CN118702670B

CN118702670B - Color and afterglow co-responsive materials and preparation and application, labels and preparation

Info

Publication number: CN118702670B
Application number: CN202411195130.5A
Authority: CN
Inventors: 李富友; 徐�明; 李春伶
Original assignee: Shanghai Jiao Tong University
Current assignee: Shanghai Jiao Tong University
Priority date: 2024-08-29
Filing date: 2024-08-29
Publication date: 2024-12-20
Anticipated expiration: 2044-08-29
Also published as: CN118702670A

Abstract

The invention discloses a color and afterglow co-response material, which emits residual glow and changes the color of the material after being irradiated by light, wherein the color and afterglow co-response material has a molecule with a structure shown as a formula (5) to a formula (7):(5) (6) (7) The invention also discloses a preparation method and application of the color and afterglow co-response material, a label and a preparation method thereof. The color and afterglow co-response material has improved safety when used in the fields of anti-counterfeiting and cryptography, and has improved storage capacity and complexity when used for optical storage, so that the color and afterglow co-response material has wider application range.

Description

Color and afterglow co-response material, preparation and application thereof, label and preparation

Technical Field

The invention relates to the field of luminescent materials, in particular to a color and afterglow co-response material, a preparation method and an application thereof, a label and a preparation method thereof.

Background

In the age of rapid development of technology, research and application of luminescent materials have become important forces for promoting progress of a plurality of industries. Especially in the fields of optics, electronics, biomedicine and the like, the luminescent material is not only a basic stone for technical innovation, but also a key for realizing a functional device. The afterglow luminescent material, which is a novel material capable of continuously emitting light after the disappearance of an excitation light source, has unique photophysical characteristics, so that the afterglow luminescent material has great application potential in the fields of power-free illumination, anti-fake authentication, information storage, biological imaging and the like.

Compared with the common photoluminescent material, the molecular structure of the afterglow luminescent material is difficult to forge to a certain extent, so the afterglow luminescent material has higher safety in the fields of anti-counterfeiting and safety authentication, but under the condition of continuous development and progress of technology, even if the afterglow luminescent material is used, the molecular structure of the afterglow luminescent material has the possibility of being copied, and the afterglow luminescent material has the risk of being forged. Therefore, how to design the afterglow luminescent material, including how to design the molecular structure thereof, so as to further improve the complexity and difficulty of counterfeiting, further improve the safety performance, ensure the reliability of the afterglow luminescent material in the fields of anti-counterfeiting and safety authentication, further expand the application range of the afterglow luminescent material, and also be considered and to be solved.

In addition, when the afterglow luminescent material is used in the field of optical storage, if the afterglow luminescent material can further realize storage with larger capacity by designing a molecular structure, the afterglow luminescent material can be widely applied.

Disclosure of Invention

In order to solve the technical problems, the embodiment of the invention discloses a color and afterglow co-response material, which changes the color of the color and afterglow co-response material when the color and afterglow co-response material emits residual glow after being illuminated, and the color and afterglow co-response material has a molecule with a structure as shown in a formula (5) to a formula (7):

(5) (6)

(7)。

By adopting the technical scheme, the self-color and long-afterglow co-response material can be obtained, specifically, the material can show afterglow phenomenon under the illumination condition, namely, after illumination is stopped, the material can still continuously emit light for a period of time, meanwhile, the self-color of the material also changes, and the color change and the afterglow phenomenon are mutually independent. Therefore, when the material is used in the field of anti-counterfeiting or cryptography, the possibility of being copied and counterfeited is small through the dual guarantee of afterglow and self color change, and the safety is greatly improved. And, when it is used in the field of optical storage, the range for encoding and storing information is wider, and the storage capacity is improved.

Optionally, the color and afterglow coresponsive material is irradiated with light having a wavelength ranging from 200 to 1200nm, the color and afterglow coresponsive material emitting a afterglow and the ultraviolet absorption of the molecule ranging from 400nm to 500nm being varied.

According to another embodiment of the present invention, a method for preparing a color and afterglow co-responsive material is disclosed, comprising the steps of 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), preparing the compound having a molecular structure as shown in formula (5) into 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), preparing the compound having a molecular structure as shown in formula (6) into 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), preparing the compound having a molecular structure as shown in formula (7) into the color and afterglow co-responsive material;

(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 5-10 h.

By adopting the technical scheme, the color and afterglow co-response material can be obtained simply and conveniently, and the yield is higher.

According to another embodiment of the invention, the use of color and afterglow co-responsive materials for anti-counterfeiting, cryptography, homogeneous detection and optical storage is disclosed.

By adopting the technical scheme, the security of anti-counterfeiting and cryptographic security authentication can be improved, and the storage capacity of optical storage can be enlarged.

According to another embodiment of the present invention, an anti-counterfeit label is disclosed having an authentication layer coated with an ink comprising the color and afterglow coresponsive material described above and a photosensitizer, the authentication layer capable of emitting a residual glow upon exposure to ultraviolet light and having a color change itself.

By adopting the technical scheme, the security performance of the anti-counterfeit label is improved, and the reliability is stronger.

Optionally, the photosensitizer is tetraphenylporphyrin, the anti-counterfeit label further comprises a shielding layer, the shielding layer is a polyester film, the shielding layer covers the identification layer when anti-counterfeit identification is not performed, and the shielding layer can be removed to expose the identification layer when anti-counterfeit identification is performed.

According to another specific embodiment of the invention, the embodiment of the invention discloses a preparation method of an anti-counterfeiting label, which comprises the following steps of mixing a color and afterglow co-response material and a photosensitizer to obtain an initial mixture, mixing the initial mixture with polystyrene, dissolving the mixture in ethanol to obtain a mixed solution, regulating the viscosity of the mixed solution to be 1-20 cP, uniformly stirring to obtain ink, performing inkjet printing on a substrate, heating and drying to obtain an identification layer, and covering a shielding layer on the identification layer to obtain the anti-counterfeiting label.

By adopting the technical scheme, the anti-counterfeiting label with better safety performance can be conveniently manufactured.

Drawings

FIG. 1 shows a nuclear magnetic resonance spectrum of example 1 of the present invention;

FIG. 2 shows a nuclear magnetic hydrogen spectrum of example 1 of the present invention;

FIG. 3 shows a nuclear magnetic resonance spectrum of example 2 of the present invention;

FIG. 4 shows a nuclear magnetic hydrogen spectrum of example 2 of the present invention;

FIG. 5 shows a nuclear magnetic hydrogen spectrum of example 3 of the present invention;

FIG. 6 shows a nuclear magnetic resonance spectrum of example 3 of the present invention;

FIG. 7 shows a nuclear magnetic hydrogen spectrum of example 4 of the present invention;

FIG. 8 shows a nuclear magnetic resonance spectrum of example 4 of the present invention;

FIG. 9 shows a nuclear magnetic hydrogen spectrum of example 5 of the present invention;

FIG. 10 shows a nuclear magnetic resonance spectrum of example 5 of the present invention;

FIG. 11 shows the afterglow spectrum of example 1 of the present invention at an excitation wavelength of 532 nm;

FIG. 12 is a graph showing fluorescence spectrum at 532nm excitation wavelength in example 1 of the present invention;

FIG. 13 shows an ultraviolet absorption spectrum of the embodiment 1 of the present invention with an excitation wavelength of 532nm in the range of 400-700 nm;

FIG. 14 shows an ultraviolet absorption spectrum of embodiment 3 of the present invention with an excitation wavelength of 532nm in the range of 400-700 nm;

FIG. 15 shows an ultraviolet absorption spectrum of embodiment 2 of the present invention with an excitation wavelength of 532nm in the range of 400-700 nm;

FIG. 16 shows an ultraviolet absorption spectrum of the embodiment 5 of the present invention with an excitation wavelength of 532nm in the range of 400-700 nm;

FIG. 17 is a photograph showing a mixture of tetraphenylporphyrin and example 1 of the present invention before being irradiated with light;

FIG. 18 is a photograph showing a mixture of the tetraphenylporphyrin and example 1 of the present invention after being irradiated with light;

FIG. 19 shows a photograph of a tetraphenylporphyrin solution of the present invention prior to illumination;

FIG. 20 shows a photograph of a solution of example 1 of the present invention before illumination;

FIG. 21 is a graph showing ultraviolet absorption spectra at various times after illumination in example 1 of the present invention;

FIG. 22 shows a nuclear magnetic resonance spectrum of the product of example 1 of the present invention after illumination;

FIG. 23 shows a nuclear magnetic resonance spectrum of the product of example 1 of the present invention after illumination;

FIG. 24 shows the measured mass spectrum of the product of example 1 of the present invention after illumination.

Detailed Description

Further advantages and effects of the present invention will become apparent to those skilled in the art from the disclosure of the present specification, by describing the embodiments of the present invention with specific examples. While the description of the invention will be described in connection with the preferred embodiments, it is not intended to limit the inventive features to the implementation. Rather, the purpose of the invention described in connection with the embodiments is to cover other alternatives or modifications, which may be extended by the claims based on the invention. The following description contains many specific details for the purpose of providing a thorough understanding of the present invention. The invention may be practiced without these specific details. Furthermore, some specific details are omitted from the description in order to avoid obscuring the invention. It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other.

In embodiments of the invention, the term "color and afterglow co-response" means that the material is capable of simultaneously responding to both its own color and afterglow luminescence, i.e., changes in its own color, and emits a residual glow upon external excitation (e.g., illumination).

It should be noted that in this specification, like reference numerals and letters denote like items in the following figures, and thus once an item is defined in one figure, no further definition or explanation thereof is necessary in the following figures.

For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be described in further detail below with reference to the accompanying drawings.

First, it is generally considered that there is a difference between an intrinsic color change of a substance and an emission color change of the substance, and the intrinsic color generally refers to a color that the substance exhibits upon irradiation with white light (including all visible light wavelengths). This is because the substance absorbs light of some wavelengths and reflects or transmits light of other wavelengths, and the human eye perceives light waves that are not absorbed, thus determining the inherent color of the substance. The luminescence color refers to the color of light emitted (emitted) by a substance itself, and this phenomenon is referred to as luminescence, and may be fluorescence, phosphorescence (afterglow), chemiluminescence, etc., and the luminescence process involves absorption of energy (usually light energy) by the substance, causing electrons to transit from a ground state to an excited state, and when the electrons return to a ground state with a low energy level, energy is released in the form of light. The emission color depends on the energy difference between the excited state and the ground state energy level, which corresponds to a specific wavelength of light, i.e., the emission color seen by the naked eye. Thus, the two colors may actually change due to different physicochemical mechanisms, the intrinsic color may change due to a change in chemical composition or a change in structure of a substance, resulting in a change in absorption/reflection/transmission characteristics of light of different wavelengths, and the emission color may change due to a change in electron energy level structure, which may be caused by a change in molecular structure, doping with other elements or compounds, or changing the microscopic environment of the substance (e.g., a change in pH value).

Afterglow materials are materials that are capable of storing energy after being irradiated by an excitation light source (e.g., ultraviolet or visible light) and emitting light for a period of time after the excitation light source has disappeared, i.e., afterglow materials have the luminescent color change response mechanism described above. Compared with the common photoluminescent material, the afterglow material does not need continuous energy input, can have longer afterglow luminous life and has wider application. At present, how to further expand the functions of the afterglow materials and further improve the application value of the afterglow materials is also an important problem. Therefore, the inventor discovers a new molecular structure in the experimental process, and the molecules can make the afterglow material respond to the inherent color and afterglow of the substance simultaneously, namely, respond to the two color change mechanisms simultaneously, so that the material can have the application of luminescence and color change simultaneously, the possibility of creating a novel multifunctional material is provided, and the application field of the material can be expanded due to the unique property of the material.

In a first aspect the present invention discloses a colour and afterglow co-responsive material which, upon illumination, not only is excited to glow like conventional afterglow materials, but more particularly the intrinsic colour of the material itself is also changed in that the colour and afterglow co-responsive material has a molecular structure as shown in formula (1):

(1)

Wherein R ₁ is halogen or hydrogen, and R ₂ is one of hydrogen, halogen and amino substituent.

Specifically, the color and afterglow co-response material has a molecule with a structure as shown in formula (5) to formula (7):

(5) (6)

(7)。

The molecular structure contains afterglow luminescent groups The afterglow luminescent group is a heterocyclic group containing oxygen and sulfur, i.e., the structure of such a group comprises a five-membered ring in which two carbon atoms are replaced by oxygen and sulfur atoms, respectively, and one carbonyl group (c=o) is attached to the other carbon atom in the ring. Two benzene rings are connected with the afterglow luminescent group to form a conjugated structure. The mechanism of afterglow generation of afterglow luminophores under illumination is schematically shown as follows:

。

That is, upon exposure to light, the original molecule releases the small molecule and produces an unstable intermediate, which is then oxidized by singlet oxygen produced by the photosensitizer to produce a diketone structure. Thus, the inventors believe that the original molecule may first absorb light energy under light to an excited state, and upon release of the small molecule, unstable intermediates formed contain unsaturated bonds or other structures capable of capturing energy, which may store some of the excitation energy in some form, and then glow. Meanwhile, the color of the material changes after illumination because the change of the molecular structure influences the electron distribution of the molecules, thereby influencing the absorption spectrum of the molecules. In addition, diketone structures generally provide a broader pi electron cloud through conjugated double bond systems, which can cause molecules to absorb light from different parts of the ultraviolet to visible regions of the spectrum, thereby changing the color of the substance. And, before the reaction and Two benzene rings are connected, the two benzene rings are not changed before and after illumination, a longer conjugated system can be formed in the molecule, organic molecules with longer conjugated systems have stronger absorption to visible light, so that the color change of the material is also obvious.

The inventors found that the above molecule has a triangle structure, and the heterocyclic group as the "vertex" of the triangle changes upon irradiation to form an intermediate product and a diketone structure, resulting in afterglow phenomenon and change of self color, which can be said to be a "functional region" of the whole 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 influenced or changed, so that the molecule has a stable main framework structure and has the modifiable property. In particular, R ₁ and R ₂ may be relatively stable groups or elements, such as hydrogen and halogen, which generally have less effect on the stability of the molecular host and are relatively stable under light, hydrogen generally does not significantly alter the electron density distribution of the molecular host. In addition, R ₂ may also be an amino substituent, which refers to a group in which at least one of two H groups attached to N in an amino group is substituted with another group, for example, substituted with an alkyl group, an aryl group, a nitrogen-containing heterocycle, a halogen, a hydroxyl group, or the like. The inventors found that if R ₂ is designed as an amino substituent, the electron cloud of the molecular structure can be further changed, so that the luminescence or self-color change of the material can be further optimized.

In one embodiment of the invention, the color and afterglow coresponsive material has a molecule having a structure according to formula (2):

(2)

Wherein R ₁ is halogen, R ₃ and R ₄ are each independently selected from alkyl.

In the structure of formula (2), the benzene ring in the lower right corner is directly linked to N, which in turn is linked to the other two structures (R ₃ and R ₄). On the basis of the above, N has a triple bond structure, so that the bond energy between molecules is very high, and therefore, the N is not easy to participate in chemical reaction, and meanwhile, N has large relative electronegativity and electron withdrawing effect, and further modification and change can be carried out on the conjugated structure.

Based on the dual properties of the luminescence of the color and afterglow co-response material and the self color change, the application value of the material is further improved. In particular, if the color and afterglow co-response material is applied to the fields of anti-counterfeiting and safety authentication, the anti-counterfeiting capability and safety are improved. For ordinary afterglow materials or color-changing materials, since they have only a single mechanism of afterglow luminescence or inherent color change, both the molecular structure of the material and the effect of luminescence or color change are likely to be broken and thus counterfeited. The material of the application has a double mechanism, and a heavy 'insurance' is added on the basis of the prior art, thus greatly increasing the difficulty of copying and counterfeiting. In addition, the dual mechanism of the color and afterglow co-response material can be realized through only one molecular structure, both mechanisms can simultaneously respond to illumination, namely the afterglow spectrum and absorption spectrum of the molecular structure can simultaneously respond, and even if the copy effect is forged through the blending of different materials, the copy of the related spectrum of the molecular structure layer is difficult to realize. Therefore, the color and afterglow co-response material of the embodiment of the application can greatly improve the safety performance and the application value. In addition, in the field of optical storage, the storage capacity can be greatly improved due to the existence of a dual mechanism, the coding complexity can be enhanced, and the method has high practical value.

In certain embodiments of the present invention, the alkyl groups have, in particular, 1 to 4 carbon atoms. Alkyl groups generally provide chemical stability, do not readily participate in reactions, and provide more robust support for the molecular structure of the material. The inventor finds that R ₁ is halogen, R ₃ and R ₄ are alkyl groups with 1-4 carbon atoms, the three-dimensional configuration of molecules is less influenced, and the performance is more stable.

In certain embodiments of the invention, in particular, the color and afterglow coresponsive material comprises a molecule having the structure of formula (3) through formula (6):

(3) (4)

(5) (6)

Wherein in the formula (3), bu represents butyl group including n-butyl (n-Bu), isobutyl (i-Bu) and tert-butyl (t-Bu).

More specifically, the color and afterglow coresponsive material includes a molecule having a structure represented by formula (7) to formula (9):

(7) (8)

(9)。

The inventor finds that the molecular structure can lead the color and afterglow co-response material to have obvious afterglow luminescence and color change phenomena, has high response speed and obvious ultraviolet absorption after illumination for 10 seconds. In particular, the structural stability is stronger, and the method is particularly suitable for the application fields of anti-counterfeiting, cryptography and optical storage.

Specifically, the color and afterglow co-response material is irradiated by light with the wavelength range of 200-1200 nm, the color and afterglow co-response material emits afterglow, and the ultraviolet absorption of molecules in the wavelength range of 400-500 nm is changed. That is, after exposure to light, the ultraviolet absorption spectrum of the molecule changes in the 400nm to 500nm wavelength range, for example, before light, the molecule does not exist or has less ultraviolet absorption in the 400nm to 500nm wavelength range, while after light, the molecule has more ultraviolet absorption in the 400nm to 500nm wavelength range, and the color of the material changes.

In a second aspect, the invention discloses a method for preparing a color and afterglow co-responsive material, comprising the following steps.

Mixing a compound having a molecular structure represented by formula (a) with a compound having a molecular structure represented by formula (c) in a solvent, and refluxing to obtain a compound having a molecular structure represented by formula (1):

(a) (c)

(1)。

Namely, the preparation route is specifically shown as follows:

。

subsequently, the compound having the molecular structure shown in formula (1) is prepared as a color and afterglow coresponsive material, and for example, the color and afterglow coresponsive material can be obtained by mixing with a photosensitizer.

In a specific embodiment of the invention, the preparation method comprises the following steps.

Mixing a compound having a molecular structure represented by formula (b) with a compound having a molecular structure represented by formula (c) in a solvent, and refluxing to obtain a compound having a molecular structure represented by formula (2):

(b) (c)

(2)。

Namely, the preparation route is as follows:

。

Subsequently, the compound having the molecular structure shown in formula (2) is prepared as a color and afterglow coresponsive material, and for example, the color and afterglow coresponsive material can be obtained by mixing with a photosensitizer.

Specifically, the solvent used is one or more of benzene, toluene, xylene, ethylbenzene, isopropylbenzene, styrene, chlorobenzene, nitrobenzene, dichlorobenzene and trichlorobenzene, and the solvents are suitable for synthesizing the molecular structure in the invention, and are stable and easy to remove. In addition, the reflux time is 5-10 h.

Mixing a compound having a molecular structure shown in formula (a-5) with a compound having a molecular structure shown in formula (c) in a solvent, refluxing to obtain a compound having a molecular structure shown in formula (5), preparing the compound having a molecular structure shown in formula (5) into the color and afterglow co-responsive material, or mixing a compound having a molecular structure shown in formula (a-6) with a compound having a molecular structure shown in formula (c) in a solvent, refluxing to obtain a compound having a molecular structure shown in formula (6), preparing the compound having a molecular structure shown in formula (6) into the color and afterglow co-responsive material, or mixing a compound having a molecular structure shown in formula (a-7) with a compound having a molecular structure shown in formula (c) in a solvent, refluxing to obtain a compound having a molecular structure shown in formula (7), preparing the compound having a molecular structure shown in formula (7) into the color and afterglow co-responsive material;

(a-5) (a-6)

(a-7)(c)。

the method can synthesize the needed molecular structure conveniently and efficiently, has high molecular yield up to more than 78%, particularly the molecular with the structure of formula (7) to formula (9), has the yield up to more than 82%, and is suitable for large-scale production and manufacture of color and afterglow co-responsive materials.

In a third aspect the invention discloses the use of color and afterglow co-responsive materials useful in the fields of anti-counterfeiting, cryptography, homogeneous detection and optical storage. The color and afterglow co-responsive material of the present invention can be used for both luminescence and color change applications, providing the possibility of creating new multifunctional materials. In particular, in the fields of anti-counterfeiting and cryptography, the material can be used for manufacturing invisible ink marks, security labels and anti-counterfeiting technologies, wherein the inherent color of a substance is difficult to perceive in daily environment, and afterglow and inherent color change can be displayed under specific illumination, so that the safety and confidentiality are improved. In the field of optical storage, the color change and afterglow characteristics of materials can be used in advanced information storage and display technologies, such as unique display screens, or systems that display different information under different lighting conditions. In some other application scenarios, such materials may be used, for example, to develop new types of sensors for detecting and responding to certain types of light or other environmental stimuli, such as indicators for monitoring ultraviolet exposure. In environmental monitoring, such materials are capable of indicating the presence of a particular chemical or radiation, visually displaying the environmental change through a color change and afterglow luminescence.

In a fourth aspect, the invention features an anti-counterfeit label having an authentication layer coated with an ink comprising a color and afterglow coresponsive material and a photosensitizer, the authentication layer capable of emitting a glow after being irradiated with ultraviolet light and having a color that changes itself. Wherein the color and afterglow coresponsive material comprises a molecule having a structure according to formula (1):(1)

In another embodiment of the present invention, further, the color and afterglow coresponsive material has a molecule having a structure according to formula (2):

(2)

Wherein R ₁ is halogen or hydrogen, R ₃ and R ₄ are each independently selected from alkyl.

In the anti-counterfeiting label, the identification layer can emit residual glow after being irradiated by ultraviolet light, the color of the identification layer changes, and the response speed is high. The anti-counterfeiting label with double guarantee has higher copying and counterfeiting difficulties, is suitable for the anti-counterfeiting requirement of higher level, and has wider application range.

In certain embodiments of the present invention, the color and afterglow coresponsive material in the discriminating layer has a molecular structure represented by formula (3) through formula (6):

(3) (4)

(5) (6)

(7) (8)

(9)

the molecular structure can make the identification layer possess obvious afterglow luminescence and color change phenomena, and has fast response speed and high yield.

Further, the color change of the molecules in the structure shown in the formulas (3) to (6) is different, and if the color and afterglow co-response material contains more than two of the molecules, the effect of the material can be more complicated, and the forging difficulty can be higher.

In addition, in particular, a plurality of discrimination layers may be provided, each of which uses an ink including molecules of different structures in the above formulae (3) to (6), so that each discrimination layer may produce a different color change. The complexity of the color change effect is improved through the multi-layer identification layer, and the security performance of the anti-counterfeiting label can be greatly improved.

In some embodiments of the present invention, the photosensitizer is tetraphenylporphyrin, the security tag further comprises a shielding layer, the shielding layer is a polyester film, the shielding layer covers the authentication layer when no security authentication is performed, a certain protection is provided, and the shielding layer can be removed when the security authentication is performed so that the authentication layer can be exposed to receive illumination. More specifically, for example, after the shielding layer is irradiated with ultraviolet light, the shielding layer can be changed from light red to yellow, and can also emit a glow.

The fifth aspect of the invention discloses a manufacturing method of an anti-counterfeiting label, which comprises the steps of mixing a color and afterglow co-response material and a photosensitizer to obtain an initial mixture, mixing the initial mixture with polystyrene, dissolving the mixture in ethanol to obtain a mixed solution, adjusting the viscosity of the mixed solution to be 1-20 cP, uniformly stirring to obtain ink, performing inkjet printing on a substrate, heating and drying to obtain an identification layer, and covering a shielding layer on the identification layer to obtain the anti-counterfeiting label.

The authentication layer can be simply prepared by the method.

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

The following description will be made in connection with more specific embodiments.

Examples 1 to 5 are compounds having different molecular structures, wherein the molecular structure of example 1 is represented by 1b, the molecular structure of example 2 is represented by 2b, the molecular structure of example 3 is represented by 3b, the molecular structure of example 4 is represented by 4b, and the molecular structure of example 5 is represented by 5 b. The structures described in examples 1 to 5 can be used as color and afterglow coresponsive materials, and these structures impart unique afterglow characteristics and dynamic color changing capabilities to the materials.

And (one) preparation mode.

(1) Preparation of example 1:

。

The mixture of the compound (1 mmol) having the molecular structure 1a and the compound (1.5 mmol) having the molecular structure c shown above in 5mL of toluene was refluxed for 5h, the reacted mixture was cooled, washed with water, 10% HCl, again with water, and dried over MgSO ₄, and the solvent was concentrated in vacuo, and the residue was recrystallized from ethanol to give example 1 having the molecular structure 1b in 78% yield of example 1.

Referring to FIGS. 1 and 2, the nuclear magnetic carbon spectrum and the nuclear magnetic hydrogen spectrum of example 1 gave the following results ：¹³C 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.;¹H NMR (400 MHz, CDCl₃) δ 7.50 - 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)..

(2) Preparation of example 2:

。

The mixture of the compound having molecular structure 2a (1 mmol) and the compound having molecular structure c (1.5 mmol) shown above in 5mL of xylene was refluxed for 10h, the reacted mixture was cooled, washed with water, 10% HCl, again with water, and dried over MgSO ₄, the solvent was concentrated in vacuo, and the residue was recrystallized from ethanol to give example 2 having molecular structure 2b, the yield of example 2 was 84%.

Referring to FIGS. 3 and 4, the results of the nuclear magnetic carbon spectrum and the nuclear magnetic hydrogen spectrum of example 2 are ：¹³C 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.;¹H NMR (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)..

(3) Preparation of example 3:

。

the compound (1 mmol) having molecular structure 3a and the compound (2 mmol) having molecular structure c shown above were refluxed in ethylbenzene solvent for 7h, the reacted mixture was cooled, washed with water, 10% HCl, again with water and dried over MgSO ₄, the solvent was concentrated in vacuo, and the residue was recrystallized from ethanol to give example 3 having molecular structure 3b in example 3 in 80% yield.

The nuclear magnetic hydrogen spectrum of example 3 is shown in FIG. 5, and the nuclear magnetic carbon spectrum is shown in the graph 6,¹H 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).;¹³C 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..

(4) Preparation of example 4:

。

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

The nuclear magnetic hydrogen spectrum of example 4 is shown in FIG. 7 and the nuclear magnetic carbon spectrum is shown in the figure 8,¹H NMR (500 MHz, CDCl₃) δ 7.44 - 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) δ 169.69, 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..

(5) Preparation of example 5:

。

The compound (1 mmol) having molecular structure 5a and the compound (1.5 mmol) having molecular structure c shown above were refluxed in a benzene solvent for 10h, the reacted mixture was cooled, washed with water, 10% HCl, again with water, and dried over MgSO ₄, the solvent was concentrated in vacuo, and the residue was recrystallized from ethanol to give example 5 having molecular structure 5b in 81% yield of example 5.

The nuclear magnetic hydrogen spectrum of example 5 is shown in FIG. 9, and the nuclear magnetic carbon spectrum is shown in the graph 10,¹H NMR (500 MHz, CDCl₃) δ 7.76 (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).;¹³C NMR (126 MHz, CDCl₃) δ 191.50, 182.33, 139.46, 131.56, 131.47, 130.25, 126.97, 124.16, 122.12..

Comparative examples 1 to 5 are simple photochromic materials, and comparative examples 1 to 5 have the following structures, respectively.

Comparative example 1:;

Comparative example 2: ;

Comparative example 3: ;

Comparative example 4: ;

comparative example 5: 。

the specific preparation modes of comparative examples 1 to 5 are as follows.

(1) The synthesis procedure of the molecular structure in comparative example 1 is as follows:

indigo (1.0 eq.), cuCl (0.4 eq), K ₃PO₄(4.0 eq.)、Ar₂ I (OTf) (2.4 eq.) and CH ₂Cl₂ (30 mL/mmol indigo) were added to a round bottom flask with a magnetic stirrer. The mixture was stirred at room temperature or heated overnight under argon in a 40 ^o C oil bath. After cooling the resulting mixture to room temperature, it was concentrated, redissolved in ethyl acetate and washed with brine, and then the aqueous layer was extracted with ethyl acetate. The combined organic layers were dried over Na ₂SO₄ and the filtrate was concentrated. The crude product was first purified by column chromatography (EtOAc/CHC 1 ₃) followed by purification by cyclic GPC to give a blue solid.

(2) The synthesis procedure of the molecular structure in comparative example 2 is as follows:

Sodium hydroxide solution (3.74g,93.6mmol,1.5M,8.2 eq.) and 1H-indole-3-acetate (2.00g,11.4 mmol,1.0 eq.) were added to the round bottom flask with magnetic stirring and heated to 100 ^o C for 15 minutes. 4- (dimethylamino) benzaldehyde (1.70g,11.42 mmol,1.0 eq) was then suspended in methanol (11.4 mL, 1M) added at 0 ^o C and stirred at 23 ℃ for 3 days. After the mixture was neutralized with hydrochloric acid (1.0M), it was 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 recrystallisation from ethanol/water as dark purple crystals.

(3) The synthesis procedure of the molecular structure in comparative example 3 is as follows:

Aqueous sodium hydroxide (0.41g,10.3mmol,1.5M,8.2 eq) and 1H-indole-3-acetate (0.22g,1.26 mmol,1.0 eq) were added to the round bottom flask with magnetic stirring and the mixture was heated to 100 ^o C for 15min. Then, 9-aldehyde julolidine (0.25g,1.25 mmol,1.25 eq.) was added at 0 ^o C and stirred at 23 ℃ for 3 days. The mixture was neutralized with hydrochloric acid (1.0M), extracted with ethyl acetate, and 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 ethanol/water recrystallisation.

(4) The synthesis procedure of the molecular structure in comparative example 4 is as follows:

Solution of 4-methoxybenzaldehyde and piperidine (0.05 mL) benzothiophene was added to benzene (20. 20 mL) and the reaction mixture was heated under reflux. Saturated NH ₄ Cl (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. Followed by further purification by column chromatography and recrystallisation from n-heptane.

(5) The synthesis procedure of the molecular structure in comparative example 5 is as follows:

To 2-phenylthioacetic acid (1.0 eq.) and thionyl chloride (9.0 eq.) were added a few drops of DMF. The reaction mixture was stirred at 23 ^o C for 12 hours. Residual thionyl chloride was removed under vacuum at 50 ^o C. 1, 2-Dichloroethane (DCE) was added to the remaining 2-phenylsulfonyl chloride and the solution was cooled to 0 ^o C. AlCl ₃ (1.5 eq.) was added in portions over 2 minutes at 0 ^o C. The reaction mixture was stirred at 0 ^o C for 30min and 23 ^o C for 2 h. Ice/water (150 mL) was added to the mixture to quench and the aqueous phase was extracted with CH ₂Cl₂. The organic phase was separated, dried over Na ₂SO₄ and the solvent removed in vacuo. The crude 1-benzothiophen-3 (2H) -one was used in the next synthesis step without further purification. 1 benzothien-3 (2H) -one is dissolved in benzene. 9-Aldollopidine (180 mg,0.9 mmol) and a drop of piperidine. The reaction mixture was stirred at 100 ℃ for 2 hours, cooled to 23 ℃ 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 Na ₂SO₄. 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 give the purple product.

And (II) performance test.

(1) Afterglow spectrum test:

Afterglow spectrum test is carried out by using the example 1 as a buffer agent, tetraphenylporphyrin is adopted as a photosensitizer, 1mM of the example 1 solution and 0.1mM of the tetraphenylporphyrin solution are prepared in toluene, the prepared example 1 solution and the tetraphenylporphyrin solution are uniformly mixed, and a sample cell containing the mixed solution is placed into a spectrometer. The spectrometer was turned on, the excitation light wavelength was set to 532nm, the afterglow spectrum was measured, and spectral data was recorded. The results are shown in FIG. 11, which demonstrates that example 1 has afterglow properties.

(2) Fluorescence spectrum test:

Example 1 was dissolved in toluene to prepare a 1mM solution and stirred well to complete dissolution. Taking a proper amount of solution and injecting in a quartz cuvette. The fluorescence spectrum of the solution was recorded using a fluorescence spectrometer before no illumination. The cuvette containing the solution was exposed to 532nm laser light for 30min. Immediately after illumination, the fluorescence spectrum of the solution was again recorded using a fluorescence spectrometer. Referring to fig. 12, it can be seen from fig. 12 that the fluorescence spectrum of example 1 hardly changed significantly before and after illumination, and that example 1 showed a more significant fluorescence peak at 470nm at an excitation wavelength of 532 nm. It is explained that the illumination conditions may have less influence on the fluorescence spectrum.

(3) Ultraviolet absorption spectrum test:

The samples of examples 1 to 3 and 5 were weighed accurately by pipette, dissolved in toluene to prepare 1mM solutions, and transferred to a quartz cuvette to ensure uniformity and bubble-free solution. Putting the cuvette containing each solution into an ultraviolet-visible spectrometer, setting the wavelength range of the spectrometer to be 200-800 nm, recording the absorption condition in the range of 400-700 nm, and storing spectral data. And then irradiating the cuvette with 532nm excitation light, immediately placing the cuvette into an ultraviolet absorption-visible spectrometer after the illumination treatment is finished, repeating the spectrum measurement process, and recording the ultraviolet absorption change in the wavelength range of 400-700 nm. Referring to fig. 13 to 16, fig. 13 shows the change in the ultraviolet absorption spectrum before and after the irradiation of example 1, fig. 14 shows the change in the ultraviolet absorption spectrum before and after the irradiation of example 3, fig. 15 shows the change in the ultraviolet absorption spectrum before and after the irradiation of example 2, and fig. 16 shows the change in the ultraviolet absorption spectrum before and after the irradiation of example 5. It can be seen that the absorption of examples 1 to 3 and 5 is very small in the wavelength range of 450 to 500nm before illumination, but after illumination for 10 seconds, the absorption of examples 1 to 3 is significantly smaller in the wavelength range of 450 to 500nm, and the absorption of example 5 is relatively small.

(4) Color change condition:

The solution color before and after the illumination of example 1 was photographed while the afterglow spectrum test was performed, the solution before the illumination was found to be light pink (fig. 17), the solution after the illumination was found to be yellow (fig. 18), in order to investigate the solution color of tetraphenylporphyrin alone and example 1 in toluene, the solution color was photographed by dissolving tetraphenylporphyrin and example 1 alone in toluene, respectively, the toluene solution of tetraphenylporphyrin alone was found to be light pink (fig. 19), and the toluene solution of example 1 alone was found to be transparent (fig. 20), so that it was possible to infer that the light pink in fig. 17 was mainly the color of tetraphenylporphyrin, and fig. 18 was a mixed color of tetraphenylporphyrin and the molecular structure after the illumination occurred.

(5) Color change time recording:

The color change time of the solution after the illumination of the example 1 was recorded while the ultraviolet absorption spectrum test was performed, as shown in fig. 21, and it was found that the ultraviolet absorption (most obvious at the wavelength range of 450-500 nm) was present in the example 1 when the illumination was performed for 2s, and the absorption was almost complete when the illumination was performed for 40s, and the response time of the example 1 was short. Meanwhile, with reference to fig. 14 and 15, both the embodiment 3 and the embodiment 2 have very obvious ultraviolet absorption within 10 seconds, and the response speed is also faster.

The color change time of comparative examples 1-5 was also detected and recorded by performing an ultraviolet-visible absorption test after irradiating the solution with a laser of a specific wavelength for a fixed period of time, testing an absorption change-illumination time curve, fitting to obtain τ _1/2, and recording the results as shown in table 1, wherein τ _1/2 represents the time required for absorption to 1/2.

Table 1:

	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

As shown in Table 1, the color change time τ _1/2 of comparative examples 1 to 5 was as short as 18 minutes.

(6) Characterization of the illumination product:

For further investigation of the illuminated product, the nuclear magnetic characterization of the illuminated product of example 1 was performed. Wherein the hydrogen spectrum is shown in FIG. 22 and the carbon spectrum is shown in FIG. 23. The test result is ：¹H 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).;¹³C NMR (126 MHz, CDCl₃) δ 194.39, 191.69, 154.57, 132.48, 132.34, 132.19, 131.29, 129.79, 120.61, 111.04, 40.09..

Thus, according to the result of nuclear magnetism, the illuminated product is as follows:

。

(7) Mass spectrometry test:

MALDI-TOF test-test using Brookfield autoflex speed TOF/TOF. The sample was dissolved in methylene chloride to prepare a 10mM solution. 1. Mu.L of the sample was pipetted off using a pipette and added dropwise to the sample target. The sample target was placed in maldi-tof instrument, excited with laser, signal acquisition was performed, and the mass spectrum data was processed and analyzed, as shown in fig. 24, by comparison with standard spectra in the database, to substantially agree with molecular weight.

Application example 1 is an anti-counterfeit label, and its manufacturing method is as follows.

Mixing example 1 with tetraphenylporphyrin photosensitizer according to a mass ratio of 1:1, adding the mixture into a polystyrene matrix, uniformly mixing according to a mass ratio of 1:10, adding a proper amount of ethanol as a solvent, adjusting the mixture to a viscosity suitable for ink-jet printing, specifically 16 cP, and uniformly stirring until uniform ink is formed. And uniformly coating the prepared ink on the surface of a substrate by using an ink-jet printer to form a discrimination layer, and heating and drying to ensure that the ink is completely solidified. Covering the surface of the identification layer with a polyester film to form a strippable shielding layer, and printing a 'uncovering check anti-counterfeiting effect' on the shielding layer.

When anti-counterfeiting authentication is carried out, the shielding layer is uncovered, the authentication layer is exposed, the authentication layer is irradiated by ultraviolet light 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 the application example 1 shows afterglow while the authentication layer changes from pale red to yellow under the irradiation of ultraviolet light, and that the common anti-counterfeit label only shows afterglow. Therefore, the true and false products can be accurately distinguished, and the safety and reliability of the anti-counterfeiting system are effectively improved.

Application example 2 is an anti-counterfeit label, which is manufactured as follows.

Mixing example 2 with tetraphenylporphyrin photosensitizer according to a mass ratio of 1:1, adding the mixture into a polystyrene matrix, uniformly mixing according to a mass ratio of 1:10, adding a proper amount of ethanol as a solvent, adjusting the mixture to a viscosity suitable for ink-jet printing, specifically 13 cP, and uniformly stirring until uniform ink is formed. And uniformly coating the prepared ink on the surface of a substrate by using an ink-jet printer to form a discrimination layer, and heating and drying to ensure that the ink is completely solidified. Covering the surface of the identification layer with a polyester film to form a strippable shielding layer, and printing a 'uncovering check anti-counterfeiting effect' on the shielding layer.

When anti-counterfeiting authentication is carried out, the shielding layer is uncovered, the authentication layer is exposed, the authentication layer is irradiated by ultraviolet light 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 the application example 2 shows afterglow while the authentication layer changes from pale red to yellow under the irradiation of ultraviolet light, and the common anti-counterfeit label only shows afterglow. Therefore, the true and false products can be accurately distinguished, and the safety and reliability of the anti-counterfeiting system are effectively improved.

Application example 3 is an optical tag used in the field of cryptography, and on the basis of conventional password verification, the optical tag manufactured in example 2 is introduced, so as to enhance the security of identity authentication, and the manufacturing method of the optical tag is as follows.

Example 2 was dissolved in a suitable amount of solvent to prepare an ink suitable for inkjet printing or screen printing. And uniformly coating the prepared ink on the surface of a substrate by using an ink-jet printer to form the optical label. Heating (40 ℃) to dryness ensures complete curing of the ink, resulting in a stable optical label. The verification device is matched with the optical tag, and comprises a color sensor, an afterglow detection sensor, a control unit and an ultraviolet light source, when the identity is verified, the verification device prompts a user to verify by using the optical tag after the user inputs a traditional password, the user places the optical tag on the verification device, the device emits ultraviolet light with specific wavelength to irradiate the tag, the device detects the color change and afterglow response of the tag, the result is compared with a preset value, if the comparison is successful, the identity verification is completed, and otherwise, the access is refused. Because of the performance of afterglow and color change, the optical label has high copying difficulty and improves the safety compared with an optical label which can only emit afterglow or color change. Thus, the embodiment combines the traditional password and optical verification, and greatly improves the security and the anti-attack capability of the identity verification.

Comparative example 1. Conventional security labels have only afterglow.

Taking rhodamine in the prior art as a common anti-counterfeiting label material, mixing the rhodamine with a tetraphenylporphyrin photosensitizer according to a mass ratio of 1:1, adding the mixture into a polystyrene matrix, uniformly mixing according to a mass ratio of 1:10, adding a proper amount of ethanol as a solvent, adjusting the mixture to be suitable for ink-jet printing, and uniformly stirring until uniform ink is formed. And uniformly coating the prepared ink on the surface of a substrate by using an ink-jet printer to form a discrimination layer, and heating and drying to ensure that the ink is completely solidified. Covering the surface of the identification layer with a polyester film to form a strippable shielding layer, and printing a 'uncovering check anti-counterfeiting effect' on the shielding layer.

When anti-counterfeiting authentication is carried out, the shielding layer is uncovered, the authentication layer is exposed, ultraviolet light is used for irradiating the authentication layer, the irradiation time is 0.3h, and the color change and afterglow response of the illuminated area and the non-illuminated area are observed. The result shows that under the irradiation of ultraviolet light, the common anti-counterfeiting label only shows afterglow and has no color change. Therefore, the genuine-fake product cannot be distinguished by the color change, which reduces the security and reliability of the anti-counterfeit system.

In addition, besides the application shown above, the color and afterglow co-responsive material of the embodiment of the invention can also be used for homogeneous detection, the color and afterglow co-responsive material is coated in donor microspheres and acceptor microspheres, then the color and afterglow co-responsive material is marked on target molecules such as antibodies, the color and afterglow co-responsive material in a sample is excited, an afterglow luminescence signal is recorded after an excitation light source is removed, and detection can be carried out after the background signal is weakened due to the persistent luminescence characteristic of the material, so that the signal to noise ratio is improved.

While the invention has been shown and described with reference to certain preferred embodiments thereof, it will be understood by those skilled in the art that the foregoing is a further detailed description of the invention with reference to specific embodiments, and it is not intended to limit the practice of the invention to those descriptions. Various changes in form and detail may be made therein by those skilled in the art, including a few simple inferences or alternatives, 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 the color and afterglow co-responsive material according to claim 1, characterized in that it comprises the following steps:

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 according to 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, the identification layer is coated with ink, and the ink comprises the color and afterglow co-responsive material as claimed in claim 1 and a photosensitizer.

6. An anti-counterfeiting label as described in claim 5, characterized in that the photosensitizer is tetraphenylporphyrin, and the anti-counterfeiting label also includes a shielding layer, the shielding layer is a polyester film, and 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 it comprises the following steps:

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.