Color and afterglow co-responsive materials and preparation and application, labels and preparation

Abstract

The present invention discloses a color and afterglow co-response material, which changes its own color while emitting afterglow light after being irradiated with light. The color and afterglow co-response material has a molecule with structures shown in formula (5) to formula (7): #imgabs0# (5) #imgabs1# (6) #imgabs2# (7) The present invention also discloses a preparation method and application of the color and afterglow co-response material, as well as a label and a preparation method thereof. When the color and afterglow co-response material is used in the fields of anti-counterfeiting and cryptography, the security is improved. When it is used in optical storage, the storage capacity and complexity are improved, so the application range is wider.

Description

Technical Field

[0001] The invention relates to the field of luminescent materials, and in particular to color and afterglow co-responsive materials and their preparation and application, as well as labels and their preparation. Background Art

[0002] In today's era of rapid technological development, the research and application of luminescent materials has become an important force in promoting the progress of many industries. Especially in the fields of optics, electronics, biomedicine, etc., luminescent materials are not only the cornerstone of technological innovation, but also the key to realizing functional devices. Afterglow luminescent materials, as a new type of material that can continue to emit light after the excitation light source disappears, have unique photophysical properties that make them show great application potential in many cutting-edge fields such as power-free lighting, anti-counterfeiting authentication, information storage, and biological imaging.

[0003] Compared with ordinary photoluminescent materials, the molecular structure of afterglow luminescent materials is more difficult to forge to a certain extent. Therefore, afterglow luminescent materials have higher security in the field of anti-counterfeiting and security authentication. However, with the continuous development and progress of science and technology, even if afterglow luminescent materials are used, their molecular structure has the possibility of being copied and has the risk of being forged. Therefore, how to design afterglow luminescent materials, including how to design their molecular structure, to further increase the complexity and difficulty of forgery, thereby further improving safety performance, ensuring the reliability of afterglow luminescent materials in the field of anti-counterfeiting and security authentication, and then expanding their scope of application, is also a problem that should be considered and needs to be solved.

[0004] In addition, when afterglow luminescent materials are used in the field of optical storage, if larger capacity storage can be further achieved by designing the molecular structure, it will also be conducive to the wider application of afterglow luminescent materials. Summary of the invention

[0005] In order to solve the above technical problems, the embodiment of the present invention discloses a color and afterglow co-responsive material. When the color and afterglow co-responsive material is exposed to light, it emits afterglow light and its own color also changes. The color and afterglow co-responsive material has a molecule with a structure shown in formula (5) to formula (7):

[0006] (5) (6)

[0007] (7).

[0008] By adopting the above technical solution, a material with its own color and long afterglow can be obtained. Specifically, under illumination conditions, the material can show afterglow phenomenon, that is, after the illumination stops, it can still continue to emit light for a period of time. At the same time, its own color also changes, and the color change and afterglow phenomenon are independent of each other. Therefore, when the material is used in the field of anti-counterfeiting or cryptography, the possibility of being copied and forged is small through the dual protection of afterglow and its own color change, which greatly improves security. Moreover, when it is used in the field of optical storage, it can be used to encode and store information in a wider range, which improves storage capacity.

[0009] Optionally, the color and afterglow co-responsive material is irradiated with light in the wavelength range of 200-1200 nm, the color and afterglow co-responsive material emits afterglow light and the ultraviolet absorption of the molecule in the wavelength range of 400 nm-500 nm changes.

[0010] According to another specific embodiment of the present invention, the embodiment of the present invention discloses a method for preparing a color and afterglow co-responsive material, comprising the following steps: mixing a compound having a molecular structure as shown in formula (a-5) with a compound having a molecular structure as shown in formula (c) in a solvent, refluxing, to obtain a compound having a molecular structure as shown in formula (5), and preparing the compound having a molecular structure as shown in formula (5) as the color and afterglow co-responsive material; or, mixing a compound having a molecular structure as shown in formula (a-6) with a compound having a molecular structure as shown in formula (c) in a solvent, refluxing, to obtain a compound having a molecular structure as shown in formula (6), and preparing the compound having a molecular structure as shown in formula (6) as the color and afterglow co-responsive material; or, mixing a compound having a molecular structure as shown in formula (a-7) with a compound having a molecular structure as shown in formula (c) in a solvent, refluxing, to obtain a compound having a molecular structure as shown in formula (7), and preparing the compound having a molecular structure as shown in formula (7) as the color and afterglow co-responsive material;

[0011] (a-5) (a-6)

[0012] (a-7) (c)

[0013] Wherein, the solvent is one or more of benzene, toluene, xylene, ethylbenzene, isopropylbenzene, styrene, chlorobenzene, nitrobenzene, dichlorobenzene and trichlorobenzene, and the reflux time is 5 to 10 hours.

[0014] By adopting the above technical solution, color and afterglow co-responsive materials can be easily obtained with high yield.

[0015] According to another specific embodiment of the present invention, the embodiment of the present invention discloses the application of color and afterglow co-responsive materials, and the color and afterglow co-responsive materials are used in the fields of anti-counterfeiting, cryptography, homogeneous detection and optical storage.

[0016] The adoption of the above technical solution can improve the security of anti-counterfeiting and cryptographic security authentication and expand the storage capacity of optical storage.

[0017] According to another specific embodiment of the present invention, an embodiment of the present invention discloses an anti-counterfeiting label, which has an identification layer, and the identification layer is coated with ink, and the ink includes the above-mentioned color and afterglow co-responsive material and a photosensitizer. After being irradiated with ultraviolet light, the identification layer can emit afterglow light and its own color changes.

[0018] By adopting the above technical solution, the security performance of the anti-counterfeiting label is improved and the reliability is stronger.

[0019] Optionally, the photosensitizer is tetraphenylporphyrin, and the anti-counterfeiting label further comprises a shielding layer, which is a polyester film. When anti-counterfeiting identification is not performed, the shielding layer covers the identification layer; when anti-counterfeiting identification is performed, the shielding layer can be removed to expose the identification layer.

[0020] According to another specific embodiment of the present invention, the embodiment of the present invention discloses a method for preparing an anti-counterfeiting label, comprising the following steps: mixing a color and afterglow co-responsive material and a photosensitizer to obtain an initial mixture; mixing the initial mixture with polystyrene and dissolving the mixture in ethanol to obtain a mixed solution; adjusting the viscosity of the mixed solution to 1-20 cP, stirring evenly to obtain ink; inkjet printing the ink on a substrate, heating and drying to obtain an identification layer; covering the identification layer with a shielding layer to obtain an anti-counterfeiting label.

[0021] By adopting the above technical solution, anti-counterfeiting labels with better security performance can be easily manufactured. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 The NMR carbon spectrum of Example 1 of the present invention is shown;

[0023] Figure 2 The nuclear magnetic hydrogen spectrum of Example 1 of the present invention is shown;

[0024] Figure 3 The NMR carbon spectrum of Example 2 of the present invention is shown;

[0025] Figure 4 The nuclear magnetic hydrogen spectrum of Example 2 of the present invention is shown;

[0026] Figure 5 The nuclear magnetic hydrogen spectrum of Example 3 of the present invention is shown;

[0027] Figure 6 The NMR carbon spectrum of Example 3 of the present invention is shown;

[0028] Figure 7 The nuclear magnetic hydrogen spectrum of Example 4 of the present invention is shown;

[0029] Figure 8 The NMR carbon spectrum of Example 4 of the present invention is shown;

[0030] Fig. 9 The nuclear magnetic hydrogen spectrum of Example 5 of the present invention is shown;

[0031] Fig.10 The NMR carbon spectrum of Example 5 of the present invention is shown;

[0032] Fig.11 The afterglow spectrum of Example 1 of the present invention at an excitation wavelength of 532 nm is shown;

[0033] Fig.12 The fluorescence spectrum of Example 1 of the present invention at an excitation wavelength of 532 nm is shown;

[0034] Fig.13 The ultraviolet absorption spectrum of Example 1 of the present invention at an excitation wavelength of 532 nm in the range of 400-700 nm is shown;

[0035] Fig.14 The ultraviolet absorption spectrum of Example 3 of the present invention is shown at an excitation wavelength of 532 nm in the range of 400-700 nm;

[0036] Fig.15 The ultraviolet absorption spectrum of Example 2 of the present invention at an excitation wavelength of 532 nm in the range of 400-700 nm is shown;

[0037] Fig.16 The ultraviolet absorption spectrum of Example 5 of the present invention is shown at an excitation wavelength of 532 nm in the range of 400-700 nm;

[0038] Fig.17 A photograph showing a mixed solution prepared by Example 1 of the present invention and tetraphenylporphyrin before illumination;

[0039] Fig.18 A photograph showing the mixed solution prepared by Example 1 of the present invention and tetraphenylporphyrin after illumination;

[0040] Fig.19 A photograph showing the tetraphenylporphyrin solution of the present invention before illumination;

[0041] Fig. 20 A photograph of the solution of Example 1 of the present invention before illumination is shown;

[0042] Fig.21 The ultraviolet absorption spectra of Example 1 of the present invention at different times after light exposure are shown;

[0043] Fig. 22 The H NMR spectrum of the product after illumination in Example 1 of the present invention is shown;

[0044] Fig.23 The NMR carbon spectrum of the product after illumination in Example 1 of the present invention is shown;

[0045] Fig.24 The measured mass spectrum of the product after illumination in Example 1 of the present invention is shown. DETAILED DESCRIPTION

[0046] The following specific embodiments illustrate the implementation of the present invention, and those skilled in the art can easily understand other advantages and effects of the present invention from the contents disclosed in this specification. Although the description of the present invention will be introduced in conjunction with the preferred embodiment, this does not mean that the features of this invention are limited to this implementation. On the contrary, the purpose of introducing the invention in conjunction with the implementation is to cover other options or modifications that may extend based on the claims of the present invention. In order to provide a deep understanding of the present invention, the following description will include many specific details. The present invention can also be implemented without using these details. In addition, in order to avoid confusion or blurring the focus of the present invention, some specific details will be omitted in the description. It should be noted that the embodiments of the present invention and the features in the embodiments can be combined with each other without conflict.

[0047] In the embodiment of the present invention, "color and afterglow co-response" means that after being stimulated by external factors (such as light), the material can respond simultaneously in terms of its own color and afterglow luminescence, that is, while its own color changes, it also emits afterglow light.

[0048] It should be noted that in this specification, similar reference numerals and letters denote similar items in the following drawings, and therefore, once an item is defined in one drawing, it does not need to be further defined and explained in the subsequent drawings.

[0049] In order to make the objectives, technical solutions and advantages of the present invention more clear, the embodiments of the present invention will be further described in detail below with reference to the accompanying drawings.

[0050] First of all, it should be noted that it is generally believed that there is a difference between the change in the inherent color of a substance and the change in the luminescent color of a substance. The inherent color usually refers to the color displayed by a substance under white light (including all visible light wavelengths). This is because a substance absorbs certain wavelengths of light and reflects or transmits other wavelengths of light. The human eye perceives the unabsorbed light waves, which determines the inherent color of the substance. The luminescent color refers to the color of the light emitted (luminescent) by the substance itself. This phenomenon is called luminescence, which can be fluorescence, phosphorescence (afterglow), chemiluminescence, etc. The luminescence process involves the absorption of energy (usually light energy) by the substance, causing the electron to transition from the ground state to the excited state. When the electron returns to the lower energy level of the ground state, it releases energy in the form of light. The luminescent color depends on the energy difference between the excited state and the ground state energy levels. This energy difference corresponds to a specific wavelength of light, which is the luminescent color seen by the naked eye. Therefore, the changes in these two colors actually involve different physical and chemical mechanisms. The change in the intrinsic color may be due to the change in the chemical composition or the structure of the material, resulting in changes in the absorption / reflection / transmission characteristics of light of different wavelengths, while the change in the luminescent color may be due to the change in the electronic energy level structure, which may be caused by changes in the molecular structure, doping with other elements or compounds, or changes in the microenvironment of the material (such as changes in pH value).

[0051] Afterglow materials are a type of material that can store energy and continue to emit light for a period of time after being irradiated by an excitation light source (such as ultraviolet light or visible light) after the excitation light source disappears, that is, the afterglow material has the above-mentioned luminescent color change response mechanism. Compared with ordinary photoluminescent materials, afterglow materials do not require continuous energy input, and can have a longer afterglow luminescence life, and are more widely used. At present, how to further expand the functions of afterglow materials and further enhance their application value is also a relatively important issue. To this end, the inventors discovered a new type of molecular structure during the experiment. This type of molecule can make the afterglow material respond to both the inherent color of the substance and the afterglow at the same time, that is, respond to the above-mentioned two color change mechanisms at the same time. This type of material can have the application of luminescence and color change at the same time, providing the possibility of creating new multifunctional materials, and because of the unique properties of this type of material, its application field can be expanded.

[0052] The first aspect of the present invention discloses a color and afterglow co-responsive material. When the color and afterglow co-responsive material is exposed to light, it will not only be stimulated to emit afterglow light like a conventional afterglow material, but more specifically, the inherent color of the material itself will also change. The reason is that the color and afterglow co-responsive material has a molecule with a structure as shown in formula (1):

[0053] (1)

[0054] Wherein, R1 is halogen or hydrogen, and R2 is one of hydrogen, halogen and amino substituents.

[0055] Specifically, the color and afterglow co-responsive material has a molecule having a structure as shown in formula (5) to formula (7):

[0056] (5) (6)

[0057] (7).

[0058] The above molecular structure contains afterglow luminescent groups , the afterglow luminescent group is a heterocyclic group containing oxygen and sulfur, that is, the structure of this group includes a five-membered ring, in which two carbon atoms are replaced by oxygen atoms and sulfur atoms respectively, and the other carbon atom in the ring is connected to a carbonyl group (C=O). There are also two benzene rings connected to the afterglow luminescent group to form a conjugated structure. The mechanism of afterglow luminescent group producing afterglow under light is shown as follows:

[0059] .

[0060] That is, after the original molecule is exposed to light, a small molecule is released and an unstable intermediate product is produced. The intermediate product is then oxidized by the singlet oxygen produced by the photosensitizer to generate a diketone structure. Therefore, the inventor believes that the original molecule may first absorb light energy under light and reach an excited state. After releasing the small molecule, the unstable intermediate product formed contains unsaturated bonds or other structures that can capture energy. These intermediates may store a portion of the excitation energy in some form and then emit afterglow light. At the same time, the color of the material itself changes after exposure to light because the change in the molecular structure affects the electron distribution of the molecule, which in turn affects the absorption spectrum of the molecule. In addition, the diketone structure generally provides a wider π electron cloud through a conjugated double bond system, which may cause the molecule to absorb light from different parts of the spectrum from the ultraviolet region to the visible light region, thereby changing the color of the substance. Moreover, before and after the reaction There are also two benzene rings connected. The two benzene rings did not change before and after illumination. A longer conjugated system may have been formed inside the molecule. Organic molecules with a longer conjugated system have stronger absorption of visible light, making the color change of the material more obvious.

[0061] The inventors found that the above-mentioned molecule has a triangular structure. The heterocyclic group as the "vertex" of the triangle will change after being exposed to light, generating intermediate products and diketone structures, resulting in afterglow phenomenon and changes in its own color, which can be said to be the "functional area" of the entire molecule. The benzene rings on the other two "points" of the triangle are relatively stable before and after the reaction, and the benzene ring structure is not affected or changed, so that the molecule has a stable main skeleton structure and also makes the molecule modifiable. Specifically, R1 and R2 can be relatively stable groups or elements, such as hydrogen and halogens, which usually have little effect on the stability of the main body of the molecule and are relatively stable under light. Hydrogen usually does not significantly change the electron density distribution of the main body of the molecule. In addition, R2 can also be an amino substituent, which refers to a group in which at least one of the two H connected to N in the amino group is replaced by other groups, for example, substituted by alkyl, aryl, nitrogen-containing heterocyclic, halogen, hydroxyl, etc. The inventors found that if R2 is designed as an amino substituent, the electron cloud of the molecular structure can be further changed, thereby further optimizing the luminescence or self-color change of the material.

[0062] In a specific embodiment of the present invention, the color and afterglow co-responsive material has a molecule having a structure as shown in formula (2):

[0063] (2)

[0064] Wherein, R1 is halogen, and R3 and R4 are each independently selected from alkyl.

[0065] In the structure of formula (2), the benzene ring in the lower right corner is directly connected to N, which is in turn connected to the other two structures (R3 and R4). Based on the above, N has a triple bond structure, which makes the bond energy between molecules very high, so it is not easy to participate in chemical reactions. At the same time, N has a relatively large electronegativity and has an electron-withdrawing effect, which can further modify and change the conjugated structure.

[0066] Based on the dual properties of the color and afterglow co-response material's luminescence and its own color change, its application value is further improved. Specifically, if the color and afterglow co-response material is applied to the field of anti-counterfeiting and security authentication, the anti-counterfeiting ability and security will be improved. For ordinary afterglow materials or color-changing materials, since they only have a single mechanism of afterglow luminescence or inherent color change, whether it is the molecular structure of the material or the effect of luminescence or color change, it is very likely to be cracked and forged. As for the material of the present application, it has a dual mechanism, which adds an extra layer of "insurance" on the basis of the prior art, which can greatly increase the difficulty of copying and counterfeiting. In addition, the dual mechanism of the color and afterglow co-response material of the embodiment of the present application can be realized by only one molecular structure, and both mechanisms can respond to light at the same time, that is, the afterglow spectrum and absorption spectrum of the molecular structure can respond at the same time. Even if the effect is copied by mixing different materials for counterfeiting, it is difficult to copy the relevant spectrum at the molecular structure level. Therefore, the color and afterglow co-response material of the embodiment of the present application will greatly improve the safety performance and the application value will be greatly improved. In addition, in the field of optical storage, the existence of a dual mechanism will greatly increase the storage capacity and enhance the encoding complexity, which also has high practical value.

[0067] In certain embodiments of the present invention, the alkyl group has 1 to 4 carbon atoms. The alkyl group generally provides chemical stability, is not easy to participate in the reaction, and provides a more stable support for the molecular structure of the material. The inventors have found that R1 is a halogen, and R3 and R4 are alkyl groups with 1 to 4 carbon atoms, which has less effect on the three-dimensional configuration of the molecule and more stable performance.

[0068] In certain specific embodiments of the present invention, the color and afterglow co-responsive material includes a molecule having a structure as shown in Formula (3) to Formula (6):

[0069] (3) (4)

[0070] (5) (6)

[0071] In formula (3), Bu represents a butyl group, including n-butyl (n-Bu), isobutyl (i-Bu), and tert-butyl (t-Bu).

[0072] More specifically, the color and afterglow co-responsive material includes a molecule having a structure as shown in formula (7) to formula (9):

[0073] (7) (8)

[0074] (9).

[0075] The inventors found that the above molecular structure can make the color and afterglow co-responsive material have obvious afterglow luminescence and color change phenomenon, and the response speed is fast, and the ultraviolet absorption is obvious after 10 seconds of illumination. In particular, these structures are more stable and are particularly suitable for application fields such as anti-counterfeiting, cryptography, and optical storage.

[0076] Specifically, when the color and afterglow co-responsive material is irradiated with light in the wavelength range of 200-1200nm, the color and afterglow co-responsive material emits afterglow light and the ultraviolet absorption of the molecule in the wavelength range of 400nm-500nm changes. That is, after being irradiated with light, the ultraviolet absorption spectrum of the molecule will change in the wavelength range of 400nm-500nm. For example, before irradiation, the molecule has no or less ultraviolet absorption in the wavelength range of 400nm-500nm, and after irradiation, the molecule has more ultraviolet absorption in the wavelength range of 400nm-500nm, and the color of the material changes.

[0077] The second aspect of the present invention discloses a method for preparing a color and afterglow co-responsive material, which comprises the following steps.

[0078] A compound having a molecular structure as shown in formula (a) and a compound having a molecular structure as shown in formula (c) are mixed in a solvent and refluxed to obtain a compound having a molecular structure as shown in formula (1):

[0079] (a) (c)

[0080] (1).

[0081] That is, the preparation route is specifically as follows:

[0082] .

[0083] Subsequently, the compound having the molecular structure shown in formula (1) is prepared as a color and afterglow co-responsive material. For example, the compound can be mixed with a photosensitizer to obtain a color and afterglow co-responsive material.

[0084] In a specific embodiment of the present invention, the preparation method comprises the following steps.

[0085] A compound having a molecular structure as shown in formula (b) and a compound having a molecular structure as shown in formula (c) are mixed in a solvent and refluxed to obtain a compound having a molecular structure as shown in formula (2):

[0086] (b) (c)

[0087] (2).

[0088] That is, the preparation route is as follows:

[0089] .

[0090] Subsequently, the compound having the molecular structure shown in formula (2) is prepared as a color and afterglow co-responsive material. For example, the compound can be mixed with a photosensitizer to obtain a color and afterglow co-responsive material.

[0091] Specifically, the solvent used is one or more of benzene, toluene, xylene, ethylbenzene, cumene, styrene, chlorobenzene, nitrobenzene, dichlorobenzene and trichlorobenzene, which are suitable for the synthesis of the molecular structure of the present invention, are relatively stable and easy to remove. In addition, the reflux time is 5 to 10 hours.

[0092] In a specific embodiment of the present invention, the preparation method comprises the following steps.

[0093] A compound having a molecular structure as shown in formula (a-5) and a compound having a molecular structure as shown in formula (c) are mixed in a solvent and refluxed to obtain a compound having a molecular structure as shown in formula (5), and the compound having a molecular structure as shown in formula (5) is prepared as the color and afterglow co-responsive material; or, a compound having a molecular structure as shown in formula (a-6) and a compound having a molecular structure as shown in formula (c) are mixed in a solvent and refluxed to obtain a compound having a molecular structure as shown in formula (6), and the compound having a molecular structure as shown in formula (6) is prepared as the color and afterglow co-responsive material; or, a compound having a molecular structure as shown in formula (a-7) and a compound having a molecular structure as shown in formula (c) are mixed in a solvent and refluxed to obtain a compound having a molecular structure as shown in formula (7), and the compound having a molecular structure as shown in formula (7) is prepared as the color and afterglow co-responsive material;

[0094] (a-5) (a-6)

[0095] (a-7) (c).

[0096] Through the above method, the desired molecular structure can be synthesized conveniently and efficiently, and the molecular yield is relatively high, which can reach more than 78%. In particular, the molecules with structures of formula (7) to (9) have a yield of more than 82%, which is suitable for large-scale production of color and afterglow co-responsive materials.

[0097] The third aspect of the present invention discloses the application of color and afterglow co-responsive materials, which can be used in the fields of anti-counterfeiting, cryptography, homogeneous detection and optical storage. The color and afterglow co-responsive materials of the present invention can be used for luminescence and color change applications at the same time, providing the possibility of creating new multifunctional materials. Specifically, in the fields of anti-counterfeiting and cryptography, this material can be used to make invisible ink, security labels and anti-counterfeiting technology, in which the inherent color of the material is difficult to detect in daily environments, but afterglow and inherent color changes will be displayed under specific lighting, increasing security and confidentiality. In the field of optical storage, the color change and afterglow characteristics of the material can be used for advanced information storage and display technology, such as unique display screens, or systems that display different information under different lighting conditions. In some other application scenarios, for example, this material can be used to develop new sensors for detecting and responding to specific types of light or other environmental stimuli, such as indicators for monitoring ultraviolet exposure. In environmental monitoring, this material can indicate the presence of specific chemicals or radiation, and intuitively display environmental changes through color changes and afterglow luminescence.

[0098] The fourth aspect of the present invention discloses an anti-counterfeiting label, which has an identification layer, the identification layer is coated with ink, the ink includes a color and afterglow co-responsive material and a photosensitizer, and the identification layer can emit afterglow light and change its own color after being irradiated by ultraviolet light. The color and afterglow co-responsive material includes a molecule having a structure shown in formula (1): (1)

[0099] Wherein, R1 is halogen or hydrogen, and R2 is one of hydrogen, halogen and amino substituents.

[0100] In another embodiment of the present invention, further, the color and afterglow co-responsive material has a molecule having a structure as shown in formula (2):

[0101] (2)

[0102] Wherein, R1 is halogen or hydrogen, and R3 and R4 are each independently selected from an alkyl group.

[0103] In this anti-counterfeiting label, the identification layer can emit afterglow light and change its own color after being irradiated by ultraviolet light, and the response speed is fast. This anti-counterfeiting label with double protection is more difficult to copy and forge, suitable for higher-level anti-counterfeiting needs, and has a wide range of applications.

[0104] In certain specific embodiments of the present invention, the color and afterglow co-responsive material in the identification layer has a molecule having a structure as shown in formula (3) to formula (6):

[0105] (3) (4)

[0106] (5) (6)

[0107] In formula (3), Bu represents a butyl group, including n-butyl (n-Bu), isobutyl (i-Bu), and tert-butyl (t-Bu).

[0108] More specifically, the color and afterglow co-responsive material includes a molecule having a structure as shown in formula (7) to formula (9):

[0109] (7) (8)

[0110] (9)

[0111] The above molecular structure can make the identification layer have more obvious afterglow luminescence and color change phenomenon, fast response speed and high yield.

[0112] Furthermore, there are differences in the color changes of the molecules in the structures shown in Formula (3) to (6). If the color and afterglow co-responsive material contains two or more of these molecules, the effect of the material can be further complicated, making counterfeiting more difficult.

[0113] In addition, in particular, multiple identification layers can be provided, and the ink used in each identification layer includes molecules with different structures in the above formulas (3) to (6), so that each identification layer can produce different color changes. By increasing the complexity of the color change effect through multiple identification layers, the security performance of the anti-counterfeiting label can be further improved.

[0114] In certain specific embodiments of the present invention, specifically, the photosensitizer is tetraphenylporphyrin, the anti-counterfeiting label further comprises a shielding layer, the shielding layer is a polyester film, when the anti-counterfeiting identification is not performed, the shielding layer covers the identification layer to provide certain protection, when the anti-counterfeiting identification is performed, the shielding layer can be peeled off so that the identification layer can be exposed to receive light. More specifically, for example, after the shielding layer is irradiated with ultraviolet light, the shielding layer can change from light red to yellow, and can also emit afterglow light.

[0115] The fifth aspect of the present invention discloses a method for manufacturing an anti-counterfeiting label, comprising the following steps: mixing a color and afterglow co-responsive material and a photosensitizer to obtain an initial mixture; mixing the initial mixture with polystyrene and dissolving it in ethanol to obtain a mixed solution; adjusting the viscosity of the mixed solution to 1~20cP, stirring evenly to obtain ink; inkjet printing the ink on a substrate, heating and drying to obtain an identification layer; covering the identification layer with a shielding layer to obtain an anti-counterfeiting label.

[0116] The identification layer can be easily prepared by this method.

[0117] Specifically, the photosensitizer is tetraphenylporphyrin, and the shielding layer is a polyester film.

[0118] The following will describe in conjunction with more specific implementation methods.

[0119] Embodiments 1 to 5: Embodiments 1 to 5 are compounds with different molecular structures, wherein the molecular structure of Embodiment 1 is represented by 1b, the molecular structure of Embodiment 2 is represented by 2b, the molecular structure of Embodiment 3 is represented by 3b, the molecular structure of Embodiment 4 is represented by 4b, and the molecular structure of Embodiment 5 is represented by 5b. The structures described in Embodiments 1 to 5 can all be used as color and afterglow co-responsive materials, which give the materials unique afterglow characteristics and dynamic color change capabilities.

[0120] (I) Preparation method

[0121] (1) Preparation of Example 1:

[0122] .

[0123] A mixture of the compound having the molecular structure 1a shown above (1 mmol) and the compound having the molecular structure c (1.5 mmol) in 5 mL of toluene was refluxed for 5 h, the reaction mixture was cooled, washed with water, 10% HCl, washed with water again, and dried over MgSO4, the solvent was concentrated in vacuo, and the residue was recrystallized from ethanol to obtain Example 1, which had the molecular structure 1b and a yield of 78% for Example 1.

[0124] See also Figure 1 and Figure 2 , the results of the carbon NMR spectrum and hydrogen NMR spectrum of Example 1 are: 13 C NMR (101 MHz, CDCl3) δ 169.76, 150.95, 138.75, 131.83, 130.01, 128.87, 127.56, 123.15,118.06, 115.87, 112.37, 77.48, 77.16, 76.84, 40.28.; 1 H NMR (400 MHz, CDCl3) δ7.50 - 7.38 (m, 2H), 7.37 - 7.29 (m, 2H), 7.22 - 7.11 (m, 2H), 6.75 - 6.58(m, 2H), 3.03 (s, 6H).

[0125] (2) Preparation of Example 2:

[0126] .

[0127] A mixture of the compound having the molecular structure 2a shown above (1 mmol) and the compound having the molecular structure c (1.5 mmol) in 5 mL of xylene was refluxed for 10 h, the reaction mixture was cooled, washed with water, 10% HCl, washed with water again, and dried over MgSO4, the solvent was concentrated in vacuo, and the residue was recrystallized from ethanol to obtain Example 2, which had the molecular structure 2b and a yield of 84% for Example 2.

[0128] refer to Figure 3 and Figure 4 The results of the carbon NMR spectrum and hydrogen NMR spectrum of Example 2 are: 13 C NMR (75 MHz, CDCl3) δ 169.77, 148.70, 138.30, 131.70, 129.96, 128.78, 127.57, 122.92,118.20, 114.45, 111.50, 77.47, 77.04, 76.62, 50.70, 29.29, 20.32, 14.01.; 1 HNMR (300 MHz, CDCl3) δ 7.48 - 7.40 (m, 2H), 7.40 - 7.32 (m, 2H), 7.20 - 7.04(m, 2H), 6.68 - 6.50 (m, 2H), 3.39 - 3.17 (m, 4H), 1.71 - 1.49 (m, 5H), 1.38(q, J = 7.4 Hz, 4H), 0.99 (t, J = 7.3 Hz, 6H).

[0129] (3) Preparation of Example 3:

[0130] .

[0131] The compound having the molecular structure 3a shown above (1 mmol) and the compound having the molecular structure c (2 mmol) were refluxed in ethylbenzene solvent for 7 h. The reaction mixture was cooled, washed with water and 10% HCl, washed with water again, and dried over MgSO4. The solvent was concentrated in vacuo, and the residue was recrystallized from ethanol to obtain Example 3. The molecular structure of Example 3 was 3b, and the yield of Example 3 was 80%.

[0132] The H NMR spectrum of Example 3 is shown in Figure 5 , see NMR carbon spectrum Figure 6 , 1 H NMR (500 MHz, CDCl3) δ 7.49- 7.41 (m, 2H), 7.28 (dd, J = 5.2, 1.9 Hz, 3H), 7.21 - 7.17 (m, 2H), 6.72 -6.61 (m, 2H), 2.99 (s, 6H).; 13 C NMR (126 MHz, CDCl3) δ 170.00, 150.60, 139.73,129.95, 128.94, 128.52, 128.47, 127.35, 117.02, 112.30, 40.26.

[0133] (4) Preparation of Example 4:

[0134] .

[0135] The compound having the molecular structure 4a shown above (1 mmol) and the compound having the molecular structure c (3 mmol) were refluxed in a toluene solvent for 5 h. The reaction mixture was cooled, washed with water and 10% HCl, washed with water again, and dried over MgSO4. The solvent was concentrated in vacuo, and the residue was recrystallized from ethanol to obtain Example 4. The molecular structure of Example 4 was 4b, and the yield of Example 4 was 82%.

[0136] The H NMR spectrum of Example 4 is shown in Figure 7 , see NMR carbon spectrum Figure 8 , 1 H NMR (500 MHz, CDCl3) δ7.44 - 7.39 (m, 1H), 7.36 - 7.31 (m, 1H), 7.12 (d, J = 8.4 Hz, 1H), 6.57 (d, J =8.3 Hz, 1H), 3.28 (dd, J = 8.6, 6.9 Hz, 2H), 1.57 (ddd, J = 9.5, 5.4, 2.4 Hz,2H), 1.41 - 1.31 (m, 2H), 0.96 (t, J = 7.4 Hz, 3H). 13C NMR (126 MHz, CDCl3) δ169.69, 148.70, 138.32, 131.69, 129.96, 128.78, 127.56, 122.93, 118.17,114.49, 111.52, 50.71, 29.28, 20.32, 13.99.

[0137] (5) Preparation of Example 5:

[0138] .

[0139] The compound having the molecular structure 5a shown above (1 mmol) and the compound having the molecular structure c (1.5 mmol) were refluxed in a benzene solvent for 10 h. The reaction mixture was cooled, washed with water and 10% HCl, washed with water again, and dried over MgSO4. The solvent was concentrated in vacuo, and the residue was recrystallized from ethanol to obtain Example 5. The molecular structure of Example 5 is 5b, and the yield of Example 5 is 81%.

[0140] The H NMR spectrum of Example 5 is shown in Fig. 9 , see NMR carbon spectrum Fig.10 , 1 H NMR (500 MHz, CDCl3) δ7.76 (d, J = 8.5 Hz, 1H), 7.60 (d, J = 8.6 Hz, 1H), 7.56 - 7.46 (m, 7H), 7.44 -7.34 (m, 7H).; 13 C NMR (126 MHz, CDCl3) δ 191.50, 182.33, 139.46, 131.56,131.47, 130.25, 126.97, 124.16, 122.12.

[0141] Comparative Examples 1-5: Comparative Examples 1-5 are simple photochromic materials, and Comparative Examples 1-5 have the structures shown below respectively.

[0142] Comparative Example 1: ;

[0143] Comparative Example 2: ;

[0144] Comparative Example 3: ;

[0145] Comparative Example 4: ;

[0146] Comparative Example 5: .

[0147] The specific preparation methods of Comparative Examples 1 to 5 are as follows.

[0148] (1) The synthesis process of the molecular structure in Comparative Example 1 is as follows:

[0149] In a round-bottom flask with a magnetic stirrer, indigo (1.0 eq.), CuCl (0.4 eq.), K3PO4 (4.0 eq.), Ar2I(OTf) (2.4 eq.), and CH2Cl2 (30 mL / mmol indigo) were added. The mixture was stirred at room temperature or at 40 °C under argon. o C oil bath and heated overnight. After the gained mixture was cooled to room temperature, concentrated, redissolved in ethyl acetate and washed with salt water, then extracted with ethyl acetate aqueous layer. The organic layer merged Na2SO4 was dried, and the filtrate was concentrated. The crude product was first purified by column chromatography (EtOAc / CHCl3), then purified by circulation GPC to obtain a blue solid.

[0150] (2) The synthesis process of the molecular structure in Comparative Example 2 is as follows:

[0151] Under magnetic stirring, sodium hydroxide solution (3.74 g, 93.6 mmol, 1.5 M, 8.2 eq.) and 1H-indole-3-acetate (2.00 g, 11.4 mmol, 1.0 eq.) were added to a round-bottom flask and heated to 100°C. o C for 15 minutes. Then 4-(dimethylamino)benzaldehyde (1.70 g, 11.42 mmol, 1.0 eq.) was suspended in methanol (11.4 mL, 1 M) at 0. o C and stirred at 23 ° C for 3 days. The mixture was neutralized with hydrochloric acid (1.0 M) and extracted with ethyl acetate. The organic phase was dried over sodium sulfate and the solvent was removed by rotary evaporation. The product was then obtained by column chromatography (hexane / ethyl acetate 1:1) and recrystallization from ethanol / water. The product was dark purple crystals.

[0152] (3) The synthesis process of the molecular structure in Comparative Example 3 is as follows:

[0153] Under magnetic stirring, sodium hydroxide aqueous solution (0.41 g, 10.3 mmol, 1.5 M, 8.2 eq.) and 1H-indole-3-acetate (0.22 g, 1.26 mmol, 1.0 eq.) were added to a round-bottom flask, and the mixture was heated to 100 o C for 15 min. Then, at 0 o9-formyl julolidine (0.25 g, 1.25 mmol, 1.25 eq.) was added at 23 ° C and stirred for 3 days. The mixture was neutralized with hydrochloric acid (1.0 M) and extracted with ethyl acetate. The organic phase was dried over sodium sulfate and the solvent was removed by rotary evaporation. The product was then obtained by column chromatography (n-hexane / ethyl acetate 1:1) and recrystallization from ethanol / water.

[0154] (4) The synthesis process of the molecular structure in Comparative Example 4 is as follows:

[0155] A solution of 4-methoxybenzaldehyde and piperidine (0.05 mL) in benzene (20 mL) was added to benzothiophene and the reaction mixture was heated under reflux. Saturated NH4Cl (150 mL) was added to quench the reaction and the reaction mixture was extracted with ethyl acetate. The organic phase was dried over sodium sulfate, filtered, and the solvent was removed by rotary evaporation. It was then further purified by column chromatography and recrystallization from n-heptane.

[0156] (5) The synthesis process of the molecular structure in Comparative Example 5 is as follows:

[0157] To 2-phenylthioacetic acid (1.0 eq.) and thionyl chloride (9.0 eq.) was added a few drops of DMF. The reaction mixture was stirred at 23 o C for 12 hours. o The residual thionyl chloride was removed in vacuo at 40 °C. 1,2-dichloroethane (DCE) was added to the remaining 2-phenylsulfonyl chloride and the solution was cooled to 0 o C. At 0 o At 0 ° C, AlCl3 (1.5 equivalents) was added portionwise over 2 minutes. The reaction mixture was stirred at 0 o C for 30 minutes and then at 23 o C for 2 hours. Ice / water (150 mL) was added to the mixture to quench it, and the aqueous phase was extracted with CH2Cl2. The organic phase was separated, dried over Na2SO4, and the solvent was removed in vacuo. The crude 1-benzothiophen-3(2H)-one was used in the next synthetic step without further purification. 1-Benzothiophene-3(2H)-one was dissolved in benzene. 9-Formyljulolidine (180 mg, 0.9 mmol) and a drop of piperidine. The reaction mixture was stirred at 100°C for 2 hours, cooled to 23°C, and saturated ammonium chloride solution (150 mL) was added. The aqueous phase was extracted with ethyl acetate. The organic phase was separated and dried over Na2SO4. The solvent was removed in vacuo. The crude product was purified by column chromatography (n-hexane / ethyl acetate 8:2) and then washed with heptane to obtain a purple product.

[0158] (B) Performance testing.

[0159] (1) Afterglow spectrum test:

[0160] The afterglow spectrum test was performed using Example 1 as a buffer, and tetraphenylporphyrin was selected as a photosensitizer. A 1 mM solution of Example 1 and a 0.1 mM tetraphenylporphyrin solution were prepared in toluene, and the prepared solution of Example 1 and the tetraphenylporphyrin solution were mixed evenly, and the sample cell containing the mixed solution was placed in a spectrometer. The spectrometer was turned on, the excitation light wavelength was set to 532 nm, the afterglow spectrum was measured, and the spectral data was recorded. The results are shown in Fig.11 , indicating that Example 1 has afterglow properties.

[0161] (2) Fluorescence spectrum test:

[0162] Example 1 was dissolved in toluene to prepare a 1 mM solution, and stirred thoroughly until completely dissolved. An appropriate amount of the solution was injected into a quartz cuvette. Before irradiation, the fluorescence spectrum of the solution was recorded using a fluorescence spectrometer. The cuvette containing the solution was placed under a 532 nm laser and irradiated for 30 min. After irradiation, the fluorescence spectrum of the solution was recorded again using a fluorescence spectrometer. Fig.12 ,from Fig.12 It can be seen that the fluorescence spectrum of Example 1 has almost no significant change before and after illumination, and at an excitation wavelength of 532 nm, Example 1 has a relatively obvious fluorescence peak at 470 nm, which indicates that the illumination conditions may have little effect on the fluorescence spectrum.

[0163] (3) Ultraviolet absorption spectrum test:

[0164] Use a pipette to accurately weigh Examples 1 to 3 and Example 5, respectively, and dissolve them in toluene to prepare solutions with a concentration of 1 mM. Transfer each solution to a quartz cuvette to ensure that the solution is uniform and free of bubbles. Place the cuvette containing each solution in a UV-visible spectrometer, set the wavelength range of the spectrometer to 200nm to 800nm, record the absorption in the range of 400nm to 700nm, and save the spectral data. The cuvette is then irradiated with 532nm excitation light. After the light treatment, the cuvette is immediately placed in the UV absorption-visible spectrometer, and the above-mentioned spectral measurement process is repeated to record the changes in UV absorption in the wavelength range of 400~700nm. Reference Figure 13~Figure 16 ,in, Fig.13 The UV absorption spectrum of Example 1 before and after illumination changes. Fig.14 The UV absorption spectrum of Example 3 before and after illumination is shown in FIG. Fig.15 The UV absorption spectrum of Example 2 before and after illumination changes. Fig.16The figure shows the change of the ultraviolet absorption spectrum of Example 5 before and after illumination. It can be seen that before illumination, Examples 1 to 3 and Example 5 have very little absorption in the wavelength range of 450 to 500 nm, but after illumination for 10 seconds, Examples 1 to 3 have obvious absorption in the wavelength range of 450 to 500 nm, and the absorption of Example 5 is relatively small.

[0165] (4) Color change:

[0166] While testing the afterglow spectrum, the color of the solution of Example 1 before and after illumination was photographed, and it was found that the solution showed a light pink color before illumination ( Fig.17 ), the solution turns yellow after exposure to light ( Fig.18 ), in order to study the solution colors of tetraphenylporphyrin and Example 1 in toluene, tetraphenylporphyrin and Example 1 were dissolved in toluene and the solution colors were photographed. It was found that the toluene solution of tetraphenylporphyrin alone showed a light pink color ( Fig.19 ), the toluene solution of Example 1 alone is transparent ( Fig. 20 ), so it can be inferred that Fig.17 The light pink in the image is mainly the color of tetraphenylporphyrin. Fig.18 It is a mixed color of tetraphenylporphyrin and its molecular structure after exposure to light.

[0167] (5) Color change time record:

[0168] While testing the ultraviolet absorption spectrum, the color change time of the solution after illumination in Example 1 was recorded. Fig.21 As shown, it is found that Example 1 has ultraviolet absorption (most obvious in the wavelength range of 450-500nm) after 2s of illumination, and the absorption is basically complete after 40s of illumination, and Example 1 has a short response time. Fig.14 and Fig.15 , both Example 3 and Example 2 have very obvious ultraviolet absorption within 10 seconds, and the response speed is also fast.

[0169] The color change time of comparative examples 1 to 5 was also detected and recorded. The specific detection method was: after irradiating the solution with a laser of a specific wavelength for a fixed time, a UV-visible absorption test was performed to test the absorption change-illumination time curve, and after fitting, τ 1 / 2 , the results are shown in Table 1, where τ 1 / 2 Indicates the time required for 1 / 2 absorption.

[0170] Table 1:

[0171] <![CDATA[Color change time τ 1 / 2 > Comparative Example 1 408min Comparative Example 2 70d Comparative Example 3 11d Comparative Example 4 30d Comparative Example 5 18min

[0172] As shown in Table 1, the color change time τ of Comparative Examples 1 to 5 1 / 2The shortest time is 18 minutes.

[0173] (6) Characterization of light products:

[0174] In order to further study the product after illumination, the product after illumination in Example 1 was characterized by nuclear magnetic resonance. Fig. 22 , carbon spectrum see Fig.23 The test results are: 1 H NMR (500 MHz, CDCl3) δ 7.91 - 7.77(m, 2H), 7.68 - 7.58 (m, 1H), 6.76 - 6.61 (m, 1H), 3.10 (s, 3H).; 13 C NMR (126MHz, CDCl3) δ 194.39, 191.69, 154.57, 132.48, 132.34, 132.19, 131.29, 129.79,120.61, 111.04, 40.09.

[0175] Therefore, according to the results of NMR, the products after illumination are as follows:

[0176] .

[0177] (7) Mass spectrometry test:

[0178] MALDI-TOF test: Use Bruker autoflex speed TOF / TOF for testing. Use dichloromethane to dissolve the sample and prepare a 10mM solution. Use a pipette to draw 1μL of sample and drop it on the sample target. Place the sample target in the maldi-tof instrument, use laser for excitation, perform signal acquisition, and process and analyze the mass spectrometry data, such as Fig.24 As shown, by comparing with the standard spectrum in the database, the molecular weight is basically consistent.

[0179] Application Example 1: Application Example 1 is an anti-counterfeiting label, and its manufacturing method is as follows.

[0180] Take Example 1, mix it with tetraphenylporphyrin photosensitizer in a mass ratio of 1:1, add the mixture to a polystyrene matrix, mix it evenly in a mass ratio of 1:10, add an appropriate amount of ethanol as a solvent, adjust the mixture to a viscosity suitable for inkjet printing, specifically 16 cP, and stir evenly until a uniform ink is formed. Use an inkjet printer to evenly apply the prepared ink on the surface of the substrate to form an identification layer, heat and dry it to ensure that the ink is completely cured. Cover the surface of the identification layer with a polyester film to form a peelable shielding layer, and print "Uncover to view the anti-counterfeiting effect" on the shielding layer.

[0181] When performing anti-counterfeiting identification, the shielding layer is uncovered to expose the identification layer, and ultraviolet light is used to irradiate the identification layer for 40 seconds, and the color change and afterglow response of the illuminated area and the non-illuminated area are observed. The results show that under ultraviolet light irradiation, while the identification layer of Application Example 1 shows afterglow, it changes from light red to yellow, while the ordinary anti-counterfeiting label only shows afterglow. Therefore, it is possible to accurately distinguish between genuine and fake products, thereby effectively improving the security and reliability of the anti-counterfeiting system.

[0182] Application Example 2: Application Example 2 is an anti-counterfeiting label, and its manufacturing method is as follows.

[0183] Take Example 2, mix it with tetraphenylporphyrin photosensitizer in a mass ratio of 1: 1, add the mixture to a polystyrene matrix, mix it evenly in a mass ratio of 1: 10, add an appropriate amount of ethanol as a solvent, adjust the mixture to a viscosity suitable for inkjet printing, specifically 13 cP, and stir evenly until a uniform ink is formed. Use an inkjet printer to evenly apply the prepared ink on the surface of the substrate to form an identification layer, heat and dry it to ensure that the ink is completely cured. Cover the surface of the identification layer with a polyester film to form a strippable shielding layer, and print "uncover to view the anti-counterfeiting effect" on the shielding layer.

[0184] When performing anti-counterfeiting identification, the shielding layer is uncovered to expose the identification layer, and ultraviolet light is used to irradiate the identification layer for 40 seconds, and the color change and afterglow response of the illuminated area and the non-illuminated area are observed. The results show that under ultraviolet light irradiation, while the identification layer of Application Example 2 shows afterglow, it changes from light red to yellow, while the ordinary anti-counterfeiting label only shows afterglow. Therefore, it is possible to accurately distinguish between genuine and fake products, thereby effectively improving the security and reliability of the anti-counterfeiting system.

[0185] Application Example 3: Application Example 3 is an optical label used in the field of cryptography. On the basis of traditional password verification, Example 2 is introduced to produce an optical label to enhance the security of identity authentication. The method for producing the optical label is as follows.

[0186] Example 2 is dissolved in an appropriate amount of solvent and prepared into an ink suitable for inkjet printing or screen printing. Use an inkjet printer to evenly apply the prepared ink on the surface of the substrate to form an optical label. Heat (40°C) and dry to ensure that the ink is completely cured to form a stable optical label. The optical label is equipped with a verification device, which includes a color sensor, an afterglow detection sensor, a control unit, and an ultraviolet light source. When performing identity authentication, after the user enters the traditional password, the verification device will prompt the user to use the optical label for verification. The user places the optical label on the verification device, and the device emits ultraviolet light of a specific wavelength to illuminate the label. The device detects the color change and afterglow response of the label, and compares the result with the predetermined value. If the comparison is successful, the identity authentication is completed; otherwise, access is denied. Due to the simultaneous presence of afterglow and color change performance, the optical label is difficult to copy, and the security is improved compared to optical labels that can only emit afterglow or can only change color. In this way, this embodiment combines traditional passwords and optical verification to greatly improve the security and anti-attack capabilities of identity authentication.

[0187] Application Comparative Example 1: Ordinary anti-counterfeiting labels only have afterglow.

[0188] Take rhodamine in the prior art as a common anti-counterfeiting label material, mix it with tetraphenylporphyrin photosensitizer at a mass ratio of 1:1, add the mixture to a polystyrene matrix, mix it evenly at a mass ratio of 1:10, add an appropriate amount of ethanol as a solvent, adjust the mixture to a viscosity suitable for inkjet printing, and stir it evenly until a uniform ink is formed. Use an inkjet printer to evenly apply the prepared ink on the surface of the substrate to form an identification layer, heat and dry it to ensure that the ink is completely cured. Cover the surface of the identification layer with a polyester film to form a peelable shielding layer, and print "Uncover to view the anti-counterfeiting effect" on the shielding layer.

[0189] When conducting anti-counterfeiting identification, the shielding layer is uncovered to expose the identification layer, and ultraviolet light is used to irradiate the identification layer for 0.3 hours to observe the color change and afterglow response of the illuminated area and the unilluminated area. The results show that under ultraviolet light irradiation, ordinary anti-counterfeiting labels only show afterglow without color change. Therefore, it is impossible to distinguish genuine products by color changes, which reduces the security and reliability of the anti-counterfeiting system.

[0190] In addition, in addition to the applications shown above, the color and afterglow co-responsive materials of the embodiments of the present invention can also be used for homogeneous detection. The color and afterglow co-responsive materials are coated in donor microspheres and acceptor microspheres, and then labeled on target molecules such as antibodies. The color and afterglow co-responsive materials in the sample are excited, and the afterglow luminescence signal is recorded after the excitation light source is removed. Due to the persistent luminescence characteristics of the material, detection can be performed after the background signal is weakened, thereby improving the signal-to-noise ratio.

[0191] Although the present invention has been illustrated and described with reference to certain preferred embodiments of the present invention, it should be understood by those skilled in the art that the above is a further detailed description of the present invention in conjunction with specific embodiments, and it cannot be determined that the specific implementation of the present invention is limited to these descriptions. Those skilled in the art may make various changes in form and details, including making several simple deductions or substitutions, without departing from the spirit and scope of the present invention.

Claims

1. A color and afterglow co-responsive material, characterized in that: The color and afterglow co-responsive material has a structure as shown in formula (5) to formula (7): （5） （6） （7）。 2. A method for preparing a color and afterglow co-responsive material as claimed in claim 1, characterized in that: The steps include: Mixing a compound having a molecular structure as shown in formula (a-5) and a compound having a molecular structure as shown in formula (c) in a solvent, and refluxing to obtain a compound having a molecular structure as shown in formula (5); Alternatively, a compound having a molecular structure as shown in formula (a-6) and a compound having a molecular structure as shown in formula (c) are mixed in a solvent and refluxed to obtain a compound having a molecular structure as shown in formula (6); Alternatively, a compound having a molecular structure as shown in formula (a-7) and a compound having a molecular structure as shown in formula (c) are mixed in a solvent and refluxed to obtain a compound having a molecular structure as shown in formula (7); (a-5) (a-6) (a-7) (c) Wherein, the solvent is one or more of benzene, toluene, xylene, ethylbenzene, isopropylbenzene, styrene, chlorobenzene, nitrobenzene, dichlorobenzene and trichlorobenzene, and the reflux time is 5 to 10 hours.

3. The use of the color and afterglow co-responsive material as claimed in claim 1, characterized in that: The color and afterglow co-responsive material is used in the fields of anti-counterfeiting, cryptography and optical storage.

4. Use of the color and afterglow co-responsive material as claimed in claim 1 in the preparation of a homogeneous detection reagent.

5. An anti-counterfeiting label, characterized in that: The anti-counterfeiting label has an identification layer coated with ink, wherein the ink comprises the color and afterglow co-responsive material as claimed in claim 1 and a photosensitizer.

6. An anti-counterfeiting label as claimed in claim 5, characterized in that: The photosensitizer is tetraphenylporphyrin, and the anti-counterfeiting label further comprises a shielding layer, which is a polyester film. When anti-counterfeiting identification is not performed, the shielding layer covers the identification layer; when anti-counterfeiting identification is performed, the shielding layer is peeled off to expose the identification layer.

7. A method for preparing an anti-counterfeiting label according to claim 5, characterized in that: The steps include: mixing the color and afterglow co-responsive material and the photosensitizer to obtain an initial mixture; The initial mixture is mixed with polystyrene and dissolved in ethanol to obtain a mixed solution; The viscosity of the mixed solution is adjusted to 1-20 cP, and stirred evenly to obtain ink; The ink is inkjet printed on the substrate, and heated and dried to obtain an identification layer; The masking layer is covered on the identification layer to obtain an anti-counterfeiting label.

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