Long-afterglow anti-counterfeiting ink composition and preparation method thereof

Abstract

The invention discloses a long-afterglow anti-forgery ink composition and a preparation method thereof, the long-afterglow anti-forgery ink composition is prepared from long-afterglow luminescent nano powder, thermoplastic compound resin and a resin defoaming agent, the ratio of the long-afterglow luminescent nano powder to the thermoplastic compound resin is 1: (5-10), and the addition amount of the resin defoaming agent is 0.002-0.2% of that of the thermoplastic compound resin. According to the invention, the manufacturing is simple, the anti-counterfeiting discrimination is easy, the encrypted information capacity is expanded, the innovative and environment-friendly tunable multi-encryption mode is invented, the multi-information encryption anti-counterfeiting application is realized by regulating and controlling the luminescence performance of the long-afterglow luminescent nano-powder, and the anti-counterfeiting effect of avoiding the interference of fluorescence on the anti-counterfeiting application is realized. The expansion of the anti-counterfeiting encryption form has profound research significance and wide application prospect.

Description

Technical Field

[0001] The invention belongs to the technical field of anti-counterfeiting inks, and in particular relates to a long afterglow anti-counterfeiting ink composition and a preparation method thereof. Background Art

[0002] In recent years, with the proliferation of fake banknotes, fake certificates, and fake goods, anti-counterfeiting has gradually become an important and independently developed industry. Companies specializing in anti-counterfeiting technology development and the production and service of security and anti-counterfeiting products have emerged, applying a large number of high-tech technologies and achievements to anti-counterfeiting practice. The existing anti-counterfeiting encryption technology has the defects of single encryption method, limited storage capacity, low security, poor photochemical stability of anti-counterfeiting optical materials, high synthesis conditions, heavy atom pollution, environmental pollution, and high cost of rare earth metals. Summary of the invention

[0003] The present invention aims to overcome the defects of the prior art and provide a long afterglow anti-counterfeiting ink composition.

[0004] Another object of the present invention is to provide a method for preparing the long afterglow anti-counterfeiting ink composition.

[0005] The technical solution of the present invention is as follows:

[0006] A long afterglow anti-counterfeiting ink composition is prepared from long afterglow luminescent nano powder, thermoplastic compound resin and resin defoamer, wherein the ratio of the long afterglow luminescent nano powder to the thermoplastic compound resin is 1:5-10, and the amount of the resin defoamer added is 0.002-0.2% of the thermoplastic compound resin;

[0007] The excitation light of the long afterglow luminescent nanopowder is ultraviolet light, with an emission wavelength of 510-600nm, and has a long afterglow of yellow-green or orange-red;

[0008] The thermoplastic compound resin has a solid content of 38-42% and a softening point of 85-95°C, and is compounded from at least two of polyester resin, aldehyde-ketone resin, epoxy resin, petroleum resin, acrylic resin, chlorinated polypropylene resin, polyurethane resin, rosin resin and polyamide resin.

[0009] In a preferred embodiment of the present invention, the thermoplastic composite resin is composited from acrylic resin, polychlorinated resin and polyurethane resin.

[0010] More preferably, the resin defoamer is an acrylic resin defoamer.

[0011] More preferably, the ratio of the acrylic resin, the polychlorinated resin and the polyurethane resin is 2:4:4.

[0012] In a preferred embodiment of the present invention, the method for preparing the long afterglow luminescent nanopowder comprises:

[0013] A. tetraethylenepentamine, phosphoric acid and water are mixed, subjected to microwave reaction, water is added, centrifuged and filtered to obtain a carbon dot filtrate;

[0014] B. Add ammonia water and ethyl orthosilicate to the above carbon dot filtrate, and stir the mixture at 60-65℃ for 5-7h to obtain the afterglow luminescent nanopowder.

[0015] Further preferably, the molar ratio of tetraethylenepentamine to phosphoric acid is 1:2.

[0016] Further preferably, the volume ratio of the carbon dot filtrate, ammonia water and tetraethyl orthosilicate is 1.8:0.4:2.0, the concentration of ammonia water is 25%, and the density of tetraethyl orthosilicate is 0.932 g / mL.

[0017] More preferably, the step B comprises: adding ammonia water, ethyl orthosilicate and rhodamine B to the carbon dot filtrate, and performing hydrothermal stirring reaction at 60-65° C. for 5-7 hours to obtain the long afterglow luminescent nanopowder.

[0018] Still further preferably, the final concentration of Rhodamine B is 0.018 mol / L.

[0019] The preparation method of the long afterglow anti-counterfeiting ink composition comprises: uniformly mixing the long afterglow luminescent nano powder, thermoplastic compound resin and resin defoaming agent.

[0020] The beneficial effects of the present invention are:

[0021] 1. The invention is simple to make and easy to identify for anti-counterfeiting, expands the capacity of encrypted information, is innovative and environmentally friendly, and invents a tunable multiple encryption method. By regulating the luminescence properties of long afterglow luminescent nanopowders, multiple information encryption anti-counterfeiting applications are realized. It has profound research significance and broad application prospects for avoiding the interference of fluorescence on anti-counterfeiting applications and expanding anti-counterfeiting encryption forms.

[0022] 2. The long afterglow luminescent nanopowder of the present invention can replace traditional luminescent materials, reduce costs, be simple to prepare, and be green and environmentally friendly. It integrates long afterglow, multi-color luminescence and stimulating luminescence, and is expected to develop into a new generation of environmentally friendly multi-dynamic anti-counterfeiting, high-capacity and high-resolution, environmentally friendly optical anti-counterfeiting materials.

[0023] 3. The long afterglow luminescent nanopowder of the present invention can be used in the ink composition to realize reusable and tunable dynamic anti-counterfeiting application; the dual color can enhance the visual anti-counterfeiting effect; and the ultraviolet light source can be used to excite the anti-counterfeiting identification, so as to meet the requirements of concealment, portability and ease of use. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 (a) is a digital photo of two different colors of long afterglow luminescent nano powders and their long afterglow anti-counterfeiting ink compositions prepared in Examples 1 and 2 of the present invention.

[0025] Figure 2 The excitation spectrum and emission spectrum of the long afterglow anti-counterfeiting ink compositions A and B prepared in Examples 1 and 2 in Example 3 of the present invention are shown.

[0026] Figure 3 This is the anti-solvent interference graph of the long afterglow anti-counterfeiting ink compositions A and B prepared in Examples 1 and 2 in Example 4 of the present invention after being coated and dried and a solvent is added.

[0027] Figure 4 This is a graph showing the anti-photobleaching and light stability of the long afterglow anti-counterfeiting ink compositions A and B prepared in Examples 1 and 2 in Example 6 of the present invention.

[0028] Figure 5 This is a digital photo of the afterglow of the long afterglow anti-counterfeiting ink compositions A and B prepared in Examples 1 and 2 in Example 7 of the present invention, which are dripped on different printing substrates under the fluorescent lamp, the ultraviolet lamp, and afterglow after the ultraviolet lamp is turned off. DETAILED DESCRIPTION

[0029] The technical solution of the present invention is further illustrated and described below through specific implementation modes in combination with the accompanying drawings.

[0030] Example 1: Preparation of long afterglow anti-counterfeiting ink composition A

[0031] (1) Preparation of long afterglow luminescent nanopowder A:

[0032] A. Add a mixture of tetraethylenepentamine, phosphoric acid and water into a reaction vessel, react with microwaves for 130 seconds, add 25 mL of water, centrifuge and filter to obtain a carbon dot filtrate; wherein the molar ratio of tetraethylenepentamine to phosphoric acid is 1:2;

[0033] B. Take 1.8 mL of the carbon dot filtrate, add 0.4 mL of ammonia water (mass percentage concentration is 25%) and 2 mL of tetraethyl orthosilicate (density is 0.932 g / mL), and heat at 65° C. with stirring for 6 h to obtain long afterglow luminescent nanopowder A (excitation wavelength is 360 nm, emission wavelength is 510 nm); the long afterglow luminescent nanopowder A is white powder under fluorescent light, and exhibits blue fluorescence under ultraviolet light radiation. After turning off the ultraviolet light, it emits a yellow-green long afterglow for several seconds (such as Figure 1 shown).

[0034] (2) Preparation of thermoplastic composite resin: acrylic resin B811, polyvinyl chloride resin e22 / 48a and polyurethane resin fym321 in a ratio of 2:4:4 are softened at 80-130°C to prepare a thermoplastic composite resin with a solid content of 40% and a softening point of 90°C;

[0035] (3) Preparation of long afterglow anti-counterfeiting ink composition A: Mix the above-mentioned long afterglow luminescent nanopowder A, thermoplastic composite resin and acrylic resin defoaming agent, and shake them evenly with an oscillator to prepare the composition; wherein the ratio of long afterglow luminescent nanopowder A to thermoplastic composite resin is 1:8, and the amount of acrylic resin defoaming agent added is 0.005% of the thermoplastic composite resin.

[0036] A two-dimensional code was designed and printed using the long afterglow anti-counterfeiting ink composition A.

[0037] Example 2: Preparation of long afterglow anti-counterfeiting ink composition B

[0038] (1) Preparation of long afterglow luminescent nanopowder B:

[0039] A. Add a mixture of tetraethylenepentamine, phosphoric acid and water into a reaction vessel, react with microwaves for 130 seconds, add 25 mL of water, centrifuge and filter to obtain a carbon dot filtrate; wherein the molar ratio of tetraethylenepentamine to phosphoric acid is 1:2;

[0040] B. Take 1.8 mL of the carbon dot filtrate, add 0.4 mL of ammonia water (mass percentage concentration is 25%), 2 mL of tetraethyl orthosilicate (density is 0.932 g / mL) and rhodamine with a final concentration of 0.018 mol / L, and heat at 65°C with stirring for 6 hours to obtain a long afterglow luminescent nanopowder B (excitation wavelength is 360 nm, emission wavelength is 600 nm); the long afterglow luminescent nanopowder B is a red powder under a fluorescent lamp, and exhibits orange-red fluorescence under ultraviolet lamp radiation. After turning off the ultraviolet lamp, it emits an orange-red long afterglow for several seconds (such as Figure 1 shown).

[0041] (2) Preparation of thermoplastic composite resin: acrylic resin B811, polyvinyl chloride resin e22 / 48a and polyurethane resin fym321 in a ratio of 2:4:4 are softened at 80-130°C to prepare a thermoplastic composite resin with a solid content of 40% and a softening point of 90°C;

[0042] (3) Preparation of long afterglow anti-counterfeiting ink composition B: Mix the above-mentioned long afterglow luminescent nanopowder B, thermoplastic composite resin and acrylic resin defoaming agent, and shake them evenly with an oscillator to prepare the composition; wherein the ratio of long afterglow luminescent nanopowder B to thermoplastic composite resin is 1:8, and the amount of acrylic resin defoaming agent added is 0.005% of the thermoplastic composite resin.

[0043] A two-dimensional code was designed and printed using the long afterglow anti-counterfeiting ink composition B.

[0044] Example 3: Optical properties of long afterglow anti-counterfeiting ink composition

[0045] This example optimizes and characterizes the optical properties of the long afterglow anti-counterfeiting ink compositions A and B prepared in Examples 1 and 2. Figure 2 As shown, the afterglow spectrum of the long afterglow anti-counterfeiting ink compositions A and B of different colors is characterized, and the excitation wavelength is preferably 360nm; the emission band is preferably 370nm-650nm; the scanning speed is preferably 240nm / min; the excitation slit is preferably 10nm:10nm compared to the emission slit; the response time is preferably 2s; the extension time is preferably 0s; and the PMT voltage is preferably 700V. The characterization results show that the best optical response excitation wavelength corresponding to the two long afterglow anti-counterfeiting ink compositions A and B is 360nm, and the optical response emission wavelengths are 510nm and 600nm, respectively, corresponding to green and orange-red, respectively.

[0046] Example 4: Long afterglow anti-counterfeiting ink resists solvent interference

[0047] Long afterglow anti-counterfeiting ink compositions will encounter various solvent interferences in actual anti-counterfeiting applications. If the performance of the long afterglow anti-counterfeiting ink compositions is affected, the application will be affected. In this embodiment, the long afterglow anti-counterfeiting ink compositions A and B prepared in Example 1 and Example 2 are transferred to label paper, and solutions including water (H2O), salt (1.7M NaCl), strong base (1.0M NaOH), strong acid (30wt.% HNO3, 98wt.% H2SO4, 30wt.% HCl), strong oxidizing (30wt.% H2O2), and organic polar solvents (absolute ethanol EtOH; methanol MeOH; N,N-dimethylformamide DMF; acetonitrile ACN; chloroform CHCl3) are added dropwise to the surface of the label paper, and the fluorescence (365nm ultraviolet light irradiation) and phosphorescence (turn off the ultraviolet light) are observed, and it is found that there is basically no effect, such as Figure 3 As shown, the two long afterglow anti-counterfeiting ink compositions A (green light) and B (red light) prepared in Example 1 and Example 2 have stable luminescence and are not easily weakened by environmental influences, and can be applied to information anti-counterfeiting in actual production and life.

[0048] Example 5: Dynamic encryption of long afterglow anti-counterfeiting ink response to temperature stimulation

[0049] The long afterglow anti-counterfeiting ink composition can achieve optical response to temperature changes. In this embodiment, the long afterglow anti-counterfeiting ink compositions A and B prepared in Embodiments 1 and 2 are heated and cooled by a hair dryer to achieve reversible changes in response to temperature stimulation.

[0050] In this embodiment, after the long afterglow anti-counterfeiting ink compositions A and B prepared in Embodiment 1 and Embodiment 2 were coated, they were heated with hot air from a hair dryer for 10 minutes and then cooled with cold air for 10 minutes, and the cycle was repeated five times, and digital photos of the long afterglow anti-counterfeiting ink compositions after each heating and cooling were recorded. After repeated heating and cooling, the anti-counterfeiting optical properties can still be restored, indicating that the temperature change has no effect on the interference of the application of the long afterglow anti-counterfeiting ink compositions A and B, and the long afterglow anti-counterfeiting ink compositions A and B can achieve dynamic encryption through temperature changes.

[0051] Example 6: Long afterglow anti-counterfeiting ink resists light interference

[0052] This example tests the photobleaching resistance of the long afterglow anti-counterfeiting ink compositions A and B prepared in Example 1 and Example 2: a certain amount of long afterglow luminescent nanopowders A and B are placed in a powder sample tank, and continuously irradiated for 60 minutes under a 360nm xenon lamp light source, and the afterglow spectra of the long afterglow luminescent nanopowders A and B before and after irradiation are measured to explore the effect of ultraviolet light irradiation time on the afterglow intensity, and the long afterglow luminescent nanopowders A and B before and after irradiation are formulated into long afterglow anti-counterfeiting ink compositions A and B, which are transferred into a QR code. The experimental results are shown in Figure 1. Figure 4 As shown in (a) and (b), long-term continuous illumination does not affect the optical properties of the material, and the optical properties of the long afterglow anti-counterfeiting ink compositions A and B are stable.

[0053] The photostability of the long afterglow anti-counterfeiting ink compositions A and B was tested: a certain amount of long afterglow luminescent nanopowders A and B were taken, and the afterglow spectra were measured at the optimal excitation wavelength of 360nm. Figure 4 The long afterglow anti-counterfeiting ink compositions A and B were cycled 30 times within 5 days, and the change of afterglow luminescence intensity each time under 360nm excitation is shown in Figure 4(a) and 4(b). Figure 4 The experimental results show that repeated light stimulation does not affect the optical properties of the material, and the long afterglow anti-counterfeiting ink compositions A and B can be reused.

[0054] Example 6: Optical response of long afterglow anti-counterfeiting ink on different printed substrates

[0055] The long afterglow anti-counterfeiting ink compositions A and B prepared in Example 1 and Example 2 were dripped onto different printing substrates: paper substrate, metal substrate such as tin foil, polymer such as plastic, inorganic silicate substrate such as glass, and the digital photos taken with fluorescent lamp, ultraviolet lamp and after the ultraviolet lamp was turned off were as follows: Figure 5 As shown, it is shown that the long afterglow anti-counterfeiting ink compositions A and B prepared in Example 1 and Example 2 can be applied on different printing substrates. On printing substrates with fluorescent reactions, fluorescence interference can be avoided to achieve multiple encryption, meeting various printing requirements.

[0056] The above description is only a preferred embodiment of the present invention, and therefore cannot be used to limit the scope of the present invention. That is, equivalent changes and modifications made according to the patent scope of the present invention and the contents of the specification should still fall within the scope of the present invention.

Claims

1. A long afterglow anti-counterfeiting ink composition, characterized in that: It is prepared from long afterglow luminescent nano powder, thermoplastic compound resin and resin defoamer, the ratio of long afterglow luminescent nano powder to thermoplastic compound resin is 1:5-10, and the amount of resin defoamer added is 0.002-0.2% of the thermoplastic compound resin; The excitation light of the long afterglow luminescent nanopowder is ultraviolet light, with an emission wavelength of 510-600nm, and has a long afterglow of yellow-green or orange-red; The thermoplastic compound resin has a solid content of 38-42% and a softening point of 85-95°C, and is compounded from at least two of polyester resin, aldehyde-ketone resin, epoxy resin, petroleum resin, acrylic resin, chlorinated polypropylene resin, polyurethane resin, rosin resin and polyamide resin.

2. The long afterglow anti-counterfeiting ink composition according to claim 1, characterized in that: The thermoplastic compound resin is compounded from acrylic resin, polychlorinated resin and polyurethane resin.

3. A long afterglow anti-counterfeiting ink composition as claimed in claim 2, characterized in that: The resin defoamer is an acrylic resin defoamer.

4. The long afterglow anti-counterfeiting ink composition according to claim 3, characterized in that: The mixing ratio of the acrylic resin, the polychlorinated resin and the polyurethane resin is 2:4:

4.

5. A long afterglow anti-counterfeiting ink composition according to any one of claims 1 to 4, characterized in that: The preparation method of the long afterglow luminescent nano powder comprises: A. tetraethylenepentamine, phosphoric acid and water are mixed, subjected to microwave reaction, water is added, centrifuged and filtered to obtain a carbon dot filtrate; B. Add ammonia water and ethyl orthosilicate to the above carbon dot filtrate, and stir the mixture at 60-65℃ for 5-7h to obtain the afterglow luminescent nanopowder.

6. The long afterglow anti-counterfeiting ink composition according to claim 5, characterized in that: The molar ratio of tetraethylenepentamine to phosphoric acid is 1:

2.

7. The long afterglow anti-counterfeiting ink composition according to claim 5, characterized in that: The volume ratio of the carbon dot filtrate, ammonia water and tetraethyl orthosilicate is 1.8:0.4:2.0, the concentration of ammonia water is 25%, and the density of tetraethyl orthosilicate is 0.932 g / mL.

8. The long afterglow anti-counterfeiting ink composition according to claim 7, characterized in that: The step B comprises: adding ammonia water, ethyl orthosilicate and rhodamine B to the carbon dot filtrate, and performing hydrothermal stirring reaction at 60-65° C. for 5-7 hours to obtain the long afterglow luminescent nano powder.

9. The long afterglow anti-counterfeiting ink composition according to claim 8, characterized in that: The final concentration of the rhodamine B is 0.018 mol / L.

10. A method for preparing a long afterglow anti-counterfeiting ink composition according to any one of claims 1 to 9, wherein Features include: The long afterglow luminescent nano powder, thermoplastic compound resin and resin defoamer are mixed evenly. Serve.

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