Application of a photocurable adhesive in inducing long-lasting emission of organic dyes

Abstract

The present invention discloses the use of a photocurable adhesive for inducing long-lasting emission from organic dyes. The photocurable adhesive is a mixture of one or more of UV-curable adhesive 3491, UV-curable adhesive 3492, UV glue D-606, and UV shadowless adhesive V-3218. The organic dye is a mixture of one or more of safranin, basic fuchsin, Nile blue, hematoxylin, acid fuchsin, fluorescein, and solvent green 7. By mixing the photocurable adhesive with a conventional organic dye, the present invention can induce long-lasting emission from the conventional organic dye.

Description

Technical Field

[0001] The present invention relates to the technical field of organic long afterglow materials, and in particular to application of a photocurable adhesive in inducing long afterglow emission of an organic dye. Background Art

[0002] Organic long-afterglow materials have the advantages of low price, simple synthesis, good biocompatibility and easy modification of functional groups, which have attracted widespread attention from scientific researchers. At present, many organic small molecules with long-afterglow luminescence properties have been prepared and are widely used in three-dimensional display, anti-counterfeiting and information encryption, as well as biological imaging and other fields.

[0003] Among various wavelengths of excitation, afterglow excited by visible light is particularly suitable for applications such as display, information encryption, and lighting equipment. However, this usually requires modification of the chemical structure of organic compounds or chromophores. This method usually requires complex molecular design and chemical synthesis, hindering researchers from conducting deeper exploration. According to literature reports, dye molecules with charge transfer state (CT) characteristics help absorb light in the visible light region [Garain S, Ansari SN, Kongasseri AA, et al. Room temperature charge-transfer phosphorescence from organic donor-acceptor co-crystals[J]. Chemical Science, 2022, 13(34): 10011-10019; Garain S, Wagalgave SM, Kongasseri AA, et al. Anion-π-induced room temperature phosphorescence from emissive charge-transfer states[J]. Journal of the American Chemical Society, 2022, 144(24): 10854-10861; Wang J, Yang Y, Li K, et al. Purely organic fluorescence afterglow: visible-light-excitation, inherent mechanism, tunable color, and practical applications with very low cost[J]. Angewandte Chemie International [Editor's note: 2023, 62(30): e202304020.] By blending organic dyes with polymer matrices (such as PVA), various environmental stimulus responses based on LPL emission can be achieved. However, the diversity of the molecular structures of commercial organic dyes still poses a challenge to finding a universal and convenient material composite strategy to induce their LPL phenomenon, especially under visible light excitation. This challenge prompted us to develop a simple and universal strategy to conveniently endow organic traditional fluorescent dyes with excellent afterglow emission in the solid state under visible light excitation. Summary of the Invention

[0004] The technical problem to be solved by the present invention is how to induce long afterglow emission of organic dyes.

[0005] The present invention solves the above technical problems through the following technical means:

[0006] A photocurable adhesive is used to induce long-lasting emission of organic dyes. The photocurable adhesive is a mixture of one or more of UV-curable adhesive 3491, UV-curable adhesive 3492, UV glue D-606, and UV shadowless adhesive V-3218. The organic dye is a mixture of one or more of safranin, basic fuchsin, Nile blue, hematoxylin, acid fuchsin, fluorescein, and solvent green 7.

[0007] The structural formula of the organic dye is shown below:

[0008]

[0009] Preferably, the UV curing adhesive 3491 is from Henkel Loctite (China) Co., Ltd. AA3491, UV curing adhesive 3491 of Guangdong Youyang New Materials Co., Ltd., or a mixture of two.

[0010] Preferably, the UV curing adhesive 3492 is from Henkel Loctite (China) Co., Ltd. AA3492, UV curing adhesive 3492 of Guangdong Youyang New Materials Co., Ltd., or a mixture of two thereof.

[0011] Preferably, the UV glue D-606 comes from Foshan Jinggu Adhesive Co., Ltd.; the UV shadowless glue V-3218 comes from Dongguan Lelai Adhesive Products Co., Ltd.

[0012] The present invention also provides a method for inducing long afterglow emission of an organic dye using a photocurable adhesive, which comprises the following steps: uniformly mixing the photocurable adhesive and the organic dye, and curing them by irradiating with ultraviolet light.

[0013] Preferably, the weight ratio of the photocurable adhesive to the organic dye is 300-600:1; during the irradiation process, a UV lamp with a power of 15W is used for irradiation, and the irradiation time is 20-40s.

[0014] Preferably, the mixture is stirred and mixed at room temperature.

[0015] The present invention also provides a method for preparing a long afterglow material, comprising the following steps: uniformly mixing the photocurable adhesive and the organic dye, and curing the mixture with ultraviolet light to obtain the long afterglow material.

[0016] Preferably, the weight ratio of the light-curing adhesive to the organic dye is 300-600:1; and a 15W ultraviolet lamp is used for irradiation curing for 20-40 seconds.

[0017] Preferably, the method further comprises coating a product obtained by uniformly mixing the light-curing adhesive and the organic dye on the substrate.

[0018] Preferably, the coating method is drop coating.

[0019] Preferably, the coated substrate is glass.

[0020] The present invention also provides a long afterglow material, which is prepared by adopting the preparation method of the long afterglow material.

[0021] Preferably, the long afterglow material is a film, a coating or a luminescent body.

[0022] The advantages of the present invention are:

[0023] (1) By mixing photocurable adhesive with organic traditional dyes, the curable adhesive provides a rigid environment for the dye molecules, which can induce the long afterglow emission of organic traditional dyes.

[0024] (2) The preparation method of the present invention is simple in preparation process (prepared at room temperature, without heating), environmentally friendly and readily available (no additional organic solvent is added); and the obtained film is flat and smooth, with good and stable afterglow performance. The mild and non-harsh conditions for obtaining the film will be very beneficial for the application of LPL materials in various scenarios. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 Macroscopic LPL images of the long afterglow film obtained in Example 1 of the present invention at room temperature (from left to right: at the time of excitation, 1 second after turning off the 430nm visible light lamp, and 2 seconds after turning off the 430nm visible light lamp);

[0026] Figure 2 This is the afterglow performance attenuation spectrum of the long afterglow film obtained in Example 1 of the present invention;

[0027] Figure 3 Macroscopic LPL images of the long afterglow film obtained in Example 2 of the present invention at room temperature (from left to right: during excitation and 1 second after turning off the 430nm visible light lamp);

[0028] Figure 4 This is a graph showing the afterglow performance attenuation spectrum of the long afterglow film obtained in Example 2 of the present invention;

[0029] Figure 5 Macroscopic LPL images of the long afterglow film obtained in Example 3 of the present invention at room temperature (from left to right: during excitation and 1 second after turning off the 430nm visible light lamp);

[0030] Figure 6Macroscopic LPL images of the long afterglow film obtained in Example 4 of the present invention at room temperature (from left to right: during excitation and 1 second after turning off the 430 nm visible light lamp);

[0031] Figure 7 Macroscopic LPL images of the long afterglow film obtained in Example 5 of the present invention at room temperature (from left to right: during excitation and 1 second after turning off the 430nm visible light lamp);

[0032] Figure 8 This is the afterglow performance attenuation spectrum of the long afterglow film obtained in Example 6 of the present invention;

[0033] Figure 9 Macroscopic LPL images of the long afterglow film obtained in Example 7 of the present invention at room temperature (from left to right: during excitation and 1 second after turning off the 430 nm visible light lamp);

[0034] Figure 10 The present invention is a traditional organic dye safranin in Example 1 and Afterglow performance decay spectrum of the long afterglow film obtained from AA3492 at room temperature;

[0035] Figure 11 Macroscopic LPL images of the long afterglow film obtained from the traditional organic dye safranin and the UV-curable adhesive 3491 in Example 1 of the present invention at room temperature (from left to right: upon excitation, 1 second after turning off the 430nm visible light lamp, and 2 seconds after turning off the 430nm visible light lamp);

[0036] Figure 12 Macroscopic LPL images of the long afterglow film obtained from the traditional organic dye safranin and UV-curable adhesive 3492 (Guangdong Youyang New Materials Co., Ltd.) at room temperature (from left to right: upon excitation, 1 second after turning off the 430nm visible light lamp, and 2 seconds after turning off the 430nm visible light lamp);

[0037] Figure 13 Macroscopic LPL images of the long-afterglow film obtained from the traditional organic dye safranin and UV glue D-606 in Example 1 of the present invention at room temperature (from left to right: upon excitation, 1 second after turning off the 430nm visible light lamp, and 2 seconds after turning off the 430nm visible light lamp);

[0038] Figure 14 These are macroscopic LPL images of the long afterglow film obtained from the traditional organic dye safranin and UV shadowless adhesive V-3218 in Example 1 of the present invention at room temperature (from left to right: during excitation, 1 second after turning off the 430nm visible light lamp, and 2 seconds after turning off the 430nm visible light lamp). DETAILED DESCRIPTION

[0039] To make the objectives, technical solutions, and advantages of the embodiments of the present invention more clear, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts shall fall within the scope of protection of the present invention.

[0040] Unless otherwise specified, the test materials and reagents used in the following examples can be obtained from commercial sources.

[0041] If no specific techniques or conditions are specified in the examples, they can be carried out according to the techniques or conditions described in the literature in the field or according to the product instructions.

[0042] The sources of the drugs involved in the following Examples 1-7 and Comparative Examples 1-3 are as follows:

[0043] The organic dye was purchased from Tianjin Xiens Biochemical Technology Co., Ltd. (purity: 98%); the light-curing adhesive was purchased from Henkel Loctite (China) Co., Ltd. AA3491, AA3491 is a transparent, low viscosity, modified acrylate liquid adhesive that cures after a few seconds of 365nm UV exposure.

[0044] The instruments and models involved in the following examples and comparative examples are as follows:

[0045] Ocean Optics multi-band spectrometer;

[0046] Room temperature: 20~25℃.

[0047] The substrate may be glass or paper. In the following embodiments, the substrate is glass.

[0048] In the following examples and comparative examples, the power of the UV lamp is 15 W (365 nm), and the power of the visible light lamp is 30 W (430 nm).

[0049] Examples 1 to 7

[0050] A method for inducing long afterglow of an organic dye with a photocurable adhesive, comprising: mixing 500 mg of photocurable adhesive and 1 mg of an organic dye, stirring the mixture at room temperature of 20°C to 25°C for 5 minutes to obtain a mixed solution of the photocurable adhesive and the dye, dropping 0.5 mL of the mixed solution onto a glass substrate, and curing the mixture with a 15W ultraviolet lamp for 30 seconds to obtain a long afterglow film. The organic dyes used in Examples 1-7 are respectively shown in Table 1, Examples 1-7.

[0051] Comparative Examples 1 to 3

[0052] A method for inducing long afterglow of an organic dye with a photocurable adhesive, comprising: mixing 500 mg of photocurable adhesive and 1 mg of an organic dye, stirring the mixture at room temperature of 20°C to 25°C for 5 minutes to obtain a mixed solution of the photocurable adhesive and the dye, dropping 0.5 mL of the mixed solution onto a glass substrate, and curing the mixture with a 15W ultraviolet lamp for 30 seconds to obtain a thin film. The organic dyes used in Comparative Examples 1-3 are respectively shown in Comparative Examples 1-3 in Table 1.

[0053] Table 1 Organic dyes used in Examples 1-7 and Comparative Examples 1-3 and afterglow time of the obtained films

[0054]

[0055]

[0056] After the light-curing adhesive is introduced into the present invention and a light-curing process is performed, an LPL film with relatively uniform luminescence can be obtained.

[0057] Figure 1 This is a macroscopic LPL image of the long afterglow film obtained in Example 1 at room temperature. The film is excited by a 430nm visible light lamp. After irradiation for 3 seconds, the visible light lamp is turned off and the film can maintain afterglow for 2 seconds. It can be seen that the obtained film emits relatively uniform light, indicating that the introduction of the photocurable adhesive in the present invention induces the long afterglow emission of the traditional organic dye safranin.

[0058] Figure 2 This is a graph showing the attenuation of the afterglow performance of the film obtained in Example 1 at room temperature. As can be seen from the graph, from -2s to 0s, the organic long afterglow material (i.e., the obtained long afterglow film) is irradiated by a 430nm visible light lamp, and the organic long afterglow material exhibits photoluminescence characteristics; from 0s to 2s, the organic long afterglow material exhibits orange-red long afterglow luminescence after the visible light lamp is removed, and the afterglow time is about 2s, which is similar to the afterglow time observed by the naked eye.

[0059] Figure 3 This is a macroscopic LPL image of the long afterglow film obtained in Example 2 at room temperature. The film is excited by a 430nm visible light lamp. After irradiation for 3 seconds, the visible light lamp is turned off and the film can maintain afterglow for 1 second. It can be seen that the obtained film emits relatively uniform light, indicating that the introduction of the photocurable adhesive in the present invention induces the long afterglow emission of the traditional organic dye basic fuchsin.

[0060] Figure 4This is a graph showing the attenuation of the afterglow performance of the film obtained in Example 2 at room temperature. As can be seen from the graph, from -2s to 0s, the organic long afterglow material (i.e., the obtained long afterglow film) is irradiated by a 430nm visible light lamp, and the organic long afterglow material exhibits photoluminescence characteristics; from 0s to 1s, the organic long afterglow material exhibits red long afterglow luminescence after the visible light lamp is removed, and the afterglow time is about 1s, which is similar to the afterglow time observed by the naked eye.

[0061] Figure 5 This is a macroscopic LPL image of the long afterglow film obtained in Example 3 at room temperature. The film is excited by a 430nm visible light lamp. After irradiation for 3 seconds, the visible light lamp is turned off and the film can maintain afterglow for 1 second. It can be seen that the obtained film emits relatively uniform light, indicating that the introduction of the photocurable adhesive in the present invention induces the long afterglow emission of the traditional organic dye Nile blue.

[0062] Figure 6 This is a macroscopic LPL image of the long afterglow film obtained in Example 4 at room temperature. The film is excited by a 430nm visible light lamp, and the visible light lamp is turned off after irradiation for 3 seconds. The film can maintain afterglow for 1 second. It can be seen that the obtained film emits relatively uniform light, indicating that the introduction of the photocurable adhesive in the present invention induces the long afterglow emission of the traditional organic dye hematoxylin.

[0063] Figure 7 This is a macroscopic LPL image of the long afterglow film obtained in Example 5 at room temperature. The film is excited by a 430nm visible light lamp. After irradiation for 3 seconds, the visible light lamp is turned off and the film can maintain afterglow for 1 second. It can be seen that the obtained film emits relatively uniform light, indicating that the introduction of the photocurable adhesive in the present invention induces the long afterglow emission of the traditional organic dye acid fuchsin.

[0064] Figure 8 This is a graph showing the attenuation of the afterglow performance of the film obtained in Example 6 at room temperature. As can be seen from the graph, from -2s to 0s is when the organic long afterglow material (i.e., the obtained long afterglow film) is irradiated by a 430nm visible light lamp, and the organic long afterglow material exhibits photoluminescence characteristics; from 0s to 1s is when the organic long afterglow material exhibits long afterglow luminescence after the visible light lamp is removed, and the afterglow time is about 1s.

[0065] Figure 9 This is a macroscopic LPL image of the long afterglow film obtained in Example 7 at room temperature. The film is excited by a 430nm visible light lamp, and the visible light lamp is turned off after irradiation for 3 seconds. The film can maintain afterglow for 1 second. It can be seen that the obtained film emits relatively uniform light, indicating that the introduction of the photocurable adhesive in the present invention induces the long afterglow emission of the traditional organic dye Solvent Green 7.

[0066] In the above embodiments 1 to 7, the light curing adhesive is replaced by 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.), UV glue D-606 (Foshan Jinggu Adhesive Co., Ltd.), UV shadowless adhesive V-3218 (Dongguan Lelai Adhesive Products Co., Ltd.), V-3018 (Dongguan Lelai Adhesive Products Co., Ltd.) were prepared according to the above steps. Among them, the film prepared by V-3018 and the above dye molecules had no afterglow effect. The films prepared by the other five light-curing adhesives were able to achieve the same effect as the above embodiment, as shown in the effect diagram. Figure 10-14 shown.

[0067] Figure 10 The organic traditional dye safranin in Example 1 is The afterglow performance attenuation spectrum of the long afterglow film obtained from AA3492 (Henkel Loctite (China) Co., Ltd.) at room temperature shows that from -2s to 0s, the organic long afterglow material (i.e., the obtained film) is irradiated with a 430nm visible light lamp, and the organic long afterglow material exhibits photoluminescence characteristics; from 0s to 2s, the organic long afterglow material exhibits orange-red long afterglow luminescence after the visible light lamp is removed, and the afterglow time is about 2s, which is similar to the afterglow time observed by the naked eye.

[0068] Figure 11 This is a macroscopic LPL image of a long-afterglow film obtained from the traditional organic dye safranin and the UV-curing adhesive 3491 (Guangdong Youyang New Materials Co., Ltd.) in Example 1 at room temperature. The film was excited with a 430nm visible light lamp, and after irradiation for 3 seconds, the visible light lamp was turned off. The film can maintain an afterglow for 2 seconds. It can be seen that the obtained film emits relatively uniform light, indicating that the introduction of the photocurable adhesive in the present invention induces the long-afterglow emission of the traditional organic dye safranin.

[0069] Figure 12 This is a macroscopic LPL image of a long-afterglow film obtained from the traditional organic dye safranin and the UV-curing adhesive 3492 (Guangdong Youyang New Materials Co., Ltd.) in Example 1 at room temperature. The film was excited with a 430nm visible light lamp, and after irradiation for 3 seconds, the visible light lamp was turned off. The film can maintain an afterglow for 2 seconds. It can be seen that the obtained film emits relatively uniform light, indicating that the introduction of the photocuring adhesive in the present invention induces the long-afterglow emission of the traditional organic dye safranin.

[0070] Figure 13This is a macroscopic LPL image of a long-afterglow film obtained from the traditional organic dye safranin and UV adhesive D-606 (Foshan Jinggu Adhesive Co., Ltd.) in Example 1 at room temperature. The film was excited with a 430nm visible light lamp. After irradiation for 3 seconds and then the visible light lamp was turned off, the film could maintain an afterglow for 2 seconds. It can be seen that the obtained film emits relatively uniform light, indicating that the introduction of the photocurable adhesive in the present invention induces the long-afterglow emission of the traditional organic dye safranin.

[0071] Figure 14 This is a macroscopic LPL image of a long afterglow film obtained from the traditional organic dye safranin and UV shadowless adhesive V-3218 (Dongguan Lelai Adhesive Products Co., Ltd.) in Example 1 at room temperature. The film was excited with a 430nm visible light lamp, and the visible light lamp was turned off after irradiation for 3 seconds. The film can maintain an afterglow for 2 seconds. It can be seen that the obtained film emits relatively uniform light, indicating that the introduction of the photocurable adhesive in the present invention induces the long afterglow emission of the traditional organic dye safranin.

[0072] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the various embodiments of the present invention.

Claims

1. Application of a photocurable adhesive in inducing long afterglow emission of an organic dye, characterized in that: The method for inducing long afterglow emission of an organic dye by using a photocurable adhesive comprises the following steps: uniformly mixing the photocurable adhesive and the organic dye, and curing the mixture by ultraviolet light, wherein the weight ratio of the photocurable adhesive to the organic dye is (300-600):1, the photocurable adhesive is a mixture of one or more of ultraviolet curing adhesive 3491, ultraviolet curing adhesive 3492, UV drip glue D-606, and UV shadowless glue V-3218; and the organic dye is a mixture of one or more of basic fuchsin, hematoxylin, acid fuchsin, and fluorescein; The UV curing adhesive 3491 is from Henkel Loctite (China) Co., Ltd. AA3491, UV curing adhesive 3491 of Guangdong Youyang New Materials Co., Ltd., or a mixture of two thereof; The UV curing adhesive 3492 is from Henkel Loctite (China) Co., Ltd. AA3492, UV curing adhesive 3492 of Guangdong Youyang New Materials Co., Ltd., or a mixture of two thereof; The UV glue D-606 comes from Foshan Jinggu Adhesive Co., Ltd.; the UV shadowless glue V-3218 comes from Dongguan Lelai Adhesive Products Co., Ltd.

2. The use of the photocurable adhesive according to claim 1 in inducing long afterglow emission of organic dyes, characterized in that: During the irradiation process, a UV lamp with a power of 15W is used for irradiation, and the irradiation time is 20-40s.

3. The use of the photocurable adhesive according to claim 1 in inducing long afterglow emission of organic dyes, characterized in that: Before irradiating with ultraviolet light, the method further includes coating a product obtained by uniformly mixing the light-curing adhesive and the organic dye on the substrate.

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