A time-effective fluorescent anti-counterfeiting material and its preparation method and application

Abstract

A time-effective fluorescent anti-counterfeiting material and its preparation method and application belong to the technical field of anti-counterfeiting materials. The time-effective fluorescent anti-counterfeiting material of the present invention comprises an aggregated color-changing fluorescent material, a sublimable dispersed matrix and a solvent. The mass concentration of the aggregated color-changing fluorescent material after being dissolved in the solvent is 0.01%-5%, and the mass concentration of the sublimable dispersed matrix after being dissolved in the solvent is 5%-50%. The time-effective fluorescent anti-counterfeiting material of the present invention can be used for writing or inkjet printing of time-effective fluorescent anti-counterfeiting ink, and the ink is applied to the surface of paper, woven fabrics, textiles and polymer materials to form a time-effective fluorescent pattern that changes stably over time. Among them, the sublimable dispersed matrix gradually sublimates over time, and the agglomeration state of the fluorescent material changes continuously, so that the fluorescent color also gradually changes over time, and a fluorescent anti-counterfeiting pattern that can gradually and stably change over time is obtained, thereby achieving high security and time-effective anti-counterfeiting protection.

Description

Technical Field

[0001] The present invention belongs to the technical field of anti-counterfeiting materials, and in particular relates to a time-sensitive fluorescent anti-counterfeiting material whose fluorescent luminescence changes stably over time. Background Art

[0002] Fluorescent anti-counterfeiting technology utilizes the properties of specialized luminescent materials that are colorless under visible light but luminescent under ultraviolet light to print "invisible" anti-counterfeiting text and patterns. This technology is widely used to protect coins, documents, bills, and various high-value consumer products from counterfeiting. In recent years, while fluorescent anti-counterfeiting technology has proven effective in protecting high-value documents and products from counterfeiting, it has also faced increasing challenges from counterfeiters. Simple single-color or multi-color fluorescent anti-counterfeiting technologies have proven inadequate for the protection of high-value products. Furthermore, the value of products such as archives, bills, certificates, pharmaceuticals, food, and health supplements is significantly time-sensitive, making it difficult for existing anti-counterfeiting technologies to effectively protect these products from counterfeiting while also effectively protecting their time-sensitive value. If a fluorescent anti-counterfeiting material could be constructed whose fluorescent pattern or luminescent color could change stably over time, it would significantly enhance anti-counterfeiting security and effectively protect the time-sensitive value of the documents and products being protected. Summary of the Invention

[0003] In response to the problems existing in the above-mentioned prior art, the purpose of the present invention is to provide a time-effective fluorescent anti-counterfeiting material whose fluorescent luminescence color can stably change over time. The anti-counterfeiting material of the present invention utilizes a solid solution formed by aggregating color-changing fluorescent materials and sublimable solid materials to form fluorescent traces. When the sublimable solid in the solid solution gradually sublimates over time, the concentration of the fluorescent material in the solid solution gradually increases, and its agglomeration state continuously changes, so that the fluorescent color of the obtained handwriting or pattern also gradually changes over time. By formulating this material into a time-effective fluorescent anti-counterfeiting ink, and printing it on the packaging of documents or goods through writing, printing or inkjet printing, a fluorescent anti-counterfeiting pattern that can gradually and stably change over time is obtained, thereby achieving high security and time-effective anti-counterfeiting protection.

[0004] In order to achieve the above object, the present invention adopts the following technical solutions:

[0005] A time-effective fluorescent anti-counterfeiting material comprises an aggregated color-changing fluorescent material, a sublimable dispersed matrix and a solvent.

[0006] In the time-effective fluorescent anti-counterfeiting material, the mass concentration of the aggregated color-changing fluorescent material after being dissolved in a solvent is 0.01%-5%, and the mass concentration of the sublimable dispersed matrix after being dissolved in a solvent is 5%-50%.

[0007] The time-effective fluorescent anti-counterfeiting material, the aggregation color-changing fluorescent material includes a mixture of one or more of graphene quantum dots, fluorescent carbon dots, Nile red, pyrene, perylene, diisobutyl perylenedicarboxylate, and aggregation-induced fluorescent materials with hexaphenylsilole and tetraphenylethylene groups.

[0008] In the time-effective fluorescent anti-counterfeiting material, the sublimable dispersed matrix includes a mixture of one or more of cyclododecane, menthol, menthol lactate, and menthyl succinate.

[0009] The solvent of the time-effective fluorescent anti-counterfeiting material includes a mixture of one or more of ethanol, ethylene glycol, glycerol, propylene glycol acetate, ethyl acetate, and ethyl lactate.

[0010] Any method for preparing a time-effective fluorescent anti-counterfeiting material comprises the following steps: weighing an aggregated color-changing fluorescent material and dissolving it in a solvent, and then adding a sublimable dispersion matrix to obtain a time-effective fluorescent anti-counterfeiting ink.

[0011] A time-effective fluorescent anti-counterfeiting ink is characterized by being prepared by using any of the time-effective fluorescent anti-counterfeiting materials described above.

[0012] The method for using the time-sensitive fluorescent anti-counterfeiting ink is characterized by comprising the following steps: writing or printing the time-sensitive fluorescent anti-counterfeiting ink on the surface of the anti-counterfeiting protection product to form a time-sensitive fluorescent pattern that changes stably over time.

[0013] The method of use is characterized in that the method of writing or printing includes writing, inkjet printing, offset printing, and the anti-counterfeiting protection product includes paper, woven fabrics, textiles and polymer materials.

[0014] The use of any of the aforementioned time-sensitive fluorescent anti-counterfeiting materials or the aforementioned time-sensitive fluorescent anti-counterfeiting ink as an anti-counterfeiting material that changes stably over time in identifying and protecting products.

[0015] When the time-sensitive fluorescent anti-counterfeiting material of the present invention is painted or printed on the surface of paper, woven fabrics, textiles and polymer materials, after the solvent is absorbed or evaporated, the sublimable matrix and the aggregated color-changing fluorescent material form a fluorescent coating on the surface and internal gaps of the paper, textiles and polymer materials, and as the sublimable dispersed matrix gradually sublimates, a time-sensitive fluorescent pattern that changes stably over time is presented.

[0016] The present invention utilizes a solid solution formed by agglomerated color-changing fluorescent materials and sublimable solid materials to create fluorescent traces on the surfaces of paper and other items. As the sublimable solid components in the solid solution gradually sublime over time, the aggregation state of the fluorescent materials within it also gradually changes, causing the fluorescent color of the writing or pattern to gradually change over time. Because the sublimable solid's sublimation rate is largely unaffected by factors such as light, humidity, and atmospheric composition at room temperature, the fluorescent color can be stably changed over a long period of time, effectively protecting the time-sensitive value of documents and goods.

[0017] At the same time, by selecting the types of aggregated color-changing fluorescent materials and sublimation materials and adjusting the mass ratio of aggregated color-changing fluorescent materials to sublimation materials, the fluorescent color of the prepared material and the speed of change of the fluorescent color over time can be effectively controlled to meet the needs of different application scenarios.

[0018] In particular, since the color-changing mechanism of this material is based on the nanoscale microphase separation process of the solid solution, its color-changing process is irreversible and cannot be reset or tampered with artificially. Using other fluorescent materials, it may be possible to obtain a fluorescent color similar to that of this material at a certain stage, but the same time-changing effect cannot be achieved. It is only necessary to place the genuine and counterfeit products for a period of time to determine their authenticity from the changes in their fluorescence.

[0019] Compared with the prior art, the present invention has the following beneficial effects:

[0020] 1. The fluorescent color of the time-sensitive fluorescent anti-counterfeiting material of the present invention can stably change over time and can be used for high-security and time-sensitive anti-counterfeiting.

[0021] 2. The time-sensitive fluorescent anti-counterfeiting material of the present invention can be formulated into a time-sensitive fluorescent anti-counterfeiting ink, which can be easily printed on documents or product packaging to achieve anti-counterfeiting through writing, printing or inkjet printing.

[0022] 3. The property of fluorescence color changing over time can be used to identify counterfeit products with similar fluorescence colors, making it more unforgeable. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 It is a schematic diagram of the principle of the present invention;

[0024] Figure 2 The time-sensitive fluorescent anti-counterfeiting material sample prepared in Example 1 and its fluorescence under ultraviolet light;

[0025] Figure 3Fluorescent photographs of writing written on the time-effective fluorescent anti-counterfeiting material prepared in Example 1, as well as a comparison of the fluorescent colors of writing written on the non-time-effective fluorescent material and the time-effective fluorescent anti-counterfeiting material after being placed for different periods of time;

[0026] Figure 4 The fluorescence emission spectrum of the time-sensitive fluorescent anti-counterfeiting material prepared in Example 1 changes over time;

[0027] Figure 5 The fluorescent pattern is printed using the time-effective fluorescent anti-counterfeiting ink prepared in Example 4. DETAILED DESCRIPTION

[0028] The present invention will be further described below with reference to the accompanying drawings and examples.

[0029] Example 1

[0030] Weigh 0.1g of graphene quantum dot material and dissolve it in 100mL of ethanol. Stir magnetically at 500 rpm for 2 hours at 25°C. After the graphene quantum dots are evenly dissolved in the ethanol solvent, add 25.0g of menthol and 5g of menthol lactate. Continue to stir magnetically at 500 rpm for 2 hours to fully dissolve and mix, and obtain 120mL of time-effective fluorescent anti-counterfeiting material. Figure 1 Shown is a schematic diagram of the principle of the present invention.

[0031] like Figure 2 It is a time-sensitive fluorescent material that appears light yellow under visible light and emits bright fluorescence under ultraviolet light.

[0032] like Figure 3 The figure compares the effects of non-time-effective fluorescent materials (above) and time-effective fluorescent materials (below) after 50 days, 30 days and newly written fluorescent writing. It can be seen that the fluorescent color of the time-effective fluorescent material gradually changes from green to blue, while the fluorescent color of the non-time-effective fluorescent material does not change.

[0033] like Figure 4 This is the fluorescence emission spectrum of the time-sensitive fluorescent material that changes with time. It can be observed that as time passes, the peak at a wavelength of 520 nm in the emission spectrum of the time-sensitive fluorescent material gradually decreases, thereby proving the change in its fluorescence color.

[0034] Example 2

[0035] Weigh 0.5 g of fluorescent carbon dot material and dissolve it in 100 mL of ethanol. At 25°C, magnetically stir at 500 rpm for 2 hours. After the fluorescent carbon dots are evenly dissolved in the ethanol solvent, add 50 mL of ethylene glycol and 25 g of menthyl succinate. Continue magnetically stirring at 500 rpm for 2 hours to fully dissolve and mix the mixture to obtain 150 mL of time-sensitive fluorescent anti-counterfeiting material.

[0036] Example 3

[0037] Weigh 0.2 g of Nile red and dissolve it in 100 mL of a mixed solvent of propylene glycol acetate and ethyl acetate (the volume ratio of propylene glycol acetate and ethyl acetate is 1:1). Stir magnetically at 500 rpm for 2 hours at 25°C. After Nile red is uniformly dissolved in the mixed solvent of propylene glycol acetate and ethyl acetate ethanol, add 50 g of cyclododecane and continue to stir magnetically at 500 rpm for 2 hours to fully dissolve and mix the mixture to obtain 150 mL of time-effective fluorescent anti-counterfeiting material.

[0038] Example 4

[0039] Weigh 1.5g of graphene quantum dot material and dissolve it in 100mL of ethanol. Stir magnetically at 500 rpm for 2 hours at 25°C. After the graphene quantum dots are evenly dissolved in the ethanol solvent, add 10.0g of cyclododecane and dissolve and mix thoroughly to obtain 100mL of time-sensitive fluorescent anti-counterfeiting ink that can be used for inkjet printing. Use the time-sensitive fluorescent anti-counterfeiting ink to print by inkjet printing, such as Figure 5 The figure shows the fluorescent pattern printed by the obtained time-effective fluorescent anti-counterfeiting ink. It can be seen that the time-effective fluorescent anti-counterfeiting ink can obtain a time-effective fluorescent pattern whose fluorescent color changes within 20 days.

[0040] Example 5

[0041] 0.3g of graphene quantum dots (GQDs) were weighed and dissolved in 100mL of ethanol. The mixture was magnetically stirred at 500 rpm at 25°C for 2 hours. After the GQDs were evenly dissolved in the ethanol solvent, 10.0g of cyclododecane was added and thoroughly mixed to obtain 100mL of a time-sensitive fluorescent anti-counterfeiting ink suitable for inkjet printing. Using this time-sensitive fluorescent anti-counterfeiting ink, inkjet printing can produce a time-sensitive fluorescent pattern that changes color within 60 days.

Claims

1. A time-effective fluorescent anti-counterfeiting material, characterized in that The time-effective fluorescent anti-counterfeiting material comprises an aggregated color-changing fluorescent material, a sublimable dispersed matrix and a solvent; The aggregated color-changing fluorescent material is selected from a mixture of one or more of graphene quantum dots, fluorescent carbon dots, Nile red, pyrene, perylene, diisobutyl perylenedicarboxylate, and materials with hexaphenylsilole and tetraphenylethylene groups; The sublimable dispersion matrix is ​​selected from a mixture of one or more of cyclododecane, menthol, menthol lactate, and menthyl succinate.

2. The time-effective fluorescent anti-counterfeiting material according to claim 1, characterized in that The mass concentration of the aggregated color-changing fluorescent material after being dissolved in the solvent is 0.01%-5%, and the mass concentration of the sublimable dispersed matrix after being dissolved in the solvent is 5%-50%.

3. The time-effective fluorescent anti-counterfeiting material according to claim 1, characterized in that The solvent includes a mixture of one or more of ethanol, ethylene glycol, glycerol, propylene glycol acetate, ethyl acetate, and ethyl lactate.

4. The method for preparing a time-effective fluorescent anti-counterfeiting material according to any one of claims 1 to 3, characterized in that The method comprises the following steps: weighing an aggregated color-changing fluorescent material and dissolving the material in a solvent, and then adding a sublimation dispersion matrix to obtain a time-effective fluorescent anti-counterfeiting ink.

5. A time-effective fluorescent anti-counterfeiting ink, characterized by The anti-counterfeiting material is prepared using the time-effective fluorescent anti-counterfeiting material as described in any one of claims 1 to 3.

6. The method for using the time-effective fluorescent anti-counterfeiting ink according to claim 5, characterized in that The following steps are involved: Time-sensitive fluorescent anti-counterfeiting ink is written or printed on the surface of the anti-counterfeiting protection product to form a time-sensitive fluorescent pattern that changes stably over time.

7. The method of use according to claim 6, wherein The writing or printing methods include writing, inkjet printing, offset printing, and the anti-counterfeiting protection products include paper, woven fabrics, textiles and polymer materials.

8. Use of the time-sensitive fluorescent anti-counterfeiting material according to any one of claims 1 to 3 or the time-sensitive fluorescent anti-counterfeiting ink according to claim 5 as an anti-counterfeiting material that stably changes over time in identifying and protecting products.

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