Time-dependent anti-counterfeiting material based on organic room-temperature phosphorescence as well as preparation method and application of time-dependent anti-counterfeiting material
By developing time-dependent anti-counterfeiting materials based on organic room temperature phosphorescence, the existing anti-counterfeiting technology is solved and the problem of difficult counterfeiting problems is achieved, achieving efficient and stable anti-counterfeiting identification results.
Patent Information
- Application Number
- CN202411797639.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-06
- Publication Date
- 2025-03-21
AI Technical Summary
Existing anti-counterfeiting technologies are difficult to effectively deal with the increasingly severe counterfeiting problem, and the effectiveness of traditional methods is gradually weakening with the development of replication and imitation technologies.
A time-dependent anti-counterfeiting material based on organic room temperature phosphorescence is developed. By embedding specific phosphorescence chromophores, the printed logo shows unique changes under different time scales, increasing the difficulty of forgery for criminals.
It provides stable and repeatable luminescent properties, can generate charge separation states under light activation, store excitation energy, and slowly release it in the form of light, significantly improving the identification effect and complexity of anti-counterfeiting materials.
Smart Images
Figure CN119662243A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of luminescent materials, and in particular to a time-dependent anti-counterfeiting material based on organic room temperature phosphorescence, and a preparation method and application thereof. Background Art
[0002] In today's globalized business environment, the proliferation of counterfeit and substandard products has seriously damaged the rights of consumers and posed a threat to brand reputation and the economic interests of legitimate businesses. Although traditional anti-counterfeiting technologies, such as optical anti-counterfeiting labels and chemical markers, provide certain anti-counterfeiting capabilities, the effectiveness of these methods has gradually weakened with the development of copying and imitation technologies. Therefore, there is an urgent need for a new type of anti-counterfeiting technology to effectively deal with the increasingly serious counterfeiting problem. Organic room temperature phosphorescent materials can exhibit unique luminescence characteristics under room temperature conditions, breaking through the limitations of the use of traditional low-temperature phosphorescent materials. On this basis, time-dependent anti-counterfeiting materials have been developed, which can not only provide effective anti-counterfeiting means in dynamic environments, but also show different optical characteristics over time, thereby providing a more reliable basis for the identification of counterfeit and substandard products.
[0003] Anti-counterfeiting materials with time-dependence embed specific phosphorescent chromophores, which make the printed logo show unique changes at different time scales. Consumers can verify the authenticity of the product through simple observation or detection methods. This dynamic change characteristic increases the complexity of anti-counterfeiting labels and makes it more difficult for criminals to forge. With the increasing market requirements for product safety and traceability, the time-dependent anti-counterfeiting technology based on organic room temperature phosphorescence not only meets the new needs of enterprises for anti-counterfeiting labels, but also provides innovative solutions for the security prevention of related industries. Therefore, the promotion and application of this technology will provide strong support for combating counterfeit and shoddy products and protecting the rights and interests of consumers and enterprises. However, the development of this type of anti-counterfeiting materials is still in its infancy, and there are few time-dependent anti-counterfeiting materials available. Summary of the invention
[0004] The present application provides a time-dependent anti-counterfeiting material based on organic room temperature phosphorescence, and a preparation method and application thereof. The time-dependent anti-counterfeiting material of organic room temperature phosphorescence provided has stable luminescent properties and high repeatability, and can provide clear and unambiguous identification features.
[0005] In a first aspect, the embodiments of the present application provide a time-dependent anti-counterfeiting material based on organic room temperature phosphorescence, comprising a host material and a guest material, wherein the chemical structure of the host material (I) is as shown in formula (I-1) or (I-2),
[0006]
[0007] Where X = any one of O, S, N,
[0008] R=CH3, C(CH3)3, OCH3, OH, NH2, NHCH3, N(CH3)2, any one of them,
[0009] The chemical structure of the guest material is shown in formula (II):
[0010]
[0011] In some embodiments, the guest material is added in an amount of 0.1 wt % to 10 wt % of the host material by weight.
[0012] In some embodiments, the time-dependent anti-counterfeiting material based on organic room temperature phosphorescence has a yellow afterglow.
[0013] In some embodiments, the intensity and duration of the yellow afterglow are adjustable depending on the type of luminophore.
[0014] In some embodiments, the intensity and duration of the yellow afterglow are adjustable according to different ultraviolet light excitation times.
[0015] In a second aspect, an embodiment of the present application provides a method for preparing a time-dependent anti-counterfeiting material based on organic room temperature phosphorescence, comprising the following steps: preparing a time-dependent anti-counterfeiting material based on organic room temperature phosphorescence by a host-guest doping method using a host material and a guest material.
[0016] In some embodiments, the method comprises the following steps: mixing the host material and the guest material and heating them to a molten state, and obtaining the time-dependent anti-counterfeiting material based on organic room temperature phosphorescence after annealing.
[0017] In some embodiments, the method comprises the following steps: mixing the host material and the guest material and dissolving them in an organic solvent, and stirring to obtain the time-dependent anti-counterfeiting material based on organic room temperature phosphorescence.
[0018] In a third aspect, an embodiment of the present application provides an application method of a time-dependent anti-counterfeiting material based on organic room temperature phosphorescence, comprising: applying the time-dependent anti-counterfeiting material based on organic room temperature phosphorescence to an anti-counterfeiting printing product.
[0019] The technical solution of this application has the following technical effects:
[0020] (1) The time-dependent anti-counterfeiting material based on organic room temperature phosphorescence provided in the present application can generate a charge separation state under light activation, store excitation energy, and slowly release the energy in the form of light after the excitation stops. The luminescence property is stable, the repeatability is high, the recognition effect is good, and the material can respond to light signals with a fast response recovery speed, so that continuous anti-counterfeiting recognition can be performed, thereby providing users with clear and unambiguous identification features;
[0021] (2) The time-dependent anti-counterfeiting material based on organic room temperature phosphorescence provided in this application can easily and conveniently realize anti-counterfeiting detection whether it is rapid detection on the production line or identification by consumers when purchasing products, bringing new breakthroughs to anti-counterfeiting technology. BRIEF DESCRIPTION OF THE DRAWINGS
[0022] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings required for use in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative work.
[0023] Figure 1 is the phosphorescence emission spectrum of the time-dependent anti-counterfeiting material based on organic room temperature phosphorescence prepared in Example 1;
[0024] Figure 2 is the phosphorescence emission spectrum of the time-dependent anti-counterfeiting material based on organic room temperature phosphorescence prepared in Example 2;
[0025] Figure 3 is the phosphorescence emission spectrum of the time-dependent anti-counterfeiting material based on organic room temperature phosphorescence prepared in Example 3;
[0026] Figure 4 is the phosphorescence emission spectrum of the time-dependent anti-counterfeiting material based on organic room temperature phosphorescence prepared in Example 4;
[0027] Figure 5 It is a photo of the security label "OPEN" in daylight;
[0028] Figure 6 This is a time-dependent afterglow photograph of the anti-counterfeiting label "OPEN" under light stimulation. DETAILED DESCRIPTION
[0029] In order to facilitate the understanding of this specification, the specification will be described more fully below with reference to the relevant drawings. The preferred embodiments of this specification are given in the drawings. However, this specification can be implemented in many different forms without departing from the core spirit of this specification and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the understanding of the disclosure of this specification more thorough and comprehensive.
[0030] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those generally understood by those skilled in the art to which this specification belongs. The terms used herein in this specification are only for the purpose of describing specific embodiments and are not intended to limit this specification. The term "and / or" used herein includes any and all combinations of one or more of the related listed items.
[0031] In a first aspect, the embodiments of the present application provide a time-dependent anti-counterfeiting material based on organic room temperature phosphorescence, comprising a host material and a guest material, wherein the chemical structure of the host material (I) is as shown in formula (I-1) or (I-2),
[0032]
[0033]
[0034] Where X = any one of O, S, N,
[0035] R=CH3, C(CH3)3, OCH3, OH, NH2, NHCH3, N(CH3)2, any one of them,
[0036] The guest material is dinaphtho[2,1-B:1',2'-D]furan, and its chemical structure is shown in formula (II).
[0037]
[0038] In some embodiments, the amount of the guest material added is 0.1wt%-10wt% of the mass of the host material. For example, the mass percentage of the guest material added to the mass of the host material can be 0.1wt%, 0.5wt%, 1wt%, 2wt%, 4wt%, 6wt%, 8wt%, 10wt%, or any mass percentage value between any two of the above mass percentage values. For example, when the mass of the host material is 1000mg, the mass of the guest material can be 10mg, at which time, the mass percentage of the guest material added to the mass of the host material is 1wt%.
[0039] In some embodiments, the time-dependent anti-counterfeiting material based on organic room temperature phosphorescence has a yellow afterglow.
[0040] In some embodiments, the intensity and duration of the yellow afterglow are adjustable depending on the type of luminophore. The guest material is dinaphtho[2,1-B:1',2'-D]furan, the host material can be selected from formula (I-1) and (I-2), and the X and R groups in formula (I-1) can be selected from a variety of functional groups, and the R group in formula (I-2) can also be selected from a variety of functional groups, which means that different anti-counterfeiting materials can be obtained according to different host materials and different functional groups, corresponding to different luminophores, and accordingly, the intensity and duration of the yellow afterglow exhibited by the anti-counterfeiting material are also different. Therefore, the time-dependent anti-counterfeiting material based on organic room temperature phosphorescence provided in the embodiment of the present application can show adjustability of the intensity and duration of the yellow afterglow according to the type of luminophore.
[0041] In some embodiments, the intensity and duration of the yellow afterglow are adjustable according to the different ultraviolet light excitation times. The inventors have found through experiments that the time-dependent anti-counterfeiting material based on organic room temperature phosphorescence provided in the embodiments of the present application can exhibit yellow afterglow of different intensities when it is irradiated with ultraviolet light at different times, and the duration of the yellow afterglow is also different.
[0042] In a second aspect, an embodiment of the present application provides a method for preparing a time-dependent anti-counterfeiting material based on organic room temperature phosphorescence, comprising the following steps: preparing a time-dependent anti-counterfeiting material based on organic room temperature phosphorescence by a host-guest doping method using a host material and a guest material.
[0043] In some embodiments, the method comprises the following steps: mixing a host material and a guest material and heating them to a molten state, and obtaining a time-dependent anti-counterfeiting material based on organic room temperature phosphorescence after annealing. The preparation method is a molten liquid preparation method, and a crystalline time-dependent anti-counterfeiting material based on organic room temperature phosphorescence can be prepared by the preparation method.
[0044] In some embodiments, the method comprises the following steps: mixing a host material and a guest material and dissolving them in an organic solvent, and stirring to obtain a time-dependent anti-counterfeiting material based on organic room temperature phosphorescence. This method is an organic solution preparation method, and the time-dependent anti-counterfeiting material based on organic room temperature phosphorescence in the form of ink can be prepared by this preparation method.
[0045] In a third aspect, an embodiment of the present application provides an application method of a time-dependent anti-counterfeiting material based on organic room temperature phosphorescence, comprising: applying the time-dependent anti-counterfeiting material based on organic room temperature phosphorescence to an anti-counterfeiting printing product.
[0046] The following are specific preparation examples involved in the above content of the present disclosure. It should be clear that the following examples are only for illustrating a time-dependent anti-counterfeiting material based on organic room temperature phosphorescence and its preparation method and application disclosed above, and the specific implementation methods and parameters used therein are only one or several methods in accordance with the many processes and methods described above. Those skilled in the art can use other parameters according to the content introduced in this specification to prepare time-dependent anti-counterfeiting materials based on organic room temperature phosphorescence according to the above method without deviating from the core spirit disclosed in the application.
[0047] The sources of the reagents used in the examples of this application are as follows:
[0048] Dibenzofuran, purchased from Shanghai Titan Technology Co., Ltd., brand number 20469B;
[0049] Methyl 4-(methylamino)benzoate, purchased from Shanghai Titan Technology Co., Ltd., brand number 32377C;
[0050] Dibenzothiophene, purchased from Shanghai Titan Technology Co., Ltd., brand number 20472C;
[0051] Methyl 4-(amino)benzoate, purchased from Shanghai Titan Technology Co., Ltd., brand number 70948A;
[0052] Dinaphtho[2,1-b:1',2'-d]furan was purchased from Shanghai Titan Technology Co., Ltd. with the brand number 34100A;
[0053] The above reagents were purified before use.
[0054] Example 1
[0055] The present embodiment provides a time-dependent anti-counterfeiting material based on organic room temperature phosphorescence, and the preparation method thereof includes the following steps: weighing 1000 mg of dibenzofuran (host material) and 10 mg of dinaphtho[2,1-b:1',2'-d]furan (guest material), mixing the host material and the guest material at 100°C and stirring them thoroughly to melt, and then annealing them to obtain a time-dependent anti-counterfeiting material based on organic room temperature phosphorescence, recorded as "Crystal 1".
[0056] Figure 1 The phosphorescence emission spectrum of the time-dependent anti-counterfeiting material based on organic room temperature phosphorescence prepared in Example 1 is shown.
[0057] Example 2
[0058] The present embodiment provides a time-dependent anti-counterfeiting material based on organic room temperature phosphorescence, and the preparation method thereof includes the following steps: weighing 1000 mg of 4-(methylamino)benzoic acid methyl ester (host material) and 10 mg of dinaphtho[2,1-b:1',2'-d]furan (guest material), mixing the host material and the guest material at 100°C and stirring them thoroughly to melt, and then annealing them to obtain a time-dependent anti-counterfeiting material based on organic room temperature phosphorescence, recorded as "Crystal 2".
[0059] Figure 2 The phosphorescence emission spectrum of the time-dependent anti-counterfeiting material based on organic room temperature phosphorescence prepared in Example 2 is shown.
[0060] Example 3
[0061] The present embodiment provides a time-dependent anti-counterfeiting material based on organic room temperature phosphorescence, and the preparation method thereof includes the following steps: weighing 1000 mg of dibenzothiophene (host material) and 10 mg of dinaphtho[2,1-b:1',2'-d]furan (guest material), mixing the host material and the guest material at 100°C and stirring them thoroughly to melt, and then annealing them to obtain a time-dependent anti-counterfeiting material based on organic room temperature phosphorescence, recorded as "Crystal 3".
[0062] Figure 3 The phosphorescence emission spectrum of the time-dependent anti-counterfeiting material based on organic room temperature phosphorescence prepared in Example 3 is shown.
[0063] Example 4
[0064] The present embodiment provides a time-dependent anti-counterfeiting material based on organic room temperature phosphorescence, and the preparation method thereof includes the following steps: weighing 1000 mg of 4-(amino)benzoic acid methyl ester (host material) and 10 mg of dinaphtho[2,1-b:1',2'-d]furan (guest material), mixing the host material and the guest material at 100°C and stirring them thoroughly to melt, and then annealing them to obtain a time-dependent anti-counterfeiting material based on organic room temperature phosphorescence, recorded as "Crystal 4".
[0065] Figure 4 The phosphorescence emission spectrum of the time-dependent anti-counterfeiting material based on organic room temperature phosphorescence prepared in Example 4 is shown.
[0066] Example 5
[0067] The present embodiment provides a time-dependent anti-counterfeiting material based on organic room temperature phosphorescence, and its preparation method includes the following steps: weigh 1000 mg of dibenzofuran (host material) and 10 mg of dinaphtho[2,1-b:1',2'-d]furan (guest material), mix and dissolve the host material and the guest material in 10 ml of dichloromethane solution, stir well, and obtain a time-dependent anti-counterfeiting material based on organic room temperature phosphorescence, recorded as "Ink 1".
[0068] Example 6
[0069] The present embodiment provides a time-dependent anti-counterfeiting material based on organic room temperature phosphorescence, and its preparation method includes the following steps: weigh 1000 mg of 4-(methylamino)benzoic acid methyl ester (host material) and 10 mg of dinaphtho[2,1-b:1',2'-d]furan (guest material), mix and dissolve the host material and the guest material in 10 ml of dichloromethane solution, and stir well to obtain a time-dependent anti-counterfeiting material based on organic room temperature phosphorescence, recorded as "Ink 2".
[0070] The time-dependent anti-counterfeiting materials based on organic room temperature phosphorescence prepared in Example 5 and Example 6 were subjected to a combined test. The specific method is as follows: use seal "O" to dip into "Ink 1", and use seal "PEN" to dip into "Ink 2", and place the seals dipped in ink on the filter paper in turn. After naturally drying, the anti-counterfeiting label "OPEN" is obtained. Figure 5 A photo of the security label "OPEN" under sunlight is shown. Figure 5 As shown, the time-dependent anti-counterfeiting materials based on organic room temperature phosphorescence prepared in Examples 5 and 6 have color development capabilities under sunlight.
[0071] Continue to test the afterglow performance of the anti-counterfeiting label "OPEN" under ultraviolet light stimulation, Figure 6 The time-dependent afterglow photograph of the anti-counterfeiting label "OPEN" under light stimulation is shown. Figure 6 The specific results are as follows:
[0072] (1) The 365 nm UV flashlight was irradiated for 0.2 s and then turned off. The label on the filter paper showed a weak yellow afterglow of "PEN" which lasted for 1 s.
[0073] (2) After irradiating with a 365nm UV flashlight for 1 second, the label on the filter paper showed a yellow afterglow of "OPEN" that lasted for 2 seconds, and the yellow afterglow of "O" was relatively weak.
[0074] (3) After irradiating with a 365nm UV flashlight for 5 seconds and then turned off, the label on the filter paper showed a bright yellow afterglow of "OPEN". The afterglow of "O" lasted for 3 seconds and was relatively weak, and the afterglow of "PEN" lasted for 4 seconds. Overall, the label "OPEN" gradually turned into "PEN" after 2 seconds.
[0075] Depend on Figure 6 It can be seen that the time-dependent anti-counterfeiting materials based on organic room temperature phosphorescence prepared in Examples 5 and 6 both exhibit yellow afterglow. Moreover, the intensity and duration of the yellow afterglow are adjustable according to the type of luminophore. In addition, the intensity and duration of the yellow afterglow are adjustable according to the ultraviolet light excitation time.
[0076] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.
[0077] The above-described embodiments only express several embodiments of the present invention, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the invention patent. It should be pointed out that, for those of ordinary skill in the art, several variations and improvements can be made without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. It should be understood that the technical solutions obtained by those skilled in the art through logical analysis, reasoning or limited experiments on the basis of the technical solutions provided by the present invention are all within the protection scope of the claims attached to the present invention. Therefore, the protection scope of the patent of the present invention shall be based on the attached claims, and the description and drawings may be used to interpret the contents of the claims.
Claims
1. A time-dependent anti-counterfeiting material based on organic room temperature phosphorescence, characterized in that: It includes a host material and a guest material, wherein the chemical structure of the host material (I) is as shown in formula (I-1) or (I-2), Where X = any one of O, S, N, R=CH3, C(CH3)3, OCH3, OH, NH2, NHCH3, N(CH3)2, any one of them, The chemical structure of the guest material is shown in formula (II):
2. The time-dependent anti-counterfeiting material based on organic room temperature phosphorescence according to claim 1, characterized in that: In terms of mass percentage, the added amount of the guest material accounts for 0.1wt%-10wt% of the mass of the host material.
3. The time-dependent anti-counterfeiting material based on organic room temperature phosphorescence according to claim 1, characterized in that: The time-dependent anti-counterfeiting material based on organic room temperature phosphorescence has a yellow afterglow.
4. The time-dependent anti-counterfeiting material based on organic room temperature phosphorescence according to claim 3, characterized in that: Depending on the type of luminophore, the intensity and duration of the yellow afterglow are adjustable.
5. The time-dependent anti-counterfeiting material based on organic room temperature phosphorescence according to claim 3, characterized in that: The intensity and duration of the yellow afterglow are adjustable according to the ultraviolet light excitation time.
6. A method for preparing a time-dependent anti-counterfeiting material based on organic room temperature phosphorescence, characterized in that: The method comprises the following steps: preparing a time-dependent anti-counterfeiting material based on organic room temperature phosphorescence by subjecting a host material and a guest material through a host-guest doping method.
7. The method for preparing the time-dependent anti-counterfeiting material based on organic room temperature phosphorescence according to claim 6, characterized in that: The method comprises the following steps: mixing the main material and the guest material and heating them to a molten state, and obtaining the time-dependent anti-counterfeiting material based on organic room temperature phosphorescence after annealing.
8. The method for preparing a time-dependent anti-counterfeiting material based on organic room temperature phosphorescence according to claim 6, characterized in that: The method comprises the following steps: mixing the host material and the guest material and dissolving them in an organic solvent, and stirring to obtain the time-dependent anti-counterfeiting material based on organic room temperature phosphorescence.
9. An application method of a time-dependent anti-counterfeiting material based on organic room temperature phosphorescence, characterized in that: include: The time-dependent anti-counterfeiting material based on organic room temperature phosphorescence is applied to anti-counterfeiting printing products.