A label for quality assurance monitoring of food, pharmaceuticals, or cosmetics and its application

Abstract

This invention belongs to the field of intelligent packaging technology for food, pharmaceuticals, or cosmetics, specifically relating to a quality assurance monitoring label for food, pharmaceuticals, or cosmetics and its application. This quality assurance monitoring label has the following characteristics: 1) The label comprises a long-afterglow luminescent material (including organic and inorganic long-afterglow luminescent materials) and a carrier material; the raw materials are inexpensive, widely available, and diverse; 2) The label is easily modularly integrated into traditional packaging and is perfectly compatible with current commercial packaging; 3) The label is convenient to use, quick to identify, and reusable. Utilizing the characteristic of long-afterglow luminescent materials to capture energy that gradually dissipates over time, achieving self-evolving intensity decay, it can accurately predict the environment and storage duration experienced by the product during storage. This quality assurance monitoring label has broad application prospects and commercial value in the food industry, food engineering, or cosmetics industry.

Description

Technical Field

[0001] This invention belongs to the field of intelligent packaging technology for food, pharmaceuticals, or cosmetics, and specifically relates to a label for quality assurance monitoring of food, pharmaceuticals, or cosmetics and its application. Background Technology

[0002] Goods inevitably pass through warehousing and logistics distribution stages from producers and sellers to the final consumer. Environmental factors such as temperature, humidity, and warehouse hygiene at each stage of distribution will more or less affect the actual quality and remaining shelf life of goods, especially perishable products such as food and pharmaceuticals. Taking food as an example, statistics show that for every 6 degrees Celsius increase in temperature, the growth rate of microorganisms that cause food spoilage doubles. Due to the unpredictability of the logistics process, traditional methods of labeling expiration dates obviously cannot fully guarantee the actual quality of goods. Therefore, with the rapid development of industrial technology, product packaging is also moving towards intelligentization. Intelligent packaging design allows product packaging to be both attractive and effectively monitor the transportation environment and predict its true quality, alleviating customer concerns about quality and safety to some extent. As an important branch of intelligent packaging technology, the development and research of time and temperature indicators is of great significance.

[0003] Unlike the best-before date or expiration date printed on the outer packaging, time-temperature indicators (Time-Temperature Indicators / Integrators) can effectively record and provide historical information on the time and temperature experienced by food and medicine, allowing users to make judgments. Therefore, they can be used to ensure the safety of perishable bottles. [Ghorbani L, et al. Bioprinting, 2021, 21:e00109.] There are three common types of time-temperature indicators: physical diffusion type, polymerization reaction type, and microbial type. Physical diffusion type time-temperature indicators obtain quality information based on the distance the colorimetric reagent diffuses in the substrate over time. The diffusion rate of the indicator substance is correlated with temperature [AJUK, BKG, AJA, et al. LWT-Food Science and Technology, 2016, 67(5838)]. This type of indicator has a simple structure, but it ignores the problem of unclear interface in the later stage of concentration gradient diffusion and the influence of air humidity on the diffusion interface during actual circulation. Polymerization reaction type time-temperature indicators use the color change caused by the polymerization reaction to indirectly indicate freshness. While these types of time-temperature indicators can respond rapidly to external stimuli, they have poor biocompatibility and are prone to causing environmental pollution. Microbial time-temperature indicators primarily reflect food quality information by coupling the growth of microorganisms within the indicator with the proliferation of microorganisms in the food, offering higher accuracy [Mataragas M, et al. Innovative Food Science & Emerging Technologies, 2018, 52.]. However, existing microbial species are very complex, and the stability of microbial indicators still requires extensive validation. In addition, the cost of use is another factor that must be considered before the widespread adoption of time-temperature indicators. Summary of the Invention

[0004] In view of the shortcomings of the prior art, the purpose of this invention is to provide a new type of quality assurance monitoring label and its application method, which aims to solve the problem of dynamic quality monitoring of products during storage and sales.

[0005] To achieve the above objectives, the present invention provides a quality assurance monitoring mark, which comprises a long afterglow luminescent material with light energy storage characteristics and a carrier material;

[0006] After excitation, the label can release its stored light energy upon additional thermal stimulation or near-infrared laser stimulation, responding synchronously with the environment in response to stored food, pharmaceuticals, cosmetics, or similar products. The label is used for quality assurance monitoring of food, pharmaceuticals, or cosmetics at room temperature.

[0007] Furthermore, the quality assurance monitoring label is modularly integrated into existing commercial packaging.

[0008] Furthermore, the trap depth of the long-afterglow luminescent material with light energy storage properties is 0.5 to 2.0 eV; the excitation light source includes ultraviolet light, visible light, X-rays, etc.

[0009] Furthermore, the long-afterglow luminescent material with light energy storage properties includes one or both of inorganic and organic long-afterglow luminescent materials.

[0010] Furthermore, the inorganic long-afterglow luminescent material with optical energy storage characteristics is an inorganic fluorescent material doped with rare earth ions, transition metal ions, or main group ions, which can be synthesized by high-temperature solid-state synthesis, combustion method, hydrothermal method, solvothermal method, etc.

[0011] Taking an inorganic long-afterglow fluoride nanomaterial as an example, the chemical formula for the time-temperature indicator of the inorganic long-afterglow fluoride nanomaterial is KZn. 1-x Mn x F3, where x is Mn 2+ Partially replaces Zn located at the octahedral coordination center 2+ The molar ratio of x is 0.5% ≤ x ≤ 11%. Preferably, the composition of the inorganic long afterglow fluoride nanomaterial is 3% ≤ x ≤ 5%. The crystal structure of the inorganic long afterglow fluoride nanomaterial belongs to the cubic crystal system. The inorganic long afterglow fluoride nanomaterial needs to undergo pre-excitation and energy storage via X-rays.

[0012] A method for preparing inorganic long-afterglow fluoride nanomaterials includes the following steps:

[0013] a) K is made from its fluoride, acetate or nitrate, Zn is made from its acetate or nitrate, and transition metal Mn ions are made from its nitrate. The raw materials for each metal element are weighed according to their stoichiometric ratio. The ratio of manganese salt to zinc salt is 0.5% ≤ x ≤ 11%.

[0014] b) Dissolve the raw material from step a) in a mixed solution of ethanol and water, then add oleic acid and stir for 0.5 to 1 hour to form a precursor solution. Transfer the solution to a reaction vessel and keep it at 180°C in an oven for 12 hours. After the reaction, allow it to cool naturally to room temperature. After repeated centrifugation, washing and drying at 80°C, a white powder is obtained.

[0015] Furthermore, the organic long-afterglow luminescent material is a host-guest doped material, the host material is an organic compound with carrier transport characteristics, and the guest material is a thermally activated delayed fluorescence organic compound. The highest occupied molecular orbital energy level of the guest material is higher than that of the host material, and the lowest unoccupied molecular orbital energy level of the guest material is lower than that of the host material.

[0016] Furthermore, the organic long afterglow composition is composed of a guest material with a mass percentage of 0.1 to 50.0% and a host material with a mass percentage of 50.0 to 99.9%; it is prepared in an oxygen-free environment by a melt-cooling method, a solution processing method, or a vacuum phase deposition method.

[0017] The host materials possessing charge carrier transport properties include, but are not limited to: 1,3,5-tris(1-phenyl-1H-benzimidazol-2-yl)benzene (TPBi), 1,3,5-tris[(3-pyridyl)-3-phenyl]benzene (TMPyPB), etc.

[0018]

[0019] The thermally activated delayed fluorescence guest materials include, but are not limited to: 4-(6-(4-(9H-carbazole-9-yl)phenyl)-1,3-dioxy-1H-benzo[de]isoquinoline-2(3H)-yl)benzonitrile (CPN), 4-(6-(4-(diphenylamino)phenyl)-1,3-dioxy-1H-benzo[de]isoquinoline-2(3H)-yl)benzonitrile (TN), etc.

[0020]

[0021] The synthesis steps of the flexible label prepared by the quality assurance monitoring label through the co-coating method include: uniformly mixing the inorganic long afterglow nanomaterial with the elastic polymer material, and preparing a long afterglow fluorescent film by the coating method.

[0022] The synthesis steps of the quality assurance monitoring mark, prepared on a rigid substrate material by a melt-rapid cooling method, include: weighing the host and guest samples according to a specific mass percentage in an oxygen-free glove box, pouring them onto a quartz glass slide, placing the slide on a heating stage, heating the sample to 300-400°C until it melts, mixing the molten mixture thoroughly, and then rapidly cooling it to room temperature to obtain a transparent glassy film. This film is then encapsulated with a UV-curable adhesive to obtain the target quality assurance monitoring mark.

[0023] Furthermore, the carrier material is selected from rigid carrier materials or flexible carrier materials;

[0024] The rigid carrier material includes quartz glass templates, metal templates, plastic templates, etc.; the rigid carrier material is used to encapsulate and fix the long afterglow luminescent material.

[0025] The flexible carrier material includes epoxy resin, acrylic resin, amino acrylate material, etc.

[0026] Furthermore, the application of the identifier in storage specifically includes the following steps:

[0027] 1) At room temperature, the quality assurance monitoring mark is illuminated with an excitation light source to write optical information;

[0028] 2) When stored at room temperature for a period of time, the stored light energy is slowly released at a certain rate;

[0029] 3) After purchasing a product, consumers can remove the label and heat it to a temperature higher than the storage temperature, or excite it with near-infrared light (760–1500 nm) or visible light (380–760 nm) to fully release the light energy stored in the label. A photodetector is then used to read the released photons to obtain a pyroluminescence curve. The stored energy intensity value is obtained by integrating the area of ​​the pyroluminescence curve and comparing it to a standard curve showing the relationship between storage time and stored light energy. If the obtained stored light energy intensity value is higher than the intensity corresponding to the standard curve, it indicates that the food, medicine, cosmetic, or similar product requiring quality assurance has not changed and is deemed qualified. If the obtained stored energy intensity value is below the standard curve, it indicates that the food, medicine, cosmetic, or similar product requiring quality assurance has been exposed to higher temperatures during storage or has exceeded its shelf life, and is deemed unqualified.

[0030] This invention also provides an application of a quality assurance monitoring identifier in storage, specifically including the following steps:

[0031] 1) At room temperature, the quality assurance monitoring mark is illuminated with an excitation light source to write optical information;

[0032] 2) When stored at room temperature for a period of time, the stored light energy is slowly released at a certain rate;

[0033] 3) After purchasing the product, consumers can remove the label and heat it to a temperature higher than the storage temperature, or excite it with near-infrared light (760–1500 nm) or visible light (380–760 nm) to fully release the light energy stored in the label. They can then use a spectrometer to obtain the emission spectrum and compare it with the standard emission spectrum. If the two are consistent, the label is genuine; if they are inconsistent, the label is fake.

[0034] The stored light energy released by the label in response to additional thermal stimulation or near-infrared laser stimulation is recorded by a spectrometer to identify the authenticity of the quality assurance monitoring label.

[0035] The quality assurance monitoring label provided by this invention has the following characteristics:

[0036] 1) The label includes long-afterglow luminescent materials with light energy storage properties (including organic and inorganic long-afterglow luminescent materials), with inexpensive raw materials, wide availability, and numerous varieties;

[0037] 2) It is easy to modularly integrate into traditional rigid packaging, or to embed long-afterglow luminescent materials into flexible carriers to prepare flexible labels, which can be perfectly compatible with current commercial packaging;

[0038] 3) The label is easy to use, quick to identify, and reusable. Utilizing the characteristic of long-afterglow luminescent materials to capture energy that gradually dissipates over time, it achieves self-evolving intensity decay, accurately predicting the environment and storage duration experienced by the product during storage. This quality assurance monitoring label has broad application prospects and commercial value in the food industry, food engineering, and cosmetics industries. Attached Figure Description

[0039] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of the present invention or further illustrate the present invention using the drawings, and therefore should not be regarded as a limitation of the scope. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort.

[0040] Figure 1 A schematic diagram illustrating the usage process of the quality assurance monitoring label;

[0041] The use of quality assurance monitoring labels mainly includes three steps: 1) Optical information writing: After the quality assurance monitoring label is excited by ultraviolet-visible light for a period of time at room temperature, it is affixed to the goods to be stored; 2) Storage and optical information storage; 3) Optical information reading.

[0042] Figure 2 The organic long afterglow composition storage identifier prepared by the melt-rapid cooling method for the main body TPBi and guest TN (doping concentration 1wt%) in Example 1 is shown in (a) the thermoluminescence curve of temperature versus light intensity at different storage times at 298K and (b) the intensity integration of the thermoluminescence curve of storage time versus integrated intensity at different storage times at 298K.

[0043] Figure 3For Example 2, a flexible storage label was prepared by a blending and coating method. (a) The thermoluminescence curves of temperature versus light intensity at different storage times at 283K and (b) The intensity integration of the thermoluminescence curves at different storage times at 283K were obtained to obtain the fitting curve of storage time versus integrated intensity.

[0044] Figure 4 Example 3: Flexible storage labels prepared by coating method using nano-fluoride powder and flexible matrix material. (a) Thermoluminescence curves of temperature versus light intensity at different storage times at 303K and (b) The intensity integration of thermoluminescence curves at different storage times at 303K to obtain the fitting curve of storage time versus integrated intensity. Detailed Implementation

[0045] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of 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 some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0046] Example 1:

[0047]

[0048] In an oxygen-free glove box, a sample was weighed at a ratio of 1 wt% guest TN and 99 wt% main TPBi, poured onto a quartz glass slide, and then placed on a heating stage. The sample was heated to 350°C until it melted. The molten liquids were then mixed evenly and rapidly cooled to room temperature to obtain a transparent glassy film, which is the target organic long afterglow composition 1 wt% TN@TPBi storage identification tag.

[0049] like Figure 2 As shown in (b), the identification tag was irradiated with 365nm ultraviolet light at 298K for optical information writing; it was then stored at 298K for 0.5 to 24 hours; finally, the temperature was raised to 400K, and the pyroluminescence curve was read. Experimental data showed that the intensity of pyroluminescence gradually decreased with increasing storage time. Figure 2 As shown in (b), by fitting the intensity decay of the pyroluminescence curves from 0.5 hours to 24 hours, the fitting curve of storage time versus integral intensity can be plotted and the correlation function can be calculated, i.e., I = 1.13exp(-t / 2.94) + 0.03.

[0050] In actual storage-monitoring applications, after storing for a period of time, the tag is removed and heated to 400 K to fully release the stored optical information. The optical information is read using a photomultiplier tube detector, a thermoluminescence curve of light intensity versus temperature is made, and the area of the thermoluminescence curve is integrated to obtain the stored energy intensity value. The stored energy intensity curve is compared with the standard time. If the obtained stored energy intensity value is on the standard curve, it indicates that the food, drug, cosmetic or similar product that requires quality assurance has not mutated and is judged to be qualified. If the obtained stored energy intensity value is below the standard curve, it indicates that the food, drug, cosmetic or similar product that requires quality assurance has been exposed to a higher temperature or exceeded the quality assurance period during storage, and is judged to be unqualified. The authenticity of the storage identification tag can be determined by the specific spectrum emitted by the long afterglow.

[0051] Example 2:

[0052] At normal temperature and pressure, 4 mmol of zinc acetate and 12 mmol of potassium fluoride, the solid raw materials, are accurately weighed and dissolved in a mixed solution of deionized water and absolute ethanol. An appropriate amount of 1 mol / L manganese nitrate solution and 5 mL of oleic acid are added according to the doping concentration. The mixture is stirred at room temperature and magnetically stirred at a speed of 600 revolutions per minute for 1 hour. The obtained milky white precursor solution is transferred from the beaker to the inner liner of a polytetrafluoroethylene reaction kettle and sealed. The reaction kettle is placed in a constant temperature drying oven and heated to 180 °C for 12 hours. After the reaction is completed, it is naturally cooled to room temperature. The reaction product solution is taken out, centrifuged at 6000 revolutions per minute, and the bottom precipitate is retained. The precipitate is washed three times by repeated ultrasonic dispersion and centrifugation with 95% ethanol solution. Finally, the obtained product is placed in an oven and dried at 80 °C for 10 hours to obtain the long afterglow nanophosphor.

[0053] 0.2 g of the nano-fluoride powder obtained by the above method is weighed in a small beaker, and epoxy resin AB glue (the mass ratio of A glue to B glue is 2:1) is added according to a certain powder-to-glue ratio. The mixture is stirred with a glass rod to fully mix the powder and the flexible carrier material. The mixture is evenly spread on aluminum foil paper with a scraper. The scraped film is transferred to an oven and pre-cured at 80 °C for 1 hour, and then heated to 150 °C for 3 hours to obtain the inorganic long afterglow flexible material time-temperature indicating tag.

[0054] As Figure 3 (a) shows that at a temperature of 283 K, the identification tag is irradiated with X-rays for optical information writing; at a temperature of 283 K, it is stored for 0 to 120 minutes; first the temperature is lowered to 203 K and then raised to 550 K, and the thermoluminescence curve is read. From the experimental data, it can be seen that the thermoluminescence intensity decreases with the extension of the storage time. As Figure 3(b) As shown, the integral intensity of the thermoluminescence curve stored for 0 to 120 minutes is fitted with a mathematical function, and the corresponding fitting curve and related function can be plotted, that is, y = 0.32exp(-x / 24.08)+0.67.

[0055] In actual storage - monitoring applications, after storing for a period of time, the label is removed and heated to 550K to fully release the stored optical information. The optical information is read with a photomultiplier tube detector, and the thermoluminescence curve of temperature vs. light intensity is made. The area of the thermoluminescence curve is integrated to obtain the stored energy intensity value, and it is compared with the standard curve of storage energy intensity vs. time. If the obtained stored energy intensity value is on the standard curve, it means that the food, medicine, cosmetics or similar products that need quality assurance have not mutated and are judged as qualified; if the obtained stored energy intensity value is below the standard curve, it means that the food, medicine, cosmetics or similar products that need quality assurance have been exposed to higher temperatures or exceeded the quality assurance duration during storage, and are judged as unqualified. And the authenticity of the storage identification label can be determined by the specific spectrum emitted by the long afterglow.

[0056] Example 3:

[0057] Under normal temperature and pressure, accurately weigh 2 mmol of zinc acetate and 6 mmol of potassium fluoride, solid raw materials, and dissolve them in a mixed solution of deionized water and absolute ethanol. Add an appropriate amount of 1 mol / L manganese nitrate solution and oleic acid according to the doping concentration, stir and mix at room temperature, and maintain magnetic stirring at a speed of 1000 revolutions per minute for 0.5 hours. Transfer the obtained milky white precursor solution from the beaker to the inner liner of a polytetrafluoroethylene reaction kettle and seal the lid. Place the reaction kettle in a constant temperature drying oven and heat it to 180 °C, keep it warm for 12 hours, and naturally cool it to room temperature after the reaction is completed. Take out the reaction product solution, centrifuge it at 8500 revolutions per minute, and retain the bottom precipitate. Add a mixed solution of ethanol and water for repeated ultrasonic dispersion and centrifugal washing for many times. Finally, place the obtained product in an oven and dry it at 70 °C for 12 hours to obtain the long afterglow nanophosphor.

[0058] Weigh 0.2 g of the nano - fluoride powder obtained by the above method in a small beaker, add epoxy resin AB glue according to a certain powder - glue ratio (the mass ratio of A glue to B glue is 2:1), stir the mixture with a glass rod to fully mix the powder and the flexible carrier material, and evenly scrape the mixture onto aluminum foil paper with a spatula. Transfer the scraped film to an oven and pre - cure it at 80 °C for 1 hour first, and then raise the temperature to 150 °C and cure it for 3 hours to obtain the inorganic long afterglow flexible material time - temperature indicating label.

[0059] As Figure 4(a) As shown, at a temperature of 303K, the identification label is irradiated with X-rays for optical information writing; it is stored for 0 to 120 minutes at a temperature of 303K; first the temperature is reduced to 203K and then raised to 550K, and the corresponding thermoluminescence curve is recorded. From the experimental data, it is obtained that the thermoluminescence intensity decreases with the extension of the storage time. As Figure 4 (b) As shown, by performing a mathematical function fitting on the integrated intensity of the thermoluminescence curve stored for 0 to 120 minutes, the corresponding fitting curve and related function can be obtained, that is, y = 0.39exp(-x / 21.35) + 0.59.

[0060] In actual storage - monitoring applications, after storing for a period of time, the label is removed and heated to 550K to fully release the stored optical information, and the optical information is read using a photomultiplier tube detector. A thermoluminescence curve of temperature versus light intensity is made, and the area of the thermoluminescence curve is integrated to obtain the stored energy intensity value, and it is compared with the standard curve of storage energy intensity versus time. If the obtained stored energy intensity value is on the standard curve, it indicates that the food, medicine, cosmetics or similar products that need quality assurance have not mutated and are judged as qualified; if the obtained stored energy intensity value is below the standard curve, it indicates that the food, medicine, cosmetics or similar products that need quality assurance have been exposed to a higher temperature during storage or exceeded the quality assurance duration, and are judged as unqualified. And the authenticity of the storage identification label can be determined by the specific spectrum emitted by the long afterglow.

[0061] In summary, the present invention provides an identification for quality assurance monitoring and its application. By replacing the long afterglow luminescent material and selecting different carrier materials, the present invention can achieve the preparation of an identification for quality assurance monitoring that is reusable, reliable and stable, and easy to detect. And an application method of this type of identification for quality assurance monitoring in the storage field is provided. Through experimental data, it fully demonstrates the feasibility of using the long afterglow luminescent material as a storage identification and its excellent photophysical properties. It can be foreseen that this type of identification for quality assurance monitoring will have a wide range of applications in the storage field.

[0062] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that: they can still modify the technical solutions recorded in the foregoing embodiments, or perform equivalent replacements on some of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A quality assurance monitoring label, characterized in that, The quality assurance monitoring label includes a long-afterglow luminescent material and a carrier material; the long-afterglow luminescent material has light energy storage characteristics and includes one or two of inorganic long-afterglow luminescent materials and organic long-afterglow luminescent materials. The inorganic long afterglow luminescent material is an inorganic fluorescent material doped with rare earth ions, transition metal ions, or main group ions, and is synthesized by high-temperature solid-state synthesis, combustion method, hydrothermal method, or solvothermal method. The inorganic long-afterglow luminescent material is an inorganic long-afterglow fluoride nanomaterial, and the time-temperature indicator chemical formula of the inorganic long-afterglow fluoride nanomaterial is KZn. 1-x Mn x F3, where x is Mn 2+ Partially replaces Zn located at the octahedral coordination center 2+ The molar ratio is such that x takes the value of 0.5%≤x≤11%; the crystal structure of the inorganic long afterglow fluoride nanomaterial belongs to the cubic crystal system; the inorganic long afterglow fluoride nanomaterial needs to be pre-excited and stored by X-rays; The organic long afterglow luminescent material is a host-guest doped material. The host material is an organic compound with carrier transport characteristics, and the guest material is a thermally activated delayed fluorescence organic compound. The highest occupied molecular orbital energy level of the guest material is higher than that of the host material, and the lowest unoccupied molecular orbital energy level of the guest material is lower than that of the host material. The marker stores a portion of light energy after photoexcitation at room temperature, and releases the stored light energy upon high-temperature thermal activation or excitation by near-infrared or visible light. The quality assurance monitoring label is used for quality assurance monitoring of food, medicine, or cosmetics at room temperature.

2. The quality assurance monitoring label according to claim 1, characterized in that, The quality assurance monitoring label is modularly integrated into existing commercial packaging for food, pharmaceuticals, or cosmetics.

3. The quality assurance monitoring label according to claim 1, characterized in that, The trap depth of the long-afterglow luminescent material with light energy storage properties is 0.5 to 2.0 eV; the excitation source includes ultraviolet light, visible light, and X-rays.

4. The quality assurance monitoring label according to claim 1, characterized in that, The organic long afterglow composition consists of a guest material with a mass percentage of 0.1% to 50.0% and a host material with a mass percentage of 50.0% to 99.9%; it is prepared in an oxygen-free environment by a melt-cooling method, a solution processing method, or a vacuum phase deposition method.

5. The quality assurance monitoring label according to claim 1, characterized in that, The carrier material is used to support or disperse the long afterglow luminescent material, and can be a rigid carrier material or a flexible carrier material. The rigid carrier material includes quartz glass templates, metal templates, and plastic templates; the rigid carrier material encapsulates and fixes the long afterglow luminescent material. The flexible carrier material includes epoxy resin, acrylic resin, and amino acrylate material.

6. The application of the quality assurance monitoring identifier as described in any one of claims 1 to 5 in storage specifically includes the following steps: 1) At room temperature, the quality assurance monitoring label is illuminated with an excitation light source to write optical information; 2) When stored at room temperature for a period of time, the stored light energy is slowly released at a certain rate; 3) After purchasing the goods, consumers can remove the label and heat it to a temperature higher than the storage temperature, or use 760~1500 nm near-infrared light or 380~760 nm visible light to light-excite the label and fully release the light energy stored in the label. Then, they can use a photodetector to read the released photons and obtain the pyroluminescence curve. The storage energy intensity value is obtained by integrating the area of ​​the pyroluminescence curve and comparing it with the standard relationship curve of storage time versus storage light energy. If the obtained storage light energy intensity value is higher than the intensity corresponding to the standard curve, it means that the food, medicine, and cosmetics that need to be stored have not changed and are judged as qualified. If the obtained storage energy intensity value is below the standard curve, it means that the food, medicine, and cosmetics that need to be stored have been exposed to higher temperatures or exceeded the shelf life during storage and are judged as unqualified.

7. The application of the quality assurance monitoring identifier as described in any one of claims 1 to 5 in storage specifically includes the following steps: 1) At room temperature, the quality assurance monitoring label is illuminated with an excitation light source to write optical information; 2) When stored at room temperature for a period of time, the stored light energy is slowly released at a certain rate; 3) After purchasing the product, consumers can remove the label and heat it to a temperature higher than the storage temperature, or excite it with 760~1500 nm near-infrared light or 380~760 nm visible light to fully release the light energy stored in the label, and use a spectrometer to obtain the emission spectrum and compare the emission spectrum with the standard emission spectrum; if the two are consistent, the label is genuine; if the two are inconsistent, the label is fake.

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