Vegetable oil-based photocuring 3D printing resin with temperature response and / or fluorescence and / or phosphorescence performance as well as preparation method and application of vegetable oil-based photocuring 3D printing resin

Abstract

The invention belongs to the technical field of anti-counterfeiting and information encryption, and particularly discloses plant oil-based light-cured 3D printing resin with temperature response and / or fluorescence and / or phosphorescence performance as well as a preparation method and application of the plant oil-based light-cured 3D printing resin. A ring-opening reaction, an esterification reaction and an etherification reaction are adopted to introduce an unsaturated bond and a fluorescent / phosphorescent chromophore into a vegetable oil chain, and the unsaturated bond can be subjected to free radical polymerization and can also be subjected to a sulfydryl-alkene click reaction, so that environmental pollution and irritant harm to a human body caused by a traditional acrylic monomer are avoided; and meanwhile, the thiol-ene click reaction also reduces the shrinkage rate and the oxygen inhibition influence of photocuring 3D printing, and the printing precision is improved. Through photocuring 3D printing, a luminescent device with temperature response, fluorescence and phosphorescence properties is rapidly prepared, and the luminescent device can be used for anti-counterfeiting and information encryption labels.

Description

Technical Field

[0001] This invention relates to the field of anti-counterfeiting and information encryption technology, and in particular to a plant oil-based photocurable 3D printing resin with temperature response and / or fluorescence and / or phosphorescence properties, its preparation method and application. Background Technology

[0002] Information security has always been a core issue throughout human societal development, and its importance is increasingly prominent in today's deeply digitalized world. After years of development, anti-counterfeiting technology has been deeply integrated into numerous fields such as finance, healthcare, government affairs, and consumer goods, becoming a fundamental support for safeguarding information authenticity and ensuring the orderly operation of various industries. However, with the rapid iteration of modern information extraction, decryption, and forgery technologies, traditional single-layer defense, low-level technology, and limited information capacity anti-counterfeiting models are gradually becoming insufficient to cope with increasingly complex information security challenges, and their limitations are becoming increasingly apparent in practical applications. Therefore, developing multi-layered and multi-level anti-counterfeiting technologies with higher protection levels and more comprehensive information capacity has become an inevitable choice to address current information security challenges, with particularly prominent practical significance and strategic value.

[0003] However, traditional anti-counterfeiting methods based on responsive color-changing mechanisms have significant limitations: on the one hand, their anti-counterfeiting level and information carrying accuracy are low, making it difficult to meet the high security requirements in complex scenarios; on the other hand, most products require specific testing equipment for verification, and some systems suffer from low signal response sensitivity, while information storage capacity is limited. These shortcomings collectively restrict their convenience and applicability in practical scenarios. Photopolymerization 3D printing technology, as an advanced manufacturing technology that achieves three-dimensional molding through light-induced polymerization reactions, provides a new approach to solving these problems. Among them, g-DLP (g-light processing 3D printing) technology exhibits significant advantages: this technology can pre-design and control the three-dimensional molding process through precise control of exposure parameters, printing layer thickness and number of layers, and digital model editing. It not only possesses the core characteristics of high-precision molding, multi-level structural control, and rapid fabrication, but also achieves high-density information storage and high-level anti-counterfeiting by constructing complex three-dimensional devices. This characteristic precisely compensates for the shortcomings of traditional responsive color-changing anti-counterfeiting technologies, such as "low level, low accuracy, limited information, and reliance on special conditions," and has become one of the feasible strategies for achieving high anti-counterfeiting levels through device structural design.

[0004] Therefore, developing a simple and rapid method to prepare plant oil-based photocurable 3D printing resins with temperature response and / or fluorescence and / or phosphorescence properties, and constructing multi-mode anti-counterfeiting and information encryption labels with adjustable shape and structure through photocurable 3D printing technology, has potential application value in the field of constructing multi-layered, high-security 3D printing anti-counterfeiting and information encryption systems. Summary of the Invention

[0005] To address the aforementioned technical problems, this invention provides a plant oil-based photocurable 3D printing resin with temperature response and / or fluorescence and / or phosphorescence properties, its preparation method, and its applications.

[0006] To achieve the above objectives, the present invention is implemented according to the following technical solution: The first technical solution provided by this invention is a method for preparing a vegetable oil-based photocurable 3D printing resin with temperature response and / or fluorescence and / or phosphorescence properties, comprising the following steps: S1. Synthesis of unsaturated monomers: By utilizing the nucleophilic addition-elimination reaction of (meth)acrylate monomers containing hydroxyl groups with 5-norbornene-2,3-dicarboxylic anhydride, an unsaturated carboxylic acid monomer with two active C=C double bonds, hydroxy methacrylate phthalic acid monoester, is synthesized. Specifically, the following molar ratios are used: (50-100):(50-100):(5-10):1. A hydroxyl-containing (meth)acrylate monomer, 5-norbornene-2,3-dicarboxylic anhydride, triphenylphosphine catalyst, and p-methoxyphenol are added to a three-necked round-bottom flask. The flask is then heated and stirred in a 70°C oil bath until the 5-norbornene-2,3-dicarboxylic anhydride, triphenylphosphine catalyst, and p-methoxyphenol are completely dissolved. The mixture is then heated to 95°C and reacted for 5 hours. The resulting product is stored in a 4°C refrigerator to obtain a white solid product, which is the unsaturated monomer HMANA. S2. Synthesis of epoxy vegetable oil-based photocurable oligomers: Take epoxy vegetable oil and the unsaturated monomer HMANA at a molar ratio of 1:(2.5-5), add 0.1%-0.3% of the polymerization inhibitor p-methoxyphenol by molar mass of epoxy vegetable oil, and stir to dissolve at 90℃; then raise the temperature to 110-120℃, add 1%-3% of the catalyst triphenylphosphine by molar mass of epoxy vegetable oil, and continue the reaction until the acid value of the reaction system is stable and unchanged, then terminate the reaction; dissolve the obtained crude product in dichloromethane, wash three times with hot 10wt% NaCl aqueous solution; after drying, remove dichloromethane by rotary evaporation, and finally obtain a light yellow viscous liquid resin, which is the epoxy vegetable oil-based photocurable oligomer; S3. Synthesis of fluorescent / phosphorescent modified photocurable oligomers: The epoxy vegetable oil-based photocurable oligomer, fluorescent / phosphorescent small molecules, dicyclohexylcarbodiimide solution, and 4-dimethylaminopyridine are taken in a molar ratio of (10-30):(30-100):(5-10):1. More preferably, the molar ratio of the epoxy vegetable oil-based photocurable oligomer, fluorescent / phosphorescent small molecules, dicyclohexylcarbodiimide solution, and 4-dimethylaminopyridine is (10-15):(30-45):(5-6):1. Dissolved in anhydrous dichloromethane, under a nitrogen atmosphere, stirred in an ice-water bath at 0-10℃ for 30 min, then dicyclohexylcarbodiimide solution was added dropwise over 30-60 min. After the addition was complete, the reaction was continued at room temperature for 48 h. Then, dichloromethane was added for dilution and the mixture was filtered. The dichloromethane was removed by rotary evaporation of the filtered solution. The precipitate was then washed in sodium bicarbonate solution and dissolved in dichloromethane. This process was repeated 3 times. Finally, the mixture was dried in a vacuum drying oven to constant weight to obtain the fluorescent / phosphorescent modified photocurable oligomer. S4. Take epoxy plant oil-based photocurable oligomer, reactive diluent, thiol functional monomer, thermochromic powder, and photoinitiator in a mass ratio of (30-60):(20-40):(20-40):(1-5):(1-6). Mix the epoxy plant oil-based photocurable oligomer, photoinitiator, reactive diluent, and thiol functional monomer evenly, and then add the thermochromic powder to obtain a plant oil-based photocurable 3D printing resin with temperature response. Alternatively, take fluorescent / phosphorescent modified photocurable oligomers, reactive diluents, thiol functional monomers, and photoinitiators in a mass ratio of (30-60):(20-40):(20-40):(1-6), mix them evenly, and obtain a plant oil-based photocurable 3D printing resin with fluorescent properties or a plant oil-based photocurable 3D printing resin with phosphorescent properties.

[0007] Further, the hydroxyl-containing (meth)acrylate monomer is one or more combinations of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, and hydroxypropyl methacrylate. More preferably, the hydroxyl-containing (meth)acrylate monomer is one or both of hydroxyethyl acrylate and hydroxypropyl methacrylate.

[0008] Further, the epoxidized vegetable oil is one or more of epoxidized soybean oil, epoxidized palm oil, epoxidized cottonseed oil, epoxidized rice bran oil, and epoxidized sunflower oil. More preferably, the epoxidized vegetable oil is one or two of epoxidized soybean oil and epoxidized palm oil.

[0009] Furthermore, the fluorescent / phosphorescent small molecule is an aggregation-induced emission fluorescent small molecule or a phosphorescent small molecule; the aggregation-induced emission fluorescent small molecule is a tetraphenylethylene derivative (TPE), and its structural formula is as follows: ; Wherein: group R is one of carboxyl, hydroxyl, hydroxymethyl, carboxymethyl, bromine, aldehyde; more preferably, the aggregation-induced emission fluorescent molecule is one or two of 1,1,2,2-tetra-(4-hydroxyphenyl)ethylene TPE-OH and 4-(1,2,2-triphenylvinyl)benzoic acid TPE-COOH; The phosphorescent small molecule is one or more combinations of aniline-2,5-disulfonic acid, 1,4,5,8-naphthalenetetracarboxylic anhydride, 4-bromo-1,8-naphthalenedicarboxylic anhydride, 4-bromo-N-butyric acid-1,8-naphthalimide, and 1-pyrenecarboxylic acid; more preferably, the phosphorescent small molecule is one or more of aniline-2,5-disulfonic acid, 4-bromo-N-butyric acid-1,8-naphthalimide, and 1-pyrenecarboxylic acid.

[0010] Furthermore, the temperature change range of the thermochromic powder is 30-90℃. More preferably, the temperature change range of the thermochromic powder is 30-60℃.

[0011] Further, the photoinitiator is one or more combinations of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexylphenyl ketone, ethyl 2,4,6-trimethylbenzoylphenylphosphonate, 2-dimethylamino-2-benzyl-1-[4-(4-morpholinyl)phenyl]-1-butanone, 2-methyl-2-(4-morpholinyl)-1-[4-(methylthio)phenyl]-1-propanone, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone, thiopropoxythionone, and methyl benzoylcarbamate. More preferably, the photoinitiator is one or more of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2-hydroxy-2-methyl-1-phenylpropanone, and ethyl 2,4,6-trimethylbenzoylphenylphosphonate.

[0012] Further, the reactive diluent is one or more combinations of trimethylolpropane triacrylate, 1,6-hexanediol diacrylate, polyethylene glycol diacrylate, pentaerythritol triacrylate, neopentyl glycol diacrylate, and tripropylene glycol diacrylate. More preferably, the reactive diluent is one or more of trimethylolpropane triacrylate, polyethylene glycol diacrylate, and neopentyl glycol diacrylate.

[0013] Further, the thiol functional monomer is one or both of pentaerythritol tetra(3-mercaptopropionate) and trimethylolpropane tri(3-mercaptopropionate). More preferably, the thiol functional monomer is pentaerythritol tetra(3-mercaptopropionate).

[0014] The second technical solution provided by the present invention is a plant oil-based photocurable 3D printing resin with temperature response and / or fluorescence and / or phosphorescence properties prepared by the above method.

[0015] The third technical solution provided by this invention is the application of a plant oil-based photocurable 3D printing resin with temperature-responsive and / or fluorescent and / or phosphorescent properties in the preparation of anti-counterfeiting and information encryption materials with temperature-responsive and / or fluorescent and / or phosphorescent properties. The specific steps are as follows: A plant-oil-based photocurable 3D printing resin with fluorescent properties, a plant-oil-based photocurable 3D printing resin with phosphorescent properties, or a plant-oil-based photocurable 3D printing resin with temperature response is injected into the resin tank of an LCD photocurable printer. The printing parameters are set as follows: layer thickness 0.02 mm, number of bottom layers 10, bottom layer exposure time 50 seconds, normal layer exposure time 6-15 seconds. The LCD additive manufacturing process is then performed to obtain anti-counterfeiting and information encryption devices with fluorescent properties, phosphorescent properties, or temperature response. Alternatively, a "multi-layer ink-changing-layer thickness control" strategy can be used to 3D print using prepared plant oil-based photocurable 3D printing resins with fluorescent, phosphorescent, and temperature-responsive properties. When the printing process progresses to a specific number of layers, information storage and encryption based on different printing layers can be achieved by switching functional inks. The printing parameters are set as follows: layer thickness 0.02 mm, bottom layer number 10 layers, bottom layer exposure time 50 seconds, normal layer exposure time 6-15 seconds, and LCD additive manufacturing process is executed to obtain a multi-layer 3D printed anti-counterfeiting and information encryption device with temperature-fluorescence-phosphorescence properties.

[0016] Compared with the prior art, the present invention has the following beneficial effects: (1) This invention uses biomass-based epoxidized vegetable oil as raw material and introduces unsaturated bonds and fluorescent / phosphorescent chromophores into the vegetable oil chain through ring-opening, esterification, and etherification reactions. Employing a "multi-layer ink-changing-layer-thickness control" photopolymerization 3D printing strategy, light-emitting devices with temperature response, fluorescence, and phosphorescence properties are prepared in one step and rapidly. This preparation method is simple, the raw materials are biodegradable, and temperature-fluorescence-phosphorescence devices with different structures and shapes can be constructed through photopolymerization 3D printing for anti-counterfeiting and information encryption, realizing a rapid, green, and environmentally friendly new preparation method.

[0017] (2) The unsaturated bonds introduced in the epoxy plant oil chain in this invention can undergo both free radical polymerization and mercapto-ene click reaction, avoiding the environmental pollution and irritation to the human body caused by traditional acrylic monomers, which is in line with the concept of green and sustainable development. At the same time, the double bonds in the ring in its molecular structure can only participate in mercapto-ene click reaction, which reduces the shrinkage rate and oxygen inhibition effect of photopolymerization 3D printing and improves the printing accuracy.

[0018] (3) The present invention utilizes a plant oil-based anti-counterfeiting and information encryption device with temperature response, fluorescence and phosphorescence properties. The fluorescence and phosphorescence information can be controlled by turning ultraviolet light on and off. At the same time, the information can be reversibly erased by causing the color change of the thermochromic powder through temperature control. Utilizing this characteristic in the field of multi-level dynamic anti-counterfeiting and information encryption can greatly increase the difficulty of counterfeiting. Attached Figure Description

[0019] Figure 1 The image shows the effect of the anti-counterfeiting and information encryption device with fluorescent properties obtained in Example 1.

[0020] Figure 2 This is a rendering of the anti-counterfeiting and information encryption device with phosphorescent properties obtained in Example 2.

[0021] Figure 3 This is a rendering of the anti-counterfeiting and information encryption device with temperature response obtained in Example 3.

[0022] Figure 4 This is an illustration of the effect of the 4D encryption pattern arrangement and decoding process of the multilayer 3D printed anti-counterfeiting and information encryption device with temperature-fluorescence-phosphorescence properties obtained in Example 4. Detailed Implementation

[0023] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to embodiments. The specific embodiments described herein are for illustrative purposes only and are not intended to limit the invention.

[0024] Example 1: Preparation of anti-counterfeiting and information encryption devices with fluorescent properties 1) In a 500 mL round-bottom flask, add hydroxyethyl methacrylate (HEMA) (52.06 g, 0.4 mol), 5-norbornene-2,3-dicarboxylic anhydride (NA) (65.66 g, 0.4 mol), triphenylphosphine catalyst (TPP) (13.12 g, 0.05 mol), and p-methoxyphenol (MEHQ) (0.62 g, 0.005 mol). Place the flask in a 70 °C oil bath and stir continuously until the 5-norbornene-2,3-dicarboxylic anhydride is completely dissolved. Then, raise the reaction temperature to 95 °C and continue the reaction for 5 hours. The resulting product is then stored in a refrigerator at 4 °C to obtain a white solid product, HEMANA. Epoxidized soybean oil (ESO) (100 g, 0.105 mol), unsaturated monomer HEMANA (98.84 g, 0.334 mol), and polymerization inhibitor p-methoxyphenol (MEHQ) (0.013 g, 0.105 mmol) were added to a three-necked flask and stirred to dissolve. The temperature was then raised to 110°C, and triphenylphosphine (TPP) catalyst (0.83 g, 3.15 mmol) was added. The reaction continued until the acid value stabilized, at which point the reaction was terminated. The resulting crude ESO-HEMANA product was dissolved in dichloromethane and washed three times with hot 10 wt% NaCl aqueous solution. The resulting organic phase was dried over anhydrous Na₂SO₄, and the dichloromethane solvent was removed by rotary evaporation, finally yielding a light yellow viscous liquid resin, which is the epoxidized soybean oil-based photocurable oligomer. The reaction formula is shown below: ; 2) In a 500mL round-bottom flask, take 100g of epoxidized soybean oil-based photocurable oligomer ESO-HEMANA, 7.5g of aggregation-induced emission small molecule 4-(1,2,2-triphenylvinyl)benzoic acid TPE-COOH (7.5g, 0.02mol), and 0.122g of 4-dimethylaminopyridine (0.001mol), dissolve them in 200mL of anhydrous dichloromethane, and stir for 30 minutes at 0-10℃ in an ice-water bath under a nitrogen atmosphere. After n, a dicyclohexylcarbodiimide solution (2.06 g, 0.01 mol, dissolved in 50 mL of anhydrous dichloromethane) was added dropwise over 30 min. After the addition was completed, the reaction was continued at room temperature for 48 h. Then, dichloromethane was added to dilute the solution and the mixture was filtered. The dichloromethane was removed by rotary evaporation of the filtered solution. The solution was then added to sodium bicarbonate solution to precipitate and wash the precipitate. The precipitate was then dissolved in dichloromethane. This process was repeated 3 times. Finally, the solution was dried in a vacuum drying oven to constant weight to obtain the fluorescent modified photocurable oligomer.

[0025] 3) In a 1000mL beaker, add 200g of fluorescently modified photocurable oligomer, 15g of photoinitiator 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (TPO), 150g of reactive diluent trimethylolpropane triacrylate (TMPTA), and 135g of thiol functional monomer pentaerythritol tetra(3-mercaptopropionate) PETMP. Mix mechanically for 30 minutes until homogeneous to obtain a fluorescently responsive UV-curable 3D printing plant oil-based resin formulation. Inject the prepared fluorescently responsive UV-curable 3D printing plant oil-based resin into the resin tank of an LCD photocurable printer. Printing parameters are set as follows: layer thickness 0.02 mm, 10 layers for the bottom layer, bottom layer exposure time 50 seconds, normal layer exposure time 6-15 seconds (gradient optimization). Perform LCD additive manufacturing process to obtain a fluorescent anti-counterfeiting and information encryption device. The effect is shown in the image below. Figure 1 As shown, Figure 1 a is a schematic diagram of the process of 3D printing using photopolymer LCD; Figure 1 b shows photos of various precision 3D structural devices printed by photopolymer LCD 3D printing. The patterns under 365nm ultraviolet light and visible light exhibit obvious photoluminescence characteristics, which can be used for fluorescent anti-counterfeiting. Figure 1 c represents a QR code 3D printed using a photopolymer LCD. It hides information under visible light but emits light and displays the QR code information under ultraviolet light. The hidden information can be further obtained by scanning the QR code with a mobile phone, and it can be used for information encryption.

[0026] Example 2: Preparation of anti-counterfeiting and information encryption devices with phosphorescent properties 1) In a 500 mL round-bottom flask, add hydroxyethyl methacrylate (HEMA) (52.06 g, 0.4 mol), 5-norbornene-2,3-dicarboxylic anhydride (NA) (65.66 g, 0.4 mol), triphenylphosphine catalyst (TPP) (13.12 g, 0.05 mol), and p-methoxyphenol (MEHQ) (0.62 g, 0.005 mol). Place the flask in a 70 °C oil bath and stir continuously until the 5-norbornene-2,3-dicarboxylic anhydride is completely dissolved. Then, raise the reaction temperature to 95 °C and continue the reaction for 5 hours. The resulting product is then stored in a refrigerator at 4 °C to obtain a white solid product, HEMANA. Epoxidized soybean oil (ESO) (100 g, 0.105 mol), unsaturated monomer HEMANA (98.84 g, 0.334 mol), and polymerization inhibitor p-methoxyphenol (MEHQ) (0.013 g, 0.105 mmol) were added to a three-necked flask and stirred to dissolve. The temperature was then raised to 110°C, and triphenylphosphine (TPP) catalyst (0.83 g, 3.15 mmol) was added. The reaction continued until the acid value stabilized, at which point the reaction was terminated. The resulting crude ESO-HEMANA product was dissolved in dichloromethane and washed three times with hot 10 wt% NaCl aqueous solution. The resulting organic phase was dried over anhydrous Na₂SO₄, and the dichloromethane solvent was removed by rotary evaporation, finally yielding a light yellow viscous liquid resin, which is the epoxidized soybean oil-based photocurable oligomer. The reaction formula is shown below: ; 2) In a 500mL round-bottom flask, take 100g of epoxidized soybean oil-based photocurable oligomer ESO-HEMANA and 7.6g of phosphorescent small molecule 4-bromo-N-butyric acid-1,8-naphthalimide BZ-SA. 0.02 mol) and 4-dimethylaminopyridine (0.122 g, 0.001 mol) were dissolved in 200 mL of anhydrous dichloromethane. Under a nitrogen atmosphere, the mixture was stirred in an ice-water bath at 0-10 °C for 30 min. Then, dicyclohexylcarbodiimide solution (2.06 g, 0.01 mol, dissolved in 50 mL of anhydrous dichloromethane) was added dropwise over 30 min. After the addition was completed, the reaction was continued at room temperature for 48 h. Then, dichloromethane was added to dilute the solution and the mixture was filtered. The dichloromethane was removed by rotary evaporation of the filtered solution. The solution was then added to sodium bicarbonate solution to precipitate and wash the precipitate. The precipitate was then dissolved in dichloromethane. This process was repeated 3 times. Finally, the solution was dried in a vacuum drying oven to constant weight to obtain the modified photocurable oligomer.

[0027] 3) In a 1000mL beaker, add 175g of phosphorescently modified photocurable oligomer, 15g of photoinitiator 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (TPO), 200g of reactive diluent trimethylolpropane triacrylate (TMPTA), and 110g of thiol functional monomer pentaerythritol tetra(3-mercaptopropionate) PETMP. Mix mechanically for 30 minutes until homogeneous to obtain a phosphorescently responsive UV-curable 3D printing plant oil-based resin formulation. Inject the prepared phosphorescently responsive UV-curable 3D printing plant oil-based resin into the resin tank of an LCD photocurable printer. Printing parameters are set as follows: layer thickness 0.02 mm, 10 layers for the bottom layer, bottom layer exposure time 50 seconds, normal layer exposure time 6-15 seconds (gradient optimization). Perform LCD additive manufacturing process to obtain a phosphorescent anti-counterfeiting and information encryption device. The resulting image is shown below. Figure 2 As shown, Figure 2 a is a phosphorescent light-emitting device printed by photopolymer LCD 3D. It has good light-emitting characteristics under ultraviolet light. At the same time, it still has phosphorescent light-emitting performance of 1.6s after the ultraviolet light is turned off, and can be used for phosphorescent anti-counterfeiting. Figure 2 b is a photograph of a precision 3D structural device printed by photopolymerization LCD 3D printing. It exhibits obvious photoluminescence characteristics under 365nm ultraviolet light and good phosphorescence characteristics after the ultraviolet light is turned off, which can be used for information encryption.

[0028] Example 3: Fabrication of a temperature-responsive anti-counterfeiting and information encryption device 1) In a 500 mL round-bottom flask, add hydroxyethyl acrylate (HEA) (58.06 g, 0.5 mol), 5-norbornene-2,3-dicarboxylic anhydride (NA) (65.66 g, 0.4 mol), triphenylphosphine catalyst (TPP) (13.12 g, 0.05 mol), and p-methoxyphenol (MEHQ) (0.99 g, 0.008 mol). Place the flask in a 70 °C oil bath and stir continuously until the 5-norbornene-2,3-dicarboxylic anhydride is completely dissolved. Then, raise the reaction temperature to 95 °C and continue the reaction for 5 hours. The resulting product is then stored in a refrigerator at 4 °C to obtain a white solid product, HEANA.

[0029] 2) In a three-necked flask, add epoxidized soybean oil ESO (100 g, 0.105 mol), unsaturated monomer HEANA (93.83 g, 0.334 mol), and polymerization inhibitor p-methoxyphenol MEHQ (0.013 g, 0.105 mmol), and place in an oil bath at 90°C with stirring to dissolve. Then, raise the temperature to 110°C, add the catalyst triphenylphosphine TPP (0.83 g, 3.15 mmol), and continue the reaction until the acid value stabilizes. Dissolve the resulting crude ESO-HEMANA product in dichloromethane and wash three times with hot 10 wt% NaCl aqueous solution. After drying the resulting organic phase with anhydrous Na2SO4, remove the dichloromethane solvent by rotary evaporation, finally obtaining a light yellow viscous liquid resin, which is the epoxidized soybean oil-based photocurable oligomer. The reaction formula is shown below: ; 3) In a 1000mL beaker, add 200g of epoxidized soybean oil-based photocurable oligomer, 15g of photoinitiator 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (TPO), 150g of reactive diluent trimethylolpropane triacrylate (TMPTA), and 135g of thiol functional monomer pentaerythritol tetra(3-mercaptopropionate) PETMP. Mix mechanically for 30 minutes until homogeneous. Add 15g of thermochromic powder (color-changing at 40℃ and 60℃), and stir until homogeneous to obtain a temperature-responsive UV-curable 3D printing plant oil-based resin formulation. Inject the prepared temperature-responsive UV-curable 3D printing plant oil-based resin into the resin tank of an LCD photocurable printer. Printing parameters are set as follows: layer thickness 0.02 mm, 10 layers for the bottom layer, bottom layer exposure time 50 seconds, normal layer exposure time 6-15 seconds (gradient optimization). Perform LCD additive manufacturing process to obtain a temperature-responsive anti-counterfeiting and information encryption device. Its renderings are as follows Figure 3 As shown, Figure 3 a) This describes the color-changing process of a temperature-responsive color-changing device 3D printed using a photopolymer LCD under visible light and infrared thermal imaging systems. The device changes color with different temperatures and can be used as a temperature-responsive anti-counterfeiting device. Figure 3 b is a photograph of a precision 3D structural device printed using photopolymer LCD 3D printing. By adjusting the temperature, the color changes in visible light and infrared thermal imaging systems, exhibiting excellent temperature-sensitive color-changing characteristics, which can be used for information encryption.

[0030] Example 4: Fabrication of a multilayer 3D-printed anti-counterfeiting and information encryption device with temperature-fluorescence-phosphorescence properties 1) In a 500 mL round-bottom flask, add hydroxyethyl methacrylate (HEMA) (52.06 g, 0.4 mol), 5-norbornene-2,3-dicarboxylic anhydride (NA) (65.66 g, 0.4 mol), triphenylphosphine catalyst (TPP) (13.12 g, 0.05 mol), and p-methoxyphenol (MEHQ) (0.62 g, 0.005 mol). Place the flask in a 70 °C oil bath and stir continuously until the 5-norbornene-2,3-dicarboxylic anhydride is completely dissolved. Then, raise the reaction temperature to 95 °C and continue the reaction for 5 hours. The resulting product is then stored in a refrigerator at 4 °C to obtain a white solid product, HEMANA.

[0031] 2) In a three-necked flask, add 100 g (0.105 mol) of epoxidized soybean oil (ESO), 98.84 g (0.334 mol) of unsaturated monomer HEMANA, and 0.013 g (0.105 mmol) of polymerization inhibitor p-methoxyphenol (MEHQ). Place the flask in an oil bath at 90°C and stir to dissolve. Then, raise the temperature to 110°C, add the catalyst triphenylphosphine (TPP) (0.83 g, 3.15 mmol), and continue the reaction until the acid value stabilizes. Dissolve the resulting crude ESO-HEMANA product in dichloromethane and wash three times with hot 10 wt% NaCl aqueous solution. After drying the resulting organic phase with anhydrous Na2SO4, remove the dichloromethane solvent by rotary evaporation, finally obtaining a light yellow viscous liquid resin, which is the epoxidized soybean oil-based photocurable oligomer. The reaction formula is shown below: ; 3) In a 1000mL beaker, add 200g of fluorescent modified photocurable oligomer, 15g of photoinitiator 2,4,6-trimethylbenzoyl-diphenylphosphine oxide TPO, 150g of reactive diluent trimethylolpropane triacrylate TMPTA, and 135g of mercaptofunctional monomer pentaerythritol tetra(3-mercaptopropionate) PETMP. Mix mechanically for 30 minutes until homogeneous to obtain formulation 1 of UV-curable 3D printing plant oil-based resin with fluorescence response.

[0032] In a 1000mL beaker, add phosphorescent modified photocurable oligomer (175g), photoinitiator 2,4,6-trimethylbenzoyl-diphenylphosphine oxide TPO (15g), reactive diluent trimethylolpropane triacrylate TMPTA (200g), and mercaptofunctional monomer pentaerythritol tetra(3-mercaptopropionate) PETMP (110g). Mix mechanically for 30 minutes until homogeneous to obtain phosphorescent-responsive UV-curable 3D printing plant oil-based resin formulation 2.

[0033] In a 1000mL beaker, add 200g of epoxidized soybean oil-based photocurable oligomer, 15g of photoinitiator 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (TPO), 150g of reactive diluent trimethylolpropane triacrylate (TMPTA), and 135g of mercaptofunctional monomer pentaerythritol tetra(3-mercaptopropionate) PETMP. Mix mechanically for 30 minutes until homogeneous. Add 15g of thermochromic powder (color changes at 40℃ and 60℃) and stir until homogeneous to obtain temperature-responsive UV-curable 3D printing plant oil-based resin formulation 3.

[0034] Three prepared photocurable resins (Formula 1, Formula 2, and Formula 3) were used to create a multi-layer 3D-printed anti-counterfeiting device with temperature-fluorescence-phosphorescence properties using a "multi-layer ink-changing-layer-thickness control" strategy. The core design logic depends on the parameter settings during the model customization stage: when the printing process reaches a specific number of layers, switching functional inks allows for information storage and encryption based on different printing layers. The printing parameters were set as follows: layer thickness 0.02 mm, 10 bottom layers, bottom layer exposure time 50 seconds, and normal layer exposure time 6-15 seconds (gradient optimization). LCD additive manufacturing was employed to fabricate a multi-layer 3D-printed anti-counterfeiting and information encryption device with temperature-fluorescence-phosphorescence properties. A multi-channel, multi-level anti-counterfeiting and encryption mechanism for information storage was constructed through coding design, as shown in the following diagram. Figure 4 As shown, multi-layer 3D-printed anti-counterfeiting and information encryption devices with temperature-fluorescence-phosphorescence properties are arranged in a 6×6 array. Figure 4a) The position of each sample in the array forms a one-to-one mapping relationship with the letters at the same coordinates in the codebook (Figure 4b). By extracting the letters corresponding to samples with the same color in the array and combining them into words, the target numbers or symbols can be decoded, ultimately achieving efficient storage of multiple types of information. From the perspective of performance response characteristics (Figure 4c), before UV irradiation and heat treatment, the cured array samples exhibit the intrinsic color of the oil-based material. At this time, the encrypted information is completely hidden and cannot be extracted. Under daytime conditions, after UV irradiation, the fluorescence and phosphorescence properties of the TPE and BZ-SA functional components in the system are effectively excited. The fluorescence information "7" and "3" can be extracted through the corresponding decoding strategy, forming the number combination "73". Subsequently, the samples are heated. Since the thermochromic response temperature of TCPB40 is lower than that of TC-G60, it undergoes a color change first. Therefore, the symbol "-" and the number "4" can be extracted successively, updating the information combination to "-73" and "-734" respectively. In dark environments, the color change of thermochromic materials stems from structural transformations rather than photosensitive responses, thus the relevant information remains hidden. However, in daylight, the long afterglow characteristic of the BZ-SA system, which remains hidden, becomes apparent. A noticeable afterglow is observed within 1.5 seconds after the UV light source is removed, and the information "8" can be extracted through decoding. It is noteworthy that the true target information "8" is hidden within a series of interfering signals and can only be effectively read within the 1.5-second afterglow period following the UV light's shutdown. This invention constructs a multi-layered, multi-dimensional anti-counterfeiting coding mode based on fluorescence, phosphorescence (afterglow), thermochromism, and day / night environmental responses. This mode achieves novel multi-level anti-counterfeiting through multi-channel, multi-dimensional collaborative response, possessing significant advantages such as advanced encryption mechanisms, large information storage capacity, strong anti-imitation capabilities, ease of operation, and low reading requirements, demonstrating broad application prospects in the field of photothermal information storage.

[0035] The technical solutions of the present invention are not limited to the specific embodiments described above. Any technical modifications made in accordance with the technical solutions of the present invention fall within the protection scope of the present invention.

Claims

1. A method for preparing a vegetable oil-based photocurable 3D printing resin with temperature-responsive and / or fluorescent and / or phosphorescent properties, characterized in that, Includes the following steps: S1. Take a (meth)acrylate monomer containing hydroxyl groups, 5-norbornene-2,3-dicarboxylic anhydride, triphenylphosphine catalyst, and p-methoxyphenol in a molar ratio of (50-100):(50-100):(5-10):1 and add them to a three-necked round-bottom flask. Place it in an oil bath at 70°C and heat and stir until 5-norbornene-2,3-dicarboxylic anhydride, triphenylphosphine catalyst, and p-methoxyphenol are completely dissolved. Then, raise the temperature to 95°C and continue the reaction for 5 hours. After that, store the product in a refrigerator at 4°C to obtain a white solid product, which is the unsaturated monomer HMANA. S2. Take epoxy vegetable oil and the unsaturated monomer HMANA at a molar ratio of 1:(2.5-5), add 0.1%-0.3% of the polymerization inhibitor p-methoxyphenol by molar mass of epoxy vegetable oil, and stir to dissolve at 90°C; then raise the temperature to 110-120°C, add 1%-3% of the catalyst triphenylphosphine by molar mass of epoxy vegetable oil, and continue the reaction until the acid value of the reaction system is stable and unchanged, and then terminate the reaction; dissolve the obtained crude product in dichloromethane, wash three times with hot 10wt% NaCl aqueous solution; after drying, remove dichloromethane by rotary evaporation, and finally obtain a light yellow viscous liquid resin, which is the epoxy vegetable oil-based photocurable oligomer; S3. Take the epoxy vegetable oil-based photocurable oligomer, fluorescent / phosphorescent small molecules, dicyclohexylcarbodiimide solution and 4-dimethylaminopyridine in a molar ratio of (10-30):(30-100):(5-10):

1. Dissolve them in anhydrous dichloromethane. Under a nitrogen atmosphere, stir in an ice-water bath at 0-10℃ for 30 min. Then, add dicyclohexylcarbodiimide solution dropwise for 30-60 min. After the addition is complete, continue the reaction at room temperature for 48 h. Then, dichloromethane is added for dilution and filtration. The dichloromethane is removed by rotary evaporation of the filtered solution. Then, the solution is added to sodium bicarbonate solution for precipitation and washing. The solution is then dissolved in dichloromethane. This process is repeated 3 times. Finally, the solution is placed in a vacuum drying oven and dried to constant weight to obtain the fluorescent / phosphorescent modified photocurable oligomer. S4. Take epoxy plant oil-based photocurable oligomer, reactive diluent, thiol functional monomer, thermochromic powder, and photoinitiator in a mass ratio of (30-60):(20-40):(20-40):(1-5):(1-6). Mix the epoxy plant oil-based photocurable oligomer, photoinitiator, reactive diluent, and thiol functional monomer evenly, and then add the thermochromic powder to obtain a plant oil-based photocurable 3D printing resin with temperature response. Alternatively, take fluorescent / phosphorescent modified photocurable oligomers, reactive diluents, thiol functional monomers, and photoinitiators in a mass ratio of (30-60):(20-40):(20-40):(1-6), mix them evenly, and obtain a plant oil-based photocurable 3D printing resin with fluorescent properties or a plant oil-based photocurable 3D printing resin with phosphorescent properties.

2. The method for preparing the vegetable oil-based photocurable 3D printing resin with temperature response and / or fluorescence and / or phosphorescence properties according to claim 1, characterized in that: The hydroxyl-containing (meth)acrylate monomers are one or more combinations of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, and hydroxypropyl methacrylate.

3. The method for preparing the vegetable oil-based photocurable 3D printing resin with temperature response and / or fluorescence and / or phosphorescence properties according to claim 1, characterized in that: The epoxidized vegetable oil is one or more of the following: epoxidized soybean oil, epoxidized palm oil, epoxidized cottonseed oil, epoxidized rice bran oil, and epoxidized sunflower oil.

4. The method for preparing the vegetable oil-based photocurable 3D printing resin with temperature response and / or fluorescence and / or phosphorescence properties according to claim 1, characterized in that: The fluorescent / phosphorescent small molecule is an aggregation-induced emission fluorescent small molecule or a phosphorescent small molecule; the aggregation-induced emission fluorescent molecule is a tetraphenylethylene derivative (TPE), and its structural formula is as follows: ； Wherein: group R is one of carboxyl, hydroxyl, hydroxymethyl, carboxymethyl, bromine, or aldehyde; The phosphorescent small molecule is one or more combinations of aniline-2,5-disulfonic acid, 1,4,5,8-naphthalenetetracarboxylic anhydride, 4-bromo-1,8-naphthalenedicarboxylic anhydride, 4-bromo-N-butyric acid-1,8-naphthalimide, and 1-pyrenic acid.

5. The method for preparing the vegetable oil-based photocurable 3D printing resin with temperature response and / or fluorescence and / or phosphorescence properties according to claim 1, characterized in that: The temperature range of the thermochromic powder is 30-90℃.

6. The method for preparing the vegetable oil-based photocurable 3D printing resin with temperature response and / or fluorescence and / or phosphorescence properties according to claim 1, characterized in that: The photoinitiator is one or a combination of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexylphenyl ketone, ethyl 2,4,6-trimethylbenzoylphenylphosphonate, 2-dimethylamino-2-benzyl-1-[4-(4-morpholinyl)phenyl]-1-butanone, 2-methyl-2-(4-morpholinyl)-1-[4-(methylthio)phenyl]-1-propanone, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone, thiopropoxythionone, and methyl benzoylcarbamate.

7. The method for preparing the vegetable oil-based photocurable 3D printing resin with temperature response and / or fluorescence and / or phosphorescence properties according to claim 1, characterized in that: The reactive diluent is one or a combination of trimethylolpropane triacrylate, 1,6-hexanediol diacrylate, polyethylene glycol diacrylate, pentaerythritol triacrylate, neopentyl glycol diacrylate, and tripropylene glycol diacrylate.

8. The method for preparing the vegetable oil-based photocurable 3D printing resin with temperature response and / or fluorescence and / or phosphorescence properties according to claim 1, characterized in that: The thiol functional monomer is one or two of pentaerythritol tetra(3-mercaptopropionate) and trimethylolpropane tri(3-mercaptopropionate).

9. A vegetable oil-based photocurable 3D printing resin having temperature-responsive and / or fluorescent and / or phosphorescent properties, prepared by the method according to any one of claims 1-8.

10. The application of a vegetable oil-based photocurable 3D printing resin with temperature-responsive and / or fluorescent and / or phosphorescent properties as described in claim 9 in the preparation of anti-counterfeiting and information encryption materials with temperature-responsive and / or fluorescent and / or phosphorescent properties, characterized in that, The specific steps are as follows: A plant-oil-based photocurable 3D printing resin with fluorescent properties, a plant-oil-based photocurable 3D printing resin with phosphorescent properties, or a plant-oil-based photocurable 3D printing resin with temperature response is injected into the resin tank of an LCD photocurable printer. The printing parameters are set as follows: layer thickness 0.02 mm, number of bottom layers 10, bottom layer exposure time 50 seconds, normal layer exposure time 6-15 seconds. The LCD additive manufacturing process is then performed to obtain anti-counterfeiting and information encryption devices with fluorescent properties, phosphorescent properties, or temperature response. Alternatively, a "multi-layer ink-changing-layer thickness control" strategy can be used to 3D print using prepared plant oil-based photocurable 3D printing resins with fluorescent, phosphorescent, and temperature-responsive properties. When the printing process progresses to a specific number of layers, information storage and encryption based on different printing layers can be achieved by switching functional inks. The printing parameters are set as follows: layer thickness 0.02 mm, bottom layer number 10 layers, bottom layer exposure time 50 seconds, normal layer exposure time 6-15 seconds, and LCD additive manufacturing process is executed to obtain a multi-layer 3D printed anti-counterfeiting and information encryption device with temperature-fluorescence-phosphorescence properties.

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