a LPL film with relatively uniform luminescence can be obtained.

[0086] Depend on Figure 1As can be seen from a, regular rectangular crystals of uniform size can be clearly seen under an optical microscope. The crystals are square flakes with a single crystal size of approximately 20 μm, proving that the (pure) organic long-afterglow material obtained in Comparative Example 1 is indeed a crystalline structure. When the crystals were excited with a 365 nm UV lamp for 3 seconds and then turned off, the crystals still maintained an afterglow for 6 seconds. Figure 1 Figure b is a macroscopic LPL image of the film obtained from Example 1 at room temperature. The film is excited by a 365nm ultraviolet lamp, and the ultraviolet lamp is turned off after irradiation for 3 seconds. The film can maintain afterglow for 9 seconds. It can be seen that the film emits light more uniformly, indicating that the introduction of photocurable adhesive and photocuring in the present invention enhances the luminescence properties of the (pure) organic long afterglow material.

[0087] Figure 2 a is the XRD of the (pure) organic long afterglow material obtained in Comparative Example 1. As can be seen from the figure, it has obvious and sharp peaks, indicating that it has good crystallization properties. Figure 2 From b, we can see that after the introduction of photocuring adhesive and the photocuring process to obtain the film, the crystallinity decreases.

[0088] Depend on Figure 3 From a, we can see that -2s to 0s is the time when the (pure) organic long afterglow material of Comparative Example 1 is irradiated by a 365nm UV lamp, and the organic long afterglow material exhibits photoluminescence characteristics; 0s to 6s is the time when the (pure) organic long afterglow material emits long afterglow light after the UV lamp is removed, and the afterglow time is about 6s, which is similar to the afterglow time observed by the naked eye. Figure 3 As can be seen from b, the film prepared in Example 1 exhibits photoluminescence from -2s to 0s when irradiated with a 365nm UV lamp. The film exhibits photoluminescence from 0s to 9s after the UV lamp is removed, with a long afterglow duration of approximately 9s, similar to that observed with the naked eye. This indicates that the introduction of a photocurable adhesive and photocuring enhances the luminescence properties of organic long-afterglow materials.

[0089] Depend on Figure 4 As can be seen from a, regular rectangular crystals with relatively uniform size can be clearly seen under an optical microscope. The crystals are square flakes with a single crystal size of approximately 20 μm, proving that the (pure) organic long-afterglow material obtained in Example 2 is indeed a crystalline structure. The white crystals were excited with a 365 nm UV lamp for 3 seconds and then turned off. The crystals still maintained afterglow for 3 seconds. Figure 4 Figure b is a macroscopic LPL image of the film prepared by Example 2 at room temperature. The film was excited by a 365nm ultraviolet lamp, and the ultraviolet lamp was turned off after irradiation for 3 seconds. The film can maintain afterglow for 7 seconds. It can be seen that the obtained film emits light more uniformly, indicating that the introduction of photocurable adhesive and photocuring in the present invention enhances the luminescence properties of the (pure) organic long afterglow material.

[0090] Depend on Figure 5 From a, we can see that -2s to 0s is the time when the (pure) organic long afterglow material is irradiated by 365nm UV light, and the organic long afterglow material shows photoluminescence characteristics; 0s to 3s is the time when the organic long afterglow material is removed from the UV light, which is about 3s, similar to the afterglow time observed by the naked eye. Figure 5 As can be seen from b, the film prepared in Example 2 exhibits photoluminescence from -2s to 0s when irradiated with a 365nm UV lamp. The film exhibits photoluminescence from 0s to 7s after the UV lamp is removed, with a long afterglow duration of approximately 7s, similar to that observed with the naked eye. This indicates that the introduction of a photocurable adhesive and photocuring enhances the luminescence properties of organic long-afterglow materials.

[0091] Depend on Figure 6 As can be seen from a, regular rectangular crystals with relatively uniform size can be clearly seen under an optical microscope. The crystals are square flakes with a single crystal size of about 20 μm, proving that the organic long-afterglow material obtained in Comparative Example 3 is indeed a crystalline structure. The white crystals were excited with a 365 nm UV lamp for 3 seconds and then turned off. The crystals still maintained afterglow for 3 seconds. Figure 6 Figure b is a macroscopic LPL image of the film prepared in Example 3 at room temperature. The film was excited by a 365nm ultraviolet lamp, and the ultraviolet lamp was turned off after irradiation for 3 seconds. The film can maintain afterglow for 7 seconds. It can be seen that the obtained film emits light more uniformly, indicating that the introduction of photocurable adhesive and photocuring in the present invention enhances the luminescence properties of organic long afterglow materials.

[0092] Depend on Figure 7 From a, we can see that from -2s to 0s, the organic long afterglow material is irradiated by 365nm UV light, and the material exhibits photoluminescence characteristics; from 0s to 3s, the (pure) organic long afterglow material emits long afterglow light after the UV light is removed, and the afterglow time is about 3s, which is similar to the afterglow time observed by the naked eye. Figure 7 As can be seen from b, the film prepared in Example 3 exhibits photoluminescence from -2s to 0s, when irradiated with a 365nm UV lamp. The film exhibits photoluminescence from 0s to 7s after the UV lamp is removed, with a long afterglow duration of approximately 7s, similar to that observed with the naked eye. This demonstrates that the introduction of a photocurable adhesive and photocuring enhances the luminescence properties of (pure) organic long-afterglow materials.

[0093] Figure 8 This is a macroscopic LPL picture of the film in Example 4 at room temperature. The film is excited by a 365nm ultraviolet lamp. After irradiation for 3 seconds, the ultraviolet lamp is turned off. The film can maintain afterglow for 9 seconds. It can be seen that the obtained film emits light more uniformly.

[0094] Depend on Figure 9It can be seen that from -2s to 0s, the film in Example 4 was irradiated with a 365nm ultraviolet lamp, and the film exhibited photoluminescence characteristics; from 0s to 9s, the film had a long afterglow after the ultraviolet lamp was removed, and the afterglow time was about 9s, which was similar to the afterglow time observed by the naked eye.

[0095] Depend on Figure 10 As can be seen from a, regular rectangular crystals of relatively uniform size can be clearly observed under an optical microscope. The crystals are square flakes with individual crystals approximately 20 μm in size, proving that the (pure) organic long-afterglow material obtained in Comparative Example 5 is indeed a crystalline structure. When the white crystals were excited with a 365 nm UV lamp for 3 seconds and then turned off, the crystals still maintained an afterglow for 1 second, but no afterglow was observed after 2 seconds. Figure 10 Figure b is a macroscopic LPL image of the film in Example 5 at room temperature. The film is excited by a 365nm ultraviolet lamp, and the ultraviolet lamp is turned off after irradiation for 3 seconds. The film can maintain afterglow for 3 seconds. It can be seen that the obtained film emits light more uniformly, indicating that the introduction of photocurable adhesive and photocuring in the present invention enhances the luminescence properties of the (pure) organic long afterglow material.

[0096] Depend on Figure 11 From a, we can see that -2s to 0s is the time when the (pure) organic long afterglow material is irradiated by 365nm UV light, and the material exhibits photoluminescence characteristics; 0s to 1s is the time when the (pure) organic long afterglow material emits long afterglow light after the UV light is removed, and the afterglow time is about 1s, which is similar to the afterglow time observed by the naked eye. Figure 11 As can be seen from b, the film in Example 5 exhibits photoluminescence from -2s to 0s when irradiated with a 365nm UV lamp. The film exhibits long-lasting luminescence from 0s to 3s after the UV lamp is removed, with an afterglow duration of approximately 3s, similar to that observed with the naked eye. This demonstrates that the introduction of a photocurable adhesive and subsequent photocuring enhances the luminescence properties of (pure) organic long-lasting luminescence materials.

[0097] Depend on Figure 12 As can be seen from a, regular rectangular crystals of relatively uniform size can be clearly observed under an optical microscope. The crystals are square flakes with individual crystals approximately 20 μm in size, proving that the (pure) organic long-afterglow material obtained in Example 6 is indeed a crystalline structure. When the white crystals were excited with a 365 nm UV lamp for 3 seconds and then turned off, the crystals still maintained an afterglow for 1 second, but no afterglow was observed after 2 seconds. Figure 12 Figure b is a macroscopic LPL image of the film in Example 6 at room temperature. The film is excited by a 365nm ultraviolet lamp, and the ultraviolet lamp is turned off after irradiation for 3 seconds. The film can maintain afterglow for 3 seconds. It can be seen that the obtained film emits light more uniformly, indicating that the introduction of photocurable adhesive and photocuring in the present invention enhances the luminescence properties of the (pure) organic long afterglow material.

[0098] Depend on Figure 13 From a, we can see that -2s to 0s is the time when the (pure) organic long afterglow material is irradiated by 365nm UV light, and the organic long afterglow material shows photoluminescence characteristics; 0s to 1s is the time when the (pure) organic long afterglow material emits long afterglow light after the UV light is removed, and the afterglow time is about 1s, which is similar to the afterglow time observed by the naked eye. Figure 13 As can be seen from b, the film in Example 6 exhibits photoluminescence from -2s to 0s when irradiated with a 365nm UV lamp. The film exhibits long-lasting luminescence from 0s to 3s after the UV lamp is removed, with an afterglow duration of approximately 3s, similar to that observed with the naked eye. This demonstrates that the introduction of a photocurable adhesive and subsequent photocuring enhances the luminescence properties of (pure) organic long-lasting luminescence materials.

[0099] Figure 14 This is a macroscopic LPL picture of the film in Example 7 at room temperature. The film is excited by a 365nm ultraviolet lamp. After irradiation for 3 seconds, the ultraviolet lamp is turned off. The film can maintain afterglow for 2 seconds. It can be seen that the obtained film emits light more uniformly.

[0100] Depend on Figure 15 It can be seen that from -2s to 0s, the film in Example 7 was irradiated with a 365nm ultraviolet lamp, and the film exhibited photoluminescence characteristics; from 0s to 2s, the film had a long afterglow after the ultraviolet lamp was removed, and the afterglow time was about 2s, which was similar to the afterglow time observed by the naked eye.

[0101] Figure 16 It can be seen that from -2s to 0s, the film in Example 8 was irradiated with a 365nm ultraviolet lamp, and the film exhibited photoluminescence characteristics; from 0s to 2s, the film had a long afterglow after the ultraviolet lamp was removed, and the afterglow time was about 2s, which was similar to the afterglow time observed by the naked eye.

[0102] Depend on Figure 17 From a, we can see that -2s to 0s is the time when the (pure) organic long afterglow material is irradiated by 365nm UV light, and the material exhibits photoluminescence characteristics; 0s to 1s is the time when the (pure) organic long afterglow material emits long afterglow light after the UV light is removed, and the afterglow time is about 1s, which is similar to the afterglow time observed by the naked eye. Figure 17 As can be seen from b, the film in Example 9 exhibits photoluminescence from -2s to 0s when irradiated with a 365nm UV lamp. The film exhibits long-lasting luminescence from 0s to 4s after the UV lamp is removed, with an afterglow duration of approximately 4s, similar to that observed with the naked eye. This demonstrates that the introduction of a photocurable adhesive and subsequent photocuring enhances the luminescence properties of (pure) organic long-lasting luminescence materials.

[0103] Depend on Figure 18From a, we can see that -2s to 0s is the time when the (pure) organic long afterglow material is irradiated by 365nm UV light, and the organic long afterglow material shows photoluminescence characteristics; 0s to 1s is the time when the (pure) organic long afterglow material emits long afterglow light after the UV light is removed, and the afterglow time is about 1s, which is similar to the afterglow time observed by the naked eye. Figure 18 As can be seen from b, the film of Example 10 exhibits photoluminescence from -2s to 0s when irradiated with a 365nm UV lamp. The film exhibits long-lasting luminescence from 0s to 4s after the UV lamp is removed, with an afterglow duration of approximately 4s, similar to that observed with the naked eye. This demonstrates that the introduction of a photocurable adhesive and subsequent photocuring enhances the luminescence properties of (pure) organic long-lasting luminescence materials.

[0104] Figure 19 It can be seen that from -2s to 0s, the film in Example 11 was irradiated with a 365nm ultraviolet lamp, and the film exhibited photoluminescence characteristics; from 0s to 2s, the film had a long afterglow after the ultraviolet lamp was removed, and the afterglow time was about 2s, which was similar to the afterglow time observed by the naked eye.

[0105] Depend on Figure 20 It can be seen that from -2s to 0s, the film in Example 12 is irradiated with a 365nm ultraviolet lamp, and the film exhibits photoluminescence characteristics; from 0s to 2s, the film emits long afterglow light after the ultraviolet lamp is removed, and the afterglow time is about 2s, which is similar to the afterglow time observed by the naked eye.

[0106] Depend on Figure 21 From a, we can see that -2s to 0s is the time when the (pure) organic long afterglow material is irradiated by 365nm UV light, and the material exhibits photoluminescence characteristics; 0s to 1s is the time when the (pure) organic long afterglow material emits long afterglow light after the UV light is removed, and the afterglow time is about 1s, which is similar to the afterglow time observed by the naked eye. Figure 21 As can be seen from b, the film in Example 13 exhibits photoluminescence from -2s to 0s when irradiated with a 365nm UV lamp. The film exhibits long-lasting luminescence from 0s to 6s after the UV lamp is removed, with an afterglow duration of approximately 6s, similar to that observed with the naked eye. This demonstrates that the introduction of a photocurable adhesive and subsequent photocuring enhances the luminescence properties of (pure) organic long-lasting luminescence materials.

[0107] Depend on Figure 22 From a, we can see that -2s to 0s is the time when the (pure) organic long afterglow material is irradiated by 365nm UV light, and the material exhibits photoluminescence characteristics; 0s to 1s is the time when the (pure) organic long afterglow material emits long afterglow light after the UV light is removed, and the afterglow time is about 1s, which is similar to the afterglow time observed by the naked eye. Figure 22As can be seen from b, the film in Example 14 exhibits photoluminescence from -2s to 0s when irradiated with a 365nm UV lamp. The film exhibits long-lasting luminescence from 0s to 6s after the UV lamp is removed, with an afterglow duration of approximately 6s, similar to that observed with the naked eye. This demonstrates that the introduction of a photocurable adhesive and subsequent photocuring enhances the luminescence properties of (pure) organic long-lasting luminescence materials.

[0108] Example 15 (for comparison)

[0109] A host material, a guest material, and a solvent were mixed and stirred at room temperature (20-25°C) for 5 minutes to obtain a solution. The solution was applied to a metal surface, and excess solution from the metal surface was removed using dichloromethane as a cleaning agent. The ratio of host material to guest material by mass was 100:1, and the ratio of host material by mass to solvent by volume was 1:10. The units of mass fractions were g, and the units of volume fractions were ml. The solvent was dichloromethane. The host material and guest material were the same as those in Example 1, respectively.

[0110] When UV light is used to illuminate a metal surface, the long afterglow emitted by opening defects on the metal surface is not fully imaged (or even not imaged at all if the opening defect is small). This is because the lack of a photocurable adhesive causes the solvent to evaporate quickly, causing the host and guest materials to form crystals, which can be easily wiped off.

[0111] Example 16

[0112] A solution containing an organic long-afterglow material and a photocurable adhesive is prepared by mixing a photocurable adhesive, a host material, a guest material, and a solvent, and stirring the mixture at room temperature of 20-25°C for 5 minutes to obtain a solution. The photocurable adhesive, host material, guest material, and solvent are the same as those in Example 1. The ratio of the host material to the guest material to the photocurable adhesive is 100:1:400 by mass, and the ratio of the mass of the photocurable adhesive to the volume of the solvent is 4:10. The units of mass are g and volume are mL. The solvent is dichloromethane.

[0113] The application of photocuring adhesive in metal flaw detection is to apply a solution containing organic long afterglow material and photocuring adhesive on the metal surface, use dichloromethane as a cleaning agent to wipe off the excess solution on the metal surface, and after the dichloromethane evaporates, use a 365nm ultraviolet lamp to cure it, and use the long afterglow material in the solution as a penetrant and developer for penetrant flaw detection: use ultraviolet lamp to irradiate the metal surface, and judge the position and size of the defect by the afterglow. When there is an open defect on the metal surface, the open defect emits a long afterglow, and when there is no open defect on the metal surface, no long afterglow is emitted.

[0114] like Figure 23As shown, under the excitation of 365nm ultraviolet light, the open defect shows strong blue-purple fluorescence ( Figure 23 Left), when the UV lamp excitation light source is removed, a long afterglow can be seen from the opening defect ( Figure 23 Right), showing a yellow-green afterglow lasting up to 9 seconds. The afterglow phenomenon can be used to determine the location and size of defects, thereby achieving non-destructive testing of metal flaws.

[0115] Example 17

[0116] The use of light-curing adhesive in anti-counterfeiting. The specific method includes the following steps:

[0117] Step 1: Mix a photocurable adhesive, a host material, a guest material, and a solvent, and stir at room temperature of 20-25° C. for 5 minutes to obtain a solution, wherein the photocurable adhesive, the host material, the guest material, and the solvent are the same as those in Example 1. The ratio of the host material, the guest material, and the photocurable adhesive is 100:1:400 by mass, the ratio of the mass of the photocurable adhesive to the volume of the solvent is 4:10, the units of mass are g, the units of volume are mL, and the solvent is dichloromethane;

[0118] Step 2: Spray the solution onto the surface of a real object to be tested, let it stand at room temperature until the dichloromethane evaporates, and then cure it using a 365nm ultraviolet lamp. The object to be tested can be glass, plastic, fabric, paper, etc. In this embodiment, the surface of a glass bulb emitting 365nm ultraviolet light is used.

[0119] Step 3: When distinguishing the authenticity, use ultraviolet light to illuminate the surface of the object to be tested, and determine the authenticity of the object to be tested based on whether the surface of the object to be tested emits long afterglow light or long afterglow time.

[0120] For example: when the surface of the object to be tested emits a long afterglow light, the object to be tested is judged to be true; when the surface of the object to be tested does not emit a long afterglow light, the object to be tested is judged to be false. Figure 24 As shown in a, after curing is completed, it is excited by a 365nm ultraviolet lamp, and the surface of the object to be tested emits bright blue-purple fluorescence. When the 365nm ultraviolet lamp is turned off, the surface of the object to be tested emits a yellow-green afterglow for up to 9 seconds. Anti-counterfeiting is achieved based on the presence or absence of afterglow.

[0121] For example, the difficulty of counterfeiting can be increased by using organic long-afterglow materials with different afterglow times and colors. For example, when the surface of the object to be tested is irradiated with ultraviolet light, if the surface of the object to be tested emits long afterglow light for a certain length of time, it is judged to be authentic, otherwise it is fake.

[0122] Example 18

[0123] The use of light-curing adhesive in anti-counterfeiting is basically the same as Example 17, with the only difference being that the host material and guest material in this example are the same as those in Example 3.

[0124] like Figure 24 As shown in b, after curing is completed, it is excited by a 365nm ultraviolet lamp, and the surface of the object to be tested emits bright blue-purple fluorescence. When the 365nm ultraviolet lamp is turned off, the surface of the object to be tested emits a cyan afterglow for up to 7 seconds. Anti-counterfeiting is achieved based on the presence or absence of afterglow.

[0125] Example 19

[0126] The use of light-curing adhesive in information encryption.

[0127] The method of improving the afterglow performance of organic long afterglow materials by light-curing adhesive can prolong the afterglow time of organic long afterglow materials, make different afterglow times and colors represent different meanings, and realize information encryption.

[0128] In the above embodiments 1 to 19, by replacing the photocuring glue with LOCTITE@AA3492 (Henkel Loctite (China) Co., Ltd.), UV curing adhesive 3491 (Guangdong Youyang New Materials Co., Ltd.) and UV curing adhesive 3492 (Guangdong Youyang New Materials Co., Ltd.), the technical effects consistent with the above embodiments can be achieved.

[0129] The above is an exemplary description of the present invention. It should be noted that, without departing from the core of the present invention, any simple deformation, modification or other equivalent replacement that can be made by other skilled in the art without expending creative labor falls within the scope of protection of the present invention.

Claims

1. A method for improving the afterglow performance of organic long afterglow materials by using a photocurable adhesive, characterized in that: A photocurable adhesive, a host material, a guest material, and a solvent are mixed and stirred at room temperature for at least 5 minutes to obtain a solution. The solution is allowed to stand for at least 2 hours to allow the solvent in the solution to evaporate completely, and then cured by ultraviolet light. The ratio of the host material, the guest material, and the photocurable adhesive is 100:1:(400-600) by weight. The photocurable adhesive is LOCTITE@AA3491. The object material is: R1 is H, CH3, OCH3, CN, CHO, NO2 or CH=CH(C6H5), R2 is H, CH3, OCH3, CN, CHO, NO2 or CH=CH(C6H5), R3 is H, CH3, OCH3, CN, CHO, NO2 or CH=CH(C6H5), X=C or Si; The main material is: Among them, X1, X2 and X3 are independent of each other, and X1, X2, X3 are H, C n H 2n+1 , OCH3, CN, CHO, NO2 and CH=CH(C6H5).

2. The method according to claim 1, characterized in that The ratio of the mass fraction of the light-curing adhesive to the volume fraction of the solvent is 4:(5-15), the unit of the mass fraction is g, and the unit of the volume fraction is ml. The solvent is dichloromethane, and the curing time is 20-40s.

3. A method for preparing a thin film, characterized in that: include: A photocurable adhesive, a host material, a guest material, and a solvent are mixed and stirred at room temperature of 20-25° C. for at least 5 minutes to obtain a solution, which is coated on a substrate. After the solvent evaporates, the solution is cured by ultraviolet light to obtain a film, wherein the ratio of the host material, the guest material, and the photocurable adhesive is 100:1:(400-600) by weight; the photocurable adhesive is LOCTITE@AA3491; The object material is: R1 is H, CH3, OCH3, CN, CHO, NO2 or CH=CH(C6H5), R2 is H, CH3, OCH3, CN, CHO, NO2 or CH=CH(C6H5), R3 is H, CH3, OCH3, CN, CHO, NO2 or CH=CH(C6H5), X=C or Si; The main material is: Among them, X1, X2 and X3 are independent of each other, and X1, X2, X3 are H, C n H 2n+1 , OCH3, CN, CHO, NO2 and CH=CH(C6H5).

4. The preparation method according to claim 3, characterized in that The solvent is dichloromethane.

5. The preparation method according to claim 4, characterized in that The ratio of the mass fraction of the light-curing adhesive to the volume fraction of the solvent is 4:(5-15), the unit of the mass fraction is g, and the unit of the volume fraction is mL.

6. A luminous body, characterized in that: include: An organic long-afterglow material and a cured photocurable adhesive, wherein the organic long-afterglow material is located within the photocurable adhesive, and a host material and a guest material form the organic long-afterglow material, wherein the ratio of the host material, the guest material, and the photocurable adhesive is 100:1:(400-600) by weight; the photocurable adhesive is LOCTITE@AA3491; The object material is: R1 is H, CH3, OCH3, CN, CHO, NO2 or CH=CH(C6H5), R2 is H, CH3, OCH3, CN, CHO, NO2 or CH=CH(C6H5), R3 is H, CH3, OCH3, CN, CHO, NO2 or CH=CH(C6H5), X=C or Si; The main material is: Among them, X1, X2 and X3 are independent of each other, and X1, X2, X3 are H, C n H 2n+1 , OCH3, CN, CHO, NO2 and CH=CH(C6H5).

7. The application of light-curing adhesive in metal flaw detection is characterized by: A photocurable adhesive, a host material, a guest material, and a solvent are mixed and stirred at room temperature of 20-25° C. for at least 5 minutes to obtain a solution. The solution is applied to a metal surface, excess solution on the metal surface is wiped off, and the solution is cured with ultraviolet light. The metal surface is then irradiated with ultraviolet light, and the location and size of the defect are determined by afterglow. When an open defect exists on the metal surface, the open defect emits a long afterglow, and when no open defect exists on the metal surface, no long afterglow is emitted. The ratio of the host material, the guest material, and the photocurable adhesive is 100:1:(400-600) by mass. The photocurable adhesive is LOCTITE@AA3491. The object material is: R1 is H, CH3, OCH3, CN, CHO, NO2 or CH=CH(C6H5), R2 is H, CH3, OCH3, CN, CHO, NO2 or CH=CH(C6H5), R3 is H, CH3, OCH3, CN, CHO, NO2 or CH=CH(C6H5), X=C or Si; The main material is: Among them, X1, X2 and X3 are independent of each other, and X1, X2, X3 are H, C n H 2n+1 , OCH3, CN, CHO, NO2 and CH=CH(C6H5).

8. The use according to claim 7, characterized in that The ratio of the mass fraction of the light-curing adhesive to the volume fraction of the solvent is 4:(5-15), the unit of mass fraction is g, the unit of volume fraction is ml, the solvent is dichloromethane, and the curing time is 20-40s.

9. Application of light-curing adhesive in anti-counterfeiting, characterized in that: When distinguishing authenticity, ultraviolet light is used to illuminate the surface of the object to be tested, and the authenticity of the object to be tested is determined based on whether the surface of the object to be tested emits long afterglow light or a long afterglow time. The emission of long afterglow light on the surface of the object to be tested is achieved by the following method: Step 1: Mixing a photocurable adhesive, a host material, a guest material, and a solvent, and stirring at room temperature for at least 5 minutes to obtain a solution, wherein the ratio of the host material, the guest material, and the photocurable adhesive is 100:1:(400-600) by weight; the photocurable adhesive is LOCTITE@AA3491; The object material is: R1 is H, CH3, OCH3, CN, CHO, NO2 or CH=CH(C6H5), R2 is H, CH3, OCH3, CN, CHO, NO2 or CH=CH(C6H5), R3 is H, CH3, OCH3, CN, CHO, NO2 or CH=CH(C6H5), X=C or Si; The main material is: Among them, X1, X2 and X3 are independent of each other, and X1, X2, X3 are H, C n H 2n+1 , one of OCH3, CN, CHO, NO2 and CH=CH(C6H5); Step 2: Spray the solution onto the surface of the real object to be tested, wait for the solvent to evaporate, and then cure it with ultraviolet light.

10. Use of light-curing adhesive in information encryption, characterized in that: A method for improving the afterglow performance of an organic long afterglow material by using a photocuring adhesive to extend the afterglow time of the organic long afterglow material, so that different afterglow times and colors represent different meanings, thereby achieving information encryption, wherein a host material and a guest material are used to generate the organic long afterglow material; wherein, by weight, the ratio of the host material, the guest material, and the photocuring adhesive is 100:1:(400-600); and the photocuring adhesive is LOCTITE@AA3491; The object material is: R1 is H, CH3, OCH3, CN, CHO, NO2 or CH=CH(C6H5), R2 is H, CH3, OCH3, CN, CHO, NO2 or CH=CH(C6H5), R3 is H, CH3, OCH3, CN, CHO, NO2 or CH=CH(C6H5), X=C or Si; The main material is: Among them, X1, X2 and X3 are independent of each other, and X1, X2, X3 are H, C n H 2n+1 , OCH3, CN, CHO, NO2 and CH=CH(C6H5).

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