CN116790206A - Application of photo-curing adhesive in improving afterglow performance of organic long afterglow material - Google Patents
Application of photo-curing adhesive in improving afterglow performance of organic long afterglow material Download PDFInfo
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Abstract
The invention discloses an application of photo-curing glue in improving afterglow performance of organic long afterglow materials, which is characterized in that the photo-curing glue, a host material, a guest material and a solvent are mixed, stirred for at least 5min under the condition of room temperature to obtain a solution, and the solution is stood for at least 2 hours to volatilize the solvent completely and is cured by ultraviolet irradiation. The preparation method can realize solution processing, and the film obtained by the photo-curing adhesive is flat and smooth, and has better afterglow performance and stable afterglow performance. The invention also discloses a novel nondestructive metal flaw detection technology, and the application range of the organic long afterglow material in information encryption and anti-counterfeiting is enlarged.
Description
Technical Field
The invention belongs to the technical field of organic long afterglow materials, and particularly relates to application of a photo-curing adhesive in improving afterglow performance of the organic long afterglow materials.
Background
In recent years, research and development of organic long-afterglow luminescent materials (OLPLMs) have been receiving attention because of their green preparation process, adjustable luminescence characteristics (color, brightness or duration, etc.), more sensitive external environment response characteristics (pressure, temperature or humidity, temperature, etc.), and unique performance advantages in the fields of biosensing and imaging, information encryption or anti-counterfeiting, etc.
Numerous studies on OLPLMs have shown that a rigid matrix of material favors the radiation attenuation of stable triplet states, resulting in Room Temperature Phosphorescent (RTP) materials with long afterglow luminescence properties. In particular, some crystalline OLPLMs having host-guest doped structures exhibit environmentally stable afterglow characteristics, where LPL duration can vary from a few seconds to tens of seconds, by building up the rigid crystal structure of the host to promote radiative decay of the triplet state and extend the life of RTP in the presence of water and oxygen. However, such crystalline OLPLMs have difficulty in achieving solution processing and uniform light emission over a large area due to the severe conditions of crystal formation and limited reproducibility. Meanwhile, by doping or copolymerizing fluorescent powder into a specific rigid amorphous polymer matrix, molecular vibration can be effectively inhibited, and continuous RTP and LPL emission can be obtained in a targeted and efficient manner. However, due to the lack of a well-defined and efficient rigid environment construction strategy, there is still relatively little research to utilize a rigid environment to facilitate the performance of amorphous OLPLMs. This has prompted the development of a general strategy to build the rigidity of amorphous OLPLMs to improve their reproducibility and processability for large-scale applications.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for improving the afterglow performance of an organic long afterglow material by using a photo-curing adhesive.
Another object of the present invention is to provide a method for preparing a film.
It is another object of the present invention to provide a luminaire.
It is another object of the present invention to provide the use of organic long persistence materials in metal inspection.
It is another object of the present invention to provide the use of a photo-curable glue in security.
It is another object of the present invention to provide the use of a photo-curable glue in information encryption.
The aim of the invention is achieved by the following technical scheme.
A method for improving afterglow performance of organic long afterglow material by photo-curing glue is one or two modes:
mode one: uniformly mixing the photo-curing adhesive, the solvent and the organic long afterglow material to volatilize the solvent completely, and curing by ultraviolet irradiation, wherein the ratio of the photo-curing adhesive to the organic long afterglow material is (4-6) 1 in parts by weight;
mode two: mixing the photo-curing adhesive, the host material, the guest material and the solvent, stirring for at least 5min at room temperature to obtain a solution, standing for at least 2 hours to volatilize the solvent in the solution completely, and curing by ultraviolet light irradiation, wherein the ratio of the host material to the guest material to the photo-curing adhesive is 100:1 (400-600) in parts by weight.
In the technical scheme, the ratio of the mass parts of the photo-curing adhesive to the volume parts of the solvent is 4 (5-15), the unit of the mass parts is g, and the unit of the volume parts is ml.
In the above technical solution, the solvent is dichloromethane.
In the technical scheme, the curing time is 20-40 s.
A method of making a film comprising: mixing the photo-curing adhesive, the host material, the guest material and the solvent, stirring at room temperature of 20-25 ℃ for at least 5min to obtain a solution, coating the solution on a substrate, and irradiating and curing the solution by ultraviolet light after the solvent volatilizes to obtain a film, wherein the ratio of the host material to the guest material to the photo-curing adhesive is 100:1 (400-600) in parts by weight.
In the above technical solution, the solvent is dichloromethane.
In the technical scheme, the ratio of the mass parts of the photo-curing adhesive to the volume parts of the solvent is 4 (5-15), the unit of the mass parts is g, and the unit of the volume parts is mL.
In the technical scheme, the coating method is dripping coating.
A luminaire, comprising: the organic long afterglow material and the cured photo-curing glue are positioned in the photo-curing glue.
In the above technical solution, the guest material is:
R 1 h, CH of a shape of H, CH 3 、OCH 3 、O(CH 2 ) 5 、CN、CHO、NO 2 Or ch=ch (C 6 H 5 )，R 2 H, CH of a shape of H, CH 3 、OCH 3 、O(CH 2 ) 5 、CN、CHO、NO 2 Or ch=ch (C 6 H 5 )，R 3 H, CH of a shape of H, CH 3 、OCH 3 、O(CH 2 ) 5 、CN、CHO、NO 2 Or ch=ch (C 6 H 5 ) X= C, O, P or Si;
the main materials are as follows:
wherein X is 1 、X 2 And X 3 Each independently, X 1 、X 2 、X 3 H, C respectively n H 2n+1 、OCH 3 、O(CH 2 ) 5 、CN、CHO、NO 2 And ch=ch (C 6 H 5 ) One of them.
The application of the organic long afterglow material in metal flaw detection.
In the technical scheme, the photo-curing adhesive, the host material, the guest material and the solvent are mixed, stirred for at least 5min at the room temperature of 20-25 ℃ to obtain a solution, the solution is coated on the metal surface, the superfluous solution on the metal surface is wiped off, the metal surface is cured by ultraviolet light, the position and the size of the defect are judged through afterglow, the opening defect emits long afterglow when the opening defect exists on the metal surface, and does not emit long afterglow when the opening defect does not exist on the metal surface, wherein the ratio of the host material, the guest material and the photo-curing adhesive is 100:1 (400-600) in parts by weight.
In the technical scheme, the ratio of the mass parts of the photo-curing adhesive to the volume parts of the solvent is 4 (5-15), the unit of the mass parts is g, and the unit of the volume parts is ml.
In the above technical solution, the solvent is dichloromethane.
In the technical scheme, the curing time is 20-40 s.
The use of photo-curable glue in anti-counterfeiting.
The use of the photo-curing adhesive in anti-counterfeiting, when the authenticity is identified, ultraviolet light is used for irradiating the surface of an object to be detected, and the authenticity of the object to be detected is judged according to whether the surface of the object to be detected emits long afterglow or long afterglow time, wherein the surface of the object to be detected emits the long afterglow by the following method:
step 1, mixing a photo-curing adhesive, a host material, a guest material and a solvent, and stirring at room temperature for at least 5min to obtain a solution, wherein the ratio of the host material to the guest material to the photo-curing adhesive is 100:1 (400-600) in parts by weight;
in the step 1, the solvent is dichloromethane.
In the step 1, the ratio of the mass parts of the photo-curing adhesive to the volume parts of the solvent is 4 (5-15), the unit of the mass parts is g, and the unit of the volume parts is ml.
And 2, spraying the solution on the surface of a true object to be detected, and irradiating and solidifying the solution by ultraviolet light after the solvent volatilizes.
In the step 2, the curing time is 20-40 s.
The use of photo-curing glue in information encryption can prolong the afterglow time of organic long afterglow material by using the method of improving afterglow property of organic long afterglow material by photo-curing glue, and can make different afterglow time and color represent different meanings so as to implement information encryption.
The beneficial effects of the invention are as follows:
1. the afterglow performance of the existing pure organic long afterglow material can be enhanced by introducing photo-curing glue into the main guest material for photo-curing;
2. the preparation method can realize solution processing, and the obtained film is flat and smooth, and has better afterglow performance and stable afterglow performance. The obtained film has the advantages of improved afterglow time, mild and not harsh conditions, and is very beneficial to the application of the LPL material in various scenes. Can realize large-area preparation of films;
3. the invention discloses a novel nondestructive metal flaw detection technology.
4. The invention prolongs the afterglow time of the organic long afterglow material by introducing the photo-curing adhesive, can realize the large-area preparation of the film, and expands the application range of the organic long afterglow material in information encryption and anti-counterfeiting.
Drawings
FIG. 1 shows (a) the optical microscope (from left to right, at 2s after turning off the UV lamp and at 6s after turning off the UV lamp) of the organic long afterglow material obtained in comparative example 1, (b) macroscopic LPL pictures (from left to right, at 4s after turning off the UV lamp and at 9s after turning off the UV lamp) of the film obtained in example 1 at room temperature;
FIG. 2 shows (a) XRD of the organic long afterglow material obtained in comparative example 1, and (b) XRD of the thin film obtained in example 1;
FIG. 3 is a graph showing (a) the afterglow characteristic attenuation spectrum of the organic long afterglow material of comparative example 1 and (b) the afterglow characteristic attenuation spectrum of the thin film of example 1;
FIG. 4 shows (a) the optical microscope (from left to right, at 1s after turning off the UV lamp and at 3s after turning off the UV lamp) of the organic long afterglow material obtained in comparative example 2, (b) macroscopic LPL pictures (from left to right, at 3s after turning off the UV lamp and at 7s after turning off the UV lamp) of the film obtained in example 2 at room temperature;
FIG. 5 is a graph showing the afterglow property attenuation spectrum of (a) the organic long afterglow material obtained in comparative example 2 and (b) the afterglow property attenuation spectrum of the thin film prepared in example 2;
FIG. 6 shows (a) the optical microscope (from left to right, at 1s after turning off the UV lamp and at 3s after turning off the UV lamp) of the organic long persistence material obtained in comparative example 3, (b) macroscopic LPL pictures (from left to right, at 3s after turning off the UV lamp and at 7s after turning off the UV lamp) of the films prepared in example 3 under room temperature conditions;
FIG. 7 is a graph showing the afterglow property attenuation spectrum of (a) the organic long afterglow material obtained in comparative example 3, and (b) the afterglow property attenuation spectrum of the thin film prepared in example 3;
FIG. 8 is a macroscopic LPL picture of the film of example 4 at room temperature (from left to right for excitation, 4s after turning off the UV lamp, and 9s after turning off the UV lamp);
FIG. 9 is an afterglow property attenuation spectrum of the thin film of example 4;
FIG. 10 shows (a) the optical microscope (from left to right, at 1s after turning off the UV lamp and at 2s after turning off the UV lamp) of the organic long persistence material obtained in comparative example 5, (b) the macroscopic LPL picture (from left to right, at 1s after turning off the UV lamp and at 3s after turning off the UV lamp) of the film of example 5 at room temperature;
FIG. 11 is a graph showing the afterglow property attenuation spectrum of (a) the organic long afterglow material obtained in comparative example 5 and (b) the afterglow property attenuation spectrum of the thin film of example 5;
FIG. 12 shows (a) the optical microscope (from left to right, at 1s after turning off the UV lamp and at 2s after turning off the UV lamp) of the organic long persistence material obtained in comparative example 6, (b) the macroscopic LPL picture (from left to right, at 1s after turning off the UV lamp and at 3s after turning off the UV lamp) of the film of example 6 at room temperature;
FIG. 13 is a graph showing (a) the afterglow characteristic attenuation spectrum of the organic long afterglow material obtained in comparative example 6, and (b) the afterglow characteristic attenuation spectrum of the thin film of example 6;
FIG. 14 is a macroscopic LPL picture of the film of example 7 at room temperature (from left to right for 1s after turning off the UV lamp and 2s after turning off the UV lamp);
FIG. 15 is an afterglow property attenuation spectrum of the thin film of example 7;
FIG. 16 is an afterglow characteristic attenuation spectrum of the thin film of example 8;
FIG. 17 is a graph showing the afterglow property attenuation spectrum of (a) the organic long afterglow material obtained in comparative example 9, and (b) the afterglow property attenuation spectrum of the thin film of example 9;
FIG. 18 is a graph showing the afterglow property attenuation spectrum of (a) the organic long afterglow material of comparative example 10 and (b) the afterglow property attenuation spectrum of the thin film of example 10;
FIG. 19 is an afterglow property attenuation spectrum of the thin film of example 11;
FIG. 20 is an afterglow property attenuation spectrum of the thin film of example 12;
FIG. 21 is a graph showing the afterglow property attenuation spectrum of (a) the organic long afterglow material obtained in comparative example 13, and (b) the afterglow property attenuation spectrum of the thin film of example 13;
FIG. 22 is a graph showing the afterglow property attenuation spectrum of (a) the organic long afterglow material of comparative example 14 and (b) the afterglow property attenuation spectrum of the thin film of example 14;
FIG. 23 is a photograph showing the application of the photo-curable adhesive of example 16 in metal inspection;
fig. 24 is a photograph showing the use of the photo-curable adhesive of example 17 in information encryption and anti-counterfeit.
Detailed Description
The technical scheme of the invention is further described below with reference to specific embodiments.
In examples 1 to 19 and comparative examples below, the manufacturers of the host material and the guest material were: tianjin Seen Biochemical Co., ltd (purity: 98%); the manufacturers of photo-curing adhesives are: LOCTITE@AA3491,AA3491 is a transparent, low viscosity, modified acrylate liquid adhesive that cures after irradiation with 365nm uv light for several seconds.
The instruments and models involved in the tests in the following examples:
lycra DM2700M functional optical microscope;
ocean optics multiband spectrometer;
room temperature: 20-25 ℃.
The substrate may be a glass sheet or paper, and in the embodiments described below, glass is used as the substrate.
The power of the UV lamp in the examples described below was 15W (365 nm).
Examples 1 to 14
The application of the photo-curing adhesive in improving the afterglow performance of the organic long afterglow material comprises the following steps: mixing the photo-curing adhesive, the host material, the guest material and the solvent, stirring for 5min at the temperature of 20-25 ℃ to obtain a solution, dripping 0.5mL of the solution on a substrate, standing for 2h at the room temperature to enable the solvent in the solution to volatilize completely (the host material and the guest material generate organic long afterglow materials at the moment), and curing for 30s by using a 15W ultraviolet lamp to obtain a film, wherein the ratio of the host material to the guest material to the photo-curing adhesive is 100:1:400 in parts by weight, the ratio of the mass fraction of the photo-curing adhesive to the volume fraction of the solvent is 4:10, the unit of the mass fraction is g, the unit of the volume fraction is mL, and the solvent is dichloromethane. The host material and guest material of the different examples are shown in table 1 (the "1 to 14" in examples 1 to 14 are shown in the serial numbers in table 1). The manufacturers of photo-curing adhesives are: dark state city, have LOCTITE@AA3491, tay trade Inc.
Comparative examples 1 to 14
A method for preparing an organic long afterglow material, comprising the following steps: mixing a host material, a guest material and a solvent, stirring for 5min at the room temperature of 20-25 ℃ to obtain a solution, dripping 0.5mL of the solution on a substrate, standing for 2h at the room temperature to completely volatilize the solvent in the solution to obtain the organic long afterglow material, wherein the ratio of the host material to the guest material is 100:1, the ratio of the mass fraction of the host material to the volume fraction of the solvent is 1:10, the unit of the mass fraction is g, the unit of the volume fraction is mL, and the solvent is dichloromethane. The host materials and guest materials of the different comparative examples are shown in Table 1 (the "1 to 14" in comparative examples 1 to 14 are shown by the numbers in Table 1). The manufacturers of photo-curing adhesives are: dark state city, have LOCTITE@AA3491, tay trade Inc.
TABLE 1
The organic long afterglow material is formed by forming regular flaky crystals of the host material, and the guest material is uniformly and freely dispersed in the flaky crystals of the host material. After the photo-curing adhesive is introduced and the photo-curing process is carried out, the LPL film with uniform light emission can be obtained.
As can be seen from fig. 1 a, the optical microscope can clearly see regular cuboid crystals, the size is uniform, the crystals are square flaky, and the single crystal size is about 20 μm, so that the (pure) organic long afterglow material obtained in comparative example 1 is proved to be truly in a crystal structure. Exciting the crystal by using a 365nm ultraviolet lamp, and turning off the ultraviolet lamp after irradiating for 3 seconds, wherein the crystal can still keep afterglow for 6 seconds; b in FIG. 1 is a macroscopic LPL picture of the film obtained in example 1 at room temperature, the film is excited by a 365nm ultraviolet lamp, the ultraviolet lamp is turned off after 3 seconds of irradiation, the film can keep afterglow 9s, and the film can be seen to be relatively uniform in luminescence, which shows that the invention introduces photo-curing glue and performs photo-curing to enhance the luminescence property of the (pure) organic long afterglow material.
FIG. 2 a is an XRD of the (pure) organic long afterglow material obtained in comparative example 1, showing that it has a distinct and sharp peak, indicating good crystallization properties. As can be seen from fig. 2 b, after the photo-curable adhesive is introduced and the photo-curing process is performed to obtain a thin film, the crystallinity is reduced.
As can be seen from FIG. 3 a, irradiation of the comparative example 1 (pure) organic long afterglow material, which exhibited photoluminescent characteristics, with an ultraviolet lamp ranging from-2 s to 0s at 365 nm; the 0s to 6s is the long afterglow luminescence of the (pure) organic long afterglow material after the ultraviolet lamp is removed, the afterglow time is about 6s, and the afterglow time is similar to that observed by naked eyes. As can be seen from FIG. 3 b, the film prepared in example 1 was irradiated with an ultraviolet lamp having a wavelength of 365nm for-2 s to 0s, and the film exhibited photoluminescence characteristics; and 0s to 9s are long afterglow luminescence of the film after the ultraviolet lamp is removed, the afterglow time is about 9s, and the afterglow time is similar to that observed by naked eyes. The invention enhances the luminous performance of the organic long afterglow material after the photo-curing glue is introduced and photo-curing is carried out.
As can be seen from FIG. 4 a, the optical microscope clearly sees regular rectangular crystals, the size is uniform, the crystals are square flaky, and the single crystal size is about 20 μm, which proves that the (pure) organic long afterglow material obtained in example 2 is truly in a crystal structure. Exciting white crystals by using a 365nm ultraviolet lamp, and turning off the ultraviolet lamp after irradiating for 3 seconds, wherein the crystals can still keep afterglow for 3 seconds; in fig. 4 b is a macroscopic LPL picture of the film prepared in example 2 at room temperature, the film is excited by a 365nm ultraviolet lamp, the ultraviolet lamp is turned off after 3 seconds of irradiation, the film can keep afterglow for 7s, and the obtained film can be seen to be relatively uniform in luminescence, which shows that the invention introduces photo-curing glue and performs photo-curing to enhance the luminescence property of the (pure) organic long afterglow material.
As can be seen from FIG. 5 a, the irradiation of an ultraviolet lamp at 365nm for-2 s to 0s with (pure) organic long afterglow materials, which exhibit photoluminescent properties; the afterglow time of the organic long afterglow material after the ultraviolet lamp is removed is about 3s from 0s to 3s, which is similar to the afterglow time observed by naked eyes. As can be seen from FIG. 5 b, the film prepared in example 2 was irradiated with an ultraviolet lamp having a wavelength of 365nm for-2 s to 0s, and exhibited photoluminescence characteristics; and 0s to 7s is long afterglow luminescence of the film after the ultraviolet lamp is removed, the afterglow time is about 7s, and the afterglow time is similar to that observed by naked eyes. The invention enhances the luminous performance of the organic long afterglow material after the photo-curing glue is introduced and photo-curing is carried out.
As can be seen from FIG. 6 a, the optical microscope clearly sees regular rectangular crystals, the size is uniform, the crystals are square flaky, and the single crystal size is about 20 μm, which proves that the organic long afterglow material obtained in comparative example 3 is truly in a crystal structure. Exciting white crystals by using a 365nm ultraviolet lamp, and turning off the ultraviolet lamp after irradiating for 3 seconds, wherein the crystals can still keep afterglow for 3 seconds; in fig. 6 b is a macroscopic LPL picture of the film prepared in example 3 at room temperature, the film is excited by a 365nm ultraviolet lamp, the ultraviolet lamp is turned off after 3 seconds of irradiation, the film can keep afterglow for 7s, and the obtained film can be seen to be uniform in luminescence, which shows that the invention introduces photo-curing glue and performs photo-curing to enhance the luminescence property of the organic long afterglow material.
As can be seen from a of FIG. 7, -2s to 0s is 365nm ultraviolet light irradiation of organic long afterglow material, the material shows photoluminescence characteristics; and 0s to 3s are long afterglow luminescence of (pure) organic long afterglow materials after the ultraviolet lamp is removed, the afterglow time is about 3s, and the afterglow time is similar to that observed by naked eyes. As can be seen from FIG. 7 b, the film prepared in example 3 was irradiated with an ultraviolet lamp having a wavelength of 365nm for-2 s to 0s, and the film exhibited photoluminescence characteristics; and 0s to 7s are long afterglow luminescence of the film after the ultraviolet lamp is removed, the afterglow time is about 7s, and the afterglow time is similar to that observed by naked eyes. The invention enhances the luminous performance of the (pure) organic long afterglow material after the photo-curing glue is introduced and photo-curing is carried out.
FIG. 8 is a macroscopic LPL picture of the film of example 4 at room temperature, the film was excited by a 365nm ultraviolet lamp, the ultraviolet lamp was turned off after 3 seconds of irradiation, the film remained afterglow 9s, and it was found that the obtained film was relatively uniform in luminescence.
As can be seen from FIG. 9, the film of example 4 was irradiated with an ultraviolet lamp ranging from-2 s to 0s at 365nm, and the film exhibited photoluminescence characteristics; and 0s to 9s are long afterglow luminescence of the film after the ultraviolet lamp is removed, the afterglow time is about 9s, and the afterglow time is similar to that observed by naked eyes.
As can be seen from FIG. 10 a, the optical microscope clearly sees regular rectangular crystals, the size is uniform, the crystals are square flaky, and the single crystal size is about 20 μm, which proves that the (pure) organic long afterglow material obtained in comparative example 5 is truly a crystal structure. Exciting white crystals by using a 365nm ultraviolet lamp, turning off the ultraviolet lamp after irradiating for 3 seconds, and keeping afterglow for 1s of the crystals, wherein afterglow is not observed at 2 s; in fig. 10 b is a macroscopic LPL picture of the film of example 5 at room temperature, the film is excited by a 365nm ultraviolet lamp, the ultraviolet lamp is turned off after 3 seconds of irradiation, the film can keep afterglow for 3 seconds, and the obtained film can be seen to be relatively uniform in luminescence, which shows that the invention introduces photo-curing glue and performs photo-curing to enhance the luminescence property of the (pure) organic long afterglow material.
As can be seen from FIG. 11 a, the irradiation of an ultraviolet lamp at 365nm for-2 s to 0s with (pure) organic long afterglow materials, which exhibit photoluminescent properties; the 0s to 1s is the long afterglow luminescence of the (pure) organic long afterglow material after the ultraviolet lamp is removed, the afterglow time is about 1s, and the afterglow time is similar to that observed by naked eyes. As can be seen from FIG. 11 b, the film of example 5 exhibits photoluminescence characteristics when irradiated with an ultraviolet lamp having a wavelength of 365nm from-2 s to 0 s; and 0s to 3s are long afterglow luminescence of the film after the ultraviolet lamp is removed, the afterglow time is about 3s, and the afterglow time is similar to that observed by naked eyes. The invention enhances the luminous performance of the (pure) organic long afterglow material after the photo-curing glue is introduced and photo-curing is carried out.
As can be seen from FIG. 12 a, the optical microscope clearly sees regular rectangular crystals, the size is uniform, the crystals are square flaky, and the single crystal size is about 20 μm, which proves that the (pure) organic long afterglow material obtained in example 6 is truly in a crystal structure. Exciting white crystal with 365nm ultraviolet lamp, irradiating for 3 seconds, turning off the ultraviolet lamp, and keeping afterglow for 1s and 2s, wherein afterglow is not observed; FIG. 12 b is a macroscopic LPL picture of the film of example 6 at room temperature, the film is excited by a 365nm ultraviolet lamp, the ultraviolet lamp is turned off after 3 seconds of irradiation, the film can keep afterglow for 3 seconds, and the obtained film can be seen to be relatively uniform in luminescence, which shows that the invention introduces photo-curing glue and performs photo-curing to enhance the luminescence property of the (pure) organic long afterglow material.
As can be seen from FIG. 13 a, the irradiation of an ultraviolet lamp at 365nm for-2 s to 0s with (pure) organic long afterglow materials, which exhibit photoluminescent properties; the 0s to 1s is the long afterglow luminescence of the (pure) organic long afterglow material after the ultraviolet lamp is removed, the afterglow time is about 1s, and the afterglow time is similar to that observed by naked eyes. As can be seen from FIG. 13 b, the film of example 6 was irradiated with an ultraviolet lamp having a wavelength of 365nm for-2 s to 0s, and exhibited photoluminescence characteristics; and 0s to 3s are long afterglow luminescence of the film after the ultraviolet lamp is removed, the afterglow time is about 3s, and the afterglow time is similar to that observed by naked eyes. The invention enhances the luminous performance of the (pure) organic long afterglow material after the photo-curing glue is introduced and photo-curing is carried out.
FIG. 14 is a macroscopic LPL image of the film of example 7 at room temperature, the film was excited by a 365nm UV lamp, the UV lamp was turned off after 3 seconds of irradiation, the film remained afterglow 2 seconds, and it was found that the resulting film was relatively uniform in luminescence.
As can be seen from FIG. 15, the film of example 7 was irradiated with an ultraviolet lamp at 365nm for-2 s to 0s, and exhibited photoluminescence characteristics; and 0s to 2s is long afterglow luminescence of the film after the ultraviolet lamp is removed, the afterglow time is about 2s, and the afterglow time is similar to that observed by naked eyes.
FIG. 16 shows that the film of example 8 was irradiated with an ultraviolet lamp at 365nm for-2 s to 0s, and the film exhibited photoluminescence characteristics; and 0s to 2s is long afterglow luminescence of the film after the ultraviolet lamp is removed, the afterglow time is about 2s, and the afterglow time is similar to that observed by naked eyes.
As can be seen from FIG. 17, from-2 s to 0s, the material exhibits photoluminescent properties when irradiated with a 365nm ultraviolet lamp; the 0s to 1s is the long afterglow luminescence of the (pure) organic long afterglow material after the ultraviolet lamp is removed, the afterglow time is about 1s, and the afterglow time is similar to that observed by naked eyes. As can be seen from FIG. 17 b, the film of example 9 was irradiated with an ultraviolet lamp having a wavelength of 365nm for-2 s to 0s, and exhibited photoluminescence characteristics; and 0s to 4s are long afterglow luminescence of the film after the ultraviolet lamp is removed, the afterglow time is about 4s, and the afterglow time is similar to that observed by naked eyes. The invention enhances the luminous performance of the (pure) organic long afterglow material after the photo-curing glue is introduced and photo-curing is carried out.
As can be seen from FIG. 18 a, the irradiation of an ultraviolet lamp at 365nm for-2 s to 0s with (pure) organic long afterglow materials exhibiting photoluminescent characteristics; the 0s to 1s is the long afterglow luminescence of the (pure) organic long afterglow material after the ultraviolet lamp is removed, the afterglow time is about 1s, and the afterglow time is similar to that observed by naked eyes. As can be seen from FIG. 18 b, the film of example 10 was irradiated with an ultraviolet lamp at 365nm for-2 s to 0s, and exhibited photoluminescence characteristics; and 0s to 4s are long afterglow luminescence of the film after the ultraviolet lamp is removed, the afterglow time is about 4s, and the afterglow time is similar to that observed by naked eyes. The invention enhances the luminous performance of the (pure) organic long afterglow material after the photo-curing glue is introduced and photo-curing is carried out.
FIG. 19 shows that the film of example 11 was irradiated with an ultraviolet lamp at 365nm for-2 s to 0s, and the film exhibited photoluminescence characteristics; and 0s to 2s is long afterglow luminescence of the film after the ultraviolet lamp is removed, the afterglow time is about 2s, and the afterglow time is similar to that observed by naked eyes.
As can be seen from FIG. 20, the film of example 12 was irradiated with an ultraviolet lamp ranging from-2 s to 0s at 365nm, and the film exhibited photoluminescence characteristics; and 0s to 2s is long afterglow luminescence of the film after the ultraviolet lamp is removed, the afterglow time is about 2s, and the afterglow time is similar to that observed by naked eyes.
As can be seen from FIG. 21, from-2 s to 0s, the material exhibits photoluminescent properties when irradiated with a 365nm ultraviolet lamp; the 0s to 1s is the long afterglow luminescence of the (pure) organic long afterglow material after the ultraviolet lamp is removed, the afterglow time is about 1s, and the afterglow time is similar to that observed by naked eyes. As can be seen from FIG. 21 b, the film of example 13 was irradiated with an ultraviolet lamp having a wavelength of 365nm for-2 s to 0s, and exhibited photoluminescence characteristics; and 0s to 6s are long afterglow luminescence of the film after the ultraviolet lamp is removed, the afterglow time is about 6s, and the afterglow time is similar to that observed by naked eyes. The invention enhances the luminous performance of the (pure) organic long afterglow material after the photo-curing glue is introduced and photo-curing is carried out.
As can be seen from FIG. 22 a, the irradiation of an ultraviolet lamp at 365nm for-2 s to 0s with a (pure) organic long afterglow material exhibiting photoluminescent characteristics; the 0s to 1s is the long afterglow luminescence of the (pure) organic long afterglow material after the ultraviolet lamp is removed, the afterglow time is about 1s, and the afterglow time is similar to that observed by naked eyes. As can be seen from FIG. 22 b, the film of example 14 was irradiated with an ultraviolet lamp at 365nm for-2 s to 0s, and exhibited photoluminescence characteristics; and 0s to 6s are long afterglow luminescence of the film after the ultraviolet lamp is removed, the afterglow time is about 6s, and the afterglow time is similar to that observed by naked eyes. The invention enhances the luminous performance of the (pure) organic long afterglow material after the photo-curing glue is introduced and photo-curing is carried out.
Example 15 (for comparison)
Mixing a host material, a guest material and a solvent, stirring for 5min at the room temperature of 20-25 ℃ to obtain a solution, coating the solution on the metal surface, and wiping off redundant solution on the metal surface by using methylene dichloride as a cleaning agent, wherein the ratio of the host material to the guest material is 100:1, the ratio of the host material to the solvent is 1:10, the unit of the mass fraction is g, and the unit of the volume fraction is ml. The solvent is dichloromethane. The host material and the guest material are the same as those in example 1, respectively.
The metal surface is irradiated by an ultraviolet lamp, and imaging of long afterglow emitted by opening defects of the metal surface is incomplete (even can not be imaged when the opening defects are small). Because the absence of the photo-curable glue causes the solvent to evaporate rapidly, so that the host material and the guest material form crystals, which are easily rubbed off.
Example 16
The preparation method of the solution containing the organic long afterglow material and the photo-curing glue comprises the following steps: the photo-setting paste, the host material, the guest material and the solvent were mixed and stirred at room temperature of 20 to 25 ℃ for 5 minutes to obtain a solution, wherein the photo-setting paste, the host material, the guest material and the solvent were the same as in example 1. The ratio of the host material to the guest material to the photo-curing adhesive is 100:1:400, the ratio of the photo-curing adhesive to the solvent is 4:10, the unit of the mass portion is g, the unit of the volume portion is mL, and the solvent is dichloromethane.
The application of the photo-curing adhesive in metal flaw detection is that a solution containing an organic long afterglow material and the photo-curing adhesive is coated on the surface of metal, dichloromethane is used as a cleaning agent to wipe off redundant solution on the surface of the metal, after the dichloromethane volatilizes, a 365nm ultraviolet lamp is used for curing, and the long afterglow material in the solution is used as a penetrating agent and a developing agent for penetrating flaw detection: the metal surface is irradiated by an ultraviolet lamp, the position and the size of the defect are judged through afterglow, when the opening defect exists on the metal surface, the opening defect emits long afterglow, and when the opening defect does not exist on the metal surface, the long afterglow is not emitted.
As shown in FIG. 23, under excitation of 365nm ultraviolet lamp, the opening defect shows strong blue-violet fluorescence (left in FIG. 23), when the ultraviolet lamp excitation light source is removed, the opening defect can be seen to emit long afterglow (right in FIG. 23), the yellow-green afterglow as long as 9s is displayed, and the position and the size of the defect can be judged through afterglow phenomenon, so that nondestructive detection of metal flaw detection is realized.
Example 17
The use of photo-curable glue in anti-counterfeiting. The specific method comprises the following steps:
step 1, mixing the photo-curing glue, the host material, the guest material and the solvent, and stirring for 5min at the temperature of 20-25 ℃ to obtain a solution, wherein the photo-curing glue, the host material, the guest material and the solvent are the same as those in the embodiment 1. The ratio of the host material to the guest material to the photo-curing adhesive is 100:1:400, the ratio of the photo-curing adhesive to the solvent is 4:10, the unit of the mass fraction is g, the unit of the volume fraction is mL, and the solvent is dichloromethane;
step 2, spraying the solution on the surface of a true object to be detected, standing at room temperature, and curing by using a 365nm ultraviolet lamp after the dichloromethane volatilizes; the object to be measured can be glass, plastic, fabric, paper, etc., and in the embodiment is the surface of a glass bulb emitting 365nm ultraviolet light;
and 3, when the authenticity is identified, the surface of the object to be detected is irradiated by an ultraviolet lamp, and the authenticity of the object to be detected is judged according to whether the surface of the object to be detected emits long afterglow or long afterglow time.
For example: when the surface of the object to be measured emits long residual glow, judging the object to be measured as true; and when the surface of the object to be detected does not emit long residual glow, judging that the object to be detected is false. As shown in fig. 24 a, after curing, the surface of the object to be measured emits bright blue-violet fluorescence by excitation with a 365nm ultraviolet lamp, the 365nm ultraviolet lamp is turned off, the surface of the object to be measured emits yellow-green afterglow of 9s, and anti-counterfeiting is realized according to the existence of afterglow.
And the following steps: the difficulty of counterfeiting can be increased by using organic long afterglow materials of different glow time and color, for example: when the surface of the object to be measured emits long residual glow with a certain length of time after the surface of the object to be measured is irradiated by the ultraviolet lamp, the object to be measured is judged to be true, otherwise, the object to be measured is judged to be false.
Example 18
The use of photo-curable glue in anti-counterfeiting. Substantially the same as in example 17, except that: the host material and the guest material in this example are the same as those in example 3, respectively.
As shown in fig. 24 b, after curing, the surface of the object to be measured emits bright blue-violet fluorescence by excitation with a 365nm ultraviolet lamp, the 365nm ultraviolet lamp is turned off, and the surface of the object to be measured emits a dark green afterglow of 7s, so that anti-counterfeiting is realized according to the existence of afterglow.
Example 19
Use of a photo-curable glue for encryption of information.
The method for improving the afterglow performance of the organic long afterglow material by the photo-curing adhesive prolongs the afterglow time of the organic long afterglow material, so that different afterglow time and colors represent different meanings, and information encryption is realized.
In the above-described embodiments 1 to 19, the technical effects consistent with the above-described embodiments can be achieved by replacing the photo-curable adhesive with the loctite@aa3492 (chinese Gao Letai, ltd), the ultraviolet curable adhesive 3491 (guangdong you yang new materials limited), and the ultraviolet curable adhesive 3492 (guangdong you yang new materials limited).
The foregoing has described exemplary embodiments of the invention, it being understood that any simple variations, modifications, or other equivalent arrangements which would not unduly obscure the invention may be made by those skilled in the art without departing from the spirit of the invention.
Claims (10)
1. A method for improving afterglow performance of organic long afterglow material by photo-curing adhesive is characterized in that the method is one or two modes:
mode one: uniformly mixing the photo-curing adhesive, the solvent and the organic long afterglow material to volatilize the solvent completely, and curing by ultraviolet irradiation, wherein the ratio of the photo-curing adhesive to the organic long afterglow material is (4-6) 1 in parts by weight;
mode two: mixing the photo-curing adhesive, the host material, the guest material and the solvent, stirring for at least 5min at room temperature to obtain a solution, standing for at least 2 hours to volatilize the solvent in the solution completely, and curing by ultraviolet light irradiation, wherein the ratio of the host material to the guest material to the photo-curing adhesive is 100:1 (400-600) in parts by weight.
2. The method according to claim 1, wherein the ratio of the parts by weight of the photo-curing adhesive to the parts by volume of the solvent is 4 (5-15), the parts by weight are in g, the parts by volume are in ml, the solvent is dichloromethane, and the curing time is 20-40 s.
3. A method of producing a film comprising: mixing the photo-curing adhesive, the host material, the guest material and the solvent, stirring at room temperature of 20-25 ℃ for at least 5min to obtain a solution, coating the solution on a substrate, and irradiating and curing the solution by ultraviolet light after the solvent volatilizes to obtain a film, wherein the ratio of the host material to the guest material to the photo-curing adhesive is 100:1 (400-600) in parts by weight.
4. A method of preparation according to claim 3, wherein the solvent is methylene chloride;
the ratio of the mass parts of the photo-curing adhesive to the volume parts of the solvent is 4 (5-15), the unit of the mass parts is g, and the unit of the volume parts is mL.
5. A light emitter, comprising: the organic long afterglow material and the cured photo-curing glue are positioned in the photo-curing glue.
6. The method according to one of claims 1 to 2 and the preparation method according to claims 3 to 4, wherein the guest material is:
R 1 h, CH of a shape of H, CH 3 、OCH 3 、O(CH 2 ) 5 、CN、CHO、NO 2 Or ch=ch (C 6 H 5 )，R 2 H, CH of a shape of H, CH 3 、OCH 3 、O(CH 2 ) 5 、CN、CHO、NO 2 Or ch=ch (C 6 H 5 )，R 3 H, CH of a shape of H, CH 3 、OCH 3 、O(CH 2 ) 5 、CN、CHO、NO 2 Or ch=ch (C 6 H 5 ) X= C, O, P or Si;
the main materials are as follows:
wherein X is 1 、X 2 And X 3 Each independently, X 1 、X 2 、X 3 H, C respectively n H 2n+1 、OCH 3 、O(CH 2 ) 5 、CN、CHO、NO 2 And ch=ch (C 6 H 5 ) One of them.
7. The application of the photo-curing adhesive in metal flaw detection is characterized in that the photo-curing adhesive, a host material, a guest material and a solvent are mixed, stirred for at least 5min at the temperature of 20-25 ℃ to obtain a solution, the solution is coated on the metal surface, the superfluous solution on the metal surface is wiped off, the metal surface is cured by ultraviolet light, the position and the size of a defect are judged through afterglow, the opening defect emits long afterglow when the opening defect exists on the metal surface, and does not emit long afterglow when the opening defect does not exist on the metal surface, wherein the ratio of the host material, the guest material and the photo-curing adhesive is 100:1 (400-600) in parts by weight.
8. The use according to claim 7, wherein the ratio of the parts by weight of the photo-curable glue to the parts by volume of the solvent is 4 (5-15), the parts by weight are in g, the parts by volume are in ml, the solvent is dichloromethane, and the curing time is 20-40 s.
9. The application of the photo-curing adhesive in anti-counterfeiting is characterized in that when the authenticity is identified, ultraviolet light is used for irradiating the surface of an object to be detected, and the authenticity of the object to be detected is judged according to whether the surface of the object to be detected emits long afterglow or long afterglow time, wherein the surface of the object to be detected emits the long afterglow by the following method:
step 1, mixing a photo-curing adhesive, a host material, a guest material and a solvent, and stirring at room temperature for at least 5min to obtain a solution, wherein the ratio of the host material to the guest material to the photo-curing adhesive is 100:1 (400-600) in parts by weight;
and 2, spraying the solution on the surface of a true object to be detected, and irradiating and solidifying the solution by ultraviolet light after the solvent volatilizes.
10. The use of photo-curing glue in information encryption is characterized in that the method for improving the afterglow performance of organic long afterglow materials by photo-curing glue prolongs the afterglow time of the organic long afterglow materials, and makes different afterglow time and color represent different meanings, thereby realizing information encryption.
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